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278 BRIQGIS THE THEORY OF DUPBEX AFPINITY. XX1X.-The Theory of Duplex Afinity. By SAMUEL HENRY CLIFFORD BRIGGS. IN a former paper (T. 1908 93 1564) it was shown how the old conception of duplex affinity cap be applied in devising con-stitutional f o m u l z for complex inorganic compounds. In a sub-sequent paper (ibid. 1917 111 253) the theory of duplex affinity was treated from the point of view of the electrical structure of matter. It was assume! that every element is able to exert both positive and negative affinity positive affinity being a tendency to lose electrons and negative affinity a tendency to attract electrons. A further distinction was made between primary and secondary affinity the secondary affinity being opposite in sign to the primary affinity and only coming into action after the primary affinity has been satisfied.By means of these assumptions it was possible to correlate a number of apparently disconnected pheno-mena including the structure and stability of complex compounds, the strength of acids and bases polymerisation etc. The present communication is concerned more particularly with secondary affinity and some conclusions have been reached which have made it possible to apply the theory of duplex affinity in several new directions. Secondary Negative A fltritg and Secondary Positive Affinity. As in the previous paper (T. 1917 111 253) Lodge’s view (Nature 1904 70 176) that’ the electrons in an atom are bound to the positive charge not by a sir,gle line of attraction or elastic thread but by a bundle of a very large number of lines of force, is adapted.For the sake of simplicity it is supposed that the atoms are spheres although this is not an essential feature of the general argument. The volumes of the atomic spheres are assumed to be directly proportional to the so-called atomic volumes of the elements. The term ((valency” is used in this paper in a strictly electro-chemical sense in accordance with Sir J. J. Thomson’s theory (Phil. Mag. 1914 [vi] 27 757). Consider the case uf two univalent atoms A and B which c m -bine to form a compound A B as the result of the transfer of an electron from A to B A having positive primary affinity and B havipg negative primary affinity. Owing t o the attraction of B for the electron a number of lines of force which united th BRICKS THE $HEORY OF DUPLEX AFFINITY.279 electron to the positive nucleus of the atom A are broken. Call this number u. Then in the atom B u lines of force joining electrons in the atom B (previous to its combination with A ) t o its positive nucleus will be loosened as a result of the passage of the electron from A to B. Suppose now that the compound A B undergoes electrolytic dissociation in solution into the ions rl and B f . The positive nucleus of the cation A' will be able to bind u lines of force from electrons in other atoms that is to say, the cation A' will have negative affinity and in this way the secondary negative afiity of the element A arisa. The electrons in the anion B' on the other hand will have u. lines of force loosened and therefore be able to attach themselves to the positive nuclei of other atoms.Consequently the anion B f has positive affinity which is the secondary positive affinity of the element 13. Attention must now be directed to a fundamental difference between secondary negative affinity and secondary positive affinity. According to the modern views on the electrical struc-ture of matter the positive nucleus is situated a t the centre of the atom and its spatial dimensions are extremely minute compared with the volume of the atom as a whole. As we have seen above, however secondary negative affinity arises from the power of the iiucleus to attract lines of force (or electrons). Since the nucleus is a t the centre and is so exceedingly'small it follows so far as the effect on other atoms is concerned that secondary negative affinity may be regarded as an attractive force distributed equally over the surface of the atomic sphere.Secondary positive affinity on the other hand emanates from the outer electrons (valency electrons or mobile corpuscles) in the atom. The secondary positive affinity cannot therefore be regarded as being equally distributed over the atomic sphere but must be confined to certain individual electrons or rings of electrons. In other words secondary negative affinity conforms to Werner's theory of affinity (" Neuere Anschauungen auf dem Gebiete der anorganischen Chemie," 3rd ed. p. 83) whereas secondary positive affinity does not. This difference between secondary negative affinity and secondary positive affinity appears to be of consider-able importance in the building up of inorganic compounds as will be more clearly seen below.When the ions A' and B f combine to form the molecule AB, some of the looeened lines of force in B will be attached to the positive nucleus of A as shown by the "ionic formula" .-.-+A'-B'--+ (T. 1917 111 253). If the number of lines of force thus attached is denoted by v then in the compound AB the positive nucleus of A is still able to bind u-u lines of force 280 BRIGGS THE THEORY OF DUPLEX AFFINITY. whereas the electrons in B have still u-v lines of force loosened and capable of attachment to the nuclei of other at,oms. The number u-v theref ore represents the unsaturated secondary negative affinity of A and the unsatura.ted secondary positive affinity of B indicated by the dotted arrows in the “atomic (T.1917 111 253).* formula ” -..-+A-B.--t and in the “ ionic formula ” --.+A *-B’--Imfluence of A tonaic Volume. Sinco the secondary negative affinity is distributed equally over the surface of the atomic sphere it follows that when the atomic volume is large v will be correspondingly small and u-v propor-tionat’ely large (see p. 286). When the compound A B is dissolved in a dissociating medium such as water the molecules of the solvent combine with A and B by means of the unsaturated secondary affinity thereby bringing about dissociation into the ions A’ and B’ (compare T. 1908 93 1564). Therefore i f u-v is large A B will be a strong electrolyte. As shown above however, u-v is large when the atomic voluine of A is large and this is the reason why the salts of the alkali metals are the st’rongest electro-On the other hand although when the atomic volume of A is large the total unsaturated affinity is correspondingly large never-theless the intensity of the affinity per unitn area of the atomic sphere varies in8versely as the square of the radius and is there-fore large when the atomic volume of A is small.Consequently, the molecular compounds (nX. A)B formed by satisfying the free secondary negative affinity of A4 by the free secondary positive affinity of n molecules of a compound ikf (such as ammonia or water) (T. 1917 111 253) will be most clearly defined and stable lyte6. * Three types of combination are distinguished (1) Combination due t o primary affinity only as in the formula --+ A - B -+ the passage of the electron from A to B being indicated by the thick arrow pointing from A to B.(2) Combination due to secondary affinity only as seen in molecular corn-pounds such as 2H,N -+ CuCl the union of the electrons in the nitrogen atom to the positive nucleus of the copper atom being indicated by the thin arrow pointing from nitrogen t o copper. (3) Combination due to both primary and secondary affinity as in the non-polar compound A It should be noted that the formulze --t A 3 B -- and A Z? B represent the limiting cases of the strongest possible electrolyte and the truly non-polar compound respectively. Most compounds will come in between the two formula A compound of intermediate properties might therefore be Written --+ A B--t but it is often convenient to write it as a compound of charged ions rather than of atoms and in this way the “ionic formula” B.---+ A’ c B’ -+ derived BRIGIGS THE THEORY OF DUPLEX AFXINITY. 281 when the volume of A is small. As a matter of fact those elements which form the most stable complex compounds are all found in the depressions of the atomic volume curve (chromium, manganese iron cobalt nickel copper zinc ruthenium palladium, rhodium silver osmium platinum iridium and gold) (see also the work of Ephraim on the effect of the atomic volume of the central atom on the stability of metal-ammonia compounds Bw., 1912 45 1322). Conversely the same reasoning elucidates the somewhat contra-dictory phenomenon that many of the salts of the alkali metals which are readily soluble in water separate from solution in the anhydrous state.These salts dissolve readily because of the large value of u-21. They do not give stable hydrates because of the small intensity of the affinity per unit area of the atomic sphere which results from the large atomic volume of the alkali metals. Non-polar Compounds. If the two ions A' and B/ were to combine in such a way that the secondary affinities completely saturated each otlher then the electron would be pulled back into A and the atoms would be held in combination by means of two equal bundles of lines of force one passing from the nucleus of A to the electrons of B and t'he other from the nucleus of B to the electrons in A .That is t o say A B would be a non-polar compound as shown by the formula A = B. The conception of secondary negative affinity developed above (p. 279) leads to the following conclusions with regard to the con-ditions for the formation of non-polar compounds in those cases in which the valency of the element ,4 with primary positive affinity is fully saturated. The conclusions do not however apply when .-I is not exerting its full valency as the mobile corpuscles still remaining on A introduce complications. The compounds to be considered therefore are those represented by the formula AB, in which x varies from 1 to 8 when B is a univalent atom. When x = l the secondary negative affinity of A is only partly saturated as already explained (p.2803 because only a part of the spherical surface of A comes under the influence of B. I f x=2 and A is therefore united to two atoms of B a larger part of the spherical surface of A is affected and in general as s in-creases more and more of the spherical surface of A is brought under the influence of B. Hence as x increases the tendency of A B to undergo electsolytic dissociation decreases (see p. 280) 282 BRIGQS THE THEORY OF DUPLEX AB"ITY. The salts of the metals in the earlier groups of the periodic table are theref ore the strongest electrolytes and the electrolytic proper-ties become less marked in the compounds of tho metals with higher valency (when they are exerting their full valency). If however AB is to be a truly non-polar compound the secondary negative affinity of A which is distributed equally over the surface of the a t m i c sphere must be completely saturated, and the optimum condition for such complete saturation will be reached when the atoms of B are symmetrically distributed in space around the spherical surface of A .Since the maximum valency is S the number of cases of sym-metrical distribution is strictly limited. If B is univalent x may be 4 6 or 8 when the atoms of B will be distributed around the spherical surface of A a t the corners of a regular tetrahedron a regular octahedron and a cube respectively. If B is bivdent the only possible case is x=4 when the B atoms are situated a t the corners of a regular tetrahedron. We should therefore expect to find the non-polar propertdes most strongly marked in compounds having the fomulz AB, AB, and AB when B is univalent and AB when B is bivalent.Since the forces between the molecules of non-polar compounds are small (Thornson Zoc. cit. p. 760) such compounds in addition to their inability to undergo electrolytic dissociation will also be comparatively volatile and more o r less inert. There are several striking instances of compounds with these characteristics in the four classes of substances under discussion. I n the group AB we have the,typically non-polar compounds, methane and carbon tetrachloride. The formula AB is represented by the gaseous sulphur hexa-fluoride SF, which is almost as inert as nitrogen (Moissan and Lebeau Compt. rend. 1900 130 865 954; Berthelot Ann. Chim.Phys. 1900 [vii] 21 205) and by the gaseous tungsten hexa-fluoride (Ruff and Eisner Ber. 1905 38 742) WB,. Only one compound of the formula AB has hitherto been pre-pared. This is osmium octafluoride (Ruff and Tschirsch Ber., 1913 46 929) which boils below 50° and is a highly stable although reactive substance. The class AB, in which B is bivalent includes the remarkable tetroxides of ruthenium and osmium RuOI and OsO,. These com-pounds both boil a t about looo and are so completely saturated that they are incapable of combination with alkali hydroxides. Indeed osmium tetroxide can be distilled off from its solution to which an alkali has been added (compare Ostwald " The Principles of Inorganic Chemistry," p. 757) BRIUQS THE THEORY OB DUPLEX AFFINITY. 283 Although symmetry of structure is thus often associated with, and conduces to non-polarity it does not follow that a 1 sym-metrical compounds will be without polarity as other factors such as the relative atomic volumes of A and B will also exert an influence.Conversely when A is not exerting its full valency non-polar combination is possible in subst4ances which are not spatially sym-metrical. Thus according to Thomson (loc. cit.) carbon monoxide and nitrous oxide are non-polar compounds. Other examples given by Thomson bring out the relationship between symmetry and non-polarity in another way. Although both carbon tetrachloride CCl, and methane CH4 are truly non-polar nevert'heless clilorof orm CHCI, and methyl chloride CH3C1, are polar compounds. Werner's Co-ordination Nzi,mbers md the Co-ordination Formula.Suppose the cation A' combines with molecules of a com-pound M pwsessing free secondary positive affinity such as dmmonia or water to give the complex ion (rtM . A ) * . Here also the conditions for maximum saturation of the secondary negative affinity of A will involve spatial symmetry in precisely the same way as was seen to apply in the formation of non-pdar compounds. The maximum value of n should therefore be either 4 6 or 8, according to the relative volumes of the atom A and the molecule M ; but the maximum value of n is the maximum co-ordination number of the element A and Werner (Isc. cit, p. 52) has shown that this is either 4 6 or 8. It would appear also that the geo-metrical relationship existing between the volumes of the central atom A and the molecule M is of more importance than the intensity of the affinity in determining the value of the co-ordina-tion number.We find f o r example that barium with a com-paratively large atomic volume has the maximum co-ordination number 8 as seen in the compound (Ba8NH3)C1, whereas cobalt, with a much smaller atomic volume has the maximum ceordina-tion number 6 in the compound (Co6NH,)C13 in spite of the fact that cobaltic salts have a much greater tendency to combine with ammonia than is shown by barium salts. Similarly boron with a very small atomic volume has the maximum co-ordination number 4 in the compound (BF4)H. Attention must now be directed to the limiting case in which the secondary negative affinity of A is cornpZeteZy saturated by the free positive affinity of M giving the complex ion ( n M .A ) * . In what way will the anion H' combine with this complex cation t 284 BRIGUS THE THEORY OF DUPLEX AFE'INTTY. give the molecule (mM . A ) B ? suppose that ill is a molecule of ammonia. (T. 1908 93 1564; 1917 111 253) ammonia was written I n discussing this question we may In the former papers =H = [I This formula was derived from the facts (1) that the hydrogeii atoms do not undergo electrolytic dissociation in solution in water, and therefore have both primary and secondary affinity saturaLeed, and (2) that the nitrogen atom has free secondary positive affinity, d s shown by the ease with which ammonia molecules can combine with the free secondary negat.ive affinity of metals in their salts to give metal-ammonia compounds.From the reasoning developed above however (p. 280) it is clear that this formula for ammonia, although correct so far as it goes is not quite complete because if the nitrogen atom still has u-2 lines of force loosened as expressed by the dotted arrow then each hydrogen atom must be able to +-- NZZH , bind *?I! lines of force to its nucleus. In other words each 3 hydrogen atom has still a litkle free secondary negative affinity. Since however the free secondary positive affinity in the ammonia molecule is confined to one atom only (the nitrogen atom) it masks the free secondary negative affinity which is distributed over the three hydrogen atoms. I n the general case of a compound A,B,, in which A and B have free secondary affinity if nz is greater than n the molecule A,B will react as if it had the free secondary affinity of B only.This characteristic will be the more strongly marked &he greater the difference between m and n and it will be all the more intensified the greater the volume of A (the atom with primary positive affinity) and vice versB. Thus we find that ammonia water and potassium chloride react as if they had free secondary positive affinity only in forming complex compounds, whereas cupric chloride ferric chloride etc. behave liike substances with free secondary negative affinity. The complete formula for ammonia should therefore be written in which each hydrogen atom hss a little free secondary negative affinity.Returning now to t.he combination of the complex (izM.A)' with t.he anion B' t o give the salt (mM.A)B we may take the concrete case in which the complex is (CO~NH,)"' and the anion is Cl' and assume that the secondary negative afiinity of the cobalt atom is completely saturated by the free secondary posit'ive affinity of the nit.rogen in the six molecules of ammonia BRIGGS THE THEORY OF DUPLEX AFFINITY. 285 The only possible way in which the chloride ions can unite with the complex to give the salt (C06NH3)C13 is by the saturation of the free secondary negative affinity of the eighteen hydrogen atoms by the positive affinity of ths chlorine ions. This gives Werner's co-ordination formula (Co6NII3)CI3 exactly in which according to Werner's phraseology the chlorine atoms are united to the outer sphere of the complex.It should be carefully noted however that the co-ordination formula only applies to the limitiizg case in which the secondary negative affinity of A is completely saturated by ?LM in the com-plex (%Ma A ) ' . If this saturation is not complete then the posi-tive nucleus of A will exert an attraction on the electro'ns in B, as shown by the "ionic formula " 7zM-A'-B'--+ (T. 1917 111, 260). A familiar example is seen in aquopentammine cobaltic chloride (Co H,03 a, which changes spontaneously into chloro-pentammine cobaltic chloride (Co c S)Cl,. Unless the cobalt atom exerts a direct attraction on the chlorine atoms as shown by the formula 5NH,-Co"'-CI,"'.-.~ H,O- it is impossible t o understand EiNH 5NH ) this spontaneous change.Application of t h c Tlieoiy of Buplex A f i l l i t y t o Oxygen Compounds. In the former papers (Zoc. c i t . ) most of the examples considered were halogen compounds. The development of the theory of secondary negative affinity in the present communication has made it possible to study oxygen compounds from the point of view of duplex affinity in such a way as to bring out some general relation-ships which are not touched on by other theories of affinity and valency . Take the case of a metal M which folrms a series of oxides, MO MO, MO, MO,. I n the oxide 1510 in which the oxygen atom has received two electrons from the atom M only part of the atomic sphere of M will come under the influence of the oxygen atcorn.Hence the secondary affinity of both atoms will be partly unsaturated and the formula will be ..-.&o*-+ * * Instead of denoting the passage of two electroizs by two thick arrows M 0 it is more convenient to write one arrow only with a small figure above to express the number of electrons which it represents for example, M - 0. 286 BRIQQS THE THEORY OF DUPLEX AFBINITY. When & I 0 is oxidised to give MO, a greater part of the spherical surface of M will come under the influence of the oxygen atoms, and the saturatian of the secondary affinity will be more complete than i n the first oxide MO. This will apfily still more in MO,, and most of all in MO, in which the oxygen atoms are distributed symmetrically in space around M. I n MO we therefore have the possibility of complete saturation of the secondary affinity with t,he production of a non-polar compound.The oxides OSO and RuO, referred to above (p. ZSZ) appear to approximate closely to this condition. The four oxides should therefore be written (assuming that MO is non-polar): 2 4 6 R .-+Mta ...-+ --+ MtO,--+ --+afz()3- -+ Mcr-0,. It may perhaps be better to write the non-polar oxide M S O , rather than MtO, as the electrons will not have left the M atom in this case. It should be carefully noted that since the secondary affinity of M is increased by each addition of an oxygen atom the satura-tion of the secondary affinity of the first oxygen atom becomes more complete as oxidation proceeds because the secondary affinity of M being distributed equally over the surface of the atomic sphere the intensity of the affinity present on that part of the spherical surface which comes under the influence of the first oxygen atom will increase with increase in the number of oxygen atoms combined.The free secondary affinity of the first oxygen atom will therefore decrease with increasing oxidation of M until in the final non-polar stage the secondary affinity of the first oxygen atom will be completely saturated. The same reasoning applies of course to all the other oxygen atoms as well. The Hydration of Oxides.-When potassium oxide and water are brought together tlhere are two ways in which combination may occur. The strongly marked free secondary positive affinity of the oxygen atom in the potassium oxide may attract the hydrogen atoms of the water which have slight unsaturated secondary negative affinity or the unsaturated secondary negative affinity of the potassium may combine with the slight free secondary positive affinity of the oxygen atom in the water molecule.We may therefore obtain a .-- +K,O-H ,O. .. f or -- +H,O-K,O -...+ or perhaps a ring st,ructure K,+O o-H2. I n potassium u-v is large, owing to the large atomio volume of potassium (see p. 280) and therefore the unsaturated secondary affinities of the potassiu BRIGGS THE THEORY OF DUPLEX AFFINITY. 287 atoms and the oxygen atoms are large. I n water on the other hand u-v is small (as seen from the very slight extent to which it is dissociated into hydrogen and hydroxyl ions); hence the un-saturated secondary affinities of the hydrogen atoms and the oxygen atom are small.I n each of the three folrmulae for K,O,H,Q we consequently have the two potassium atoms electrically equal the two hydrogen atoms electrically equivalent but the two oxygen atoms very different from each other. The tendency will be for bhe.affinities t o be redistributed in such a way as to make the two oxygen atoms also electrically equal and we therefore have the change K,O,H,O *- 2KOH. Similar considerations will apply to ~~ the hydration of other oxides. Bases and Acids.-When an oxide is hydrated the product may be either a base or an acid according t o l the manner in which it undergoes electrolytic dissociation i n solution. I f MOH were a base of the strongest possible type the formula would be written as (I) and i f it were the strongestl possible type of acid as (11) (T.1917 1111 253). It has already been shown (p. 286) khat increase in the number of oxygen atoms implies a more complete saturation of the secondary affinity of all the oxygen atoms already present in the oxide (anhydrous or hydrated). As the secondary affinity of the oxygen atom of the hydroxyl group becomes more completely saturated by the secondary affinity of M there is less affinity left to saturate the secondary affinity of the hydrogen of the hydroxyl group and the free secondary a4inity of the hydrogen therefore increases. Consequently the tendency of the hydrogen atom to be electrolytically dissociated becomes greater and the structure of the hydroxyl group changes from -0-H (basic) to Z0-H- (acidic) with increase in the number of oxygen atoms united to the element M .We therefore have the following general rule : W h e n a series of oxides of t h e same elemend M a r e hydrated, t h e hydrate of t h e highest oxide i s t h e strongest acid ( o r weakest base). I n other words in a series &LOH the greater the value of x the stronger the acidic properties (or the weaker the basic properties). Y j. 0 288 BRIGGS THE THEORY OF DUPLEX AFFINITY. This rule appears to hold good throughout the periodic table. It is exemplified most clearly in the compounds of the elements in the sixth seventh and eighth groups these being the elements which exhibit the most numerous stages of oxidation.Thus ferrous oxide is basic ferric oxide less basic (as shown by the greater ease with which ferric salts are hydrolysed) and iron tri-oxide is acidic. The oxides of chromium form a similar series from the basic chromous and chromic oxides to the acidic chromium tri-oxide. Manganous oxide is basic manganic oxide less basic and manganese dioxide no,t definitely basic or acidic whereas man-ganese trioxide is acidic and dimanganic heptoxide strongly acidic. The oxides of chlorine give rise to a series of acids increasing in strength from the very weak hypochlorous acid HOC1 to the strong chloric and perchloric acids HOC10 and HOCIO,. Among nitrogen compounds hyponitrous acid is very weak nitrous acid is stronger and nitric acid is one of the strongest acids known.The fact that ruthenium and osmium tetroxides are not acidic, although diruthenium heptoxide is strongly acidic is only an apparent exception t o the rule. Owing to their highly saturated character as has already been shown (p. 282) these compounds are incapable o f combination with water and cannot therefore give rise to hydrated oxides. They therefore do not come within the scope of the rule which applies t o hydrated oxides only. The Hydrogen Ion and the Catalytic Activity of Acids. From the point of view of the theory of duplex affinity the hydrogen atom is particularly interesting. According to the views of van den Broek and others (Ann. Reports 1913 18 271) the hydrogen atom is *built up of a positdve nucleus and one electron (compare Allen T. 1918 113 390).Consequently the hydrogen ion H’ must consist of a positive nucleus only. The secondary negative affinity of the hydrogen ion must theref me be considered to be concentrated in a “ point” uf nuclear dimensions rather than distributed over the surface of a (comparatively) very large sphere. The conclusions which have been arrived a t i n the above discussion from the consideration of the atomic sphere will therefore not neces-sarily apply to hydrogen. Thus it is not essential for the produc-tion of non-polar compounds that the hydrogen atom should be surrounded by negative atoms as in the cases of sulphur and osmium for example (see p. 282) methane being a typical non-polar compound. The identity of the hydrogen ion with the positive nucleus of the hydrogen atom may perhaps ultimately furnish a rational ex BRIGGS THE THEORY OF DUPLEX AFFINITY.289 planation of the catalytic activity of acids somewhat on the follow-ing lines. Take a molecule AZ-B with a tendency to dissociate according to the equation ABe2ZA-t-B. A hydrogen ion (nucleus) if brought into contact with such a molecule will attract to itself some of the lines of force joining the electrons in A to the positive nucleus of B or the electrons in B t o the positive nucleus of A , --+AZB+ -giving \ J H 4 The bond uniting ,4 to B will therefore become weaker and the tendency of AB to dissociate will be increased. It is consequently tm be expected that the hydrogen ion will accelerate a chemical change which is already taking place or even induce a change which would not otherwise occur.Theoretically speaking other positive ions should act in a similar manner ; but since the secondary negative affinity of all other element5 is distributed over the surface of a comparatively very large sphere instead of being concentrated in a “point” of nuclear dimension the catalytic activity of other cations will be exceedingly small compared with that of hydrogen ions. According to the theory of acids developed in the former paper (T. 1917 111 253) i f we neglect unsaturated affinity the general formula for acids may be written H Z X . I f x is the value of the saturated primary affinities and y the value of the saturated secondary affinities in the formula H S X y may vary from y=x (the weakest possible acid) to y = 0 (the strongest possible acid).If we now write the formulae to sho’w the unsaturated affinities, the strongest possible acid has the forniula (I) and the weakest possible acid the formula (11). -.-*H-X- H Z X (1.) (11.) The formula (I) is the case where v (see p. 279) is vanishingly small. Strictly speaking it is the formula of the dissociated acid (21 = 0). The unsaturated secondary negative affinity of the hydrogen atom in a molecule of the strongest possible acid (I) is hherefore equal to that of the hydrogen ion itself and as we pass down the series through acids of decreasing st*rength the un-saturated secondary negative affinity of the hydrogen atom becomes less until it vanishes as seen in formula (11). It therefore follows that the undissociated molecule of a very strong acid should also exert catalytic activity which catalytic activity should decreas 2 90 BRIGCGIS THE THEORY OF DUPLEX AFPINITY.with decreasing strength of the acid becoming zero in the weakest possible acid (11). It has been shown experimentally that the undissociat>ed molecule of an acid has catalytic activity the activity diminishing with decreasing strength of the acid (Goldschmidt and Thuesen Zeitsch. physikal. Chem. 1912 81 39 ; Dawson and Powis, T. 1913 103 2135; Dawson and Reiman ibid. 1915 107 1426; Snethlage Zeitsch. physikal!. C'hem. 1913 85 211) but according to Dawson and Powis the activity of the undissociated acid in some cases is much greater than that of the hydrogen ion. I n considering this question i t is necessary to take into account the effect of solvation.According to the theory of duplex affinity the chief cause of electrolytlic dissociation is the combination of solute and solvent ky means of unsatnrated secondary affinity (see p. 280). I n a solu-tion of an acid we therefore have the following equilibria: Undissociated molecule + solvent E-Z solvated molecule. Solvated molecule EZiZ solvated hydrogen ion + solvated anion. Solvated hydrogen ion Z5iG solvent + hydrogen ion. Solvated anion EZsolvent + anion. Hydrogen ion + anion T5G undissociated molecule of acid. Take now the extreme case in which the secondary negative affinity of the hydrogen ion is completely saturated by the secondary positive affinity of n. molecules of the solvent S (as i n a very basic liquid) to give the complex ion nS.TI*. The positive charge will now be distributed over the comparatively very large outer' sphere of the complex (compare p. 284) instead of being concentrated in the nucleus of the hydrogen ion and the catalytic activity of the complex will therefore be comparatively very small. Solvation will therefore reduce the catalytic activity of both hydrogen ion and undissociated molecule and the observe'd catalytic activity of the hydrogen ion and 'the undissociated molecule in any given experiment will not be proportional to t h e real catalytic activity of each when unsolvated but will depend on the degree of solva-tion of acid and hydrogen ion in accordance with the abovemen-t>ioned equilibria. Again if the solvation is slight the solvated ion and the solvated molecule may also have appreciable catalytic activity.These principles are in agreement with the experimental observa-tions on the relative catalytic activities 5 f acids in different media. Wat'er forms complexes much more readily than alcohol ; therefore in aqueous solution solvation should be greater than in alcoholic solution and the catalytic activity of acids should be less in water than in alcohol (compare Kistiakowski Zeitsch. physikal. Chem. BRIGCIS TEE THEORY Ol? DUPLEX AFFINITY. 291 1898 27 253 and especially Dawson T. 1911 99 1). Dawson has found that in alcoholic solutions the catalytic activity may be one hundred times as great as in water. Further the addition of water has been found to decrease the catalytic activity in alcoholic solutions and this has been shown to be due t o combination of the water with the hydrogen ions (Goldschmidt and Udby, Zeitsch.physikal. Chem. 1907 60 728; Lapworth T. 1915 107, 857). It would be of considerable interest from the point of view of this paper if experiments could be made on the catalytic activity of acids in some truly non-polar medium such as benzene or carbon tetrachloride. In such a medium solvation and ionisation would be reduced to a minimum because non-polar compounds are fully saturated and therefore unable to. combine with the solute. It has been shown for instance that benzene a t 1 8 O dissolves 2 per cent. of its weight of hydrogen chloride and that the solution is without electrical conductivity (Falk and Walker A mer. Chem . J . 1904 31 398). The catalytic activity in a truly non-polar medium would therefore be due t o the unsdvated molecule only, and in the case of a very strong acid would probably be very great compared with the activity of the undissociated molecule in aqueous o r alcoholic solution. F o r the sake of simplicity it has been assumed throughout this paper that the atoms are spheres. It must be emphasised in con-clusion however that the atomic sphere so often referred to is a purely geometrical conceptmion. We may suppose it la be a sphere described around the atom with the positive nucleus a t the centre, and the radius sufficient to include all the constituents of the atom (valency electrons etc.) within the sphere. The use of this con-ception is justified by the atomic volume relationships of the elements and by the fact that the atoms are not capable of inter-penetration when endowed with such smdl amounts of energy as correspond with the motions of thermal agitation of molecules (compare R . A. Millikan “The Electron,” pp. 139 191). [Received October 23rd 1918.

ISSN:0368-1645    

DOI:10.1039/CT9191500278

出版商:RSC    

年代:1919

数据来源: RSC

摘要:

292 GHOSH CURCUMIN. XX X.-Curcumin. By PRAPHULLA CHANDRA GIIOSH. THE work described in this paper was in progress and in fact' ccm-pleted before an account of the synthesis of curcumin by Lampe (Ber. 1918 51 1347) appeared. A portion of the work was devoted to proving the presence of .the CO*CH,*CO* group which in any case is now clear from the OMe OMe synthesis confirming the formula, HO/ \CH:CH~CO.C~~,~CO~CH:\-/ \-/ previously put forward by Milobendzki Kostanecki and Lampe (Ber. 1910 43 2163). The results bearing on tnhis point' are there-fore given in an exceedingly abbreviated form. With benzaldehyde curcumin forms a benzylidene derivative and i t also forms a condensation product with nitrosodimethylaniline. The action of bromine on curcumin and some of its derivati-Jes was also studied with the object of testing the presence' of two double bonds.There were obtained mono b romoc urcumin C,,H,,O,Br mono-bromodicarb e thox y curcumin C2,H1704Br (0- CO,E t)2 monob romo-dicarb ethoxycurcumin tetra bromide C2,H,704Br,(O*C02Et)2 cli-bromdicurb e t Jboxy curcumin t c trabromide C2,H,,04Br,( O*CO,Et) , monobromodiacetylcurcumin C21,H,70,Br(OAc)2 dibromodiucetyl-curcumin tetra b romide C2,H1604Br6 ( O h ) mono b romodime t hyl-curcumirc C2,H,,04Br(OMe), and clibromocFimethylcurc~~mi~ tetra-bromide C21H&&k6(OMe)2. In the course of this investigation it was discovered that dicarb-ethoxycurcumin could be converted into dicarbethoxyisocurcumin simply by boiling with acetic anhydride and pyridine. to the view that one of the two known diacetyl derivatives of curcumin was probably diacetylisocurcumin.Ciamician and Silber described a diacetylcurcumin melting a t 169-1 70° whilst JackJon prepared an isomeric substance melting a t 1 5 4 O by acetylating curcumin with acetic anhydride and sodium acetate. It vas suspected that the latter was probably diacetylisocurcumin and this suspicion was found to be correct. Jackson's compound which can also be formed by acetylating aureumin with acetic anhydride and pyridine gives Heller's iso-curcumin (Her. 1918 47 887) on hydrolysis. It is therefore quite Thi GHOSH (YURQUMIN. 293 easy t o convert curcumin into isocurcumin. represented graphically thus : These reactions can be Dicarbethoxycurcumin + Curcumin Boiling with I ace.Dicarbethoxyisocurcumin +- isoCureurnin. This simple conversion of curcumin into isocurcumin confirms Heller's view that the two substances are geometrical isomerides. Frqm the ferric chloride reaction Heller considers that curcumin exists in the enolic form (I) and as there is considerable OMe CM~-CH:CH/-\OH c (0 H ) CH c H ~ \ O H CO-CH:CH/-\OH CO- CH :CH<>OH \-/ \-/ 1, OMe ""\ OMe L/ (1.1 (11.1 resemblance between this formula and that of divanillylidenc-mesityl oxide (11) the latter has been prepared in the course of this investigation by condensing two molecular proportions of vanillin with one of mesityl oxide by means of hydrochloric acid and it is intended ta compare the absorption spectra of this substance with that of curcumin; similarity of absorption spectra would speak in favour of similarity of molecular configuration.The condensation of mesityl oxide with some other aromatic aldehydes has been studied and p-hydroxyb enaylidenemesityl oxide, 0-hydroxybenzylidememesityl oxide piperonylidenemesityl oxide, and cinnamylidenemesityl oxide have been isolated. I n connexion with the geometrical isomerism of curcumin and isocurcumin there is some evidence that cinnamylidenemesityl oxide and piperonylidenernesityl oxide exist in two forms. Most of the compounds examined in the course of this investiga-tion are fluorescent. They are arranged in the following list in the order of their intensity of fluorescence: VOL. cxv. 294 GHOSH aURUUMIN. Substances arranged in gradually diminishing order of fluorescence.Curcumin . . . . . . . . . . . . . . . . . . Benzylidenecurcumin, CHPh:C( CO'CH:CH'C6H,[OMe]'OH), pHydroxybenzylidenemesity1 oxide, OE'C,B;CH:CH'CO'CH:CMe, .................. o . H y droxyben z ylidenemesit yl oxide Dicarbthoxycurcumin, CH,(CO'CH:CH*C,H,[OMe]*O*CO,Et), Diacetylcurcumin, CR,(CO*CH:CH'C,H,[OMe]*OAc), Divanillylidenemesityl oxiclo .............................. Solvent in which the greatest intensity is observed. Chloroform. Acetone. Toluene Toluene. Ace tone. Acetone. Acetone. Monobromocurcumin, Moaobrorno&aarbethoxycuwumin tetrabromide. Dibromo dicarbe t hox ycur cumin tetrabromide, CHBr(CO'CH:CH'C,H,[OMe]'OH) Acetone. CHBr( CO'CHBr'CHSr'C sH,[OMe]'O'CO,Et) Chloroform. CBr,( CO'CHBr'CHBr'C ,H ,[OMe~O*CO,Et) Chloroform.From these observations it may be ipferred that (1) auxochromic groups (2) the labile hydrogen atoms (3) the double bonds and (4) the symmetry of the molecule increase fluorescence butt are not the invariable factors of fluorescence. EXPERIMENTAL. RenzyZide.neczirczcmi,l. C,H,*CH:C,,H,,O,.-A current of dry hydrogen chloride was passed through a mixture of benzaldehyde (0.5 gram) curcumin (1.8 gram) and alcohol (40 c.c.) cooled with ice. The colour became dark violet probably owing to the form-aticm of curcumin hydrochloride and in about a day the whole of the curcumin dissolveld and the colour changed to orange-red. After forty-eight houm the mixture was poured into ice-cold water, when a greenish-yellow precipitate was obtained which could not be crystallised.It was purified by solution in acetic acid and frac-tional pxecipitation by sodium. acetate (sample E) and subsequently in the sitme way by precipitation from an alcoholic solution by water (sample 11). E t is soluble in alcohol acetic acid acetone, or chloroform shrinks slightly a t 170° and melts a t ZOOo: C=73*5; € 3 ~ 5 . 4 . I. 0-1000 gave 0.2695 CO and 0.0486 H,Q. 11. 0.1104 , 0.2965 CO , 04.0527 B,O. C=73.25; H=5*3. CzsH2*0 requires C=73*68; H=5.26 per cent. Condensation Product of Curcumin md Nitrosodime t hylaniline , N( CH3)2,*C6H,'N:C2,Hl,06.-o.ne part of curcumin and one part of nitrosodimethylaniline were dissolved in alcohol two parts of zin chloride were added and the mixture was warmed for a few minutes on the water-bath.When the colour became brown the product was precipitated by water. A good deal of tarry matter was dis-solved by treatment with 30 per cent. acetic acid. The residue could not be crystallised but was purified by fractional precipita-tion from acetic acid solution by water. The substance obtained in this way .is fairly readily soluble in alcohol acetic acid or acetone shrinks a t 98O and melts and decomposes at 144-145O. Two fractions obtained by precipitation with water from acetic acid solution had the same melting point and gave the following results on analysis : I. 0.1502 gave 7.6 C.C. N a t 30° and 760 mm. N=5.7. 11. 0-1430 , 7.1 C.C. N , 29" , 758 mm. N=5*61. C,,H,O,N requires N = 5.8 per cent. Monobromocurczcmh C,,H,,O,Br.-Ha~f a gram of curcumin was dissolved in 35 C.C.of warn chloroform the solution cooled until curcumin began to separate and 4.5 C.C. of a 5 per cent. solu-tion of bromine in chloroform were then gradually added avoid-ing rise of temperature. The solution became quite dear on the first addition of the bromine solution (1 c.c.) and hydrogen bromide was evolved. After ten minutes air was blown through the mix-ture to drive off the chloroform and the residual emulsion was rubbed with a little alcohol. Needle-shaped crystals of mbno-bromocurcumin separated which were soluble in alcohol chloro-form acetic acid acetone or toluene shrank a t 131° and melted a t 136": 0.1187 gave 0:0510 AgBr. Br=18.2. C2,H,,0,Br requires Br = 17.9 per cent. Monobromodicnrbeth~xyczrrczLmii C,,H,,O,Br(O*CO,Et), pre-pared in a similar way from dicnrbethoxycurcumin cryst'allises from much alcohol in needles melting a t 165-170°: 0.1172 gave 0.0382 AgBr.Non80 b romodicarb e t h ox y curcu min t e trab romide, Br = 13.87. C2,H2,010Br requires Br= 13.47 per cent. C,,H1,0,Br,( O*CO,E t)2. -Dicarbethoxycurcumin (1 gram) was dissolved in the minimum quantiby of mld chloroform and treated with 40 e.c. of a 2.5 per cent. solution of bromine in the same solvent. After remaining at the ordinary temperature for one and a-half hours the chlrorobrm was driven off by a current of air. The product was extracted succeasiveliy with boiling ethyl and methyl alcohols leaving a residue which could not be crystallised but was purified by dissolving in chloroform and fractionally precipitating with alcohol.Et is N 296 GHOSH ClURCUMIN. sparingly soluble in alcohol or light petroleum and melts and decomposes a t 209-210°. Different fractions gave the same analytical results : 0.1397 gave 0-1438 AgBr. Br=43*8. Dibromodicarb et hoxycurcumin tetrabromide, C;7H2701,Br requires Br = 43.9 per cent. C21H1,04Br6( Co,E t)2, was obtained by broininating dicarbethoxycurcumin in cold chloro-form solution with excess of bromine. It separated from alcohol in colourless crystals softening a t 148O and melting a t 152O. It remains unchanged on boiling with water : 0.1278 gave 0.1460 AgBr. Br=48-61. C27H,010Br6 requires Br = 48.48 per cent. Monob rom diace t yl curcumin C2,H170,Br (OAc),.-Ciamician and Silber’s diacetylcurcumin was brominated in cold chloroform solu-tion with a little more than the theoretical quantity of a chloro-form solution of bromine (as in the preparation of monobromodi-carbethoxycurcumin) .It crystallises from alcohol in needles melt-ing a t 173-174O and is brighter in colour than diacetylcurcumin itself : 0.1162 gave 0.042 AgBr. Br=15*38. C,H,08Br requires Br= 15-03 per cent. Dibromodiacetylc~rcumilz tetrabromide C2,H,,0,Br6(OAc), was obtained by brominating diacetylcurcumin in cold chlorofom solu-tion with excess of bromine and was crystallised from alcohol. It melts and decomposes a t 80-83O: 0.1477 gave 0.1785 AgBr. Br=51.43. C2,H,,0,Br6 requires Br = 51-45 per cent. Mono b romdm e t h y l cu rczcmin C,,H170,Br (OMe) was obtained by treating dimethylcurcumin in cold chloroform solution with a little more than the theoretical quantity of bromine.It crystallises from alcohol in needles melting a t 140-141° : 0-1200 gave 0.0468 AgBr. Br=16*6. cBH,06Br requires Br = 16-49 per cent. D.i.brolmodimethylczLrculrzi7-L tetrabromide c21H1604Br6(oM0)~.-Dimethylcurcumin dissolved in chlorof o m was treated with excess of bromine when hydrogen bromide was evolved and after half an hour the chloroform was evaporated. This substance could not be crystallised but was purified by precipitation from its hot alcoholic solution with water. Distinct fractions possessed the same melting point (softens a t 96O melts a t 102-104°) and gav QHOSH CURCUMIN. 297 identical analytical results, acid : It is soluble in chloroform or acetic 0.1120 gave 0.1437 AgBr.Br=54.6. c,H,o,Br requires Br = 54.87 per cent. Conversion of Dicarbethoxycurcumk into Heller's Dicadethoxy-isocurcumin. A mixture of 1 gram of dicarbethoxycurcumin 10 C.C. of acetic anhydride and 1 C.C. of pyridine was digested a t the boiling point for forty-five minutes. Alcohol (6 c.c.) and a little water were added to the cooled mixture and tho supernatant liquid was decanted from the viscous mass which thus separated. From the lat.ter by stirring with 2 C.C. of glacial acetic acid a solid product was obtained and this when crystallised from alcohol melted a t 1 4 2 O which is identical with the melting point given by Heller for dicarbethoxyisocurcumin . Found C= 63-0; H =5-5 C,,H,O, requires GI= 63.28 ; H = 5.46 per cent.Acetylation of Curcumin with Acetic ,49thydride and Pyridine. Curcumin was digested with acetic anhydride and pyridine under the same conditions as described in the last paragraph and a solid product isolated. The yellow solid obtained in this way was frac-tionally crystallised from acetic acid. The first fraction (which was ofily a minor portion) melted a t 169-170° and was found to be identical with Ciamician and Silber's diacetylcurcumin (mixed melt-ing point). The second fraction (major portion) melted a t 1 5 4 O , and this it is interesting to note is identical with that given by Jackson for his diacetyl compound obtained by means of acetic anhydride and sodium acetate. Found C=66-4; H=5*23. C,,H,,O requires C = 66.37 ; H,= 5.3 per cent.Dleacetyla'tion of Diacetylczwcumin (m. p. 1 5 4 O ) and Isolation of Heller's isoCurcumin. One gram of this diacetiyl compound was dissolved hi 15 C.C. of acetic acid 1 C.C. of sulphuric acid (D 1-84) added the mixture warmed for a minute cooled and poured into water. The yellow precipit,ate was dried on porous porcelain and extracted with hot benzene. The benzene solution on cooling deposited the substance as a yellow amorphous powder soluble in cold alcohol acet.ic acid, acetone ethyl acetate or chloroform sintering a t 140° and meltin a b u t 2$Oo. identical with Heller's isocurcumin : There could be little doubt that this compound was 0.1130 gave 0.2822 CO and 0.0571 H20. p-Hydroxybenzylidene~esityt oxide, C-68.1; H=5*6.C21Rm06 requires C=68*4; H=5*43 per cent. OH*C&H,*CH CH COO @H C (CH,) 2. -To an alcoholic solution of 2.4 grains of phydroxybenzaldehyde and 1 gram of mesityl oxide 1.5 grams of zinc chloride were added, and the liquid was boiled for two hours. The solution after concentration was poured into water causing the deposition of oily drops which became crystalline on agitation. On recrystal-lisation from alcohol yellow crystals were obtained which melted a t 120° and dyed yelIow shades on chrome-mordanted wool : 0.1210 gave 0.3590 CO a i d 0.0784 H,O. o-HydroxybenzylideiiemesityZ olm'de was prepared in a similar way to the corresponding y-hydroxy-compound. The crude pro-duct separated as an oil which was obtained crystalline' by dissolv-ing in aqueous potassium hydroxide allowing t o remain for a few days and precipitating with hydrochloric acid.The substance dis-solves with a very beauti€ul orange-red colour in potassium hydroxide solution : C=80-91; H-7-2. C13H1402 requires C= 81.25 ; H = 7.36 per cent. 0'1000 gave 0.2970 CO and 0.0667 H,O. Piperony lidenemesit y 1 oxide, C=81*0; H=7*42. C13H14O2 requires C-81.25 ; R='i*36 per cent. CH,~0,:C,H3-CH:C13*CO*CI~:C(CH,),. -Piperonal (2.6 grams) and mesityl oxide (2 grams) were dis-solved in alcohol and alcoholic potassium hydroxide was added t o render the solution fairly alkaline. The1 mixture was boiled for a few minutes when an orange-coloured substance began to separate. On cooling this solid was collected dissolved in acetic acid and reprecipitated with water when i t melted a t 130-135O ( A ) .This proved to be a mixture of two substances melting at' 148-153O and 175-1 78O respectively which can be separated either by fractional precipitation by alcohol from acetic acid or by extraction with alcohol in which the substance of higher melting point is scarcely soluble. The hot alcoholic extract on cooling deposits the sub-stance which melts a t 148-153O ( B ) . The insoluble residue dis-solved in chloroform and fractionally precipitated by alcohol (the first fraction being rejected) melted a t 175-178O (C): (A) 0.1000 gave 0.2662 CO and 0.0558 H,O. c'=72*6; H=6.2. ( B ) 0.1150 , 0'3040 COY , 0.0580 H20. C=72*1; H=5.6. ( C ) 0.1021 , 0'2710 CO , 0.0533 H20. C=72.4; H=6*8. CI4Hl4O3 requires C = 73.0 ; H = 6-08 per cent Ciil.na~~lidene,mesityl oxide, C,H,*CH:CH-CH:CH*CO*CH:C(CH,),, was prepared in the same ~ b .7 as the abom piperobylideae m-p u n d . On coding the reaction mixture some viscous substance was deposited from which the supernatant liquid was decanted and poured into water. The semi-solid mass was dissolved in acetic acid and precipitated with alcohol. It melts and decomposes a t 180-182O (a). Addition of water to the filtrate caused the separa-tion of a second substance which welted and decomposed a t 8 8 O (8). Both the a- and P-cmnpounds were soluble in alcohol chloroform, acetone or toluene but could not be cryst8allised from any of these solvents. Experiment showed that them -pounds were inter-convertible ; the former (a) on boiling with acetic acid for two to three minutes and adding water to the solution gave the &corn-pound melting a t 88O whereas the' latter on boiling with alcohol for about five minutes gave on cooling the solution t h ~ s obtained, a deposit of the a-compound melting a t 180-182°.The ocoompound is less readily soluble in alcohol than the 8 : (a) 0-1082 gave 0.3365 CO and 0.0670 H20. C=84-4; H=6*8. (p) 0.1494 , 0'4610 W2 , 0*'0808 B20. C=84*1; H=6.0. CT,,H,,O requires C=84.4; H=6.4 pet cent. Divainittytidenemesityt oxide (11 p . 293).-A current o€ dry hydrogen chloride was passed into an ice-cooled alcoholic solution of 2.6 grams of vanillin and 1 gram of mesityl d d e the liquid became deep blue. After two days the solution was potired into cold wate? the precipitate collected and triturated with sodium acetate solution. The brown amorphous powder obtaihed in this way 2ouid not be crystallised and was purified by fractional pre-cipitation from acetic acid %ith water solution. It is soluble in alcohol chloroform or acetone softens a t 1 6 5 O and melts a t 178O. Distinct fractions obtained by the above described method gave identical analytical results : I. 0.1200 gave 0.316 CO and 0.067 H20. C=71.8; H=6*2. 11. 0.1065 , 0.282 CO , 0.059 €&O. C=72*21; H=6*1. C22n2205 requires C=72*1; H=6 per cent. I take this opportunity of thanking Prof. B. N. b a s for his kind CHEMICAL LABORATORY, help and encouragement during the progress of the work. DACCA COLLEGE BBNQAL INDIA. [Received December 30th 1 9 1 ~

ISSN:0368-1645    

DOI:10.1039/CT9191500292

出版商:RSC    

年代:1919

数据来源: RSC

摘要:

300 LOWRY AND DRAM THE ROTATORY DISPERSIVE XXXI .-The R o t a t o y Dispersive Power of Organic Compounds. Part I X . Simple Rotatory Dis-persion in the Terpene Series. By THOMAS MARTIN LOWRY and HAROLD HELLING ABRAM. IN a paper on “The Form of the Rotatory Dispersion Curves,” published in 1913 (T. 103 1067) i t was shown: (a) That the rotatory dispmion in a large number of simple organic compounds may be expressed by the formula a=k/(h2-h02), where k is the (‘ rotation constant ” and h02 is the ‘‘ dispersion con-stant ” of the substance. ( b ) That this formula can be applied both to magnetic and to natural rotatory powers. ( c ) That a very simple method of testing the form of the dispr-sion curves is to plot the reciprocals of the rotatory powers against the squares of the wave-lengths.When the simple dispersion formula is valid the observations will plot out t a a straight line. ‘The validity of this simple dispersion formula was established in several ways. Thus: (1) Twenty-five hydrocarbons alcohols and acids for which the ratio a4358/a5461= 1.636 were grouped together and their magnetic dispersion ratios were averaged for six different wave-lengths ; these averages showed a remarkable agreement with the ratios calculated by means of the simple dispersion formula. (2) I n the same way the optical dispersion ratios of eight second-ary alcohols for which a,,,/ a5461 = 1.651 were found to agree clmely with ratios calculated by the simple formula. (3) A few optical and magnetic rotations of larger magnitude showed a similar close agreement in individual cases without the necessity f o r averaging which arises when the readings are small.(4) I n the case of a- and &methyl glucosides very concordant results were obtained when the two constants of the simple equation were calculated (a) from the mercury readings and a54617 ( 6 ) from the cadmium readings a5086 and q 4 3 8 (Lowry and Abram, T r m . Faraday Soc. 1914 10 108). These earlier observations showed that the simple dispersion formula can be applied very generally to compounds of simple structure such as the optically active secondary alcohols which contain only a single asymmetric carbon atom and also to com POWER OF ORGANIC COMPOUNDS. PART IX. 301 pounds such as the glucosides which contain several asymmetric carbon atoms associated with the simplest possible radicles f o r example hydrogen hydroxyl and the like.An opportunity has, however occurred recently of testing the validity of this same simple formula in the1 case of a large number of optically active compounds in which these elements of simplicity in the molecular structure are conspicuously absent. The striking results of this further test form the subject of the present communication. The new data now under consideration were provided by the observations of Prof. Rupe who in continuation of earlier experi-ments on the (‘Influence of Constitution on the Rotatory Power of Optically Active Substances ” (Annalen 1903 327 157; 1909 369, 311; 1910 373 121; 1913 395 87 136; 1913 398 372; 1914, 402 149) has published a series of measurenients of the optical rotatory power of (1) twelve derivatives 6f methylenecamphor, (2) merhhol and eleven of its esters (3) myrtenol and eleven of its esters (4) three hydrocarbons derived from citronellaldehyde, (5) camphor pulegone and carvone (Annalen 1915 409 327).Unlike the previous series of measurements which were confined to observations with sodium light the last series included in the case of almost every compound readings for four different wave-lengths in the visible region of the spectrum. It was therefore possible to study not only the optical rotatory power of the various com-pounds but also the character of their rotatory dispersion. The four wave-lengths selected from a continuous spectrum, were A = 6563 5898 5463 and 4861 corresponding closely with the Frauntofer lines C = 6563 D = 5893 F= 4861 and the green mercury line Mg 5461.I n order to preserve a convenient sequence of lettering these four wavelengths were described as C B E? and F ; but as the symbol E has long been applie’d t o the Fraun-hofer line of wave-length 5270 the’ symbol Q is used below for the green (quicksilver) line in the series which thus becomes C D, Q F . Thel various substances were examined either in the pure state as liquids a t 20° or dissolved in benzene a t 20° since this solvent was found to have no very great influence on the rotatory powers; several substances were examined both in the pure state and in solution. When the experimental work was approaching completion the data were handed over for detailed analysis to Dr.A. Hagenbach, Professor of Physics in the University of Basle. The important deductions which he was able to make are set out in a paper on ‘‘ Rotatory Dispersion in Homologous Series ” (Zeitsch. physikal. N %z LOWRY AND ABRAM THE ROTATORY DIBPERSIVE Chem. 1915 8@ 570). The chief points of this paper are as (1) The dispersion ratis ap/qo is practically constant in each series of closely-related compounds. Compoupda which differ in any marked degree from the average are regarded as “relatively anomalous.” (2) A similar statement may be made in reference to all the six ratios d a a r upla, QF/ag aQlaw rFQ/aol d a a 88 WBS shown by tbbul&iog $hew ratios for (i) eight derivatives of methylene-urtmphor (ii) menthol and se,ven of its esters (iii) three hydro-carbons from citronellaldehyde.(3) It follows therefore that if the dispersion law for one member pf the series be given by the equation a= +(A) the rotatory dispersion in every compound may be expressed by equations, such as: fOllQW8 : [all = Q14 (A) -[a21 = c24) (A) -[as1 = C34(h) * This proportionality of rotatory powers was demonstrated by tabu-lating the ratios a2/al u3/a1 a / a l eta in each of the three series of uompounds. Attempts were made t o determine mainly by graphical methods, the nature of the unknolwn function +(A). Thus the equations of Biot, and of Stefan, were1 tested by plotting a against 1 /A2. Cb=B/A2, a=A+B/Xa, Boltzmann’s equation : ~ = A / A ~ + R / x ~ or ahzcA+B/h2, was tested by plotting aha against 1 1 ~ 2 .I n neither case was an exact linear law disclosed. The equations of Lommel and the two-term equation which Drude used t o express the rotatory power of quartz could not be tested in this way; but the empirical equa-tions : p = A + B / h n and loga=A+B/h were tested by plotting log a against log 1 / A and against 1 / x ; sub-sequently log a was also1 plotted against A and a against 1 / X (&4nnaZen 1915 409 349 351) but again without disclming any simple linear relation between these quantities. The nature of the function in the equation a=+(X) thus remained still undis-covered. The present paper serves to supply this deficiency by showing that in almost every case the new dispersion data can b POWER OF ORGANIC COMPOUNDS.PART IX. 303 expressed by a simple equation of the type first put forward by Drude. The fact that Drude’s equation was not used by Hagenbach and in general failed during many years to secure the practical recog-nition which it deserves may be accounted f o r in two ways. I n the first place the equation was put forward as an approximation only in a very general form: containing an indefinite number of arbitrary constants. The arbi-trary constants A12 h22 As2 . . . in the denominator were deduced from measurements of refractive dispersion and it was not even suggested that they could be derived (in a still mare satisfactory way and often with much greater exactness) from the rotations themselves. In the second place Drude demonstrated the validity of his equation only in one single case namely that of quartz, the equation f o r which took the form 76 k a= 1 - __ A2 -x,2 A2‘ No data whatever were given for optically active liquids and the magnetic rotatory dispersion in carbon disulphide and in creosote (!) was expressed by a different formula also depending on measurements of refractive dispersion.The first extensive prac-tical application of Drude’s formula was therefore made less than six years ago in the second paper of the present series. The easiest (although perhaps the least exact) method of testing the simple dispersion law .a = 7c/ ( ~ 2 - ~ 2 ) is to plot the reciprocals of the rotations against the squares of the wavelengths. The dramatic effects which are produced by plotting 1 /a against ~2 are shown by comparing- the straight lines of Figs.1 to 4 with the broken lines* or curves which were given by all other methods of plotting. It is specially reniarkable that plotting a against 1 1 ~ 2 (Stefan’s formula) should give curves where1 plotting 1 /a against ~2 (Drude’s formula) gives very exact straight lines. These lines indicate clearly that where half a dozen other relationships have failed the simple Drude formula gives a t once a satisfactory expression of the experimental data.? Hagenbach appears t o have plotted his curves on the assumption that the ‘‘ E ” line used by Rupe was the Fraunhofer line cS2,,, and not the mercury line u5461. t More exact data may perhaps compel the use of additional terms as in the case of quartz which requires one two or three terms according to the range and accuracy of the data employed but there are no indications of this in the data examined hitherto.N” 304 LOWRY AND ABRAM THE ROTATORY DISPERSWE A marked exception mcurs in the case of pulegone which gives a smooth full curve and evidently shows ‘ I complex ” rotatory dis-persion. Diphenylrnethylenecamphor C,,H,,O:CPh, the dis-persion ratios of which are much lower than those of all the related compounds gives a curve; so also does menthyl b-phenylcinnamate, C,,H,,O*CO*CH:CPh, the rotatory dispersion of which must be complex since the dispersion ratio alF/ac = 1.72 falls below the Rotatory dispersion in derivatives of rnethylenecarnphor. Notice curvature in the case of the diphenyl derivative.minimum value uF/uC = XcZ/XFz = 1.818 beyond which hO2 would become negative and A an imaginary quantity; the fact that both these compounds contain the group :CPh can a t present only be regarded as a coincidence. All the other compounds appear as a result of this rough graphical analysis over a narrow range of wave-lengths to give simple rotatory dispersion. A more exact test of the’dispersion formula is given by numerical calculation. The following table shows that the specific rotations POWER OF ORGANIC COMPOUNDS. PART IX. 306 observed and calculated of a series of typical compounds lie well within the range of possible experimental errors. TABLE I. Specific Rotations 0 bserved and Cdculated. E,thylidenecamphor,* [a]= 47.322 / (hz - 0.0829). Obs.......... 136.37' 178.58' 219.31' 308.49' Calc. ......... 136-05 178.58 219.55 308-49 0 - C ......... +Om32 f - 0.24 f Hydroxymethylenecamphor,* [a] = 22*843/ (hz - 0.0874). Obs. ......... 66-53 87-66 108.57 153.41 Calc. ......... 66.53 87-70 108.26 153.41 0-c ......... f -0.06 +Om33 f Benzylmethylenecamphor [a] = 33.431 / (h2- 0.0887). Obs. ......... 97.87 129.00 156.26 Calc. ......... 97-75 129.00 156.39 0-c ......... +0.12 rt -0.13 Menthol,* [a] = 15.0681 (A2 - 0*0236). Obs. ......... 37.01 46-58 54.78 Cdc. ......... 37.01 46.47 54.82 0-c ....... *. f +Om11 -0.04 Menthyl benzoate,* [a] = 29*364/ (A2 - 0.0255). Obs. ......... 72-41 91.10 107.76 Calc. ......... 72.46 91.10 107.59 0 - C ......... -0.05 f +0-17 Myrtenol [a]= 14*700/(h2-0~0316). Obs........ .. 36-83 46.49 55-04 Calc. ......... 36-83 46-48 55-09 0-c ......... f $0.01 -0.05 Myrtenyl benzoate a = 11.505 / (A2 - 0.0341). Obs. ......... 29.01 36.67 43.51 Cdc. ......... 29.01 36-67 43.52 0-c ......... f -0.01 * Dissolved in benzene. 226.50 226.60 f 70.84 70.84 f 139-30 139-30 rt: 71.81 71.81 f 5d.90 56.90 f In view of the fact thatl the readings for solutions in benzene were multiplied by ten to convert them into specific rotations, whilst hhe others wem approximately doubled the agreement shown above is practically perfect 306 LOWRY AND ABRAM THE ROTATORY DISPERSIVE Even clearer evidence of t'he validity of the simple dispersion formula is afforded by a study of the average dispersion ratios observed and calculated f o r groups of relate'd compounds.Three such groups were' avelraged by Hagenbach namely : benzene) uF/aC = 2.310. (a) Eight derivatives of methylenecamphor (dissolved in ( b ) Seven esters of menthol (pure or in benzene) alF/ao =1*920. FIG. 2. ENTHOL ,i-= PHEN$ ACETATE. 1 I ESTERS. I 1 15 0-40 0.36 0.30 0.25 Rotatory dispersion in menthol and its esters. Notice curvatture in the case of 8-phenylcinnamate. ( c ) Three derivatives of citronellaldehyde (in the pure state) , To these there are now added average ratios for: (da) Six derivatives of methylenecamphor (in the pure state), (e) Ment.ho1 and seven esters (dissolved in benzene) aP/uc = a,/a = 1.991. ctpIQc = 2.303. 1.911 POWER OF ORGIAWIC! COMPOUNDS. PART IX. 307 (f) Myrtenol afid eight esters (in the pure state) up/aC =1*958.The close agteement betweeh the observed ahd calctilated values of these ratios is shown in table 11. Rotatory dispersion in myrtenol and its esters. TABLE 11. Dispersion. Ratios 0 bserved and Calculated. (a) Obs. ...... 2-310 1-751 1.415 1.G33 1.237 1-319 h,2= aplac. aplag. aFfa8. aglttc. ayfan. anlac. {Gala. ... 2.310 1-752 1.418 1.629 1.236 1-318}0.0879 ( b ) Obs. ...... 1.920 1.529 1.294 1.488 1.181 1.259) AU2= { cfalc. ... 1.921 1-529 1,294 1.484 I.181 2.257f0.0250 Obs ...... 1.991 1.561 1.313 1.6.15 1.1818 1.274 A@%= {Cali. ... 1.992 1.569 1.316 1.513 1.191 1-269)0*0401 (d) Obs. ...... 2.303 1.756 1.423 1.619 1.234 1.3121 Aoz= {Calc. ... 2.303 1.748 1.417 1.626 1.234 1.318 /0.0871 (c) jobs. ......1.911 1.521 1.289 1.482 1.180 1.256 A,’= [Calc. ... 1.911 1.522 1.292 1.479 1.179 1.255}0.0227 ( f ) fobs. ...... 1.958 1.550 1.306 1-499 1.186 1.264\ A 2= 1CaIc. ... 1.958 1.550 1.306 1-499 1,186 1.264j0.833 308 LOWRY AND ABRAM THE ROTATORY DISPERSIVE This agreement is nearly as clme as in the case of the data by which the validity of the simple Drude formula was first estab-lished and even the largest differences are usually less than the average errors of the individual ratios. The “simple” character of the rotatory dispersion could therefore only be called in question i f data were available of greater exactnws or over a wider region of the spectrum. A further opportunity of testing the validity of the simple dis-FIG. 4. R o m y dispersion in derivatives of camphor pulegone and carvone.Notice curvature in the case of pulegone. persion law is provided by the inclusion in a more recent paper by Prof. Rupe (Helu. Chint. Acta 1918 1 452) of dispersion data for four sample,s of camphylcarbinol, a compound containing three asymmetric carbon a b as corn POWER OF ORGANIC COMPOUNDS. PABT IX. 309 ponents of a complex ring system. observed and calculated rotations is shorn in table 111. The agreement between the TABLE 111. Rotatory Dispersion in Camphylcarbirtol. First sample [a] = 15*980/ (A2- 0.10220). ~ = 6 5 6 3 5898 5463 4861 Obs. ...... 48-64' 65-24' 81-87' 119.17' C ~ C . ......... 48-64 65.05 81.43 119-17 0-c ...... +0-19 +0*14 f Obs. ......... 46.31 62-11 77-67 113.48 Calc. ......... 46.31 61-93 77.53 113.48 0-c ......f +O.lS +0.14 f Obs. ......... 46.45 62.22 77-74 113.90 C ~ C . ......... 46-45 62.13 77-79 113.90 0-c ...... f +049 -0.05 f Second sample [aj=15*213/(h2- 0.10223). Third sample [a]=15'252/(A2-0*10239). Fourth sample [a] = 16.10/(h2- 0*10304). Obs. ......... 49-13 65-73 82.44 120.82 C ~ C . ......... 49.13 65.76 82.39 120.82 0-c ...... f -0.03 +0.05 f It will be observed that the sample having the highest rotatory power which was also probably the purest gives a remarkably close agreement the differences being in opposite directions and amounting only to a few hundredths of a degree or abuut 1 part in 2000. This exact agreement suggests that the simple dispersion law may b'e of value as a test of purity and that deviations from it may in some cases justify a further examination of the chemical composition of the material used for the measurements.It is of interest to notice the chemical character of the comr pounds to which the ('simple" dispersion formula has now been applied. They are as follows: CHMe, I ~H,*O*CO*R 1. Methylene camphors. 2. Menthol eshrs. 3. Myrtenol esters. CMe2:CH*CHz*CH2*CHMe*CH:CHR. 4. Hydrocarbons from citronellaldehyde 310 L0WR.P AND’ ABBAM THE ROTATOkY DISPEkgIVE Nearly all are complex ring compounds or loaded with double bonds. The fact that the simple formula applies to compounds of such complex structure is remarkable evidence of the broad and sound basis on which the formula rests. Ghuructeristic W’ave-Zengt hs.-In Drude’s simple equation the rotatory dispersion is defined completely by the ‘‘ dispersion con-stant”’ ~ 2 ; this is the square of a wave-length which is that of a hypothetical absorption band usually in the ultra-violet region of the spectrum.This wave-length defines the whole course of the dispersion curve and is independent of the particular wavelengths used to determine itl; thus the value of A may be deduce’d equally well from the mercury ratio a4,,/a5.iF,1 from the cadmium ratio a,,,,,/~ry;~~ or from the ratio aF/a derived from the data now under discussion. A preliminary study of these data by Prof. Rupe had however disclosed the fact that in the case of the methylene-camphors u,/aC =a, whilst in the case of the citronellaldehycke hydrocarbons a p - a = a that is for each series there is a (‘ characteristic wave-length,” A (Zeitsch.physikal. Chem. 1915, 89 SSl) for which the rotation is equal to the difference between the rotations for the F and C lines. This wave-length is not a fundamental constant of the dispersion curve like the Ao2 of Drude’s equation since it depends on the two standard wave-lengths for example F and C which are select’ed as determining the differ-ence; but it usually lies within the limits of tohe visible spectrum and affords a picturesque method of setting out the essential features of the dispersion curve. By assuming the va1idit.y of Stefan’s formula Hagenbach showed that this waverlength can be deduced from the expression or taking in all the four rotatory powers, Drude’s equation on the other hand which is the one that actually fits the curves gives for the (( characteristic wave-length ” the expression XC2 - (n - 2)Ap2 - 0.4307 - 0*2363(n-3) (n - 1)2 (n - 1)2 where is the dispersion ratio a,,,/a,.Thus for t,he citronell-aldehyde hydrocarbons for which n = 2.00 this equation gives ha2=hc2 as was observed experimentally whsn it was found that aF - ac = a,. Ad2 = - POWER OF ORGANIC COMPOUNDS. PART IX. 311 Constant Rotatory Dispersion in Homologous Series.-In the compounds now under consideration new radicles are introduced into t-he molecule atl points which are separate’d from the asym-metric carbon atoms by a considerable chain including in every case either an oxygen atom or a double bond. A constant dis-persion ratio is therefore observed from the beginning and any substance of which the rotatory dispersion differs largely from the average of the series is noteworthy and exceptional.The only conspicuous exceptions amongst some thirty-six compounds under consideration in the present research were found in two substances containing the group :CPh,. These have now been shown t o differ from the others also in giving complex instead of simple dispersion curves so that the rule appears to apply without excq-tion to all compounds showing simple rotatory dispersion. A different state of affairs prevails however in the secondary alcohols of Pickard and Kenyon which have a “growing chain” attached directly to the asymmetric carbon atom. The dispersion is here always simple but the dispersion constant varies i n the different series and only assumes a steady value in each s e r i ~ when the “growing chain” of carbon atoms has definitely estab-lished itself as the heaviestl radicle attached to the asymmetric carbon atom (Lowry Pickard and Kenyon T.1914 105 101). The lowest homologues usually show an exceptionally high rotatory dispersion but this is not accompanied by any change in the type of the dispersion curve and is therefore entirely distinct from the “ anmalous rotatory dispersion,” of which an exact definition was given in a former paper of the present series (T. 1915 107 1195). It would be a real misfortune if substances which are perfectly normal in their rotatory dispersion were to be regarded even as ‘ I relatively anomalous ” whenever they happen to differ slightly from their homologua and it is hoped that this unnecessary and misleading description will be abandoned. Summary, a = Ic/ (12 - A,?) can be applied to express the rotations produced by a large number of compounds of the terpene series including (a) derivatives of methylenecamphor including camphylcarbinol ( b ) menthol and its esters ( c ) myrtenol and its esters and fd) hydrocarbons derived from citronellaldehyde. Pulegone and two compounds containing the group :CPh, show complex rotatory dispersion. It is shown that the simple dispersion formula GUY’S HOSPITAL, LONDON 833. [Received March 20th 1919.

ISSN:0368-1645    

DOI:10.1039/CT9191500300

出版商:RSC    

年代:1919

数据来源: RSC

摘要:

312 LEWIS A NEW SECTOR SPECTROPHOTOMETER. XXXII. -A New Sector Spectrophotometer. By SAMUEL JUDD LEWIS. IN a paper by the author on “The ultra-violet absorption spectra of blood sera” (Proc. Roy. Soc. 1917 [B] 89 327) it was stated that the work described had been done with two sector spectro-photometers that these were not adequate to the exacting nature of the investigation although they were the best and most modern instruments available and t.hat a new photometer to the author’s design was under construction. That apparatus has now been in use for several months and the purpose of this paper is to describe it. A short account of the method of using such instruments is given in the reference mentioned above. As was 5he case with the work detailed in the paper cited the present development of the sector spectrophotometer has been generously supported by the Beit Research Fund Committee the trl-ustees of a fund which has been placed a t the dispwal of the British Homeopathic Association by Mr.Otto Beit for purposes of scientific research. The new instrument was designed by the author in 1915 with a view to meeting the requirementa of the work on blood serum. No instrument can be unnecessarily refined for this and should it be desired to employ the method of ultra-violet absorption spectre graphy for clinical purposes whether for blood serum or for any other subst.ances an instrument which is a t once trustworthy and easy to manipulate is essential. Incidentally an instrument which fulfils these conditions should satisfy most of the demands of scien-tific research and bring the practice of ultra-violet absorption spectroscopy within the range of applied chemistry.Unless or until the ideals set out are attained absorption spectroscopy can have little motre than academic significance ; but perfect easily adjustable spectrophotometers may be expected in course of time to occupy a place in the general laboratory not less important than that filled by the polarimeter or the refractmeter. Among the objects aimed a t in the new design were the following : ( :) The utmost accuracy and refinement in the resulting spectra, because for the serum work i t is required to discover with certainty very m a l l differences of detail in the absorption curve as explained in the paper cited.( b ) To work quickly as well as accurately since it is necessary to undertake the examination of a serum a t very short notice and there is no reasonable opportunity of revising the observation a D. ^ . a ; [ 7'0,jUce Imyc 313 LEWIS A NEW SECTOR SPECTROPHOTOMETER. 313 the serum will usually have changed in character by the time the absorption curve is drawn; this presumes quick and perfect adjust-ment of the instruments. ( c ) To maintain this excellent adjustment throughout an experi-ment or to restore it from time to time during the progress of an observation without the necessity of other disturbances. ( d ) Precise quantitative values for the extinction coefficients, since the amplitude of the curve has important significance. ( e ) To attain this high standard and yet to be able to use the one spectrograph alternately with the photometer and for other purposes as circumstances may require.The photograph exhibits the general appearance of the new photometer; it exposes the vanes in the upper sector the front of the sector box having been removed; aIso only one platform bear-ing a tube carrier is shown. The arrangement of parts is displayed in the diagram. Q represents a suitable lamp light from which falls on the two lenses L, L, which fender the light parallel. These pencils of light pass through the face aA,b in the reflecting prism P and through the face a& in the reflecting prism Pz in the manner shown and are reflected approximately a t right angles by the inclined faces alcl in p r i m P and a2c2 in the prism P2 so that in each case the light follows a course parallel to the main axis of the prism to a second inclined face b,d in prism P and b 2 4 in prism P, where i t is reflected again a t right angles.The parallel beam reflected from b,d passes through the sector D, the diaphragm 0, and the lens L to the inclined face elfl in reflecting prism Y, where it is reflected a t right angles along the main axis of the prism on to the inclined face g,h, where i t is again reflected a t right angles and passes out of the prism on to the face hi of the rhomb R placed in front of the slit S of the spectrograph or in the absence of the rhomb directly on to the slit. The pencil from b,d undergoes similar treatment and eventu-ally passes out of the photometer on to the face kj of the rhomb.The rhomb may be dispensed with if the pencils of light are directed so as to fill the angles of the prisms a t 9 and g., provided that one prism slightly overlaps the other as shown in the figure, so that' the prominent edge may define the line of juxtaposition. It will be seen that any &ray parts of the pencils of light would be refleched or escape out of the field. The essential part between the two prisms in either path is the sector B, D, capable of cutting off any desired portion of the light passing along that path 314 LEWIS A NEW SEUTOR SPEUTROPHOTOMI?ITER. It should be observed that the prisms and sectors are enclosed in dustrproof metal boxes provided with quartz windows. The sector systelm is placed in a part of the path where the light is parallel.It consists of four vanes Vl V2 V3 V4 as shown in the side elevations in the figure. Each vane has t3wo edges a t right angles and when the four vanes are disposed to one another in one plane so that the four angles meet a t a point the system is closed and no light can pass. This arrangement is repre-sented in the upper path in the figure. The common point of the four angles is on the optic axis to which the plane is a t right angles. Each vane can be turned by means of suitable mechanism about its bisectors m, m2 m3 m4. When all the vanes are turned simultaneously through an angle of 90° about their respective bisect'ors lightl can pass in the direction of the optic axis without any interruption except -that caused by the slight obst.ruction due 60 the thickness of the material of the vanes as shown in the figure for the lower path.By turning t h e vanes through any other given angle about their bisectors a known proportion of the light may be allowed to pass. Each of the four vanes is carried on a wheel by means of a spindle which coincides with the bisector of the vane and also forms the axle of the wheel. These wheels are mounted on t(he outside of the walls of the box enclosing the sector a t right angles t o one another and fit into one another by bevelled cogs. They move simultaneously and the fitting is so close that back-lash is reduced to an insignificant minimum. The amount of rotation of the vanes is measured by a pointer I , mounted on the front wheel and moved against an arc graduated in half degrees from 0 to 90.A diaphragm or stop O, 0, is placed in front of each sector to reduce the section of the beam of light to suitable dimensions, say 9 mm. in diameter when the observation tubes or cells have a lumen of 12 mm. I n order to correct the error causeld by the obstruction due t o the thickness of the material of the vanes their edges are reduced to knife edges and the thickiiess along the bisector is graduated from the minimum a t its extremity at the optic axis to what is necessary say 1 mm. a t a distance of 10 nun. The two sides of each vane are equally made and each of the four surfaces is plane or concave. Hence a sectdon through a vane a t right angles to its bisector has the form of a rhombus having two very obtuse and two very acute angles; also a section which includes the bisector has the form of an isosceles triangle.It follows that when the sector system is open as shown in the lower path in the figure the obstruction or shadow produced b LEWIS A NEW SECTOR SPECTROPHOTOMETER. 316 each vane has the form of a geometrical sector of known dirnensions, and therefore the sectional area of the pencil of light passing through the sector system is reduced by four times the area of one small sector shadow ; also each of the four apertures has the form of a geometrical sector. Compensation for this reduction in area is made by employing for the path in which thel light is to be of whole or 100 per cent. intensity khat is for the path in which the substance under observa-tion is placed a diaphragm the aperture of which is appropriately larger than that of the diaphragm in the other path.In the author’s instrument the diameter of the larger aperture is 9.3 mm and that v€ the smaller 9.0 mm. These diaphragms are loose and may be used with either sector according to whether it is desired to use the upper or lower sector. The only limitation to this arrangement is that the sectors do not operate for those angles which are included by the small angle covered by the thickness of the vanes. In the author’s instrument this is 2*6O so that the range of operation is from 2 ’ 6 O to 90’. The lenses L, L, placed between the sectors and the second set of prisms focus the light on the slit the focus being that for light of a wavelength of about 3000.The edge of the rhomb is placed close to the slit so that the two pencils of light when they emerge from either side of it into the slit may be a t the focus of the collimating lens; the line of juxtaposition between the two spectra is thus v0ry clearly defined without the least overlapping or intervening space with the result that the lines in the two spectra whether visual or photographic, can be compared for their relative intensities a t the best advantage. The cell containing the substance under observation is placed in the parallel beam of light between the sector and the central lens; roam is provided for tubes up to 100 mm. in length and tubes of this length were used successfully in an investigation relating to Lambert’s law.As the pencil of light is 9.3 mm. in diameter it is desirable for long tubes that the lumen of the tube should be a t least 12 mm. in diameter so as to avoid serious reflec-tion from ths inner walls of the tube. When the lumen is small and the layer of substance thin it may be placed in the convergent beam immediately in front of the prism P3 as shown a t w and a still smaller cell might be interposed between th4 prism P and the face ki of the rhomb but only with due regard to existing con-ditions. Inwmucb as the system in the lower path of light is identical with that in the upper the cell may be placed.in the lower with equal advantage or as explained later cells may be placed in both beams simultaneously 316 LEWIS A NEW SECTOR SPECTROPHOTOMETER.The new instrument is characterised chiefly by its sectors; these are distinguished both in their construction and in the principles upon which they operate. I n comparison and contrast with &her sectors they accommodate the whole beam of light and not merely half as is the case with some others; this enables exposures to be reduced to one-half in order to produce a photograph of the same intensity ; the exposures being continuous calibration of the photo-graphic plate is avoided; the direct function of the new sectors is to cut down the intensity of the light and not to do so indirectly by altering the exposure as is the case with the Hilger instrument; the sector is sbill which is a great convenience. The whole aper-ture of the sector system is made up of four sector-shaped apertures arranged diagonally about the optic axis that is they are dis-posed a t an angle of 4 5 O to the vertical.This has the advantage of utilising all parts of the circular beam of light in proper pro-portion ‘whatever the magnitude of the effective aperture a t the moment. I n this it differs from the iris and other forms of stop or sector which reduce the int’ensity of the light by cutting down the light from the periphery of the beam inwards or by cutting it down in some other way which assumes that every part of the field is equally illuminated. Under the oonditions of ordinary practice this assumption lacks sufficient justification where precise photometry is required. The size of the sector aperture is measured in terms of the angle which it forms a t the optic axis.The angle 4 5 O represents an aperture of 100 per cent. and the angle formed at the optic axis by the shadow cast by one half of a vane in any given position is 4. Hence the sector aperture is proportional to 45”-4. Thjs method of measuring the size of t.he aperture is exceedingly con-venient both for simplicity of calculation from the angle 0 which is read on the graduated arc and for the fact that apertures of any odd value may be produced a t will. This will become evident from the following explanation of the manner of calculation. When the vane acb in the figure ( a ) (front elevation) is turned through an angle 8 as measured by the graduated arc so as to take up the position ecf each half of the vane ec or cf creates a sector-shaped shadow in a beam of light) in the direction of the arrow ; e ’ d is a projection of ed.It is shown again in the figure ( B ) in side elevation where e’d’ is the projection of ed. If the beam of light were rectangular in section the shadow would be triangular in shape (e’d’o) and proportional in area to sin@ since ed which subtends the angle 8 is equal to e,dl which subtends the angle 4 a t the optic axis 0 for edl and d’o are equal since they form the right angle in the isosceles triangle ed’o; therefore ed/edl L’IPWIS A NEW SECTOR SPECTROPHOTOMETER. 317 e’d’/d’o that is sin 8= tan 4 whence 8 being k n m 9 may be found directly from the tables. The beam of light however is circular in section; hence the area of any sector in the circle is proportional to the angle which it cont,ains that is to + for the shadow and 4 5 O - 4 for the sector aperture.Only oneeighth of the whole circular aperture has been con-sidered but itl will be seen on cancelling common factors that the whole aperture a t any moment is measured by 4 5 O - + where 4 5 O is taken to represent the fully open sector. Itl is convenient to express the apertures as percentages of the whole aperture that is, (45 - 4)100. The percentage apertures and values for logI,/Z’ as 45 corresponding with each half-degree on the graduated arc have been calculated by Miss Gartha Thompson t’o whom’the author is indebted for valuable assistance throughout the inquiry. Examples are given in the following table: 8. 10 25 40 40-5 41 55 70 80 80.5 81 85 85.6 88 Sin 8 or tan 9.0.1 736482 0.4226183 0.6427876 0.6494480 0.6560590 0-8191520 0.9396926 0.9848078 0-98@2856 0.9876883 0.9961947 0.9969173 0.9993908 9. 9.85 108 22.90981 32.73241 33.00163 33.27239 39.32269 43.2191 8 44.56143 44,60441 44.64512 44.89078 44.9 1 155 44.9 82 55 45 - @. 35.14092 22.0901 9 12.26759 11-99837 11.72760 5-67731 1.78082 0.43857 0.39559 0.35488 0.10922 0.08846 0.01745 Sector aperture, Der cent. (46-$4 100 45 78-11 49.08 27.27 26.67 26.07 12.62 3-958 0-975 0.870 0.789 0.243 0.197 0.0888 Log I / I ’ , 45-t$ log L* 0.1073 0.3091 0.5644 0.5740 0.5839 0.8991 1.4026 2.01 11 3.0559 2.1031 2.6150 2.7065 3.41 14 It is evident that the values in the table can be applied to graduating the arc on the instrument so that it may read directly in terms of logZ/Z/ as has been done with other instruments.This is convenient where it is intended to use the instrument for routine work only but for versatile research and especially where it is desired occasionally to elaborate a particular part of an absorption curve the freedom conferred by the ordinary scale and tables will be appreciated. There is however no difficulty in providing both scales on the same arc. The effect produced by the size of the shadow cast by the vane being a function of the sine of the angle through which the vane has been turned is significant. From the above figures it will b 3 18 LEWS A NEW SECTOR SPECTROPHOTOMETEB.seen that the difference in the sector aperture produced by a constant difference of 1 5 O in 8 decreases continuously thus : Per cent. Between PO" and 25' the aperture decreases by (78.11-49.08) 29-93 Y Y 25" Y 40" ? Y 9 ) (49.08-27-27) 21.81 Y 55" Y 70" ? 7 Y Y ? 9 , (12.62- 3.96) 8.66 , 700 ? 850 y 7 , ( 3.96- 0-24) 3.72 Y Y 9 , Again for half -degree int'ervals in 8 : Between 20" and 20.5O the aperture decreases by (58.03-67.09) 0-94 ,¶ 40" , 40.5" ? , ,) y y (27.27-26.67) 0.60 80" ? 80*5" y y ,? , , (0.975-0.879) 0.096 , 85" ) 85.5" ) , ) , (0.243-0.197) 0.047 For any of the apertm-es of small size i t is evident therefore, that a nioveinent of the pointer on the arc over one or more divisions alters the size of the aperture by only a small fraction so that any probable error in construction or manipulation can have no detectable effect on the measurement of the size of the aperture.The possibility of regulating the size of the m a l l apertures with such precision is a valuable advantage since it is with these that much of the more important and delicate work is done. I n an investigation of uric acid undertaken to see i f it obeyed Lambert's law it. was proved thatl the results for all the small apertures down to 0.29 per cent. (reading 84-5O on the graduated arc and giving the value 2.53 for logI/Z') harmonised perfectly with those found for the larger apertures. The still smaller ones were not" quite so true owing t o a slight imperfection in the setting of the vanes but this can be avoided in reproducing the instru-ment.That it is not only so but that i t is also precise follows from the examination of a standard piece of glass which was supplied by Messrs. Adam Illilger with their photometer for calibration purposes. The figures obtained are tabulated below. The two sets of values for logI/I' are as follows ( n ) those obtained by the new photometer; ( t ) ) the figures given by Hilger : The instrument is absolute in all its measurements. Wave-leng th. (a). ( b ) . 2751 0.281 0.278 2636 0.665 0.810 2564 0.919 0.888 2478 1.318 1.330 2435 1.605 1-608 2389 1.970 1-940 Of the two methods the one with the new photometer has the advantage of being direct and of not depending on the assumptio LEWTS A NEW SECTOR SPECTROPHOTOMETEk 319 that photometry in the ultra-violet is uniform with that in the visible region and on the use of accessory apparatus as i n the m&hod published by Hilger.I n any case the two series of results are sufficiently similar to one another to call for a discussion as to which is the more accurate expression of the phenomena. Considerable advant'age is gained by having two sectors which are equal in all respects as in the new photometer. As already stated the substance can be placed in tjhe first and second paths alternately so thatl any slight imperfections in the sectors or in any part of the optical train will express themselves in opposite senses in the tlwo series of spectra; also the work will be confirmed and experimental error corrected a t the same time,.The mean of the two closely concordant results must be a very near approxim-ation to the truth. Further opportunity is provided for eliminating the effect of the solvent directly. Most of the solvents alcohol for example, give feeble absorption spectra which spoil the accuracy of the extinction coefficients of the dissolved substance under investiiga-tion. It is not altogether satisfactory to correct the absorption constants of the solution by subtracting those due to the solvent, which have been ascertained separately and in any case it is laborious to do so; for example it is not safe to assume that a standard curve for absolutely pure alcohol applies to commercially pure spirit. Indeed some of the impurities commonly occurring in rectified spirit are strongly absorbent of ultra-violet light. It is better t o place i n the one path a tube of the solution and in front of the constant sector a similar tube filled with the same solvent as that used in making the solution. It is a good plan to have a tube of the given solvent in each of t.he two paths when adjusting the instrument and then to replace the solvent in one of them by the solution in question. It is perhaps unnecessary tlo do so but it lends a sense of satisfaction while it adds little or nothing to the experimental work. It is certain that the differ-ences then observed in the two spectra are due entirely t o the substance in the dissolved state and hence its absorption curve can be derived directly. There is however the possibility of t.he absorption spectrum being modified by the association of the solute with the solvent but that is a matter for other inquiry in each particular case and does not affect either the general truth of the proposition or the operation of the instrument. STAPLE INN BUILDINGS, HIGE HOLBORN W.C. 1. [Received March 39-4 1919.

ISSN:0368-1645    

DOI:10.1039/CT9191500312

出版商:RSC    

年代:1919

数据来源: RSC

摘要:

320 INaOLD AND THORPE THE FORMATION AND XXXIII.-lhe Formation and Stability of spiro-Compounds. Part II. Bridged- spiro-compounds Derived from cycloHexane, By CHRISTOPHER KELK INGOLD and JOCELYN FIELD THORPE. INTRODUCTION. (A> General. IN Part I. of this series (Beesley Ingold and Thorpe T. 1915, 107 1080) a comparison was drawn between the conditions of formation and the stability of the bromo-esters of PB-dimethylglu-taric acid and cyclohexane-1 1-diacetic acid. These two acids con-tain respectively the structures I and 11 and the object with which (1.1 (II.) these comparisons were made may be indicated by reference to Figs. (i) and (ii) which are drawn to correspond with structures I and 11. The question discussed was whether the forcing apart of the valpncies (a) and ( b ) of a carbon atom from an inclination of 2 tan-12/?2 to one of $?r radians which according to Baeyer’s strain theory necessarily accompanies the production of the cyclohexane ring would cause the other two valencies (c) and (d) tol approach one another.They might i t was suggested approach one another in such a way as to divide the remaining space into three equal angles as in Fig. (iiA); or alternatively they might be quite unaffected by the straining of (a) and ( b ) and remain as Fig. (ii B) shows a t the normal angle of 2 tan-lJ% It was pointed out that if the first of these hypotheses that represented in Fig. (ii A) were correct and side-chains attached t o (c) and (d) were in closer proximity when (a) and ( 6 ) were bound in a cyclohexane ring than is the case in Fig.(i) where (a) and ( b ) are free then the elimination of groups or elements such as for example hydrogen and bromine as hydrogen bromide from the side-chains of substitution products of cyclohexanediacetic acid should proceed with greater readiness than when corresponding derivatives of dimethylglutarie acid are employed. Further the ring compounds formed its a result of the elimination might be expected t o possess a greater general stability in the former case than in the1 latter. If on the other hand the second alternative STABILITY OF SPIRO-COMPOUNDS. PART 11. 321 for which Fig. (ii B) is drawn is the correct one there should be no difference in the two cases. Experimental evidence was as a matter of fact clearly in favour of the first hypothesis.Thus for example trains-cyclohexanes~n'ro-cychpropane-1 2-dicarboxylic acid which contains the carbon -2p-Rj.(i) 4 skeleton IV was found to possess a distinctly greater stability than trans-caronic acid represented by the outline 111 : CH2*CH 71) CH2<CH,*cH,>:<c~n, (111.) W.1 The present paper extends the comparison t o substances of a more complex type which contain a cycbbutane ring joined rather to th 322 INGOLD AND THORPE THE FORMATION AIUD cyclopropane ring by two carbon atoms common toq both. The struc-tures of these compounds are indicated by the outlines V and VI : (1) (1) CH C - p CH,=Cf12>C<F-$h CH2<CB2*CH2 ( 6 ) C-C(3) (4) CH 3>e<b-c(3) (v.)'4' w.1 It is apparent that the presence of the cyclobutane ring in struc-tures V and VI will make a considerable difference in the kind of effect that one might expect to' observe.This can best be under-stood by representing the strained valencies according t o a graphical niethdd which depends for its rational basis on the following con-siderations. I n Fig. (iii) which is drawn t o correspond with formula 111 the axis. - .. . . carbon atoms of the c?yclopropane ring are represented as points at the corners of an equilateral triangle. Now in the case of such a compound as ethane it can scarcely be doubted that the resultant o f the attracting forces which bind the two carbon atoms together, that is to say the vslency is directed along the straight line joining the centres of the carbon atoms.With cyclopropane however the case is different. For here according t o the strain theory we have each one of the carbon atoms of the ring reacting on those of its valencies which participate in the ring in such a way as to t e n d to make them emanate from the atom in directions inclined to one another a t an angle of 2 tan-ld/2 I f the carbon atoms were entirely successful in bringing about this result then since tw STABILITY OE SPXRO-CO~~PO~IXS. PART n 323 valencies emanating from the same carbon atom a t an angle of 2 t a n - l d y h a v e to reach the two remaining corners of the equi-lateral triangle it is clear that the ouly way in which they could do so is by describing curved paths. The simplest curve which in these circumstances a valency could deecribe would be the arc of a circle each of the terminal tangents of which makes an angle of tan-1JZ with the median through the corresponding corner of the equilateral triangle.This path is drawn in the case 01 the valency ( 3 l ) in Fig. (iii). It represents a state in which the carbon atoms would be entirely free from distortion of the kind we are consider-ing the whole bleing borne by the valencies; that is t o say the physi-cal stress would reside solely on the inter-atomic medium in which the forces of valency are propagated. The valencies will 'however, on their part tend t o reduce their potential energy by shortening their paths and if t l ~ e y completely succeeded would stretch them-selves along the straight lines joining the carbon atoms.This would throw the whole of the strain back on the latter sinoe now the initial directions in which the ring-valencies leave a carbon atom are inclined not a t 2 t a n - I J z but at ~ / 3 . It is probable, therefore that an equilibrium of stresses will be set up and that the valencies will occupy paths which li0 between the straight lines and the limiting ascs the arrangement being of such a kind as t o cause part of the strain to' be taken up by the distorted carbon atoms and part by the bent valencies. Experimental support can he claimed for this view. For in Part I. there were recorded experiments which yidded decided evi-dence that part a t least of this kind of strain is actually taken up by the carbon atoms. In particular it was shown that when two valencies of a carbon atom are bound in a cyclohexanel ring groups attached to the other two valencies apparently take up an altered relative position.It is obvious that this could never happen if the strains existing in the cyclohexane ring resided solely on the valen-cies participating in the ring none a t all being borne by the carbon atom wliicli carries the side-chains. Similarly strains existing in one ring of a sp'ro-compound could not possibly make themselves felt in the second ring unless communicated by a spirane carbon atom which itself is in a state of strain. According to the expri-nients described in Part I. such communication of strain a c r w the spirane carbon atom appears actually t o take place and one can only conclude therefrom that the spirane atom itself is by no means in an unstrained condition.If it be true that part; a t least of the strain of the cyclohexane ring is actually taken u p by the carbon atoms then regarding the matter from the graphical point of view we may say that th 324 INGOLD AND THORPE THE FORMATION AND valencies of the cyclohexane ring and presumably of any other alicyclic ring occupy paths which are distinctly flatter than the limiting arcs the terminal tangents of which meet a t the normal angle 2 tan-1J2. On%he other hand it will be shown in the present paper that it is more difficult to close the cyclobutane ring in the formation oE certain bridged-spko-compounds of the type VI (p. 322) than it is in the formation of corresponding bridged-ring compounds of the type V (p.322). Further the former when obtained are less stable than the latter in certain specific positions entirely in accord with the views here put forward. I f the stresses existing in the cyclohexane ring can be communicated to the cyclobutane ring or to side-chains attached to the cyclopropane ring before the cyclo-butane has been closed then it follows that the valencies of the cyclopropane ring as well as the spirane carboneatom must take part in the transmission of stress. With entirely unstrained valen-cies this is inconceivable and one is therefore forced to the conclu-sion that the valencies themselves are strained. The graphical aspect of this is that the valencies concerned and therefore probably all ring-bound valencies must occupy paths which are not straight lines which are in fact distinctly curved.The curvature of such a path will as we have already seen be less than that of the limiting arc the terminal tangents of which meet a t 2 t a n - l d z and the path may therefore be regarded as lying somewhere between a straight line on the one hand and a limiting curve on the other. Exactly where the position of equilibrium of a particular valency lies and what the precise shape of its true path is it is impossible a t present to say; but the view that the true equilibrium-path lies somewhere between the rectilinear path which represents the limit-ing case in which the valency is unstrained and the curved path which stands for the other limit. in which the whole of the distortion resides on the valency and none1 a t all on the carbon atom affords a simple and so far as it goes a fairly adequate hypothesis in regard to the facts observed.I f we accept the point of view that the more strained a valency is the more prone it is t o break then among the factors which determine the equilibrium of strain-distri-bution will certainly be found the number of groups attached to tho carbon atoms concerned; for the tendency which ring compounds have to undergo fission between quaternary carbon atoms is well known. The electrochemical character of the substituents will of course; be another determining factor. Thus it would seem that there are three causes affecting th STABILITY OF SPIRO COMPOUNDS. P*AIlT 11. 325 stability of any valency which participates in a fully reduced alicyclic structure : (1) The number of carbon atoms in the ring, (2) The character and mode of attachment of any attached rings, and (3) The number distribution and character of the substitucnt groups.I n regard to the first of these causes Baeyer’s simple conception has had a very great degree of success in explaining the broad facts; so much so that one cannot but accept it as an approximation to the truth. I n its elemental form however it does not consider the question as t o whether the atoms or the valencies are the seat of the postulated strain and consequently is not in a position to take into account the mode of operation of causes (2) and (3) which present us with two unsolved problems. The series of which this paper is Part 11.is an attack on the former of these. I n regard to the latter all that can at the moment be said is that the present considerations lead to the view that whilst causes (1) and (2) deter-mine the maximal strain o r curvature which any particular valency can be called on to bear cause (3) operates in such a way as to settle exactly what’ fraction of that maximum it shall bear. The uncertainty which surrounds the operation of cause (3) con-stitutes a difficulty which one meets with in planning experiments with a view to study the mode of action of cause (2). If however, one is careful only t o compare substances in which similar and similarly situated substituent groups are present the strain on a valency may fairly be taken t o be measured by the1 greatest strain which thatvalency could be called on t o bear in the limiting equili-brium.It will actually of course be just a fraction’of this but if the groups are alike i t will be the same fraction for all the substances. I n such cases therefore the strain existing on a valency is from the graphical point of view measured by the degree of curvature of the limiting curved path. Fig. (iii) p. 322 is an application of this method to the cydo-propane ring structure I11 (p. 321) and has already been men-tioned. The limiting curve for the valency ( 3 l ) is drawn. Its terminal tangents make angles of tan-1 d3 with the corresponding medians and its curvature taking the side of the triangle as unity, is d 5 - i J T . Applying the same method to the c?/cZohsxane-s~.rocycZopropane structure IV (p.321) we obtain Fig. (iv) (p. 322) in which for reasons referred to a t the beginning of this paper and given in detail in Part I. the terminal tangents of the limiting curve of the VOL. cxv. 326 INCOLD AND THORPE THE E'ORMATION AND valency ( 3 l ) are drawn t o make angles with the corresponding medians less than the normal value t a n - l f i by say I. radians. The curvature of this curve is less than that of the curve in Fig. (iii) by about -$(7 - 2 dz)p a figure which may be taken as a measure of the increase in stability of the bond ( 3 l ) which was proved experimentally in Part I. The structure V (p. 322) is interesting as exhibiting a difference in exactly the opposite sense. The fact that two of the valencies of the carbon atom (1) are held in a cyclobutane ring will according to the views put forward in Part I.tend to make the initial directions in which the other two valencies leave the carbon atom spread out in such a way as to foran angles with one anotherandwiththecyclo-butane-ring-bound valencies greater than would be the case if the cyclobutane ring 'had not been closed. This will involve) an increase in the initial divergence of the valencies (1 :4) and (1 5 ) . The limiting arc between the carbon atoms (5) and (1) is therefore drawn (Fig. v p. 322) to suit terminal tangents inclined to the corresponding medians a t angles which are greater than t a n - l d 2 by,say p radians. The curvature is therefore greater than J2-gJ3by about i ( 7 - 2 d q q . The point of present interest is of course to see how a bridged-ring compound of the type V compares with a bridged-spko-com-pound of the type VI (p.322). It will be observed that in the latter case the limiting curve for the vnlency (5 1) cannot possibly be symmetrical. For whilst the carbon atom (5) is on account of the cyclohexane ring tending to reduce the angle which the ter-minal direction of the curve makes with the median $0 the value tan-1dZ-p radians the carbon atom (l) as a result of its being involved in the cyclobutane ring is endeavouring to enhance the corresponding angle a t that end of the curve to t a n - l J 2 f q radians. The true curve therefore will lie between the dotted arcs of curvatures J2-4d73-p/6(7-2d6) and approximating to the inner arc near the carbon atom (5) and to the outer near the carbon atom (1).Such a path it is clear from Fig. (vi) (p. 322) must contain a region of comparatively great curvature and we may therefore expect the bond (5 1) in bridged-spire-compounds of the type V I (p. 322) t o be noticeably less stable than the same bond in corresponding compounds of the bridged-ring series V. The effect just noticed will of course be by far the greatest which the cyclohexane ring could be expected to have on the attached dicyclic system. The reactions on the bonds (1 2) and (1 4) will 0- * J 3 + Pl6(7 - 2 d 6) STABILlTY OF SPIRO-COMPOUNDS. PART II. 323 be next in importance but of the second order. It is however of interest briefly to examine them. The fact that the limiting curve of the valency (5 1) is on the whole depressed below the arc which corresponds with the limiting curve of the same valency in Fig.(v) necessitates that the true path of the same valency in Fig. (vi) is, even near the carbon atom (l) rather less divergent from the recti-linear path than is the case in Fig. (v). This will involve a small effect on the valency (1 :3) in the direction of an increase in the curvature of its limiting curve. The bond (1 :2) should therefore be slightly mcre strained and less stable in the series V I than in the series V. The effect of the strains in the cyclo’hexane ring on the bridge-bond (1 4) is also of the second order the depression of the bond (5 1) being the determining factor. I n this case the fact that the bonds (1 5) (1 4) and (1 2) have their curves in different planes makes the geometricai construction more complicated.It would appear however that the effect should be in the direction of a decrease of stability although of course a very slight one. There remains for consideration the bond (2 3). The effect in this case will be still smaller of the third order in fact and prob-ably beyond the limits of detection. It should be in the direction of an increase in stability. It may be stated here that the results of the experiments described in this paper are in the most complete accord with all the above conclusions. The must striking fact which emerged during the experimental study was the marked decrease in the stability of the bond (5 l) of compounds of the type VI when compared with corresponding sub-stances of the type V (see sections C D and G).The fission of this bond was brought about with great ease in certain substances of the former type by alkaline reagents which appeared to be without effect on the latter. This is in agreement with the first of the main conclusions reached as a result of the conception of flexible valencies. The agreement is particularly interesting in this case, for whereas in the comparison of the cychprupane derivatives of types I11 and I V (p. 321) carried out in P a r t I. it wits found in agreement with the requirements of theory that the cyclohexane ring had a stabilising influence in the bridged series V and VI the hypothesis leads us t o anticipate exactly the reverse. Definite experimental evidence (section B) was also obtained on the effect on the bond (1 2) of the presence of the cyclohexane ring in the spiro-compounds.The expected effect is in the nature of an increase in strain that is a decrease in stability and is small in magnitude. Actually we were not able to find a reagent whicb 0 32s INGOLD AND THORPE THE FORMATION AND woulcl break this bond in a compound of the type V I (p. 322) and would not also break the same bond in one of the type V. This was a t any rate in part due to the fact that i t did not appear to be possible t o break the bond (1:2) in the series V I without first breaking the less stable bond (5 1). This so far as it goes, is valuable as i t indicates that the effect of the cyclohexane ring on the bond (1 2) is of a smaller order than the effect on the bond (5 1).Fortunately there is however a more precise and more delicate method of experiment. The cyclohexaneup*rodicyclopen-tane structure V I was in our exEeriments obtained from cyclo-hexane-1 1-diacetic acid by a method which involved first the clos-ing of the cyclopropane ring and then of the cyclobutane ring by the establishment of the bond (3:4). Now the1 additional in-stability which we have been led to expect the bond (1 2) in the spiro-structure V I to exhibit is due t o the tendency which there is owing to the cyclohexane ring f o r the arrgle between the bonds (1 :4) and (1 :5) to increase. It is obvious that this tendency will have greater effect if the bond (3 4) has not been established than would be the case if i t had for in the former case the tendency will n o t be resisted by the strained bonds of the cyclobutane ring.The result. will be to magnify the' effect by drawing further apart the carbon atoms (3) and (4) t o an extent which might quite well be sufficiently great to make i t appreciably more difficult to close the cyclobutane ring in the series V I than in the series V. A set of comparative experiments made in order t o discover whether sucli an effect could be detected revealed its existence very clearly. The interest of these experiments lies in the fact that they show that the stresses in the cyclohexane ring have been communicated to the bond (1 2) a phenomenon which would seem necessarily to involve the assumption that the bond (5:1) as well as the carbon atoms (5) and ( l ) are in a state of strain.With regard to the bond (1 4) in the structures V and VI (p. 322) there is available quite a good method of experiment since sodium amalgam readily breaks this bond in certain substances belonging to these types without attacking in the slightest degree any of the other bonds in the molecules (see section E). The reduc-tions occupy several hours and can readily be conducted a t con-stant temperature and under comparable conditions. By making comparative1 experiments along these lines it was discovered that, although the reactions proceeded in much the same way in the two cases there was a considerable difference in the reaction velocities, the reductions proceeding more rapidly in the bridged-spiro-series VI than in the bridged-ring-seriag V.This is in agreement with the conclusions already reached on theoretical grounds (p. 327) but it STABILITY OF SYIRO-COMPOUNDS. P,4RT 11. 329 llas also some interest from another point of view. It might be thought possible that valencies are so extremely elastic as to be capable of stretching as we11 as of bending. I f that be so the valency (1 :4) ought t o be less stretched out in the structure VI in which the cyclohexane ring is tending t o reduce the angle a t which the bonds (5 1) and (5 4) emerge from the spirane carbon atom (5) than in the structure V which contains no cyclohexane ring. Any such difference in the degree of elongation of the bond (1 4) ought 50 manifest itself as a marked difference of stability since the forces between two carbon atoms must vary as some power, probably a high power of the distance between them.As a matter of fact the difference of stability which the reduction experiments reveal is in precisely the opposite sense from that which this view requires. This appears to us t o show that no appreciable lengthen-ing occurs and that probably all carbon-to-carbon valencies have the same fixed length. It may also be noticed that the effect observed is the opposite t o what would be expected if the bonds occupied inflexible skraight lilies. For in this case the tendency which the cyclohexane ring has t o reduce the angle between the bonds (5 1) and (5 4) (compare Part I.) should operate in such a way as t o increase the stability of the bond (1 4).These facts, therefore constitute a strong argument in support of the conception of flexible valencies. There remains to be mentioned finally a set of experiments which were undertaken in order to obtain information regarding the bond (2 3). This bond according to the conclusions expressed on p. 327, should be practically unaffected by the strains in the cyclohexane ring. Actually we were n o t successful in finding a reagent which would attack this bond in a compound of the type VI even when the stability of the bond was reduced by the introduction of an alkyl group a t the carbon atom (a) without first attacking one of the cyclopropane bonds adjacent to the1 spirane carbon atom. However the experiments were interesting as confirming our pre-vious experiences regarding the instability of these bonds and were in harmony with the conclusions already reached in regard t o the insignificance of the effect which the cycluhexane should have on the bond (2 :3).I n order t o avoid confusion in what follows it ought perhaps t o be pointed out that the bonds (5 1) and (5 4) are equivalent in the carbon skeletons V and VI (p. 322) and only become dissimilar when substituent groups are introduced unsymmetrically. This is actually the case with the corripounds with which we have experi-mented and i t so happens that the bond split in all the substances which were subjected t o fission by alkalis is according t o the metlior 330 INGOLD AND THORPE THE FORMATION AND of numbering employed throughout the bond (5 4) not the bond (5 1).This it is clear invalidates nothing and in fact the agree-ment would be formal as well as actual if in the formulae which follow we had numbered the dicyclopentane ring the other way round. The objection t o doing this is that one would then meet with the same lack of formal consistency in regard to the bonds (1 2) and (3 4). (B) Formation of the Bridgehhq Systems V and V I (p. 322): Closing of the cycloBzctane Bond (3 4). Some time ago in a paper published by one of us in conjunction Gyitli W. H. Perkin (T. 1901 79 729) it was shown that when the dibromo-ester of PB-dimethylglutaric acid (VII) was treated with ethyl malonate and sodium ethoxide condensation took place in two stages the ultimate product being an insoluble yellow sodium deriv-ative of ethyl dimethyldicyclopntanonetricarboxylate (IX).It was (VII.) (VII1.)-(IX. 1 therefore to be expected that if cyclohexane-1 1-diacetic acid were used in place of dimethylglutaric acid a similar condensation would ensue1 : (XI. 1 (2) crr,<C H,* C Ha>(1! c( CO E t) $! C( ONa) 0 E t CH,*CH k<b( CO$t)*cOn (4) (XII.) The sodium derivatives IX and XI1 clearly belong respectively to the types V and VI (p. 322) and it was therefore decided to 9ake their formation and decompositions sub jechs of comparison. It was found possible t o prepare the sodium spirmompound (XII) direct from ethyl dibromocydohexanediacetake (X) and ethy STABILITY OF SPIRO-COMPOUNDS. PART 11. 331 sodiomalonate under the same conditions as are employed in pre-paring the sodium ring compound (IX) from ethyl dibromodi-methylglutarate (VII) .Direct comparison of the two condensations is however complicated by the fact that whilst ethyl dibromo-dimethylglutarate (VII) can readily be obtained in a state of purity by distillation the corresponding cyclohexane derivative (X) decom-poses when distilled. We were therefore forced to use a crude bromination product containing only 76-80 per cent. of the dibromo-ester- Nevertheless the difference between the two cases is significant. Two experiments one with the bromo-ester of dimethylglutaric acid and the other with the bromo-ester of cyclo-liexanediacetic acid carried out under comparable conditions (except that sufficient excess of the crude cyclohexane ester to allow for the impurities was used) gave in the first case a 62 per cent.yield of the sodium compound (IX p. 330) and in the second a 13 per cent. yield of the sodium sera-compound (XII p. 330). I n order to make the comparison more definite the tetraethyl ester XI (p. 330) was prepared in a state of purity. The internal condensations of the esters V I I I and XI (p. 330) with alco-holic sodium ethoxide whereby alcohol is eliminated and the bridged structure formed were then carried out in a series of experiments made under comparable conditions. Several pairs of parallel experiments were1 made in which the two esters were boiled with alcoholic sodium ethoxids under standard conditions for dif-ferent lengths of time a t the end of which the insoluble sodium compounds’were collected and weighed.The results are given in the experimental part of this paper (p. 359). The figures for the yields in the two cases lie upon fairly smooth but widely divergent curvea (Fig. vii). These curves clearly show that the velocity of formation of the bridged-ring structure is much greater than the velocity of formation of the sp.ro-compound. The times required for a 20 per cent. conversion are in the ratio of approximately 10 ik~ 1. An examination of the curves shows that if x is the yield (per cent.) and t the time the quantity - a/ax(dx/dt) is almost invariable with time and has a definite positive value for each curve, being about 0.97-1 hours for the! bridged-ring compound and a b u t 0‘33-1 hour for the1 bridged-spire-derivative.The velocity constants for the’formation of the sodium compounds are therefore approxi-mately in the ratio of 3 t o 1. The best yields obtainable in the two cases are 77 per cent. and 38 per cent. respectively but a longer time is necesqary to produce1 a 38 per cent. yield of the spiro-com-pound than is required to obtain a 77 per cent. yield of the ring compound. The fact appears to be that the spko-ester XI (p..330) will only condense with itself when present in the sodium ethoxid 332 INGOLD AND THORPE THE PORMATIOX AND in considerable concentration. For whereas under the experimental conditions which give the best yield (77 per cent.) of the sodio-ester, IX the tetraethyl e,ster VIII (p. 330) almost entirely disappears from the reaction mixt,ure when the ester X I is treated so as t o produce a maximal yield of the sodio-spiro-ester (38 per cent.) then, 100 90 80 70 60 u c: 2 50 t 40 30 20 10 0 0 2 4 6 S 10 12 hours although longer time is allowed in this case the conversioii is found t o be only partial about 15 per cent.of the tetraethyl ester being recoverable. Yet prolonging t.he time of resctioii does not appear appreciably to increase the yield of sodium compound or reduce the quantity of tetraethyl ester recovered. These experiments clearly show that i t is more difficult t o estab STABILITY OF SPIRO-COMPOUNDS. PART 11. 333 lisli the bond (3 4) o l the cyclobutane ring to form tlie spire-conl-pound XI1 than it is in tlie formation of the ring compound I X .Indeed the low yield of the former compound was one of the greatest practical difficulties of tlie research. (C) Hydrolytic i7econiliositioii.r of tJie Bridyerl-Riiig l l m i z w t i c e s I S (znr? X I 1 (p. 330) Strtbility of tJhe cyclol'ropane Bond' (4 5). The first evidence of a difference of stability between compounds o l the bridged-spiro-series V I and those of the bridged-ring series V (p. 322) was obtained in the coarse1 of some experiments on the hydrolysis of the sodium spiro-compound XI1 (p. 330). The efect of hydrolysing agents on the sodium compound IX has already been described in the paper with W. H. Perkin (Zoc. cit.), and the general coiiclusicii reached was that the end-product of the action of alcoholic potassium hydroxide was a mixture of the dibasic and monobasic acids XI11 and XIV and that the same two acids (XIII.) (XIV.) were formed by the action of dilute sulphuric acid.The dibasic acid XI11 when heated with water in a sealed tube was found t o yield the monobasic acid XIV. On experimenting along these lines with the yellow sodium spiro-compound XI1 (p. 330) it soon became. apparent that the. spiro-conipounds were behaving very differently ; the hydrolytic products were therefore investigated in some detail. When the yellow sodium splil-o-compound XI1 was treated with cold dilute acid a colourless solid ester C19H2607 (XV) was pro-C(C0,Et) * yIi*C'O,Et C 5 H 1 0 C < & ( p ~ 2 ~ q . co (XV.) duced. This ester could be transf orined by cold alcoholic potassium hydroxide into the yellow potassium salt XVI and thence by acids into the colourless acid-ester XVII.C( CO,H)-yH* CO,Et (CO,K)-$X C(OK)* QEt ".Hio:4oo,Et) co c5a10:C<($C0,Et). co (XVI.) (XVII.) Regarding tile question as t o which of the three carbethoxyl groups has been attacked by the reagent i t is clear t h a t it cannot be that attsched t o the carbon atom (2); for if it were the forma-O 334 INGOLD AND TRORPE THE FORMATION AND tion of a yellow insoluble ptassio-compound so very similar to the original sodium compound would be exceedingly improbable. The fact that it is the 1-cerbethoxyl group and not the 4carbethoxy1, which has been attacked follows from the production by further hydrolysis of the acid-esters XVlII and XXI about the constitu-tion of which no doubk exists.The first product of the action of boiling alcoholic potassium fiydroxide on either of the compounds XVI or XVII was a colour-less very readily soluble potassium salt of tho ethyl dihydrogen ester XVIII : (XVIII. ) The constitution of the acid-ester XVIII follows from the fact that it is obviously formed by the hydrolysis of the metal-substi-tuted carbethoxyl group in the yellow potassium compound of the diethyl hydrogen ester. The other possible formula (XIX) of the diethyl hydrogen ester would give an ethyl dihydrogen ester of the constitution XX. The formula XX was however easily shown to (CO,Et)*C K* C0,Et C(CO,Et)* CH*CO,H (XIX.) (XX). CbH J 4 ( C * f l )-&I ~~5~~o:c<~(co2H)-Lo 1 be incorrect by an experiment on the effect of treating the substance with acetyl chloride.With this reagent it readily yielded an anhy-dride which on treatment with water furnished the original acih-ester. These facts clearly favour formula XVIII in which the free carboxyl groups are attached to contiguous carbon atoms and rules out the alternative formula XX. We must also regard XVII as the true formula of the diethyl hydrogen ester since a substance of the formula XIX could not possibly yield the ethyl dihydrogen ester XVIII. The acid-ester XVIII can also be produced from the triethyl ester XV (p. 333) by hydrolysis with hydrochloric acid. Indeed, up to this point hydrolysis with alcoholic potassium hydroxide and with hydrochloric acid proceeds along the same lines. The first product of the action of boiling hydrochloric acid on the ester XV is the diethyl hydrogen ester XVII (p.333) which by continued action of the same reagent is converted into the ethyl dihydrogen ester XVIII (above). The further action of hydrochloric acid causes the substance to decompose simultaneously in two ways losing in the one case a carboxyl group and in the other a carbethoxyl group. The groups eliminated will of course be those in the positions (2) and (4) con STABILITY OF SPIRO-COMPOUNDS. PART 11. 335 tiguous to the carhnyl group and the products must therefore possess the constitutions XXI and XXII: (CO,H)* H*CO,H C H lo :Q<~(co~L1)-~!? C(CO,Et)* 0 C,H,o C<ZH-& (XXI.) (XXII.) These formulze are in complete accord with the properties of the substances.The acid-ester XXI folr example melted without decomposition and gave no coloration with ferric chloride showing that the free carboxyl group is not adjacent tu the carbonyl group, and that the carboxyl group which was attached to the carbon atom (2) in the acid-ester XVIII has been removed. The dibasic acid XXII on the other hand melted with decomposition gave a crim-son colour with ferric chloride and when treated with acetyl chloride gave an anhydride from which the original acid could be regenerated by treating with water. These facts clearly establish formula XXII. The formation side by side of the acids XXI and XXII does not constitute quite the final stage of the hydrolysis by hydrochloric acid of the ethyl dihydrogen ester XVIII (p.334). For the acid-ester XXI on prolonged boiling with hydrochloric acid loses its 4-carbethoxyl group yielding the monocarboxylic acid XXIII : (CO,H)*CH, C5Hl*:C<~H-bo (XXIII.) The dibasic acid XXII on the other hand was not changed appre-ciably even on boiling for eighty-seven hours with hydrochloric acid. The final product of the action of this reagent on the acid-ester XVIII was therefore a mixture of the dihasic acid and the mono-basic acid (XXII and XXIII). Further the dibasic acid XXII was readily converted into the monobasic acid XXIII by heating for a few minutes a t 200° with water. All the acid-esters (XVII XVIII and XXI) of the series reacted a t this temperature with water giving the same monobasic acid usually in very good yield. The neutral triethyl ester XV (p.333) however required the presence of a trace of an acid such as acetic or hydrochloric acid in the'water. The presence of a small quantity of butyric acid even was found to be quite sufficient so that in the cases of the acid-esters the reaction is in all probability autocatalytic the catalyst being the hydrogen ions produced initially by the electrolytic dissociation of the acid-esters themselves and in the later stages of the reaction by the dissociation of the mono-carboxylic acid XXIII or of carbonic acid. In t,he case of the o+ 336 INGOLD AND THORPE THE FORMATIOW AND triethyl ester i t is necessary artificially to introduce some hydrogen ions in order t o start; the reaction. Alkaline hydrolysis of the acid-ester XVIII (p.334) proceelded in quite a different direction the product being an acid of the formula C,,H,,O,. This substance is a dibasic acid. It is not an aldehyde, and contains no lactone ring. It is therefore a fission product formed by the breaking of one of the bonds (1 :a) (1 :4) (1 :5) or (4 5) of the dicyclic system : One of the three carboxyl groups originally present in the molecule has been lost and since the substance gives no colour reaction with ferric chloride i t is to be presumed that i t is tlie carboxyl group attached to the carbon atom (2) which has disappeared. The ques-tion as to which of the four possible bonds has been btroken is settled very clearly by the properties of the substance. Thus fission of the cyclobutane ring a t the Eond (I 2) should yield either a derivative containing an open-chain acetoacetic acid residue or a hydroxy-com-pound capable of forming a y-lactone according to the way in which the elements of water are added t o the molecule a t the point of fission.The substance actually obtained was found t o be remark-ably stable towards boiling alkalis and showed no tendency to pass i n b a lactone. On the other hand although a tram-acid i t forms an anhydride with the greatest ease. For this reason i t may be safely assumed that the 1- and the 4-carboxyl groups are attached t o contiguous carbon atoms and t h a t the bridge-bond (1 :4) has remained intact. The bond which has been broken is therefore one of the cyclopropane bonds (I 5) and (4 5) and since the substance is not a y-hydroxy-acid i t must have one of the two following formuke : (XXIV.) (XXV.) Although both these formulae are in harmony with the properties of the substance there can be little doubt that formula XXIV and not formula XXV is correct for this reason The monobasic acid XXIII (p.335) does not undergo fission with alcoholic potassium hydroxide. The fission therefore seems to be connected with tli STABILITY OF SPIRO-COMPOUNDS. PART 11. 337 quaternary carbon atom in the position (4). If this be so it is reasonable to assume that splitting takes place a t a point adjacent to this carbon atom. An indirect. but interesting confirmation of this conclusion will subsequently be referred to (p. 345). The substance to which the formula XXIV has been assigned separates from water with two molecules of water of crystallisation.The anhydrous compound when heated a t 250° was found to pass into an anhydride which gave with water a new dibasic acid also of the composition C,,H,,O,. This did not take up wate? of crystallisation and melted with tho immediate elimination of water-vapour. On boiling with hydrochloric acid i t was quantitatively converted into the isomeride previously mentioned. These relation-ships clearly indicate that geometrical isomerism of the cis-traits-type is here being encountered both the acids C,,HI6O having the structure represented by the f mmula XXIV which clearly requires the existence of this kinu of ibomerism. The relationships between the various substances obtained by the hydrolysis of ethyl cyclohexanesphodicyclopentanonetricarboxylate and of its sodium derivative are collected together for convenience in table I.In order to study more closely the contrast presented by the hydrolytic reactions in the dimethyldicyclopentane and the cyclo-hexanwyirodicyclopentans series a number of direct comparative experiments were made in order to determine the relative speeds a t which the acid-esters of the two types decomposed in the presence of alkali. - The substances chosen were the ethyl dihydrogen ester XXVI," and the analogous substance in the bridged-CH,>,<F(CO,H)-FH*CO,H CH C(CO,EL)*CO (XXVI.) spir-o-series namely the acid-ester XVIII (p. 334). The bridged-ring ester XXVI decomposes under the prolonged action of boiling alcoholic potassium hydroxide yielding the monobasic acid XIV (p.333). The bridged-spiro-ester XVIII on the other hand, undergoes fission with the same reagent giving the cyclohexyl-cyclobutane acid XXIV (p. 336). There is however a remarkable difference in the ease with which the two reactions proceed. Thus in one pair of parallel experi-ments made under comparable conditions the acid-ester XVIII of the bridged-spbo-series gave an 85 per cent. yield of the fission * This substance was not isolated during the earlier research. Its properties and mode of formation are therefore given in a note at the end of the experimental part of this paper TABLE I C0,Et +- 4-cold EICL cold NaOH C,Hlo: CO,Et (Yellow FeCl crimson.) KOfI in I MeOH cold J. CO,K (M. p. 46-47', short C0,Et (Yellow FeCl violet.) (Gum, CO,H H*CO,H > C 5 H o C < ~ ~ o KOH in EtOH hot 60,Et (M.p. 206 dec. FeC1 violet. co*o*co CO,H -4 C~H~,, C H - ~ < ~ ~ ~ ~ > C O ~ ! C ~ H ~ ~ cH;c<;tij>c 0 C,H o c<X-X~ C, iO,Et (tmna M. p. 206' dec.) (cia M. p. 145' dec.) (U. p. 126".) ''zH GO H I C0,H I co*o*co (M. p. 155" ; anilic acid m. p. 202' dec. ; anil m. p. 199".) (M 340 INQOLD AND THORPE THE FORMATION AND product whilst on the contrary the bridged-ring acid-ester XXVI was recovered unchanged to the extent of 93 per cent. only a trace of the1 monocarboxylic acid being isolated. No fission pro-duct of the dimethyldicyclopentane series was isolated in the course of these experiments. These experimental comparisons are interesting as showing the extraordinary facility with which the bond (4 5) in the bridged-spiro-series is broken.They have however interest from another point of view. For if they had not been made i t would have been poasible to advance an explanation of the difference in the ease of fission of the bond (4:5) in the t'wo series based not on the] strain effects of the cyclohexane ring but on steric hindrance caused by the attached groups. It has already been noticed that i t appears t o be necessary to have a quaternary carbon atom in the position (4) in order to bring about the fission of the bond (4 5) by alkalis. One might assert therefore that in the bridged-syirol-series the C,HIo group attached to the carbon atom (5) has the effectl of preventing the elimination of the 4-carbethoxyl group.The carbon atoms (4) and (5) therefore both remain quaternary in the presence of the alkaline reagent and splitting occurs between them. One would have to assume of course that although the steric effect of the C5H,,, group attached to the carbon atom (5) is sufficiently powerful to prevent the atkack of the reagent on the 4-carbethoxyl group yet for some reason unknown i t does not inhibit the attack of the same reagent on the bond (4:5). I n the bridged-ring series on the contrary the (CH,), group attached to the carbon atom (5) might not have any appreciable steric effect. Splitting therefore might not t'ake place in this case owing to the fact that when the acid-ester XXVI (p. 337) is treated with alcoholic potassium hydroxide the 4-carbethoxyl group is so quickly eliminated that the carbon atom (4) becomes tertiary before the reagent has had time to react appreciably on the bond (4 5).We were of the opinion a t one time1 t-hat there might be some truth in this way of explaining the phenbmena and it7 was the desire to test this hypothesis that! furnished our chief motive for undertaking the comparative experiments with the acid-esters XXVI and XVIII. It will be seen however that the experi-ments effectively dispose of this explanation since they show that the 4-carbethoxyl of the acid-ester XXVI is not a t all readily eliminated under the experimental conditions employed. We consider this to be strong evidence that the bond (4:5) in the bridged-spire-series is actually under considerable strain much more so than in the bridgsd-ring series and that the fission reac-tions are not to be accounted for as secondary phenomena due t ST.4BILITY OF SPIRO-COMPOUNDS.PART 11. 341 steric hindrance or ot,her such causes. Several other examples of the splitting of the bond (4 5) in the bridged-sp’ro-series will sub-sequently be given (sectmiom D and G). (D) Hydrolytic Decoinpositioiis of the Methylation Products of the Bridged-ri?iy Derivatives IX and X I 1 (p. 330) Stability of the cycloiPropane Bond ( 4 5 ) and of the cycloBiitatze Botzd (2 3). I n the paper on bridged-ring derivatives to which reference has already been made interesting results were obtained by methyl-ating the yellow sodium compound IX (p.330) and subjecting the methyl derivative to alkaline hydrolysis. It was found that the entrance of the methyl group a t the carbon atom (2) in XXVII created a point of instability between the carbon atoms (2) and (3) and that fission took place with the1 formation apparently of the cyclopropane acid XXVIII which t-hen underwent a second fission giving the dibasic lactonic acid XXIX. C(C0,Et)-CMe*CO,Et CH, ,C( CO,H)*CHMe*CO,H CHs\,C/ I -+ C ’ CH/ \c(co,Etj*ko CH,,’ \~H*CO,H (XXVII.) (XXVIII.) CH C(CO,H).OHMe*CO,H CH,/ \CH,*CO% --3- \(/\-. (XXIX.) The sodium spiro-compound was quite readily methylated by means of methyl iodide. When the ester thus obtained was treated with alcoholic potassium hydroxide the principal product was a dibasic lactonic acid evidently a double-fission product, which however did not appear to be constituted analogously to the lactonic acid XXIX.It would appear that. there are two quite probable ways in which hydrolytic action might proceed. I n the first place the attack on the ester XXX mightl commence a t the bond adjacent to the C(CO,R)-CHMe-CO,H / I C(CO,Et)*CMe*CO,Et C,H,,:C / I I -+ c,Hlo:c -‘C(CO,Et)*ko \~H~CO,H (XXX.) (XXX I .) \CH2*CO* 0 C(CO2H)*CHMe*CO2H 4 C,H,,:C’ ‘‘-\ (XXXII 342 INGOLD AND THORPE THE FORMATION AND methylated residue and give as the first product a spirocycZo* propane acid XXXI which is similar to XXVIII and would ultimately yield a lactonic acid XXXII strictly analogous to XXIX. On the other hand we know that the cyclopropane bond (4 5) is a very vulnerable point in the molecule of the unmethylated ester XV (p.333) and it can scarcely be supposed that the entrance of a methyl group a t the carbon atom (2) would stabilise it to any marked degree. If in spite of the weakening of the bond (2:3) by the methyl group the bond (4:5) still remains the most readily attacked part of the molecule we should expect from the behaviour of the unmethylated ester to obtain a cyclohexyl-cyclobutane acid XXXIII which would then split again this time across the bond beside the methylated residue giving ultimately a dibasic lactonic acid of the formula XXXIV. C0,Et CO,H . CO,Et (XXX.) C0,E (XXXIII. CO,H /C-CH Me CO.0 ,//--3 C,H,,:CH I ____- -CH*CO,H (XXXIV.) In seeking evidence to enable us to decide between the formulae XXXII and XXXIV we made a study of the conditions of anhydride formation of the substance.It will be noticed that both formulse represent substances which as they have carboxyl groups attached to contiguous carbon atoms ought easily to form anhydrides. A substance of the formula XXXII would however, belong to the type of ad-dimethylsuccinic acid which yields two stereoisomeric anhydrides corresponding with the two stereoisomeric acids (Bone and Perkin T. 1896 69 266). The trans-acid on treatment with acetyl chloride gives a trans-anhydride which on distillation passes into the anhydride of the &-acid as shown in Scheme 1. - HzO Heat + H2O trans-Acid Tz trans-anhydride -+ cis-anhydride 7- cis-acid. Scheme 1. The lactonic acid XXIX (p.341) to which XXXII is strictly analogous actually* does form two anhydrides related to one +H@ - Hz STABILITY OF SPIRO-CIOMPOUNDS. PART II. 343 another and to their acids in this way. Consequently a substance of the formula XXXII should do the same. On the other hand in formula XXXIV the bond uniting the two carboxyl-bearing carbon atoms forms part of a ring and hence such a substance would be expected to dehydrate in the manner customary with carboxylated alicyclic compounds the trans-acid, in which the carboxyl groups are on opposite sides of the ring, being incapable of forming its own anhydride but passing on dehydration directly into the anhydride of the &-acid as indi-cated in Scheme 2. - HzO +H20 trans- Acid -+- cis-anhydride zz cis-acid.Scheme 2. - TT29 Experiment showed that the lactonic acid obtained by the hydro-lysis of the ester XXX (p. 342) actually dehydrated in accordance with Scheme 2. The original product of hydrolysis was the tram-acid. It did not eliminate water a t the melting point but was readily dehydrated by acetyl chloride. The anhydride formed was the same substance whether tbe product of dehydration was dis-tilled or not and on treatment with water yielded the cis-acid. This substance melted with the immediate elimination of water vapour and was instantly dehydrated by acetyl chloride. These facts point most distinctly to formula XXXIV (p. 342) as repre-senting the true structure of the stereoisomeric acids. It is obvious however that we have by no means exhausted all the possible formulae in the above considerations since either of the intermediate compounds XXXI and XXXIII (pp.341 342) could split and take up water in a variety of ways. Indeed besides XXXI and XXXIII there are a number of other formulze which the single-fission product might have. When however all these possibilities are examined it would appear that there are only two formulae besides XXXII and XXXIV (pp. 341 342) which fulfil the following conditions relating to the tram-lactonic acid isolated : ( a ) That it is a dibasic lactonic acid of the composition C13H1806, forming in neutral solution a silver salt C13H1606Ag2 and in alkaline solution a barium salt (C,,H,,O,),Ba,. ( b ) That ih free carboxyl groups are attached to contiguous carbon atoms.We regard the behaviour of the substance on dehydration as a proof of this. ( c ) That it is a y-lactane. Experiment showed that there was an exceedingly strong tendency for the lactone ring to be formed, and in spite of many attempts we were unable to prepare the free hydroxy-acid 344 INUOLD AND THORPE THE FORMATION AND The two formulz which along with XXXII and XXXIV fulfil the above condit,ions are XXXV and XXXVI. C,H,, $ -F(CO,H)* CH Me*CO,H C,H,, $l--$!( CO,H)~CH,~ CO,H O*CO*CH O*CO*CHMe (XXXV.) (XXXVI.) Of these the first XXXV possesses an anhydride-forming group exactly similar to that of the lactonic acid XXXII (p. 341). A substance of the formula XXXV ought therefore for reasons given when XXXII was considered to behave like aa'-dimet.hylsucQnic acid and like the acid XXIX (p.341) and form anhydrides in accordance with Scheme 1. The formula XXXVI on the other hand does not contain two asymmetric carbon atoms in its anhydride-forming group and is therefore out of the question. It will be seen that of the four possible formulz XXXIV (p. 342) is the only one which accords with the facts of the case, namely that the dehydration of the substance proceeds according to Scheme 2. It may be added that the cis-lactonic acid is converted by boiling hydrochloric acid into the tram-isomeride thus completing the cycle of transformations which in Scheme 2 is only fragmentary. The trans-lactonic acid XXXIV (p. 342) was not the only pro-duct obtained by the alkaline hydrolysis of the methylated ester XXX (p.342). There was always formed side by side with it a somewhatl smaller quantiky of a dibasic acid of the composition C13H1806. Both the dibasic acid and the lactonic acid appeared to be end-products of the reaction; that is to say they were quite stable towards the reagent used in their preparation. The dibasic acid had properties practically identical with those of the dibasic acid C,,H1606 (XXIV p. 336) which was obtained by the alkaline hydrolysis of the unmethylated ester XV (p. 333). It has there-fore' without. much doubt been formed in a manner precisely analogous to that' in which the acid XXIV was produced and has the structure shown in the formula XXXVII. CO,H C0,H (XXXVII.) Like the parent substance XXIV the homologous acid XXXVII was isolated in cis- and trcrm-forms t,hat originally obtained being the trans-form STABILITY OF SPIRO-COMPOUNDS.PART 11. 345 'l'he formatimi side by side of the acids XXXIV (p. 342) a d XXXVII (p. 344) is readily explained if we accept the view put forward on p. 342 that the cyclopropane bond ( 4 5 ) of the methylated ester XXX is the first point in the molecule attacked by the alkaline reagent. For if this is so t"he substance XXXIII which is first formed may undergo disruption beside the methylated residue in two ways corresponding with the two hydrolytic decom-positions of ethyl acetoacetate. It may either split the cyclo-butane ring between the carbon atoms (2) and (3) to give the lactonic acid XXXIV as shown on p. 342 or itl may split between the methyl-bearing carbon atom and the attached carboxyl group, giving the acid XXXVII.C( CO,H)-$!Me'CP,H C( CO,Et)*C Me* CO,F,t ~ H o ~ < t ) ( C o 2 E t ) . ~ o -+ cAo:CH'' C(C0 H)(OH)*CO (XXX .) (XXXIlI.) /C(CO,H)- -7HMe -+ C,H,,:CH I C( CO,H )(OH) CO (XXXVII.) It is interesting once again tto refer to the parent substance of which the acid XXXVII is the methyl derivative. It was noticed on p. 336 that formulce XXIV and XXV were equally in harmony with t.he properties of the substance but that for reasons there given formula XXIV was t o be preferred. We have just seen that the formula which follows from this for the methylated substance enables us to explain the simultaneous production of this com-pound and of the lact'onic acid XXXIV in a very straightforward manner.The alternative formula XXXVIII for the methylated C0,H C,H,, C H C<<g:A>C H Me (XXXVIII.) dibasic acid strictly analogous to the formula XXV has not this advantage. Such a substance could not be produced side by side with the lactonic acid XXXIV (p. 342) exceptl as a result of the simultaneous occurrence of two totally different sets of reactions ; also the lactonic acid which one might expect to be produced along with a compound of the formula XXXVIII would have properties diffe'rent from those which t>he lactonic acid isolated was found to possess. We therefore think that we were right in selecting formula XXIV rather than XXV. The results of tQhe experiments on the alkaline hydrolysis of the &0$ 346 INQOLD AND THORPE SPIRO-COMPOUNDS.methylation product of the yellow sodium sp*ro-compound are summarised in table 11. These "experiments have an interest inasmuch as they confirm, and even emphasise the remarkable instability of the bond (4 5) in the bridged-spiro-series. For in spite of the fact that t-he entrance of the methyl group a t the carbon atom (2) of the methylated ester XXX creates a point of instability between the carbon atoms (2) and (3) the reagent commences its attack not a t the bond ( 2 3) but a t the bond (4 5 ) . (E) Reduction of the Monocarb oxykated Bridged-ring Derivatives Sta'bility of the Bridge-When the bridged-ring acid XIV is reduced by sodium amalgam, there is formed a cydopentane acid XXXIX which contains two more atoms of hydrogen than the original acid.The reduction product is a ketonic acid and on further reduction yields the corre-sponding hydroxy-acid XL. The fact t'hat the ketonic acid has been formed by the addition of hydrogen a t the bridge-bond (1 4) is shown (Zoc. cit.) by the production on oxidising with nitric acid of BB-dimethylglutaric acid and as-ctimethylsuccinic acid. The reduction is therefore to be represented thus: XZV and XXZII (pp. 333 and 335). bond (1 :4). CO,H C0,H CO,H b CH-CH FH3>C< CIH-CiH, C4>c<Y-QH? cH CH*CO + CH3>C<CH2,b0 CH CH CH,*CH*OH (XIS-.) (XXXIS.) FL.1 The remarkable feature of this reaction is that the bond (1 4) is actually more susceptible of attack by the reducing agent than is the carbonyl group and that consequently the bridged hydroxy-acid XLI cannot be isolated.(XLI.) (XLII,) A series of experimente using the monobasic acid XXIII yielded precisely comparable results. I n spite of careful search among the products of reductions carried out under varying conditions no bridged hydroxy-acid of the formula XLII was isolated. The firgt product of the action of sodium amalgam on the ketonic acid XXIII (p. 335) was a substance which contained two atoms of added hydrogen. It did not appear to react with acetyl chloride, but readily gave a semicarbazone. On subjecting it to furthe 0 U-0 V E ;\g '3 .. 0 m 54 X-u" 348 INGOLD AND THORPE THE FORMATION AND reduction by sodiuiri mialgam two more atoms of hydrogen were taken up and there was formed a subst'ance which gave an acetyl derivative on treatment with acetyl chloride.The successive reduc-tions are theref ore apparently analogous in the dimethyldieyelo-pentane and cyclohexaiiespirodieydopentane series and in the latter case may be represented thus : C0,H CO,H CO,H (XXIII). (XLIII.) (XLIV.) The fact that i t was realJy the bond (1 4) and not the bond (4 5) or the. bond (5 l) which had been broken by the reducing agent was clearly proved by the manner in which the reduced sub-stances behaved with oxidising agents. These experiments are dealt. with in Section F. I n our earliest experiments on the reduction of the bridged ketonic acid XXIII we used conditions which were known to give a good yield of the reduced acid XXXIX when applied to the reduction of the bridged ketonic acid XIV.As a result we obtained a product of indefinite melting point which proved to be a mixture of the ketonic and hydroxy-acids XLIII and XLIV. It was therefore apparent thatl the' reduction was proceeding more easily in the bridged-sp-ro-series than in the bridged-ring series. I n order to establish this point more definitely a series of com-parative experiments were instituted. I n the first place the bridged ketonic acid XIV (p. 333) was reduced under standard con-ditions for different lengths of time and the products were isolated. They were in general a mixture of three acids XIV XXXIX, and XL. The proportion of hydroxyl group in this mixture was determined by est'imating the acetic acid obtained by acetylation and subsequent hydrolysis.This method was found t o give good results when applied to the pure hydroxy-acid XLIV. I n this way a certain time of reduction was discovered during which no appreciable quantity of hydroxy-acid was produced. The hydrogen content was determined by combustion and it was found that the formation of hydroxy-acid began to be appreciable after the addi-tion of about 1.7 atoms of hydrogen to the molecule. A similar set of experiment6 with the bridged ketonic acid of the spiro-series showed that the production of hydroxy-acid in this case became appreciable only after the addition of about 1.9 atoms of hydrogen to t8he molecule. The two bridged ketonic acids XIV and XXIII were t.hen reduced under the same standard conditions for a certain length of time the same in both cases sufficiently short to ensur STABILITY OF SPIRO-COMPOUNDS.PART II. 349 that in neither case would any measurable amount of hydroxy-acid be formed. The products were then isolated and the hydrogen contents determined by combustion. Several pairs of experiments were made with different? lengths of time and the results obtained 2.2 2.0 1.54 1.6 1.4 & 1.2 B 1.0 B 5 0.8 0.6 0.4 0.2 0.0 0 2 4 6 8 10 12 Aours are given in the experimental part of this paper (p. 375). The figures lie fairly well on smooth but widely separated curves (Fig. viii) and graphically interpolated they show t h a t if we take the time required for a 50 per cent. conversion that is the time during which the molecule of the bridged acid takes up on 350 INQOLD AND THORPE THE FORMATION AND a t a n of hydrogen as the standard of comparison then this time, in the case of the spiro-acid XXIII is about 0.55 times as long as in the case of the ring derivative XIV.That is to say the periods of half-change are in the ratio of approximately 1.8 1. As a check on this result the reduced acids XXXIX and XLIII (pp. 346 and 348) were prepared in a state of purity and further reduced under standard conditions for different lengths of time. The figures obtained in these experiments (p. 375) lie with slight irregularities on one and the same curve (Fig. ix). The periods FIG. (ix). Reduction of the ketone group. 1.4 1.2 1.0 x 2 3 0.8 9 0.6 0.4 0.2 0.0 0 2 4 6 8 hours of half-change are therefore as 1 1 as nearly as the experimental figures can be interpreted.Thus there appears to be a very real difference in the ease of reduction of the monocarboxylic acids of the bridged-ring- and bridged-sp-yo-series. It will be noticed that the difference is in the sense anticipated from theoretical considerations (see Section A). It also would appear to be of the correct order of magnitude. For whilst the first-order effect that on the bond (5 l) is manifested by a reaction which proceeds at a considerable speed in one series but does not go a t all in the &her SQ fsr qt STABILITY OF SPIRO-COMPOUNDS. PART II. 35 1 can be detected both the second-order effects that is those on the bonds (1 2) and (1 4) exhibit themselves experimentally as moderate differences in reaction-velocities which are finite quantd-ties in both the series.The third-order effect that on the bond (2 3) was not detected experimentally. (F) Oxidation of the Fission-Products Derived front tJbe Bridged-spiro-compound X I 1 (p. 330). All the products of fission of the cyclohexanespirodicyclopentane ring structure so far considered belong t o one or other of the three following classes : (1) Substances in which the bridge-bond (1 :4) only has been broken. (2) Those in which the cyclopropane-bond (4 :5) only has been broken. (3) Those in which the cyclapropane-bond (4 5) and the cyclo-butane-bond (2:3) have both been broken. I n order if possible to obtain some confirmatory evidence regard-ing the constitutions of these substances a t least one typical example from each class was subjected to the action of oxidising agents.In class (1) the first substance taken was the cyclohexanespbo-cyclupentanone acid XLIII (p. 348). By far the most suitable reagent in this case is nitric acid. Dilute nitric acid however, appears to have little action on the substance. With 'hot concen-trated nitric acid a dibasic acid of the composition C8H,,0 was obtained. This substance when distilled gave off carbon dioxide with the formation of cyclohexanecarboxylic acid (hexahydrobenzoic acid). The dibasic acid is therefore evidently cyclohexane-1 l-di-carboxylic acid XLV. The same dicarboxylic acid was obtained when the hydroxy-acid XLIV (p. 348) was used in place of the ketonic acid.These experiments arekteresting as leaving little room for doubt that the bond broken in the reduction of the bridged-ketonic acid XXIII (p. 335) was actually the bond (1 4). The example taken from class (2) was the trans-cyclohexylcyclo-butane acid XXIV (p. 336). In this case nitric acid appeared t o be without effect. Warm alkaline permanganate was however, quickly decolorised. The acid product was a liquid substance whic 352 INGOLD SND THORPE THE FORMATION AND distilled apparently without a serious amount of decomposition and was identified as cyclohexanecarboxylic acid XLVI : CO,H (XXlV.) (XLVI.) The member of the series (3) experimented on was the tmtLs-P-cycZohexyI-92-butane lactonic acid XXXIV (p. 342). This acid was also1 unacted on by nitric acid and required an alkaline solution of permanganate kept a t above TOo t o oxidise it a t all rapidly.The product was as in the former case cyclohexylcarboxylic acid : Y c,B,,,:cH&o,H I c' H (0 H ) CO,H (Hydroxy-acid of XXXIV.) (XLVI.) Both these oxidations with periliarigailate were carried out under various conditions and in both cases the products were carefully examined for any traces of polybasic or lactonic acids in which two side-chains might be attached to bhe c!ycZohexane carbon atom. No such products were detected and in view of the formula of the oxidised substances none would be expected. On the other hand, if for example in the procluctioii of the cyclohexylc~clobutane acid XXIV (p. 336) some bond in the dicyclopentane structure other than one of those attached to the spiraiie carbon atom had been ruptured one would expect t o find products with two side-chains among the oxidation products.The cyclohexanecarboxylic acid XLVI obtained in the course of the above experiments appeared on careful examination to be in all cases identical with the product obtained by the reduction of beiizoic acid. The various reactions by which the dicyclopentane ring in the original bridged-spiro-compound XI1 (p. 330) has been broken down forming ultimately cyclohexanecarboxylic acid are suminar-ised for eoiivenieiice in table 111 TABLE 111. C0,Et C0,H tic1 C6HIQ:C<8H.KE2 f-bO,Et (Yellow solid.) (M. p. 236' ; semicarbazone, m. p. 259' dec.) sodium amalgam .I. GOSH . c---y H, C,H,, CH' I C(OH)-Cl> C0,H (31.p. 20Vdec.) (M. p. 136-138' ; semicarbazone, m. p. 310' dec.) (31. p. 12.?-127"; acetyl derivative m. p. 158-163'.) (31. p. 207' dw. 354 INGOLD AND THORPE THE FORMATION AND (G) Examination of the By-products obtained i n the Prepuratiou of the B r i ~ ~ e d - s p i r o - c ~ r n ~ o u ? ~ XIZ (p. 330) Isolation of Products of Fission Derived from this Substance through Side Reactions. During the preparation of the yellow sodium compound XI1 (p. 330) there was formed a considerable quantity of an oily by-pro-duct from which a number of acids were obtained by hydrolysis with hydrochloric acid. Amongst those isolated were n-butyric acid cyclohexane-1 1-diacetic acid and tram-cy clohexanesp'ro-cy clopropane-1 2-dicarboxylic acid.The formation of these acids is evidently traceable to the presence in the crude ethyl dibromo-cycluhexanediacetate used for the condensation of the corresponding monobromo-ester of the unbrominated ester and of ethyl bromide as impurities. There was also obtained a cyclohexanespirocyclo-propane acid of the formula XLVII. This substance proved to be identical with the acid obtained by the action of acid hydrolysing C(C0,H) *CH,*CO,H C5H10:C<&~.c0s~ (XLVII.) agents on the tetra-ethyl spirocyclupropane ester XI (p. 330) which clearly establishes the constitution of the compound. I n addition to the above-mentioned acids there were isolated two others to which the formula XLVIII and XLIX have been C0,H (XLVIIT.) E t CK- -CO I I C5H1,:CH*U*C02H LH( CO,R)*O (XLIX.) assigned.These are clearly the products respectively of acid and of alkaline hydrolysis of the ethylated ester L. This ester is doubt-(L.) less produced by the action of ethyl bromide on the yellow sodium compound XII and apparently behaves towards alkaline hydrolys-ing agents similarly to the corresponding methylation product XXX (p. 342). We did not investigate the action of acids on the methyl derivative XXX but the corresponding substance XXVII (p. 341) of the dimethyldicydopentane series was found (loc. cit ) to yield with acid hydrolysing agents a monocarboxylic acid to which XLVIII is strictly analogous STABILITY OF SPIRO-COMPOUNDS. PART U. 356 The most interesting of these substances is the fission product. XLIX of the ester L and it is of interest to examine what possi-bilities there are of alkaline hydrolysis of the ester L taking place.No 'hydrolysis to a lactone of hydroxy-ester would be likely to occur in the anhydrous alcoholic solution in which the oily by-product was formed. The oil was however separated from the sdium compound XI1 by means of 95 per cent. alcohol and since some sodium ethoxide would certainly be adhering to the crude sodium compound the alcoholic washings would contain sodium hy.droxide, which must have brought about the fission of the ethylated ester L. The lactonic acid XLIX was found to possess properties practi-cally identical with those of its prototype the fission product XXXIV (p. 342) of the methylated bridged ester XXX. Like the lactonic acid XXXIV it was isolated in cis- and trans-forms the substance originally obtained being the trans-form.One notable point of difference was noticed between these compounds and the methylated lactonic acids previously obtained. The ethylated cis-lactonic acid differed from the trans-form and from both forms of the lactonic acid XXXIV in the fact that it was found possible to isolate from it the free tribasic hydroxy-acid. This substance was, however very unstable. It slowly gave up water when exposed to' air a t the ordinary temperature the product being the cis-lactonic acid. On boiling with hydrochloric acid it was converted into the trans-lactonic acid. The other relationships between these ethyl-ated products may be seen by reference to table IV in which they are shown in relation to the ethylated ester L the decompositions of which form another example of the great ease with which the bond (4 5) is ruptured by alkalis.E X P E R I M E N T A L. (a) Condensation of Ethyl Dibromocyclohexane-1 ; 1-dincetate utith Ethyl Sodiomalonate. cycloHexane-1 1-diacetic acid was prepared for use in these experiments by the method given by Thole and Thorpe (T. 1911, 99 422). Ethyl DibromoqyclohexaneJ 1-diacetate.-The bromination of the acid was effected by the Hell-Volhard-Zelinsky method as described in Part I. of this series. The neutral product contained about 80 per cent. of dibromo-ester 356 INGOLD AND THORPE THE FORMATIOX AND h n ? c f- I 0, A 1 ; \ + I E 'k s L $\2 -4" -I -'2 4 z 0 -+ h ?3 STABLLrPY OF SPIRO-COMPOUNDS.PART II. 357 Ethyl cycloHexunespiro-1-methylcyclopropune-1 11 11 2-tetra-carboxylate (XI p. 330). Forty-six grams of the crude dibromo-ester were added t o a solu-tion in 60 grams of alcohol of 4.6 grams of sodium and 32 grams of ethyl malonate. The solution was boiled for three hours and then p u r e d into dilute hydrochloric acid. The oil was extracted w i t h ether and the extract washed with a solution of sodium carbonate dried and distilled. The estw was obtained as a colourless liquid which on reldistilla-tion boiled at 250-260°/10 mm. On boiling with hydrochloric acid i t was hydrolysed with the formation of the tricarboxylic acid (XLVII p. 354) dealt with on p. 379: 0.1209 gave 0.2708 CO and 0.0849 H,O.C = 61.09 ; H = 7.80. C,,H,,O requires C=61*2; H=7.8 per cent. (b) Formation of the B&dge&spiro-ester and i t s Sodium Compound. The formation of the bridged-sp'ro-compound by the condensation of the above-mentioned tetraethyl ester with itself has already been referred to in the Introduction (Section B). The compound was, however usually prepared direct from the dibromo-ester by treat-ing it with ethyl malonate and excess of sodium ethoaide. Many experiments were1 made in order t o determine1 the best conditions. Ethyl Sodiocyclohexanespirodicyclope~tan-3-one-l 2 4-tricarb-oxylate (XII p. 330). Nine grams of sodium dissolved in 140 grams of absolute alcohol were treated with 30 grams of ethyl malonate. The solution was carefully under-cooled to about 35O and 40 grams of dibromo-ester were gradually added the temperature being kept blow 40°.Half an hour after the addition was complete the liquid was heated on a steam-bath and kept boiling for thirty hours. A t the end of that time the greater part of the alcohol was boiled off and water added to the residue in the flask. The mixture was then shaken vigor-ously and filtered by the aid of the pump. I n these circumstances the whole of the oil precipitated by the water adhered to the solid sodium compound. The filtrate which gave no precipitate on acidi-ficahion was discarded. The purification of the sodium compound was effected by washing on the filter with 95 per cent. alcohol and VOL. cxv. 358 INUOLD AND THORPE THE FORMATION rW'D finally by triturating with the same solvent until the weight of the dry solid was not altered on repeating the treatment.The alcoholic filtrates contained the oily by-product. The sodium compound was obtained as a bright yellow insoluble substance which gave a crimson colour with aqueous ferric chloride containing a trace of alcohol: (Section j p. 377.) 0.3132 gave 0.0590 Na,SO,. Na=6'10. C1QH2507Na requires Na = 5.93 per cent. Ethyl cycl~~exanespiralicyclopen tan-3-one-1 ; 2 ; 4-tm'carb-oxylate (XV p. 333). When the yellow sodium compound was shaken with cold dilute aqueous hydrochloric acid and ether it passed quickly into solution, the yellow colour being discharged. The ethe'real layer on drying and evaporating the solvent yielded a mass of crystals melting a t 46A7O.The ester was exceedingly readily soluble in the usual organic solvents and did not appear capable of being easily recrystallised. It gave a crimson coldur with ferric chloride and on treating with cold aqueous sodium hydroxide yielded the original sodium com-pound : 0.1331 gave 0.3036 CO and 0.0842 H,O. C=62.21; H=7*03. C,,H2,07 requires C=62.3; H=7.1 per cent, (c) Comparative Experiments on the Formationi of the Bridged-ring- and Bridged-spiro-cmpounds (IX and XII p. 330). /3/3-Dimethylglutaric acid was prepared by tlhe mathod of Thole and Thorpe (T. 1911 99 422). Ethyl Dibromodimethy1gEutwate.-The acid was first converted into its anhydride (T. 1899 75 48) which was then brominated (T. 1901 79 776). The dibromocester was redistilled and collected for use in subsequent experimenb a t 182-185O/24 mm.Ethyl 1 3 3-Trirnethzylcyclopr~pan~e-1 1 1 1 1 2-tetracwrboxylate. This wter was prepared by condensing the dibromo-ester with ethyl sodiomalonate in alcoholic solution under the conditions used by Perkin and Thorpe (ibid.) and purified by distillation the frac-tion boiling a t 231-236O/34 mm. being taken as sufficiently pure for the experiments herennder described. Et'hyl trimathylcyclloprolpanetetracarboxylate and ethyl cyclo STABILITY OF SPIRO-COMPOUNDS PART II. 359 h exa nespirum ethyl c y el opr op an etetr a ca r b ox y 1 ate were then employed in a series of experiments which were carried out with the object of determining the relative speeds with which the two esters under-went internal condensation in the presence of sodium ethoxide.The method was as follows One molecular proportion of each ester was treated with two atomic proportions of sodium dissolved in fifteen molecular proportions of absolute ethyl alcohol. The solutions were kept in a thermostat for known lengths of time after which the alcohol was boiled off under diminished pressure and water was added. The precipitates were then collected washed with alcohol dried and weighed. The following percentage yields of the sodium compounds IX and XI1 (p. 330) were obtlained the temperature being 7 5 O : Time (hours) 1.0 2.0 4-0 7.0 10.0 14.0 24.0 TABLE V. Bridged-ring-compound IX. (Per cent.) 49.8 64.7 73.0 76.6 75.3 75.3 -Bridged-qiro -compound XII.(Per cent,) 10.1 17.9 26.5 32.4 32.9 37.7 -(d) Hydrolysis of the Bridged-spiro-ester and of its Pellow Sodium Compound. The remarkable diversity in the characters of the substances which can be obtained by hydrolysing the yellow sodium spiro-compound or the corresponding free ester under different conditions has already been alluded to in the Introduction. The following is a summary of the principal experimental details. Die thy1 Potassium Potassiocyclohexanespirodicyclope n~tan-3-one-1 2 4-t~icarbolxylute (XVI p. 333). When the original yellow sodium compound was left in cont,act with cold alcoholic potassium hydroxide f o r ten hours it gradually dissolved and a canary-yellow potassium salt separated. This compound was found to be insoluble in water but quite appreciably soluble in methyl alcohol.When recrystallised from a large bulk of this solvent it separated in long yellow needles, which gave a violet colour with ferric chloride: 0.1354 gave 0.0580 K2S0,. K = 19.16. C,,H2,O7K2 requires K = 18 -8 per cent. P 360 INQOLD AND THORPE THE FORMATION AND Diet h yl Hydrogen cycloH exanespir~icyclopentan-3-one-1 2 4-tricarboxylate (XVII p. 333). When the potassium salt was treated with cold dilute hydro-chlorio acid a gummy precipit'ate was obtained. This could not be induced to crystallise and on distillation underwent extensive decomposition. It was therefore extsacted with pure ether and, after drying and evaporating the solvent left for some days in an exhausted desimator : 0.1249 gave 0.2751 CO and 0.0730 H,O.CI7H,O7 requires C = 60.4 ; H = 6.5 per centr. This acid-ester is also the first product of the action of boiling hydrochloric acid on the triethyl ester (XV p. 333) as is proved by the following experiment. The yellow sodium compound was boiled with 20 per cent. hydrochlorio acid for one hour. The liquid was evaporated and the residue dissolved in the minimal quantity of water. The hot aqueous solution was rapidly cooled, and the oily precipitate which separated was collected by pouring the liquid through a wet filter. The oil on the filter was then washed through with alcohol and caused to crystallise as corn-pletely as possible from 15 per cent. alcohol. The crystals con-sisted of the ethyl hydrogen ester X X I (p. 335).The ultimate oily residue from these crystallisations was dissolved in methyl alcohol and treated with a slight excess of cold methyl-alcoholic potassium hydroxide. The yellow precipitate which immediately separated was collected and recrystsllised from methyl alcohol. On analysis it gave K=19*03 whilst the free acid-ester obtained on acidification gave C=60*21 H=6.60 per cent. With ferric chloride the acid-ester gave a violet coloration. Cola methyl-alcoholic potassium hydroxide converted it into the potassium compound. It distilled a t about 200-260°/23 mm., with however considerable decomposition. Attempts were made to hydrolyse the gummy distillate both by acids and by alkalis, but no pure substance was isolated from the products. ct=60.07; H=6.50.Ethyl Bih ydrogen cyclolHexanaspirod/icyclo pentan -3 -one-1 2 4-tricarboxylate (XVIII p. 334). Five grams of the yellow sodium compound were suspended in 20 C.C. of 3N-ethyl-alcoholic potassium hydroxide and the mixture was boiled until the yellow colour was discharged. The colourless precipitate which was very hygroscopic was collect'ed as rapidly as poasible and drained on porous porcelain in a desiccator. I STABILITY OF SPIRO-COMPOUNDS. P m T Iz. 361 was then dissolved in a small quantity of water and decomposed with hydrochloma acid. The acid which separated out was re-crystallised from water. The potassium salt XVI may be used in place of the sodium compound in this preparation. The same acid-ester may also be obtained by acid hydrolysis of the triethyl ester (XV p.333) or of its sodium compound. Thus, when the sodium compound was boiled for one hour with 20 per cent. hydrochloric acid and the acid-esters XVII and XXI separated by precipitating them together as an oil in the manner described on p. 360 it was found that in the filt'rate from the oil there were present two crystalline substances. These were isolated by treating the solution after concentration with sufficient con-centrated hydrochloric acid to clear the turbidity. The crystals which were then deposited from solution were separated by fraction-ally crystallising from water into the acid-ester XVIII and the dibasic acid XXII the latter being the more readily soluble. The acid-ester formed long colourless needles which melted and decomposed a t 206O.It gave a bluish-violet colour with ferrio chloride : 0.1298 gave 0-2745 CO and 0.0683 H,O. The mhy&o-ester, C=57*68; H=5*84. Cl,Hl,O requires C=58*1; H=5*8 per cent. co-0-co I was prepared by treat'ing the acid-ester at looo for one hour with acetyl chloride in a closed . flask. The residue obtained on evaporation was crystallised from ether. The crS;stalline anhydride melted a t 126O and was converted into the original acid-ester on boiling with water : 0.0751 gave 0.1705 CO and 0.0385 H,O. C=61*92; H=5.70. (&&&)6 requires C=61*6; H=5.5 per cent. E t hy 1 H ydroyen 5-cycloHexanespirodicy clopen tan-3-one- 1 4-dicarboixylate (XXI p. 335). The formation of this substance has already been alluded to on p. 360. It is best prepared by boiling the triethyl ester (XV, p.333) with 20 per cent. hydrochloric acid for five hours or by boiling the acid-ester (XVIII p. 334) with the same reagent for two hours. In either case the product obtained on evaporation was found to be a mixture of three acids. It was crystallised fro 362 INGOLD AND THORPE THE FORMATION AND the minimal quantity of boiling 50 per cent. ethyl alcohol. The crystals which separated consisted principally of the monobasic acid (XXIII p. 335) and were collected the filtrate being then evaporated until most of the alcohol had been removed. It was then cooled as rapidly as possible and the oil which separated was collected on a wet filber. The filtrate on concentrating and mixing with concentrated hydrochloric acid deposited the dibasic acid (XXII p.335). The oil on the filter was dissolved in alcohol and recrystallised several times from a mixture of alcohol and water. The acid-ester obtained in this way melted a t 104-106° and gave no colour with ferric chloride. It did not decompose appreci-ably when heated to 250O: 0.0887 gave ?*2061 CO and 0.0548 H,O. 0.1200 required 18.62 C.C. of Ba(OH) solution (0-0243N) for C=63.37; H=6*88. Cl4HI8O5 requires C= 63.2 ; H = 6.8 per cent. neutralisation. C,,H,80 (monobasic) requires 18.6 C.C. 5 -cycloHexan~espirod~cyclopen tun- 3- 011 e - 1 2-dicarb ox y lic A cid (XXII p. 335). The formation of this substance as a by-product in the pre-paration of the various acid-esters of the series has already been noticed; It was found to be produced in good yield by boiling either the yellow sodium compound or the acid-ester (XVIII, p.334) with 10 parts by weight of 20 per cent. aqueous hydro-chloric acid for twelve hdurs. As the boiling proceeded oily pro-ducts separated out and subsequently passed again into solution. Then crystals appeared in the boiling liquid. A t the end of the period the mixture was cooled and allowed to remain a t &he ordinary temperature for twenty-f our hours after which practically the w b l e of the organic material had crystallised out. The crystalline mixture consisted of about three parts of the dibasic acid XXII to one part of the monobasic acid XXIII (p. 335). It was boiled with four times its weight of water and the suspension cautiously cooled and quickly filtered.By this means the mono-basic acid was separated almost quantitatively from a solution which in the cold was supersaturated witlh respect to the dibasic acid. The agitation caused by filtering usually caused the filtrate to set to a stiff pasfa of crystals of the dibasic a&d. These were recrystallised from water. The acid separated from water in rosettes of long silky needle-shaped crystals which melted and decomposed a t 2 3 4 O . It gave a deep crimson colour with ferric chloride butl did not appear t-o be acted on when boiled with hydrochloric acid for several days STABILITY OF SPIRO-COMPOUNDS. PART 11 363 0,1087 gave 0.2407 CO and 0.0584 H,O. 0-0715 required 24-65 C.C. Ba(OH) solution (0.0243N) for C=60.39; H=5*97. Cl2H1405 requires C = 60-5 ; H = 5.9 per cent.neutralisation. CI2Hl4~ (dibasic) requires 24.7 C.C. co-0-co I free acid was treated with acetyl chloride a t looo in a closed flask. The solid residue obtained on evaporation was triturated with aqueous sodium hydrogen carbonate and recrystallised from ether. It melted a t 154O and on treating with aqueous sodium hydroxide gave the sodium saltl of the original dibasic acid: 0-1050 gave 0.2515 CO and 0-0518 H,O. @=65*32; H=5*48. C,,H,,O requires C=65*5; H=5*5 per cent. 5-cycloHexanespirod~cyclope~t~n-3-on~e-l-carboxylic Acid (XXIII p. 335). Al mixture of aboutl one part of this acid to three parts of the dibasio acid (XXII p. 335) was formed when either the triethyl ester XV or its sodium compound or the diethyl hydrogen ester, XVII or its potassium compound or the ethyl dihydrogen ester, XVIII was boiled for twelve hours with 20 per cent<.hydrochloric acid. The ethyl hydrogen ester XXI was found to be converted quantitatively into the monobasic acid by boiling hydrochloric acid. The dibasic acid XXII on the other hand did not appear to be affected by this reagent. The dibasic acid when heated above its melting point however, evolved carbon dioxide and from the dark-coloured residue a small amount of monobasic acid could be isolated. A good yield was obtained when the dibasic acid was heated with water a t 200° for about ten minutes. The acid-esters XVII and XVIII also gave excellent yields of the monobasic acid when treated in this way. The triethyl ester XV however required the presence of a trace of acid in the water.A small quantity of hydrochloric acid or acetic acid or even of butyrio acid was found to be sufficient. The most convenient way of preparing the monobasic acid is by heating the yellow sodium compound with a slight excess of dilute hydrochloric acid a t 200O. When preparing considerable quanti-ties however it was found desirable. to drive off as much carbon dioxide and alcohol as possible before closing the vessel. Th 364 INGOLD AND THOR,PE THE FORMATION AND sodium compound in portions of about 10 grams was boiled with ten times its weight of 20 per cent. hydrochloria acid for twelve hours in a strong flask provided with a short reflux air-condenser. Enough aqueous sodium hydroxide was then added t;o reduce the concentration of free mineral acid to 2 or 3 per cent.and the solution was again boiled to expel the air. The flask was then securely corked and immersed' in an oil-bath a t 200° for ten minutes. After cooling to the ordinary temperature the crystals were collected and recrystallised from 96 per cent. alcohol using a little animal charcoal to remove the dark impurities. The yield was 85 per cent. The monobasic acid was sparingly soluble in hot or cold water and in most cold organic solvents but it crystallised well from hot ethyl alcohol in long needles. It melted a t 236" without decom-position and gave no colour with ferric chloride. It was found to be unacted on by boiling aqueous or alcoholic potassium hydr-oxide and by prolonged boiling with hydrochloric acid.Cold alkaline permanganate was however instant'ly decolorised : 0.1337 gave 0.3310 (70 and 0.0860 H,O. C=67*52; H=7.14. C,,H,,O requires C = 68.0 ; H = 7.2 per cent. prepared by boiling the acid with an aqueous solution of semicarbazide acetate for a few seconds. On coding the solution, the semicarbazone separated out ,and was recrystallised from alcohol. It melted and decomposed at 2 5 9 O : C,,H$3N3 requires C!=57.4 ; H = 6.8 per cent. 0.1071 gave 0.2240 CO and 0.0661 H,O. Cr=57-04; H=6*85. trans-3-Hydrox y-4-cyclohexylcyclobutan-2-one-3 4-dicarb oxylic Acid (XXIV p. 336). Five grams of the yellow sodium compound were boiled with 30 C.C. of 4N-alcoholic potassium hydroxide the boiling being. con-tinued for one hour after the suspended matter had become colour-less; or alternatively 5 grams of the acid-ester (XVIII p.334) were boiled with 30 C.C. of the same reagent for one hour. I n either case the product was isolated by evaporating the 9 alcohol and adding water and hydrochloric acid. The acid solution was extracted ten times with its own volume of ether and the extract dried over calcium chloride for at least three days. This was found to be necessary since the acid was present in the ether in its hydrated form which apparently gave up water ix the calcium chloride very slowly and incomplete dehydration interfered wit STABILITY OF SPIRO-COMPOUNDS. PART 11. 365 the subsequent purification. When quite dry the ether was evaporated and the viscid residue triturated with Chloroform. The crystals which were caused to separate by this treatment were drained on porous porcelain and washed with fresh ether.The acid prepared in this way was fairly pure and melted and decomposed a t 203O. It was very readily soluble in water and in all the usual organic solvents except chloroform and light petroleum. I n these solvents it was only sparingly soluble but it did not appear t801 crystallise well from mixtures of solvents. It gave no colour wit'h ferric chloride and did not appear to be acted on by boiling acetyl chloride (compare Part I). The acid was purified for analysis through the hydrate (see below): 0.1331 gave 0.2734 CO and 0.0748 H,O. 0.0352 required 11-25 C.C. Ba(OH) solution (0*02431\7) for Tho hydrated form @12H,,06,2H,0 separated in large dense prisms when the anhydrous acid was dissolved in hot water and the solution cooled.The hydrated acid readily dissolved in dry ether and was much more readily soluble in chloroform than the anhydrous substance. A t looo it evolved water vapour leaving the anhydrous acid in a very pure form melting a t 206O tol a colour-less liquid which evolved steam and after coding set to a solid mass which melted a t about 135O: C=5692; H=6.24. C,,H160 requires C=56*2; H= 6.2 per cent. neutralisation. C,,H,,O (dibasic) requires 11.3 C.C. 0.1648 lost 0.0201 a t looo. The siluey salt was precipitated by silver nitrate from a neutral 0.1435 gave 0.0656 Ag. Ag=45-71. 0.1729 , 0.1929 CO and 0.0473 H,O. C=30*43; €1=3.03. C,,H,,O,Ag requires C = 30.6 ; H = 3.0 ; Ag= 45.9 per cent.The barium salt was precipitated from a solution of the acid 0.1007 gave 0.0595 BaSO,. Ba=34.74. H,O=12*20. C,2H,606,2H20 requires H,O = 12.3 per cent'. solution of the ammonium salt: in water by adding an excess of barium hydroxide: C,2H,,0,Ba requires Ba = 35.1 per cent. cis-3-~y&oxy-4-cyclohexy~~yc~obutan-2-one-3 4-diciwb oxylic Acid (XXIV p. 336). This acid was prepared by dissolving its anhydride (see below) in a slight excess of 4N-aqueous sodium hydroxide and then add ing a slight excess of concentrated hydrochloric acid. The p r e cipitated acid was collected and dried. It was then dissolved in P 366 INGOLD AND THORPE THE FORMATION AND dry ether containing a trace of alcohol and caused to crystallise from this solution by adding benzene.The crystals were finally purified by t,riturating with pure dry ether and again recrystal-lising from a mixture of ether and benzene containing alcohol. The pure cis-acid melted at 145O and rapidly evolved water vapour. It readily dissolved in water or alcohol but was almost insoluble in pure dry ether. Unlike the trams-form it did not appear to take up water of crystallisation: 0.0929 gave 0.1912 CO and 0.0548 H,O. 0,0446 required 14.40 C.C. Ba(OH) solution (0.0243N) for C=56.13; H,=6.55. C12Hl6O6 requires C = 56.3 ; H = 6.3 per cent. neutralisation. C1,HI6O6 (dibasic) requires 14-3 C.C. The Anhydride of the cis-A cid C,H,,:CH*C<-CH2->C0. / C(OH) The tram-acid on heating above its melting point gave off water vapour. The transformation was however by no means complete unless the fused material was raised to 240-250° and maintained a t this temperature until it began to darken in colour.The product solidified on cooling and after triturating with aqueous sodium hydrogen carbonate and drying was recrystallised from dry ether. It separated in large oblique prisms which melted a t 155O. The substance was also recrystallised from benzene. The same anhydride was obtained by heating the cis-acid above it8 melting point: 0.1335 gave 0.2959 CO and 0.0709 H,O. C=60*45; H=5*90. CI2H,,O5 requires C'= 60.5 ; H = 5.9 per cent. -CH2-The cis-Anilic Acid 1 bO,H C~H~~~CH*c<C(OH)>Co (-?O*NHDC6H, This substance was a t once precipitated when the cis-anhydride was dissolved in benzene and treated with a solution of aniline in the same solvent.It was purified by first triturating with ether and then recrystallising from dilute alcohol. It separated in minute crystals which melted and decomposed a t 202O : C18Hz10,N requires C = 65.3 ; H = 6.3 per cent. 0.1145 gave 0-2721 CO and 0.0666 H,O. C=64*81; H=6*46 STABILITY OF SPIRO-COMPOUNDS. PART II. 367 U,H,~:CH ~ p ~ ~ f ! ~ c o . Co j The cis-Ad, C,H,*N-CO The cis-anil was readily obtained by heating the anilic acid a t 21O0 until the evolution of st'eam had ceased. The product was triturabed with sodium hydrogen carbonate and then recrystallised from absolute alcohol. It separated in long silky needles which melted a t 199O: 0.1098 gave 0.2778 CO and 0.0592 H,O. C=69.00; H=5.99. C,,H190,N requires C = 69.0 ; H = 6.1 per cent.(e) C'ompara,tiPie Experimemts with the A cid-Esters (XXVI g. 337, and XVIII p. 334) of the Dimethyldicyclopentane and c y clo H e xa ri espirodic yclopen t a ne Series .* One molecular proportion of each acid-ester was boiled for fifteen minutes with 6 molecular proportions of potassium hydroxide in 3.6N-solution in ethyl alcohol. The bulk of h e alcohol was evapor-ated under diminished pressure and water and excess of hydro-chloric acid were added to the residue. The acid products were then extracted quantitatively with ether. The percentage yields were as follows : TABLE VI. Bridged-ring-acid-ester XXVI. I Bridged-spiro-acid-ester XVITI. icid- Monocarb- Fissio 1 Acid- Products of Fissi.n product I ester loss Of ** products ester recovered.fzL:d. formed. I recovered. carbethoxyl €armed. 1 A / oxylic group. 85 1.5 0 0 0 85 81 4 O r 5 0 78 In all cases a small quantity of gummy material was formed and for this reason the whole of the original material was never accounted for as cryst.alline products. The small quantity of mono-carboxylic acid XIV was readily isolated by reason of its sparing solubility in cold water. The recovered acid-ester XVIII was also quite easily separated from the fission product by means of dry chloroform in which the latter if quite anhydrous is almost insoluble. * See note p. 337. P* 368 INGOLD AND THORPE THE FORMATION AND (f) Prepration and Hydrolysis of the Methylatiom Product of the Ph?ow SoAum spiro-Compundr (XII p. 330).The yellow sodium compound does not react a t all readily with methyl iodide under the usual conditions even a t looo in a close4 flask. If however four or five times the theoretical quantity of methyl iodide is used methylation proceeds rapidly. Ethyl cycloHexanespiro-2-me t hyldicyclopentan-3-one-1 2 4-tri-carboxylate (XXX p. 342). Twenty grams of the yellow sodium compound were heated with a solution of 20 grams of methyl iodide in 100 grams of absolute alcohol a t looo for one and a-half hours in a closed flask which, from time to time was vigorously shaken. The excess of the methyl iodide and most of the alcohol were then distilled off and the residue poured into 400 C.C. of water. The precipitated oil was extracted with ether the extract being washed with water and sodium car-bonate solution dried and evaporated.The oily residue was found to decompose on attempting to distil it under diminished pressure. It was therefore allowed to remain in an exhausted desiccator for several days and then analysed: 0.1109 gave 0.2556 CO and 0.0729 H20. C2,H2,0 requires C=63*2; H=7.4 per cent. The figures quoted are those for one of three closely agreeing analyses. They indicate that a partial conversion into the methyl diethyl ester has taken place : C,,HB07 requires C=62*2; H=7.0 per cent. This is perhaps a natural result of the use of a large excess of methyl iodide in the preparation. C=62*86; H=7.30. trans-lactonic Acid of y-Hydrox~-~-cyclohexyl-a-methyltri-carbaLlylic Acid (XXXIV p. 342). Twenty-five1 grams of the methylated ester were boiled under a reflux condenser with 170 C.C.of 4iV-alcoholic potassium hydroxide for two and a-half hours. The mixture was then cooled and the precipitated salts were collected and drained on porous prcelain in a desiccator. They were then dissolved in water and the solution was acidified and repeatedly extracted with ether. The residue left after drying and evaporating the extract was caused to deposit crystals by triturating with benzene the process being repeated until an ultimate gummy residue was obtained from which no crystals would separate STABILITY OF SPIRO-COMPOUNDS. PART 11. 369 The crystals were placed in a twtrtube with just sufficient benzene to cover them. The benzene was then boiled for a few minutes and the suspension filtered while hot.The filtrate on cooling deposited crystals of the lactonic acid. The ultimate gummy residue was esterified with alcohol and sul-phuric acid in the usual way and after adding water the esters were extrachd with ether. From the extract the acid products were shaken out with aqueous sodium hydroxide and again ex-tracted from the aqueous solution after acidification. The residue obtained on evaporating the ether was hydrolysed by boiling hydro-chloric acid. After twelve hours the liquid was rendered alkaline and extracted with ether then re-acidified and again extracted with ether. On drying and evaporating the latter extract a residue was obtained which when treated with benzene yielded a further quantity of the crystalline lactonic acid.The substance after recrystallisation from benzene melted a t 1 7 2 O without decomposition and did not appear to decompose appre-ciably a t 2 6 0 O . It dissolved very readily in water or alcohol and fairly readily in benzene or chloroform : 0.1310 gave 0.2774 C02 and 0.0800 H20. C=57*75; H=6*78. The silver salt was a t once precipitated when silver nitrate was 0*1118 gave 0.0449 Ag. Ag=44*63. C13H1806 requires C=57.8; H=6*7 per cent. added to a boiled solution of the lactonic acid in ammonia : C13H,,0,Ag2 requires Ag = 44'6 per cent. trans- y-Hydroxy-S-cycloi~exyl-a-met~yltm'carballylic ,4 cid. The hydroxy-acid appeared to be stable only in the1 form of its salts and in spite of several attempts it was not found possible to obtain it free. However when the trans-lactonic acid was dissolved in water and slowly titrated with barium hydroxide an end-point correspnding with the neutralisation of three carboxyl groups was obtained : 0.0434 of the trams-lactonic acid required 19.90 C.C.Ba(OH)2 solu-tion (0.0243N) for complete neutralisation. C,,H,,O changing in solution t o C13H2,0 (tribasic) requires 19.85 C.C. The barium salt was prepared by treating a solution of the trms-lactonic acid in water with an excess of aqueous barium hydroxide: 0.1671 gave 0.1202 BaSO,. Ba.=42.34. (C,,H,,O,),Ba requires Ba = 42.0 per cent 370 INGOLD AND THORPE THE FORMATION AND cis-Lactonic A cid of y-Hydroxy-/3-cyclohexyl-a-met hyltricarballylic Acid (XXXIV p. 342). This substance was readily obtained by dissolving its anhydride (see belo,w) in boiling sodium hydroxide solution and acidifying with 'hydrochloric acid.Microscopic crystals separated and were recrystallised from water. The cis-lactonic acid melted a t 1 5 2 O with the immediate eslimina-tion of water vapour. It was more readily soluble in water than the trans-acid : 0.1182 gave 0.2489 CO and 0.0724 H,O. The silver salt was prepared by adding a solution of silver nitrate 0.1029 gave 0'0457 Ag. Ag=44.41. On boiling with concentrated hydrochloric acid the cis-lactonic C=57*43; H=6*81. C,,HI8O requires C =I 57.8 ; H = 6.7 per cent. to a boiled solution of the cis-lactonic acid in ammonia: CI3HI,O,Ag requires Ag = 44.6 per cent. acid was partly converted into the trans-isomeride. cis- y-Hydroxy-P-cycloh ezyl-a-me t hyltricnrbnllylic A cid.Like the tram-modification this substance appeared to be stable only in the form ,of its salts. The cis-lactonic acid on titration with aqueous barium hydroxide gave however an end-point correspond-ing with salt-€ormation in respect of three carboxyl groups : 0.0260 of the cis-lactonic acid required 11.9 C.C. Ba(OH)2 solution (0*02431\7) for complete neutralisation. C,,H,,O changing in solu-tion to C,,H,,O (tribasic) requires 11.9 C.C. The barium salt was precipitated from a solution of the cis-lactonic acid in water by the addition of an excess of barium hydroxide solution : 0.1403 gave 0*1011 BaSO,. Ba = 42.42. (C,3H,707),Ba requires Ba = 42.0 per cent. co-0-co The cis-lactouic Anhydride C,H,,:CH*F--YH ' I 1 MeCH-COO0 The lactonic anhydride was prepared by heating the truns-lac-tonic acid with amsty1 chloride a t looo in a closed flask.The product was evaporated in a vacuum and the residue crystallised from ether STABILITY OF SPIRO-COMPOUNDS. PART II 371 when it separated in small crystals melting a t 170O. be purified by distillation under diminished pressure. acid with acetyl chloride a t atmospheric pressure : It could also The same anhydride was also obtained by boiling the cis-lactonic 0*1170 gave 0.2637 CO and 0.0679 H20. C=61.47; H=6.45. C13H1605 requires C= 61.9 ; H = 6.3 per cent. trans-3 -Hydrox y -4-cychh ex y l- I-me th ylcyclo butcun-2-one-3 4-dicaroxylic Acid (XXXVII p. 345). The portion of the cryfitalline mixture obtained in the prepara-tion of the trans-lactonic acid (p.369) which did not diissolve in the hiling benzene consisted essentially of the cyclobutane acid XXXVII and was recrystallised from aqueous alcohol. The ethereal solution QP the eshrified gummy residue (p. 369), a f h r shaking out the acid products with aqueous sodium hydroxide, was dried and evaporated. The residue on distillation under diminished pressure yielded a fraction passing over a t about 260°/ 25 mm. which was hydrolysed by boiling hydrochloric acid. The product was rendered alkaline and extracted with ether then acidi-fied and again extracted with ether. The latter extract on drying, and evaporating the solvent yielded a residue which deposited crystals of the cyclobutane acid on adding benzene. The crystals were washed with benzene and recrystallised from aqueous alcohol.The trams-cyclobutanel acid melted and evolved steam at 185O, without appreciable discoloration. The liquid on cooling solidified, and on reheating melted at about 140*: 0*1008 gave 0.2132 CO and 0.0618 H20. 0*0600 required 18.37 C.C. Ba(OH) solution (0-0243N) for C=57.68; H=6*81. C,,H,,O requires C=57.8; H=6*7 per cent. neutralisation. C,,HI8O6 (dibasic) requires 18.3 C.C. cis-3-~ydro~-4-cycl<zhexy~- 1-meth ylcyclobutan-2-one-3 :4dicadoxylic Acid (XXXVII p. 345). The cis-acid was prepared by boiling its anhydride (see below) On cooling the solution the anhydride separated in tho The acid melted a t 148O with the immediate elimination of water-It was more readily soluble in water than the trams-modi-with water.pure condition. va.pour. ficat,ion 372 INGOLD AND THORPE THE FORMATION AND 0.0704 gave 0.1497 CO and 0.0430 H,O. C=57*99; H=6*78. 0.0481 required 14.65 C.C. Ba(OH)2 solution (0-0243N) for When boiled for four hours with concentrated ‘hydrochloric acid C13H1806 requires C=57*8; H=6.7 per cent. neutralisation. C13H180 (dibasic) requires 14.7 C.C. the cis-acid was quantitatively convel-ted into the trans-isomeride. C,H,,:CH-O<CHMe>CO. O H ) / Anhydride of the cis-Acid, c0*0*60 A t its melting point the trans-acid evolved water-vapur but the elimination was by no means complete a t this temperature. The melted substance was therefore raised to 230° and maintained a t this temperature until it began to darken in colour. The product was triturated with aqueous sodium hydrogen carbonate dried and recrystallised from dry ether.The same anhydride was obtained by heating the cis-acid above its melting point: 0.0833 gave 0.1886 CO and 0.0483 H,O. It melted a t 158O. C=61*75; H=6*44. C13H1605 requires C = 61.9 ; H = 6.3 per cent. (g) Reduction. of the Monobasic Bridged-spiroacid (XXIII, p. 335) b y Sodium Amalgam. It was found necessary in order to be able to repeat the results, to standardise carefully the method of experiment. The reductions were always carried out with 3 per cent. amalgam which passed through a 10-mesh sieve but not through a 16-mesh sieve. The solu-tions were contained in round-bottomed flasks of capacity two and a-half times the volume of the solution and kept a t a definite tem-perature.During a reduction a stream of carbon dioxide was led into the flask but was not- allowed to bubble through the liquid. These oonditions apply t o all the experiments described in this and the next section. 5-qycloHexanespirocyclopentan-3-one-l-carb~xylic Acid (XLIII, p. 348). Five grams of the ketonic acid (XXIII p. 335) were dissolved in an amount of sodium carbonate sufficient to give a neutral solu-tion and the whole made up t o 200 C.C. This solution was kept a t 14O by immersing it in cold water and reduced under the standar STABILITY OF SPIRO-COMPOUNDS. PART II. 373 conditions by adding 10 grams of amalgam once every half hour until 120 grams in all had been used. Half an hour after the addi-tion of the last of the. amalgam the mercurial layer was removed and the aqueous layer acidified.The oily precipitate was allowed to solidify and was then collected and rscrystallised from dilute alcohol. 'The acid melted a t 136-13So and was found to be very readily soluble in all usual organic solvents except light petroleum; in this solvent as in water it was sparingly soluble: 0.0867 gave 0.2145 CO and 0.0635 H,O. Cz67.49; H=8*14. Cl1HI6O3 requires C = 67.3 ; H= 8.2 per cent. CH(C0,H) p2 The Semicarbaaone C,H,,:C< CH,--CN*NH*CO*NH, The semicarbazone separated when a solution in which the acid and se-nicarbazide acetate had been boiled together was cooled. After recrystallising from alcohol it melted and decomposed a t 210°: 0.1079 gave 0.2262 CO and 0.0757 H20. C=57*17; H=7-80.C,,]EI&N3 requires C = 56.9 ; H = 7-5 pe;r cent. 5 -cycloHe xanespirocyclopen t an- 3- ol-1 - cap6 ox y lic A cid (XLIV , p. 348). Five grams of the above cyclopentanone acid were dissolved in a quantity of aqueous sodium carbonate sufficient to give an approxi-mately neutral solution which was made up to 400 C.C. This solu-tion was kept a t 17O and reduced under standard conditions with 240 grams of amalgam 10 grams being added every half hour. Half an hour after the addition of the last of the amalgam the mercurial layer was run off and the aqueous layer acidified and extracted with ether. The solid residue obtained after the ether had been dried and distilled off was recrystallsised from a mixture of benzene and light petroleum. The hydroxy-acid melted a t 125-127O and was very readily soluble in all the usual organic solvents except light petroleum.It was much more readily soluble in water than was the corresponding ketonic acid : 0.1092 gave 0.2672 CO and 0.0884 H,O. C = 66.93; H = 9.00. C,,HI8O3 requires C = 66.7 ; H = 9.1 per cent 374 INOOLD AND THORPE THE FOBMATION AN.D When the hydroxy-acid was boiled with acetyl chloride for four hours and the solution evaporated there was left a solid residue which was recrystallised from benzene. It melted a t 157-160° : 0.0887 gave 0.2122 CO and 0.0680 H,O. C = 65-24 ; H = 8.52. 0.1552 gavel acetic acid requiring 26.4 C.C. Ba(OH) solution Cl3H2,O4 requires C = 65.0 ; €1 = 8.3 per cent. (0.0243N) for neu tralisation. Cl3H,,O4 requires 26.6 C.C. (h) Comparative Experiments on the Reduction of the Bridged-rin,g- and Bridged-spiro-acids X I V (p.333) and X X I I I (p. 335). The general plan which was followed in these experimelnts has already been sketched in the Introduction (Section E). The most convenient method of preparing the bridged-ring acid XIV was found to be by treatsing the sodium compound IX (p. 330) according to the method (p. 364) used in the preparation of the acid XXIII from the sodium compound XII. The reductions of the bridged-ketonic-acids XIV and XXIII were carried out under t,he usual conditions (p. 372). The experiments were conducted in pairs using 0.80 gram of the acid XIV and 1-00 gram of the acid XXIII. The neutral solutions of the acids were immersed in the same water-bath and treated with 1 gram of amalgam every fifteen minutm 50 long as the experimeat lasted.The aqueous layers were then acidified and extracted quantitatively with pure ether. The solid residues obtained on evaporating the solvent were allowed to remain in an exhausted desiccator for f orty-eight hours. Usually about 0-4 or 0.5 gram was taken and the water formed by combustion deter-mined. I n certain cases the substance was also acetylated and the product left after evaporating desiccated over potassium hydroxide and quantitatively hydrolysed,' the acetic acid being distilled off in a current of steam and estimated by titration with standard alkali. This figure gave the quantity of hydroxy-acid which had been formed in the reduction whilst the water formed on combustion enabled one to calculate the total quantity of hydrogen which had been ir,troduced during the reduction.The accompanying table (table VII) gives the results of these experiments the figures within the brackets (. . . . . .) representing the calculated limits. Another set of experiments similar to the above was instituted, me dried products were then analysed STABILITY OF SPIRO-COMPOUNDS. PART 11. 375 in which the reduced ketonic-acids XXXIX (p. 346) and XLIII (p. 348) were used in place of the bridged-ketonic-acids XIV and XXIII. The quantities taken for each experiment were 0.80 gram of the acid XXXIX and 1.00 gram of the spiro-acid XLIII. The other quantities and conditions of experiment were the same as in the fo'rmer case. In this instance the products were not acetylated and hydrolysed but the water formed on combustion was deter-mined.The results of these experiments are given in table VIII, the figures in brackets (. . . . . .) representing as before the calculated limits. TABLE VII. Time Amalgam (hours). (grams). 0 4 8 2 4 16 6 24 10 40 14 56 (? (03 03 Time Amalgam (hours). (grams). 0 8 16 4 7 28 '2" (a 00 Bridged-ring-acid (0.80 gram). -A-+; e-u 8.- 0 a$ 2% 6.49 6.67 6.85 7.20 7.27 7-46 7.79 8-86 0.00 0 0.30 -0.60 -1.18 -1-30 0 1-62 3 2.16 21 4.00 100 TABLE VIII. Ring-acid (O-bO gram). - Per cent Atoms of H of H in product. introduced. 7.69 0.00 7-92 0.39 8.13 0.75 8-42 1.25 8.86 2.00 Bridged-spiro-acid (1.00 gram).2.2 5 p{ $3 7.22 7-49 7.64 7.97 8.09 8.30 9.09 -0.00 0) 0.58 -0.89 -1.68 -1-85 2 2.30 18 4.00 100) - -spiro-Acid (1.00 gram). - Per cent. 4 Atoms of H of H in product. introdmed. 8.39 0.49 8.51 0.75 8.67 1-10 8.16 0-00) 9.09 2.00) (i) Oxidation of Fissiovn-products Derived from the Bridged-spiro-sdo-ester X I 1 (p. 330). Oxidation experiments were tried with three types of fission-product including t'he spirocyclopentanone acid XLIII (p. 348), the transcyclohexylcyclobutane acid XXIV (p. 336) and the trams-lactonic acid of hydroxycyclohexylmethyltricarballylic acid XXXIV (p. 342). None of these apEeared to be1 acted on by boiling dilute nitric acid. Concentrated nitric acid however 376 INGOLD AND THORPE THE FORMATION AND readily oxidised the first of bhese three acids but did not react with the last two.These however were readily attacked by warm alkaline parmanganatei. Two crystalline oxidation products cyclo-hexanecarboxylic acid and cyclohexanel 1-dicarboxylic acid were obtained in tihe course of these experiments. cycloHexane-1 1-dicarboxylic Acid (XLV p. 351). This acid was prepared by oxidising both the sp’rocyclopentan-one acid XLIII (p. 348) or the corresponding s@rocycZopenhnol acid XLIV (p. 348) with concentrated nitric acid. Ths organic acid (2.5 grams) was warmed with an excess of concentrated nitric acid until most of the red fumes had been evolved. The resulting solution was &en boiled for a few minutes and finally evaporated to dryness.The residue was treated with water and again evaporated. I n this way a semi-solid mass was obtained from which the crystals were separated by spreading on porous porce-lain. After recrystallising from water the acid melted at 207O with the evolution of carbon dioxide and a certain amount of dis-doration : 0.1008 gave 0.2058 GO and 0.0650 H,O. 0.0412 required 19-75 C.C. Ba(OH) solution (0-0243R) for C=55-68; H=7-16. C,H,,O requires @= 55.8 ; H = 7.0 per cent. neutralisation. C8H,,04 (dibasic) requires 19.7 C.C. cyclolirexanecarb oxylic A cid (HexahydTobeneoic A cid). This acid was obtained in two ways: (1) B y distilling cyclohexarrzre-l 1-dicarboxylic acid. The di-carboxylic acid m distillation under ordinary pressure gave off carbon dioxide and yielded a distillate which boiled a t 230-235O and solidified when cooled by ice.The crystals melted a t 18-23O. (Found C= 65.42 ; H =9.51. Calc. C= 65.6 ; H =9.4 per cent.) (2) By 0xidisilz.g cyclohexyl derivatives. Either the trans-lactonic acid of hydroxycyclohexylmethyltricarballylic acid XXXIV (p. 342) or the trams-cycl~hexylcyctobutanone acid XXIV (p. 336) may be used. The organic acid (10 grams) was dissolved in an excess of a solution of sodium carbonate and treated with 30 grams of potassium permanganate. The permanganate was added in successive small quantities sufficient time being allowed between each addition for the solution to become decolorised the reaction being aided by heating. When all the permanganate ha STABILITY OF SPIRO-COMPOUNDS.PART 11. 377 been added and decolorised the liquid was filtered and extracted with ether to remove any neutral oxidation products. The aqueous solution was then acidified with hydrochloric acid and the add products were extracted with ether. From the residue obtained on drying and evaporating the solvent some gummy material was separated *by distilling under diminished pressure, and the liquid distillate was fractionally distilled under atmo-spheric pressure. I n this way there was obtained a fraction boil-ing at 232-236O which solidified on cooling in ice to a mass of crystals melting a t 21-25O. (Found C= 65.63 ; H = 9.51. Calc. C=65*6; H=9.4 per cent.) The adid prepared by both these methods melted a t a tempera-ture a few degrees lower than the recorded melting point namely, 29O (Lumsden T.1905 87 91). The same experience in regard to it is recorded by Hawmth and Perkin (T. 1894 65 103). It certainly appears to be exceedingly difficult to obtain preparations showing the correct melting point when working with small quanti-ties of material. Crystals' of the acid when left exposed to air rapidly liquefied and it did not appear to be possible to induce the acid t o separate in a crystalline form by cooling a solution in light petroleum below Oo. These observations agree preciwly with the statements made by Lumsden and along with the analytical figurw are regarded as leaving no doubt as to the identity of the substance. (j) Examination of the Oily By-product obtained in the Prepration of the Bridged-spirclsodio-ester XZI (p.330). The alcoholic solution of the oily by-product obtained during the preparation of the yellow sodium spiro-compound (p. 357) was distilled to remove the alcohol the residue dissolved in ether and shaken with water. The ethereal solution was then dried and evaporated the residue being distilled under diminished pressure. Three fractions were obtained (1) below 1ZOo/20 mm., (2) betweea this and 250°/11 mm. and 43) a t 250-160°/11 mm., together with a small dark-coloured non-volatile residue. Fraction (1) .-The first fraction contained practically the whole of the ethyl malonate present in the original oil. It was redis-tiIIed and the small residue of high boiling point was added to the second fraction (2). Fraction (2).-The second fraction which did not appear to be capable of separation into pure compounds by distillation was boiled with hydrochloric acid for forty-eight hours.During the reaotion a strong d o u r of butyric acid was developed. Whe 378 INQOLD AND THORPE THE FORMATION AND the hydrolysis was complete the butyric acid was distilled off in a current of steam and the residual solution boiled with charcoal, filtered and evaporated to dryness. Five acids were isolated from the crystalline residue. cycloHexame-1 1-diacetic A cid-The crystalline residue was recrystallised from the minimal quantity' of 35 per cent. alcohol. The crystals which separated contained thre,e of the five acids the separation from the other two which remained in the mother liquor being very nearly quantitative.The crystals melted at 1 60-200° approximately. They were dissolved in dilute ammonia and after the excess of ammonia had been evaporated were treated in the cold with a solution of zinc sulphate. The pre-cipitate was collecbd washed with cold water and then digested with hydrochloric acid. The acid thus precipitated melted a t 174-179O and was again precipitated as its zinc salt. The free acid was then liberated and recrystallised from water when it melted a t 18l0 and was identified as cycluhexane-1 1-dicarboxylic acid by direct comparison with a specimen of that substance. The preparation together with some small residues obtained subse-quently constituted 15 per cent. of the original crystalline mixture. trans-cyclolHexanespirocyclolpropane-1 2 d i ~ b o x y l i c A cid.The combined filtratles from the zinc salt of cyclohexane-1:l-diacetic acid were concentrated and treated with concentrated hydrochloric acid. The precipitated acids were dissolved in ammonia and after conceatrating the solution treated in the cold with a considkrable excess of a saturated solution of lead nitrate. The lead salts were collected and recrystallised from the minimal quantity of boiling water and then decomposed with a slight excess of dilute nitric acid. This treatment separated the last trace of cyclohexanediacetic acid which along with a small quantity of the tra~s-slrirocyczopropane acid remained in the filtrates from the lead salt. These traces were separated by means of their zinc salts as described above. The combined cycla-hexanediacetic acid-free preparations were extracted twice with three parts by weight of boiling benzene.The undissolved portion melted a t 234-237O and on recrystallisation from dilute alcohol melted sharply a t 237O. It was identified as cycbhexanesp-ro-cyclopropanedicarboxylic acid by direct comparison with a speci-men. The. preparation together with some residues subsequently obtained amounted to 65 per cent. of the original crystalline mixture STABILITY OF SPIRO-COMPOUNDS. PART 11. 379 3-cyclolHexanespiro-1-methylcyclopro~e-1 1 f 2-tricarrb oxyCic Acid (XLVII p. 354). The solut'ion in the 35 per cent. alcohol from which the above two dicarboxylic acids were crystallised (p. 378) was evaporated, and the residue resolved by crystallisation from 50 per cent.alcohol into three distinct fractions (1) a small quantity of a mixture of the same two dicarboxylic acids (2) a much more readily soluble crystalline substance melting a t about 208O and (3) a viscous gum. The first fraction was treated according to the methods already described for the separation of the two dicarboxylic acids. The second consisted essentially of the sp+ocyclopropanetricarb-oxylic acid. It represented about 8 per cent. of the original crystalline mixture and on recrystallising from water melted a t 215O with the immediate eliminatiun of water vapour : 0.1156 gave 0.2386 CO and 0.0675 H,O. 0.0453 required 21.95 C.C. Ba(OH) solution (0.0243,N) for C=56*30; H=6*49. CI2H,,O requires C = 56.2 ; H = 6.2 per cent. neutralisation.C,,H,,O (tribasic) requires 21 *9 C.C. co*o*co CH,*CO,H C-bH I c-co I The Anhydro-acid C1,H,,:C<&H.CO,H or C 5 ~ 0 W & a.co>O. The anhydro-acid was prepared by boiling the free tricarboxylic acid with acetyl chloride for two hours and evaporating the excess of the reagent. The residue on treating with benzene set to a mass of crystals. After recrystallising from the same solvent, the anhydro-acid melted a t 128O. It was immediately soluble in cold sodium hydrogen carbonate solution and could be recovered un-changed by acidifying. On boiling a solution of the anhydro-acid in aqueous sodium hydroxide for a few minutes and then acidify-ing the free tribasic acid was regenerated: 0.1548 gave 0.3418 CO and 0.0823 H,O. C=60.23; H=5.90. C12H,,0 requires @= 60.5 ; H =5.9 per centl.5-cycloHexanespiro-2-e thyldicyclope~tan-3-o~~e-~-cwb oxylic Acid (XLVIII p. 354). The two benzene filtrates obtained in the preparation of the spirocyclopropanedicarboxylic acid (p. 378) were combined and evaporated. The residue which still contained about three part 380 INGOLD AND THORPE THE FORMATION AND of the dicarboxylic acid to one of the bridged-monocarboxylic acid (this was indicated by a titration) was weighed and ext<racted with three times its weight of boiling benzene. The extract was evaporated and the residue treated again in this way the treat-ment being repeated until the residue obtained after evaporating an extract was completely soluble in three parts of boiling benzene. The product was fractionally crystallised from benzene.After a considerable number of fractional crystallisations a preparation was obtained which did not appear to change in melting point when again recrystallised. This substance separated from benzene in long needles which melted a t 191-194O. It was sparingly soluble in water and gave no colour with ferric chloride: 0.0610 gave 0.1537 CO and 0.0432 H,O. 0.0376 required 7.20 C.C. Ba(OH) solution (0.0243N) for The analytical figures especially those for the titration do not correspond with the formula so well as could be desired. The dis-crepancies are however all in a direction that may be taken to indicate that the preparation still contained a small quantity of the spirocyclopropanedicarboxylic acid which owing to the small-ness of the quantity of material it was not possible to rmove.The preparation constituted about 0.1 per cent. of the original crystalline mixture. cf=69.75; H=7.99. CI3Hl8O3 rquires C=70.3; H=8*1 per cent. neutsalisation. C,,H,,O (monobasic) requires 7.0 C.C. trans-lac tonic A cid of y-Hydroxy-&cyclohexyl-a-et h yl t r i c w b d l y l i c Acid (XLIX p. 354). The viscous gum which was obtained as the third fraction in the separation by means of 50 per cent. alcohol mentioned on p. 379 was distilled under diminished pressure. More than three-quarters of i t passed over at.240-250°/40 mm. and this on treatment with benzene solidified to a mass of colourless crystals. These represented about 3 per cent. of the original crystalline mixture the residue in the dist'illing flask which was not further examined accounting for about 1 per cent.The crystalline lactonic acid after recrystallisation from either water or benzene melted a t 149O. It dissolved readily in water and all the usual organic solvents except light petroleum: 0.1228 gave 0.2660 CO and 0.0962 H,O. The silver salt was precipitated by adding silver nitrate solution C=59*08; H=7*09. C,H,,O requires C = 59.2 ; H= 7.0 per cent. to a boiled solubion of the lactonic acid in ammonia STABILITY OF SPIRO-COMPOUNDS. PART 11. 381 0.1063 gave 0.0461 Ag. Ag=43*37. C,,13[,@,Ag2 requires Ag= 43.4 per cent. tran~y-~€ydroll;.~-~-cycl~~exyl-a-ethyltricarbally~~c Acid. This hydroxy-acid (contrast the cis-form) appeared t o be stable only in the form of its salts.All attempts to obtain it in the free state were unsuccessful. However when the tram-lactunic acid was dissolved in water and the solution titrated slowly with barium hydroxide in the cold an end-point corresponding with the neutral-isation of three carboxyl groups was obtained : 0.0516 required 22-40 C.C. Ba(OH) solution (0.0243N) for com-plete neutralisation. C14H2006 changing in solution to CI4HBO7 (tribasic) requires 22.4 C.C. The barium salt was precipitated from an aque'ous solution of the trans-lactonic acid by adding an excess of a solution of barium hydroxide : 0.1678 gave 0.1179 BaSO,. Ba=41*36. (C,,H,90,)2Ba requires Ba = 40.8 per cent. cis-Lactonic Acid of y-Hydroxy-/3-cyclohexyLa-ethyltricarbaUylic Acid (XLIX p. 354). The cis-lactonic acid was readily prepared by heating the free cis-hydmxy-acid (see below) a t looo for a few minutes.When dissolved in water the lactonic acid regenerated the hydroxy-acid which could either be crystallised out or titrated in solution. The lactonic acid could however be recrystallised from a mixture of benzene and light petroleum without any change taking place. It melted a t 198O with the evolution of water-vapoar : 0-1040 gave 0-2244 CO and 0.0664 H20. C,,H,,O requires C = 59.2 ; H = 7.0 per cent. The silver salt was prepared by dissolving either the cis-lactonic acid o r the cis-hydroxy-acid (see blow) in dilute ammonia boiling, and adding an excess of silver nitrate solution : C=58*84; H=7*10. 0-1041 gave 0.0449 Ag. Ag=43*13. On boiling the cis-lactonic acid with hydrochloric acid a partial C,4H,806Ag2 requires Ag = 43.4 per cent.conversion into the tra-rzs-lactonic acid took place 382 INGOLD AND THORPE THE FORMATION AND cis- y -H ydrox y-b-cycloh ex$-a- e t h yltricarb ally lic A cia?. This substance was prepared by boiling the cis-lactonic anhydride (see below) with a slight excess of aqueous sodium hydroxide and acidifying with hydrochloric acid. !C'he cis-hydroxy-acid slowly separated out. The1 substance is very unstable and loses a molecule of water with great readiness giving the cis-lactonic acid. The change was found to proceed with rapidity a t 60° in an exhausted desiccator a t the ordinary temperature and slowly when the acid was exposed t o air under ordinary conditions. I n cold aqueous solution the sub-stance bmehaved in every way as a tribasic acid : 0.1003 gave 0.2045 CO and 0.0666 H,O.C=55.60; H=7*38. 0.0382 required 16.65 C.C. Ba(OH) solution (0'0243fl) for The barium salt was precipitated when the hydroxy-acid was dis-solved in water and treated with an excess of barium hydroxide solution : C,,H,,O requires C = 55.6 ;< H = 7.3 per cent. neutralisation. C,,H,,O requires (tribasic) 16.6 C.C. 0.1057 gave 0.0740 BaSO,. Ba=41-18. When the cis-hydroxy-acid was boiled with 20 per cent. hydro-chloric acid f o r some hours a partial conversion into the trans-(C14H,90,),Ba3 requires Ba = 40.8 per cent. lactonic acid took place. T h' e cis- Lac t o iaic The trans-lactonic acid appreciable extent when co-0-co I Anhydride C,H,,:CH*C- &H I E~.~H*COW did not appear t o be dehydrated to any 'heated above its melting point or when distilled under diminished pressure. It readily eliminated water, however wheln heated a t looo f o r half an hour with acetyl chloride. On evaporating the product and treating the residue with benzene, crystals of the Iactonic anhydride were obtained. After being recrystallised from benzene the substanoe melted a t 154O. It did not dissolve ab an appreciable rate in cold aqueous sodium hydrogen carbonate but on warming with sodium hydroxide both oxygen rings were opened up and the cis-hydroxy-acid was formed: 0*1023 gave 0.2356 CO and 0.0625 H,O. C=62*81; H=6*79. Fraction (3).-The third fraction which was obtained on distilling C,,H,,O requires C = 63.2 ; H = 6.7 per cent STABILITY OF SPIRO-COMPOUNDS. PART 11. 383 the oily by-product (p. 377) boiled a t 250-260°/11 mm. and con-sisted of fairly pure ethyl cyclohexanespiromethylcyclopropanetetra-carboxylate (XI p. 330). When hydrolysed with hydrochloric acid it yielded the tricarboxylic acid (XLVII p. 354) dealt with on p. 379. (k) Note on Ethyl Dihydrogert) 5 5-;T)imethyldicyclopentm-3-me-1 2 4-tricarboxybate (XXVI p. 337). This member of the dimethyldicyclopentane series which was made use of in this research has not been previously described. The yellow sodium compound X (p. 330) was boiled with five times its weight of a '31;2T-solutioii of potassium hydroxide in alcohol until the suspended matter just became colourless. The precipitate was collected and drained on porous porcelain in a desiccator. It was then dissolved in the minimal quantity of water and decom-posed with excess of concentrated hydrochloric acid. The crystals obtained were recrystallised from 15 per cent. hydrochloric acid. The acid-ester melted and decomposed a t 162O and gave a purple colour with ferric chloride. It was readily converted into the mono-carboxylic acid XIV (p. 333) by heating for a few minute a t 200° with a little water. When heated in the dry state it evolved carbon dioxide and steam and from the charred residue a small amount of the acid XIV was isolated. It is perhaps worthy of note that the moiiocarboxylic acid should be obtained in this way but it is doubtless the result of the hydrolytic action of the steam which is evolved as the substance decomposes : 0.1261 gave 0.2453 CO and 0.0599 H,O. C=53*05; H=5.28. 0.1070 required 32.7 C.C. Ba(OH) solution (0.0243fl) for CI2Hl4O requires C = 53.3 ; H = 5.2 per cent. neutralisation. C,,H,,O (dibasic) requires 32.6 C.C. IMPERIAL COLLEGE OF SUIENOE RESEARCH LABORATORIES, CASSEL CYANIDE COMPANY LTD., [Received March 131h 1919.1 AND TECHNOLOGY, SOUTH KENSINOTON. GLASGOW

ISSN:0368-1645    

DOI:10.1039/CT9191500320

出版商:RSC    

年代:1919

数据来源: RSC

摘要:

ANNUAL GENERAL MEETING, THURSDAY MARCH Z ~ T H 1919 AT 4 P.M. SIR WILLIAM J. POPE K.B.E. F.R.S. President in the Chair. Dr. T. S. PRICE and Dr. C. K. TINKLER were elected Scrutators, and the ballot was opened for the election of Officers and Council. The Report of Council for 1917-1918 was formally presented t o the meeting by the PRESIDENT. After statements by one of the Secretaries as to the progress made in the revision of the Bye-laws and by the Treasurer as t o the financial position of the Society the adoption of the Report of Council together with the Statement of Acoounts for the year ending December 31st i918 was proposed by Professor G. BARGER seconded by Dr. G. W. MONIER-WILLIAMS, and carried unanimously. REPORX OF COUNCIL 1918-1919. The Council are gratified to report a substantial increase in the membership of the Society.On December 31st 1917 the number Qf Fellows was 3,270. During 1918 249 Fellows were elected and 13 reinstated making a gross total of 3,532. The Society has lost 62 Fellows by death; 16 have resigned; the elections of 6 have been declared void and 47 have been removed for non-payment of Annual Subscriptions. The total number of F0110ws therefore, a s a t December 31st 1918 was 3,401 showing an increase of 131, as compared with 72 in 1917. It is with regret they report that the following Fellows have died on Service: John Percy Bates (1913). Charlea William Dick (1917). Edward Frank Harrison (1894). Leonard Isoiz Pitt (1911) ANNUAL GENERAL MEETING. and that the death of the following has also occurred: 385 Richard Leburn Barnes (1875).James Bayne (1874). William Henry Elake (1890). Arthur Clegg Bowdler (1865). Joseph John Bowley (1896). Harry Broadbent (18891. William Edward Callister (1909). Thomas Charles Cloud (1878).-Jam- Mason Crafts (1870). William Adam Dixon (1862). John Ern& Dunstan (1917). Thomas Farries (1870). Charles Thomas Foreman (1907). Edward Francis (1879). Charles James Pemeller Fuller (1896). George Thomas Glover (1872). Walter Augustus Handcock (1900). Egerton Bargreaves (1909). Henry Jam@ Helm (1872). Richard Pendarves Hodges (1913). Henry Tylshton Hodgson (1873). William Lamond Howie (1876). Edward Lewis James (1912). David Smith Jardin (1902). Edgar Dingle Jones (1912). John Sydney Keel (1917).Douglas Rayment Keller (1913). William Joel Kemp (1882). Hassum Alidina Lakhani (1909). Edmund Albert Letts (1879). Thomas Stratford Logan (1902). Thomas Watson Lovibond (1882). Sydney Lupton (1872). George Cannon McRhhry (1889). Charles Stewart Maries (1918). Edward Matthey (1884). Elias Mendozn (1918). Alexander Milne (1885). Sir Alexander Pedler (1870). Mulgrave Daniel Penney (1870). George Frederick Tyler Phillips William Ping (1889). Joseph Price Remington (1886). Alfred Gordon Salamon (1880). John Scudamore Sellon (1875). Alfred Senier (1875). Walter Dalrymple Severn (1896). John William Shepherd (1899). Richard Spencer (1886). James Carter Spensley (1917). Henry Charles Stephens (1880). Edward Cumming Thompson (1894).John Bishop Tingle (1889). Thomas Tyrer (1876). Herbert William Milk Willett (1906). Christopher Wilson (1894). Reginald Cowdell Woodcock (1871). John Young (1874). (1904). Resignations have been received from : William James Bees (1905). Hugh Garner Bennett (1909). Kula Bhushan Bhaduri (1903). Frederick Raine Ennos (1914). Nagardas Punushottam Gandhi (1915). John Thomas Hall (1903). Herbert Edwin Macadam (1896). David James Morgan (1895). Frederick Filmer de Morgan (1897). Joseph Morris (1891). Malur Srinivasa Rnu (1910). Abhayacharan ,Sanyal (1891). Rabert Qreig Smith (1891). Thomas May Smith (1910). Alfred Tingle (1904). James Woodward (1888). The congratulations of the Society are offered to Professor William Odling Paslipresident elected a Fellow on January 17th, 1848 who has now completed seventy-one years as a Fellow.The Society's congratulations are also extended t o ; Dr. Augustus George Vernon Harcourt (Past-President) .. . ... John Spiller . . ....... ... ....... .. .. .... . . . .. ... . .. . .... . . . . .. . .. .. . . .. . .. . . . . . Josiah Wyckliff e Kynaston ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Thomas William Salter ..................................................... Elected. Feb. 3rd 1850. Feb. 3rd 1859. Beb. lTith 1859. Feb. 17th 1859 386 ANNUAL GENERAL MEETINQ. who have been Fellows for more than sixty ymrs9 and to the following who have attained their jubilee as Fellows : John Hnghes ..................................................................Edward Knowles Muspratt ............................................... Thomas Bolas ................................................................ Frank Clowes ................................................................ Elected. Dec. 17hh 1868. Jan. 21& 1869. Mar. 18th 1869. Mar. lab 1869. The volume of Transactions for 1918 contains which 849.pages are occupied by 89 memoirs the 995 pages of remaining 146 pages being devoted to the Obituary Notices three lectures on special subjects the Report of the Annual General Meeting and the Presidential Address. The volume fur the preceding year con-tained 95 memoirs occupying 960 pages. The Journal for 1918 contains also 2,436 abstracts occupying 1,032 pages whilst the abstracts for 1917 numbered 2,858 and occupied 1,308 pages.The great decrease in the number of. memoirs in journals devoted t o chemistry and allied subjects referred to in the Reports for 1916 and 1917 became as was expected still more marked in 1918; there is however some slight reason t o hope that the lowest point has been reached and that an increase in the number of papers abstracted may now be anticipated. Whilst most of the Continental journals have been obtained for abstraction no Russian journals have come to hand during the year. I n the last Report an account was given of the arrangements made by a Joint Committee of the Chemical Society and Society of Chemical Industry to minimise duplication in the abstracts pub-lished in the Journals of the two Societies.This arrangement has been in force during the year with satisfactory results. The abstracts may be classified as follows: PART I. No. of Pages. Abstracts. Organic Chemistry ..................................................... - 771 Physiological Chemistry ............................................. - 237 160 Chemistry of Vegetable Physiology and Agriculture ... -564 PART 11. General and Physical Chemistry .............................. -Inorganic Chemistry ................................................. -Mineralogical Chemistry ............................................. -Analytical Chemistry ................................................. -468 Total in Parts I. and I1 ....................................1,032 1,168 557 205 59 447 1,268 2,43 ANNUAL QENERAJ; MEETING 387 The scheme for supplying the abstracts of the Chemical Society and of the Society of Chemical Industry to the members of b&h Societies has been further considered but owing to many difficul-ties arising out of the war such as the greatly increased cost of production it has been postponed for the present. The Report on the progress of Radioactivity for 1917 which was omitted from the last volume of Annual Reports is included with that for 1918 in the current Volume XV; it has been decided t o postpone the Report on Crystallography and Mineralogy for 1918 and to combine this with the Report for 1919. Permission has been given for the publication of a French translation of Volume XV of the Annual Reports.The publication of the List of Fellows has been resumed but, owing to the need for economy the list has been issued only to those Fellows who made application. Following the scheme initiated three years ago arrangements have been made for the delivery of Lectures to the Society during the present session. The first entitled “The conception of the chemical dement as enlarged by the study of radioactive change,” was given by Professor F. Soddy on December 19th; on March 6th a lecture on ‘ I Emission spectra and ahmic structure” was delivered by Professor Nicholson whilst Professor Jeans will give a ldcture on May 1st dealing with “The quantum theory and new theories of atomic structure.” The address delivered by the President a t the last Annual Meeting was by order of the Council widely circulated through-out the country The emphasis laid in t h i s address on the desirability of closer co-operation between the societies represent-ing the various branches of chemistry has given rise to a definite step in this direction by the promotion of “The Federal Council for Pure and Applied Chemistry.” The Federal Council consists of representatives appointed by the following eleven societies the Chemical Society the Society of Chemical Industry the Associa-tion of British Chemical Manufacturers the Institute of Chemistry, the Society of Public Analysts the Faraday Society the Bio-chemical Society the Iron and Steel Institute the Institute od Brewing the Society of Dyers and Colourists and the Society of Glass Technology.The delegates elected by the Council t o repre-sent the Society on this body are Professor H. E. Armstrong Sir William J. Pope and Sir William A. Tilden. The primary objects of the new body a m to consider and act upon all matters involving the common interests of the constituent societies and to deal with any question which these may place before it. The provision of a House adequate to the requirements of the chemical profession i 388 ANNUAL GENERAL MEETING. which a complete scientific and technical Library could be assembled is now under the consideration of the Federal Council. The Council have had under consideration the present conditions of chemical research and they have given particular attention to the question of the adequacy of the sums available for grants and to the restricted supply of pure chemicals.Since it appeared desirable that united action should be taken in these matters the Federal Council has been requested to consider them and has already taken action in both directions. The demobilisation of chemists has also had the earnest atten-tion of the Council and joint representlation with the Royal Society the Institute of Chemistry and the Chemical Warfare Department has been made to the proper authorities. The Council have recently received a valuable report from the General Committee of Chemical and Allied Societies on the pro-posed publication of chemical compendia in the English language. The report has also been placed before the Federd Council and the councils of other interested societies including those of the American and French Chemical Societies with the view of securing their co-operation.During the past year a Committee has been appointed to con-sider what changes it is desirable to make in the Bye-laws of the Society. I n their report the Committee have recommended *con-siderable changes but these are in several respects inconsistent with the terms of the present Charter and therefore cannot be made until a supplemental Charter has been obtained. The question whether application fur a supplemental Charter should be made will shortly be laid before an Extraordinary General Meeting. Sir William A. Tildm represented the Society on the Sectional Committee of the British Scientific Products Exhibition.Professor P. F. Frankland and Dr. A. Scott continue to act as the Society’s representatives on the Conjoint Board of Scientific Societies whilst Sir William J. Pope has been appointed a delegate to the International Association of Chemical Societies in place of the late Sir William Ramsay. The Council are glad to report that as a result of the Confer-ence of Chemical and Allied Societies a scheme has been prepared and is now in operation for increasing the use of the Library and extending its technical equipment. The co-operation and financial assistance of the Assmiation of British Chemical Maauf acturers, the Biochemical Society the Faraday Society the Institute of Chemistry the Society of Chemical Industry the Society of Dyers and Colourists and the Society of Public Analysts have been obtained.The members of these societies are now able to use th BNNUAL GENERAL MEETIEG. 389 Library on the same terms as Fellows and their representatives have heen added to the Library Committee. As already announced the Library is now open to 9 p.m. on Tuesdays and Fridays and to 5 o’clock on Saturdays in addition to those evenings on which the Society meets. The number of books borrowed from the Library during 1918 was 2,905 as against 2,157 in the previous year and 1,610 in 1916. The additions to the Library comprise 126 books 255 volumes of periodicals and 31 pamphlets compared with 155 books 282 volumes of periodicals and 54 pamphlets in 1917. The Council have the pleasure to report that a valuable gift of handsomely bound volumes of periodicals and systematic works has been received as a bequest from the late Mr.Sydney Lupton. The accounts for the year 1918 show a balance of income over expenditure amounting t o 22,489 4s. 4d. as against 321,652 9s. l l d . reported last March for the previous year. Whilst the income from all sources has been $10,082 14s. l l d . and is thus greater than that recorded for 1917 by $1,552 16s. Od. the expenditure has exceeded that of 1917 by $716 1s. 7d. reaching the sum of $7,593 10s. 7d. Thus although the increased expenditure exceeds the similar increase on the outlay for 1916 indicated by the Report of last year it has been amply covered by the larger revenue. The latter factor is composed of additional life compositions, $102 and admission fees 2352 whilst the subscriptions account reveals an improvement by X381 10s.Od. To these are added increases of 289 12s. 7d. from interest on investments 2262 9s. 10d. from the sale of publications and 292 15s. l l d . from advertise-ments in the Journal although the net gain to the Society from this source is only $32 5s. 4d. owing t o increased cost of printing. Donations to the Library amounting t o $280 5s. Od. and not having a corresponding reference in the Report for 1917 cannot properly be regarded as increased revenue as more than this sum will be expended by the Society during the current year in augmenting the usefulness of the Library to members of the sub-scribing bodies. As was anticipated from the conditions prevailing during 1918, expenses in producing the various publications have been greater than the corresponding costs for 1917 the total increase being S390 19s.7d. of which 3128 5s. 2d. is due to the list of Fellows, a publication suspended in 1917. The fact that this compilation cost &73 1s. 6d. in 1914 273 6s. 7d. in 1915 and 273 16s. 4d. in 1916 throws an interesting light on the increase in printing charges and on the period of the War a t which this became acute. Administrative expenditure has also increased from $1,472 4s. 56 VOL. cxv. 390 ANNUAL GENERAL MEETING. to $1,681 6s. 5d. the principal items on this account being €161 14s. 10d. in staff salaries and war bonus whilst miscel!aneous printing stationery and postages have together increased by €85 18s.8d. On the other hand the exceptional outlay in library furniture required in 1917 has not been repeated and is reflected in a saving of 261 9s. 9d. in the year under review. The War has continued to affect the volume of TransactiQns and Abstracts as indicated by the following synopsis : Number of Pagea. Trans. Abstr. Total: 1914 . . . . . . . . . . . . 2,909 2,068 4,977 1915 1,862 1,944 . . . . . . . . . . . . 3,806 2,900 1916 . . . . . . . . . . . . 1,368 1,532 1917 . . . . . . . . . . . . 1,128 2,436 2,027 1918 . . . . . . . . . . . . 995 Nevertheless the cost of printing the Journal has been E2,750 8s. 3d. instead of ;E2,543 79. 9d. in 1917 so that a reduc-tion of 409 pages corresponds to an increase of &207 0s. 6d. in expenditure; this is owing to further appreciation in the cost of paper and to the necessity of raising the bonus paid to the printers, which now stands a t 72h per cent.on the pre-war rates. €2,000 National War Bonds were purchased during the year ascl the estimated value of the Society’s other investments has improved by $414 so that having regard to the fact that on December 31st, 1918 the cash account was about 2420 higher than on the last day of 1917 the assets of the Society show an increase of 22,831 or a total increase of &3,640 if the Research Fund a t its present estimated value is included. The following grants have been made from the Research Fund during the year: Organic derivatives of bismuth. F. Challenger. . . . . . . An investigation of the phthalein series.M. Copisarow. ... The velocity of reaction between the alkyl iodides and sodium methoxide. H. E. Cox. . . . . . . . . . . . . Formation of heterocyclic ring systems by the condensation of chlorocarbamic esters and alcohols. R. L. Datta. ... The action of alcohols on urea nitrate. P. K. Dutt. ... Influence of the nitro-group on the mobility of the sub-ahituents in the benzene nucleus. J. Kenner. ... The composition and structure of soaps. J. W. McBain. ... Melting points of the substituted amides of thc normal fatty acids. P. W. Robertson. . . . . . . . . . . . . . . . Syntheeis of /3-phenyl-B-hydroxymethylethylamine from cin-namic acid or ethyl cinnamate. E. H. Todd. . . . . . . The space formuls of diphenyl and its derivatives (con-tinued). E. E. Turner.. . . . . . . . . . . . . . . rE15 0 0 10 0 0 10 0 0 10 0 0 5 0 0 5 0 0 15 0 0 6 6 0 10 0 0 10 0 0 Total . . . . . . 296 6 I BALANCE SHEET.-THE CHEBllCAL SOCIhTY, Liabiiities. i x. d . E 8. d . To Llubncriptions received in advance ............... 231 0 0 1 1 0 0 235 10 0 , Bundry Creditors$ ........................... 841 5 4 - - - - - --, Research Fund :-As per last Ba:ance Sheet .................. 14357 3 4 Add Excess of lncorne over Expenditure for the year 539 13 9 Chemical Society Excess of Assets over Liabilities :-As per last Balance Sheet ..................... 24758 7 5 Add Excessof Income over Expenditure for the year 2169 J 4 14896 17 1 -27247 11 0 / i-/ / 24.7211 4 2 By Inveatnients (value L8730 Metropolitan €1050 London cent.Debenture f1520 148. 3d. &1400 India 2) E2400 Bristol Corporation S434l Midland €1200 Leeds Corporation f1500 Transvaal3 41200 North British Stock ................................. S700 Canada 3+ €2100 5 per cent $3100 5 per cent: (Estimated )) Sundry Debtors , Bubscriytions in Arrear , Cash a t Bank-Deposit ,) Current Account ) Cash iu hand . . , Research Fand :-Investiiieuts (value 52000 North British A4400 Metropolitan El034 Great Western , Insurance paid in Preference Stock ture Stock €1121 MetroDolitan e l 1 4 2 166. NG Stock ... 1. €1305 Midland E4498 114. Od. 5 &806 Victoria 3 (Estiriiated present Fund Investiuents. , Cash a t Bank ............................. lo N in accordance therewith.I have examined the ahove Balance Sheet 'and acconipanying Income and Expenditare Accounts with I hare also verified the Balancekt the Bankers and the Investiuents. Chartered drcountanl. W. B. KEES, 23. QVLRN V r m o ~ l r 8 T R EKT F,.C. Mwclr 5th 1919 392 ANNUAL GENERAL MEETING . INCOME AND EXPENDITURE ACCOUN'l' IrLcomc . E .? . d . To Life Compositions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. Adinission Pees ....................................... .. Annunl Subscriptions-Roceived in advance. on account of 191s . . . . . . . . . . . . . . . . . . . . 139 3 4 .. during 191s .. l!17 .................... 4729 1 6 5 ..................... 392 0 0 .. . . . . .. 1916 and previous ............ G2 0 0 9 99 .. . . 5323 0 0 Arrears as per last Balance Sheet ........................ 400 0 0 Lexa atnnunt included in last year's Incoiue. being valuation of 4923 0 0 Add Arrears a t dato 191s. iG'70; 1917 and previous. €524. estimated to realise as per Balance Sheet .................. .I ... 460 0 0 .. Lady Subscrihers ..................... ._ ............... Dividends on 66730 Metropolitan Consolidated 34 per cent . Stock €1520 14s . 3d . Cardiff Corporation 3 per cent . Stock Investments :- ... .. El050 London and North Western Hailway 3 per cent . Debenture Stock ........................... .. &1400 India 24 per cent . Stock .................. .. E2400 Brktol Corporation 24 per cent . Debenture Stock .. $4341 Midland Railway 24 per cent . Prefmenca Stock &1200 Leeds Corporation 3 per cent .Debenture Stock ... .. $3500 Transvaal 3 per cent . Guaranteed Stock l923/53 .. €1200 North British Railway 3 per cent . Dhentura Stock ................................. .. €700 Canada 3& per cent . Stock 1930/50 . . . . . . . . . . . &5200 5 per cent . War Stock and War Bonds ......... .. Income Tax Recovered . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. Interest on Deposit Account .. ... .. .. ............................. li0 15 s 23 4 7 33 1 6 25 T 6 42 0 0 7s 7 2 26 2 0 31 10 0 25 18 1 2 0 0 t; 205 8 3 150 0 1 27 7 2 .. Publication Sales :-Journals ........................ Proceedings ..................... Collective Index .................. Library Catdoglie . . . . .. . . . . . . . . . . . . Atomic Weight Tables ............... Annnal Reports on Progress of Clienrktrg Memorial Lectiires . . . . . . . . . . . . . . Jubilee Voluines .................. .................. l7%8 6 0 . . . . . . . . . . . . . . . . . 2 4 6 .................. 33 1 7 2 .................. 1 1 9 . . . . . . . . . . . . . . . . . 10g .................. 245 9 6 .................. 3 1 1 . . . . . . . . . . . . . . . . . . 0 1 7 6 2015 8 0 Less Publishers' Commission ........................... 194 1 2 1 1 .. Proceeds of Advertisements in Journal ....................... €403 5 0 Lee8 Commission . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29 5 4 .. Miscellaneous Receipts ................................. .. Suharriptionx from other Societies ..........................Donations to Lihrary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5383 0 0 9 0 0 850 8 0 1S20 15 1 373 19 8 562 2'2 1 0 280 5 0 f10. 082 14 11 ANNUAL UENERAL MEETING . 393 Expenditure . J? 8 . d . E 1 . d . 'B) Expenees on account of Journal :-Salary of Editor. including Indexing Salary of Sub-Editor and Assistant Editorial Postages ............ Abstractors' Fees ............ Printing of Journal ........... Banding ..................... Printing of Advertisements ...... Wrappers and Addressing ...... Distribution of Journal ......... Authors' Copiea ............... Insurance of Stock ............ ... ... ... ... ... ... ... ... ... ... ... ......... ......... ......... .................. ......... ......... ......... ......... ......... ......... ............ ............ ............ ............ ............ ............ ............ ............ ............ ............ ............ .. Autlual Reports on the Progress of Chemistry .. Purchase of back nnmberg of JoiimRl .. List of Fellows . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .................. ........................ 620 n 0 250 0 0 21 1s 5 240 12 1 2750 8 3 S J 'L 6 164 13 2 . 4 5 4 398 19 4 111 11 1 14 11 8 46.59 1 10 460 '1 9 6 4 3 125 5 '2 .. Library Expenses :-Salary of Librarian and Assistant ........................... 3 i 1 17 0 Books and Periodicals ................................. 199 1 8 Binding .............................................42 4 6 613 3 2 .. Indexing for International Catalogue ............ ... .. Donation to internationul Commission oik'udiication OF Annual Thles of Constants and Numerical Data. Chemical. Physical and Teohno-logical ............................................. .. Donation to Board of ScientiRc Societies . . . . . . . . . . . . . . . . . . . . . . . . [Jalarv of Staff ... ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . War Bonus ....................................... Wages (CommisRionaire. Hoiisekeeper. and Charwornanj" ......... Coal and Lighting .................................... House Expemses and Repairs ........................... Furniture .......................................... Tea Expenses .......................................Insurances ....................................... Accountants"Charges ................................. Coinmisaion on Recovery of Income Tax ..................... Law COBtS .......................................... Miscellaneous Printing ................................. Stationery .......................................... POEtageS ........................................... Miscellaneous Expenses .............................. . Administrative Expeuses :-539 15 254 6 215 I n 61 IS 87 2 8 3 35 3 39 6 21 0 s 10 11) 10 129 4 129 17 10.5 19 34 11 30 0 0 1 0 0 0 5 5 u 0 7 0 1 4 0 7 6 0 0 0 6 4 8 2 . 1681 6 5 Ralance; being excess of Income over Expenditure carried to Balartce Sheet ............................................24S9 4 4 f10. 082 14 11 KESEARCH FUND INCOME AND EXPENDITURE ACCOUNT FOB THE YEAR Income. To Dividends on :- B 1. a. E 8 . d . SlonO North British Railway4 per cont. No. 1 Preference 84400 Metropolitan Consolidated 3) per cent. Stock ... 111 13 0 E.1034 Great Western Railway 2) per cent. Debenture Stock 10 1 3 El122 Metropolitan Water Board 3 per cent. “B” Stock 24 11 5 61365 Midland Rsilway 24 per cent. Debenture Stock ... 25 3 4 Stock ................................ 29 10 6 81152 16s. New South Wales 3 per cent. Stock... ...... 24 17 2 8808 Victoria 3 per cent. Stock .................. 17 10 7 E4498 11s. OJ. 5 per cent. War Loan ............... 217 0 0 469 7 3 Repayment of CQst of Apparatus .. . . . . . . . . . . . . . . . 712 0 s1 10 1 Income Tax Recovered . . . . . . . . . . . . . . . . . . . . . . 106 19 11 I Repayments of Research.Qrants . . . . . . . . . . . . . . . . . . By Grants . . . . . , Bankrrs’ Charges , Advertisements , Do. do. Commission on Recovery Longstaff Mednl Balance being carribd to Bslunce f665 9 ANNUAL GENERAL MEETING. 395 Although one disbursement (SlO) only was made in 1917 the balance of income over expenditure for 1918 is S539 13s. 9d. as against f.553 2s. Od. for the previous year. This is explained by an increase of &50 11s. 3d. in the proceeds from investments of &20 8s. 3d. in repayments of research grants and of $14 0s. 3d. in the amount of income-tax recovered. 2816 19s. 9d. Five Per Cent.War Loan was purchased for this account during 1918. A vote of thanks to the Auditors proposed by the TREASURER was seconded by Mr. R. G. DURRANT Dr. G. SENTER making acknowledgment. On the motion of Mr. W. BARLOW seconded by Mr. W. F. REID, a vote of thanks was proposed to the Treasurer Secretaries Foreign Secretary and Council for their services during the past year. Acknowledgment was made by Dr. F. L. PPMAN. The ballot was then declared closed. The PRESIDENT delivered his Address entitled (‘ Chemistry in the National Service.” A vote of thanks to the President for his services in the Chair and for his Address coupled with the request that he would allow the Address t o bs printed in the Transactions, was moved by Professor H. E. ARMSTRONG.Col. C. T. HEYCOCK seconded the motion which was carried with acclamation the PRESIDENT making brief acknowledgment. The report of the Scrutators was presented and the PRESIDENT announced that the following had been elected as Officers and Council for the ensuing year: President.-Sir James Johnston Dobbie M.A. D.Sc. F.R.S. IGce-Presidents who have filled the Oflice of President .-Henry Edward Armstrong Ph.D. LL.D. F.R.S. ; Alexander Crum Brown, D.Sc. LL.D. F.R.S.; Sir William Crookes O.M. D.Sc. F.R.S.; Sir James Dewar M.A. LL.D. F.R.S.; Harold Baily Dixon, C.B.E. M.A. Ph.D. F.R.S. ; Percy Faraday Frankland Ph.D., LL.D. F.R.S. ; Augustus George Vernon Harcourt M.A. D.C.L., F.R.S. ; William Odling M.A. M.B. F.R.S. ; William Henry Perkin Sc.D. LL.D. F.R.S. ; Sir William Jackson Pope,* K.B.E., M.A. D.Sc. F.R.S.; James Emerson Reynolds Sc.D. M.D., F.R.S. ; Alexander Scott M.A. D.S’c. F.R.S. ; Sir Edward Thorpe, C.B. LL.D. F.R.S.; Sir William Augustus Tilden D.Sc. LL.D., F.R.S. Vice-Presidents.-Frederick George Donnan M.A. Ph.D., F.R.S. ; Henry John Horstman Fenton M.A. Sc.D. F.R.S. ; Arthur Smithells C.M.G. F.R.S.; James Walker D.Sc. LL.D,, F.R.S. ; William Palmer Wynne D.Sc. F.R.S. ; Sydney Young, D.Sc. F.R.S 396 ANNUAL GENERAL MEETING. Treasz4rer.-Martin Onslow Forster D.Sc. Ph.D . F.R.S. Secretaries.-Samuel Smiles O.B.E. D.Sc. F.R.S. ; James Charleq Philip O.B.E. M.A. D.Sc. Ph.D. Foreign Secretary.-Arthur William Crossley C.M.G. D .Sc., F.R.S. Ordinarg Members of CozinciZ.-Julian Levett. Baker ; Alexander Findlay M.A. D.Sc. Ph.D. ; Francis Ernest Francis D.Sc. Ph.D. ; John Addyman ‘Gardner M.A. ; Arthur Harden D.Sc. Ph.D., F.R.S. ; Thomas Anderson Henry D.Sc. ; Charles Alexander Hill, B.Sc. ; James Colquhoun Irvine D.Sc. Ph.D. F.R.S. ; Charles Alexander Keane D.Sc. Ph.D. ; Robert Howson Pickard D.Sc., Ph.D. F.R.S.; Sir Robert Robertson K.B.E. M.A. D.Sc. F.R.S. ; Edward William Voelcker

ISSN:0368-1645    

DOI:10.1039/CT9191500384

出版商:RSC    

年代:1919

数据来源: RSC

摘要:

PRESIDENTIAL ADDRESS. Delivered a t the ANNUAL GENERAL MEETING March 27th 1919. By SIR WILLIAM J. POPE K.B.E. F.R.S. Cliernzstry in the National Service. SINCE the autumn of 1914 a great change has taken place in the public attitude towards the natural sciences and towards chemistry in particular. One of the recognised duties of the spokesmen of science during the past sixty years or more has been that of endeavouring t~ bring home to the general public and to its administrators the danger of neglecting the cultivation of pure and applied science. The eloquent discourses of our predecessors, Lyon Playfair Roscoe hleldola and the veterans happily still with us Tilden and Armstrong all past-presidents of our society, on the national importance of chemistry are well known to all of us but we cannot claim that these utkerances produced an effect compatible with their gravity.Recent events have however given a stimulus to the popular appreciation of the need for wider application to scientific investi-gation of all kinds which is incomparably greater than had been excited by the previous half-century of the spoken and written word. It may be useful a t the present time to consider a few of the causes for this change in public opinion partly because of the clarification of ideas which emerges from free discussion partly because of the desirability of recording certain facts and particulars which may be of value to future historians of the strenuous period now ending and giving place to another still more strenuous. A t this t h e four years ago an urgent call was made for the services in a military capacity of all the chemists who could be spared from civil life.Large numbers were taken into the Army and formed the nucleus of the magnificent Gas Warfare Service, which has been slowly but efficiently developed. Many of these colleagues of ours are now returning to their legitimate spheres in the industrial and scientific life of the Empire but many will not return; among those who have fallen I would refer more par-ticularly to one who is well known to most of us present for the Q 298 POPE CHEMISTRY IN THE NATIONAL SERVICE. invaluable services which he rendered on the defensive side of chmical warfare. Lieut.-Colonel Harrison was one of the great discoveries of the War and his death on the eve of the armistice was one of its many great tragedies; the protection against gas poison-ing which has been employed by our own and allied troops a pro-kction far more efficient than that ensured by the devices elabor-ated a t leisure by the Central Powers was due mainly to his wide knowledge great organising ability and unfailing resourcefulness in emergency.A movement for the establishment of a memorial to Colonel Harrison was set on foot by the Chemical Warfare Com-mittee of which he was the Controller a t the time of his death, and a considerable sum has been collected from those who had been associated with him in his work for the Services. The Chemical Warfare Committee have approached the Council of the Chemical Society and have offered under certain conditions to place a memorial tablet or other suitable permanent memorial in these rooms and also to establish under certain further conditions a trust fund to be held by the Society.The Council have with great. pleasure intimated their willingness to accept these gifts and one of the first duties of your new Council will be to decide how best to carry out the provisions of the trust deed. The efficiency of the British gas protection which called for the exhibition of so much sciehtific skill both in research and in manu-facture and led to its adoption by our Allies is one striking illwtration of the paramount importance of science which has appealed to the general public. This subject is however but a small branch of the enormous chemical problem which presented itself to the nation nearly five years ago and led t o the organisa-tion under Lord Moulton of the Department of Explosives Supplies.During the working out of this problem issues presented them-selves which are probably dissimilar from any that have ever arisen before. Thus as the magnitude of the struggle became gradually obvious, it was realised that the whole of the resources of the Empire would have to be utilised fully if success was to be attained. A census of all available chemical products had to be taken and schemes for their exploitation laid down; all materials had to be appor-tioned o u t in accordance with the principle that whatever was used for the manufacture of one particular war material left a corresponding shortage of raw material in connexion with the manufacture of some other and perhaps equally essential, product.The intricacy of gauging the chlorine output of the country of determining how to increase i t a t the rrlaximum rate without unduly disturbing other interests of apportioning i POPE CHEMISTRY IN THE NATlONAL SERVICE. 399 most advantageously for use as liquid chlorine and for the manu-facture of phosgene sulphur chloride carbon tetrachloride bleach-ing powder and many other war materials is such as would dis-arm criticism even i f the result had been failure instead of brilliant success This novel mode of presentment involving recognition of the principle that the Empire could only dispose of certain limited and measurable quantities of raw materials was but one of many fresh views which forced themselves upon a newly created Minis-terial Department.Labour fuel and transport had t o be discussed in an analogous manner. The cessation of hostilities found this country manufacturing, roughly 100,000 tons per annum of nitric acid and sulphur tri-oxide with an efficiency of about 93 and 91 per cent. respectively of that theoretically obtainable ; we were also making 60,000 tons of T.N.T. and 35,000 tons of cordite per annum. These produc-tions were for all practical purposes on a permanent basis and could have been continued indefinitely. The factories necessary for securing this huge production were erected by the Government, and for several reasons. First for economy in production. In spite of the large initial cost of installation and including rapid amortisa-tion the national production of cordite was better in quality than, and of approximately one-half the cost of that imported from America.Secondly for certainty of supply which could be ensured only by a home production not subject t o the risks of over-sea transport. With this necessity for gigantic production the urgency for economy in manufacture necessarily went hand in hand. One of the most interesting documents .of the war is the second report on costs and efficiencies for H.M. factories controlled by the Depart-ment of Explosives Supplies which has been recently issued. This report contains a minute analysis of the working costs for each period of each factory engaged on individual items of manufacture ; i t states what proportion of the cost per ton of product is borne by labour raw materials fuel maintenance etc.and provides an incitement to further effort towards economy of working by giving a ‘(bogey” cost sheet made up of the most efficient details of cost selected from the complete analysis of expenses. It will be clear that an immense amount of organising power was required to achieve this stupendous result; it was due largely to the genius and energy of Mr. K. B. Quinan. It must be remembered however that this permanent memorial to British chemical activity in production was rendered possible only by the intense effort of the army of chemists and engineers enlisted under the command of Lord Moulton. The necessity for Q* 400 POPE OHEMISTRY IN THE NATIONAL SBRVIOE.utilising all the chemical resources of the country to the utmost led in direct relationship with the census of raw materials pre-viously mentio’ned t o the attempt to extract the last possible frac-tion of efficiency in each component prmss. The huge production just indicated made i t very profitable to carry out a vast amount of careful scientific investigation of details of manufacture ; so many Fellows of this Society devoted their best efforts to this work that i t would be invidious to mention names. Our colleagues have had ample opportunity to realise that the romance of war is now t o be found in the laboratory the workshop and the factory quite as much as on the battlefield. An instsuctive example of the operations of the struggle €or economy in the production of a given effect is found in the rivalry which arose between picric acid and ammonium nitrate for use as high explosives.Picric acid costs about 2,185 per ton to make, ammonium nitrate about X50 and T.N.T. about 3100 per ton; the high cost of picric acid rnmns of course limited production. A mixt8ure of 80 parts of ammonium nitrate with 20 parts of T.N.T., known as amatol was introduced early by the Research Department a t Woolwich as beiiig about 5 per cent. more powerful as a high explosive less “brisant,” and more difficult to detonate and of course far less costly to manufacture. The course of the war has been marked by continued progress a t the hands of our research chemists in the preparation and applications of amatol; the grow-ing appreciation of the merits of this material led t o the discon-tinuance of the manufacture of picric acid in this country last summer to the adoption of amatctl in place of picric acid as &he American standard high explosive to the approaching elimination of picric acid from the Italian military programme and to the replacement in the main of picric acid by amatol in the French service.A very pertinent question arises in connexion with the fact that our production of the chemical materials needed for a great European war was negligibly small in 1914 and has gradually attained satisfactory dimensions. We know that the great chemical factories of Central Europe could divert their peace production of chemical products to a war output a t very short notice.None of these huge installations requires much time for the design and con-struction of chemical plant for new purposes; all possess a series of standard items of equipment which oan be fitted togehher rapidly to form a piece of plant capable of use for throwing any ordinary laboratory operation into large-scale practice. Stills condensers, pressure vessels filter prwses cooling arrangements of coils an POPE CHEMISTRY IN THE NATlONAL SERVICE. 401 the like are available in standard sizes and with standard fittings in such a manner that the installation on a works scale of a labora-tory operation is deprived of its most formidable difficulties. The question which demands an answer is why when the German works were in existence and could attain a war production so quickly, were the Allied nations given time to gradually develop their war production of explosives noxious materials etc.from nothing ? The question is best answered by an example. I n July 1917 the Germans first used against the Allies a new offensive material fib-dichloroethyl sulphide (CH2C1*CH,),S and with very great success. This substance the so-called " mustard gas," has but little d o u r and exposure to it causes comparatively few fatalities; inhalation of or contact with its vapour gives rise to acute pneumonia to the production of painful sores and to temporary or even permanent blindness. Whilst as has been stated the actual mortality is low and the use of the substance may to this extent be described as humane the casualties produced are very numerous; slight exposure to a material so toxic and so difficult to detect leads in general to six weeks in hospital.The preparation of Bp-dichlorwthyl sulphide was described by Victor Meyer in 1886 and involved the several operations indicated by the following set of equations: (1) CH2:CH2 + HClO = CH,Cl*CH,*O€I. (2) 2CH,Cl*CH,*OH + Na,S = (HO*CH,*CH,),S + 2NaC1. (3) (HO*CH2*C'H2),S + 2HC1= (CHZC1*CH2),S + 2H20. When i t is realised that operation No. 1 is difficult and that the products of reactions (1) and (2) are soluble in water it will be undershod that no small difficulties must presentl themselves in the manufacture of pj3-dichloroethyl sulphide by this process on a large scale. The examination of the German product made it quite clear however that the process of manufacture adopted was that indicated by the above set of equations; the over-all yield of pro-duct is perha'ps 40 to 60 per cent.of the theoretical. I n view of the difficulties of manufacture itt was fairly certain that no chemical installation for its production could be established under the control of the Allies within any reasonable time; the Central Nations thus supposed that they held the monopoly of a very powerful instrument of war. Most British organic chemists were I think +mazed a t the method of production adopted by the German manufacturers ; to apply such a technically cumbrous process for the manufacture of so simple a compound seemed quite irrational. By the end o 402 POPE CHEMISTRY IN THE NATIONAL SERVIUE.January 1918 a process for making SS-dichloroethyl sulphide had been worked out in the British laboratories which consisted of the reaction expressed by the following equation : 2CH2:CH,+ S2c12 = (CH2Cl.CH2),S + S; the yield obtained in the laboratory was 98 to 99 per cent. of that theoretically possible. The new method was communicated t o France and America and installed by the three Great Allies on a large scale; a t the conclusion of the armistice the available daily production of mustard gas by the Allies was equal to t.he monthly production of the Central Nat,ions. The German chemical service was inefficient ; the scientific chemists under its control were incompetent. The Allied production of mustard gas had a potentiality of the order of thirty times as great as that of the German; the cost of the German material was of the order of thirty times as great as that of our product.Cost of production under the conditions pre-vailing for this particular material means in the end expenditure in labour; that we were able to produce a t something of the order of one-thirtieth of the cost of the German production means that by the allocation of the same quantity of raw materials we could secure thirty t’imes the output. The relative strain on the pro-ductive resources of the Allies and the Central Nations caused by a demand for a certain quantity of “mustard gas” is measured roughly by the indicated ratio of one to thirty. Whilst many instances similar to that of mustard gas might be quoted to show that Germany has been badly served by her scien-tific men during the war i t would be difficult to overrate the effects of the skill and perseverance exhibited by the German chemical manufacturer.The command of great and long-established factories for fine chemical manufacture enabled the Geman technologist to throw faulty academic projecte rapidly into large-scale production ; the cost namely the strain on national resources, was enormous but that an output could have been achieved is a significant tribute to the potentialities represented by the large German fine chemical factories. Both in Britain and Germany production in chemical manufacture has been multiplied during the war but necessarily in a different manner. Our large produc-tion is almost entirely of war importance and most of the works installed during the war must now be dismantled as a result of ths cessation of hostilities ; the German expansions on the sother hand, constitute a permanent addition to the potentialities of peace manu-facture of staple marketable products.The war has left Germany The answer to the question just put is now available POPE CHEMISTRY IN THE NATIONAL SERVICE. 403 with vastly increased resources as a manufacturer of much needed chemical products. The view that our country is superior to Germany in the posses-sion of creative scientific power has always been maintained in modern times by students of philosophy and history; the correcb ness of the view has been amply demonstrated during the last four years. Whilst our nation has overcome its initial handicap by a continuous flow of novel scientific devices of military value our enemies passed through the war with little more in the shape of novel effects than those laboriously elaborated during the preceding years of peace.The more brilliant position which Germany has so long held in applied science arose from the keen appreciation ex-hibited by German public and official authorities of the rich economic fruits to be reaped from the systematic exploitation of scientific industry as compared with the neglect of scientific effort shown by corresponding classes in this country. Even yet but small encouragement exists for those who desire to see pure and applied science flourish as i t deserves in Great Britain; although it may be long before the scientific industriea of Central Europe regain their former predominance there seems but little prospect of sufficient official encouragement being given in this country to scientific and industrial initiative to ensure our position in the competition with other nations.I n this connexion it is interesting to notice what is happening in the United States. Immediately after her entry into the war America initiated a census of chemists and in July 1917 a fully detailed description was available of some 15,000 chemists resident in the States; a research staff consisting of 1200 technical men with appropriate assistance was enlisted for the Research Division of the Chemical Warfare Service alone. Since America was only in the war for about eighteen months this powerful organisation had not time to make its efforts properly felt.Apart from small improve-ments or changes in detail practically all the American chemical equipment both for offence and defence was manufactured on the detailed plans furnished by Great Britain or France; the available time was too short to allow full play to American genius f o r novelty and for magnitude of production. The necessity for co-operation brought large numbers of young and active American chemical officers to Europe; i t gave those officers f o r eighteen months the entry to practically every chemical works of importance in England and France and unrivalled opportunities for accurately judging European chemical methods and markets. These men have now returned to their ordinary scientific and technical pursuits in the States and it cannot be expected that they have left behind the 404 POPE CHEMISTRY IN THE NATIONAL SERVICE.the unique experience which they have gained of European condi-tions. We may anticipate that competition in pure and applied chemistry between Europe and America will become increasingly keener during the years to come. The competition is already iiitense and gives little promise as yet of turning in our favour; it is in fact difficult t o see ’how many of the staple products of fine chemical manufacture can hold their own in Great Britain against American competition under the conditions which a r m during the first three years of the war. During these years peace production flourished in the States free from Government control whilst in this country the establishment of a fine chemical industry in war time was naturally rendered far more difficult by State control of works materials and labour.The bearing of this may be made clear by an instance. The manufacture of “saccharin” was in-stalled in England after the outbreak of war but the production was controlled in that the manufacturers were only permitted to sell a t a profit of 10 per cent’. on the cost this profit being in turn subject to the excess profits tax; further to prevent the economic difficulties which were foreseen if “ saccharin ” competed with sugar the price of English-made ‘(saccharin” was fixed a t a figure which involved the very large addition of thirty shillings per pound to the price this addition being appropriated by the Government.Simultaneously, ‘(saccharin” was manufactured free of all control in the States; it came into this country unrestricted and on such terms that tlie American producer took the thirty shillings per pound just men-tioned in addition to the considerable profit previously made by reason of lower cost of manufacture. America having thus been assisted by our Government to build u p a large reserve of profits is now actually selling “ saccharin ” in England at eleven shillings per pound-a price a t which it cannot be produced here-apparently with the legitimate trade purpose of destroying the English manu-facture and subsequently running up the price. Many cases may be quoted as closely analogous to that of ‘(sac-charin,” notably in connexion with acetic acid glycerol acetone and methyl alcohol and their products in which British procedure has facilitated profiteering in foreign countries during the war.The excess profib tax operated insidiously in tempting British manufac-turers to keep prices high so as to retain a margin with which t o write off capital expenditure in spite of the tax; the foreign coma petitor free from Government control of raw materials and exempt from the excws profits tax was able to take full advantage of the ruling high rates. It will be of interest to see how the problems introduced by these actual occurrences are to be solved advantage POPE CHEMISTRY IN THE NATIONAL SERVIUE. 405 ously for Great Britain in the great reconstruction upon whiah our administrators are now engaged.Sufficient has probably now been said in justification of the rapid appreciation of science and especially of that branch of science with which we are particularly concerned in the public and administrative eye. The sudden incidence of new scientific modes of military and naval attack and the quick improvisation and development of equally scientific means of reply both of which have been so frequently exhibited during the past five years must have seemed uncanny to the lay observer who only realised the effects but did not understand the causes. A t the present time however most Fellows of this Society have little leisure to reflect on the ghastly tragedy in which it has been our privilege to assist; the curtain has fallen upon this but is rising again on the greatest epoch in the history of the world.The coming struggle for scientific and industrial position on the results of which must rest the whole intellectual artietic and material future of our race will call for longer greater more persistent and more intelligent effort than any which we have hitherto exerted. We are forced to consider whether we have reason to hope that the recent lessons have been well brought home and whether the free play given to scientific creation and production during the last five years is to persist unhampered in the future. For purposes of war our administrators gave every incentive to scientific investigation; money men and material were provided for the asking free from Treasury control free in fact from all control other than that of the scientific worker able and willing to organise and execute a necessary piece of work.I see no reason to think that the lesson has been properly learnt and every reason to anticipate a re-establishment of that parsimoni-ous treatment of scientific effort which seems now to belong to a past age but with which we were all’well acquainted five years ago. m e control of scientific research is again leaving the hands of the scientific man and being resumed by the lay administrator. The old remark has been resuscitated quite recently that “it is a common-place among administrators to fear the expert.” The non-technical administrator has no means of distinguishing the expert from the charlatan; he has perforce to regard the scientific expert as the lineal descendant of the “adept” of alchemical times whose claim to recollection is based upon tho adroitness with which he was able to divert public funds to his own base purposes.It is quite clear that if scientific research is to be assisted by the State-and unless so aided it will languish and carry with it into decadence every activity of the E m p i r e i t must be adminis 406 POPE CIHEMISTRY IN THE NATIONAL SERVICE. tered by men of scientific training and eminence; any other mode of procedure will necessarily lead to the strangulation of scientific effort by departmental red-tape. In this connexion it is again instructive to refer to American practise ; our blood-relatives across the Atlantic had three years in which to study in peace the efforts which we were making in war and it cannot but be useful to observe the manner in which they propose to profit by our experi-ence.In 1916 President Wilson a University professor and an expert, now one of the most imposing figures in terrestrial affairs called upon the National Academy of Sciences a t Washington to nomin-ate the members of a " National Research Council " ; the object of this new organisation was stated to be that of co-ordinating the scientific work of the country in order that the scientific problems both of war and of peace might be more efficiently solved. T h e National Research Council is under the presidency of one of the most eminent among the active American men of science Professor George E.Hale of the Mount Wilson Observatory and has large funds a t its command for research purposes. Two points are con-spicuous in connexion with the American programme first the substitution of the professional lay administrator by the ordinary office staff; secondly the recognition of the close interdependence of pure and applied science. The contention which has long been advanced in this country that an adequate output of purely aca-demic chemical research work and the existence of a flourishing, fine chemical industry are mutually essential is here tacitly ac-cepted; the former seeks in the industries remunerative positions for the products of its training and the fine chemical industry looks b the scientific investigator for inspiration and new' directions for enterprise.The nation which possesses an extensive organic chemi-cal industry controls chemical warfare the production of pharma-ceutical and photographic products the textile industry and many other great departments of 'human activity. The operations of the great American organisation for the stimu-lation of scientific research work are already making themselves felt. They have produced just recently an entirely novel method for oxidising naphthalene to phthalic acid presumably by the use of atmospheric oxygen and a catalyst which gives a 95 per cent. yield, and are responsible for the huge nitrogen fixation scheme now under installation in the Stafes. These two illustrations alone the one small and the other large leave us in no doubt as to the influence which the National Research Council is destined to exert on scien-tific and technical progress throughout the world.If British science is to make itself adequately felt in the grea POPE CHXMISTRY IN TRE NATIONAL SERVICE. 407 intellectual and material advances of the near future British men of science must be entrusted with the initiative power and t b com-mand of money which they have enjoyed during the past few years; unless this is done our Empire will as before continue to fall behind other great nations as a contributor to the increasing mass of pure and applied scientific knowledge. I n an address which I had the honour of delivering in this room a year ago attention was called to the necessity for closer co-opera-tion between the large Societies representing the various chemical interests in Great Britain.During the past year action has been taken in this matter and some fifteen of the Societies have colla-borated in the establishment of a Federal Council for Pure and Applied Chemistry the functions of which is t o advance safe-guard and voice the interests of chemical science. The Federal Council consists of representatives nominated by the component bodim and is already occupying itself actively with the questions within its purview; it has moved with some success in connexion \ v i a the claims of experimental science to recognition in the recently established scheme for eduoation within the Army with the provision of fine chemicals for research purposes with the remuneration of scientific posts and with other matters. The Federal Council will continue t o apply itself to those questions which are of importance to chemists as a class leaving more specific chemical interests to be dealt with by the appropriate constituent societies. A very similar project for the consolidation of the larger chemical interests is in couwe of execution by our French col-leagues. It is beyond question that a central h o w for accommodating the chemical societies in a manner more proportionate t o their import-ance than is a t present possible should be provided that a common chemical library far more complete than any now available in this country should be a t our service and that some comprehensive scheme for the publication of compendia of chemical knowledge should be put into operation. A very imposing and costly pro-gramme confronts the recent amalgamation of chemical interests, but the universal approval which greeted the proposition for creating a Federal Council for Pure and Applied Chemistry is a happy augury for the future usefulness of the new organisation

ISSN:0368-1645    

DOI:10.1039/CT9191500397

出版商:RSC    

年代:1919

数据来源: RSC

摘要:

OBITUARY NOTICES. JOHN PERCY BATEY. BORN MARCH 22ND 1889; ICILLED IN ACTION APRIL gTH 1918. J@m PERCY BATEY M.Sc.(Tech.) was educated a t the Manchester Municipal Secondary School where he was awarded a three years’ scholarship to the Mancliester School of Technology. He took the degree of B.Sc.(Tech.) in 1908 when nineteen years of age and was also awarded the Schuster Research Scholarship. Twelve months later he was made M.Sc.(Tecli.). For a time he was lecturer and demonstrator and in 1911 he became assistant to Dr. Liebmann of Weybridge where1 he remained until he enlisted in January 1915. He joined the Public Schools Battalion the Middlesex Regiment, transferring later to the Royal Engineers and went to France in August 1915. He was promoted to the rank of Company Sergt.-Major in September 1916.I n 1917 he was awarded the Belgian Croix de Guerre and in 1918 the D.C.M. With regard t o the D.C.M. the Gazette published ths follow-ing : “He volunteered on no less than eleven times in one month to conduct parties carrying rations and supplies over a very much exposed area that was being heavily shelled by the enemy to gun emplacements in the front line. The fine example of courage and devotion t o duty of this warrant officer had an excellent effect on the N.C.O.’s and men of his company.” F. B. LIEUT. CHARLES WILLIAM DICK. BORN APRIL ~OTH 1895; DIED ON SERVICE NOVEMBER ~ T H 1918. LIEUT. CHARLES WILLIAM DICK R.A.F. died of pneumonia on November 9th last in Cliff Military Hospital Felixstowe. Mr. Dick, who was the younger son of the late Mr.J. Dick schoolmaster, North Shields took 1st Class Honours in his Inter B.Sc.(London) 011 leaving Rutherford College Newcastle-on-Tyne in June 1912 OBITUARY NOTICES. 409 arid in the autumn of the same year gained an open science scholar-ship a t Cambridge University and became a scholar of Trinity Hall in the autumn of 1913. €10 passed his final for the B.Sc.(Lond.) iii 1914 and on completing two years’ residence he postponed further study to become a chemist a t Messrs. Curtiss’ and Harvey’s explosives works a t Cliffe near Chatham and whilst there was elected a Fellow in 1917. H e joined the Meteorological Section of the R.N.V.R. in April 1918 and after completing his training was appointed meteorological officer a t Felixstowe Air Station and on the creation of the R.A.F.wits transferred to its establishment in August 1918. J. E. D. JAMES HECTOR BARNES D.Sc. BORN 1879; DIED 1917. ‘‘ I AM sorry t o say I have been in very poor health all the summer and had to take six weBks’ leave in Kashmir this autumn; it was no holiday however for I spent four weeks of it in bed with an irregular pulse-the old story of India malaria and the doctors say overwork. I hope t o come home next summer f o r I do not think I can stand another Indian summer here without first having it rest in a decent climate. I shall look you up then and I hope you will be kind and put me in the way of being useful while a t home on leave as I really cannot idle about.” These extracts am from a letter dated November 30th 1916, received from Hector sBarnes.He did not come home and his prophecy was fulfilled; h0 did not stand another Indian summer but a t the age of thirty-eight in the fullness of his intel-lectual powers with high hopes and with great opportunities open-ing before him he died in India. It is difficult indeed to write any adequate record of the worth and work of such a man. The scien-tific work which he acconiplished had it been carried out in the most favourable environment was such as any chemist might be proud t o have to his name. But it was carried out under condi-tions which would only be met by a man of heroic temperament. Such a man Barnes in truth was. In the plains of Northern India a t Lyallpur a remote station, on lan’d recently transformed from a sterile desert into a luxuriant agricultural colony by the marvellous system of Indian irrigation, Barnes betook himself in 1906.Born in 1879 he had received his scientific training a t the University of Birminzham where h 41 0 OBITUARY NOTICES. studied chemistry and physics under Professors Frankland and Poynting and graduated B.Sc. He had previously been appren-ticed t o Messrs. Southall and Barclay pharmaceutical chemists and the experience of the practical conditions of manufacturing opera-tions which he there acquired no doubt added greatly to his equip-ment for the work that was in store for him. A t Lyallpur he held the position of agricultural chemist to the Punjab Government and professor of chemistry in the Agricultural College then a t the stage of inception.He threw himself wholeheartedly into the work of designing the chemical laboratories and in 1908 his responsibilities were increased by his appoint’ment as Principal of the College. A year later the College was open for the reception of students. There was an immediate response as there is t o every new educational enterprise in India; but when it was found that the College was not as it was expected to be a certain path to Government service, the numbers fell with great rapidity and any belief that there was widespread zeta1 among neighbouring landowners for agricultural science could not be sustained. Barnes however had cherished no illusions and he knew from the first that the foundation on which he must build was sound scientific research addressed as directly as possible to vital questions of Indian agriculture and to this he and his colleagues bent their energies.It is not easy to give an idea of whht that meant. The physical obstacles imposed by tlie climate and ever-recurrent sickness the isolation from the scientific world and from the meagre supplies of apparatus anywhere avail-able in India-these alone might daunt a strong man. Add thereto, only in a more intense form what we have in England-Govern-ment officials in authority whose ‘‘ humanisation ” has precluded the slightest knowledge of what science is what it does and how i t can be applied t o do ‘more-and it may be understood that it is only the very exceptional man who can succeed. This Barnes did in the most colnspicuous degree.Standing in the laboratories a t Lyallpur after some hours’ journey from Lahore through great tracts of solitude and finding apparently all the resources of a European university science department and men busily engaged in employing the experimental methods of modern physical chemistry in the elucidation of fundamental problems in agriculture the greatness of the achievement was very striking to the imagination. Within a stone’s throw were the mud walls of an Indian village with its population living unchanged in the beliefs the thoughts the habits of life and work that belong to distant centuries of the past. The chief lines of work on which Barnes was engaged were salt lands and their reclamation ; seepage and the rising of ground water OBITUARY NOTICES.41 1 level under irrigation conditions ; the sugar cane and the sugar in-dustry in the Punjab; the intensihy of solar radiation; the Kangra tea industry; the chemical aspect of wwvil attacks upon wheat. It is to be feared that his published papers and records will g v e no adequate idea of the comprehensive plans which he had in his mind in relation to the elucidation of these problems. He talked of them eagerly and in the most interesting way showing a t once his wund knowledge of fundamental science and his appreciation of practical conditions. He had erected a workshop and turned out from it many of the fine tools required in his work and his laboratory rriethods exhibited the play of great experimental skill and resource. Space does not admit of any extended account of these investiga-tions but a little more may be said of one of them.On ’his last visit to Lyallpur in 1914 the writer was taken by Barnes to Narwala. This spot is twelve miles distant from Lyallpur and is or was, infertile salt-land that is land which owing to triumph of evapora-tion over rainfall has become impregnated with a variety of salts, carbonates chlorides and sulphates especially of sodium calcium, and magnesium evident as a crust of “white alkali” or “black alkali ” upon the soil. This condition of soil has been the subject of much study in America but Barnes believed that t h e work had “ failed to prove useful and practical for want of a better knowledge of the scientific principles of the causes of sterility. If such causes had bsen first investigated time and money would have been saved, and in the end tihe practical result would as it always does justify the scientist.” Accordingly Barnes set himself t o study as closely as possible the physical chemical and biological aspects of the problem.Having satisfied himself of the principles involved he applied himself to the practical problem of redeeming the land a t Narwala and a t the time of the visit referred to a tract of infertile land was being mole drilled. Leaving fields where the leisurely ryot was urging his bullock t o pull the wooden plough and gently scratch the surface soil one passed to the Narwala tract where a Yorkshire artisan was found in contest doubly bitter to him by the futility of his native tongue with native inaptitude in dealing with a steamdriven mechanical monster from Leeds.The plan was to mole drain the land and then irrigate out so much of the salts as was shown by Barnes’s biological methods to be necessary. The results of this trial were extraordinarily SuccessfuI and it is scarcely possible to believe that the luxuriant crops (of which photographs afterwards arrived) can have been grown on what was just before the war a stricken desert. Barnes in the end estimated that the system of reclamation would pay between 300 and 400 per cent. on the capital outlay and its general application would of course ad 412 OBtTUARY millions to the wealth of India. the system to non-irrigated areas the subsoil. I n 1914 Barnes married Nora NOTICES. He was proposing also to apply by the use of water pumped from daughter of the late Colonel Francis Thomas Steven Indian Army.As soon as the war began he bestirred himself to bring into action all the scientific and material resources that India could supply but i t is impossible a t present to quote his important observations on this subject. Shortly before his death Barnes not without some reluctance on his part left Lyallpur to take up at Pusa the post of chief agricul-tural chemist to the Government of India. What he might have accomplished from there it is idle to conjecture but the thought, of i t only deepens the sense of calamity both to India and to Science that surrounds his untimely death. When the writer first saw him he had just come from among his students in the playing fields and was in football attire a splendid figure of a man eager resolute honest and kindly.He was beloved by 'his students and colleagues and respected by everyone. I n summing up his qualities in our mind it is impossible not to be struck with the strength and number of endowments that are needed to produce the type of man who; is to be the true pioneer of progress in India-endowment of body mind and spirit. Happily such pioneers have been found in the past. They will long be needed in the future of India and it is difficult to think of any better service to mankind than is open there to those who can bring themselves to the standards that ruled the life and work of Hector Barnes. A t Lyallpur his portrait and an annual prize have been set up to preserve his memory and shortly before his death he was made a Doctor of Science of his University of Birmingham.His work and influence will endure in many fields and many hearts. Barnes was every inch a man and an Englishman. A. S. GEORGE CAREY FOSTER. BORN 1835; DIED FEBRUAWY ~ T H 1919. IN the death of Professor Carey Foster in his eighty-fourt,h year on February 9th there are many who will feel the loss of a kind and generous friend to whose gentle sympathy and encouragement much of the happiness as well as much of the success of their own lives has been due. A man of extreme modesty and of hig OBITUARY NOTICES. 413 if not commandiiig ability Carey Foster had made few direct con-tributions to scientific literature ; but the soundness of his judgment his almost passionate love of exact knowledge and his enthusiasm earned the respect of all and made his presence invalu-able on the many committees of learned societies the British Association and the various university boards of which he became a member.An extreme diffidence and a nervous shyness that was not without a peculiar charm to those who came to know him well as well as a hesitation to express a definite opinion on subjects on which he did not feel on the firmest ground made it easy to undervalue the services he rendered to science and education during the course of a long and active life. George Carey Foster was t-he only son of George Foster a calico printer and a Justice of the Peace for Lancashire and the West Riding of Yorkshire and was born a t Sabden in Lanca-shire in 1835.After an early education a t private schools he entered as a student gt University College London where his studies were a t first mainly directed to chemistry. He graduated in Honours and with a prize in chemistry in his twentieth year, and acted for some years as chemical assistant t o Professor Alexander Williamson who had then occupied the Chair of Chein-istry for six years and a warm attachment and regard sprang up between the two men. He left England in 1858 and spent some years in study a t the foreign Universities of Ghent where he was a student under Auguste KekulB a t Paris and a t Heidelberg. A t this time however while he continued his chemical studies, his interest became more and more directed to physical science, which was then assuming a position of increasing importance through the work of such men as Clausius Lord Kelvin and Clerk Maxwell and it was natural that the refined accuracy of physical measurements and the readiness which they admitted of mathe-matical treatment should have presented a strong attraction to a man of his type of mind.The first evidence of his new interest was the appearance in 1863 of two articles on ‘‘ Heat” in the first edition of Watts’s ‘‘ Dictionary of Chemistry.” These articles, extending together t o more than 150 pages of closely printed matter formed an admirably concise and critical statement of the position of an important branch of science and a t once established Carey Foster’s reputation as a clear thinker and able exponent of physics.I n the meantime in 1862 Carey Foster had accepted an invita-tion to assume the duties of professor of natural philosophy at, the Andersoniaii University alasgow and in 1865 he was encouraged by his friend and former teacher Williamson t 414 OBITUARY NOTICES. become a candidate for the vacant professorship of experimental physics a t University College. His elecfon was mainly due to the high reputation he had established as the author of the articles in Watts’s Dictionary and in October 1865 he entered on his career a t the London College of which he was elected a fellow in 1867 and with which his name will always be associated. He resigned his professorship in 1898 a t the age of sixty-three but was recalled to act as principal of the college for a period of four years from 1900 during a critical time in its history.The last years of his life were spent in the quiet and refinement of a country life on a small estate a t Rickmansworth although until quite near the end he was always ready to place his services a t the disposal of the educational causes that had been so near his heart in former times. He became a Justice of the Peace for Hertford-shire and took an interest in politics in which he was a supporter of the Liberal Party. Towards the end of 1917 after the death .of his wife he began to feel the weight of advancing years but up to within two weeks of his death he was a t work on manu-scripts submitted to him for publication in the Philosophical Magazine. At the end of January of the present year he had a slight abtack of congestion of the lungs which his heart was not strong enough to resist and after gradually becoming weaker he passed away in the presence of his children on February 9th.Carey Foster’s contributions to chemistry were published between 1857 and 1867. The writer who is profoundly ignorant in chemical matters is indebted to his friend Dr. Forster Morley for the following summary of these researches. Dr. Morley was engaged in several physical researches under the direction of Carey Foster while a student a t University College and was intimately acquainted with him during the remainder of his life. “The first paper by Carey Foster appeared in the notes and abstracts appended to the British. Associatiop Reports for 1857.It is entitled On suggestions towards a more systematic nomen-clature for organic bodies.’ Gerhardt having introduced the term lzomoEogous ta denote that two carbon compounds differed in their formulae by CH or a multiple thereof Foster now proposed a new adjective isolugous t.o indicate a difference of H or a multiple of H,. This adjective is still employed to denote the difference. He further suggested words composed of two Greek numerals the first of which related to homology and the second to isology. Thus dcutbtic would mean ‘belonging to the second homologous series and the third isologous series.’ This suggestion together with many other ingenious proposals for new nomenclature did not receive support from other writer OBITUARY NOTICES.416 “ I n 1859 Carey Foster presented a preliminary report to the British Associat?on ‘On the Recent Progress and Present State of Organic Chemistry’ (Rep. Brit. Assoc. 1859 1). This was a review of recent work particularly from the point of view of the development of ideas about formulae. “ I n the Chemical Society’s Quarterly Journal (1860 13 235) we find a paper ‘On Acetoxybenzamic an Isomer of Hippuric Acid,’ by G. C. Foster. It is dated Ghent 1860 and is an account of a very careful piece of work carried out under the direction of Pro-f essor KekulB and describes the first preparation of m-acetylamino-benzoic acid which is shown to be related to hippuric acid from which it might in imagination be derived by an interchange between the radicles of benzoic and acetic acids.“ A paper published in 1861 ‘ On Piperic and Hydropiperic Acids ’ appeared in the Chemical Society’s Journal (1862 15 17; also in Rep. Brit. Assoc. 1861 78 and BmaZen 1862 124 115). I n this it is shown that piperic acid C1&1004 is reduced to hydro-piperic acid Cl,Hl,O, and a large number of the salts of the labter are described. “ The post important chemical work carried out by Carey Foster is contained in three papers published in conjunction with Matthiesen. The first is entitled ‘ Preliminary Notice of Researches into the Chemical Constitution of Narcotine,’ and was read before the1 Royal Society in 1860 (PTOC. Roy. Soc. 1861 ii, 55; Phil. Mag. 1861 [iv] 22 398). I n this the authors establish the formula C,,H,O,N for narcotine and show that this alkaloid gives off methyl iodide when heated with hydriodic acid.The oxidation of narcotine to opianic acid is discussed and the formula for opianic acid C10H1005 correctly determined. It is also shown that on heating with concentrated potash opianic acid can be neatly split up into meconin and hemipic acid. A new acid, cotarnic acid was obtained by the gentle oxidation of cotarnine. “The second paper on this subject entitled ‘Research& into the Chemical Constitution of Narcotine and of its Products of Decom-position,’ was published in 1863 (Phil. Trans. 1863 345; an abridgment is given in J. Chem. Soc. 1863 16 342). The authors here describe how by acting on hemipic acid with hydr-iodic acid an acid C7HF04 which they call ‘hypogallic acid,’ but which is now known as probcatechuic acid is obtained.As an intermediate product they isolated methylhypogallic acid,’ now called ‘ isovaleric acid .’ “The third paper is entitled ‘Researches into the Chemical Con-stitution of Narcotine and its Produch of Decomposition Part 11,’ and was read before the Royal Society in 1867 (Proc. Roy 416 OBITUARY NOTIOES. Soc. 16 39; J . Clhem. SOC. 1868 21 357). It is shown that opianic acid when heated wit4h hydrochloric or hydriodic acid, forms methyl chloride or iodide and a new acid ‘ methylnoropianic acid,’ C,H,O,. Thus opianic acid may be called dimethyl-noropianic acid. Methylnoropianic acid yields with nitric acid nitromethylnoropianic acid. Meconin on heating to looo with concentrated hydrochloric or hydriodic acid yields methyl chloride or iodide and methylnormeconic acid or rather methyl-normeconin C,H,O,.By similar means narcotine can be con-verted into methylnornarcotine C,,H,,O,N. “ These three papers by Foster and Matkhiessen made a long step forward in the knowledge of the constitution of the alkaloids and may indeed be termed classical. The accuracy of the work has been amply confirmed by subsequent investigation. “While this work was in progress Carey Foster published two papers entitled ‘On Chemical Nomenclature and chiefly on the Use of the Word Acid.’ Both appeared in 1865 (Phil. Mag. [iv], 29 262; 30 57). I n these he protests against t.he word acid being used to denote’ an oxide and recommends that SO,.be called sulphurous oxide SO sulphuric oxide and C,H,O acetic oxide.“ I n 1869 Carey Foster took part in a discussion on the atomic theory held a t the Chemical Society the subject having been introduced in a lecture by Professor A. W. Williamson. An account of the discussion will be found in the Chemical Society’s Journal for 1869. “Carey Foster’s work in chemistry shows that if he had decided to devote himself to‘ that science he would have taken a dis-tinguished position among his colleagues. He was a member of the Council of the Chemical Society from 1865 to 1868 again from 1872 to 1875 and again from 1885 to 1886 and Viice-Presi-dent from 1888 to 1890. His Fellowship of the Society dates from 1856.” During the early years a t University College Carey Foster made a number of contributions of niinor interest to scientific journals, but his first important paper “On a Modified Form of Wheat-stone’s Bridge and Methods of measuring Small Resistances,” was read before a meeting of the Society of Telegraph Engineers in 1872 (Telegraph Engitieed Joicrnal 1872-1873 1 196).Previous to this date Wheat-stone’s bridge had provided electricians with a convenient and fairly accurate method for comparing resistances and as is well known the result of the experiment expresses the ratio of one resistance to the ot,her. Carey Foster OBITUARY NOTICES. 417 however so modified the bridge method that the difference between instead of the ratio of the resistances was determined. The advantage of the change is only apparent’ where the resistances to be compared are of nearly equal value as is generally the case for instance in the testing of standard coils; but where this condition is fulfilled the new method transformed the bridge method from being merely a fairly accurate means of measurement into one of the most refined accuracy comparable with that attained in the use of a sensitive balance.It also supplied the means of dealing with a very small resistance such as that of a short? thick wire by determining the difference between it and the zero resistance of a short copper bar and it was indeed for this alone that the met-hod was first suggested. Carey Foster’s method has proved of the highest value to the science of exact electrical measurement and has made it possible to issue standards of electrical resistance of an accuracy that would otherwise have been impossible of attain-ment.Alike in its simplicity and its refined accuracy the method is thoroughly characteristic of his mind. He furtlher showed how the principle involved might be applied to the important process of calibrating the wire of the bridge. In 1881 Carey Foster published “An Account of Preliminary Experiments for the Determination of the Electromagnetic Unit of Rssistance in Absolute Measure” (Rep. Brit. Assoc. 1881, 426). The accurate determination of this important unit had been undertaken by the British Association in 1863 and the value that had been accepted in this country as well as widely in other parts of the world was expressed in the “B.A. unit of resistance,” the value of which had been determined by a Commit$tee of the Associa-tion consisting of Clerk Maxwell Fleeming Jenkin and Balf our Stewart.The classical method of experiment adopted by the Com-mittee consisted in revolving a large flat closed coil of insulated copper wire about a vertical diameter in the earth’s magnetic field and measuring the consequent deflexion of a magnet suspended a t its centre. The deflexion was due to the induced current developed in the coil and this depended on its resistance as well as on the intensity of the earths magnetic field. The last how-ever affecting the induced current and the deflexion equally, although in opposite senses disappeared in t-he final equation that expressed the result of the experiment, leaving a relation between the resistance of the coil its geometrical form and dimensions and the speed of its revolution.During the years that had elapsed since the issue of the B.A. unit the rssulta of other measurements had led to a growing con-viction that it was appreciably too mall and Carey Foste 418 OBITUARY NOTICES. described an experiment in which whilst the general principle of the British Association experiment was maintained it was modified i n an important detail. The two ends of the wire composing the coil were unconnected throughout the greater part of its revolu-tion; but for a short interval the centre of which coincided with the transit of the plane of the coil through the magnetic meridian, they were placed in connexion through sliding contacts with the two ends of a standard resistance coil that formed part of an ‘‘ auxiliary ” circuit in which a steady current was maintained by a tlhermopile.By the principle originally applied by Poggen-dorff i n the potentiometer no current is developed in the coil if the electromotive force developed in it by its rotation in the earths magnetic field is equal to the fall of potential Between the two points in the auxiliary circuit with which it is connected this being the product of the current supplied by the thermopile and the resistance of the standard coil and the method of experiment consisted in so regulating the current of the thermopile that the deflexion of a sensitive galvanometer included between the revolving coil and one of its points of connexion with the auxiliary circuit should disappear whilst a t the same time the deflexion of the magnet of a tangent galvanometer included in the auxiliary circuit was recorded.The general principle is simple and a rels-tion is readily established between the resistance of the standard coil the deflexion of the magnet of the tangent galvanometer the geometrical form and dimensions of the revolving coil and its speed of revolution. The chief refinement that Carey Foster hoped to effect in this modification of the original experiment consisted in the possibility of t’he direct determination of the resistance of the standard coil. In the original experiment the resistance determined was that of the revolving coil and the reeistance of the standard could only be obtained by subsequent comparison.To obtain the maximum induced current it was essential that the revolving coil should be wound with copper wire and as the resistance of copper with that of all pure metals is seriously affected by changes of temperature, it was necessary that the temperature of the coil should be known with great accuracy during the time that the experiment was in progress a very delicate matter. I n Carey Foster’s method how-ever the resistance of the standard coil was directly determined while it formed a part of a fixed and independent circuit. The wire composing it might equally well be of copper or of one of the many alloys the resistaices of which are scarcely affected by changes of temperature whilst it was an easy matter to determine its temperature with great accuracy.Further the new metho OBI!tWARY NOTICES. 419 reduced the correction for the self-induction of the revolving coil, an important and rather delicate detail in the original experi-ment to insignificant proportions but a t the same time it un-fcrtunately introduced the necessity of taking its capacity into consideration a feature that Carey Foster did not probably a t first realise. The apparatus for carrying out the experiment was constructed with great refinement and was erected a t University College and a series of preliminary experiments were made by Carey Foster with the assistance of Mr. G. W. van Tunzelmann. These experi2 ments showed that the method was capable of yielding consistent results and there is no doubt that a far higher consistency would be possible if they were repeated in a modern laboratory more completely removed from the disturbing magnetic influences of large masseg of iron of continually varying temperature.The results were not however sufficiently consistent to satisfy t.he critical judgment of Carey Foster and the experiment was aban-doned. Whilst they were in progress Lord Rayleigh and Professor Schuster were engaged in repeating the original experiment adopt-ing precautions that experience of the intervening years had been shown to be necessary and in 1882 they published an account of their experiments and during the next ten years independent evidence supplied by other methods has shown the value they obtained to be a close approximation to the truth. In 1886 Carey Foster contributed a paper t o the Physical Society of London “On a Method of determining Coefficients of Mutual Induction ” (Phil.Mag. 1887 [v] 23 121-129) the method de-pending on the cumparison between the coefficient of mutual induc-tion of two coils and the capacity of a condenser. On forming or breaking a current in one of two coils the primary a discharge of electricity takes place through a neighbouring secondary coil the discharge being determined by the coefficient of mutual induction of the two mils; also if the coatings of a condenser are oonnected to two points of the primary circuit a charge proportional to the resistance of that part of the circuit that is included between the two points of connexion enters the condenser and will be dis-charged on the cessation of the primary current.To combine these two examples of “ Ballistic ” discharge Carey Foster succeeded in so connecting the two circuits that on the break of the primary current the condenser was discharged through the secondary circuit in the opposite direction to that of the induced discharge and on varying the charge of the condenser by regulating %he resistance between the points of its connexion with the primary circuit its discharge and that of the induced current neutralised one another 420 OBITUARY NOTICES. The disappearance of discharge in the secondary was indicated by a galvanometer and a simple relation was given between the coefficient of mutual induction of the coils and the capacity of the condenser. The capability of the method had been thoroughly tested a t University College by Mr.F. Womack and i t had been shown to be capable of yielding results of a high order of accuracy. Carey Foster’s method of determining the cosffrcient of mutual induction between two circuits has taken its place among the accurate methods of elect’rical measurement. I n 1876 Carey Foster devised a method based on the principle of Wheatstone’s bridge of tracing the equipotential curves in a sheet of tinfoil conveying an electric current and in collaboration with Sir Oliver Lodge he published two papers ‘(On the Flow of Electricity in a Plane Conducting Surface” (Proc. Phys. SOC. London 1876 1 113 193) in which this method of experiment was adopted. A further paper by Carey Foster and the present writer ((On the Difference of Potential required to give Sparks in Air,” was presented to the Physical Society in 1884 (Chem.News 1884 114). I n the method of experiment adopted in this research potential differences were measured by it modified form of absolute electrometer that had been designed by Carey Foster and that was found to supply an accurate method for measuring potential differences necessary to produce sparks of from 0.1 to 5 cm. in lengt4h. Among Carey Foster’s other publicatiocs were further articles on ( ( Heat,” (‘ Thermodynamics,” (‘ Electricity,” and (( Magnetism ” in later editions of Watts’s “Dictionary of Chemistry,” and in these he fully maintained his reputation for accuracy clear judg-ment and power of scientific exposition. I n later years he pub-lished a text-book on electricity in collaboration with Professor A.W. Porter. Carey Foster became a member of the British Association in 1857 and continued to take an active part in its proceedings until late in life. Besides his direct cont’ributions to which reference has already been made he was a member of a number of its com-mittees the more important of which were those on “Standards of Electrical Resistance,” ( ( The Selection and Nomenclature of Dynamical and Electrical Units,” “The State of Knowledge of Spectrum Analysis,” and ‘( Electrolysis.” As President of the Mathematical and Physical Section in 1877 he gave an address on “The Mutual Relation between Mathematics and Physics,” in which he dwelt on his favourite theme of the importance of accurate measurement as the foundation of discovery in science.He was Treasurer to the Association from 1888 to 1904. He was one o 0 IiT.TT J A RY NOTT CE S . 431 the founders of the Physical Society Q€ London the first meeting of which was held in 1873 and of which he was President for two years from 1887. He acted as President of the Society of Tele-graph Engineers now the Institute of Electrical Engineers in 1880 and in 1881. He was elected t o the Fellowship of the Royal Society in 1859 acting as one of its Vice-Preeidents from 1891 to 1893 as well as from 1901 to 1903 and he took a keen interest in rlie work of Kew Observatory Committee of the Society. He received the1 honorary tl egrees of TAPd .I). f roni GI asgow and D. 8 c . from Manchester. From the first Carey Foster took a deep interest in the reconsti-tution of the University of London.Whilst fully recogmising its services to education in its earlier days he was sensible of the grievous anachronism by which the University of the greatest city of the world should continue t.0 be solely engaged in examining and in conferring degrees. He had a high ideal of a universitly as a body of men and women earnestly engaged in t.he pursuit and extension of knowledge rather than in preparation for ex-aminations and he strove without ceasing to bring about the foundation of a university in London that should be worthy of it. He was an active member of the many early committees the aims of which were a constructive policy that? should achieve his ideal, and he felt keen disappointment whe’n the conflicting of many interests made it impossible of full attainment in the present university alt,hough i t received his full and loyal support.He never ceased however to look forward to a time when by further reconstruction London should possess a university fully worthy of its position and he welco’med Lord Haldane’s Report as indicating tlie possibility of a further step in this direction and possibly its fill1 attainment. The writ’er is indebted to Sir T. Gregory Foster Provost of Ui1iversit.y College €or a sketch of Carey Foster’s work while act’-ing as Principal o€ the College from 1900 60 1904. “Dr. G. Carey Foster resigned the Quain Chair of Physics in 1898. It was a time of crisis in university affairs in London as the reconstitution of the University was pending.“ I n view of the impending reconstitution the Council of Uni-versity College appointed a special committee t o consider the posi-tion of the College. On the recommendation of this committee, the office of Principal later changed to Provost of the College was instituted. Dr. Carey Foster was invited t o be the first occupant of this office. “ I n his .capacity of Principal he1 was appointed to represent University College on the Senate of the University under its new VOL. cxv. R He held it from 1900 to 1904 492 ORITUARY NOTICES. constitution. He threw himself heartily into the new problems that arose and brought to them all his ripe judgment and experience . “It soon became evident that the new constitution under which the University was given a teaching side as well as an examining side made it desirable that University College which had been originally founded to be the University of London should be merged into the reconstituted University.Dr. Carey Foster took an active share in the negotiations that led up to the incorporation of the College in the University. He regarded i t as ‘ a step towards securing unity of aim and interest in all that relates to advanced education and the promotion of original research in London.’ He hoped that it was the beginning of a movement that would lead to the concentration and the consolidation of university work in TJondon. ‘‘ This view is expressed in the final paragraph of his sketch of the History of University College which is as follows: ‘“The step taken by University College has been followed by King’s College which was incorporated in the TJniversity on September lst 1909.It may be hoped that similar action will be taken by other analogous bodies and that in course of time the University of London perhaps with some modification of its present constitution may become a centre about which the various bodies in London that are qualified to take part in university work may be united into a single organised system in which they shall supplement instead of competing with each other each doing the work for which by its special circumstances it may be best fitted.’ “During the four years of his Principalship great progress was made in various directlions in t.he reorganisation and development of university work in London.The plans for the removal of University College School were matured. The buildings formerly occupied by the School were as a consequence set free fur uni-versity purposes. The accommodation provided a t University College for university work was materially increased. There was a rapid growth in the intellectual and social activities of the College and in t’hese Dr. and Mrs. Carey Poster took a prominent share. ” A t an early period of his work a t University College Carey Foster recognised the importance of practical work in physics as an essential elment in scientific education. The first physical laboratory for studenth had been opened by Magnus a t Heidelberg in 1846 and i t was followed in 1863 by the addition of a physical laboratory to the University of Berlin.From 1845 Lord Kelvi OBITUARY NOTIOES. 423 had invited his senior studdnts to work in his laboratory for a time a disused wine cellar a t Glasgow and his example was followed by Carey Foster who thus introduced the teaching of practical physics in this country. A t the beginning this work formed no recognised part of the College curriculum but regular practical courses in physics were arranged in 1867 the laboratories a t that time consisting of two of the College rooms only one of which was fitted with benches. Later a third room in the base-ment known as the “dungeon”-it was indeed a veritable dungeon-was added and the privilege of working in it was reserved for the professor and students engaged in research.For s m e years the only apparatus available was of the simplest character but instruments were being constantly designed by Carey Foster himself whilst tlhe designs were executed by a clever Scotch mechanic William Grant who acted as his assistant during the whole time of his professorship and without whom no reference to the laboratory would be complete. Grant who was q u i b a character in his own dour way became a permanent feature of the Physical Department. His love of the apparatus so much of which he had constructed and the agony he experienced in seeing it misused made him a source of terror to all students other than those few who proved themselves worthy to be entrusted with it; whilst many will remember with humiliation his lofty refusal of the tip that was occasionally offered either from gratlitude or from a desire to acquire merit.He was of the most faithful of servants, and was devoted to Carey Foster whilst elach regarded the other with a simple affection Sir Oliver Lodge who was a student in the laboratory in those days, and who later became Assistant Professor of Physics a t the College, has rendered a grateful as well as a graceful tribute to the educa-tional value of the work done in the old physioal laboratory of University College (Letter to Nature December 3rd 1908). I n the years that followed physical laboratories for students were opened at other colleges and it was inevitable that as many of these were attached to new institutions in which it had baeu possible to design the buildings with a view to their subsequenc use as laboratories the simple equipment a t University College should have been left behind.Carey Foster in consequence con-tinually urged the governing body of the College to undertake the building of a physical laboratory that should be worthy of its tradi-tions although no doubt by reason of financial considerations, his representations were for a long time without success. A t length however he had the satisfaction of preparing the plans for the present laboratories which were opened to studen& in of which both alike were worthy, R 424 ORITTJARY NOTICES. 1893 and forin a. fitting ineinorixl t,08 the value of his work as Professor of Physics. There was an old asphalted tennis court within the College walls from which some of us have often returned in exhilaration a1t.houg-h witb begrimed hands and flannels and now only lives in memory; the building that now occupies its former site is the ‘ I Carey Foster” Laboratory.His nervous manner prevented Carey Foster from ever becoming a good lecturer and his failure in this respect was perhaps due in addition to a conscientiousness that made it difficult for him t o be content with a simple statement that he knew t o be only an approximate expression of a hruth and a t the same time made him reluctant to adopt t,he customary method of illustrating physical laws by the use of simple alt*hough entirely imaginary, experimental data. I n place of these his illustrations would often consist of the actual results of laboratory measurements and the younger students unless they were’ of a rather exceptional type, were apt to lose both attention and interest in the details of laborious computation.The more able students however were inspired by this very quality in their teacher. They grew to rever-ence exact expression and to regard it as the foundation of all scientific knowledge. They continually brought their difficulties to the Professor and were encouraged to do so by his unlimited patience in dealing with them. It was not unusual to find Carey Foster surrounded by a small group of students engaged in close discussion half an hour aft$er the close of a lecture although the dining-room had long since claimed the attention of the rest of the College. The same quality of enthusiasm for his work and his infinite patience in dealing with its smallest det’ails appeared in his work in the students’ laboratory.He never found lecturing easy but, after. having given a lecture in the morning and having a furt.her lecture for senior students in prospect at’ the close of a long after-noon he would frequently come t o the help of some duffer in difficulties in the laboratory and would devoste the best$ part of an hour to the details of a simple experiment in physical measure-ment. On these occasions indeed there was a danger of his being led by his own love of accurate detail not only t o conduct tho whole experiment himself making all the observations but to carry out whatever computation might be involved while the student looked on wonderingly as from a distance.Iti may be that some who have worked in the old laboratory a t University College in those days have preserved the scraps of paper covered with logarithmic calculations that Carey Foster often left on th OBITUARY NOTICES. 425 benches all execut’ed in his wonderfully neat writing as a memento of the most patient of teachers and most lovable of men but such prescience is rarely bestowed on yonth. His nervousness made conversatiion with Carey Foster difficult, even to those who came to know him intimately. Whilst how-ever it remained a source of some embarrassment t o them his friends came to regard i t as so essentially a part of him that it. too became lovable and they would have feltl still more embarrassed if he had suddenly succeeded in overcoming it.Closely associated with his manner was a quaint and entirely original sense of pure humour that. found frequent opportlunity for expression both in his professional work and in his private life. That his nervous-ness and hesitation did not arise from any defect in character would be shown were any such evidence necessary from his letters. In these Carey Foster found no difficulty in expressing himself with perfect clearness and precision whilst botlh were emphasised by the beauty and strength of 11;s handwriting. It was in his letters perhaps that his quaint humour found its best opportunity for expression. Through the kindness of Mrs. Minchin the writer has before him a number of letters written by Carey Foster to her husband the late Professor G.If. Itinchin which are so character-istic that littde apology is necessary f o r the introduction of a few short extracts. A close friendship existed between Carey Foster and Minchin and in their unassuming simplicity and gentleness there was much resemblance between the characters of the two men. Carey Foster had a profound respect for Mincliin’s rnathe-Inatical powers and consulted him when he feltl a doubt as to his own grasp of the mathematical treatment of a physical problem, whilst Minchin had an equally deep regard for Carey Foster as an authority on physical matters and has expressed his regret to the writer thatt Foster’s nervous manner together with his extreme jnodesty should have1 made it difficult for some even of his friends, t o realise his true greatness.The first extract is from a letter dated 1882: “My dear Minchin, ‘‘ The lesson of the day t’ouching electric endosrnose is written iii the First Book of Wiedemann beginning a t the 392nd verse of the second chapter . . . wherein i t is written how the ions dc wander when a current passeth through their midst. This I take it is the whole secret of electric endosmose; the porous diaphragw causeth not the flow but maketh the same manifest by hindering tho returu tliercof. 426 OBITUARY NOTICYES. The second is also dated 1882 : ‘‘ My dear Minchin, and it’s bad I did not write before. ((I hope the enclosed may serve your riverence’s purpose. Sure, But I had to think and that goes slow. * * * * * * “As to your telegraphic friend; let hiin take to himself a tangent galvanometer and a set of resistance coils and sundry cells accord-ing to Daniel1 and Grove.. . .” and then follow instmctions as to what the telegraphic friend should achieve. An extract from a letter referring t,o a fairly well-known man: “ The gentleman’s surface integral suggests to me a considerable amount of self-esteem. But. I am willing to believe that the charge is purely superficial. . . . I am told by a friend who knows hiin much better t,han I do that he is a good fellow.” And tihe last is fr0.m a . letter writ,teu in 18S7 congratulating Minchin on his marriage: “My dear G. M. M., (‘1 heard awhile ago that you had entered into coinbination and were no longer a dissociated atom. Accept my warmest con-gratulatJons and my fervent1 hope that you may appreciate the blessings of home rule more fully from year to year.” Several of the letters deal with Minchin’s work with photo-electric cells.The private life of Carey Foster was one of quiet beauty. His transparent hqnesty and high regard for truth earned him the respect’ of his friends whilst has unvarying kindness and courtesy won their affection. I n 1868 he married Mary Anne Frances, daughter of Andrew Muir of Greenock. Recalling that time Dr. Forster Morley writes : “It seems only yesterday when my father (the late Professor ITeniry Morley) said to me ‘ I have been walking ro,und tlis Square with Carey Foster who has just told ine that he1 is engaged t o be married and has been speaking most charmingly ~n the subject of love of a inaii for a wornam.’ OBITUARY NOTICES.427 There was a striking resemblance between the character of Mrs. Foster and that of her husband and she even acquired a suspicion of tlhe nervousness that was so strongly marked in him that how-ever only accentuated a natural charm of manner in her. There were born to them four sons and four daughters all of whom are still living. The mutual confidence that existed between Carey Foster and his wife and the evident affection with which both parents were regarded by their children gave a peculiar charm to the visits of the many friends who were always welcome la their home. Mrs. Foster died in 1917 and a year and a-half later Carey Fost’er’s body was laid to its last rest beside hers in the peaceful cemetery a t Riclanansworth.Among the number of Carey Foster’s old students a t University College who have become distinguished were Prof. W. E. Ayrton Sir Oliver Lodge Dr. H. Forster Morley Prof. Viramu Jones Prof. A. P. Chattock Prof. J. A. Fleming Prof. T. Hud-son Beare Prof. A. W. Porter Prof. F. Wmack Prof. J. Sakurai, Sir Victor Horsley and Prof. W. D. Halliburton. It is from his having been first a student then a demonstrator and thereafter a friend of Carey Foster that the writer has been able to pay in this notice his last tribute to the memory of one he loved and admired. A. H. FISON. WILLIAM JOEL KEMP BORN 1841; DIED MARCH 22ND 1918. WILLIAM JOEL KEMP was born a t Bow in 1841. He was the youngest of three sons and was educated a t Stock’s Academy a t Poplar.Owing to his father’s death he left school a t a very early age and was placed in the office of a ship’s broker. Finding this work very uncongenial he induced his relatives to article him to Carters and Green builders of t,he famous China tea clippers in t,he yard which subsequently became the headquarters of the Tharnes Ironworks and Shipbuilding Company. His apprenticeship com-menced a t an unfortunate time for wood was rapidly being replaced by iron in the construction of ships and the old-established firms which did not move with the times were being left behind. All the sam0 this period 01 his life mast have been a particularly happy one. He met all sorts of seafaring men and in later life he never tired of relating anecdotes connected with their superstitions and adventures and it is not unlikely that their experiences quickene 428 OBITUARY NOTICES.the sense of imagiiiatioii which served him so well in after years. Shortly after cmpleting his articles he married Mary the daughter of John Cayzer who organised the emigration t o Australia of the East Anglian farm labourers in the starving ’forties and ’fifties. About this time he entered the service of Rickett Smith and Com-pany coal and coke shippers as buyer. I n this capacity he was brought in contact with t,he lime burning plaster and kindred industries and when in 1876 a company was formed to work the bed of gypsum discovered four years earlier through the Sub-Wealden boriiig a t Netherfield Susses he took a small financial interest in the undertaking.It was about this time1 that the necessity for technical education and scientific. training was first accepted in Englaiid. I n 1879 the City and Guilds of London Institute for the Advancement of Technical Education was formed, and almost immediately courses in chemistry under Armstrong in temporary premises in Cowper Street Finsbury were advertised. Althoagh nearly forty years of age Kenip knowing that the manu-facture of plaster a t Netherfield rested ent+irely on rule-of -thumb methods determined t o take advantage of the facilities which the City Guilds Institute afforded and to become an efficient chemist. A t Cowper Street he worked for one or two1 days a week encouraged and inspired by Arrristrong and he soon proved himself to be not.only a logical thinker but an esperti manipulator. The other students in the laboratory were all boys and the’ writer who worked a t the bench adjodning Kemp’s shared with them the admiration of his power of application and of his rapidly acquired skill. Kemp, influenced by Armstrong’s spirit of research soon began to make investigations 011 the production of sulphur from gypsum and from alkali waste and these occupied him for several years. He1 was the first t o suggest making alkali waste into a paste with water arid pumping carbon dioxide into the sludge contained in an inverted conical vessel thus making the gas do its own stirring and bring-ing every particle of the waste in contact with it. Some of the results of these investigations were subsequently embodied in Rawes’s patents which were worked by Chance.During these years the position of the Sub-wealden Gypsum Company a t Netherfield had becane very critical the output had fallen below 40 tons a month the quality of the plaster was bad and creditors were clamouring for payment of their accouiits which there were no funds to meet. There was already on the bank an immense tonnage of dump a grey stone considered useless which had to be hauled to the surface with the white gypsum and it. was becoming increasingly difficult and expensive to dispose of i t on the surface-. A meeting was held with the ohject of winding up thc coi~ipaiiy OBITUA ZtY NOTICES. 429 but Karnp who had already begun to experiment with the grey stone which consisted almost entirely of gypsum persisted in the view that under proper direction the operations of the company would be successful.Two of the shareholders present were impressed and agreed to provide further funds if Kemp would undertakes the management and it was thereupon decided that operations should be continued. Kemp’s experiments with the grey stone were now pushed on with the result that in a short time he had perfected a method whereby the1 waste was converted into a plaster of the Keen’s cement variety which although dark in colour set hard and evenly. He introduced this plaster under the name of (‘ Xirapite’,” and from that tlay the success of the iiiidertaking was assured. In 1891 10 tons of ‘‘ Sirapite” were soltl; ten years later the annual sale was 15,108 tons and in 1911 the sales exceeded 31,000 tons.Kemp’s genius was shown not only in the way lie’ attacked his problems on the chemical side but also in his engineering ability and in the handling of men. From the first he recognised the inefficiency of boilers fed with water almost saturated with calcium sulphate and within two years of taking control he had scrapped the steam plant and had substituted gas producers and large gas engines. He introduced kilns of large size which reduced the consumption of fuel and greatly simplified the grinding and mixing plant. H e subsequently opened up a new shaft in the mine which he equipped with electric lighting and haulage plant. Having placed the business on a profit-earning basis Keinp devoted his attention to the amelioration of the con-dition of his workpeople.Although himself prepared to work twelve hours a day or more he reduced in 1895 the working hours to eight and afforded all workmen suiLable opportunities for recreation. A t his suggestion the company built a large number of model houses standing in large1 gardens which the workpeople were permit&ed to purchase; a t cost price. I n 1903 Kemp completed his plans by bringing about an amalgamation of the chief makers of plaster in the United Kingdom. Very few of those who travel by the So’uth-Eastern Railway from Tunbridge Wells to Hastings realise that near Mountfield hidden from but within a few hundred yards of the line and in one of the most beautiful of the Sussex valleys lie a mine fully equipped and busy works employing several hundred hands a t which a large part of the plaster used in this country is produced.It was here that Kemp conducted his experiment.s which revolutionised the industry and i t was here a t the scene of his life’s work that he breathed his last. Shortly after the outbreak of war his son who for some years had assumed the management volunteered f o r It 430 OBITUARY NOTICES. service and Kmp then seventy-five years of age returned ta take charge. Always confident and cheerful ever hard-working he resumed his former duties with an activit-y and interest which might have been expected from a man thirty years his junior. On the morning of March 22nd 1918 he rose in the usual health and spirits but shortly afterwards when about to go the round of the works he suddenly expired.GERALD T. MOODY. SYDNEY LUPTON. BORN JANUARY 3RD 1850; DIED JULY 10TH 1918. SYDNEY LUPTON who was elected into the Society in 1872 and remained a Fellow until his death was the youngest and last surviving son of Darnton Lupton and of his second wife Anna Jane Busk. He was born a t Eller Close Roundhay near Leeds, on January 3rd 1850. His father a member of a well-known Yorkshire family was head of the firm of William Luphn and Co. woollen manufacturers. He was a man of considerable influence and public spirit much respected and t'oolc a leading part in the municipal politics and social life of the town and district. His son the subject of this notice was educated a t Rugby and lived i n Dr.Jex Blake's house. From Rugby he passed to Oxford, where a t Christ Church he came under the influence of Dr. Vernon Harcourt and was led to devote himself to science particularly to mathematics and chemistry. On leaving the University after taking his degree he was appointed a science master a t Harrow School. The work of school teaching was not uncongenial to him and he had a fair measure of success in it; but his mother-now a widow-having fallen into indifferent health he resigned his position in order to live with her at Harehills near Leeds where he established a small labora-tory and continued to occupy himself with experimental work. It was during this period that the writer of this notice made his acquaintance and had the opportunity of observing the pro-gress of his inquiry on the slow oxidation of potassium the longest and perhaps the most important of his investigations.On t%hs death of Mrs. Lupbn he took a smaller house a t Roundhay where he continued to live until lZis removal i;o London in 1896. During his residence in Leeds Lupton took part in the civic life of the town was a member of thel Board of Guardians and OBITUARY NOTIUES. 431 was associated wiLh the lute Caiioii Jackson Vicar of St. 3 axnt35’5, in many charitable objects. Por four yurtrs lie was a member of the Committee of Management of the Cookridge Convalescent Hos-pital and on his resignation consequent on his leaving Leeds his fellow-members recorded their appreciation of his genial and energetic help and their sincere thanks for his services “during 5 period requiring special administration.” This last sentence has reference to the assistance he was able t’o render the institution in connexion with the erection of a wing to the building to perpetuate the memory of his friend Canon Jackson. Lupton’s intellectual tastes led him t o take an interest in the activities of the Leeds Philosophical and Literary Society where he occasionally lectured on scientific subjects. H e became ;I member of its Council in 1885-6 Honorary Secretary from 1886-95 and a Vice-president in 1895-6. Practically the whole of Lupton’s experimental work was done during his residence a t Leeds. His first published paper “On ths Formula of the Alums,” appears in the Journal of the Society for 1875. Although the doctrine of valency which we owe to Frankland was fairly well established at this period there was considerable uncertainty as to the true formulz of a number of inorganic compounds owing t o doubt as to the valency of par-ticular elements.This was the case with the group of the alums. Lupton a t the suggestion of Dr. Vernon Harcourt sought to establish the generic formulze of these salts independently of con-siderations of the combining values .of their constituents by a study of the conditions under which they lose their water on heating or on exposure to a dehydrating agent under reduced pressure and he showed conclusively that they mush contain a t least twenty-four molecules of water whence the general formula now universally accepted follows, I n the same year he published a now on the preparation of cuprous chloride in which he described the different mode in which water acts on this substance depending on its method of forma-tion (Chem.News 1875 30 233). This was followed in 1876 by a number of short notices (Clzem. News 1876 33 90). He showed that in preparing nitrogen by the well-known method of passing air over red-hot copper turnings the operatJon might be rendered continuous by mixing the air with ammonia gas whereby the cupric oxide was reduced as fast as it was formed or as is more probable by the metal acting catalytically and inducing the production of water : 3(2N2 + 0) + 2NH3 = 3H20 + 7N2. R” 432 OBITUARY NOTICES. 111 ihis TH~LIIIIPI’ 011ly i t rel:Ltively s1lct.l.t 1ellgt.h OT I\cxtcd cop’pcr turnings is needed anti tho idioll proceeds unint errupt-edly.I n another communication 011 the ‘‘ Solubility oi Naphthalene in Water,” he sought. to disprove Garden’s contention that Plateau’s theory of the cause of the movement of this substance on the surface of water was invalid by showing that. its solubility, and consequent high tension of its solution are sufficient t o account for the phenomenon. IIe further described a number of reactions serving to distinguish aniline from naphthylaniine and made known a number of characteristic tests for succinic acid. Lupton’s most iinportant chemical paper was his stiitly of tlic Slow Oxidation of Po$assium,” comniuiiicated t o the Socict)y iii 1876 and published in the r70(o‘?id for that year in which he care-fully repeated the observations of Davy Berzelius.Gay 1,iiss;tc and ThBnard and Harcourt and sought to clear up certain dis-crepant statements with regard t o the number ol potassium oxides capable of existence. He confirmed Vernon I-Iarcourt’s work made fourteen years previously (Qzinrt. J O I C I ~ Z . C’hem. SOC. 1862 14, 267) carefully watching the colour changes which follow the pro-gress of the oxidation and analysing the products a t the several stages by a method he devised and of which he proved the sufficiency. H e was disposed to regard the existence of the grey suboxide K,O of Berzelius as improbable and h e concluded that the intermediate products of oxidation were mixtures of I<,O and K,O in variable proportion depending on temperature and time and the nature of the oxidising medium.He compared thess intermediate products with the successive stages in the oxidation of lead and with the several lead oxides described by various observers the general nature of the change being similar. I3c obtained analytical numbers for the yellowish-green product which corresponded with the composition of a dioxide K,O, and described a number of reactions which appeared t o indicate its individuality. He gained nol certain proof‘ of the existence of the trioxide K,O, but4 was inclined to regard the brownish-yellow stage of the colour change as some evidence of its formation. I-Ie states that “the more thoroughly the air is dried the less is its oxidising action.” as proved by Baker (PJziZ. Trans.1888) and subsequently by Holt and Sims (T. 1894 65 434) who showed that potassium may be distilled unaltered in perfectly dry oxygen Lupton’s conclusions have been confirmed in the main by the last-named observers although they found it impossible to associate the differences of colour with oxides of de’finite compositioln the oxidation proceeding apparently without any break until th OBITUARY NOTIfJEf3. 433 heated mass coiisist’ed wholly od the bright orange-yellow peroxide, K,O, described by Harcourt. Holt and Sims also repeated Lupton’s experiments on the action of the oxides of nitrogen on heated potassium and with nitrous oxide obtained evidence of the formation of the buff-coloured tri-oxide and the sulphur-yellow dioxide the existence of which in solution had already been established by Harcourt.Lupton in 1888 published a short communication in the I’roceedinp of the Society on compounds of chromium and in 1891 he contributed t o the’ I~hilosoyhical LMngcxzine a controversial paper on “The Reduction of the Results of Experiments with Special Reference t o the Hydrate Theory of Solution ” (PhiZ. Mwy.. [v] 311 418) which produced a rejoinder froin Mr. Spencer Pickering . Sydney Lupton was a painstaking and conscientious worker, scrupulously accurate and a good manipulator cautJous in draw-ing conclusions o r in forming opinions but very tenacious in hold-ing them when convinced of their soundness. His knowledge and as his published work shows his sympathies were almost ex-clusively confined to inorganic and phys.ica1 chemistry ; and owing probably to the limitations of his early training and his subse quent lack of opportunity he never seemed to be attracted by the problems of modern organic chemistry.As a fellow-townsman and a member of the well-known Mill Hill Chapel he was a great admirer of Joseph Priestlep who formerly ministered in Leeds and began his chemical career there. At one time lie conceived the idea of writing the life of the old philosopher and of bringing out an annotated edition of his com-plete works for which he had gradually accumulated material. But to do justice to Priestley’s astonishing versatility and the extraordinary range of his knowledge requires an equally excep-tional man and Lupton after playing with the project f o r some time finally relinquished it being deterred from the attempt in all probability by its very magnitude.He was however well qualified to make it, especially as regards Priestley’s scientific work and philosophical opinions for he had considerable critical acumen and literary skill was an omnivorous reader and had extensive knowledge of the literature and science of the latter half of the eighteenth century. On his removal to London Lupton ceased to take any active part in experimental inquiry. He kept up his interest however, in scientific work was a frequent attendant at meetings of scien-tific socieities and at the lectures of the Royal Institution. He also interested himself in Bedford College and in the work of St 434 OBITUARY NOTICES. George’s Hospital and was for a time a member of its Committee of Management.He was perhaps most generally known by his books on “ Elementary Chemical Arithmetic ” and “ Numerical Tables and Constants in Elementary Science,” published by Mamillan’s and based probably on his experience in science teaching at Harrow. His last production was a little book of some 120 small 8vo pages bearing the modest title “ Notes on Observations being an Outline of the Methods used for determining t.he Meaning and Value of Quantitative Observations and Experiment’s in Physics and Chem-istry and for reducing the1 Results obtained.” Notwithstanding the somewhat archaic ring of its title i t is an admirable piece of work and well worthy of careful study by all engaged in quanti-tative work.I n spite of its diminutive size it must have involved a wide range of reading no sinall exercise of criticism and con-siderable skill and thought in arrangement and condensation. It shows Lupton a t his best. It is a model of clear restrained state-ment and rigorous logic and should find a place in every physical and chemical laboratory. A t all periods of his life Lupton was fond of travel and his ample means made it easy for him to make extensive journeys. He was an acute observer and a shrewd judge of character with a keen sense of humour-qualities which added t o his wide reading and knowledge of history and his readiness t o communicate his kno~vledge made him interesting as a companion. He died a t his London house 102 Park Street Grosvenor Square on July loth 1918 and was buried a t St.John’s Cemetery, Roundhay. He showed his interest in the work of the Chemical Society by bequeathing t o i t his valuable chemical library. T. E. THORPE. GEORGE MARTINEAU C.B. BORN 1535; DIED FEBRUARY 5~11 1913. BY the death of Mr. George Martineau which occurred after a brief illness at his residence Gomshall Lodge Gomshall Surrey, we have lost a member of an old and distinguished family and a man who was perhaps the greatest authority of his time in this country on sugar from its economic point of view. The deceased was the son of Mr. George Martineau of Tulse Hill and grandson of Mr. David Martineau who in 1797 established the sugar refining firm which as Pavic! Martineau and Sons was a t one time the largest in London ; it% has remained in the family for more than OBITUARY NOTICES.435 century. The fact is not without interest to our Fellows that0 this firm was one of the first probably the first in t<his country to recognise the value of scientific control and the partners appointed the late Mr. C. Haughton Gill F.C.S. first as their chemist and subsequently as their manager. Mr. Martineau was educated a t University College London and 011 coming of age entered his father’s business in which he was actively associated until his retirement’ in 1896. His connexion with sugar refining was on the commercial side but he always took a keen interest in the general technology of the industry. Although a Liberal of the Gladstonian school he recognised the defects of our fiscal system more than forty years ago; and in 1872 when the effects of the foreign sugar bounties began to make themselves felt the British refiners appointed a Cmmittee with Mr.Martineau as Secretary. This Committee visited the principal beet-growing countries of Europe. Thus commenced the anti-bounty campaign which culminated in the abolition of the bounties by the International Convention of 1902. I n recognition of his services Mr. Martineau was appointed a Companion of the Bath by King Edward VII. Imbued with the true scientific spirit Mr. Martineau possessed a thoroughly logical mind clearly shown by his numerous writings, which were continued up to the last days of his life it may bs said indeed that he died in harness. He was a chemist by instinct and few cmmercial men had a greater appreciation of chemistry and chemical research..Keeping himself a u courant with all the chief events in the progress of our branch of science, it was doubtless with this object thatl he became a Fellow of the Chemical Society in 1871. It cannot be forgotten that equally with those members of his firm connected with the practical side of sugar refining he shareld a strong belief in the precise methods which chemical analysis affords when applied to commercial ques-tions. I n this connexion we may pointl out that he was a pioneer in the establishment of the Beetroot Sugar Association of London, the functions of which were to check the weights and make analyses of the whole of the raw beetroot sugar shipped from the Continent to the Port of London.His charm-ing personality gifted conversational powers wide erudition and his deep sincerity had secured for him a wide circle of friends. Not a few have reason to be grateful to him for the assistance and encouragement he gave them a t the commencementl of their careers ; but from these he resented open thanks being quite content to view their progress with silent satisfaction. Mr. Martineau’s memory will be cherished by many. ARTHUR R. LING 436 OBITUARY NOTICES. SIR ALEXANDER PEDLER F.R.S. BORN MAY 21m 1849; DIE.D MAY 1 3 ~ ~ 1918. LIKE many ot3her chemists who have at’tained an eminent position in the scientific world Pedler began life in connexion with pharmacy. His father Mr George Stanbury Pedler was in busi-ness as a pharmacist a t 199 Fleet Street until on the removal of old Temple Bar and the widening of Fleetl Street preparatory to the erection uf t-he Law Courts the premises were swept away.Pedler received his early education in the City of London School, which he left atj midsummer 1865. I n October of the following year a t the age od seventeen he won a Bell Scholarship and began work as a student in the laboratory of the Pharmaceutical Society in Bloomsbury Square. Here he went through tlhe usual course of analytical work and a t the end of the session he was awarded a certificate of honour in practical chemistry. Before leaving he began a piece of research suggested t o him by the present writer, who was a t that ti- Demonstrator in the laboratory. It was with great regret that he parted with the promising young student, who by this time had decided to leave the comparatively narrow field of pharmacy and proceeded to place himself under Professor (afterwards Sir Edward) Frankland a t the Royal College of Chemistry then in Oxford Street.Therc after carrying on his studies for two years further he assisted Frankland in the separa-tion of the amyl alcohols of fousel oil by Pasteur’s process. This work was done in the laboratory of the Royal Institution where Frankland had held the Frof eswrship of Chemistry in succcssion to Faraday since 1863. From the optically active and inactive alcohols Pedler prepared the corresponding valeric acids and gave an account of his work to the Chemical Society in 1868 (Journ. Chern.SOC. 21 74). Further work in this direction was inter-rupted by his taking part in the solar eclipse expedition t o Sicily in that year. From 1871 Pedler served f o r two years as lecture demonstrator to Sir Edward Frankland in the Royal College of Chemistry in succession to Mr. Herbert McLed who had been appointed t o the professorship of chemistry in the then newly instituted Royal Engineering College a t Cooper’s Hill. At the same time he assisted in the research work on gaseous spectra in which Frankland and Lockyer were jointly occupied. This naturally directed Pedler’s attention to the fascinating problems connected with the physical constitution of the sun and the stars. Consequently on receivin OBITUARY NOTICES. 437 in 1873 appointment as professor of chemistry in the Presidency College Calcutta he naturally occupied himself with subjects con-nected with celestial chwistry and soon after his arrival in India he was charged with special duty in connexioin with the eclipse expedition of 1875.On joining the Presidency College' he found that no practical work in any department of science was done by the students. To remedy this deficiency in the scheme of instruction was hts first care and ultimately he succeeded in securing the introduction of a small amount of practical work into t.he science course for the M.A. degree and a practical examination was held for the first time in 1882. Ultimately he had the satisiaction of finding the university regulations require every college sending up students to provide the necessary staff and appliances for teaching practically each of the departments of science and each candidate for B.A.or B.Sc. degree t o be examined practically. Having been born in 1849 Pedler was still a very young man on reaching India and those who knew him in his early days will gladly recall those features of his character which made him not only popular in youth but remaining unchanged to his latest years contsibuted materially ti> his success in official life. In India Pedler retained the professorship in Calcutta together with the office of Meteorological Reporter to the Government! of Bengal for twenty-two years. He then became Principal of the Presidency College and Vice-Chancellor of the University. In 1899 he was appointed Minister of Public InstructJon in Bengal and became an additional Member of the Legislative Council under the Viceroy .Among other institutions Pedler took great interest in tho Itavenshaw College a t Cuttack and was instrumental in obtaining accommodation for the physical and chemical departments in that institution. These successive steps in official life explain the fact that Pedler's original contributions to scientific chemical literature were limited to the one paper on valeric acids already mentioned, and several which arose out of the circumstances of his residence in India. Soon after his arrival in that country he examined and reported on the coal-gas and water supplies of Calcutta. I n 1878 he sent home a paper on the poison of the cobra which was printed in the Proceediruqs of the Royal Society (27 17).I n 1890 he contributed to the Journal of the Chemical Society three papers which showed that he was utilising opportunities, previously neglected by chemists of studying the action of tropical sunlight on chemical change. The first of these papers was entitle 43s OBITUARY NOTICES. “The Action of Light on Phosphorus and some of the Properties of Amorphous Phosphorus.” The second paper was on “The Action of Chlorine on Water in the Light apd the Action of Light on certain Chlorine Acids.” The third paper contaiiied an account of atternpix t’o estimate hydrogen sulphide and carbon bisulphide in gaseuus mixtures by explosion with oxygen. Pcdler was a Fellow of the Institute of Chemistry and of the Chemical Society.He was elected F.R.S. in 1892. He was also an honorary member of the Pharmaceutical Society. In recognition of his public services in India hel was created C.I.E. in 1901 and 011 his return to England in 1906 he received the honour of knighthood. On his retirement he soon found occupation in public work; he became honorary secretary to the British Science Guild which owes much to his devoted service and on the outbreak of war ho took up active duties connected with the research department of the illinistry of Munitions. Whilst attending a meeting of Committee a t that office1 on Monday May 13th 1918 he was seized with sudden illness and expired immedi-ately. His death came as a great shock and surprise to his many friends among whom no suspicion of weakness had been enter-tained.Pedler was twice married first in 1878 to Elizabeth Margaret, daughter of C. K Schmidt of Frankfurt and secondly to Mabel, youngest daughter of the late Mr. W. Warburton R.N. of Ded-ham who survives him. .He left no children. W. A. T. JOSEPH PRICE REMINGTON. BORN MARCH 2 6 ~ ~ 1847; DIED JANUARY 1ST 1918. JOSEPH PRICE REMINGTON was born a t Philadelphia on March 26th 1847 and belonged to a well-known Quaker family his ancestors having been for three generations members of tlhe Society of Friends. His father Dr. Isaac Remington was a prominent Philadelphia physician whilst his mother the daughter of John Hart was in a direct line of descent from an apothecary who prac-tised his a r t in Philadelphia early in the eighteenth centlury.An inclination for the professional pursuit of pharmacy which was manifested by Remington a t an early age would thus seem to have been inherited. At the comparatively early age of fiftesn years Remingto OBITUARY NOTICES. 439 suffered tlhe loss by death of his father and this appears to have affected his subsequent career; for a plan to supplement his pre-liminary education-obtained in private schools and in the high school a t Philadelphia-by an academic course of study had to be abandoned I n 1863 he entered the establishment of Charles Ellis, Son an*d Co. a firm of wholesale druggists in Philadelphia where he remained for four years and during that time he attended evening lectures a t the Philadelphia College of Pharmacy from which he graduated in 1866.During the years from 1867 t o 1870 Rernington was employed in the manufacturing laboratories of Dr. E. R . Squibb a t Brooklyn N.Y. and in this position he had exceptional opportunities for acquiring a knowledge of technical methods especially in their application t o chemical and pharms-ceutical products whilst also enjoying intimate association with a man who was widely known for his scientific attainments and exceedingly high ethical standards. Remingtou then returned to Philadelphia and after a sho-ri; period of service with the firm of Powers and Weightman manufacturing chemists of that city he established a pharmaceutical business on his own account which was successfully conducted for thirteen years. I n the meantime he had also served as an assistant to Professor Parrish and subse-quently to Professor Procter at’ the Philadelphia College of Pharmacy and on the decease of the latt’er in 1874 he was elected to the professorship of pharmacy in Lhes college which ha,d been his ctlma mnter.The position which Mi-. Remington was thus called on to fill he retained for the exceptionally long period of forty-four years or until the close of his life and during that’ time several thousand studenh had received instruction from him. As circumstances did not permit Professor Remington to acquire a scientific training in the modern sense his attainments and talents were directed more to what may be termed the practical side of pharmacy and to editorial work. As examples of this activity there may specially be noted his participation in several revisions of the “ United St*ates Dispensatory,” the publication of his well-known text-book entitled the “ Practice of Pharmacy,” and the arduous duties committed to him as Chairman of the Corn-niittee of Revision of the “ Unit.ed States Yharmacopeia.” Professor Remington was a Fellow of the Chemical Linnean, and Royal Microscopical Societies of London as well as an active member of several scientific societies in his own land.The esteem in which he was held by his professional colleagues had moreover, been manifested by the bestowal of honorary membership in a large number of pharmaceutical organisations both a t home and abroad. He had tsavelled widely in his own country and had 440 OBITUARY NOI’ICES. several times visited Europe the last occasion having been in the autumn of 1913 which will still be pleasantly remembered by many oE his English friends.The home life of Professor Remiiigton with a devoted wife and several children was particularly happy. His genial nature and fluency as a speaker together with the fund of interesting in-format’ion which he possessed rendered him a most pleasant com-panion. I n social as well as professional circles he was therefore always gladly seen and accorded a prominent place. The writer of these lines is grateful for the privilege of render-ing a slight tribute to the memory of one with whoiii a friendship had been sustained for more than forty years and whose qualities of mind and heart had won such extended appreciation and regard.F. B. POWER. JEAN JACQUES THEOPHILE SCHLOESING. BORN JULY ~ T H 1824 ; DIED FEBRUARY ~ T H 1919. ONE of the oldest and most distinguised of the foreign members of the Society Jean Jacques Theophile Schloesing passed away on February 8th of this year. He was in his ninety-fifth year, and almost all his life had been associated with agricultural cheni-istry. He knew its illustrious f ouiiders Boussingault, Lawes and Gilbert when they were still young men almost a t the beginning of their careers; he1 introduced new ideas atl a critical stage and, finally when development had temporarily ceased he opened up a new path which is still leading t o fruitful results. At the age of seventeen he entered the Polytechnic School and left itl two years later t o take a post in the “Service des Manufacteurs d’Etat.” He thus began his career a t the molst eventful period in the history of agricultural chemistry; it was the year 1843 in which Lawes and Gilbert started their great work a t Rotharnsted one year after Liebig’s famous report on agricultural chemistry t o the British Association and four years after Boussingault had commenced his striking investigations a t Becheslbronn.He must have done well in his first posh for three years after-wards-in 1846-he became Director of the Ecole des Tabacs and within a few months published his first paper in the Comptcs Tendus; i t was on nicotine and its estimation in leaf and manu-Schloesing was burn a t Marseilles on July 9th 1824 ORITUARP NOTICES. 442 I'nctnred tobizcco.He was the first t o obtain nicotine in any quantity; it had previously been prepared as he tells us only in '' quelques rares khantdllons . " Schloesing verified its compositioii and designed a method for estiniatiiig i t within about 1 per cent.-a very accurate detlermination for the time. 'The method consisted in displacing the nicotine with ammonia extractiog with ether, eliminating the excess of ammonia by the evaporation of the ether, and then Litrating the residual base with sulphuric acid. For five years no further publications appeared then followed an ingenious paper 'on the determination of ammonia in tobacco; milk of lime was added and the mixture placed over sulphuric acid in the cold. The ammonia volatilised and was absorbed by the acid but+ a t the low temperature) of the experiment no decomposition of other substances occurred.This paper was followed shortly afterwards by one on the estimation of nitrates in presence of organic mather; hydrochloric acid and a ferrolus saltl were added and nitric oxide produced; this was washed free from hydrochloric acid then mixed with air or oxygen converted into1 nitric acid and titrated with an alkali. Subsequently however Schlmsing found that conversion into nitric acid was unnecessary and he designed a method for direct measurement of the nitric oxide. H e also introduced con-siderable improvements into the methods for estimating ammonia in dilute liquids such as rain. As an illustration of the very cumbersome nature of some of the methods then in vogue it may be mentioned that the dehermination of ammonia in rain-water a t Rothamsted carried o a t in 1853 had involved the distillation of 2 cwt.of rain and evaporation of the distillate with sulphuric acid; in spite 09 all the laborious care bestowed on the work the figure obtained was probably double thei tirue value. For the next seven years Schloeeing published no scientific work, but' from 1860 oinwards he issued a number of important publica-tions. I n 1860 also he began some cultnral experiments with tobacco which lasbd for fifteen years and were daigned t'ol ascer-tain whether the1 physical properties and nicotine content of the leaf are characteristic of the variety or the result of environmental factors. I n the first series tobacco was raised from samples of seed coming from various regions; the resulting leaf had in each case the physical characters and nicotine content characteristic of the parent plants grown in their original home.The second series was more exkended and lasted fourteen years; ite purpose was to discover whether any marked alteration occurred in the character-istic properties when a variety is cultivated in a new district. Havanna tobacco was grown and the seed saved; some was sown and some was stored; each year a certain quantity of the seed o 442 OBITUARY NOTIOES. each generation was mwn. I n no caw was any difference CybS6PBd. It was probably in this subject; more than in any other tha? the genius of the man sBone out. Looking back a t these papers their striking feature is their modernness; one can well believe that a t the time of publication they would not be fully appreciated.Again and again he broached new subjects which neither he nor his con-temporaries developed but which later workers rediscovered thirty or forty years afterwards and showed to be of signal importance. He was essentially a pioneer rather than a builder and he had the extraordinarily good fortune to discover gold almost every time ; but he never himself developed his “finds,” and the subject was not sufficiently well organised to ensure that others should develop them for him. Schlwsing’s period of greatest activity was from 1866 to 1879, when he was between forty-two and fifty-five years of age; during this time he opened up no fewer than five new fields of soil in-vestigation three of which are now proving extremely valuable.His first soil paper was on the soil solution which he separated from the solid particles by a displacement metnhcd. The subject received very little attention for nearly forty years; its importance was not fully realised until Whitney and Cameron in America published their striking paper in 1903 when investigations began again using atl first methods similar to those that Schlwing had designed. A t the present time i t receives perhaps more atten-tJon than any branch of soil chemistry. Another subject which has come inbo prominence in recent times was investigated by him in 1868. He showed that nitrates are decomposed during certain fermentations and five years later he further showed that they are reducible to gaseous nitsrogen in soils deprived of oxygen.He also delmonstrated that oxidations rather than reductions are the normal phenomena in soils under nat’ural conditions ; surf ace soils readily absorb oxygen whilst sub-soils d o not. After a lapse of nearly thirty years this phenomenon was independently rediscovered and its investigation figures promin-ently in s m e of the most recent research programmes. His most important work however was on nitrification. For a long time ii; had been known that nitlrates are gradually formed when plant or animal residues farmyard manure etc. are in-corporated in Dhe soil. The process was of much technical import-ance in the seventeenth and eighteenth centuries as the source of nitrahs for gunpowder.During tlhe Thirty Years’ War and other great continental wars the various governments had been seriously In 1866 Schloesing began his investigations on the soil ORITlJARY NOTIUES. 443 concerned in these so-called nitre Iwds aud had done ;I great (leal to stimulate their development. An interesting collection of memoirs relating tlo the prgctical details wits published in Paris in 1776.* A study of these papers shows that the conditions of the change were tolerably well ascertained even then but nothing was known of its mechanism. It has several times happened in the history of civilisation that agriculture has benefited by knowledge gained during war. The mass of information accumulated during the eighteenth century wars and apparently rendered useless in the nineteenth century by the promise of peace and the discovery of nitrates in Chile was found ta be of fundamental importance in agriculture.Boussin-gault had realised and Schloesing a t once accepted the view that the nutrition of plants so far as nitrogen was concerned depended on the nitre-bed processes ; organic nitrogen compounds useless as plant nutrients became converted into highly valuable nitrates when added to the soil; the more rapidly this change could be brought about the better for the plant. So long however as the mechanism of the change was unknown the old knowledge was simply empirical and incapable of full utilisation. Many investi-gations had been made but the problem remained unsolved. The balance of opinion was in favour of a purely physical process but there was also a strongly supported chemical hypothesis.In 1875 a Commission was appointed to inquire into a scheme for carrying Paris sewage out to the land between Clichy and the forest of St. Germain and Schloesing was asked to draw up the report’. Rarely even in France can an essentially practical inquiry have led t o such striking scientific results. When Schloesing had finished the investigation he had not only die-covered a new and vastly improved method of treating sewage but he had realised what? was the cause of nitrification and thus founded the science of soil bacteriology. We cannot do better than let him tell the stiory in his own words: “I was selected,” he tells us “to draw up the report of this Commission. On this occasion following the plan indicat$ed in 1856 by M.€€ervQ Mangon and taking advantage also of the more recent investigations of Dr. Frankland I endeavoured to elucidate t-he principles involved in the land treatment of sewage by con-necting the process with the phenomena of slow combustion of organic matter in an atmosphere containing oxygen ; I investigated a t the same time the conditions necessary to secure satisfactmy * “Receuil de MBmoires et d’observations sur la formation et sup la f abriccttion clu Salpdtre par les Commissionnaires nomm6s par 1’Acaddmie pour le jugement du Prix du Sa1pbtre.”-Paris 1776 444 OBITTIARJP NOTTUES. ~ ~ ~ ~ i f i c a t i o ~ in pruct,ice. 1 mstle R special poiiit of distinguishing two problems which were often coiifused purification simply and solely of Paris sewage which would only require an area of 2000 hectares (SO00 acres) and ag-ricultural utilisation of Paris sewage, which would require an area twenty times as great.“ Boussingault had just published the researches on nitrification that he had carried out some time previously. Blood meat wool, straw and oil-cake did not nitrify when mixed with sand and chalk and allowed slowly to oxidise but they rapidly nitrified when mixed with soil. I had vainly tried to nitriCy ammonia by atidiiig it to sand and chalk and leaving the niixt,iire expose(1 t o air. These reaults led me t o think that t,he propertry of bringing ibhont nitlrifi-ciitiotl was peculiar to soil. “Wishing to fix my ideas on tho subject I made the following experimentl.A large tube 1 metre long was filled with 5 kg. of ignited sand mixed with 100 grams of powdered chalk. The sand was watered daily with sewage the amount being so arranged that, it took eight days to traverse the tube. For the first twenty days there was no sign of nitrification then nitrates began to appear, and the amount rapidly increased; finally the liquid flowing o u t of the tube contained neither ammonia n o r organic matter-the sewage was absolutely purified.” The quality of the man’s genius was revealed in two striking deductions drawn from this simple experiment,. One was of supreme practical importance and has revolutionised sewage dis-posal practice. “ Au point de vue de 1’6puration des eaux d’Bgor~t. l’exp4rience . . . prouve en effet qu’il n’est nullernent nMssaire que l’irriga-tion soit Btablie sur les terrains agricoles; de sables steriles se pr6tent parfaitement 8 l’6puration lorsque le ferment nitrique, apporth par les eaux nGmes a pris possession du milieu.” From this to the modern bacteria bed is no great step a t any rate in principle.The second deduction was of even greater consequence f o r the development of agricultural science. Reverting t o the delay of twenty days in the setting in of nitrification Schloesing and Muntz asked why it set in. With characteristic shrewdness they observed that this delay could scarcely arise if the process were purely physical or chemical; some biological factor seemed to be indicated. I n order to test this possibility they added a little chloroform to the sewage; nitrification a t once stopped.They then removed the chloroform and “seeded” with a little fresh sewage; after an interval nitrification began again. This showed that the process was brought about by living organisms and forthwith Schloesin OBITUARY NOTICES. 445 and Muntz announced the existence of a living ferment.. The discovery at once attracted attention ; Warington a t Rothamsbed immediately recognised its importance and proceeded to investigate nitrification i n the Rothamshd soils; he was able to confirm the accuracy of Schloesing’s deductions. Later on the proof was made more rigid by Winogradsky’s discovery of the organism. It is no diminution of the credit of the discovery that’ Yasteur in 1862 had already foreshadowed it as Schloesing himself point.ecl out in his remarkable statement : “ Beaucoup d’stres infErieurs ont la propikt6 de transporter l’oxygkne de l’air en quailtit6 considiirable sur les matikres organigues complexes c’est un des moyens doric se sert la nature pour transformer en eau acide carbonique olxyde de carbon azote, acide nitrique ammoniaque les 616ineiits des substances organiques 6labokes sur l’influeiice de la vie.” It seized the irnagiiiat ion of the.younger workers and speedily attracted recruits to the new subject. Although Schloesing did not himself develop the snbject he was satisfied that“ the “ ferment nitrique ” did not exhaust the list of soil organisms. Reverting to his earlier work on the absorption of oxygen by soils he says in one of his lectures%- ‘‘ C’Qtait lL pensait-on alors un fait purement chimique.On sait aujourd’hui que c’est principalement un fait biologigue c’est-&-dire que la combustion observge est le r h l t a t de la vie do nombreuy organismes tel par example que le ferment iiitrique lequel est charg6 de transporter l’oxyghns sur l’azote.” These investigations by 110 nieaiis represent the whole of his work on soil although they may well prove to be his most per-rrianeiit contributions t o science. By a lengthy washing process he obtained a preparation o€ tlis finest clay particles which remained iiidefiiiitely suspended in pure watel but was precipitated by traces of a calcium or magnesium salt. This was commonly regarded as being in some sense the essential clay and agricultural chemists marvelled a t the minute amount present even in heavy soils.The conception served a useful purposel but it has since been replaced by a broader one: the soil is now coiisidered t o be made up of particles varying from 1 121111. downwards to molecular dimensions the different groups merging one into another without perceptible breaks. The clay group is assigned for convenience ail upper limit of 0.002 m., but this is regarded as purely conventional. Another important investigation had to do with the movements of calcium carbonate in the soil. The conditions of solubility of This research marks the beginning of soil bacteriology. * “ Lepxis clt chixilie agricole,” 1883 446 OBITUARY NOTICES. calcium carbonate in carbonic acid were determined and the relationship between the quantities of these two substances was shown to follow a logarithmic law.Deductions were drawn which threw important light on the practice of liming and marling and on the presence of lime in natural waters. During the course of these investigations Schloesing was appointed in 1876 to the Chair of Agricultural Chemistry in the Institut Agronomique then just founded. Eleven years later in 1887 he followed the illustrious Boussingault a t the Conservatoire des Arts et Metihres. During his act’ive period his lectures were collected by his son in a volume which still remains a source of inspiration to the student. I n 1875 he began anothe’r important group of investigations : he carried out a series of determinations of the amount of ammonia in the air and published some interesting speculations as to its source.He supposed that a great natural circulation took place; the nitrates washed out from the soil find their way to streams and rivers and finally to the sea ; there they are reduced t o ammonia, some of which escapes into the atmosphere is blown over the land, and there absorbed by the soil or washed dawn by the rain. The ammonia then nitrifies and such of the resulting nitrate as is washed out from the soil by rain-water passes once more through the same cycle. In like manner he supposed a circulation of carbon dioxide between oceans and atlmosphere and in this8way he explained the smallness of the variations in amount of the carbon dioxide in the air from time to time.He considered that the proportion of carbon dioxide in the air was probably diminishing although of course very slowly. "Get appauvrissement continue-t-il encore et s’il en est ainsi, ira-Lil jusqu’an point oh il causerait la ruine de la v6g6tation et par suite la fin de t’oute vie B la surface de la terre ? La soldtion de wt probl&me d’un si haut int6rGt nous 6chappe absolument. Elle ne pourra 6tre donn6e n u e par les gGn6rations qui viendrontl longteinps apr‘es nous.” Well may we envy a man and a generation that had nothing worse to worry about! “ What,” he asked “will be the result? ” E. J. RUSSELL OBITUARY NOTICES. 447 ALFRED SENIER. BORN JANUARY Z ~ T H 1853; DIED JUNE Z ~ T H 1918. I. ALFRED SENIER was born on January 24th 1853 a t Burnley in Lancashire.Ria father wlio had been one of the early settlers in Dover Wisconsin had returned to England some six years previ-ously to engage in business as a pharmacist but for reasons of health he found it necessary to return to America shortly after the birth of Alfred his eldest son. Thus except for a brief visit to England during infancy and another during his student days, Senier’s whole youth up to the time of his graduation as M.D. at the University of Michigah in 1874 was spent in the United States, chiefly a t Mazomanie. Mr. Alfred Senier the father appears to have. been a man of romantic disposition which found its expression in a certain restlessness leading him i n early life ta spend several years a t sea and later to travel considerably in Europe.The son inherited this taste for travel and was allowed to visit both London and Paris at’ the age of eighteen in the middle of his student career. Immediately after his graduation the family finally returned to London where Senier obtained it post a t the school of the Phama-ceutical Society first as assistant to Prof. Attfield and later as demonstrator. He was elected a Fellow of the Chemical Society in 1875 and a Fellow of the Institute of Chemistry three years later. I n 1881 he left the school of the Pharmaceutical Society in order t o take charge of the chemistry teaching a t St. John’s College, Battersea where he remained for three years. During this period in London his interests extended beyond his professional duties which hitherto did not seem to offer him suffi-cient scope for his mental activities.Endowed as he was with the faculty of accurate reasoning and with clearness and breadth of mential vision his interest a t this time turned markedly to philo-sophical questions. We find him appointed as honorary secretary and treasurer of the Aristotelian Society on April 19th 1880, when it wa first organised. He acted in this capacity. until 1884, and in 1902 he was elected an honorary life1 member. AZ its fifth ineeting he delivered a lecture t o the Society on (‘Plato.” In 1882 we find him delivering a series of lectures on the “Elements and Early History ‘of Terrestrial Physics ” to the Positivist Society iu Newtoti Hall Fetter Lane. It is also interesting Gu observe that, 118 wrde It0 the Yhanmceutical Jo~mzctl in 1877 a spirited letter i 448 OBITUARY NOTICES.support of the proposal to admit lady pharmacists into the Pharma-ceutical Society. I n 1884 he left London for Berlin where he studied chemistry under A. W. von Hofmann. It was a t this period of his life that he received his greatest inspiration. Enthusiastic and imaginative by nature he threw himself wholeheartedly into his woyk and soon attracted the attention of Hofmann who became his ideal as a pro-fessor lecturer and teacher. A close friendship bound him to his old master in whose family circle he spent many happy evenings, and whose personality made a lasting impression on his mind. Later in life when fulfilling his duties in an academic chair he loved to think that the same happy relations existed between his students and himself as he had felt when a student of HoCmann.His interest in his past. students never flagged. He was ever ready to help them and always pleased t o hear of their success. Senier’s own exceptional powers as a teacher were no doubt due to a large extent to the powerful influence! of Hofmann of whom lie was never tired of speaking. Among his papers this idea is expressed in words thus ‘‘ I had special opportunities f o r studying the methods of teaching f o r which Hofmann was justly famous. H0 possessed that rare gift of inspiring his students with the dis-coverer’s enthusiasm. We discovered with him to lead us things known to science; and then without realising a difference we fol-lowed him to things that were new and thus became chemists with the habit of research.With such a leader in research with such a teacher in the riglit mea,tiing of the word no wonder that those who came within his influence became inquirers and teachers t ~ d ’ On June 25th 1887 he graduat.ed P1i.D. in Berlin and rchurnetl sliortly afterwards to London. Herel he remained for a few years writing articles for the standard dictionaries of Chemistry until he was called to act as locum tenens for Maxwell Simpson Professor of Chemistry a t Queen’s College, Cork in 1890. The latter resigned the following year atid was succeeded by Prof. A. E. Dixon of Galway. Ths vacancy thus created was filled by ths appointment of Senier t o the Chair of Chemistry a t Galway which he occupied until his death.This Chair when first estalrrlished in 1849 was filled by Edmund Itonalds wh? in the early days of the Chemical Society served as Searstary and also acted as Editor of this Journal. I n addition to fulfilling the duties as Professor of Chemistry a t Queen’s College Galway Senier acted as Lecturer in Medical Juris-prudence and Hygiene. In Galway his professorial duties liis work ou the College Couu ORITITARY NOTICES. 449 cil and his personal interest in his st,udents engaged his closcsts attention. His strong personality and buoyant enthusiasm made a powerful appeal to' the minds of his students with whom he was always immensely popular. He was a champion of students' interests and never tired of reminding them that he was and would remain '' always a student." Although not naturally attracted to athletic sports he quickly realised their healthy influ-ence and value in promoting esprit de corps and harmony among yonng men assembled from all parts of Ireland from homes repre-senting all shades of religious and political differences.They sought and obtained in Galway a University training unde'r a system which, although technically non-residential was by reason of the small-ness and isolation of the " Citie of the Tribes" virtually residen-tial. Senier seized his opportunity and quickly won the affection of all the students by becoming the active patron of their sports. He founded the athletic union and acted as its president and treasurer for seventeen years. The astonishing prowess of the football team in its competitions with the larger sister collegps of Belfast and Cork was in no small measure due to his sympathetic and generous Meanwhile the problelm of continuing his researches had t o be faced and was tackled courageously and successfully.A t first little progress could be made as Galway offered but a p m field for creat-ing and maintaining an advanced chemical atmosphere. Neverthe-less he persisted in his attempt and soon acquired a good chemical library and equipment sufficient to make a start. Well-furnished modern laboratories soon followe'd and in conjunction with various assistants demonstrators and senior students he was eventually able to contribute a large number of papers chiefly on acridines and on phototropic and thermotropic compoiinds t o the Tmns-cictions of this Society.In 1908 the Royal University of Ireland conferred on him tlic degree of D.Sc. Imnoris cnzisn. This event was made the1 occasion of a public presentation to him of an address and silver casket from his old students whose eager and liberal response even from the most distant parts of the world bore ample testimony t o the lasting feeling of reverence and goodwill in which they held their old teacher and patron of their sports. H e was elected a member of the Royal Irish Academy and in 1912 he acted as President of the Chemical Section of the British Association a t the Dundee Meeting. When the National University of Ireland was created in 1908 lie took an active part in its organisation and development. He was s u p p r t 456 OBITUARY NOTICES.a member of the Senate until his death which took place on June 29th 1918 in Galway after a brief illness. Senier married in 1887, and is survived by his wife and two daughters. W. S. M. 11. By the death of Alfred Senier the country has lost one of its most enthusiastic and devoted workers in the domain of organic c;hemistry. The loss is felt most keenly by all his students and cocworkws who will always cherish the remembrance of his sympa-thetic and inspiring personality. I n him the spirit of scientific inquiry was st’rong indeed f o r in the face of difficulties which would have baflled and beaten many a man of less sterling wol-th, his courage never failed but enabled him to pursue unwearyingly the lofty ideals which he had formed in his youth and to achieve a measure of success and distinction which will assuredly become fruitful in the future.Even before leaving America he had shown evidence of a desire t o undertake original investigations his first paper on the analysis of soap appearing in the Amem’cm Joz~rnal of Yhawnmy in 1874. At the School 09 the Pharmaceutical Society his aspirations received encouragement from Prof. Attfield and he contributed a series of articles to the Pharmaceutical Journal chiefly relating t o the investigation of pharmaceutical preparations and including a table for the qualitative analysis of scale preparations alkaloids etc. The interaction of glycerol and borax particularly engaged his attedion, because he found that he could utilise it as a m a n s for detecting.glycerol. I n 1878 he contributed to the1 Transactions of the Chemi-cal Society ‘( A New Tesb for Glycerin.” He also published a num-ber of articles in the Samitary Engineer. I n Berlin Senier came under the powerful influence of A. W. von Hofmann. The enthusiasm which Hofmann aroused in him remained with him to the end and he spoke of him almost with veneration in his public lectures. Inspired as he wa by his experience in Germany the whole course of Senier’s later life afforded abundant evidence that ’he had learned nothing of the modern German aggrewive spirit of world-domina-tion. Indeed his realisation of its existence only came to him after war was declared and its effect on him was painful in the extreme as shown in his letters t o the writer.In Berlin his attention was first directed to the action of heat on the formyl and thioformyl derivatives of ammatic mines and later to the investigation of cyanuric acid and cyanuric chloride. H e wa OBITUARY NOTICES. 451 able to show that the alleged a- and B-isomerides obtained by Herzig by the interaction of carbamide and hexabromoacehne were in reality identical with ordinary cyanuric acid. This work was embodied in his dissertation for the! degree of Ph.D. Shortly after his appointment to Galway he reverted t o the exam-ination of cyanuric acid and found that the white solid produced by the polymerisation a t Oo of freshly distilled cyanic acid was not pure cyamelide as was supposed but consisted chiefly of cyanuric :wid mixed with 30 per cent.of cyamelide. Being greatly interestzed ill all Hofmann’s work he decided to follow up the reaction by which ethylenediamines and piperazines are f ormed from arylarnines. By using methylene dihaloids insteatl of ethylene dihaloids he found that although the simplest aryl-amines give rise to methylenediamines as the molecules increase in complexity through the inclusion of methyl groups or of condensed rings the character of the reaction changes and results in the forma-tion of acridines. Thus from $-cumidine he obtained hexamethyl-acridine and from a-naphthylamine a new dinaphthacridine. This result led him to study the subject of acridines in some detail and a series of papers appeared in the Transactions. He also introduced a new and convenient system of notation in the acridine series.This work was followed by a paper on quinazolines and a series of papers on the synthesis of phototropic compounds t o which he was led by his observations on salicylidene-m-toluidine during the course of his investigations on acridines. This discovery of phototropic change led him to prepare and examine a large number of Bimi-larly constituted anils many of which were also phototropic, although the property was by no means characteristic of the class. The change from the paler variety to the darker under the influ-ence of sunlight occurs rapidly in a few minutes-whereas the reverse change requires a much longer time. This process of reversal can he found be accelerated by raising the temperatures, but there appears to be for each substance a critical temperature above which the property of phototropic change disappears.In some cases this temperature is near the melting pint; in others it is much lower; in fact in the case of two compounds examined, namely salicylidene-panisidine and 2-hydroxy-3-methoxybenzyl-idenecp-xylidine no phototropic change is observed until a &mpra-ture of -20° is reached. Similar colour changes were observed to take place under the influence of heat instead of light this pheno-menon being termed thermotropy by Senier. Themotropy appears to be much commoner than phototropy and in many instances the thermotropes were also found to1 be phototropic. The suggestion was put forward by Senier that these phototropic and thermotropi 452 OB’ITTJARY NOTICES.clianges me to bo ascribed to isomeric changes affecting the aggre-gation of molecules in solids rather than to changes in the struc-tures of the molecules themselves. I n his Presidential address t o Section B of the Dundee meeting of the British Association in 1912 ’he developed this idea of the existence of solid molecular aggre-gates. Several instances of polymorphic changes due to trituration were alsol examined chiefly in the case of p-hydroxybenzylidenearyl-amines. This work extending over several years was the subject of a series of papers in the l’m?Latrctio?/s and remains uiifinishecl. No doubt it will be possible in the future to’ throw more light 011 the subject by means of optical measurements. Apart from his purely scientific studies Senier took a deep interest in educational affairs.The difficulties which had to be encountered in Galway were due partly to the remoteness of the College from the main centre of scientific activity and partly to the anomalous character of the College during the greater part of Senier’s life in Galway. Sinoe the dissolution of the Queen’s University in 1879 the three Colleges a t Belfast Galway and Cork had been reduced from tho status of integral members of a university to that of colleges where students were able to study f o r the examinations of an external institution-the Royal University. In addition t o this loss of prestige the College a t Galway suffered through lack of active support by the people of Connaught. It was therefore not in close sympathy with its environment.This state of affairs has happily been remedied by the abolition of the Royal University and the creation in 1908 of two new teaching universities namely tlie National University of Ireland and the Queen’s University of Belfast. Tlie College a t Galway re-named ‘I University College, Galway,” became a constituent part of tJie8 National University and Senier was elected to a seat on the Senate. The existence of tlie College has often been tlireat,enetl but i t has survived and indeed, attained a flourishing condition. There is no’ doubt that Senier ’s efforts to foster the spirit of scientific research materially advanced the cause of education i n Galway and in Ireland. In his public lectures on “ A Visit to Giesseii; or Thoughts on Liebig and Chem-istry in Germany” and (( Bonn on the Rliine; Pages from its History and Stray Thoughts on Education” lie deals in a very attractive way with the history of the development of scientific research in Germany and in his lecture before the Royal Dublin Society in 1910 on (( The University :tnd Technical Training ” he made a very lucid and careful analysis of tlie various university systems in the1 world.I n view of modern needs these essays* are * Published at Dublin 1910 by Edward Ponsonby 116 Grafton Street OBITUARY NOTICES. 463 well wmth reading for he explains very clearly how industrial development does not depend on the technical education of the operatives but arises naturally from the development of the highest form of scientific activity a t the universities.P. C. AUSTIN. JOHN BISHOP TINGLE. BORN 1867; DIED AUGUST ~ T H 1918. JOHN BISHOP TINGLE Professor of Chemistry in McMaster Uni-versity Toronto who died on August 5th 1918 a t the age of fifty-one after a brief illness received his early training a t the Royal Grammar School Sheffield entering Owen's College Manchester, in 1884 under the late Sir Henry Roscoe. I n 1887 he proceeded to t.he University of Munich to study with Claisen and von Baeyer, where he took the degree of Doctor of Philosophy in 1889. While a t Munich his studies were1 essentially in organic chemistry his dissertation for the degree dealing with the action of ethyl oxalate on aliphatic ketones. On returning to England Dr. Tingle held certain junior appoint-ments which offered him opportunities for research.Owing how-ever to unforeseen family responsibilities he was compelled to give up for a time his chosen career of investigation and taught chemistry in secondary schools. I n 1896 he came t o America and was successively professor of chemistry a t the Lewis Institute Chicago (1897-1901) Illinois College Jacksonville (1901-1904) and assistant in charge of organic chemistry a t Johns Hopkins University under Professor Remsen (1904-1907). During his residence in the United States Dr. Tingle becaae sub-editor and abstractor in organic chemistry on the staff of the American Chenzical Jourtzal his work being characterised with care and precision and as his study of current literature in his chosen field was extensive and exhaustive he spared no pains to make his abstracts clear comple~te and useful.His long training as an abstractor on the staff of the Journal of the Chemical Society specially qualified him to take this impo'rtant part in organising the organic abstracts for the American journal. Dr. Tingle was a-ppointed professor of chemistry a t McMaster University Toront'o in 1907 in which post he laboured energeti-cally and faithfully until his death. It was perhape in teaching, for which he possessed a special talent that Dr. Tingle did his best VOL. cxv. 454 OBITUARY NOTICES. and most valuable work for the country of his adoption. €53 was insistent on the importance of careful accurate and clean crafts-manship and held that theory was useless and often misleading without a knowledge of how it had been deduced and how it could be applied in practice. He laid special stress on the need of mani-pulative skill of the highest order as a necessary prerequisite to orderly and clear reasoning and successful results. Dr. Tingle’s original work embodied in upwards of thirty publi-cations delals with problems of organic chehistry and is centred chiefly round the mechanism of the “ Claisen reactions ” and the products and mechanism of nitration in the benzene series. His last paper which did not appear in print until after his death, settled certain minor points previously undetermined and was intended to clear the way for a comprehensive study of the laws governing nitration and the means by which their reactions could be controlled. Dr. Tingle made organic research his life work and carried through tlo a successful issue a large number of investigations in his chosen field. He held a first place among organic chemists in Canada aad had he been spared i t was expected that he would have k e n able in a few years to devote himself almost exclusively to research. I n the sphere of Canadian war work Dr. Tingle wasathe first to recommend the intensive training of girls for employment in muni-tion and chemical factories in Canada and laid himself out ener-getically to instruct them towards this end. The extra work involved undoubtedly accelerated his death. He trapslated and edited several important works in chemistry. For a long time “ Spectrum Analysis,” by Landauer and Tingle, was the most comprehensive work on the subject in English. Dr. Tingle was a kind and geiierous man taking a great personal interest in his students and their work and exciting their ambition and enthusiasm for advanced study. Much has been lost by his death. He leaves a widow and two children. W. R. L

ISSN:0368-1645    

DOI:10.1039/CT9191500408

出版商:RSC    

年代:1919

数据来源: RSC

摘要:

R A K S m PORPHYROXINE. 456 XXXIV. -Poiphyroxine. By JKTENDRA NATH RAKSHIT. THE ethereal extract obtained in the estimation of morphine in opium by the process described by the author (Analyst 1918 48, 320) left a viscid brown crystalline residue on evaporation which when dissolved in dilute acid always gave a solution becoming more and more purple on stirring or heating. Previous authors do not agree regarding the composition of this colouring matter ; Merck in 1837 prepared from opium a substance containing its coleuring matter and called it porphyroxine ; Hesse remarked (Annate?t 1870 153 47) that the substance prepared by the former investigator was a mixture of several alkaloids one of which is meconidine and another probably rheadine. The same author (Annalen SuppZ.1864-1865 4 50) noted that Merck's porphyr-oxine agrees with rheadine in method of preparation properties, and composition. It was thought desirable to investigate whether therie is any alkaloid that may be correctly called porphyroxine in Indian opium The alkaloid now isolated was very likely a con-stituent of what Dey (Pkarrn. J. 1882 [iii] 12 397) obtained on evaporation of the ethereal extract prepared by shaking an aqueous solution of opium made alkaline with sodium carbonate or ammonia and apparently also of what Merck called porphyroxine. Considering these facts and that the alkaloid gives a purple sdu-tion with dilute acids resembling porphyry the name porphyroxine may reasonably be retained. The alkaloid isolated is fairly readily soluble in water in which respect only it resembles papaverine codamine narceine and codeine but its other properties are in striking contrast with them; the solutions sf the base or its salts are strongly laevorotatory it does not sublime like codamine and unlike codeine the aqueous solution of its hydrochloride gives a white or pale yellow precipitate with ammonia.Prepration.-Twenty parts of Indian opium powder and nine parts of freshly slaked lime were triturated in a mortar for five minutes then 100 parts of water were added gradually during one hour the trituration being continued. The solution was filtered and the filtrate shaken with an equal bulk of ether for ten m i n u h in a separator. The ethereal layer was then filtered into another separator containirig some dry lumps of calcium chloride shaken for five minutes allowed to settle the ethereal solution decanted, filtered and evaporated on a water-bath.A pale yellowish-brown, VOL cxv. 456 RAKSHIT PORPHYROXINE. soft crystalline residue was obtained which when rubbed with a spatula on a porcelain plate for three to four hours became a dry powder. One hundred grams of this powder were heated with 200 C.C. of light petroleum until the solvent boiled briskly the whole was shaken for fifteen minutes heated again to boiling and the petroleum decanted as completely as possible the insoluble residue being carefully excluded. This process of extraction was repeated five times 100 C.C. of petroleum being used each time and finally the contents of the flask were collected dried and powdered.Ten grams of this powder were triturated with 100 C.C. of 10 per cent. hydrochloric acid gradually added during half an hour and then with 100 C.C. of water gradually added during another hour, and filtered quickly the residue being washed with a little dilute hydrochloric acid. To the filtrate was added a saturated solution of sodium hydrogen carbonate a thin layer of ether being kept on the surface of the liquid and the latter was stirred until the addi-tion of a further quantity did n o t produce any effervescence. After remaining for half an hou'r for the complete separation of the pre-cipitate this was collected and washed with distilled water. The filtrate measuring about 500 c.c. was shaken with 50 C.C. of chloro-form for fifteen minutes the chloroform removed and the process of extraction was similarly repeated thrice with 30 25 and 25 C.C.of chloroform respectively. The chloroform extracts were mixed together filtered the bulk of the solvent was distilled off and the residue dried slowly on the water-bath; it. was then kept overnight in a desiccator. Sometlimes the substance formed a soft viscid, crystalline mass but generally a pale brownish-yellow viscid varnish which on rubbing with a spatula against the side of the basin for an hour became a crystalline pink powder. Five grams of this powder were heated on a water-bath with 100 C.C. of light petroleum (b. p. 100-120O) just to boiling the mixture was then shaken for fifteen minutes with a rot'atory motion heated again to boiling and the petroleum decanted through filter paper the undissolved residue being carefully excluded.The residue in the flask was again twice extracted similarly with 80 and 60 c.c., respectively of light petroleum care being always t'aken not t o inelt the substance thus causing the extraction to be incomplete. The successive petroleum extracts were collected and allowed to evaporate when the base cryst,allised in groups of radiating, shining pale yellow prisms which were carefully separated from a thin film of non-crystalline residue powdered and dried in a desic-cator. Several samples from different preparations were analysed, the results of one only being given below RAKSHIT PORPHYROXTNE. 457 0.2950 gave 007530 COz and 0.1854 H20. 0.253 , 10-6 C.C.N (moist) a t 340 and 750 mm. N=4.36. CI9H&,N requires H = 6.99 ; c= 69.30 ; N = 4-26 per cent. Porphyroxine f o m s pale yellow or white transparent prisms nlelting a t 134-135O to a clear transparent straw-coloured liquid which solidifies on cooling. It is a non-deliquescent substance appreciably soluble in water giving a strongly alkaline solution ; it is readily soluble in dilute acids acetone carbon disulphide, chloroform or glacial acetic acid moderately so in benzene carbon tetrachloride methyl or ethyl alcohol toluene or ethyl acetate, sparingly so in amyl alcohol ether light petroleum ammonia or barium hydroxide and almost insoluble in aqueous sodium hydr-oxide potassium hydroxide or lime water. When its dilute mineral acid solutions are kept exposed to air they assume a fine pink porphyry colour.The base has a strongly alkaline reaction towards cochineal methyl-orange and litmus but has no action on phenolphthalein. Iodine solution gives an orange precipitate with the aqueous solution of the base and a brick-red precipitate with its dilute hydrochloric acid solution. Mayer's reagent gives a white precipitate with its aqueous solution and the usual pale yellow one with its dilute hydrochloric acid solution. Colour reactions of the base are often vitiated by the presence of a small quantity of impurity and the following reactions were observed with a sample specially prepared by recryst'allising three times from petroleum. It gives a red colour with concentrated sulphuric acid a grass-green with concentrated sulphuric acid and a small quantity of potassium dichromate a pale yellow with concentrated nitric acid and ail orange with concentrated hydrochloric acid ; a brownish-red pre-cipitate is obtained on adding ferric chloride t o its sulphuric acid solution and when fused with potassium hydroxide it becomes brown and gives off a strongly alkaline vapour without becoming charred.0.2540 made up to 50 C.C. with chloroform gave a-4-1° (Ventzke) in a 2-dcm. tube a t 3 2 O whence [a] -139.90. The hydrochloride crystallises from water in prismatic needles. It is a stable salt and on heating softens atl 140° and melts a t 155O t o a clear pale yellow liquid which does not solidify quickly on cooling: C=69.46; H=6*98. 0.1168 gave 0.0460 AgCl. C1=9.7. C,,H,,O,N,HCl requires CI = 9.7 per cent.It is a non-deliquescent crystalline stable substance readily soluble in water chloroform methyl or ethyl alcohol or glacial acetic acid sparingly so in amyl alcohol or carbon disulphide and T 458 RAKSHIT BORPHYROXINE. almost i ~ s o h b l a in acetone benzene carbon tetrachloride ethyl a&tate ether light petroleum or toluene. 0.2920 made up to 50 C.C. with water gave &-4.0° (Ventzke) iii a 2-dcm. tube at 3 2 O whence [a] - 1 1 8 * 8 O . The pJati?tichZoSde separates from a fairly concentrated aqueous solution as a bright ochreous crystalline powder. Fouend Pt = 18.0. (C~,E,04N,HC1),PtC14 requires Pt = 18.2 per cent. When kept in a steam-oven for a long time it slowly swells up and decomposes forming a dark brown spongy mass.It darkens aA 1 8 8 O and melts and decomposes a t about 2 0 4 O . The aurichtoride was obtained as a greyish-yellow amorphous precipitate which decomposed wit'hin an hour while remaining in the mother liquor. The hydro bromide crystallism in fine white needles which melt at 148-150O to a pink liquid: 0.3367 gave 0.1555 AgBr. Br=19*7. CI9H2,0,N,HBr requires Br = 19.5 per cent. It becomes slightly pink after two or three days and is readily soluble in water methyl or ethyl alcohol or glacial acetic acid, sparingly so in acetone chloroform or ethyl acetate and insaluble in amyl alcohol benzene carbon disulphide carbon tetrachloride, ether light petroleum or toluene. 0.4209 made up to 50 C.C. with water gave a - 4-4O (Ventzke) in a 2dcm.tube a t 3 2 O whence [a] - 9 0 ~ 6 ~ . The hydrdodide was obhined as a pale brown powder which melts and decomposes a t 1 1 5 O . The salt once separated from its aqueous solution is very sparingly soluble in water and therefore in the analysis the silver iodide was precipitat'ed from its alcoholic solution : 0.1560 gave 0-8200 AgI. I=28*3. C,&,O,N,HI requires I=27.8 per cent. It is readily soluble in methyl or ethyl alcohols very sparingly so in water acetone chlorofarm ethyl acetah or glacial acetic acid and insoluble in amyl alcohol benzene carbon disulphide, carbon tetrachloride ether light petroleum or toluene. 0.3120 made up to 50 C.C. with alcohol gave a-2-8O (Y&ke)in a 2-dcm. tube a t 3 2 O whence [a] - 7 7 . 8 O . The sulphate separated from water in p d e pkk radiating plates wk& when washed with a mixture of equal pasts of absolute alcohol and sther melted a t 193O to a pink liquid with slight decompoeititm RA3SHIT BORPHYROXINE.459 0.5120 gave 0.1794 &SO,. S=4.8. It is readily soluble in carbon tetrachloride chloroform &by1 alcohol or toluene and almost insoluble in acetone amyl alcohol, benzene carbon disulphide ethyl acetate ether or light petroleum, 0.5600 made up to 50 C.C. with water gave a- 7*2O (Ventzke) in a 2-dcm. tube a t 32O whence [a] -111.4O. The phosphate did not crystallise from water but was obtained as a powder which melted a t 1 1 7 O t-o a pale brown transparent liquid : (C,gH,0,N)2,H2S0 requires S = 4.3 per cent. 0.4312 gave 0.1175 Mg,P,07.P=7.6. This salt quickly absorbs moisture when left exposed t o a damp atmosphere and becomes viscous. It is readily soluble in water, alcohol methyl alcohol or glacial acetic acid sparingly so in chloroform ethyl acetate or ether and insoluble in acetone amyl' alcohol benzene carbon disulphide carbon tetrachloride light petroleum or toluene. 0.5390 made up to 50 C.C. with water gave a - 6.1* (Ventzke) in a 2-dcm. tube a t 32" whence [a] - 9 8 - 2 O . The nitrate crystallises from water in voluminous fine leathery Lablets melting a t 1 2 2 O to a transparent pink liquid. An attempt was made to determine the nitratic nitrogen by the Crum-Prank-land met'hod but as soon as sulphuric acid was mixed with a solu-tion of 0.1367 grain of the iiitlrate in the nitrbmeter a blood-red coloration was at once produced and only 1.0 C.C.of moist nitric oxide was evolved a t 3 5 O and 750 m. The percentage of nitratic nitrogen thus found is only 0-38 whilst that required for C,,H,,O,N,HNO is 3.80 per cent. Moreover duplicat,e analyses did not always agree and the nascent nitric acid reacts with the alkaloid before it does with mercury: C,,H,O,N,H,PO requires f = 7.3 per cenf;. 0.1965 gave 0.4240 C 0 2 and 0.1090 H20. C,,H,,O,N,HNO requires C = 58.2 ; H = 6.1 per cent. It is readily soluble in water chloroform methyl or ethyl alcohol glacial acetic acid acetone or carbon disulphide sparingly so in benzene carbon tetrachloride ethyl acetate ether or toluene, and insoluble in amyl alcohol or light petroleum. 0.6835 made up t o 50 C.C.with water gave a-9.1° (Ventzke) in a 2-dcm. tube a t 3 2 O whence [a] -115.4O. The acetate was obtained as a pale brown transparent viscid varnish : C=58.7; H=6.1 460 RAKSRIT PORPHYROXINE. 0.2780 gave 0.6610 cko and 0.1920 H,O. C,,H2,04N,C,H,0 requires C = 64.8 ; H = 7.0 per cent. It is readily soluble in water chloroform methyl or ethyl alcohol or glacial acetic acid sparingly so in acetone or ethyl acetate and insoluble in amyl alcohol benzene carbon disulphide, carbon tetrachloride ether lightt petroleum or toluene. The oxalate crystallises from water in long pale yellow pris-matic crystals which darken and melt atn 182O with effervescence : 0.1670 gave 0.0492 CaC,O,. C,gH2,04N,C2H,0 requires C,H,O = 21.48 per cent. It is fairly readily soluble in water methyl alcohol or glacial acetic acid sparingly so in acetone ether or ethyl alcohol and insoluble in amyl alcohol benzene carbon disulphide carbon tetra-chloride chloroform ethyl acetate light petroleum or toluene.0.9340 made up to 50 C.C. with water gave a-12*3O (Ventzke) in a 2-dcm. tube a t 32O whence [a] -114.2O. The citrate is an amorphous yellowish-white powder which melts a t 82-85O to a t.ransparent pale brown liquid: 0.1135 gave 0.2680 C02 and 0.0735 H,O. (ClgH,,04N),C,H60 requires C= 64.1 ; H = 6.4 per centl. It is appreciably hygroscopic readily soluble in water methyl or ethyl alcohol or glacial acetic acid sparingly so in acetone, amyl alcohol carbon disulphide chloroform or ethyl acetate and insoluble in benzene carbon tetrachloride ether light petroleum, or toluene.0.1595 made up to 50 C.C. with water gave a-2-O0 (Ventzke) in a 2-dcm. tube atl 32O whence [a] -108.6O The tartrate is a pink crystalline powder which melts at 116-118O to a pale brown transparent liquid : 0.1080 gave 0.2475 CO and 0.0650 H,O. (@,,H230,N)IC4H,0 requires C= 63.4 ; H = 6.4 per cent. It is somewhat hygroscopic readily soluble in water methyl or ethyl alcohol or glacial acetic acid sparingly so in amyl alcohol, benzene carbon disulphide chloroform or ethyl acet'ate and in-soluble in acetone carbon tetrachloride ether light petroleum or toluene. 0.1635 made up to 50 C.C. with water gave a-1*8O (Ventzke) in a 2-dm. tube a t 32O whence [a] -95.5O'. The picrate is a bright yellow crystalline powder which becomes brown a t 1 7 1 O and melts a t 198O: 0.1158 gave 0.2258 CO and 0-0510 H,O. ( 2 ~ 6 4 . 8 ; H=7*6. C2H204 =,20*72. C=64*3; H=7*1. C=62*5; H=6*6. C=53.2; H=4-8. C1,H,,O,N,C,H,O,N3 requires C = 53.7 ; H = 4.7 per cent COAGULATION OF METAL SULPHIDE HYDROSOLS. PART I. 461 It is a non-deliquescent crystalline powder readily soluble in acetone chloroform methyl or ethyl alcohol glacial acetic acid, or ethyl acetate sparingly so in water amyl alcohol benzene or carbon disulphide and almost insoluble in carbon tetrachloride, ether light pet,roleum or toluene. 0.2658 made up t o 50 C.C. with water gave a - 1 - 5 O (Ventzke) in a 2-dcm. tube a t 3 2 O whence [a] - 4 9 ~ 9 ~ . OPIUM FACTORY, C AZIPUR INDIA. [Received October 31& 191S.

ISSN:0368-1645    

DOI:10.1039/CT9191500455

出版商:RSC    

年代:1919

数据来源: RSC

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COAGULATION OF METAL SULPHIDE HYDROSOLS. PART I. 461 Y XX.V.-Coag?clation qf Metal Sulphide Hydrosols. Payt I. Injhence of Distance b e t d e n the Particles of’ Q Sol on its Stability. Anomalous Pwtectiw Action of Dissolved Hydrogen Sulphide. By J%ANENDRA NATH MUKHERJEE and NAGENDRA NATH SEN. THE coagulation of the sulphide sols has been studied by a fairly large number of investigators. There is however fundamental disagreement between the results obtained by different authors. It was suggested by one of us in a previous paper (17. Amer. Chem. Soc. 1915 37 2024) that the discrepancy is due to the difference in the methods of observation some of which are undoubtedly defective. The method used in that paper is a comparative one, and is based on visual observation of the changes in the sol with time.It will be conceded that no objection can be taken against it, although it has one disadvantage in so. far as it is not instru-mental. This does not in any way interfere with the trend of the results. The method is found to be the most suitable one and gives concordant numbers. Contrary to the observations of Freundlich (Zeitsch. physikd. C’hern. 1903 44 129) it’ was shown that dilution with pure water increases the stability of arsenious sulphide hydrosols to coagulation by electrolytes. The electrolytes studied were all salts of uni-valent cations. The difficulty in explaining the observed facts on the basis of the adsorption theory as developed by Freundlich (Zoc. c i t . ; ibid. 1910 73 385; 1913 83 97; 85 398 641) was men-tioned.This point has also received attention from Kruyt and Spek. (Prnc. I<. Alcacl. T?7etensch. Amsterdam 1915 17 1158) who examined three electrolytes namely the chlorides of potassium 462 MUKHERJEE AND SEN COAGULATION OF barium and aluminium but could not find the stabilising influence of dilution of the sols for ions other than potassion. They do not seem to recognise that the adsorption theory as it stands is in-sufficient to explain all the facts observed and do not consider the influence that the distance between the particles of the sol may have on the stability of the sol. Further Yonng and Neal ( J . Physical Chem. 1917 21 14) in a thorough study of cupric sulphide hydrosols remark “the amount of electrolyte required is independent of the dilution of the sol within wide limits.This latter was found to be true within rather close limits by Freundlich for arsenic sulphide sols.” The method used by Young and Neal consists in mixing equal volumes (2 C.C. each) of electrolyte and sol and noting the respective con-centration of electrolyte that just produces complete separation of the colloid in twenty-four hours and that which just fails to do so. These two limiting concentrations give a measure of the stability of the sol o r the coagulative power of the electrolyte. This method is one due to Freundlich and generally used by other workers. Ti. will be noted that the concentrations of electrolytes employed are, necessarily such as would require a fairly long time for the com-plete separation of the colloid.I n the earlier paper (Toc. f i t . ) the process of co’agulation was discussed in detail and i t was statetl that “the time for complete settling is not vharacteristic of t . 1 1 ~ rate of coagulation.” The justification of ally rriethod lies jn so far as it indicates the progress of coalescence. The increased mass of particles wit-h progress of coalescence introduces a new factor, namely their gravitatioiial effect which masks the true behaviour of the sol as will be clear from the following observations on mercuric sulphide sols. These sols are opaque unless very di1ut.e. On the addition of electrolytes there is a quiescent period followed by a sharp clearing of the whole liquid. At this stage the liquid loses its homogeneous appearance and visible clots are found suspended throughout the liquid.As the change is sharp the times noted by different observers agree satisfactorily. I n this way it is found that a mercuric sulphide sol on saturation with hydrogen sulphide, requires a longer time for the observed change than when it is not so treated-the electrolyte concentration of coarse being identical. These experiments leave no doubt that dissolved hydrogeii sulphide iiicreases the stability of the sol. The subsequent settling of these clots however requires a very long time which is about the same for both samples. So long as the respective times required for the clearing of the sols are very small compared with the time required f o r the subsequent settling of the clots i t is found tha METAL SULPHlDE 1IYI)ROSOLS.PART I. 463 the times that are necessary for the complete separation of the colloid do not differ much in the two cases. However with electro-lyte concentrations where the clearing requires intervals comparable with that required for the subsequent settling of the clots regular differences in stability are observed even if the times necessary for complete separation of the colloid are noted. ITlufEuence of DiLutiom om the Stability of a Sol. The method employed is to mix 5 C.C. each of sol and electrolyte in carefully cleansed test-tubes. For reasons discussed in the previous paper the electrolyte is always added to the sol. Thorough mixing is secured by pouring the mixed liquids from one test-tube to another and repeating the process. The mixed liquid is shaken regularly a t short intervals and the changes with time are observed.As before the times required for perceptible change in the sol for the attainment of maximum opacity and for the first appearance of visible particles are noted. The time for com-plete separation of the colloid is also noted when thought desirable. The comparison is always carried out side by side. For sols of mercuric and cupric sulphides the time for the appearance of visible particles is noted. With dilute sols it is necessary to note the time for complete settling of the particles. Experiments were made on arsenious sulphide sols with solutions of hydrogen ammonium potassium lithium barium and aluminium chlorides aluminium sulphate and thorium nitrate. With sols of mercuric and cupric sulphides solutions of potassium, ammonium and barium chlorides aluminium sulphate and thorium nitrate only were studied.All the glass vessels were cleansed by dipping them for twenty-four hours in chromic acid d u t i o n after they had been washed with dilute alkali hydroxide. The need for scrupulous care i n the washing of the vessels and avoiding dust or other impurities cannot be too strongly emphasised. This holds especially for the extremely dilute solutions used in some cases. (a) Arseniozrs Sztlphide Sols. In the presence of salts having univalent cations dilution of the sol increases its stabilit'y in each case. The magnitude of the stabilising effect of dilution will be evident from t,able I. The electrolyte concentrations given are end concentrations that is, what results after mixing.Sols mentioned in the several tables are diff erent unless stated otherwise. Coagulation " means the T 464 MUKHERJEI!! ANb SEN COAatJLATION OF breaking up of the colloid into flakes 8 0 that the liquid is clear or very slightly coloured. T-LE I. Sol A contained 17.58 millimoles of arsenious sulphide per litre. Sol B was prepared by diluting sol A five times and sol C by diluting sol L4 ten times with pure water. Electrolyte lithium chloride. Dilution (after mixing). Sol. A. Sol. B. 5Nf16 ... - -5Nf32 ... c Coagulation after 30 seconds. Coagulation after N / 8 . . . . . . Instantaneous coagulation. half an hour. N/16 ... Change perceptible Change just after on mixing. mixingnot per-Coagulation not ceptible.observed after 1 & hours. Sol. 0. Coagulation af tor 20 seconds. Coagulation after 50 minutes. Perceptible change after 8 minutes. Coagulation after 2$ hours. Change perceptible after 45 minutes. On the other hand in the presence of the salts of aluminium and thorium the stability decreases on dilution as will be seen from table 11. The data refer to the same three sols. The observations in tables I and I1 were completed within two days, and neglecting the slight “ ageing” during t.his interval the data may be taken as comparable. TABLE 11. Electrolyte thorium nitrate. Dilution. Sol. A. N / 10,000 Instantaneous coagulation. N/20,000 Perceptible turbidity just after mixing, Sol cha.nges N/30,000 Perceptible turbidity after half an hour.slowly. N/40,000 -Sol. B. Sol. c. Instantaneous Instantaneous coagulation. coagulation. Coagulation i n 2 Coagulation within minutes. half a minute. Perceptible turbidity Coagulation in 4 - Coagulation in 53 after 5 minutes. minutes. IlliRUttXl. Solutions of salts of bivalent cations display an interesting aspect With dilute of the effect of dilution of t.he sol on its stability METAL SULPHIDE HYDROSOLS. PART I. 465 sols the stability increases on dilut,ion whereas with sols very rich in sulphide content the stability diminishes on dilution and for a rich sol it is possible to reach a limit where on further dilution t~he sol becomes more stable. Moreover from table I11 it will be seen that the stability relations on dilution vary with the concen-tration of the electrolyte itself.TABLE 111. Electrolyte barium chloride. Arsenious sulphide sol containing 19-45 millimoles per litre. Dilution of N/800 ... Complete coagula-tion in 1 minute. Electrolyte. Original Sol. N/1000 . . . Change perceptible after half a minute. Clots appear through-out after 17 minutes. Nil200 . . . Change perceptible in 2 minutes. Clots appear after 1 hour 7 minutes. Sol diluted 4 times. Change perceptible in 20 seconds. Coagulation after 4 minutes. Change perceptible in 1 minute. Clots appear throughout after 18 minutes. Change perceptible in 2 minutes. Clots appear after 52 minutes. Sol diluted 16 times. Perceptible changv after 1 minute.Coagulation afte 12 minub. Change perceptible after 2 minutes. Clots a p p e a r throughout after 26 minutes. Change perceptible a f t e r a b o u t 3 minutes. Clots appear a f t e r 1 hour 1 minute. (b) Mercuric and Cupric Sulphidc Sols. In the case of mercuric and cupric sulphide sols it is found that dilution increases the stability of the sol irrespective of the nature of the electrolyte. The effect cannot reasonably escape observation. All these apparently anomalous facts can be explained on the assumption that distance between t3he particles of a sol is an important factor in determining its stability. On the adsorption theory of Freundlich coagulation is due to the neutralisation of the charge of the particles of the sol by adsorbed cations.Other things being equal i t follows that an increase in the total surface of the colloid would mean a decrease in the surface concentration of the cation so that a higher concentration of the electrolyte would now be necessary to neutralise the charge on the particles. The amount adsorbed is necessarily small and its effect can only be perceptible when (a) the difference in surface is great compared with the total quantity of the electrolyte present that is ( b ) when the electrolyte concentration is sufficiently low. It is evident that for the concentrations employed in the case of salts of univalent T* 466 MUKHERJBX AND SBN COAGULATION OF cations the difference in stability predicted by the adsorption theory on dilution would be negligible.The adsorption theory thus pre-dicts that dilution of the sol will always diminish its stability and in the limiting case of salts of univalent cations this theoretical diminution may not be perceptible. It has been assumed in the above discusbion that the individual particles in the sol do not change in any way on dilution and hence the total surf ace of the colloidal particles will decrease proportion-ally to the dilution of the sol. The observed increase in stability cannot thus be explained by the adsorption theory as it stands. However if it is considered that dilution also increases the distance between the particles of a sol it explains easily the increase in stability observed. It may be stated here that Freundlich's adsorption theory does not con-template any effect of the distance between colloidal particles on the stability of the sol.The increased distance samehow decreases the facility Gr coalescence and thus increases its stability as will be evident from the sequel. Dilution thus brings into play two factors which have opposite effects on thb stability of the sol. The observed increase or decrease in stability is due to the predominating influence of one over the other. The observations given in table I11 are instructive. I n order that the difference in total surface may have a decisive effect on the stability the quantities withdrawn by adsorption shoald be comparable with the total quantity of electrolyte present that is, appreciable differences in the concentrations of the electrolyte in the bulk of the liquid should result with the different dilutions of the sol employed.As the dilution of the electrolyte increases the differences in h t a I surface become more dominant in determining the stability of the sol. On the other hand if the electrolyte concentration is kept constant then as the dilution of the sol increases the total surface of t'he colloid decreases rapidly and the effect of adsorption becomes counterbalanced by that. of the increase in distance. This is apparent from table IV. TABLE IV. Sol contained 19-45 millimoles of arsenious sulphide per litre. Electrolyte aluminium sulphate. Dilution N / 4000. Sol diluted Dihted Dilubd Original Sol. 4 times. 16 times. 20 times. Coagulation in Coagulates im- Coagulation in Coagulation in 7 minutes.mediately on 40 seconds. 50 seconds. mixing METAL SUL9WD!E HYDROSOLS. PART I. 407 Further dilutions could not be examined as it became increaa-ingly difficult to follow the changes in the sol. With mercuric and cupric sulphide 9019 much higher concestra-tisns of electrolytes are required for coagulation and it is interest-ing to note that in the case of these sols dilution always increases their st'ability. This may be ascribed to the fact that these sols are generally poorer in cdloid content and that the adsorption is much smaller in comparison with the arsenious sulphide sols used. It should be remarked that the total surface varies directly with the dilution whereas the mean distance between the particles varies with the cube root of the dilution.C o m p m t i v e Stability of Sols having the same Colloid Content but dijjfem'ng in the Degree of Dispersion. In the foregoing it has been assumed that on dilution the individual particles da not suffer any change. The observations of Coward (Trans. Faraday Soc. 1913 9 142)show that dilution does not bring about a proportionate decrease in the number of sub-microns and that the migration velocity of the particles in an electric field changes on dilution. Young and Neal (loc. cit.) have also observed an increase in migrabion velocity on dilution with cupric sulphide sols. I n view of these observations a comparison of a pair of sols which have the same colloid content but differ in the degree of dispersion was thought desirable. This is possible with arsenious sulphide sols.Such a comparison has the advantage that in reality two sols are compared one of which has a smaller number of larger particles whilst the 0 t h ~ has a larger number of smaller particles for the same volume. A simple calculation will glhow that the mean distance between the particles and the total surface of the colloid in a given volume differ in the same ratio. The rahio is given by ~ ( T z ) y(n2) where " njl " and " n2 " denote the number of particles present in each case. The relative effects of these factors can thus be compared directly. The finer sol will evidently contain a greater number of partides )khan the coarser one The resulh leave no doubt as to the greater stabilising effect of increased distance. Of course here also with dilute electrolyte solutions and sols differing greatly in the degree of dispersion the surf ace effect is perceptible.By varying the conditions of experiment a seriet3 of sols having the same sulphide content was prepared. For comparison bhe coarsest and the finest sols are selected 468 MIJKHERlEE AND SEN COAQULATION OF TABLE V. Electrolyte strontium chloride. Both sols contained 8.52 millimoles of arsenious sulphide per li tre. Dilution. Sol I (fine sol). N/200 ......... Coagulation after a few N/300 ......... Coagulation after 2 N/400 ......... Coagulation after seconds. minutea, 13 minutes. Sol I1 (coarse sol). Coagulation after a minute. Coagulation after 4 minutes. Turbidity perceptible after 1 minute. Aportion of the colloid had separated after 40 minutes.NlljOO] ......... The greater portion had separated after 40 minutes. It appears that the magnitude of the difference in stability is roughly the same for fhe different electrolytes. It will be seen from the sequel that dissolved hydrogen sulphide has an anomalous effect on the rate of coagulation of arsenious sulphide sol in the case of certain salts. Here also the greater stability of the coarser sol is quite marked. I n table VI are given the respective con-centrations of an electrolyte which corresponds with about the same coagulation time for these two sols. TABLE vr. Comparable concentrations. - Electrolyte. Sol I. Sol 11. SrC1 ............ N/600 N/400 ............ N/400 N/300 KCI ............ N/20 21’116 LiEi ............y;;; NH,Cl ......... $\& Remark. In presence of H,S. Influence of Dissolved Hydrogen Sulphide an the Stability of Metal Sulphide Sols. (a) Arsenious Sulpkide. I n the paper referred to it was stated that dissolved hydrogen sulphide stabilises arsenious sulphide sols against coagulation by electrolytes. The electrolytes used a t that time were salts of uni-valent cations. It has subsequently been observed that arsenious sulphide sols behave in an anomalous manner. When solutions o METAL SULPHIDE HYDROSOLS. PART I. 469 barium and strontium chlorides magnesium sulphate and thorium nitrate are used the sol containing hydrogen sulphide becomes less stable. Tables VII and V I I I show that the diminution in stability is as marked as the increase in stability observed with the other electrolytes.In each set of experiments the sol and the electrolyte were both saturated with hydrogen sulphide freed from impurities. Five C.C. of each were withdrawn by means of a pipette with the help of a rubber hand pump and kept in separate test,-tubes. The liquids were then mixed as usual and kept well corked with india-rubber stoppers. Care should be taken %hat the liquids do not touch the rubber. TABLE VII. Arsenious sulphide sol containing 17.58 millimoles per litre. Electrolyte aluminium sulphate. Dilution. Has absent. H,S present. N/24,000 ... Complete coagulation Partial coaguIation after N/30,000 ... Partial coagulation after Only slight turbidity after after 2 minutes. 34 minutes.6 minutes. Complete 21 minutee. after 11 minutes. TABLE VIII. Comparable Concentrations. Sol I. Sol 11. Sol 111. - - H,S H2S H2S H,S H,S H,S Electrolyte. absent. present. absent. present. absent. present. KCl ............ NIL8 - - N/16 NH,C?l ......... NJ20 $2 N/20 N/12 N/20 BaC1 - ............ N/800 N/1000 N/800 N/1000 - SrC1 - ............ N/300 N/400 NJ300 N/400 - Th(NO,) ...... N/10,000 N/12,000 - - - -The data with thorium nitrate refer to the sol mentioned in Sols I and I1 are the same as those in tables 'v and Sol I11 is a fine sol containing 34.8 millimoles of arsenious The resulk show that the magnitude of the stabilising effect A quantitative table VII. VI. sulphide per litre. varies somewhat with the quality of the sol used. comparison is beyond the scope of the present paper.(b) Mercuric Sulphide. Hydrogen sulphide has a similar influence on mercuric sulphide sols. Increase in stability was observed for ammonium an 470 MUKHERJEE AND SEN COAGULATION OF potassium chlorides and a diminution for barium and strontium chlorides. The sols were prepared as usual from the freshly precipitated hydroxide or sulphide after they had been washed free from electro-lytes. The coagulation of these sols differs in one respect from that of arsenious sulphide sols possibly due to the fact that they are comparatively poorer in sulphide content. Sols unless very rich in sulphide show a minimum coagulation time (as defined here); for example a mercuric sulphide so1 gave a clearance time of about two minutes from Nj20- to Nl3OO-banum chloride.With more dilute solutions the coagulation time increased rapidly as usual. The sols had a blackish-grey appearance. (c) Cupric Sulphide. It is well known that dissolved hydrogen sulphide markedly stabilises the pure sulphide sols both in aqueous and non-aqueous media (Lottermoser J. p r . Chem. 1907 [ii] 75 293) and facili-tates their solution. It is natural to conclude that the same pro-tective effect would be observed with the sulphides of different metals in the presence of electrolytes. This is however not the case here. It has been found that hydrogen sulphide diminishes the stability of cupric sulphide sols. This holds good for all the electrolytes studied namely potassium ammonium strontium, and barium chlorides and aluminium sulphate and the anomaly observed with arsenious and mercuric sulphide sols is absent.Young and Neal (Zoc. cit.) could not find any perceptible effect of hydrogen sulphide on the stability. This is probably due to the method they used. The observed diminution in stability can be understood from an observation of Young and Neal. They find that hydrogen sulphide diminishes the velocity of migration of the particles of a cupric sulphide sol in an electric field. It follows from the well-known Helmholtz-Lamb formula (Rep. Brit. Asso'c. 1887 495) that a diminution of the electric charge of the particles takes place pro-vided that other factors remain constant. The result will be a diminution in stability as a smaller amount of adsorbed cations will now be required to discharge the particles.As it is not clear that simultaneous measurements of viscosity and other properties were made the parallelism loses much of its significance. Solutions of ammonium potassium barium and strontium chlorides and aluminium sulphate were studied. With ammonium and potassium chlorides nearly satmurated solutions have to be used METAT SUIiPHIDE HYDaOSOLS. PART J. 471 TAEXLE IX. Clearance time. .A J 7 Electrolyte. Dilution. H,S absent. H,S present. KCl .................. - 6 minutes. A few seconds. BaCl .................. N/20 9 9 ) 4 minutes. Al,(SO,) N/2000 13 9 9 9 9 9 ............ Protective Action of Alkali Sulphides and Alkali Hydroxides. Solutions of potassium and sodium sulphides have a more marked protective action.This stabilising influence has been found for ammonium potassium barium and strontium chlorides and aluminium sulphate on hydrosols of cupric mercuric and arsenious sulphides. A trace greatly facilitates the preparation of sols rich in sulphide and largely increases their stability. The protective action of alkali sulphides is probably due to the free alkali hydroxide present as a result of hydrolysis. Since these substances dissolve arsenious sulphide with the form-ation of arsenites and thioarsenites i t is not possible in this case to refer the protective action observed to the hydroxidions alone. Indeed the liquid obtained by dissolving in a few C.C. of dilute alkali hydroxide as much arsenious sulphide as possible has an equally marked protective action on the sols of t.hese three sulphides.However as alkali hydroxide does not react with the other sulphides and produces similar protective action i t is prob-ably that' the effect of all these substances is due to the trace of free alkali hydroxide present as the result of hydrolysis. Freundlich (Zeitsch. physikul. Chem. 1903 44 144) has observed t'hat salts of alkali metals with organic anions of large mass have a lower coagulating power than the corresponding salts of inorganic acids. He refers this to the protective action of these anions due to greater adsorbability but in view of the preceding this can as well be due to the trace of alkali hydroxide present on hydrolysis. I n conclusion it may be stated that' the anomalous influence of hydrogen sulphide is not without? parallel. Recently Freundlich has found somewhat similar behaviour with ferric hydroxide hydrosol (Biochem. Zeitsch. 1917 81 87). An actual reversion of stability was notl however observed in this case. So far as can be understood from the abstract of the paper he explains these irregularities as due to selective adsorption (loc. cd.). It remains The behaviour of the sols is thus very regular. This is also the case with alkali hydroxides 472 ASTON A SIMPLE FORM OF APPARATUS FOR to be seen how far these observations can be explained on the basis of tjhe existing theories. Our best thanks are due t o Sir P. C. RBy and to Dr. J. C. UNIVERSITY COLLEUE OF SCIENOE, Ghosh. CALCUTTA. [Received Fehruary 41h 1919.

ISSN:0368-1645    

DOI:10.1039/CT9191500461

出版商:RSC    

年代:1919

数据来源: RSC