摘要:

THE ELECTROLYTIC PREPARATION OF DISULPHIDES. PART I. 2021 CXC V I I. - The E 1 ec t.1.o 1 y t i c P r epa r a t io 12 o f Disulphide s. Part I. By THOMAS SLATER PRICE and DOUGLAS FRANK TWISS. IN a preliminary note (Proc., 1906, 22, 260), we have shown that the electroIysis of a solution of sodium benzyl thiosulphate yields dibenzyl disulphide. The electrolysis was carried out in a beaker, the cathode consisting of a sheet of platinum foil lying close to the sides of the beaker, the anode being a piece of stout platinum wire. This apparatus was used because it was thought that the electrolysis would probably take place in a similar manner to that of sodium acetate, a, Dibenxyl Bisulphide and Diethyl Disulphide. high current density a t the anode being necessary :2022 PRICE AND TWISS: THE ELECTROLYTlO When a pure aqueous solution of sodium benzyl thiosulphate was used, the solid dibenzyl disulphide obtained mas contaminated by a quantity of a pungent oil, which, from its behaviour towards the air, was benzyl mercaptan.The formation of the latter was probably due to the decomposition of some of the complex thiosulphate by acid formed during the electrolysis. The addition of sodium bicarbonate or carbonate, in quantity sufficient to neutralise any acid formed, completely prevented the formation of any mercaptan, and the only product was then a white solid, which investigation proved to be dibenzyl disulphide. Consequently, in all later electrolyses, an equi- valent weight of sodium carbonate was added to the complex thio- sulphate taken.All the earlier experiments were carried out in the apparatus described, that is, in an undivided cell, and the results were so good, yields amounting to even 80 per cent, of the theory (calculated on the thiosulphate compound taken) being obtained, that it was assumed that the action was exactly as had been anticipated. However, on placing the thiosulphate compound in the anode chamber OF a divided cell, it was found that no disulphide was formed, whereas on carrying out the electrolysis with the thiosulphate compound in the cathode com- partment, the usual yield of the disulphide was obtained. The forma- tion of the disulphide is thus due to reduction at the cathode, hydrogen sulphite ions being produced a t the same time according to the equation : ZC,H,*CH,*S*SO,' + 21'1 -+ (C,H,*CH,),S, + 2HS0,'.One would be inclined to suppose that the product of reduction at the cathode would be the mercaptan, since it is usually stated that disul- phides are very readily reduced, but in none of the experiments where platinum electrodes and an equivalent quantity of sodium carbonate were used has any mercaptan, as indicated by the odour, been formed. This has also been the case in a few experiments where a lead cathode, at which electrochemical reductions generally take place much more readily than with platinum electrodes, has been used. Fichter and Bernoulli (Zeitsch. Elektrochem., 1907, 13, 310) have found that the reduction of p-toluenesulphonyl chloride t o p-tolyl mercaptan takes place quantitatively when lead cathodes and a low current density are used; electrodes of nickel or platinum did not give such good results.I n the present case, it seems as if the C,H,-CH,*S* residue, which is formed when the link between the two sulphur atoms in the sodium benzyl thiosulphate ' is broken, combines with another such residue before reduction to tbe mercaptan can take place. That the two residues will unite in this manner was shown by Bunge (Ber.. 1870,PREPARATION OF DISULPaIDES. PART I. 2023 3, 295, 911), who prepared disulphides (ethyl, amyl, and phepyl) by the electrolysis of alcoholic solutions of the sodium mercaptans. The disulphides were formed at the anode. Further experiments to find out the conditions necessary to obtain the best results showed that, when the pure sodium benzyl thiosulphate is used, there is no great advantage in having the anode and cathode in separate compartments, so that the apparatus required is very simple.Also, the yield of disulphide is improved by using a concentrated solution, a low current density at the cathode, and a temperature of 60--7OO. As will be seen from the figures given in the experimental part, the lower the current density a t the cathode the better is the yield of disulphide, but, since with very low current densities the time necessary for electrolysis is unduly prolonged, it is convenient to use a current density of about 1 ampere per sq. dcm., and to pass more than the theoretical current. The conditions for the electrolysis may be summarised as follows. For the electrolysis of sodium benzyl thiosulphate, a concentrated aqueous solution (5 grams in 30 C.C.of water) is used in which an equivalent quantity of sodium carbonate (3.16 grams) has been dissolved. The mixture is warmed to 60-70" and 50 per cent. more than the theoretical currant (theory =0*593 ampere-hour) is passed, using a cathode current density of approximately 1 ampere per sq. dcm. The disulphide is collected and recrystallised once from alcohol, a pure product being then obtained. Uiethyl disuZphide may be prepared in a similar manner from sodium ethyl thiosulphate, but, being a liquid, it is extracted with ether and purified by distillation. Since the isolation of the pure sodium benzyl thiosulphate is a somewhat tedious process, experiments were next carried out to find whether the mixture obtained by heating together the alcoholic solution of benzyl chloride and aqueous sodium thiosulphate could be directly electrolysed with good results, Since the mixture contains sodium chloride together with sodium benzyl thiosulphate, i t was necessary to use a divided cell for the electrolysis, otherwise the chlorine liberated a t the anode might enter into reaction with other substances in solution; the anode solution was sodium carbonate.The results were quite satisfactory, a yield of more than 80 per cent. being obtained, especially when the solution was kept well stirred by continuous rotation of the cathode. Diethyl disulphide may be also prepared by the electrolysis of the mixture obtained from the interaction of ethyl iodide and sodium thiosulphate.A yield of about 50 per cent. mas obtained. Only one such experiment was carried out, a rotating cathode being used, and the conditions necessary for obtaining a good yield were not further 6 s 22024 PRICE AND TWISS: THE ELECTROLYTIC investigated. It is noteworthy that, although in this case the disulphide is a liquid and remains in solution (which contains alcol~ol) to some extent, there does not seem to be any appreciable formation of mercaptan. The disulphide, as it is produced, remain8 distributed throughout the liquid in the form of fine drops, owing to the action of the rotating cathode, but it does not seem to be reduced, whereas p-toluenesulphonyl chloride is reduced to the mercaptan under such conditions. A t present, no further experiments have been carried out to find under what conditions disulphides may be reduced to mercaptans, as we have confined our attention to the formation of disulphides.It is possible that further investigations on the velocity of reduction of sodium benzyl thiosulphate under known cathode potentials may lead to interesting results. The formation of disulphides by electrolysis throws light on the constitution of thiosulphates. Bunte in his original communication on sodium ethyl thiosulphate (Bey., 1874, 7, 646) pointed out that the formation of ethyl mercaptan by the decomposition of sodium ethyl thiosulphate-by acids was in agreement with the formula : NaO*S0,*S*C2H5, from which it follows that the formula, of sodium thiosulphate is NaO*SO,*SNa. This is also supported by the results of the electrolytic reduction of the salt, since it is difficult to imagine how a disulphide could result, from the electrolytic reduction of a compound having the formula : :>s<:$H5 9 S ONa which is deduced from the alternative formula o>S<oNa for sodium thiosulphate.Gutmann (Bey., 1905, 38, 1728 and 3276; 1906, 39, 509 ; 1907, 40, 3614), from 8 study of the actionof sodium arsenite (and potassium cyanide) on tri- and tetra-thionates, arrives at the concliision that the formula for sodium thiosulphate is His reasons are as follows. When sodium tetrathionate reacts with sodium arsenite in alkaline solutions, the reaction takes place according to the equation : Na,S4O6 + 3Na3As03-+ 2NaOH = 2Na,AsS03 + Na,AsO, + 2Na,S03 + H,O or S,O, = 28 + 0 + 2S0, ; two molecules of monosulphoxyarsenate, one of nrsenate, and two of sulphite being formed.According to Gutmann, this cannotPREPARATION OF DISULPHIDES. PART I. 2025 be explained by Mendeldeff's formula for tetrathionate, namely, NaO*S02mS*S*S02*ONa, which is derived from the formula : O,S( ONa) (SNa) for sodium thiosulphate. If, however, thiosulphate is given the isomeric form :>S(ONB)~, the formula for tetrathionate mould then be Nag>S<E,g>S<gNa, that is, a derivative of persul- phuric acid. The above reaction could then be explained, thus : Nao>S<S 0 0.0 8>Sc=oNa ' 0 --3 y > S * o * s g ; N a + 0 + 25, Sodium pyrosulphite. corresponding with Sodium pyrosulphate. S The formula 0>S(ONa)2 is, however, not in accordance with our results, and, moreover, it mould lead to the formula OS(ONa)2 for sodium sulphite, instead of the generally accepted formula : Na*SO,*ONa.The authors are, however, of the opinion that Gutmann's results can be explained by MendelBeff's formula for sodium tetrathionate.* Although not explicitly stated, Gutmann's contention seems to be, that the two residues, *SO,*ONa, which, according to Mendeldeff's formula would be left after the withdrawal of two atoms of sulphur from a molecule of tetrathionate, should unite with the formation of a molecule of dithionate ; the dithionate would not then give arsenate and sulphite, since dithionates have no action on arsenites. Now, Friessner has shown (Zeitsch. EZekt.trochem., 1904, 10, "265) that dithionate is formed at the anode when neutral or alkaline solutions of sodium sulphite are electrolysed, and that the process is represented by the equation 2S0," + 0 + H20 = S,O," + 20H', and not by the expression 2S0," + 2@ -+ S20,"; that is to say, sulphite ions do not condense directly with the formation of dithionate ions.The reversal of the first equation mould give the two sulphite ions and the one atom of oxygen necessary for the formation of amenate; two hydroxyl ions (that is, 2NaOH) being used up at the same time as required by Gutmann's results. Ditliionates, however, are not decomposed by boiling with alkalis, so that the equation does not seem to be reversible; but in the decomposition of tetrathionate, after the * The alternative formula of Debus, namely, NaO'SO,'S'O'SO,*SKa, has not been taken into consideration, since Hertlein has shown (Zeitsch.physiknl. Chem., 1896, 19, 287) that it does not accord with the experimental facts nearly so well as that of Mendeldeff.2026 PRICE AND TWISS: THE ELECTROLYTIC two sulphur atoms are removed, the two residues, *SO,*ONa, would not combine to form dithionate (see above), and would in all probability react according to the equation : 2 S02*ONa+2NaOH=2Na2S0,+H,0+0 . . . . ( A ) which is in reality the reverse of the above equation. This at the same time probably explains why two molecules of sodium hydroxide are necessary in Gutmann’s equation, A similar explanation will hold for the action of potassium cyanide on sodium tetrathionate. Gutmann found that the reaction was expressed by the equation : Na2S40, + 2KCN + 2NaOH = 2KCNS + Na,SO, + Na,SO, + H,O. I n this case, the free atom of oxygen shown in the equation ( A ) Gutmann further found that sodium trithionate acts on sodium oxidises one of the molecules of sodium sulphite to sodium sulphate.arsenite in alkaline solution according to the equation : NaaS,O, + ZNa,AsO, + 2NaOH = 2Na2S0, + Na,AsSO, + Na,As04 + H,O This also is in accordance with the formula : NaO*SO,-S.SO2-ONa for sodium trithionate. The latest published results of Gutmann (Bw., 1907, 40, 3614) on the action of alkalis on sodium tetrathionate are explained equally as well by Mendeldeff’s formula as by that put forward by Gutmann. or S,O, = 2S0, + S + 0. EXPERIMENTAL. Electrolysis of Pure Sodium BenzyZ ThhiosuZphate.-In these experi- ments, the current was registered by an ammeter and was maintained constant by means of a variable resistance in the circuit; the total current passed was measured by a copper coulometer.The solution was stirred from time to time during the electrolysis, and an undivided cell was used. The following table shows the improved yield obtained by the addition of sodium carbonate or bicarbonate. I n the first experiment, the pure solution of the substance was electrolysed, whilst in the second and third, equivalent quantities of sodium carbonate and bicarbonate were respectively added. Five grams of sodium benzyl thiosulphate were used in each case, and the volume of the solution was 50 C.C. The current is given in terms of that theoretically required for the complete reduction of the substance, and the yields are expressed as percentages of those theoretically expected from the weight of substance taken.The yields were obtained by filtering the crude disulphide into a Gooch crucible, washing well with water, and thenPREPARATION OF DISULPHIDES. PART I. 2027 drying to constant weight in a vacuum desiccator. The crude disulphide was practically pure, the melting point scarcely altering on recrystallisation. The current density (C.D.) is expressed in amperes per sq. dcm. Cnrrent, per cent. C. D. Yield, per cent. 107.6 1 '27 35.3 1 0 6 5 1.27 61.4 97.14 1.27 61'8 The following table shows the effect of variation of (1) the concentra- tion of the solution, (2) the temperature, (3) the current densi$y a t the cathode.I n each case, 5 grams of the thiosulphate compound were taken and the equivalent quantity of sodium carbonate added. fi0. 1 2 3 4 5 6 7 8 Current, * per cent. 107'2 106.5 99.4 107-6 102.7 105.2 100'4 118.1 C . D. 1.27 1.27 1.27 1.27 1 *27 1 *27 2.54 96.0 Volume of solution, 30 C.C. 50. 9 , 100 9 , 50 J , 50 >, 50 ), 60 ), J > Temp. 15" 15 15 15 70 70 15 15 Yield, per cent. 93.8 61 *4 42.7 41'9 73.5 81.6 46.3 18.0 * I n each case, the amount of current passed was 100 per cent., according to the ammeter reading, but, since the resistance in the circuit has to be altered from time t o time in order to keep the current constant, the correct number of ampere-hours cannot be obtained from the ammeter reading, but only from the copper coulometer, Experiments 1 to 4 show that an increase in the concentration improves the yield, whilst a comparison of 2, 5, and 6 shows the beneficial effect of a higher temperature.The difference in the yield in experiments 5 and 6 is due to the fact that the beaker in the latter experiment was covered with a clock glass, thus preventing the volatilisation of disulphide which took place in experiment 5 with an open beaker. Experiments 2, 7, and 8 show clearly that a low current density is favourable to the production of the disulphide. This is what might be expected, since with a high current density a large amount of hydrogen would escape, without exerting its reducing action on the complex thiosulphate. I n order to investigate more thoroughly the effect of current density, the actual amount of hydrogen liberated a t the cathode was measured, and compared with the amount of hydrogen liberated from a voltameter {nickel electrodes in a solution of sodium hydroxide) in series with the electrolytic cell.I n these experiments, it was, of course, necessary to use a divided cell, each cathode being contained in a porous pot. The apparatus used was similar to that described by Muller and Schellhaas (Zeitsch. Elektrochem., 1907, 13, 257).2028 PRICE AND TWISS: THE ELECTROLYTIC An abstract of the results obtained is given in the following tables. The solutions contained one gram of sodium benzyl thiosulphate and one equivalent of sodium carbonate in 40 C.C. The times given are expressed in percentages of the theoretical time necessary for complete reduction, The '' per cent.H " signifies the percentage of hydrogen used in reduction. C. D. = 1'03. Time. Per csnt. H. 7.7 38 *8 30.8 38.6 53'8 (41'1) 76 '9 37.7 100.0 31 -7 123.1 24 -8 146.2 19.0 169.2 12'1 C. D. = 0.685. Time. 15.4 46-1 76.9 100-0 1309 161*5 192.3 223 '2 Per cent. H. 57.8 48.7 43.7 40.1 30.7 23.7 13-5 13.2 C. D. = 0.125. 1.4 97 -3 11'2 85.3 19 -7 81-8 28 '1 78.3 36.5 77.7 44 '9 73.1 53.4 73.9 61.8 70'4 Time. Per cent. H. A lower current density thus increases the percentage of hydrogen used in reduction. Of the following tables, the first shows that a lead cathode gives slightly better results than one of platinum, the strength of solution being the same as above. The second table shows that an increase in concentration of the solution also gives better results ; the solution contained 4 grams of sodium benzyl thiosulphate and the equivalent quantity of sodium carbonate in 40 C.C.of water. Time. 1'4 9.8 18.3 26.7 35 -1 43 -5 52.0 60.4 C.D. =0.125. Per cent. H. 100.0 100.0 88.7 89.7 89.6 81-3 79.7 77.7 Time. 1.9 9 -6 17.4 25.1 32.8 40.5 48 '3 56.0 C.D. =0*685. Per cent. H. 81.4 80.4 77.2 72.3 68.7 66.8 64-5 59.2 The crude disulphide obtained with the lead cathode was somewhat diecoloured, but one recrystallisation from alcohol gave the pure product. Other experiments showed that the addition of a larger excess of sodium carbonate (for example, 5 equivalents) had a re- tarding effect on the reduction. A few experiments have been made in which the electrolyte was vigorously stirred (the cathode was stationary).The results given in the following table show that the percentage of hydrogen consumed in reduction decreases slowly at first, since the effect of stirring is continuously to supply fresh portions of the electrolyte to the cathode, but after a time, when most of the compound has been reduced, the percentage of hydrogen used falls rapidly. Only one set of results is given, since indications have been obtained that the previous treat- ment of the cathode (platinum) must be taken into account, and so farPREPARATION OF DISULPHIDES. PART I. 2029 we have not investigated this. The solution contained one gram of sodium benzyllthiosulphate and one equivalent of sodium carbonate in 40 C.C. C.D. = 2. Time. Per cent. H. 5.6 30.9 39.3 38.1 56.2 39-1 73.0 34'0 89.9 34.3 Time, Per cent.H. 123'6 30.9 174-2 26.0 207 '9 13.1 241.6 8,5 269.6 3.7 Electrolysis without Isolating the sbcliuna Benzyl Thiosulphate. As pointed out in the introduction, i t was necessary to use a divided cell, In the first experiments, the electrodes mere stationary. The method of procedure was as follows. Five grams of benzyl chloride and 20 C.C. of 90 per cent. alcohol were added to a solution of 12 grams of sodium thiosulphate in 20 C.C. of water, and the mixture heated on the water-bat,h under a reflux condenser for one to one and a half hours. When cold, two equivalents of sodium carbonate * (1 1 *5 grams) dissolved in 30 C.C. of water were added, and the solution mas filtered from the turbidity which formed. The liquid was then electro- lysed, using a platinum cathode, the anode, either of nickel or platinum, being enclosed in a porous pot or in a parchment tube which contained a strong solution of sodium carbonate.The yields obtained were as follows : Current, per cent. C. D. Temp. Yield, per cent. 111.7 1 *27 Room temp. 53-5 97.8 1'27 Y Z , l 5 9 . i 159.4 1'40 1 1 9 3 86'4 111.8 2'54 60-70" 82.3 98.8 1'27 60-70 80.0 The hot solutions thus gave the best yields. The product from the cold solutions was purer, possessing only a faitit pink tinge, whilst that from the hot solution had a deeper colour. I n both cases, one recrystallisation gave the pure product. In the next experiments, the cathode was rotated during the electro- lysis, theanode being in the outer chamber.The inner chamber con- sisted of n wide glass tube, over the bottom end of which some parch- ment was securely fastened. The theoretical current as indicated by tbe ammeter-measurements were not made with a coulometer in circuit- was passed in each case, the current density being 1 *2 amperes per square dcm. * With a divided cell, it is not necessary to add the sodium carbonate t o tho solution at the cathode, but it is advisable, since the C0,"- and 0H'-ions will carry most of the current and thus prevent the complex ion C6H,'CH,'S,0,' from being carried to the anode. The temperature was that of the room.2030 THE ELECTROLYTIC PREPARATION OF DISULPHIDES. PART I. Zxperiment 1.-The solution was not filtered after the addition of the The crude product was white, and the Experinzent 2.-No solution of sodium carbonate was added.The Thus a rotating cathode improves the yield, and the addition of The pure dibenxyl disulphide melted a t 71" : 0.2222 gave 0.4186 BaSO,. (C,H,*CH2)2S2 requires S = 26.02 per cent. The contpouizd with silver nitrate gave Ag = 26.0 ; (CpH7),S,,AgN0, requires A g = 36.0 per cent. solution of sodium carbonate. yield 86.4 per cent. crude product was white, and the yield 79.4 per cent. sodium carbonate, although not necessary, is advisable. 8 = 25.87. Preparution of Diethyl Disulphide. (I) Ten grams of sodium ethyl thiosulphate were dissolved in 20 C.C. of water and 4 grams of sodium bicarbonate, dissolved in the minimum amount of water, added. The solution was electrolysed in a beaker with a platinum wire anode and,cathode of platinum foil, 1-4-1.5 amperes (C.D=4, approx.) being passed for one and a half hours.The oil (diethyl disulphide) which floated on the surfaceof the liquid was then separated, and the current again passed through the aqueous solution ; no more disulphide was formed. The disulphide was then extracted with ether, and the ethereal solution dried over calcium chloride, After removing the ether, a pale yellow liquid was left, which weighed 2-2 grams (a yield of 58 per cent.). On distillation, nearly all the liquid passed over a t 152'; the distillate was colourless, and had all the properties of diethyl disulphide. (2) Twenty grams of sodium thiosulphate were dissolved in 40 C.C. of water and 10 grams of ethyl iodide, and 40 C.C. of 90 per cent. alcohol added, The mixture was heated on the water-bath for one and a half hours, when a homogeneous solution was obtained. 18.5 Grams of sodium carbonate, dissolved in 40 C.C. of water, were then added to the cold solution, and the mixture electrolysed in a divided cell, using a rotating cathode. The current density was 1 ampere per sq. dcm., and five-fourths of the theoretical current was passed. The oil which separated was treated as in (l), and the distillate obtained weighed 1.7 grams (yield = 43 per cent,) : 0.2232 gave 0.8436 BaSO,. 0.1763 of the compound with silver nitrate gave 0.0651 Ag. Ag = 36.9. S = 51.9. (C2H5)2S2 requires S = 52.5 per cent. (C,H,),S,,AgNO, requires Ag = 36.9 per cent.DOUBLE NITRITES OF MERCURY AND THE ALKALI METALS. 2031 Part of the expense of the foregoing investigations was defrayed by a grant awarded by the Committee of the Research Fund, for which we wish to express our thanks. Tbe research is being con- tinued in various directions. CHEMICAL DEPARTMENT, MUNICIPAL ‘rECHNICAL SCHOOL, BIILMINGHAM.

ISSN:0368-1645    

DOI:10.1039/CT9079102021

出版商:RSC    

年代:1907

数据来源: RSC

摘要:

DOUBLE NITRITES OF MERCURY AND THE ALKALI METALS. 2031 CXCVIII.-The Double Nitdes of Mei*cu?-y und the Alkali Metals. By PRAFULLA CIIANDRA RAY. ON several occasions I have shown that when mercurous nitrite is treated with a large volume of water, it undergoes dissociation in accordance with the equation : Hg,(NO,), = Hg + Hg(NO,),, and that nearly 22 per cent. of the salt remains in solution a s such, further dilution having no effect (Zeitsch. ano2.g. Chern., 1896, 12, 372; Trans., 1897, 71, 340). I n a paper communicated to the Societyabout eight years ago I also pointed out that if a sufficient excess of potassium or sodium nitrite or even of silver nitrite is added to this solution, the unchanged portion of mercurous nitrite at once breaks up as above, whilst the alkali nitrite remains unaffected (Proc., 1899, 15, 103).I was a t that time unable t o account for this anomalous behaviour. The further dissociation of mercurous nitrite ceases as soon as a rather stable compound, mercuroso-mercuric nitri t e, (HgNO,), + 4Hg(NO,),, is formed (Trans,, 1902, 81, 645), and if to this solution an alkali nitrite is added, the latter a t once enters into com- bination with mercuric nitrite, a more stable compound being formed. The mercurous nitrite thus displaced, not being stable by itself in presence of water, at once dissociates ; and this process is further accelerated because of the tendency of one of the products of dissociation, namely, mercuric nitrite, t o unite with the alkali nitrite. A new method has thus been furnished for the pre- paration of a series of double salts.General Method of Prepamtion.-A mixture of mercurous and alkali nitrite is rubbed to a paste with a minimum quantity of water, more water is gradually added, and the undissolved portion filtered off. On evaporating the filtrate, which is of a pale yellow colour, over sulphuric acid under diminished pressure, pale yellow, glistening My more recent work, however, bzs furnished an explanation,2032 DOUBLE NITRITES OF MERCURY AND THE ALKALI METALS. tablets and prisms are obtained, which are invariably: readily soluble in water. It should be noted here that Lang (J. pr. Chem., 1862, 86, 295) and Rosenheim and Oppenheim (Zeitech. nnorg. Chena., 1901, 28, 171) have already prepared some of the compounds described below by treating mercuric nitrate with concentrated solutions of potassium and sodium nitrites and evaporating the filtrate.I. Mercuric Potassium Nitrites. I have succeeded in preparing two salts of the formula Hg(NO,),+ ZKNO, and Hg(NO,), + 3KN0, + H,O respectively. As will be shown below, mercuric nitrite combines with one, two, three, and even four molecules of the alkali nitrites, the actual number depending on the excess of the latter. (a) Hg(NO,), + 2 KNO,. Analysis gave : Found (1) Hg=41*24; K=16*99; N=12.16. ,, (2) Hg=40.99*; K=17.38. Theory requires : From the mother-liquor of this salt, Rosenheim and Oppenheim have (6) Hg(NO,), + 3KNO, + H,O. Theory requires : H g = 35.38 ; K = 20.75 ; N = 12.38 per cent. The peculiarity of this salt is that, although hydrated, it does not give up its water, but retains its lustre intact when kept in a vacuum desiccator over sulphuric acid.Knhlschutter, who has also examined this compound, found that it does not lose water when heated at looo for a long time (Bey., 1902, 35, 489). Hg=43*26; K=16.92; N=12*12 per cent. prepared another salt of the formula Hg(NO,), + KNO,. Analysis gave : Hg = 35.19 ; K = 20.24 ; N = 12*00. 11. Mercuric Sodium Nitrites. (a) Hg(NO,), + 14NaN0,. Theory requires : This compound has not been described by previous workers in ( b ) Hg(NO,), + 2NaN0, + 2H,O. Analysis gave : Hg = 50.12 ; Na = 12.87 ; hT = 8.43. Hg = 50.57 ; Na = 12.39 ; N = 8.72 per cent. this field. Analysis gave : Hg=43 15; Na=10*40; N=11*76; H,Ot=7*62. * The unusually low percentage of mercury is probably due to the salt being t The water was estimated by the direct method.contaminated with traces of ( b ) .SILVER-MERCUROSO-MERCURIC OXYNITRATES. 2033 Theory requires : This salt is deliquescent. Kosenheim and Oppenheim, as also Kohlschutter (Zoc. cit.), describe only the anhydrous variety of this compound, which I have not succeeded in preparing. The analysis given above is that of glistening, small prisms, which did not diminish in lustre even in a vacuum desiccator. The non-efflorescence of this and of the hydrated potassium salt indicate that the water is not loosely combined. Hg = 42-92 ; Na = 9.87 ; N = 12.02 ; H,O = 7.73 per cent. IIT. Mercuk Litiiiunz Nitrites. Hg(NO,), + 4LiN0, + 4H,O Analysis gave : Found (1) Hg = 36.15 ; Li = 4.68. ,, (2) Hg = 34-95 ; Li = 4-76 ; N = 15.08. Theory requires : Hg = 34.72 ; Li = 4.87 ; N = 14.58 per cent. This salt was obtained as a crystalline mass and is, like other lithium From the mother-liquor of the above, a salt of the composition Analysis gave : compounds, extremely deliquescent. Hg( NO,), + LiNO, + H,O crystallised out. H g = 48.50 ; Li = 2.89 ; N = 13.15. Theory requires : Hg = 48-08 ; Li = 3.37 ; N = 13.46 per cent. CHEMICALABORATORY, PRESIDENCY COLLEGE, CALCUTTA.

ISSN:0368-1645    

DOI:10.1039/CT9079102031

出版商:RSC    

年代:1907

数据来源: RSC

摘要:

SILVER-MERCUROSO-MERCURIC OXYNITRATES. 2033 CXCI~.-Silver-n.LercU?’oso-merc21ric Oxynitrrxtes and the h O m O ~ p h 0 U S Replucement of Univsllent Mercury by Silver. By PRAFULLA CHANURA RAY. I HAVE already shown that the action of silver nitrite on a solution of mercuroso-mercuric nitrite is similar t o that of the alkali nitrites with the addition that, not only is mercury separated, but metallic silver is also deposited in shining, minute crystals. There is, however, no evolution of nitrogen nor any change in the radicle NO, (Proc., 1899, 15, 103). Owing to the sparing solubility of silver nitrite, my former experiments2034 RAY SILVER-MERCUROSO-MERCURlC OXYNITRATES AND were made with boiling solutions. Now, however, the conditions have been somewhat modified. Mercurous and silver nitrites are rubbed to a fine paste with the minimum quantity of water, dilution with more water being theneff ected gradually, and the pale yellow filtrate evaporated under diminished pressure over sulphuric acid. By this procedure, it was expected that a double salt of the type described in the preceding pzper would be formed in which the place of the alkali nitrite would be taken by silver nitrite ; but lemon-yellow, crystalline products resulted containing both mercurous and mercuric mercury, as well as silver, and the acid radicle was nitrate instead of nitrite.Although mercuroso-mercuric nitrite is quite stable in solution, it cannot be isoInted in the solid state, for when the solution is con- centrated by spontaneous evaporation mercuroso-mercuric oxynitrates crystallise out in succession (Trans., 1905, 87, 174).I n the present instance, as the reaction takes place in the cold, only a small proportion of mercurous nitrite is replaced by silver nitrite, owing t o its slight solubility, and the solution thus contains a mixture of silver mercuric nitrite and mercuroso-mercuric nitrite. During the process of concentration two reactions evidently proceed side by side : 3Hg,(N02), = 4N0 + 3Hg,O*N,O,. 3Hg(N02), = 4N0 + 3HgO*N20,." Thus, although silver nitrite is a stable salt and can be crystallised without undergoing decomposition, it is here slowly converted into nitrate owing to the formation of nitric acid, Had there been no silver salt present, the first crop of crystals would have consisted of a-oxymercurosic nitrate, HgO*2Hg20*N20,.A salt of this type was, indeed, formed amongst others, but, as will be shown below, a portion of mercurous mercury was in each case replaced by its equivalent of silver. I t is to be regretted that as the salts were of a microcrystalline form, they could not be examined crystallo- graphically. Method of Analysis. -The finely-powdered substance was dissolved in the minimum quantity of cold dilute nitric acid. Silver and mercurous mercury were precipitated by the addition. of pure sodium chloride, the mercuric mercury remaining in solution. The precipitate, after careful washing with water, was treated with hydrochloric acid and one or two crystals of potassium chlorate and gently warmed, the solution being then largely diluted with water and set aside t o allow the silver chloride to subside.The filtrate now represented mercurous mercury, a1 though, of course, oxidised to the mercuric state, Analysis of two different preparations of this typical salt are given below, * And possi%Iyalso according t o the equation Hg(NO,)*= HgNO, + NO (Trans. 1904, 85, 527).REPLACEMENT OF UNIVALENT MERCURY BY SILVER. 2035 Owing to the fact that mercurous chloride is appreciably soluble in sodium chloride, the mercuric mercury often appears slightly higher : Found. A fl > Preparatioii I. Preparation 11. Mercurous mercury (Hg') ............ 57-80 54.83 Silver .................................... 6-13 6.77 Mercuric mercury (Hg") ............ 19.50 17.85 Nitrogen 2.85 - .................................The ratio (Hg"Ag) : Hg" : N in I is approxiinatcly 4 : 1 : 2. It should be understood that the ratio of the metals is not invariably as 4 : 1, as is shown by the analyses of two successive crops of another Preparation : ,, (Hg"Ag) : Hg" i n I1 is 4 : 1. Found. CL I Preparation 111. \ 1st crop. 2nd crop. Preparation IV. Hg' ............... 58.98 45.81 48.04 Ag ............... 7 -92 4.15 3'79 Hg" ............... 10'47 26.28 30.67 N.................. 5.80 4.04 3.60 The ratios (Hg"Ag) : Ilg": N are reqectively 7 : 1 : 8, 2 : 1 : 2, 1-8 : 1 : 1.7. Judging from the distribution of the base and acid, it will be seen that preparations I and I1 are the most basic, and preparation I11 the least, whilst that represented by the second crop of preparation 111 stands intermediate between the two. Bisczcssion of Results.The silver and mercurous nitrites mere not weighed out in fixed proportions, but simply dissolved together by trituration in a mortar with cold water ; hence at the start the components in solution often varied within wide limits. As a result of an extensive investigation on the '' conjugated sulphates of the copper-magnesium group )' (Proc. Roy. Xoc. Edin., 1888, 15, 267), it was proved by the author that if the components are dissolved in equivalent proportions and successive crops collected a t intervals, the crystals contain the component sul- phates in definite proportions. Thus in the case of copper cobalt potassium sulphate two successive crops had Cu : Co = 5 : 4, whilst in the third crop the ratio was at 1 : 1 (loc.cit., p. 275). I n the case of iron zinc ammonium sulphate, the 'first three fractions had the same composition with the ratio of Fe : Zn = 1 : 3 ; the next three fractions had also identical composition, only the ratio of the two metals was as 2:5. I n short, it was established that the change in composition between two '' crops ') WRS not in any sense continuous, but distinctly abrupt (loc. cit.) p. 281). I n the present instance, it is also evident that within fairly wide2036 SILVER-MERCUROSO-MERCURIC OXYNITRATES. limits in the distribution of the components in solution the ratio of Hg” : (Hg’OAg) = 1 : 4, and that in successive crops the change in the ratio of the metals is abrupt and not in slow gradations. Thus, in preparation 111, whilst the first crop had Hg” : (Hg’OAg) = 1 : 7, the ratio in the second was as 1 : 2.I n preparation IV, the first crop which was analysed had the ratio of Hg“ : (Hg’*Ag) = 1 : 1.8 instead of 1 : 2 ; i t will be seen that i t approached in composition the second crop of preparation 111. This apparent anomaly appears t o be due to the fact that a salt was actually formed in which Hg” : (Hg’*Ag) : N = 1 : 2 : 2 ; but owing to delay in collecting i t ariother salt richer in mercuric mercury had already begun to be deposited, I n other words, this is a case of overlapping of two consecutive crops. It is, of course, well known that in the case of a solution containing isomorphous mixtures the ordinary laws of solubility hold good-the first crop being rich in the least soluble constituent; but as the latter is to a large extent fractionally removed from the field by the first and second crystallisations, the conditions begin to alter in the reverse direction, the mother-liquor gradually becoming richer in the more soluble constituent, and this is no doubt the reason why in the second crop of preparation 111 the proportion of mercurous mercury and silver (Hg’*Ag) diminished.Although in the present series of oxynitrates the ratio between Hg” and (Hg‘OAg) appears in simple integers, the criterion of isomorphism is equally satisfied. Thus in both the pre- parations I and 11, while the ratio of Hg” : (Hg’*Ag) remains constant, the percentage of the different metals varies.” A few words on the position of univalent mercury in the periodic system may not be out of place here.Throughout the investigation on mercurous nitrite and hyponitrite, which has been going on during the last twelve years, very marked and striking similarity in pro- perties has been found to obtain between these compounds and their silver analogues (compare Trans., 1897, 71, 350 ; Annalen, 1901, 316, 253; Proc., 1907, 23, 89). The isomorphous replacement of univalent mercury by silver still further emphasises this family like- ness. The univalent metals, copper, silver, and gold, have been placed in the first group surrounded by brackets as members of the odd series. Copper and silver isomorphously replace each other in a number of native sulphur compounds as also in the complicated triple thiocyanates.? But the relationship of these two metals with gold is * Compare ‘‘ Haben die isomorphen Kijrper die Fiiiliigkeit, miteinander krystal- lisirbare Mischungen zu bilden, in welchen die Mengen der Bestandtheile in einein irrationalen Verhaltniss zu einander stehen.Diese Eigenschaft bietet zugleich aucli das beste, ja einzige Kriteriuni fur die 1somorphie.”-Dr. Arzruni in Neu Band- worlerbuch d. Chenr., Article : “ Isomorphie.” Groth’s ‘ I Chemical Crystallography,” trans. by Marshall, p. 73.THE CONSTITUENTS OF THE ESSENTIAL OIL OF NUTMEG. 2037 at best very remote. I n view of the evidm3e now adduced, it would appear more rational to substitute mercury for gold and relegate the latter to its more congenial place in the eighth group immediately after platinum. Univalent mercury should be regarded as quite a distinct metal from bivalent mercury ; the former is related by ties of closest affinity to silver, whilst the latter is related to members of the second group, namely, magnesium and zinc.* From the foregoing investigation, it follows that when a solution containing mercuroso-mercuric nitrite and silver mercuric nitrite is allowed to evaporate spontaneously, a series of hydrated silver- mercuroso-mercuric oxynitrates crystallises out, in each of which mercurous mercury is isomorphously replaced by silver. It is worthy of note that the present series of compounds are all basic and hydrated.? They retain their lustre untarnished, and do not lose water over sulphuric acid in a vacuum; they give up water, however, readily when heated. I t would appear that the predominant partner, univalent mercury, impresses its own characteristics upon silver, for silver as a rule does not form basic or hydrated salts (compare RPy, Zeitsch. anorg. Chern., 1896, 12, 374). CHEMICAL LABORATOAY, PRESIDESCY COLLEGE, CALCUTTA.

ISSN:0368-1645    

DOI:10.1039/CT9079102033

出版商:RSC    

年代:1907

数据来源: RSC

摘要:

THE CONSTITUENTS OF THE ESSENTIAL OIL OF NUTMEG. 2037 CC.-Tlie Constituents of the Essentiul Oil of N7htmeg. By FREDERICK BELDINCI POWER and ARTHUR HENRY SALWAY. ALTHOUGH the essential oil distilled from the nutmeg has been known for more than three centuries, and, being recognised by several national Pharmacopoeias, has long been an established article of commerce, it is a remarkable fact that up to the present time very little of a definite character has been ascertained respecting the nature of its constituents. The previous investigations pertaining to this subject have been recorded by Gildemeister and Hoffmann in their work entitled ‘‘ Die aetherischen Oele,” Berlin, 1899, p. 474, and aIso by Semmler in his more recent work, ‘‘ Die aetherischen Oele,” Leipzig, 1906, Bd.I, p. 768; 11, 314; 111, 211 ; IV, 165. The correct interpretation of See also Trans., 1905, 87, 180. In this respect, mercury is comparable to thallium, which with variation of valency affords a remarkable instance of variation of chemical character. t The researches of Siilc and recently of Watson have also conclusively proved the existence of silver peroxynitrates (Trans., 1906, 89, 578). * On the twofold position of mercury in the periodic system. VOL, XCI. 6 T2038 POWER AND SALWAY: THE CONSTITUENTS OF THE the results of the earlier investigations is, however, rendered some- what difficult by the fact that the essential oil of nutmeg has frequently been designated as oil of mace (compare Pharrnacopmicc Germanica, 4th Edition, p, 269), and that the source or genuineness of tho oil employed has not always been clearly indicated.It is, indeed, generally assumed that the oils of nutmeg and mace are qualitatively identical, and that they differ only in the relative pro- pQrtions of their constituents, but, inasmuch as neither of these oils has hitherto been completely examined, there is no direct evidence that this is the case. Among the more important of the ea,rlier investigations of oil of nutmeg, those of Gladstone may be considered. I n his first communica- tion on this subject (Journ. Chem. Xoc., 1864, 17, l l ) , he recorded the following observations. “ The three specimens examined consisted of varying proportions of a hydrocarbon resembling carvene, and an oxidised oil with the boiling point 224’, and sp.gr. 0.9466. As it closely resembles carvol and menthol in its properties, it may by analogy be named myristicol.” I n a later communication (Journ. Chem. Xoc., 1872, 25, 3, ll), Gladstone suggested for the above-mentioned hydro- carbon the name “ myristicene,” and remarked further regarding ” myristicol ” as follows : “ This oil has the characteristic smell of nutmeg, and . . . does not form a crystalline compound with hydro- sulphuric acid. It was found difficult to purify it by fractional dis- tillation, indeed there was some reason to think that in the process of rectification it mas subject to change. An ultimate analysis of portions boiling at somewhere about 820’ yielded rather too much carbon and hydrogen for the formula Cl,H1,O, suggesting the idea of its being still mixed with some amount of a hydrocarbon.” The constituents of nutmeg oil were next investigated by C.R. A. Wright (Journ. Chem. Xoc., 1873, 26, 549), who obtained ‘‘ a consider- able quantity of a mixture of hydrocarbons boiling below 180’ and a small quantity of an oxidised constituent boiling above 210°, apparently the ‘ myristicol ’ of Gladstone.” He noted that the purest myristicol boiled at 212-21S0, and from an analysis of this fraction concluded that it contained as its principal constituent a body isomeric with camphor, CloH,,O, but as he obtained from it, by repeated distilla- tion, a portion boiling at 250-265”, which was assumed to be a polymerised product, the conclusion respecting the composition of the fraction was evidently not justified.With regard to the hydro- carbons, Wright stated that, ‘‘ contrary to Gladstone’s experiments, the hydrocarbon of oil of nutmeg is not a single body boiling at 167’ and of formula CIOHIG, but a mixture of a terpene boiling a t 163-164’ and a hydrocarbon, apparently cymene, boiling towards 177’.” As the cymene, however, was only isolated after treating the mixture withESSENTIAL OIL OF NUTMEG. 2039 sulphuric acid, no evidence was afforded of its pre-existence in the oil. Briihl (Ber., 1888, 21, 472), with consideration of the statements respecting the character of the so-called ‘( myristicol,” and from purely physical data, which apparently mere obtained by the examina- tion of a fraction of nutmeg oil boiling at 224”, was led to the conclu- sion that, as an alcohol of the formula C,,H,,O, myristicol was to be regarded as a cyclic compound containing two ethylenic linkings.He, moreover, suggested constitutional formulte which were believed to be in accordance with the physical determinations. Wallach (Annalen, 1889, 252, 105) examined the lower boiling portions of an oil which he designated as ‘‘mace oil,” and positively established the presence of pinene and dipentene. I n this connexion, he noted that I‘ it was remarkable that the fractions containing pinene were nearly inactive (very slightly laevorotatory). The crude oil, on the other hand, as also the fractions of higher boiling point, were strongly dextrorotatory. I t is t o be assumed that in the low boiling portion, + and - pinene neutralise each other.The nature of the higher boiling, dextrorotatorg portions of mace oil still remains to be cleared up.’’ The investigation of the oils of nutmeg and mace was subsequently undertaken by Semmler (Ber., 1890, 23, 1803; 1891, 24, 3818). The oil of nutmeg supplied to him had a density of 0.8611 a t 1 5 O , and was found to consist entirely of terpenes, but these were not further examined. He particularly noted the absence of cymene, ‘‘ myristicol,” and higher boiling oils of high specific gravity, and stated that the oil in question evidently represented the portions which are most volatile in steam. These results led Semmler t o examine an oil of mace, which was found to have a specific gravity of 0.9309 a t 1 4 O , and to give a green coloration with ferric chloride, indicating the presence of a phenolic substance. A fraction collected between 70” and 144” at 10 mm.pressure was assumed to contain “myristicol,” but was not further examined, From the higher boiling portions of the oil, after treatment with sodium, a crystalline substance was isolated, to which ‘3emmler gave the name myristicin, and assigned to it the formula C,2H1403. It was subsequently shown, however, that myristicin has the formula CllH1203, and is 3-methoxy-4 : 5-methylenedioxy-1-allyl- benzene. This substance is a liquid, but, by treatment with metallic sodium or with alkalis, it is readily converted into the correspond- ing propenyl compound (m. p. 45O), which has been designated isomyristicin (compare Thoms, Ber., 1903, 36, 3446 ; Richter, Ber.Deut. pharm. Ges., 1907, 17, 152 ; Rimini, Gazzetta, 34, ii, 281 ; 35, i, 406 ; Rimini and Olivari, Atti R. Accad. Lincei, 1907, [ v], 16, i, 663). 6 T 22040 POWER AND SALWAY: THE CONSTITUENTS OF THE The purpose of the present investigation has been to ascertain the nature of the constituents of a genuine oil of nutmeg, and especially, among other points of interest, to determine the character of the so-called ‘ I myristicol.” I n addition to the statements (loc. cit.) regarding the occurrence of this compound in oil of nutmeg, Wright (Journ. Chern. Xoc., 1873, 26,552) believed’it to be also present in very small amount in the oil of sweet orange. the portion passing over a t 210-230° appeared to be identical with myristicol, as it gave numbers agreeing with the formula C10H160.” Quite recently, Thoms (Ber.Deut. phurm. Ges., 1904, 14, 27) has indicated that the essential oil distilled from the seed of Monodora Nyrigtica, Dumal, contains an oxygenated compound of the co rnposition ClOKl6O, which he regarded as probably identical with ‘‘ myristicol.” I n con- nexion with these later observations, it is, however, of interest to note that the constituent of oil of sweet orange which Wright had con- sidered to be identical with ‘‘ myristicol ” has been shown by Stephan (J. pr. Chem., 1900, [ii], 62, 531) to be nothing more than d-terpineol. He noted that EXPERIMENTAL. I. E x a m i n a t i o n of a Norrnccl O i l of Nutmeg, The oil employed in this investigation was specially distilled for us by Messrs. Stafford Allen & Sons, of London, from unlimed Ceylon nutmegs of good quality, and our thanks are due to them for the care with which the operation was conducted. The amount of oil obtained from 24.38 kilograms of nutmegs was 1693 grams, corresponding to a yield of 6.94 per cent.This oil WAS a nearly colourless, limpid liquid, having a density of 0.8690 at 15’/15”, an optical rotation of + 38’4’ in a 1-dcm. tube, and was soluble in three times its volume of 90 per cent. alcohol. A determination of the amount of free acids and esters gave the following data : 20 grams of the oil required 2.9 C.C. of an N/10 alcoholic solution of potassium hydroxide t o neutralise the free acids, corresponding to an acid value of 0-81. On subsequently adding an excess of the alkali and boiling for half an hour, it mas found that 11.2 C.C.OF the decinormal solution were required to hydrolyse the esters present, corresponding to an eater value of 3-15. The esters, if calculated as C,,H,~*C,H,O,, would therefore amount to 1.1 per cent. As a preliminary test for the presence of aldehydes or ketones, 20 grams of the oil were shaken for some time with a saturated solution of sodium bisulphite. No solid compound was formed, but the aqueous liquid, after being freed from adhering oil by shaking with ether, gave on treatment with alkali a trace of an oil which possessedESSENTIAL OIL OF NUTMEG. 2041 a fragrant odour. The amount of this substance was, however, much too small to permit of its isolation. Treatment with Sodium Hydroxide.-A quantity (1 500 grams) of the oil was extracted several times with a 5 per cent.solution of sodiuh hydroxide, in order to remove the free acids and any phenolic substances present. The combined alkaline liquids and aqueous washings were shaken with ether t o remove any adhering oil, arid then acidified with sulphuric acid, when an oily liquid separated. This was extracted with ether, and the ethereal liquid shaken a few times with a 10 per cent. solution of sodium carbonate. Ident$cation of Afyristic Acid. The liquids resulting from the extraction with sodium carbonate were acidified with sulphuric acid and distilled with steam. The distillate contained no volatile acids, but there remained in the flask a quantity of a solid substance amounting to about 5 grams, which was collected on a filter and washed with water.On crystallieation from alcohol, it yielded a product melting sharply a t 54': 0.1482 gave 0,3990 CO, and 0.1690 H,O. C = 73.4 ; H = 1207. C14H2802 requires C = 73.7 ; H = 12.3 per cent. This substance was thus identified as myristic acid. Ideiztilfication of EugenoE and isoEugenol. The ethereal liquid which had been extracted with a solution of sodium carbonate, as above described, was dried with anhydrous sodium sulphate, and the ether removed. About 3 grams of a dark brown oil were thus obtained, which possessed an intense odour of eugenol and gave with ferric chloride a deep green colour. By dis- tillation under a pressure of 75 mm., it was resolved into the following three fractions: 164-174' ; 174-180'; above 180'/75 mm., only a little non-volatile, resinous substance remaining in the flask.These products were then separately benzoylated, when from the first fraction (b. p. 164-174'/75 mm.) a benzoyl derivative was obtained, which, after fractional crystallisation from alcohol, separated in thick prisms, melting at 67-69' : 0*1705 gave 0.4760 CO, and 0-0955 H,O. C = 76.1 ; H = 6.2. CI7H,,O, requires C = 76.1 ; H = 6.0 per cent. The substance yielding this compound was thus identified as eugenol. The second fraction (b. p. 174-180'/75 mm.) yielded a mixture of benzoyl derivatives, for, when crystallised from alcohol, the first crop of crystals melted somewhat indefinitely between 68' and 84'. After2042 POWER AND SALWAY: THE CONSTITUENTS OF THE repeated fractional crystallisation, this product melted a t 96-looo, and was then analysed : 0.1500 gave 0,4158 CO, and 0.0851 H,O. C = 75.6 ; H = 6.3.011385 ,, 0,3862 CO, ,, 0,0776 H,O. C= 76.0 ; H- 6.2. CI7H,,O, requires C = 76.1 ; H = 6.0 per cent. From the melting point and analysis of this compound, it is evident that it was nearly pure benzoylisoeugenol, which is stated to melt at 103-104°. The identification of isoeugenol as a constituent of nutmeg oil is of considerable interest, inasmuch as hitherto but one instance appears to have been recorded of its occurrence in an essential oil (compare Semmler, '( Die ztherischen Oele," Bd. IT, p, 130). The fraction of the phenols boiling above 180°/75 mm. yielded no solid benzo yl derivative. Preliminary Examination of the Terpenes. The oil from which the myristic acid and phengls had been removed, as above described, was washed with water, dried with anhydrous sodium sulphate, and distilled under a pressure of 60 mm.The portion boiling below 11 0°/60 mm., which would contain practically all the terpenes, was separately collected, and amounted to about 87 per cent. of the entire oil. This portion was subsequently subjected to several fractionations under a pressure of 20 mm., and a fraction boiling below 70°/20 mm. was collected. The density of the latter was found to be 0,8526 at 15'/15', which proved the absence of any appreciable amount of an olefinic terpene. A portion of the oil which distilled at 170-172O under the ordinary pressure was speciaIly tested for phellandrene, but with a negative result.The further examination of the terpenes was conducted after the hydrolysis of the higher boiling portions of the oil. Hydrolysis cf the Oil. The portion of oil collected below 110°/60 mm., as also that boiling above this temperature, was distilled under the ordinary pressure, and the fraction passing over below 190° was collected. The entire amount of oil boiling above 190' under the ordinary pressure was heated for an hour with an alcoholic solution of 10 grams of potassium hydroxide in a flask provided with a reflux condenser, After distilling off the greater part of the alcohol, water was added, and the mixture extracted with ether. The ethereal liquid was washed, dried, and the ether removed, after which the hydrolysed oil was dietilled under 15 mm pressure in order to remove any non-ESSENTIAL bIL OF NUTMEG.2043 volatile, resinous matter. The strongly alkaline, aqueous liquid, which remained in the flask after the extraction of the hydrolysed oil, was reserved for the examination of the acids. Fractional Distillation of the Oil. The hydrolysed oil, together with the portion boiling below 130°, which had previously been separated, was next submitted to a system- atic fractional distillation a t the ordinary pressure, a Young's rod and disc column having been used up to a temperature of 205'. The following fractions were ultimately obtained : Boiling-point. 156-159" 159-161 161-163 163- 165 165-170 170-180 18 0-1 9 5 195-205 205- 215 215-225 225-235 235-245 245-255 255-265 265-275 Above 275 d 2oo/2o0. 0.2519 0.8513 0.8515 0.8516 0'851 4 0.8521 0-8754 0.9149 0.9351 0.9504 0.9656 0.9812 0.9931 1.0166 1.0436 1'0510 a, in a 1 dcin.tube. + 31'36' $45 15 +52 10 +48 48 f 3 5 46 -l- 9 1 1- 4 2 1 + l o 40 +12 44 + 9 1 2 + 4 1 2 f 5 2 0 + 5 2 4 + 5 2 0 + 2 2 5 -t 5 40 Amount in grams. 136.0 351.0 229.0 135.0 29 .O 77.0 22.0 9.2 19.5 18.0 8.1 6.8 10.2 17.1 24.2 5.0 Total ... 1097.1 grams. Ident$cation of Pinene. F~action 156--159".-This was a colourless, limpid liquid, which 0-1018 gave 0.3282 CO, apd 0.1100 I€,O. C,,H,6 requires C = 88.2 ; H = 11 .8 per cent. It is evident that this fraction consisted entirely of a hydrocarbon. The presence of pinene was determined by the formation of a crystalline nitrosochloride (m. p. lOSo), and the conversion of the latter into the corresponding nitrolbenzylamine (m.p. 123'). Frccc,!ion 159-161°.-This was the largest fraction obtained, and i t resembled in its characters the preceding one : 0.0958 gave 0.3100 CO, and 0.1034 H,O. It was found to contain a considerable quantity of pinene, since it possessed the odour of pinene : C=S7.9; H=13*0. C = 88.3 ; H = 12.0. C,,H,, requires C = 88.2 ; H = 11.8 per cent. readily yielded the above-mentioned derivatives of this terpene.2044 POWER AND SALWAY: THE COXSTITUENTS OF THE Identijcation of Camphene. Fraction 161-163°.-This was a large fraction, and resembled in 0.1441 gave 0.4650 CO, and 0,1555 H,O. The high optical rotation of this fraction suggested the pressnce of a considerable amount of camphene. Fifty grams of the liquid were therefore treated with a mixture of acetic and sulphuric acids accord- ing to the method of Bertram and Walbaum for the conversion of camphene into an isoborneol ester.After hydrolysing the product, a pale yellow oil was obtained, which was distilled under diminished pressure. A ortion which passed over a t 120-1 40"/25 mm. partially solidified in the receiver, and possessed a pronounced camphoraceous odour. On treating this fraction with phenjlisocyanate in a sealed tube at 100' for several hours, a phenylurethane was obtained, which cryetallised from alcohol in fine needles melting at 138". The latter compound, on treatment with alcoholic potash, yielded a substance which, after crystallising from methyl alcohol, melted at 207-2 12", and had all the characteristic propertios of isoborneol.The presence of camphene in this fraction of the oil wag thus established. Fractions 163-1 66' and 165-1 70°.-Ther;e fractions were similar in their general characters to the preceding one, but had a somewhat lower rotatory power, odour the preceding one : C = 88.0 ; H = 12.0. C,,H,, requires C = 88.2 ; I3 = 11.8 per cent. The fraction 165--170' was analysed : 0.1062 gsTe 0,3430 CO, and 0.1150 H,O. C,,H,, requires C = 88.2 ; H = 11.8 per cent. It was evident that these two fractions consisted of mixtures of pinene and carnphene with the constituents of the succeeding fraction. Iclentifcation of Dipeiztene. C = 88.1 ; H = 12.0. Fraction 170- 180".-This was a limpid, colourless liquid, possessing 0.1171 gave 0.3778 CO, and 0.1244 H,O. The analysis of this fraction showed that i t contained no oxygenated substances, such as cineol (b.p. 176'). The fraction readily yielded a bronco-deriva tive, which, after cryst,allisation from ethyl acetate, melted a t 124-125", thus establishing the presence of dipentene. Fvaction 1 SO- 195O.-This was a colourless liquid, possessing a somewhat lemon-like odour : 0.1567 gave 0.4867 CO, and 0-1650 H,O. C=84*7 ; H= 11.7. a distinctly lemon-like odour : C=88.0; H=11*8. C,,H,, requires C = 88-2 ; H = 11-8 per cent. No terpinene could be detected in it.ESSENTIAL OIL OF KUTMEG. 2045 The characters of this fraction indicated it to consist of a mixture of the constituents of the preceding and succeeding ones. Idsntijcation of Linaloo 1. Fraction 195-205°.-This fraction possessed a pronounced odour of 0.1145 gave 0,3352 CO, and 0.1191 H,O.Although this fraction still contained some terpene, it evidently consisted largely of an oxygenated substance. A portion of it was gently oxidised with a chromic acid mixture and the product extracted with ether. The ethereal liquid was washed, dried, and the ether removed, when a small amount of a product was obtained, which, on distillation, yielded a fraction possessing an intense lemon-like odour, The latter fraction, on treatment with P-naphtbylamine and pyruvic acid, yielded the crystalline a-citryl-P-naphthacinchoninic acid, melting at 200O. This result, togsther with the positive rotation of the original fraction, rendered it evident that d-linalool was present in the oil. No semicarbazone, oxime, or solid bisulphite compound could be obtained from the above fraction, thus indicating the absence of alde- hydes or ketones.The subsequent fractions of the oil, as previously noted, were all relatively small in amount, but they were analysed with the following results : linalool : C = 79.8 ; H= 11.6. CloH,80 requires C = 77.9 ; H = 11.7 per cent. Fraction 2 05 - 2 15'. 0,1193 gave 0.3441 GO, and 0.1210 H20. Fraction 215-235O. 0.1684 gave 0.4855 CO, and 0.1634 H,O. Fraction 225-2 35'. 0.1691 gave 0.4893 CO, and 0.1526 H,O. Fraction 235-245'. 0.1359 gave 0.3930 CO, and 0.1191 H,O. Fraction 245-255'. 0.2367 gave 0.6796 CO, and 0.2026 H,O. Fraction 2 55-2 6 5'. 0,1435 gave 0.4049 CO, and 0.1139 H,O. Frccction 3 65-2 75". 0.1855 gave 0.5090 CO, and 0.1 386 H,O.Fraction above 275'.-The amount of this fraction was only 5 grams C = 78.7 ; H = 11.3. C = 78.6 ; H = 10.8. C = 78.9 ; H = 10.0. C='i8*9; H=9.7. C = 78.3 ; H = 9.5. C=77*0; Hc8.8. C = 74.8 ; H = 8.3. and, being obviously of an indefinite character, it was not analysed.2046 POWER AND SALWAY: THE CONSTITUENTS OF THE The fractions collected between 195" and 245" were all fragrant liquids, whereas the odour of those obtained between 245' and 275O was not so distinctive. As all the fractions which distilled above 195" under ordinary pressure were too small in amount to admit of a satisfactory examina- tion, the nature of th6 oxygenated constituents of the oil was more fully determined by means of a larger quantity of material, designated as heavy oil of nutmeg, which was kindly supplied to us by Messrs.Stafford Allen & Sons. The identification of these constituents will therefore be described in connexion with the examination of the so-called I' heavy oil of nutmeg " in the second section of this paper. It may here be noted, however, that among the above fractions thoss boiling at 255-265' and 265-275' respectively contained a consider- able amount of myristicin, for they both readily yielded the dibromo- myristicin dibromide, which crystallised in silky needles melting a t 128-129' (Be?*., 1903, 36, 3446). Acids Obtained by the Hydrolysis of the Oil. The alkaline, aqueous liquid obtained by the hydrolysis of the oil, a g previously described, was acidified with sulphuric acid and distilled with steam.The distillate contained some oily drops, and towards the end of the operation a small amount of solid passed over. It was therefore extracted with ether, the ethereal *liquid washed with water, dried with anhydrous sodium sulphate, and the ether removed. About 1 gram of a dark brown, oily product was thus obtained, which was converted into a sodium salt, and from the latter five fractions of silver salts were prepared. These were washed, dried in a vacuum over sulphuric acid, and analysed : Fraction I. 0.1475 of silver salt gave 0.0459 Ag. Ag=31*1. I 7 IT. 0.1107 ,, ,, ,, 0.0366 Ag. Ag=33*1. 9 , IV. 0*1601 ,, ,, ,, 0.0815 A g . Ag=50*9. 9 9 V. 0.1583 ,, ,, ,, 0.0950 Ag. Ag=60*0. ,, 111. 0,1213 ,, ,, ,, 0,0534 Ag. Ag=44*0. It is evident from these results that the acids extracted by ether represented a rather complex mixture, apparently containing some myristic acid, since silver myristate requires Ag = 32.2 per cent.Their nature was, however, more fully ascertained by the subsequent examination of the corresponding product from ' I heavy oil of nutmeg." The aqueous distillate, which had been extracted with ether as above-described, still contained some acid, which was converted into a barium salt. The hot solution of the latter, on cooling, deposited it quantity (about 2 grams) of a salt in glistening leaflets. ThisESSENTIAL OIL OF NUTMEG. 2047 was collected, washed with a little water, dried a t l l O o , and analyeed : 0.8933 of the dried salt gave 0.8135 BaSO,. (C2H,0,),Ba requires Ba = 53.7 per oent. By the evaporation of the mother liquors, a further quantity of a salt was obtained, the solution of which abundantly reduced mercuric chloride on heating.It was likewise dried a t 110' and analysed : Ba = 53.5. 1.4219 of the dried salt gave 1,4201 BaSO,. These results established the presence of esters of both formic and acetic acid in the oil. The contents of the distillation flask, after the removal of the volatile acids by steam, were extracted with ether, but only a little resinous Ba=58-7. (CH0,)2Ba requires Ba = 60.4 per cent. matter was obtained. 11.--Examination of a I.eccvy O i l of Nutmeg. This oil, which, as previously stated, had been kindly supplied to us by Messrs. Stafford Allen & Sons, represented a product obtained by the rectification of very large quantities of normal oil of nutmeg, and consisted chiefly of the oxygenated constituents of the latter, the terpenes having been to a large extent removed.It was a pale yellow liquid, possessing the following constants : d 20'/20° = 1.102 ; aD + 1'17' in a 1-dcm. tube ; saponification value 6.10. Treatment with Sodium Hydroxide.-A quantity (6800 grams) of the oil was extracted several times with a 5 per cent. solution of sodium hydroxide. The combined alkaline liquids and washings were shaken with ether to remove any adhering oil, acidified with sulphuric acid, and the liberated acids and phenols extracted with ether. I n order to remove the acids, the ethereal liquid was shaken with a 10 per cent. solution of sodium carbonate. The liquid obtained by extraction with the last-mentioned alkali, when acidified with sulphuric acid and distilled, yielded, however, only traces of acetic and butyric acids. No crystalline acid could subsequently be isolated from the contents of the distilling flask, and therefore the heavy oil, unlike the normal oil of nutmeg, did not contain any free myristic acid.Identisficcction of Eugenol and isoZugeno2. The above-mentioned ethereal liquid, from which the traces of acid had been extracted, was washed with water, dried with anhydrous sodium sulphate, and the ether removed. About 100 grams OF crude2048 POWER AND SALWAY: THE CONSTITUENTS OF THE phenols were thus obtained, which were first distilled under diminished pressure to remove resinous matter, and then under the ordinary pressure, when the following fractions were collected : 245-250' ; 250--260° ; above 260O.Fraction 245-250°.-This amounted to about 50 grams, and evidently consisted chiefly of eugenol. Its identity was confirmed by the formation of benzoyleugenol (m. p. 69'), and also of the diphenyl- urethane, melting at 107-10S0 (Beg-., 1907, 40, 1834). Fraction 250-260°.-This amounted to 25 grams. I n attempting to prepare from it a diphenylurethane, it was found that the product did not solidify so readily as in the case of the preceding fraction, and was obviously a mixture. With consideration of the probable presence of isoeugenol, and as the diphenyEurethane of the latter had not hitherto been prepared, a little of this derivative was made from pure isoeugenol (Kahlbaum) and found to melt a t 112-113', which is but a few degrees higher than the melting point of the corresponding derivative of eugenol.It was thus evident that the diphenylurethanes are not well adapted for the differentiation of the above-mentioned isomeric phenols. It readily yielded a crystalline benxoyl derivative melting at 1 0 5 O , thus confirm- ing the observation recorded in connexion with the normal oil of nutmeg, that the phenols consist of a mixture of eugenol and isoeugenol. Fpaction above 260°.-This amounted to about 10 grams, IIydrolysis of the Oil. After the removal of the phenols by extraction with a solution of sodium hydroxide, as above described, the oil was heated with a n alcoholic solution of potassium hydroxide (1 part KOH to 100 parts of oil). The greater part of the alcohol was then removed, water added, and the separated oil collected, washed, and dried; the aqueous, alkaline liquid being reserved €or the subsequent examination of the acids.Fractional Distillation of the Hydrolysed Oil. The hydrolysed oil was subjected to a systematic fractional distillation, the portions boiling below 265' being finally collected under the ordinary pressure, whilst the remainder of the oil was fractionated under a pressure of 40 mm. The following results were obtained :ESSENTIAL OIL OF NUTMEG. 2049 Eoiling-point. Below 195" 195-205 205-215 215-225 225-235 235-245 245-255 255-265 d 2oo/20. - 0'9136 0.9432 0'9666 1.0070 1.0469 1.0729 1.1014 a,in a l-dcin. tube. + ll"22' +11 31 + 5 5 - 0 33 - 0 5 + 1 4 f 1 4 8 - Amount in grams. 184 35 440 238 151 82 74 182 165-163"/40 mm.1.1316 + 1 8 130 169-171 ,, 1.1341 -t 0 5 1 560 171-173 ,, 1.1437 i - 0 6 3420 Above 173 ,, 1'1566 + , o 0 60 I_ Total ... 5556 grams. Praction below 195O.-Since this fraction consisted chiefly of terpenes, which had been thoroughly investigated in connexion with the normal oil, it did not require further consideration. Identajication OJ Linalool. Fraction 195--205'.-This was a colourless liquid, possessing the 0.0988 gave 0.2881 CO, and 0.1046 H20. The analysis of this fraction indicated that it still contained a small amount of terpene. A quantity of it was gently oxidised with a chromic acid mixture, and the product extracted with ether, when, after the removal of the solvent, a small amount of a yellow liquid was obtained, which was distilled under the ordinary pressure.The portion boiling between 215O and 235' possessed an intense odour of citral, and readily yielded a-citryl-P-napht hacinchoninic acid, melting a t 197", thus confirming the presence of linalool in the oil. fragrant odour characteristic of linalool : C= 79.5; H= 11.8. C,,H,80 requires C = 77.9 ; H = 11 *7 per cent. Identification of Borneol and Terpineol, and Fommation of a Diketone, It was a ~,Hl,O,* Pmction 205--215".-This was a very large fraction. colourless liquid, with an odour resembling that of terpineol : 0.1409 gave 0.4015 CO, and 0.1445 H,O. CloHl,O requires C = 7'7.9 ; H = 11.7 per cent. Test for TerpineoL-A portion of the liquid was shaken with a con- centrated solution of hydriodic acid (sp.gr. 1-96), when a heavy, dark- coloured oil was formed. This was separated from the aqueous layer, dissolved in ether, and shaken with a dilute solution of sodium bisulphite to remove the free iodine. The ethereal solution was washed, dried w i t h anhydrous sodium sulphate, and the ether removed, C= 77.7 ; H = 11.4.2050 POWER APU'D SALWAY: THE CONSTITUENTS OF THE when a thick oil was obtained which solidified in a freezing mixture, This solid was dried on a porous tile and crystallised from light petroleum, from which it separated in colourless prisms, melting a t 80'. This melting point was identical with that of dipentene dihydriodide, C,,H,,I,, prepared from terpineol (m. p. 35O), and, when the two preparations were intimately mixed, the melting point remained unchanged. It was thus evident that this fraction of the oil contained a considerable amount of terpineol, and its presence was confirmed by the isolation of the ketolsctone, C1,H,,03, from the products of its oxidation.Oxidation of the Traction. Tormation of the Ketolactone, Cl0H, ,03, a Diketone, C,H,,O,, and Camphor.--A quantity (150 grams) of the fraction (b. p. 205-215O) was oxidised with a chromic acid mixture in the proportions of potassium dichromate (8 parts), sulphuric acid (12 parts), and water (36 parts) to 1 part of oil. In the beginning of the oxidation the odour developed was that of citral, but finally i t became distinctly camphoraceous. After the mixture had been gently heated on a xater-bath for about an hour, it was allowed to cool, and then extracted several times with ether.The ethereal liquid was first washed with a solution of sodium carbonate to free it from acidic substances, then with water, and the ether removed, A yellow oil was thus obtained, which was distilled with steam, when the greater portion passed over. The non-volatile portion of the oxidation product was extracted by ether, the ethereal solution being washed, dried, and the ether removed. A small quantity of a viscid, brown oil was thus obtained, which deposited no solid, even on long standing. It was finally distilled under diminished pressure, when the fraction of highest boiling point was obtained as a viscid, yellow liquid, which solidified when stirred with light petroleum. This solid was dried on a porous tile and crystallised from ether, from which it separated in colourless prisms melting a t 62-63' : 0,1165 gave 0-2782 CO, and 0.0907 H,O.CloH,,O, requires C = 65.2 ; H = 8.7 per cent. It is evident that this substance is identical with the ketolactone, ClOH,,O, (m. p. 64O), which was obtained by Wallnch by the oxidation of terpineol with chromic acid. As it is the optically inactive modification of the ketolactone, it follows that the terpineol contained in the oil must be the racemic form (compare Wagner and Brickner, Ber., 1899, 32, 2315). C = 65-1 ; H = 8.7. The portion of the above-mentioned oxidation product which was volatile in steam possessed a strongly camphoraceous odour, a1 though no solid substance separated. .The distillate was then extracted with ether, the ethereal solution dried, and the solvent removed, when aESSENTIAL OIL OF NUTMEG.2051 quantity of an oily liquid was obtained. One part of this oil, in alcoholic solution, was heated for some time on a water-bath with hydroxylamine hydrochloride (1 part) and sodium hydroxide (1.6 parts), after which water was added and the mixture carefully neutralised with sulphuric acid. As no solid oxime separated, the mixture was extracted with ether, the ethereal solution being washed, dried, and the solvent removed, when a brown oil was obtained which solidified on stirring with light petroleum. This solid substance was collected on a filter and crystallised from hot alcohol, from which, on cooling, it separated in small, rectangular prisms melting at 140'.The yield of this compound was about 3 grams : 0.1368 gave 0.2804 CO, and 0.1187 H,O. 0.1998 C=55*9 ; H= 9.6, 0.1534 ,, 0.3137 CO, ,, 0.1272 H,O. C=55*8; H=9*2. ,, 27.4 C.C. moist nitrogen at 165'and 762 mm. N = 16.1. C,H,,O,N requires C = 55.8 ; H = 9.3 ; N = 16.3 per cent. From these results, it appears highly probable that this compound is the dioxime of a diketone, C,K,,O,. The only known compound of the formula C,H,,O,N, with which i t might be identical is the dioxime of ethyl butyl diketone, CH,*CH,*C( :pu'OH)*C( :NOfl) *CH,*C€€,*CH,*CH, (m. p. 139-141°), which has been described by Fileti and Ponzio (J.pr. Chem., 1898, [ii], 58, 364). These authors also prepared an osazone, which was found to melt at 96-97'. With the object of ascertaining whether our dioxime is identical with that prepared by Fileti and Ponzio, 50 grams of the fraction (b.p. 205-215') were oxidised as previously described, and the portion of the oxidation product which was volatile in steam treated with an excess of phenylhydrazine in alcoholic solution. No solid osazone could, however, be obtained from the product of the reaction. An attempt was also made t o obtain a semicarbazone of the diketone, C8H1402, from the volatile oxidation product of the fraction 205-215', but without success. These results therefore da not permit of any conclusion respecting the identity of the compound O,H,,O,N,, here described, with the dioxime of ethyl butyl diketone prepared by Fileti and Ponzio (Zoc. cit.). The dioxime, CaH1602N2, is a colourless, odourless substance, sparingly soluble in cold, but readily in hot, alcohol, I t is also soluble in warm ethyl acetate, from which i t crgstallises in fine needles, but is only sparingly soluble in benzene, and insoluble in light petroleum and in water, When warmed with dilute sulphuric acid, it first dissolved, developing a fragrant odour, but, as resinificntion ensued, it was impossible by this means to regenerate the ketone from which it had been formed.2052 POWER AND SAZWAS: THE CONSTITUENTS OF THE Since not more than a trace of substance of aldehydic or ketonic nature was present in the fraction of the oil employed, it is evident that the above-mentioned diketone must.represent the oxidation pro- duct of an unidentified compound, which is doubtless an alcohol. The light petroleum liquid which had been separated from the dioxime, as above described, possessed a strongly camphoraceous odour.After the removal of the solvent, a brown oil was obtained which did not solidify, and was therefore distilled under diminished pressure. From the first portions of the distillate a solid separated which had the characteristic odour of camphor, and, after drying on a porous tile, melted a t 170-175". This substance readily yielded a semi- carbazone melting at 238O, and when the ldtter was mixed with camphorsemicarbazone the melting point remained unchanged. Not having obtained the camphor in the form of its oxime by the treat- ment of the original product OF oxidation with hydroxylamine, it may be assumed that the amount of the latter was only sufficient to com- bine with the diketone which was present in the mixture. The identification of camphor as a product of oxidation of the fraction boiling between 205O and 215O aff x d s conclusive evidence of the presence of borneol in the original oil.ldentajication of Geraniol. Fraction 215-225°.-This was a comparatively large fraction. It was a colourless liquid, possessing a rose-like odour : 0.1109 gave 0.3136 CO, and 0.1055 H20. This fraction was found to contain some terpineol, since it readily yielded the crystalline dipentene dihydriodide (m. p. 80') on treatment with concentrated hydriodic acid, whilst the analytical results also indicated it to contain some of the constituents of the succeeding fraction. A portion of the fraction was oxidised with a chromic acid mixture, when the odour of citral was at first strongly developed, and from the final product a further small amount of the diketone, CSHl4O2, was obtained in the form of its dioxime (m.p. 140°), which has been described in connexion with the preceding fraction. As the odour of the fraction, together with the evident formation of citral by its limited oxidation, indicated the presence of geraniol, a portion of it was treated with diphenylcarbamic chloride in the presence of pyridine, according to the method suggested by Erdmann (J. p. Chm., 1897, [ii], 56, S), when a product was obtained which crystallised from alcohol in thin, colourless needles melting at 81 -82'. This was found to be identical with the diphenylurethane (m. p. 82') C= 77.1 ; H= 10.6.ESSENTIAL OiL OF NUTRIEG.2053 prepared from a specimen of pure geraniol, and the presence of the latter compound in the oil was therefore established. IdentiJcation of Xufrole. Fraction 225-235°.-This was a pale yellow liquid, possessing a 0.1129 gave 0.3154 C3, and 0.0933 H,O. The presence of a considerable proportion of geraniol in this fraction was evident from the fact that it yielded the diphenylurethane (m. p. 82O), and, when gently oxidised, some citral was obtained, which was identified by the formation of the a-citryl-P-naphthacinchoninic acid, melting at 195-197O. The odour of the fraction, together with its high density and the analytical figures, indicated, however, that it also contained safrole. A portion was oxidised with a mixture consisting of potassium dichromate (8 parts), sulphuric acid (12 parts), and water (30 parts) t o 1 part of oil.After heating gently for two hours, a distinct odour of piperonal was observed. The mixture, after being allowed to cool, mas repeatedly extracted with ether, the ethereal liquids washed first with water, then with aqueous sodium carbonate, which removed only a trace of acidic substance, finally again with water, and the ether removed. A brown, oily residue was thus obtained, which was shaken with a saturated solution of sodium bisulphite, when a small amount of a solid compound separated. This was collected on a filter by the aid of the pump, and washed with ether. On warming with dilute alkali, a substance was liberated which had the odour of piperonal.This alkaline liquid was subsequently extracted with ether, the ethereal solution being washed, dried, and the ether removed. The residual oily liquid was placed in a freezing mixture and nucleated with a trace of piperonal, when crystallisation ensued, and the resulting pro- duct melted a t 34-35', This was identified as piperonal, thus proving the presence of safrole in the oil. The fraction (b. p. 225-235'), as well as the two preceding ones, were treated with semicarbazide hydrochloride and sodium acetate in alcoholic solution, and the uncombined oil subsequently removed by distillation with steam, when a very small amount of a solid semi- carbazone was obtained. On treatment with dilute sulphuric acid, this yielded a few drops of a yellow oil, which possessed an odour resembling that of citral, but gave a P-naphthacinchoninic acid deriv- ative which, when crystallised from alcohol, separated in pearly leaflets melting at 248' with decomposition, The substance, evidently an aldehyde, which yielded this derivative was so small in amount that it was impossible further to characterise it.distinct odour of safrole, and also the rose-like odour of geraniol : C=76*2 ; H=9*2. VOL. XCI. 6 u2054 POWER AND SALWAP: THE CONSTITUENTS OF THE As this fraction of the oil was slightly lsvorotatory, it must have contained a small amonnt of some undetermined substance, for both geraniol and safrole are optically inactive, and the preceding, as well ns the principal succeeding, fractions were dextrorotatory. Fraction 235--245'.-This was a colourless liquid, possessing a strong odour of safrole : 0.2001 gave 05502 CO, and 0,1417 H20.The presence of safrole was proved, as described in connexion with the preceding frizction, by the isolation of a small quantity of piperonal, melting a t 33-35", from the products of its oxidation. Fraction 245--255'.-This was a colourless liquid, which became slightly yellow on standing. 0.1502 gave 0,4126 GO, and 0.1021 H,O. This fraction was specially tested for the methyl ether of eugenol, but with a negative result, since it yielded neither the corresponding bromo-derivative nor could any veratric acid be isdated from the products of its oxidation. On oxidation, however, it developed a strong odour of piperonal, indicating the presence of safrole, and yielded on treatment with bromine a compound which crystallised from alcohol in small needles melting sharply a t 128-1229'. This was identified as the bromo-derivative of myristicin, which will sub- sequently be described.C= 75.0 ; H=7*9. It was comparatively small in amount : C=74*9; H=7*6. Fraction 255--265'.--This was considerable in amount : 0.1550 gave 0.4048 CO, and 0.0984 H20. It was evident that this fraction consisted largely of myristicin, together with a small amount of some dextrorotatory substance, probably a sesquiterpene, which it wbs impossible t o isolate. The subsequent fractions, which had been distilled under diminished pressure, were analysed with the following results : Fraction 165-1 69'/40 mm. 0.1500 gave 0.3854 CO, and 0,0956 H,O.Fraction 169-171°/40 mm. 0.1737 gave 0.4457 CO, and 0.1089 H,O. Each of these fractions evidently consisted chiefly of the constituent C = 71.2 ; H = 7.1. C = 70.1 ; H= 7.1. C = 70.0 ; H = 7.0. of the following fraction. Identijcation of Myristicin, C,,H,,O,. Fraction 171--173O/40 mm.-This was by far the largest fraction of the heavy oil of nutmeg, amounting to 3420 grams, or more than one- half of the total quantity of oil employed. When freshly distilled, it was zt colourless liquid, possessing only a faintly aromatic odour :ESSENTIAL OIL OF NUTMEG. 2055 0.1469 gave 0.3728 00, and 0.0844 H,O. C= 69.2 ; H=6*4. 0.1135 ,, 0.2875 CO, ,, 0.0677 H,O. C = 69.1 ; H= 6.6. 0.2424 ,, 0.6098 CO, ,, 0.1400 H,O. C = 68.6 ; H = 6.4. d ZOo/.200== 1.1437 ; a,+ 0'6' in a 1-dcm.tube ; nz 1.54032. The results of analysis and the determination of the physical constants of this fraction rendered it evident that it consisted of nearly pure myristicin. This compound has previously been obtained from material designated as mace oil (Thoms, Ber., 1903, 36, 3446), but proof of its occurrence in oil of nutmeg has hitherto been lacking. Dibvomom yristicin Dibromide, C,,H,,O,Br,.-This was prepared ac- cording to the method described by Thoms (Zoc. c k ) . When crystal- lised from a mixture of alcohol and ethyl acetate, it separated i n fine, colourless, silky needles, melting a t 128 -1 29' : C1,H1,O3 requires C = 68.7 ; H = 6.2 per cent. 0.2085 gave 0*2000 CO, and 0.0402 €I,O. Thoms described this compound as a white, crystalline powder, melting a t 130'.isoMyristicin.-A quantity (20 grams) of the fraction (b, p. 1'?1-173°/40 mm.) was heated on a water-bath for two days with an alcoholic solution of 50 grams of potassium hydroxide, and the product extracted with ether. After the removal of the solvent, it was distilled under diminished pressure, when practicalIy all passed over a t 166'/18 mm, as a colourless, viscid liquid, which, when placed in R freezing mixture, readily solidified. It was crystallised from alcohol, from which it separated in radiating clusters of needles, melting a t 44" : C = 2G.2 ; H = 2.1. C,,H,,O,Br, requires C = 25.9 ; H = 2.0 per cent. 0.1345 gave 0.3380 CO, and 0.0757 H,O. CllHl2O3 requires C = 68.7 ; H = 6.2 per cent. The refractive index of this substance, kindly determined for us by Mr.Frederic H. Lees, was IZ~''" 1-56551, whereas that of myristicin a t the same temperature was 1.52927. Dibromoisom yristicin Dibromide.-This was easily prepared by the same method as that employed for the corresponding bromo-deriv- ative of myristicin. When crystallised from a mixture of alcohol and ethyl acetate, it separated in stout needles, melting at 156': C = 68.5 ; H = 6-3. 0.2013 gave 0.1915 CO, and 0.0406 H,O. C=25*9 ; H=2*2. C,,H,,,O,Br, requires C = 25.9 ; H = 2.0 per cent. Acids Obtained by the Ilydrolysis of the Heavy Oil of Nutmeg. The alkaline liquid and aqueous washings obtained by the hydrolysis of the oil, as previously described, were concentrated, acidified with sulphuric acid, and distilled with steam, The distillate 6 u 22056 POWER AND SALWAY: THE CONSTITUENTS OF THE contained a quantity of acids in the form of a pale yellow oil, which was extracted by means of ether.From the aqueous liquid, which was still strongly acid, about 20 grams of a barium salt were obtained. This was fractionally crystallised, and each fraction analysed, when it was found to consist entirely of barium acetate. I. 0 8950 of the salt gave 0.8106 BaSO,. Fraction Ba = 53.3. ,, 11. 0.7924 ,, ,, 0,7247 BJSO,. Ba=53.8. ,, 111. 0.4997 ,, ,, 0.4573 BaSO,. Bz = 53.8. ,, IV. 0.7443 ,, ,, 0.6802 B&304. Ba = 53.7. (C,H,0J2Ba requires Ba = 53.7 per cent. The pale yellow, oily acids which had been extracted from the distillate by means of ether, as above described, amounted to about 6 grams. These were distilled under the ordinary pressure up to 2'70°, and the remainder at 20 mm.pressure, when the following fractions were obtained: (a) below 230O; ( b ) 230-250' ; (c) 250-270°/760 am.; (d) 190-230°/20 mm. Esch of these fractions was converted into a sodium salt, from which, by fractional precipitation with a solution of silver nitrate, a number of silver salts were prepared. These were washed, dried in a vacuum over sulphuric acid, and analysed : (a) 0.0882 gave 0.0386 Ag. Ag=43*8. ( b ) 0.1150 gave 0.0492 Ag. Ag = 42.8. 0.1835 ,, 0.0789 Ag. Ag=43.0. 0.1531 ,, 0.0664 Ag. Ag = 43.4. 0.1 752 ,, 0.0790 Ag. Ag ZL= 45.1. 0.1862 ,, 0.0806 Ag. Ag= 43.3. 0.1751 ,, 0.0765 Ag. Ag=43*7. 0.1231 ,, 0.0544 Ag. Ag = 44.2. 0.2145 ,, 0.0856 Ag. Ag= 39.9. 0.2309 ,, 0.0968 Ag.Ag = 41.9. (c) 0.1044 gave 0.0434 Ag. Ag= 41.6. (d) 0.1272 gave 9.0503 Ag. Ag= 39.5. C,H,,O,Ag requires Ag = 43.0 per cent. C,H,70,Ag 9 , Ag=40*8 Y Y ,? It would appear from these results that the volatile, oily acids obtained by the hydrolysis of nutmeg oil contain a considerable proportion of an octoic acid, with smaller amounts of acids of higher and lower molecular weight. Isolation of u New Monocas.boxylic Acid, C,,H,70*C0,H. After the removal oE the volatile acids by distillation with steam, as above described, there remained in the distillation flask a semi-ESSENTIAL OIL OF NUTMEG. 2057 solid mass. This was spread on a porous plate, when a quantity of tarry matter became absorbed and a crystalline solid was obtained. The latter was purified by dissolving it in hot dilute acetic acid, from which it crystallised in hexagonal prisms, melting a t 84-45', which possessed a slightly yellow tint.When crystallised from dilute alcohol, it separated in needles. The substance is extremely soluble in the usual organic solvents, but is insoluble in water: 0.1150 gave 0.2972 CO, and 0.0861 H,O. C = 70.4 ; H = 8.3. 0.1015 ,, 0.2620 GO, ,, 0.0758 H,O. C = 70.4 ; H=8.3. C13HlR03 requires C = 70.3 ; H = 8.1 per cent. 0.1640, in alcoholic solution, neutralised 7.4 C.C. N/10 NaOH. C1,H,70*C02H requires 7.4 C.C. The only known monocarboxylic acid of the formula Cl,Hl,O, possessing properties similar t o those of the above compound is carvacroxypropionic acid, which has been described by Biechoff (Ber., 1900, 33, 1270) as forming colourless prisms, melting a t 81.5-82*5O. A specimen of the latter acid was therefore prepared for the purpose of comparison with the above described compound, but the two substances were found to be not identical. The sub- stance isolated from nutmeg oil is therefore to be regarded as a new monocarboxylic acid, U12H170*C02H. Summary. The results of this investigation have shown that the essential oil of nutmeg contains t,he following substances : 1. 2. 3. 4. 5. 6. 7. 8. 9. Eugenol' }about 0.2 per cent. isoEugeno1, d-pinene' d-Camphene, Dipentene, about 8 per cent. d-Linalool, c2-Borneol, i-Terpineol , Geraniol, about 80 per cent. about 6 per cent. 10. A new C6lCOhO2, yielding on oxidation a diketone, C,HI,O,, in very 11. A trace of an aldehyde resembling citral, but yielding a 12. Safrole, about 0.6 per cent. 13. Myristicin, CllH1203, about 4 per cent. 14. Myxistic acid, in the free state, about 0-3per cent., and apparently 15. Formic, acetic, butyric, and octoic acids, and tt new mono- small amount. P-napTLthacinchoninic acid derivative melting a t 248'. a small amount in the form of esters.2055 PICKARD AND KENPON : THE RESOLUTION OF SEC.-OCTYL carboxylic acid, Cl3Hl8O3, all in the form of esters, and in relatively small amount. Although the proportions of the above-mentioned constituents are those indicated for what we have designated a normal oil of nutmeg, it, is obvious that as the 1att.er differed in its physical characters, particularly in its optical rotatory power, from the standards generally adopted for this oil, the composition is subject to considerable varia- tion, according to the character of the material employed f o r distilla- tion. This investigation has, furthermore, shown that the portion of nutmeg oil which has hitherto been designated “myristicol” is a mixture of alcohols, of which terpineol appears to be the predominating constituent. I n view of the fact that narcotic properties are attributed to the nutmeg, the authors are at present engaged in an investigation of its constituents other than the essential oil. THE WELLCOME CHEMICAL RESEARCH LABORATORIES, LOXDON, E.C.

ISSN:0368-1645    

DOI:10.1039/CT9079102037

出版商:RSC    

年代:1907

数据来源: RSC

摘要:

2055 PICKARD AND KENPON : THE RESOLUTION OF SEC.-OCTYL CC1.-The Resolution of see. -0ctyZ Alcohol [Methyl- hexy lcarbinol. Octane- 2 -011. By ROBERT HOWSON PICKARD and JOSEPH KENYON. THE method described by one of us and W. 0. Littleburp (Trans., 1906, 89, 467) for the resolution of racemic alcohols by the fractional crystallisation of an ester of I-menthylcarbamic acid fails in the case of sec.-octyl alcohol, as the ester formed by this alcohol is an oil. The resolution, however, is readily effected by another method recently described by one of us and W. 0. Littlebury (this vol., 1973) and used for the preparation of pure d- and Lisoborneol. Phthalic anhydride combines readily with sec.-octyl alcohol, and the resulting acid ester is almost quantitatively resolved by the crystallisa- tion, first of the brucine salt and then of the cinchonidine salt, of the acid ester obtained from the more soluble portion of the brucine salt.The active alcohol is very stable and not readily racemised, whilst the ease with which both optical isomerides can be obtained renders this alcohol more convenient than any other for experiments in which both the dextro- and laevo-forms are required. It has already been shown by Marckwald and McKenzie (Bey., 1904, 34, 469) that commercial see.-octyl alcohol, which is made byALCOHOL [METHYLHEXYLCARRINOL. 0Crl'ANE-2-OL]. 2059 heating castor oil with potash, is a mixture of the inactive compound with some of the laevo-alcohol, and that the same can be partially resolved by fractional esterification with d-tartaric acid.However, the maximum rotation of the product obtained by their method was not greater than [.ID lo, whereas the pure alcohol has [ a ] , 9.8". We hope shortly to communicate to the Society results of similar experiments carried out with the simpler aliphatic alcohols, EX PER I MENTAL. The octyl alcohol used in our experiments was Kahlbaum's I1 quality. (d + 1)sec.-Octyl Hydmgen, Piithalate, C8HIpO,* C,H7*C0,H. -Equal molecules of sec.-octyl alcohol and phthalic anhydride are heated at 110-120" for fifteen hours. An excess of ethyl alcohol is added, and the mixture heated on the water-bath. The mass is dis- solved in sodium carbonate solution, which is extracted with light petroleum to remove traces of neutral esters, unchanged alcohol, and ketonic impurities of the commercial alcohol.The alkaline solution is acidified, and the acid ester extracted with ether and crystallised twice from light petroleum. The crystalline mass obtained melts at 5 5 O , and is very soluble in benzene, alcohol, chloroform, and either warm acetone or acetic acid, from which it may also be readily recrystallised. l-BYucine d-sec.-Octyl Hydrogen PhthaZate.-Sixty-five grams of the inactive acid ester are dissolved in about 1 litre of acetone and boiled under a reflux condenser with 92 grams of brucine. After the alkaloid has dissolved, the solution, when cold, deposits clusters of hard, prismatic crystals of the salt, which melt at 146-148" and have [a], - 6.7" in ethyl-alcoholic solulion. Two recrystallisations from acetone give the pure salt, which melts at 151".The mother liquors can be worked up and give a further crop of the pure salt, the total yield being about 73 grams. Analysis shows the salt to be composed of 1 molecule of each component (N found 4.4, instead of 4.2 per cent.). The specific rotation of the salt is [a], -5.44" in ethyl-alcoholic solution (c = 5), and this as well as the melting point is unaltered by six recrystallisations from acetone. d-see.-Octyl Hydrogen Piithalate.-The brucine salt is dissolved in a small quantity of alcohol and poured into dilute hydrochloric acid. The precipitated acid ester crystallises very readily from a large quantity of light petroleum in large, stout prisms, which melt a t 75". When titrated, 0.4492 neutralised 0.0644 gram NaOH ; theory requires 0.0646 gram. The following polarimetric observations were made in a 2-dcm.tube : I n a 2-dcm. tube, it gave a - 0.15".2060 THE RESOLUTION OF SEC.-OCTYL ALCOHOL. 0,9617, made up to 20 C.C. with chloroform, gave a +4*13', whence 1*0150, made up to 20 C.C. with ethyl alcohol, gave a +4*88', These specific rotations were unaltered by recrystallisation of the substance. 1-Cinchonidine l-sec.-OctyZ Phtha1ute.-The mother liquora from the brucine salt are precipitated by hydrochloric acid, and yield an acid ester which has [.ID - 42.4' in ethyl-alcoholic solution. The cinchoni- dine salt is prepared in a similar manner to the brucine salt. It crystal- lises from aqueous acetone in long, felted needles, and after six recrystallieations melts indefinitely between 11 2' and 116', and has a constant rotation : 0.9497, made up to 20 C.C.with ethyl alcohol, gave Q - 6-46' in a 1-sec.- Octyl hydrogen phthalate is easily obtained from the cinchoni- dine salt. It crystallisea from light petroleum in lustrous prisms very similar in appearance to those of the dextro-ester, and melts at 75'. When titrated, 0.4543 neutralised 0.0653 gram NaOH ; theory requires 0.0653 gram. The speci6c rotation is practically identical with that of the optical antipode : 0,9635, made up to 20 C.C. with chloroform, gave a-4.17' in a 1.0049, made up to 20 C.C. with ethyl alcohol, gave a - 4.85' in A mixture of approximately equal quantities of the two phthalatos melted indefinitely at about 5 d-see.-0ctyZAZcohol.-The active acid esters readily dissolve in aqueous potash, and are quickly hydrolysed, when the solution is boiled.The alcohol, being insoluble in alkaline solutions, is easily extracted by ether, and is then fractionated under reduced pressure. Several com- parative experiments were carried out with the dextro-ester, and these [.ID + 42.94'. whence [.ID + 48.08'. 2-dcm. tube, whence [ u ] ~ - 68.02'. 2-dcm. tube, whence [.ID - 43.27". a 2-dcm. tube, whence [u]. - 48.26'. alone are recorded. The following are the rotations observed with three separate preparations : in I the acid ester was hydrolysed with the calculated amount of potash; in I1 it was partially hydrolysed with twice the calculated amount; iri I11 the residue from I1 was hydro- lysed completely with a large excess of potash : 50 mm.tube a t 17" gave a+ 4.00". 11. ,, 100 mm. ,, - 17' ,, 8.00'. 111. ,, 24.96 mm. ,, 20' ,, 1.99'. I+II. ,, 200 mm. ,, 20' ,, 15.93'. Similar products to these were mixed and redistilled twice, when The density found I. I n a the pure d-sec.-octyl alcohol boiled at 86'/20 mm.POPE AND GIBSON: THE ALKYL COMPOUNDS OF GOLD, 2061 was Dp 0.8221 and Df 0.8229, this being slightly higher than recorded by Bruhl (Annalen, 1880, 203, 28), who gave D:' 0.8193 for the racemic alcohol. The refractive index was found to be n$ 1.424, whence the moleculttr refraction is 40.28, the calculated value being 40.44. The rotation mas observed in a 2-dcm. tube a t 17O, the mean of thirteen concordant readings being a + 8.1 25', whence [a]" + 9.S7'. It was also observed in solution : 1.0335, made up to 20 C.C. with chloroform, gave at0.93' in a 1.0923, made up to 20 C.C. with ethyl alcoho1, gave a + 1.07 in a The pure dex tro-alcohol was reconverted into the acid phthalate, 2-dcm. tube, whence aD + 9.00'. 2-dcm. tube, whence [ a ] , , + 9.79'. which without recrystallisation had [.IL, + 48.19' in ethyl alcohol. Our thanks are due to Mr. Tom Thornley, who carried out pre- liminary work in the preparation of this and several other racemic acid phthalic esters, as also to the Research Fund Committee of the Society for a grant which has defrayed much of the cost of this investigation. MUNICIPAL TECHNICAL SCHOOL, BLACKBURN.

ISSN:0368-1645    

DOI:10.1039/CT9079102058

出版商:RSC    

年代:1907

数据来源: RSC

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POPE AND GIBSON: THE ALKYL COMPOUNDS OF GOLD, 2061 By WILLIAM JACKSON POPE and CHARLES STANLEY GIBSON. THE disoovery that organo-metallic compounds can in many cases be conveniently prepared by the action of zinc ethyl on the halogen compounds of the metals was made by Buckton (Proc. Roy. Soc., 1859, 9, 309); he thus obtained mercury diethyl, lead tetraethyl, and tin tetraethyl, but was unable to apply the same reaction to the preparation of alkyl compounds of silver, platinum, or copper. Pope and Peachey showed (Proc., 1903, 19, 290) that the alkyl tin compounds are conveniently prepared by the action of the Grignard reagent on stannic chloride or on halogen derivatives of the organo-tin compounds; since that time, a series of papers on the same reaction and its developments has appeared by Pfeiffer and his collaborators (Bey., 1904, 39, 319, 1125, 4617, &c.), but these authors have apparently overlooked the English work on the Bgbject.From this and allied work, it has been learnt that alkyl2062 POPE AND GIBSON: THE ALRYL COMPOUNDS OF GOLD. compounds, such as those of tin, silicon, mercury, &c., can be readily prepared by the action of alkyl magnesium halogen deriv- atives on the halogen compounds of the elements. By the use of the Grignard reagent, there have hitherto been prepared repre- sentatives of classes of alkyl compounds of those elements which belong to groups I1 to VII of the periodic classification; the existence of these was either demonstrated or foreseen by Frankland (Journ. Chern. Xoc,, 1850, 2, 297). Pope and Peachey have, however, recently prepared trimethyl- platinic hydroxide and its salts by the aid of the Grignard reagent (Proc., 1907, 23, 86), and in the present paper we describe tbe preparation of diethylauric bromide by the aid of magnesium ethyl bromide.We are thus now acquainted with organo-metallic compounds of elements of groups I to VIII of the periodic classification, and can consequently conclude that members of all the eight vertical groups yield stable alkyl compounds. I n his original periodic table, Mendeldeff places gold and platinum in the horizontal series 10 (Annulen, 1871, Supp.-Bd., 8, 151); this is of interest in connexion with his conclusion that elements occurring in the higher even-numbered series do not yield stable alkyl compounds, and that if alkyl compounds were obtainable from such elements they would be totally different in properties from previously known organo-metallic substances. Trimethylplatinic iodide and diethylauric bromide are salt-like substances of con- stitutions according with the quadrivalency of platinum and the tervalency of gold ; they correspond roughly in properties with such substances as triethylstannic and diethylthallic salts, so that it does not appear legitimate to conclude that MendelBeff’s prediction is verified by the discovery of the alkyl compounds of platinum and gold.Evidence was obtained by Wanklyn and by Frankland (Proc. Roy. SOC., 1859, 9, 341, 345) of the existence of potassium and sodium ethyl, C,H,K and C2H,Na ; although neither substance was isolated, it appears from the experimental facts quoted by these authors that ethyl iodide acts on sodium ethyl with formation of sodium iodide and gaseous products.No indication was obtained of the production of a compound having the composition (C,H,),NaI. I n the case of the organo-gold compounds, behnviour the converse of this has been observed; there seems t o be no tendency towards the production of the simpler substance, C2H5Au, but the more complex compound, (C2H5)2A~Br, has been prepared. These facts perhaps illustrate better than has been hitherto possible one well- recognised aspect of the periodic law. In a high group of the periodic table, group V, for example, whilst triethylphosphinePOPE AND GIBSON: THE ALKYI, COMPOUNDS OF GOLD. 2063 readily combines with ethyl iodide, triethylbismuthine does not ; the tendency of the tervalent element to become quinquevalent diminishes as the atomic weight increases.In the low numbered group I, the converse is to be concluded from the facts that the substances, C,H,Na and (C2H,),AuBr, are known, whilst the com- pounds, C2H,Au and (C2H5)2NaI, have not yet been prepared, Diethylauric Bromide, (C,H&AuBr. As the preparation of diethylauric bromide presents some ex- perimental difficulties, it will be convenient to state precisely the conditions under which we have been able to obtain the substance. Magnesium (5 grams) is converted into magnesium ethyl bromide by treatment with the calculated quantity of ethyl bromide dis- solved in anhydrous ether (200 c .~ . ) , care being taken that no excess of magnesium is left in the solution. The solution of the Grignard reagent is then run very slowly into a solution of dry auric bromide (22 grams) in ether (150 c.c.) by means of a drop- ping funnel; the latter solntion is well cooled by a mixture of ice and salt, and constantly stirred during the process. Reaction is instantaneous, and during the admixture metallic gold begins to separate out; as soon as t h e whole of the Grignard reagent has been run in, powdered ice is cautiously added and the mixture then allowed to warm up to the room temperature; water and dilute acetic acid are then added, and the liquid extracted several times with light petroleum. The petroleum extract is washed several times with water and transferred to a large basin, which is then placed in a warm draught cupboard so t h a t the petroleum is caused to evaporate rapidly at a temperature of 25-30'.When evaporation is complete, an almost colourless, crystalline residue is left in the basin and this, after one crystallisation by spontaneous evaporation of its solution in light petroleum, yields pure diethylauric bromide. Under the most favourable circumstances, a yield of 2 to 3 grams of the pure substance is obtained from the quantities named above. The auric bromide used in this method of preparation can be replaced by auric chloride without diminishing the yield, but no larger yield was obtained on mixing the auric bromide and magnesium ethyl bromide solutions at the temperature of boiling liquid air.The yield is diminished by running the auric bromide solution into that of the Grignard reagent. Attempts to prepare the substance by the action of zinc ethyl on auric chloride, both in ethereal solution, were unsuccessful ; the two solutions react with great2064 POPE AND GIBSON: THE ALKYL COMPOUNDS OF GOLD. violence, metallic gold is deposited, and no organic product can be isolated. Diethylauric bromide crystallises from light petroleum in long, colourless, doubly-refracting needles, which melt at 58' with slight decomposition and have an odour resembling that of monobromo- camphor. It is very soluble in benzene, petroleum, chloroform, or ether, much less so in alcohol, and insoluble in water. The substance volatilises readily a t the ordinary temperature in air or in a vacuum, and would doubtless lend itself to vapour density determinations ; when heated t o about TO", i t decomposes explosively, leaving a residue of the metal and giving volatile products which, from their odour, do not consist of simple hydrocarbons, like butane, or of halogen deriv- atives of the same.The analysis of the compound is conveniently effected by dissolving the substance in chloroform, adding a chloroform solution of bromine, slowly evaporating to dryness, and weighing the residue of gold obtained after ignition : 0.2082 gave 0.1216 Au. Diethylauric bromide is extremely sensitive to reagents. Au= 5S.41. (C,H,),AuBr requires Au = 58.82 per cent. It gives a precipitate of silver bromide with solutions of silver salts, and is a t once acted on by bromine, ammonia, or nitric acid.When exposed to light in contact with water, metallic gold is gradually formed; reduction also takes place rapidly when its solutions are warmed, so that the crystallisation of diethylauric bromide from all but the most volatile solvents is difficult. dIonoethy?auric Dibromide, (C,H,) AuBr,. On adding a dilute solution of bromine in chloroform to a solution of an equimolecular proportion of diethylauric bromide in the same solvent and allowing the solution to remain at the ordinary temperature, crystals of monoethylauric dibromide are gradually deposited, After most of the chloroform has spontaneously evaporated, the crystalline deposit is separated and mashed with chloroform. Monoethykauric dibronaide is sparingly soluble in the ordinary organic solvents, and is moderately soluble in warm water.It crystallises in transparent, dark ruby-red, doubly-refracting prisms with square ends; on heating, it decomposes gradually without melting. It was analysed by decomposing a known weight with a chloroform solution of bromine and weighing the metal remaining after ignition :POPE AND GIBSON : THE ALKYL. COMPOUNDS OF GOLD. 2065 0.3292 gave 0,1682 Au. (C,H6)AuBr2 requires Au = 51.07 per cent. This compound is much more stable than diethylauric bromide, as is seen from the fact that its solutions may be heated to a much higher temperature than those oE the latter without the occurrence of reduction. It is immediately converted by ammonia into a bright yellow powder, which is insoluble in water or acetone; this product detonates violently on gentle heating. I t is interesting to note that, whilst diethylauric bromide is quite colourless, monoethylsuric dibromide possesses a red colour almost, although not quite, as deep as that of auric bromide.A u = 51.09. Amminodieth y lcburic By-omide, ( C2H5)2 AuBr, NH,. On gently warming diethylauric bromide with dilute aqueous ammonia, solution rapidly occurs, and a f h r evaporation in a vacuum over sulphuric acid a white, crystalline substance remains. The product may be recrystallised from benzene, and forms transparent, doubly-refracting, colourless needles, which decompose gradually on heating at about 60'. It is soluble in benzene, acetone, chloroforni, dilute ammonia, o r dilute hydrochloric acid; the solution in hydro- chloric acid may be boiled without the bccurrence of reduction, and the solution is not precipitated by platinic chloride, although on prolonged standing metallic gold is deposited.The aqueous acetone solution gives a precipitate of silver bromide with silver silts. For analysis, a weighed quantity of the substance mas treated with a chloroform solution of bromine, as i n the previous cases, and the residue ignited and weighed as metal, The reaction with the bromine solution is much more violent than in the other cases : 0.1308 gave 0.0728 Au. Au= 55.66. (C,H,)2AuBr,NH3 requires Au = 55.98 per cent. This substance appears to be the first ammino-compound of gold which has been described, and in type of composition does not correspond to any other ammino-compounds which have been prepared. I t should possibly be classed with the compound of ferric chloride and ammonia, FeC13,NH3, described by H. Rose (Ann. Phys. Chem., 1832, 24, 302). The investigation of these substances and of the alkyl compounds oE the other metals of groups I t o V I I I of the periodic classification is being continued; in view, however, of the poor character of the yields of product obtained, the work necessarily proceeds but slowly.2066 PERKIN: METHYL ETHERS OF SOME We desire to express our thanks to Mr. George Matthep, F.R.S., for generously allowing us the use of the large amounts of gold which have been required in the work. MUNICIPAL SCHOOL OF TECHNOLOGY, VICTORIA UNIVERSITY OF MANCHESTER.

ISSN:0368-1645    

DOI:10.1039/CT9079102061

出版商:RSC    

年代:1907

数据来源: RSC

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2066 PERKIN: METHYL ETHERS OF SOME CCIIL-Methyl Bthers of some Hydroxya.Izthrclquinones. By ARTHUR GEORGE PERKIN. THE results of an examination of Chay root (Oldenkandia umbellntcc, an Indian dyestuff) made several years ago (Perkin and Hummel, Trans., 1893, 64, 1160, and 1895, 68, 817) indicated that t h i s con- tained, in addition to alizarin and its glucoside, ruberythric acid, numerous other non-tinctorial substances. The most interesting of the latter consisted of dimethyl ethers of anthragallol, the a-methyl ether of alizarin, the monomethyl ether of hystazarin, and m-hydroxy- anthraquinone, and these compounds were present in the sample of root examined, partly in the form of glucosides and partly in the free state, Somewhat recently Bock (Monatsh., 1902, 23, 1008) studied the methylation of anthragallol and obtained a dimethyl ether of this colouring matter, which did not agree in melting point with any of the anthragallol dimethyl ethers found to be present in Chay root.A s the result of this single observation, Bock makes the following statement : ‘‘ Es erscheint mir demnach nicht ausgeschlossen dass den Athern Perkin’s und Hummel’s nicht die vermuthete Forrnel zukommt, dass sie vielleicht hydrierte Derivate sind, . . . weiters glaube ich dass ein mirkliche Trennung den Methylather des Anthra- gallol, Alizarins und anderer Oxyanthrachinone wie sie in der Wurzel von Oldenlandia urnbellatcc vorkommen, keineswegs so leicht gelingt, wie es nach den Arbeiten Perkin’s und Hummel’s den Anschein hat.” The statements of Bock were noted at the time, but no steps were taken to reply to these criticisms, for although it was quite possible that an error had arisen in regard to one of the three anthragallol dimethyl ethers described as existing in Chay root, it appeared impossible, on considering the facts given in the paper, that the compounds in question could be otherwise than derivatives of anthra- quinone.To attempt a re-examination of the root itself would have been hardly worth while, and the subject would have remained undis-I~YDROXYANTHRAQUINONES. 2067 cussed, had not some residues remaining from the former work been recently discovered. The separation of the various substances was carried out according t o the methods given in the previous work, and they will be here alluded to in the order in which they occur in that paper.Antlmmpllol Dimethyl Ether ( A ) , m. p. 209.-This compound, as formerly shown, is distinguished by the fact that its ammonium salt can be readily isolated in the crystalline condition, and serves to dis- tinguish i t from the anthragallol dimethyl ether ( B ) which under the conditions employed is not precipitated in this manner. A re- examination of the substance corroborated previous statements, and the melting point, 209O, remained unaltered, although numerous attempts a t further purification were resorted to. Owing to the fact that the red colour of its alkaline solutions disappears on treatment with zinc dust, but returns on exposure to air, it seemed obvious that, taken in conjunction with the evidence previously given, this compound is a derivative of anthraquinone.On the other hand, should it contain an anthranolic or allied grouping by gentle oxidation with chromic acid, the corresponding hydroxyanthraquinone dimethyl ether mould be formed, and such a method was employed for the determination of the constitution of members of this class which are present in the root bark of the Fentilago madraspc6tana (Trans., 1894, 66, 923). It was found, however, that when the anthragallol dimethyl ether ( A ) was subjected to the action of chromic acid in acetic akid solution, an oxida- tion of this character did not occur, and it suffered gradual destruction with the formation of phthalic acid as previously noted. Bock (Zoc. cit.) prepared with some dificulty from anthragallol itself the trimethyl ether of this colouring matter, although from his analytical figures he was unable to pronounce this to be a pure compound.As is well known, the difficulty in dealing with phenolic substances of this class is to methylate the hydroxyl group in the ortho- position relatively to the carbinol group, and this, frequently impossible before the introduction of methyl sulphate, mas a fairly sure indication of the presence of such a grouping. In attempting to methylate one or other of the natural anthragallol dimethyl ethers, this difficulty should not necessarily occur, as both compounds might already possess the methoxy-group in the ortho-position, To determine this point as regards the anthragallol dimethyl ether ( A ) , it was dissolved in methyl alcohol, the solution gently warmed, and treated with equi- valent quantities of methyl-alcoholic potash and methyl sulphate until no red coloration was given by the final addition of the former.The mixture treated with boiling water gave a crystalline, pale yellow precipitate, which was collected and washed with hot dilute alkali, when it melted at 168'. It was practically pure, for after two2068 PERKIN: METHYL ETlIELtS OF SOME recrystallisstions from alcohol and acetic acid this melting point remained unaltered : Found, C = 68.77 ; H = 4.78 ; CH, = 14.83. It consisted of pale yellow needles sparingly soluble in alcohol, and was evidently anthagallo1 trirnetlql ether. The melting point agrees with that given by Bock for his ether, but there was every indication in this case that a pure compound had been obtained.Methylation proceeds so easily that from only a very small quantity of the dimethyl ether sufficient of the fully methylated product could be isolated for purposes of charac terisation, and accordingly it appears evident that in the original substance there is present a methoxy-group in the ortho-position relatively to the carbinol group. As previously stated, the anthragallol dimethyl ether ( A ) gives a crybtalline ammonium salt when its hot alcoholic solution is treated with ammonia, and i t appeared interesting to observe if, by means of alcoholic potassium acetate (Trans., 1899, 76, 433), a corresponding potassium compound would be precipitated. Such was found to be the case, a crystalline precipitate separating almost immediately : C14H505(CH3)3 requires C = 68.46 ; H = 4.70 ; CH, = 15.10 per cent.Found, K = 11.73. C,,H,,O,K requires K = 12.10 per cent. It consisted of glistening, violet leaflets, which on exposure to the air of the laboratory suffered somewhat rapid decomposition with pro- duction of the free dimethyl ether. This proneness to attack by carbon dioxide is not exhibited by the potassium salts of nnthragallol, alizarin, and allied colouring matters. The compound is soluble in water with a crimson colour, and the solution is unaffected when raised to the boiling point, at least for short periods. Ant/trugulzot? dhrbethyl ether (B) in general properties e'losely re- sembles the substance (A), but is characterised by the fact that its ammonium salt is readily soluble in alcohol, An elaborate series of purifications indicated that the melting point previously given for this compound (225-227') is slightly too low and should be 230-232', and the acetyl derivative melts a t 176-178' instead of 175O.With chromic acid in acetic acid solution it gave no indication of a reduced anthraquinone nucleus, and, when methylated, was readily trans- formed into anthragallol trimethyl ether, m. p. 16s'. It possesses, therefore, the constitution originally assigned to it. Potassium acetate did not precipitate a potassium salt from a hot alcoholic solution of this compound, a property which again distinguishes it from the anthragallol dimethyl ether ( A ) . Alizarin a- Lk?etlqZ Ether.-This interesting compound has not as yet beon produced synthetically from alizarin, all attempts in thisHYDROXYANTHRAQUINONES.2069 direction having resulted in the formation of the corresponding m-methoxy-derivative. The methoxy-group present in this substance is much more readily hydrolysed than is usually the case, for pro- longed digestion with boiling baryta water is sufficient for this purpose, a precipitate consisting of barium alizarate thus separating. This property therefore accounts for the difficulty in obtaining either this compound or alizarin dimethyl ether by means of methyl iodide, for in this process a prolonged digestion in the presence of free alkali is necessary. A re-examination of tho substance confirmed the melting point, 178--179O, previously given, and i t was found that by means of alcoholic potash a sparingly soluble potassium salt can readily be prepared.This compound, which crystallises in garnet-coloured, prismatic needles, has evidently the formula C,,H,O,K, but as i t was necessary to reserve the small quantity of the alizarin methyl ether available for more important experiments, it was not further studied. To be certain that the methyl ether contained but one free hydroxyl group, it was acetylated, and the acetyl derivative, which melted at 212O, was analysed by Zeisel’s method : Found CH, = 5-05, It was therefore a monoacetyl compound. As a further proof of the constitution of the methyl ether, it was interesting to study its behaviour on methylation, for containing, as is stated, the ortho-methosy-group, the production from it of alizarin dimethyl ether should proceed without difficulty.Employing methyl sulphate, such was found to be the case, and on treating the product of the reaction with hot water, pale yellow, glistening needles separated. These consisted of the substance in a practically pure con- dition, but were recrystallised from a mixture of acetic acid and alcohol : C,,H,O,(O*CH,), requires CH, = 11.19 per cent. Alizarin dimethyl ether has been prepared by Graebe (Bey., 1905, 38, 152), by the oxidation of C,,H,O;C,H,O requires CH, = 5.06 per cent, Found CH, = 11-21. The substance melted a t 210-211O. deoxyalizarin dimethyl ether, C6H4< co )C6H,(O*CH,),, and also CH2 by Graebe and Thode (Annulen, 1906, 349, 207), by the direct methylation of alizarin with methyl sulphate.As the melting point given by these authors to their compound is 215O, a small quantity of the dimethyl ether was prepared according to the latter method, and in order to be certain t h a t the alizarin employed was pure, advantage was taken of a sample which in the course of the earlier work had been prepared from Chay root. Although a considerable quantity of methyl sulphate was employed VOL. XCI, 6 s2070 PERKIN: METHYL ETHERS OF SOME the main product of the reaction was alizarin nz-monomethyl ether, and only a trace of the dimethyl ether was obtained. The latter, isolated by Graebe and Thode's method, was purified by crystallisa- tion from alcohol and acetic acid ; it melted at 210--21lo, and mas identical with the product formed by the methylation of the natural monomethyl ether.Hystaxarin monomethyl ether, contained in Chay root, was re- examined, and as a result the meiting point, 232O, and general properties assigned to this compound were corroborated. It was readily methylated by methyl sulphate in the manner previously described, and the crystalline product was washed with dilute alkali and recrystallised from alcohol arid acetic acid : Found C=71.61 ; H-4.74; CH,=11*13. CI,H,O,(O*CH,), requires C = 71.64 ; H = 4.48 ; CH3 = 11 -19 per cent. It consisted of pale yellow, glistening needles, melting a t 235--236O, sparingly soluble in alcohol, and was evidently bystaznrin, dimethyl ether. As this compound did not appear to have been previously prepared, hystazarin, obtained by the method of Liebermann and Hohenemser (Ber., 1902, 35, 1778), was methylated by means of dimethyl sulphate.The reaction proceeded without difficulty, and the product, which melted a t 235-236', was identical with that obtained from the natural monomethyl ether. The m-hydroxyanthraquinone isolated from Chay root was so evidently identical with the artificial compound as to render re- examination unnecessary. It was, however, methylated by means of methyl sulphate, and the product of the reaction crystallised from alcohol and acetic acid : Foulld CH, = 6.18. C,,H,O,*O*CH, requires CH, = 6.30 per cent. This m-hydroxyanthraquinone monomethyl ether formed pale yellow needles melting at 193-193', and was found to be identical with the substance prepared in the same way from synthetical m-hydroxy- anthraquinone.The so-called anthragallol dimethyl ether (C), previously described as existing in Cbay root, could not, unfortunately, be reinvestigated. The amount previously isolated was very small, approximately 1 gram from 2 cwts. of the root being all that was obtained. If Bock's synthetical anthragnllol dimethyl ether (Zoc. cit.), m. p. 159-160°, is a pure substance, then the compound (C) €or which the melting point 212-213' WAS given cannot have been a distinct product,, but must have been a mixture of the two anthragallol diruet,hyl ethers ( A ) and ( B ) , previously described. I n any case this reasoning must be adopted by default, as the matter is not worthy of the enormousHYDROXYANTHR AQUINONES. 2071 trouble which a re-examination of the point would necessitate, and it accordingly can now only be considered as proved that Chay root contains two dimethyl ethers of antbragallol.The Positions of the Methoxy-groups in the Anthragallol Dimethyl Ethers ( A ) and (B). Considering the difficulty with which the a- hydroxyl group present in alizarin and the allied hydroxyanthraquinones is methylat ed, and, taking into consideration the comparative ease with which the two anthragallol dimethyl ethers of Chay root are converted into anthra- gallol trimethyl ether, it appeared extremely probable that both com- pounds contain a methoxy-group in the a-position and would possess one or other of the following formulae : co co (J.) (11.1 Further, it is reasonable to suppose that Bock's synthetical ether would have the third possible formula and contain a free hydroxyl in the a-position, on account of the difficulty with which the latter group is methylated.As previously shown, the methoxy-group present in alizarin a-methyl ether somewhat readily suffers hydrolysis in boiling alkaline solutions, and it seemed therefore likely that the corresponding group present in the two anthragallol dimethyl ethers would be hydrolysed at least more readily than those present in the meta-positions relatively to one or other of the carbonyl groups. Should this be the case, anthragallol monomethyl ethers possessing respectively the con- stitutions (OH : OH : OMe = 1 : 2 : 3) and (OH : OMe : OH = 1 : 2 : 3) would be produced, and the identity of each could be ascertained.Thus the former grouping is that of a methoxyalizarin, a compound which should be solubl6 in alkali with a blue tint, whereas the latter, which represents a methoxypurpuroxanthin, should yield red alkali salts. To investigate this point a small quantity of the anthragallol dimethyl ether ( A ) was dissolved in 10 per cent. potassium hydroxide solution, and the liquid heated to 160' in a sealed tube for five hours. The product when cold appeared as a deep blue semi-solid, crystalline mass, which, on solution in boiling water and treatment with acid, deposited an orange-red precipitate, This was collected, well-drained, dissolved in boiling alcohol, and cautiously precipitated with hot water, when i t separated completely on cooling in a crydialline condition : VOL.XCI. 6~2072 PERKIN: METHYL ETHERS OF SOME Found OH, = 8.48. C,,H,O,(O*CH,), requires CH, = 10.56 per cent. From the analysis it is evident that this product, which formed salmon-red needles melting about 1954 mas a mixture of a mono- and a di-methyl ether of anthragallol. On the other hand, this result gave the necessary information, for, as the substance was soluble in alkalis with a blue colour, and readily dyed mordanted calico, there could be little doubt that the monomethyl ether present consisted of metlzoxyatlixarin. An experiment carried out with the anthragallol dimethyl ether ( B ) under the same conditions, at 160°, showed that a t this temperature practically no hydrolysis of a methoxy-group occurs, for the melting point of the recovered substance was 225', and its general properties were identical with those of the original compound, Employing, however, a temperature of 180' for five hours, it was evident that some change had now occurred, for, although the alkaline solution was still red and no trace of blue could be detected, on acidification a deep red precipitate separated.After being crystallised by the addition of boiling water to its hot alcoholic solution it commenced to sinter at 190' and melted completely at 212-213' : Found CH3 = 8.1 0. Cl,H,0,(O*CH3)2 requires CH3 = 10.56 per cent. This product was evidently a mixture, but the fact that its alkaline solutions possessed a red colour indicated that the monomethyl ether which had been formed was methoxy~u4puroxccntJ~in (OH : OMe : OH = 1 : 2 : 3).The corresponding ethoxy-derivative has been previously shown (Trans., 1899, 76, 446) to be produced when monopotassium anthragallol is heated with ethyl iodide at 230°, and the solutions of the alkali salts of this compound are red. These results therefore adduce considerable proof that the formulae I and I1 given above represent respectively the anthragallol dimethyl ethers ( A ) and ( B ) , but in case, although this was hardly likely, some change other than hydrolysis of the methoxy-group had been caused by the alkali at the temperature employed, the hydrolysis of these compounds by means of sulphuric acid was now studied. Experiments first carried out with alizarin a-methyl ether, and alizarin dimethyl ether in presence of the concentrated acid at loo', clearly showed that the o-methoxy-group is the most readily attacked in this manner.Thus whereas during half-an-hour's digestion the former compound gives alizarin, the latter, although somewhat less readily, gives alizarin m-methyl ether, which, after purification,HYDROXY ANTHRAQUINONES. 2013 melted a t 234-226." Finally, anthragallol trimethyl ether, when studied in this respect, gave at first a compound soluble in alkali with a red coloration, due no doubt to the formation of the dimethyl ether (0H:OMe :OMe = 1 : 2 : 3), but on longer heating further hydro- lysis occurred with formation of a monomethyl ether soluble in alkalis with a blue colour, and possessing mordant-dyeing properties. The latter compound, which for reasons given above is evidently the monomethyl ether (OH : OH : OMe = 1 : 2 :3), on prolonged heating with the sulphuric acid a t looo, did not appear to suffer further change, a point of interest in connexion with the constitution of the anthra- gallol dimethyl ether (B).Action of Sulphuric Acid on the Diinethyl Ether (A).-On heating this compound with excess of the acid t o loo', the alkaline solution of the product examined from time t o time soon exhibited a violet tint and finally became blue. It was isolated by addition of water to the hot solution, was purified by crystallisation from alcohol and con- sisted of orange-red needles melting a t 23 1-232'. Evidently this substance, which readily dyed mordanted calico, is the same compound, in a purer condition, as that formed by the action of potassium hydr- oxide solution on t h i s anthragallol dimethyl ether, and also by digesting antbragallol trimethyl ether with sulphuric acid; and there can be little doubt that i t possesses the constitution of a methoxyalizarin. It was noted in one of the former communications (Zoc.cit.) that when the substance is heated with hydrochloric acid at 150' for an hour, a product of this nature, but evidently contaminated with anthragallol, is formed, and Bock (Zoc. cit.), by the action of sulphuric acid on his dimethyl ether, obtained this anthragallol monomethyl ether, m. p. 233-235', apparently in a pure condition. As shown above, this methoxyalizarin is but slowly, if a t all, attacked by continued heating with sulphuric acid a t 100'. Action of Sulphuric Acid on the Dimeth3l Ether (B).-By the action of the acid on this substance at looo for half an hour, the product on solution in alkali gave a red coloration which differed but little from that given by the original compound.Even after two hours no perceptible change occurred i n this respect. The precipitate formed by the addition of water exhibited a more orange tint, and probably consisted, at least in part, of an anthragallol monomethyl ether, but on continuing the digestion for seven hours the compound thus produced was now soluble in dilute alkali with a green coloration, * It has been previously observed (Trans., 1899, 76, 446) that this melting point does not agree with that given by Schunck and Marclilewski (Zoc. cit.), namely, 228-229", but as i t has now been prepared by the author in the three distinct ways with an identical rcsult, it is necessary to assume that the lower figure is correct.B y 22074 PERKIN: METHYL ETHERS OF SOME and after purification consisted of orange-red needles, which readily dyed mordanted calico. The acetyl derivative of this colouring matter was obtained in pale yellow needles melting a t 182-1883”, and was without doubt identical with acetylanthragallol. This result, therefore, considered in conjunction with the previous experiments, shows clearly that in this compound no methoxy-group can be present in the position 3, for it has been found that the anthragallol monomethyl ether, OH: 0H:ORle = 1 : 2 : 3, is fairly stable towards sulphuric acid a t looo, and, moreover, its formation a t any stage of the reaction would have been indicated by the deep blue colour of its alkali salts.Accordingly, therefore, whereas the methoxy-groups in anthragallol dimethyl ether ( A ) , m. p. 209”, occupy the positions 1 and 3 (formula I), in the anthragallol dimethyl ether (B), m. p. 230--232’, they occur in the position 1 and 2 (formula 11). It is interesting to observe that the formation of sparingly soluble potassium salts exhibited by alizarin a-methyl ether, and by anthragallol dimethyl ether ( A ) when alcoholic potassium acetate is employed, is in harmony with the previous work in connexion with anthraquinone colouring matters, from which proof was deduced that the reactive hydroxyl occupies the meta-position relative to the carbonyl group.As regards Bock’s criticism (Zoc. cit.), that he believes that the methyl ethers of anthragallol, &c., present in Chay root, cannot be separated by any means so easily as the work of Perkin and Hummel indicates, comment is almost unnecessary. I n the first place, this author does not produce the faintest evidence that he has conducted an examination of Chay root, or even that he has been in possession of this natural dyestuff; again, there is no assertion in the papers of Perkin and Hummel that the separation of the mixed substances was easy or of a simple character. Thus it is stated on page 825 (Zoc. cit.) : ‘‘ The methods employed for the separation of the yellow substances in Chay root, soluble in baryta water, being somewhat intricate, the tables on page 825 are appended with a view to explain the course pursued more clearly.” Possibly i t is in connexion with these tables that ESck’s criticism has arisen; if so, it should be said that it was obviously unnecessary at the time to remark that these tables did not represent a scheme of quantitative analysis, for such an idea could not occur t o anyone who had read these papers carefully.ATote on the Emodin Methyl Ether contained in the Ventilago Madraspatana. It has been recently shown by 0. A. Oesterle (Arch. Pharm., 1907, 245, 287) that the wood of Morinda citryolia contains a monomethylH Y DROXYANTHRAQUINONES. 2075 ether of R trihydroxymethylanthraquinone melting a t 21 6 O , and this substance he considers is very probably identical with the compound of similar constitution, melting at 200°, isolated by Perkin and Hummel from the root bark of Tentilago nzadraspatana (Trans., 1894, 66, 923).Although it is quite possible in dealing with substances of this nature, and which exist in plants in conjunction with other compounds possessing closely similar properties, that an error of a degree or two in their melting point might occasionally arise, it seemed unlikely in this case that the conjecture of Oesterle was correct. The substance of Perkin and Hummel, which was proved with- out doubt to be a monomethyl ether of emodin, mas produced by the oxidation of two distinct isomeric compounds, CI6Hl4O4, probably anthranol derivatives, with chromic acid, and was also isolated in minute quantity from the root bark of Polygonurn cuspidaturn (Trans., 1895, 68, 1084). A3 the author was in possession of a small quantity of this emodin methyl ether, it was crystallised from acetic acid and benzene, and mas found t o melt a t 200-201' (the melting point previ- ously given is ZOO'). The acetyl derivative, crystallised from alcohol and acetic acid, melted as before a t 185-186', and when this was hydro- lysed with alcoholic potash, the regenerated methyl ether melted a t 201'. This emodin methyl ether, from Yentilago madraspatana, was, therefore, evidently pure, and the surmise of Oesterle is accordingly not correct. There is no evidence that this author has examined Ventilago madraspatana, and it is to be deprecated that criticisms of this kind should be submitted to publication without fuller proof. It is not always possible to retain specimens of such rare substances, and had not this been the case in the present instance, considerable trouble would have been occasioned in the preparation of sufficient substance from the root, in order that the minor points discussed above could be answered. CLOTHWORKERS' RESEARCH LABORATORY, DYEING DEPARTMENT, LEEDS. THE UNIVERSITY,

ISSN:0368-1645    

DOI:10.1039/CT9079102066

出版商:RSC    

年代:1907

数据来源: RSC

摘要:

2076 GREEN, DAVIES, AND HORSFALL: THE COLOURlNG CCIV.-The Colouriiig Matters of the Stilbene Gwup. Part IV. The Action of Caustic Alkalis on para-Nitrotoluene and its Derivatives. By ARTHUR GEORGE GREEN, ARTHUR HUGH DAVIES, and RONALD SMITH HORSFALL. As the results of investigations conducted by Green in conjunct?on with former collaborators (Bey., 1897, 30, 3097; 1898, 31, 1078; Trans., 1904,85, 1424, 1432), the view was advanced that the deeply- coloured (red, violet, or blue), unstable intermediate products which mark the first stage of the action of caustic alkalis on p-nitrotoluene and its derivatives are to be regarded as nitrosostilbenes, formed according to the typical scheme : NO,*C,H,*CH, + CH3*C6H4*N0, -+ NO*C,H,*CH:CH* C,H,*NO. This conclusion was arrived a t from a study of the products of oxidation, the compounds themselves being too unstable to admit of isolation.The deep colour of the alkaline solutions of these com- pounds (when neutral they are pale yellow) was accounted for by assuming for the alkali salts a tautomeric quinonoid form, or The reaction appears to be common derivatives, but is greatly facilitated negative groups in the ortho-position YH: C,H,:y (OH) *ONa CH:C,H,:N(OH)o ONa 9 :C6H4:N*ONs C: C,H,: NOONa' to p-nitrotoluene by the presence with respect t o such as : and all its of electro- the methyl -~ group.* This is seen, for example, in the more ready condensation of pnitrotoluenesulphonic acid compared with that of p-nitrotoluene itself. At the same time, it is noteworthy that in those cases in which the reaction is greatly accelerated by the presence of a strongly electronegative group, such as SO,*C,H,, CN or NO,, the colour of the intermediate compound is blue instead of red.I n order t o investigate the effect of different ortho-substituents, and to obtain further light on the course of the reaction, we have examined the behaviour to caustic alkalis of p-nitrotoluene itself, and of its o-methyl-, o-methoxy-, o-cyano-, and o-carboxy-derivatives. As in the cases previously investigated, we have endeavoured to The latter established a close parallelism between the inff uence of various ortho-substituents on the mobility of the hydrogen atoms of the methyl group when derivatives of p-nitrotoluene are submitted to the stilbene condensation, on the one hand, and to Sach's reaction (condensation with nitrosodimethylaniline), on the other.* This fact was first recopised by Green and Stainton. A. G. G .MATTERS OF THE STILBENE GROUP. PART IV. 2077 characterise the intermediate compounds by oxidation t o the stable nitro-compounds by means of air or hypochlorites. I n the cases examined by Green, Marsden, and Scholefield (the o-chloro-derivative and the o-phenylsulphonate), only stilbene compounds were obtained on oxidation, and no formation of a dinitrodibenzyl compound was observed, although Green and Wahl had previously obtained from p-nitrotoluenesulphonic acid both dinitrodibenzyldisulphonic acid and dinitrostilbenedisulphonic acid, according to the conditions under which the alkaline condensation was performed.We have now found that the ultimate product of oxidation la.qely depends on the reactivity of the particular deriv- ative, Thus, whilst the o-cyano-derivative gave only the corresponding stilbene compound, we obtained from the methyl, methoxyl, and carboxyl derivatives the corresponding dihenzyl compounds ; and from p-nitrotoluene itself, like its sulphonic acid, either dinitrodibenzyl or dinitrostilbene, according to the conditions employed, It is worthy of note that the derivatives which yield by preference dibenzyl com- pounds are those which react least easily and give red condensation products, whilst the derivatives which yield chiefly stilbene compounds are those which react most readily and form violet or blue condensation products. The results point to the conclusion that the alkaline condensation occurs in two stages, which may be more or less concurrent according t o the degree of reactivity of the substance.The product of the first stage gives rise on oxidation to a dinitrodibenzyl, that of the second stage to a dinitrostilbene. This is shown by the following scheme : Condensation CH2*C,H,*N0 Condensation CH*C,H,*NO 1 s t s t a g CH,*C,H,*NO, 2nd staz iH*C,H;NO 2 CH,*CeH4*NO, - I CH,* C,H,* NO, CH*C,H,*NO, When oxidation accompanies condensation, as in the experiments described, it would only depend on the speed with which stage one passes into stage two whether the first or the second condensation product was that chiefly attacked by the oxygen. Substituents which increase the reactivity of the substance would therefore favour the formation of stilbene compounds.That this is in fact the case will be shown later.2078 GREEN, DAVIES, AND HORSFALL: THE COLOURING Relutive InfEzLence of Vu&ous ortho-Substituents on the Rectctivity of the Methyl Group in pam- Nitrotoluene Derivutives. We have endeavoured to obtain an approximate measure of the relative influence exerted by different ortho-substituting groups on the reactivity of the p-nitrotoluene complex by observing the relative temperatures at which the colour formation commences under constant conditions of alkalinit'y and molecular concentration. The experiments were performed as follows : 0.1 gram of p-nitrotoluene or the corre- sponding molecular quantity of one of its derivatives was dissolved in 1 C.C.of pyridine and 5 C.C. of pure methyl alcohol, The solution was contained in a test-tube which could be warmed or cooled as required. Five C.C. of a saturated solution of potassium hydroxide in methyl alcohol (33 per cent, KOH) were added, the mixture was kept well stirred with a thermometer, and the noted a t which colour formation set in. obtained : Ortho- Substance. substitiient. p-Nitro toluene .................... H p-Nitro-o-xylene .................. CH, p-Nitro-o-tolylmethyl ether .. , 0 'OH, p-Nitro-o-toluidine ............... NH, p-Nitro-o-toluic acid ............ C02H Phenyl p-nitrotoluene-o-sulpho- p-Nitro-o-cyanotoluene ......... CN o-Chloro-p-nitrotoluene ......... C1 nate .............................. S03*C,& ............... 2 : 4-Dinitrotoluene NO2 minimum temperature was The following results were Minimum Coloration temperature produced.of reaction. Crimson 7 8" 9 9 79" t o 80" 9 , 75" t o 77" 9 , 81" 78" to 79" V i L t 23" to 24" B1ue about - 20" Y , ), -20" 9 , below -20" The reaction temperatures have, of course, only a relative signi- ficance, as they vary greatly with the concentration of alkali employed. The comparison shows that, whilst the methyl, methoxgl, amino-, and carboxy-groups have but little influence on the reactivity of the compound, the more strongly electronegative groups, sulphophenyl, cyano- and nitro-, exert a powerful effect, that of the nitro-group being greatest. This result is very analogous to the effect on the lability of the chlorine atom in chlorobenzene derivatives exerted by electronegative groups, such as the nitro- and sulphonic acid groups, when occupying an ortho-position.Action of Caustic Alkat'is and Air Oxidation on para-Nitrotoluene. By acting on p-nitrotoluene with alcoholic sodium hydroxide, 0. Fischer and Hepp (Bey., 1893, 26, 2231) obtained small quantities of dinitrodibenzyl and dinitrostilbene. The main product of theMATTERS OF THE STILBENE GROUP. PART IV. 2079 reaction was, however, a sparingly soluble, orange-yellow substance, which the above authors term ‘‘ dinitrosostilbene,” but which is probably the dinitroaxodistilbene, NO, C,H,*cH: CH*C,H,*N,* C,H,* CH: CH*c,H,*NO,, formed by further Condensation of the true dinitrosostilbene which is first produced. I n order to prevent the formation of this condensation product, it is necessary to proceed in such a manner that the inter- mediate nitroso-compounds are oxidised as soon as they are formed.If, for instance; powdered p-nitrotoluene is covered with 33 per cent. alcoholic potash and slightly warmed, the formation of the red ni troso-compound commences at once. The conditions preclude the employment of hypochlorites, but the oxidation of the intermediate compound is readily effected by means of air. To obtain good results and prevent contamination of the product with coloured compounds it is only necessary to take care that the oxidation keeps pace with the colour formation, since the nitroso-compound, if not at once oxidised, quickly undergoes further condensation. Five grams of p-nitrotoluene were placed in a wide-necked, conical flask together with 100 C.C.of cold 33 per cent. methyl-alcoholic potash. The red coloration which forms immediately disappears again on vigorous shaking, giving place to a pale yellow, granular precipitate. The operation was continued in the cold with constant shaking until the colour formation only took place slowly and the mixture had become a pale yellow, crystalline magma. This was then filtered by the aid of the pump, the precipitate washed with hot water and hot alcohol, and dried. The product recrystallised from benzene, formed pale yellow needles melting a t 180-182°. It was evidently the known 4 : 4’-dinitrodibenzyZ, NO,*C,H,*CH, *CH2*C,H,*N0, : .Found, N = 10-56, 10.52. Under the conditions employed above (reaction in the cold), dinitro- dibenzyl appears to be almost the sole product.If, however, the temperature of the mixture is slowly raised and the operation continued for a longer period, until finally the colour formation has practically ceased, the product is of a deeper yellow than before and then consists chiefly of a compound which, after alternate crystallisa- tion from nitrobenzene and from glacial acetic acid, was obtained in bright yellow leaflets or flat needles, melting a t 292-294O. It proved to be 4 : 4’-dirnitrostiZbene, N0,eC,H,*CH:CH*C,H,*N02, and probably represents this substance in a somewhat purer state than previously obtained. Fischer and Hepp assign to dinitrostilbene the melting point 272”, whilst Walden and Kernbaum (Bey., 1890, 23, 1958) give 280-285’ as the melting point of their higher melting C1,H1,O,N, requires N = 10.29 per cent.2080 GREEN, DAVIES, AND HORSFALL: THE COLOURING isomeride.reaction of a second isomeride. We have obtained no evidence of the formation by our Analysis gave the following results : Found, C= 61.95 ; H=3.57; N = 10.65, 10.55. The yield of the crude product is nearly theoretical. I n order to distinguish with certainty between stilbene and dibenzyl derivatives in the above and other cases described in this paper, we have made use of the following test, which depends on the more ready oxidation of the ethylene group. A small quantity of the substance is dissolved in a little pyridine, and to the cold solution is added two or three drops of an acetone solution of calcium permanganate. With stilbene compounds, the solution is at once decolorised, whilst with dibenzyl compounds the pink colour persists for several minutes even i f gently warmed.C,,Hlo04N2 requires C = 62.2 ; H = 3.7 ; N = 10.37 per cent. Action of Caustic Alkalis and Air on p-Nitro-o-xylene. The operation was carried out in the cold in the same manner as described above, I n this case,also, the crude yield was almost theoretical. The product, after recrystallisation from glacial acetic acid, formed lemon-yellow needles, melting at 222-224'. It is not oxidised by per- manganate under the conditions described above, and is without doubt 4 : d'-dinitro-2 ; 2'-dimethyldibenxyl (4 : 4-'dinitro-s-di-o-toZyZethane), NO,* C,H,Me*CH,*CH2* C,H,Me* NO,. It gave the following results on analysis : The substance is somewhat sparingly soluble in most solvents.Found, C = 64.14 ; H = 5.55 ; N = 9.58, 9.54. Under the conditions of the experiment, the corresponding stilbene Cl,Hl,O,N, requires C = 64.0 ; H = 5.33 ; N = 9.33 per cent. derivative was not obtained.* Action of Caustic Alkalis and Air on p-Nitro-o-tolyl Methyl Ether. The p-nitro-o-tolyl methyl ether employed was obtained by methyl- ation of nitro-o-cresol prepared by decomposition of tho diazo-compound of p-nitro-o-toluidine and purification in the manner described by Witt, Noelting, and Grandmougin (Bw., 1890, 23, 3636). After recrystallisation from alcohol, the ether melted at about 72O. The condensation and oxidation were effected in the same manner as before. The yield of the crude product, insoluble in alcohol, was nearly theoretical, namely, 4.9 grams from 5 grams of tolyl ether taken.The substance was crystallised two or three times from ethyl * The dinitroclimethylstilbene and dinitrodimethoxystilbene have been since obtained and are at present undergoing investigation. A. G. G.MATTERS OF THE STILBENE GROUP. PART IV. 2081 acetate, and then formed lemon-yellow leaflets melting at 178-180°. It proved to be 4 : 4 ' d n i t r o - 2 : 2'-dimethoxydibennxyl ( 4 : 4'-dinitro-2 : 2'- dimet hox y-s-diphen y $ethane), N02*C,H,(OMe)0CH2*CH2*C,H,(OMe)0N0,. Analysis gave the following results : Found, C = 58-43 ; H = 4.80 ; N = 8 - 7 2 , A methoxyl determination by Zeisel's method gave : Found, CH, = 8.78. The substance is not oxidised by permanganate under the conditions Under the conditions employed, there was no formation of the C,,H,,O,N, requires C = 57.83 ; H = 4.81 ; N = 8.43 per cent.C1,H,,O,N, requires OH, = 9.03 per cent. prescribed above. corresponding stilbene derivative. * Action of Caustic AIkulis and Hypochlorites on p-Nitro-o-toluic Acid. The p-nitro-o-toluic acid employed was obtained by saponification of the nitrile (see later) by boiling it for two or three hours with sulphuric acid diluted with half its volume of water. After recrystal- lisation from dilute alcohol, it formed long, colourless needles which melted at about 178'. When heated with aqueous sodium hydroxide, it gives n deep violet-red coloration, which is converted into a yellow stilbene dyestuff on longer heating.This colouring matter dyes unmordanted cotton direct in bright yellow shades, and is similar to Direct Yellow, The behavioiir of the carboxylic acid is therefore quite analogous to that of the eorresponding sulphonic acid. In order to oxidise the violet-red intermediate compound, we have proceeded in a similar manner to that employed for the sulphonic acid by Green and Wahl. Five grams of p-nitrotoluic acid were dissolved in 12 C.C. of water by means of 1.4 grams of sodium carbonate. To the hot solution were added 35 C.C. of sodium hypochlorite solution (7.4 per cent. active chlorine), followed immediately by 50 C.C. of sodium hydroxide (33 per cent. NaOH). The mixture was then rapidly heated to the boiling point, when the reaction sets in vigorously and the liquid boils spontaneously for about half a minute.Directly the reaction slackens and the mixture becomes pasty, but before any coloration appears, and whilst there is still a small excess of hypochlorite left (that is, in about one minute from the commence- ment of the reaction), the whole contents of the flask must be poured quickly into an excess of dilute hydrochlorio acid (100 C.C. of concen- trated hydrochloric acid and 300 C.C. of water) contained in a large beaker. The operation is somewhat difficult to carry out, as, if the * Ibid.2082 THE COLOURING MATTERS OF THE STILBENE GROUP. reaction is allowed to proceed a few seconds too long until the hypo- chlorite is exhausted, colour formation sets in, and the product caDnot be subsequently purified.When the operation is correctly conducted, the product is obtained as a pale yellow precipitate, sparingly soluble in water or alcohol. It was purified by several extractions with boiling dilute alcohol (30 per cent.), dried, and recrystallised from cresol. The product separated in colourless plates, which melted with decomposition a t 299-300O. I t s analysis and properties indicate that it is 4 : 4'-Jinitrodibenzyl-2 : 2'-dicarboxylic acid (4 ; 4'-dinitro-s-di- phenylethcine-2 : 2'-dicarboxylic acid), N02*CGH,(C02H)*CH,*CH2*C,H,(C02H)*N0, : Found, C = 53.4, 52.9, 53.5 ; H = 3.51, 3.28, 3.38 ; N = 8.07, 7.83. CI,H120,N2 requires C = 53.33 ; H = 3.33 ; N = 7.77 per cent. It is not oxidised by permanganate in cold pyridine solution or in cold dilute aqueous solution.We have not yet obtained the corresponding stilbene derivative in a pure state, although in several of our experiments, in which rather diEerent conditions from the above were employed, a product was obtained which gave the reactions of a stilbene compound. The melting point of this substance was about 270'. It is reduced to a crimson-red compound on adding phenylhydrazine or dextrose to the aqueous solution rendered alkaline with sodium hydroxide. Action of Caustic Alkalis and Air on p- Nitvo-o-cyanototuene. The nitrile was prepared from p-nitro-o-toluidine by Sandmeyer's reaction, and purified by recrystallisation from alcohol. It formed pale yellow needles which melted at 1 0 3 O . On adding alcoholic potash or strong aqueous potassium or sodium hydroxides to a cold alcoholic solution of the nitrile, excluding air by a current of hydrogen, a brilliant deep blue coloration is produced.This color- ation after some minutes slowly changes to violet, and, if air is admitted, it quickly becomes brown, and a dark tarry precipitate is deposited. The blue compound therefore, like other members of its class, is extremely unstable. Since its isolation was impossible, it was at once submitted to oxidation. Both air and sodium hypochlorite were employed as oxidising agents, the product in each case being the same. The hypochlorite, however, gave the best results. Ten grams of the nitrile were dissolved in 30 C.C. of warm pyridine and mixed with 300 C.C. of alcohol. To the cold solution were added 160 C.C. of sodium hypochlorite (4.75 per cent.active chlorine), followed immediately by 60 C.C. of strong aqueous sodium hydroxide. The mixture became warm, and a precipitate separated. This was immediately collected by the aid of the pump, and washed withTHE REPLACEMENT OF ALKYL RADICLES BY METHYL. 2083 boiling alcohol. The crude product was a pale yellow, granular precipitate, which melted above 200'. For purification, it was recrystallised several times from nitrobenzene and glacial acetic acid. NO,* C6H3( CN)*CH: CH* C6H3(CN) NO,. The compound is sparingly soluble in nitrobenzene, chloroform, or glacial acetic acid, moderately so in pyridine, and almost illsoluble in alcohol. It crystallises from glacial acetic acid in small, indistinct, yellow crystals, which melt with decomposition at about 258". Analysis gave the following results : Found, C = 60.9, 60-0, 60.2 ; H= 2.75, 2-5, 2.39 ; N = 17.50, 17.87. CIGH,O,N, requires C = 5 9 . 9 ; H = 2-52 ; N = 17.54 per cent. The substance at once decolorises permanganate in a cold pyridine solution. On reduction in cold alcoholic solution by addition of sodium hydroxide and a drop of phenylhydrazine, it is reconverted into the deep blue nitrosostilbene from which it is derived. We have not been able to isolate a second isomeride. Attempts to convert the nitrile into the carboxylic acid were also unsuccessful, owing to the occurrence of by-reactions on heating with mineral acids. It proved to be 4 : 4'-dinitro-2 : Z'-dicyanostilbene, We desire to express our thanks for a grant from the Chemical Society Research Fund, by which a portion of the expense of this Research has been defrayed. DEPARTMENT OF TINCTORIAL CHEMISTRY, THE UNIVERSITY, LEEDS.

ISSN:0368-1645    

DOI:10.1039/CT9079102076

出版商:RSC    

年代:1907

数据来源: RSC

摘要:

THE REPLACEMENT OF ALKYL RADICLES BY METHYL. 2083 CCV.-The Replacement o f Alkyl Radicles by Methyl in Substituted Ammo&um Compounds. By HUMPHREY OWEN JONES and JOHN ROBEBTSHAW HILL. IT was shown by one of us (Proc., 1901, 17, 205) that dibenzyl- aniline and quaternary ammonium compounds containing the methyl and benzyl groups, when heated with methyl iodide, yielded benzyl iodide and phenyltrimethylammonium iodide. No other alkyl iodide among those tried, namely, ethyl, propyl, iaobutyl, and allyl iodides, was found to effect this displacement of the methyl group, and it could not be shown that other groups were displaced by methyl (at this time allyl compounds were not examined). Later (Trans., 1905, 87,2084 JONES AND HILL : THE REPLACEMENT OF ALKYL RADICLES 1726), it was found that the ally1 group is displaced from benzylallyl- aniline by methyl iodide in the cold, and the benzyl group on heating.A t this time, it seemed that the allyl and benzyl groups were the only ones that could be replaced by the methyl group, since optically active compounds containing these radicles racemised readily in chlo1.o- form solution, and also their iodides have the greatest capacity for uniting with aromatic tertiary amines, the conclusion that the dis- placement was dependent on their common properties was apparently justified. This displacement of benzyl and allyl groups by methyl was found to be general, as proved by the following transformations, in addition to those already mentioned, which were found to take place rapidly when the first-mentioned compound was heated to looo with methyl iodide alone or with methyl iodide and alcohol or chloroform.Phenylbenzylmethylisoarnylammonium iodide ++ phenyldimethyl- isoamylnmmonium iodide, phenylbenzylmethylisopropylammonium iodide -+ phenyldimethylisopropylammonium iodide, phenyldimethyl- allylammonium iodide -+ phenyltrimethylammonium iodide, phenyl- methgldiallglammonium iodide -+ phenyltrimethylammonium iodide, phenylmethylisoamylallylammonium iodide -+ phenyldimethyliso- amylammoniurn iodide. Ethyl, propyl, isobutyl, and iaoarnyl iodides, when heated with benzyl and ally! compounds, did not effect any displacement, although the odour of allyl or bcnzyl iodide was always noticeable. I n 1906, some anomalous results were obtained while attempting to prepare a series of compounds containing the phenyl, methyl, and ethyl groups together with propyl, isopropyl, isobutyl, and isoamyl groups.Ethylisoamylaniline and methyl iodide were found to combine slowly in the cold, and the resulting product was, as expected, phenylmethylethylisoamylammonium iodide. EthylisopropyIaniIine and methyl iodide reacted very slowly in the cold, but eventually deposited a crystalline solid which, after repeated crystallisatioas, melted at 167-1 68O. It mas found to be identical with phenyldimethylisopropylammonium iodide (m. p. 168O), prepared from methylisopropylaniline and methyl iodide. It was evident therefore that the ethyl group was i n this case dis- placed by methyl in the cold. Ethylpropylaniline and methyl iodide reacted slowly, depositing a gum which became crystalline on standing ; after recrystallising, the following numbers were obtained on analysis : Found, C = 45.12, 45.4 ; H = 6-39, 6.4.MeEtPh(C,H,)NI requires C = 47.2 ; Me,Ph(C,H7)NI ,, C=45*12; H=6*14 ,, H = 6.56 per cent.BY METHYL IN SUBSTITUTED AMMONIUM COMPOUNDS. 2085 A similar displacement of the ethyl group has evidently taken place here. This compound and the product from methylpropylaniline and methyl iodide are very soluble, and difficult to recrystallise and purify ; hence their absolute identity has not yet bean established. Later, it was found that the series of substituted p-bromoanilines already described (Hill, Proc. Cccrnb. Phil. Soc., 1907, 14, 166) all reacted at 100' with methyl iodide and gave p-bromophenyltrimethyl- ammonium iodide.This compound is very easy to isolate and identify, even when formed in quite small quantities, on account of its small solubility in alcohol, its characteristic appearance, and melting point of 200°, a melting point which is higher than that of any of the other ammonium iodides derived from this series of amines. p - Bromometkylethylaniline or p - bromophenyldimethylethyl- ammonium iodide and the corresponding propyl, isopropyl, rc-butyl, and isobutyl compounds were found to give some p-bromophenyltri- methylammonium iodide after heating a t 100' for two hours in a sealed tube with excess of methyl iodide; the isobutyl compound appeared to be completely transformed, whilst the ethyl, propyl, and isopropyl compounds yielded a moderate quantity of the trimethyl compound.The isoamyl compound, however, seemed to react much less readily, and at first it was thought that no action had taken place; but after prolonged heating, the trimethyl compound was detected : p-bromo- phenylbenzylmethylisoamylammonium iodide yielded the trimethyl compound in somewhat larger quantity. It was clear therefore that the six saturated hydrocarbon radicles mentioned above behaved in t'he same way as the benzyl and allyl groups, but that they were not always so readily nor so completely displaced by methyl, as the benzyl and allyl groups. Attention was now directed to the corresponding series of phenyl compounds to determine whether they behaved in the same way as the bromophenyl derivatives, Phenyldimethylethylammonium iodide and the corresponding propyl, isopropyl, isobutyl, and isoamyl com- pounds were heated with methyl iodide and examined for phenyl- trimethylammonium iodide.This compound is easy t o identify on account of its slight solubility, which, however, is much greater than that of the corresponding bromo-compound, and its behaviour on heating, when it volatilises at 220'. All the compounds, except the isoamyl derivative, were found to give phenyltrimethylammonium iodide, but even after prolonged heating none could be obtained from this, It was found, however, that phenyl benzy lmeth ylisoam y larumonium iodide yielded some phenyltrimethylammonium iodide after heating with a large excess of methyl iodide.2086 JONES AND HILL : THE REPLACEMENT OF ALKYL RADICLES Here, the ease with which a radicle was displaced seemed to diminish with increasing molecular weight, except that the isobutyl group appears to be more readily replaced than the propyl; but the ease with which displacement took place in all cases was distinctly less than in the corresponding bromo-compounds.Phenylbenzylmethyl-l- amylammonium iodide (Trans., 1905, 87, 135) was found to give the trimethyl compound with difficulty, like the corresponding isoamyl derivative. It seems probable that the difference between the isoamyl and the other groups as regards the ease with which they are replaced is merely one of degree. The displacement of alkyl radicles by methyl could tnko place in one of two quite distinct ways : (1) by direct action between methyl iodide and the ammonium iodide, thus : Me,Ph(C7H7)NI G CH31 = Me3PhNI + (&H71, or (2) partial dissociation into tertiary amine and an alkyl iodide might occur in the methyl iodide solution; then the methyl iodide being present in great excess would react with t h e tertiary amine to form ao ammonium iodide until equilibrium was established in solution, thus : Me,Ph(C7H,)NI Z Me,PhN + C,H,I Me,PhN + CH31 = Me,PhNI.On consideration, the latter view appears the more probable, since we know that the dissociation postulated does occur in chloroform solution and results in gradual racemisation of active ammonium iodides. That this same dissociation also occurs in solution in alkyl iodides was shown by examining solutions of E-phenyl- benzylmethylisopropylammonium iodide (Thomas and Jones, Trans., 1906, 89, 289) in methyl iodide and in ethyl iodide.The salt is extremely sparingly soluble in the iodides, but the additionof a few drops of alcohol enabled a solution to be prepared which gave a rotation great enough for the changes to be observed. I n methyl iodide : Initial rotation, - 0.57' ; after six hours, - 0 . 3 2 O ; after twenty- four hours, - 0.14'; after thirty hours, - 0.03'; after forty-eight hours, inactive. I n ethyl iodide : Initial rotation, - 0-62 ; after six hours, - 0.40' ; after twenty- three hours, - 0.12' ; after thirty hours, - 0.07' ; after forty-eight hours, inactive. Hence this iodide racemises in methyl and in ethyl iodide solution a t practically the same rate as in chloroform (compare Trans., 1906,BY METHYL IN SUBSTITUEED AMMONIUM COMPOUNDS, 2087 89, 290).It follows, therefore, that a dissociation into tertiary amine and alkyl iodide must take place in the case of compounds containing other groups besides benzyl and allyl. Unfortunately, up to the present time, no optically active nitrogen compound is known which does not contain either the beDzyl or allyl group together with methyl, otherwise this dissociation could be shown by their auto- racemisation. The ease of replacement would then depend on the extent to which this dissociation into alkyl iodide and tertiary amine occurred. It seems probable that the order of the alkyl radicles as regards extent of dissociation would be the same as that for ease of addition. Taking Wedekind’s values for the percentage amount of ammonium salt formed from these alkyl iodides and dimethylaniline in fifty-three hours (Stereochemie des funfwertigen Xtickstofs, 1899, 21), namely, methyl, 89; ethyl, 15; n-propyl, 28; isopropyl, 5 ; n-butyl, 17; bobutyl, 1.6 ; isoamyl, 2.5 ; ally], 93 ; benzyl, 83, we see that the ease of replacement, which is determined presumably by the extent of the dissociation, is roughly in the same order as the ease of formation of quaternary salt by the alkyl iodide in question.There is, however, a n apparent exception i n the case of the isoamyl group, which we find to be the most difficolt to displace, more difficult than the isobutyl group, yet its iodide appears to combine with dimethylaniliue more readily than the latter. We therefore examined this poiut further by allowing mixtures of dimethylaniline and eqnivalent quantities of ethyl iodide, isobutyl iodide, and isoamyl iodide to remain for one month a t the ordinary temperature.The much longer time was allowed in order to avoid such a large percentage error from the solubility of the salt in the mixture of amine and iodide, which, when very small quantities such as Wedekind obtained (0-15-0.S gram) are concerned, must exert a disturbing influence on the quantitative results. One-twentieth of a gram-molecule of each mixture was taken, and after standing one month the iodide was separated, dried between filter paper, and weighed (the isobutyl compound was crystalline), and found to be 23.6 per cent. for ethyl, 2.0 per cent. for isobutyl, and 1.3 per cent.for isoamyl. Hence it would appear that the isoamyl iodide has not, a t any rate, a greater reaction velocity than the isobutyl. Methyl iodide comes third in order of rapidity of reaction with dimethylnniline, and i t is therefore surprising to find that it is the one that is capable of replacing all the others; the explanation of this is probably to be found in the very small solubility of the methyl compound as compared with the others, which also accounts for the much greater ease with which replacement takes place in thep-bromo- phenyl than in the phenyl series. The solubilities of the substituted2088 JONES AND HILL : THE REPLACEMENT OF ALKPL RADICLES ammonium iodides in alcohol at the ordinary temperature, expressed in grams in 100 grams, are as follows : p - Rrom ophen yldimethyl.< Melting Solubility. point. -methyl ......... 1.1 220" (volatilises) -ethyl ............ 45 *1 136 -isopropyl.. ....... 11 *8 168 -isobutyl ......... 24'1 155-156 -isoamyl ......... 18.4 138 , -benzyl ............ 2.7 165 , Melting Solubility. point. 0.12 200" 1-15 189 3 30 167 2 *35 176 5.69 167-168 - - It therefore appears that the ease with which a radicleis displaced by methyl is dependent on two factors ; first, the amount of dissocia- tion into tertiary amine and alkgl iodide, of which the rate of formation of the salt from alkyl iodide and amine may be regarded as a measure, and secondly, the solubility of the ammonium salt from which the group is to be displaced. The slight solubility of the trimethyl compound enables this to separate from the solution and so to be removed from the sphere of action. The ready solubility of the isobutyl compound of the p-bromophenyl series probably accounts for the fact that this group is more readily displaced than all the others.On the view expressed above, that the extent of the dissociation is determined by the velocity of addition of the alkyl iodide to the tertiary amine, ammonium salts containing the methyl group should dissociate into amine and methyl iodide to quite a considerable extent. That this is actually the case is shown by the following observations : p-bromodimethyIaniline was allowed t o stand with the iodides of the following radicles, ethyl, propyl, isopropyl, isobutyl, and isoamyl. I n the cold, the reaction was extremely slow, except in the case of the ethyl compound.The solid deposited in this case was found to consist chieff y of p-bromophenyltrimethylammonium iodide. At loo", the other four alkyZ radicles also yielded a considerable quantity of the trimethyl compound. It would appear that the following scheme is the probable ex- planation of these results : CGH4Br*Me,N + EtI C6H4Br*hTeEtNI, C,H,Br*I$e,EtNI Z C6H4Br*MeEtN + MeT, C,H,Br*Me,N + Me1 f C,H,Br-Me,NI. The quaternary salt first formed is dissociated in two distinct ways, so that in the solution we have an equilibrium between two alkyl iodides and two tertiary amines. The very small solubility of the trimethyl compound then determines the separation of this salt from the solution. A dissociation of ammonium salts into two aminesBY METHYL IN SUBSTlTUTED AMMONIUM COMPOUNDS. 2089 and two alkyl iodides on heating has been observed by Wedekind (Be?.., 1902, 35, '766). The results may be summarised as follows : the groups, allyl, benzyl, ethyl, isobutyl, propyl, isopropyl, and isoamyl, are displaced from ammonium salts by the methyl group on treating with methyl iodide, sometimes in the cold, more usually on heating. The displacement takes place owing t o the salt dissociating in methyl iodide solution into tertiary amines and alkyl iodides; a n equilibrium is set up between the dissociated amines, iodides, and the methyl iodide, and, since in each case the trimethyl compound is much less soluble than the other, this separates, and so is found in much greater quantity than the other in the solid product. The order given is roughly that of the ease of displacement of these rsdicles, which is determined by the extent of the dissociation and the solubility of the ammonium salt in question. The isoamyl group is the most difficult to displace. The expenses of this investigation have been defrayed by grants from the Government Grant Committee of the Royal Society, for which we are glad to take this opportunity of expiessing our thanks. USIVEILSITY CHEMICAL LABORATOILY, CANBILIDGE.

ISSN:0368-1645    

DOI:10.1039/CT9079102083

出版商:RSC    

年代:1907

数据来源: RSC

摘要:

INDEX OF AUTHORS’ NAMES. TRANSACTIONS AND PROCEEDINGS. 190’7. (Marked T. and P. respectively.) COMPILED BY MARGARET D. DOUGAL A. Allen, Thomas Bolcs. See William Robert Lang. Andrew, John Harold. See William Henry Bentley. Atkinson, Ernest Francis Joseph, Harry Ingham, and Jocelyn Field Thorpe, the formation and reactions of imino- compo~inds. Part JII. The formation of 1:3-naphthylenediamine aud its derivatives from o-toluonitrile, T., 578; P., 76. Atkinson, Ernest Francis Joseph, and Jocelyn Field Thorpe, the formation and reactions of imino-compounds. Part V. The formation of methyl derivatives of 1 :3-na~hthvlenediamine from the three toldacetLnitriles, T., 1687 ; P., 216. Auld, SamiLel James Manson, mercury derivatives of pseudo-acids contain- ing the group CO-NH., T., 1045 ; P., 151.the hydrolysis of aniygdalin by emul- sion, P., 72 ; discussiou, P., 72. Austin, Percy Corlett. See AIfred Senier. B. Bain, Alexandey TViZZiam, the action of ethylene dibromide and of propylene dibromide on the disodium derivative of diacetylacetone, T. , 544 ; P., 77. Bain, Alexander William. See also Samuel Smiles. Baker, Frank, the structure of carbonium salts, T., 1490 ; P., 192 ; discussion, P., 193. Baker, Frank, and Edward Charles Cyril Baly, the relation between ab- sorption spectra and chemical constitu- tion. Part VII. Pyridine and some of its derivatives, T., 1122 ; P., 167. XCI. Baker, Herhert Breretm, and (Mrs.) Muriel Baker, gaseous nitrogen tri- oxide, T., 1862 ; p., 239 ; discussion, P., 240. Baker, Berbert Brereton, and Alexander Hutcheon Bennett.the atomic weight of tellurium, T., 1849 ; P., 240 ; dis- cussion, P., 241. Baker, (Mrs.) Muriel. See Herbert Breretun Baker. Baly, Edward Charles CyriZ, William Bradshaw Tuck, (Miss) E$ie Gwendoline Marsden, and, (in part), (Miss) Maud Gazdar, the relation between absorp- tion spectra md chemical constitution. Part VIII. The phenylhydrazones and osazones of a-diketones, T., 1572 ; P., 194. Baly, Edward Charles Cyril. See also Frank Baker and William Eenry Bentley. Barger, Gorge, and Francis Eoward Carr, the alkaloids of ergot, T., 337 ; P., 27; discussion, P., 27. Barker, Thomas Vipond, note on the iodates and periodates of the alkali metals and the ammonium radicle, P., 305. Barlow, FVilZiam, and William Jackson Pope, the relation between the crystalline form and the chemical constitution of simple inorganic sub- stances, T., 1150; P., 142; dis- cussion, P., 143.note on the theory of valency, P., 15. Barrett, Emtest, and Arthur Lapworth, the velocity of reaction of bromine with some unsaturated acids in aqueous solution, P., 18. the influence of acids and alkalis on the velocity of formation of acet- oxime, P., 307. G E2092 INDEX OF AUTHORS. Barrowcliff, Marmaduke, the constitu- ents of the essential oil of American pennyroyal ; occurrence of a dextro- menthone, T., 875 ; P., 114. Barrowcliff, Marmadu ke, and Frederick Beldiny Power, the constitution of chaulmoogric and hydnocarpic acids, T., 557 ; P., 70. Barrowcliff, Marmaduke, and Frank Tutin, chemical examination of the root and leaves of Morinda ZongiJora, T., 1907 ; P., 248.Beck, Thomas Constantine. See Wil- liam Jackson Pope. Bellars, Albert Ernest. See Robert Selby Morrell. Bennett, Alexander Hutcheon. See Herbert Brereton Baker. Bentley, William Henry, Arthur Friedl, Frederiak Thomas, and Charles Weiz- mann, [with an addendum by Edward Charles Cyril Baly and William Bradshaw Tuck], derivatives of naph- thacenequinone, T., 411. Bentley, William Benry, Arthur Friedl, and Charles Weizmann, derivatives of naphthacenequinone, T., 1588 ; P., 215. Bentley, William Zenry, Henry Dent Gardner, jun., and Charles Weizmann, [with John Harold Andrew and Claude Yaxeille Temperley], researches on anthraquinones and phthaleins, T., 1626 ; P., 215. Bentley, William Henry, (ilfiss) Rona Robinson, and Charles Weizmann, 3-hydroxyphthalic and 3-methoxy- phthalic acids and their derivatives, T., 104.Bentley, William Henry, and Charles Weiamann, 4-hydroxyphthalic and 4- methoxyphthalic acids, T., 98. Berkeley, (Earl o f ) , on the more exact determination of the densities of crystals, T., 56. Bevan, Edward John. See Charles Frederick Cross. Beveridge, Heather Henderson. See James Walker. Bloxam, William Pqplewell. See Arthur George Perkin. Briggs, John Frederick. See Charles Frederick Cross. Brislee, Francis Joseph, the velocity of reduction of the oxides of lead, cadmium, and bismuth by carbon monoxide, and the existence of the suboxides of these metals, P., 286. Brown, James Campbell, some double ferrocyanides p f calcium, potassium, and ammonium, T., 1826 ; P., 233.Briihl, Julius Wilhelnz, the optical influ- ence of contiguity of unsatiirated groups, T., 115. Buckney, Frank, and Humphrey Owen Jones, the optical activity of cyclic ammonium compounds, T., 1821 ; P., 234. Buckton, George Bozudler, obituary notice of, T., 663. Burdett, (Miss) Frances. See Xennedy Joseph Previtt? Orton. Burrows, Harry, and Charles Alezander Keane, the condensation of diethyl- malonamidc with -aldehydes, T., 269 ; P., 36. C. Cahen, Edward. See Gilbert Thornas Morgan. Cain, John Cannell, the constitution of diazo-compounds, T., 1049 ; P., 158 ; discussion, P., 159. Caldwell, Robert John, and Stephen Lewis Courtauld, the hydrolysis of amyg. dalin by acids, T., 666 ; P., 71 ; discussion, P., 72. mandelonitrile glucosides ; p.rulaurasin, T., 671 ; P., 71 ; discussion, P., 72.Caldwell, William, and Emil Alphme Werner, derivatives of multivalent iodice. Part 11. Action of heat on p-iodoacetophenone dichloride, p- iodoacetanilide dichloride, and on the dichlorides derived from o-, m-, and p-iodotoluene, T., 240 ; P., 17. derivatives of multivalent iodine. Part 111. The action of heat on iodobenzene dichloride, and on the m- and p-nitro- and p-chloro-deriva- tives, T., 528 ; P., 64. Cameron, Alexander Thomas, and (Sir) William Ramsay, some properties of radium emanation, T., 1266 ; P., 178 ; discussion, P., 178. the chemical action of radium emana- tion. Part 11. On solutions con- taining copper, and lead, and on water, T., 1593 ; P., 217. Cameron, A lexander Thomas. See aIso Bugh Marshall. Carr, Francis Howard.See Qeorge Barger. Chadwick, Samuel. See David Leonard Chapman. Chapman, David Leonard, Samuel Chad- wick, and John Edwin Ramsbottom, the chemical changes induced in gases submitted to the action of ultra- violet light, T., 942 ; P., 136. Chattaway, Prederick Daniel, the oxida- tion of hydrazines by free oxygen, T., 1323 ; P., 183.INDEX OF AUTHORS. 2093 Chrystall, Edwin Bodney. See John Norman Collie. Clarke, Reginald William Lane, and Arthur Lapworth, an extension of the benzoin synthesis, T., 694 ; P., 90. Clarke, Reginald William Lane, Arthur Lapworth, and EZkan. Wechsler, con- densations of ketones containing the group .CH,f!O*CH : with esters in presence of sodium ethoxide, P., 294. Claudet, Frederic Just, obituary notice of, T., 660. Cleaverley, (Mzss) Louisa.See Albert Ernest Dunstan. Coates, Joseph Edward. See Kennedy Joseph Previtd Orton. Cohen, Julius Berend, and William Ernest Cross, the mechanism of brom- illation of acylamino-compounds ; pre- liminary notice, p., 148. Cohen, J Z L ~ ~ U S Berend, and Henry James Hodsman, the influence of substitution in the nucleus on the rate of oxidation of the side-chain. 111. The oxidation of the nitro- and chloronitro-deriva- tives of toluene, T., 970 ; P., 152. Colefax, Arthur, the action of potassium sulphite on potassium tetrathionate in aqueous solution, P., 207. Collie, John Norman, derivatives of the multiple keten group, T., 1806 ; P., 230 ; discussion, P., 231. Collie, John Norman, and Edwin Bod- Chrystall, the production of ::in01 derivatives froin the sodium salt of ethyl acetoacetate by the action of heat, T., 1802 ; P., 231.Collie, John Norman, and Thomas Percy Hilditch, an isomeric change of de- hydracetic acid, T., 787 ; P., 92. Collier, William Henry. See Benry Russsl Ellis. Compton, Arthur. See Alfred Senier. Courtanld, Stephen Lewis. See Bobert John Caldwell. Crichton, David Cowan, hydrates of some quaternary bases, T,, 1793; P., 236. Crocker, Juines Codrington, the velocity of hydrolysis of aliphatic amides, T., 593 ; P., 63. Crocker, James Codrington, and Frank Harold Lowe, the velocity of hydro- lysis of the aliphatic amides by alkali, T., 952; P., 135. Cross, Charles Frederick, EJward John Bevan, and John Frederick Briggs, interaction of alkali starch and carbon disulphide ; xan thogenic esters of starch, T., 612 ; P., 90.Cross, William Ernest. See Julius Berend Cohen. Crossley, Arthur William, and (Miss) Nora Benouf, action of reducing agents on 5-chloro-3-keto-1:l-di- methyl-A4-tetrahydrobenzene, T., 63. D. Davies, Arthur Hugh. See Arthur George Green. Davies, John Hughes. See Edgar Philip Perman. Davis, Oliver Charles Afinty, the adsorp- tion of iodine by carbon, T., 1666 ; P., 208. Dawson, Harry Medforth, and Colin Gyrth Jackson, volume changes which accompany transformations in the system Na2S,O,:5H,O, T., 552 ; P., 7 5. Denham, Hmry George, the electro- metric determination of the hydro- lysis of salts, P., 260. Divers, Edzcurd, the constitution of silver nitrite ; a correction, P., 11. mercurous hyponitrite, P., 264. decomposition of mercurous and silver hyponitrites by heat, P., 265.cuprig nitrite, P., 269. Dixon, Augustus Edward, and John Hawthorne, the action of acid chlor- ides on thioureas, T., 122. Dixon, Augustus Edward, and John Taylor, acyl-#-derivatives of imiao- thiocarbamic acid and their isomer- ides, T., 912 ; P., 119. acylogens and thiocarbamides, P., 294. Dunstan, Albeyt Ernest, note on the fsmation of abnormal platinichlor- ides ; a correction, P., 290. Dunstan, Albert &nest, and (Afiss) Louisa Cleaverley, benzoflavol (2:8- dihydroxy-5-phenyl-3:7-diniethylacr- idine), T., 1619; P., 206. Dunstan, Albert Ernest, and Thomas Percy Hilditch, the action of bromine on 5-phenylacridine and its halogen derivatives, T., 1659 ; P., 206. Dunstan, A lbcrt Ernest, and Ferdinand Bernard Theodore Thole, note on the molecular complexity of liquids, P., 19.Dunstan, Albert Erncst, Ferdinand Berizard Theodore Thole, and John Samuel Hunt, the relation between viscosity and chemical constitution. Part 1. The viscosity of pyridine solu- tions, T., 1728 ; P., 207. Dunstan, Albert Ernest, and Robert William Wilson, the viscosity of liquid mixtures, T., 83.2094 INDEX OF AUTHORS. Dun~tan, Wyndham Rowland, the rust- ing of iron, P., 63. note on the constituents of the seeds of the Para rubber tree (Hevea bradiensis), P., 168. E. Ellis, Henry Russel, and William Henry Collier, the interaction in solu- tion of ferrous sulphate and copper sulphate, P., 264. Esposito, Murio, chemistry of the rare earths. Part II., P., 64. Evans, William Charles. See Kennedy Joseph Previttf Orton. F.Fairlie, Frank Walter. See Thomu Stewart Patterson. Fenton, Henry John Horstman, the re- duction of carbon dioxide to formalde- hyde in aqueous solution, T., 687 ; P., 83. Fierc, Hans Eduard. See Martin Ons- low Forater. Findlay, Alexander, and (Miss) Evelyn Marion Hickmans, freezing point curves of the menthyl mandelates, T., 905 ; Y., 132 ; discnssion, P., 133. Fisoher, &mil, the Faraday Lecture on synthetical chemistry in its relation to biology, T., 1749 ; P., 220. synthesis of polypeptides, P., 82 ; discussion, P., 82. Fleischmann, Frederick Noel Ashcrqft, the condensation products of triaceeic lactone with acetoacetic ester and 6- aminocrotonic ester, T., 250 ; P., 16. Flurscheim, Bernhard, and Theodor Simon, the reduction of aromatic nitro-compounds to azoxy-derivatives in acid solution, P., 163.Forater, Martin Onslow, and Huns Eduard Fierz, aromatic azoimides. Part I. Para-hydroxyyhenylazo- imide, T., 855 ; P., 112 ; discussion, P., 113. stndies in the camphane series. Part XXIII. Oximes of camphoryl- semicarbazide and camphorylazo- imide, T., 867; P., 114. aromatic azoimides. Part 11. Ortho- and meta-hydroxyphenylazoimides, T., 1350 ; P., 205. aromatic azoimides. Part 111. The naphthylazoimides and their nitro- derivatives, T., 1942 ; P., 258. the triaeo-group. Part I. Triazo- acetic acid and triazoacetone (acet- onylazoimide), P., 258 ; discussion, P., 269. Foreter, Martin Onslow, and 2"mnus Jackson, studies in the camphane series. Part XXIV. Camphoryldi- thiocarbamic acid and camphorylthio- carbimide, T., 1877 ; P., 242 ; discus- sion, P., 243.Fox, John Jacob, separation of cadmium from zinc as sulphide in the presence of trichloroacetic acid, T., 964 ; P., 147. solubility of lead sulphate in concen- trated solutions of ammonium acet- ate ; preliminary note, P., 199. Friedl, Arthur, Charles Weirmann, and Max Wyler, the fluoresceins and eosins from 4-hydroxyphthalic, 4- methoxyphthalic, and hemipinic acids, T., 1584 ; P., 214. Friedl, Arthur. See also William Henry Bentley. G. Gaiiguli, Atul Chandra. See Prafulla Chandra Bay. Oardner, Henry Dent, jun. See William Henry Bentley. Gardner, Thomas Edward, and William Henry Perkin, jun., the action of tribromopropane on the sodium de- rivative of ethyl acetoacetate, T., 848; P., 115. Gazdar, (Hiss) Jfaud.See Edward Charles Cyril Baly. Qebhard, Norman Leslie, a simple ap- paratus, with stirrer, for treating a liquid a t its boiling point with two or more gases, P., 34. Gibson, Charles Xtanley. See William Jackson Pope. Gimingham, Conrad Theodore. See Alfred Danzel Hall. Godby, Michael Harry, the isomerism of the double suIphites of sodium and potassium, P., 241. Gray, Robert Whytlaw, the density of hydrogen chloride, P., 119. Green, Arthur George, the relation of colour and fluorescence to constitution, P., 12. Green, Arthur George, Arthur Hugh Davies, and Ronald Xmith Horsfall, the colouring matters of the stilbene group. Part IV. The action of caustic alkalis on p-nitrotoluene and its derivatives, T., 2076 ; P., 289. Green, Arthur George, and Percy Edgar King, the constitution of phenol- and quinol-phthalein salts ; a contribution to the quiuonoid theory of colour, P., 228 ; discussion, P.229.INDEX OF AUTHORS. 2095 aregory, Arnold William, a calori- metric method for the determination of small percentages of iron in copper alloys, P., 306. Gregory, Arnold Walliam, and James McCallum, two volumetric methods for the determination of chromium, T., 1846 ; P., 237. Qroves, Charles Edward, cobaltamine compounds, preliminary note, P., 301. H. Haas, Paul, isonitroso- and nitro-di- methyldihydroresorcin, T., 1433; P., 191. Hall, Alfred Daniel, and Conrad Theo- dore GCimingham, the interaction of ammonium salts and the constituents of the soil, T., 677 ; P., 61. Eartley, Walter Noel, and Edgar Percy Hedley, the absorption spectra of phthalic, isophthalic, and tereph- thalic acids, phthalic anhydride, and phthalimide, T., 314 ; P., 31.the absorption spectra of benzoic acid, the benzoates, and benzamide, T., 319 ; P., 31. Eawthorne, John. See Augustus Ed- ward Dixon. Hay, James Gordon. See Baphael l e l - dola. Hedley, Edgar Percy. See Walter Nod Har tley. Henderson, Andrew. See Thomas Stew- art Patterson. Henderson, George Gerald, contributions to the chemistry of the terpenes. Part 11. The oxidation of limonene with chromyl chloride, T., 1871 ; P., 247. Kenstock, Herbert, and Charles Henry Graham Sprankling, aay-trimethyl- and auyy-tetraniethyl-tricarballylic acids and ay-dimcthylbutane-aB6- tricarboxylic acid, T., 354 ; P., 32. Eenstock, Herbert, and (Miss) Bertha Elizabeth Woolley, the action of phos- phorus pentachloride on hydroxy- trimethyl succinic ester ; 1:2-di- methylcyclopropane- 1 : 2-dicarboxylic acid (1:2-diniethyltrirnethylene-l:2- dicarboxylic acid), T., 1954 ; P., 235.Hewitt, John Theodore, a new mercuric oxychloride, P., 10 ; discussion, P., 10. Hewitt, John Theodore, and Herbert Victor Mitchell, colour and constitu- tion of azo-compounds. Part I., T., 1261 ; P., 182. Eewitt, John Theodore, and Norman Walker, dibromoaminoazobenzene, T. , 1138 ; P., 161. Rewitt, John Theodore, and Thomas Field Winmill, association of phenols in the liquid condition, T., 441 ; P., 10 ; discussion, P., 10. arsenic diiodide,T ., 962 ; P., 150. Rickmans, (Miss) Evelyn Marion. See Alexander Findlay. Hilditch, Thomas Percy, the relation be- tweenunsaturation antloptical activity.Part I. The menthyl and bornyl esters of 8-phenylpropionic, cinnamic, and phenylpropiolic acids, P., 287. Hilditch, Thomas Percy, and Samuel Smiles, the influence of mercuric iodide on the formation of sulphoninm iodides, T., 1394 ; P., 206. Hilditch, Thonzns Percy. See also John illorman Collie, Albert Ernest Dunatan, and Samuel Smiles. Hill, Ernest George, and Annoda Prasnd Sirkar, a new colouring matter from Nyctanthes Arbor-tristis, T., 1501 ; P., 213. Hill, John Robertshaw. See Humphrey Owen Jonea. Eird, James Morton. See Gilbert Thomas Morgan. Hodsman, Henry James. See JZC~~ZLS Berend Cohen. Holmes, John, and Philip John sage- man: molecular aggregation in solution as exemplified in aqueous mixtures of sulphuric acid with inorganic sul- phates, T., 1606; P., 210.Homer, (Miss) Annie, the action of alnmininni chloride on naphthalene, T., 1103; P., 88. Horsfall, Ronald Smith. See Arthur George Green. Hiibner, J Z ~ ~ Z L S , experimental investi- gation into the process of dyeing, T., 1057; P., 144; discussion, P., 145. the charncterisation of mercerised cotton ; preliminary note, P., 304. See Albert Ernest Hunt, John Samuel. Dunstan. I. Ingham, Harry. See Ernest Francis Joseph Atkinson. Inglie, John Kenneth Harold, and Lottie Emily Knight, the purification of acetic ester, P., 198. Irvine, James CoZquhozcn, and (Miss) Agnes Marion Moodie, the reduction products of o- andp-dimethoxybenz- oin, T., 536 ; P., 62. derivatives of tetramethyl glucose, P., 303.2096 INDEX OF AUTHORS.Irvine, James Colquhoun, and John Weir, the application of Baeyer's reduction to benzoin and its deriva- tives, T., 1384 ; P., 205. J. Jackson, Colin Gyrth. See Harry Ned- forth Dawson. Jackson, Thomas. See Martin Onslow Forster. James, Thomas Campbell, and John Joseph Sudborough, the addition of iodine to acetylenic acids, T., 1037 ; P., 136. Jones, Francis, action of selenium and tellurium on arsine and stibine, P., 164. Jones, Hgbmphrey Owen, and John Robertshaw Rill, the replacement of alkyl radicles by methyl in substi- tuted ammonium compounds, T., 2083 ; P., 290. Jones, Humphrey Owen, and Hubert Arthur Wootton, the chemical com- position of petroleum from Borneo, T., 1146; P., 184. Jones, Humphrey Owen. See also Frank Buckney. Jowett, Hooper Albert Diekinson, and Frank Lee Pyman, relation between chemical constitution and physio- logical action in the tropeines, T., 92.E. Kahan, ( M i s ) Zelda, the effect of heat on the alkyl iodides, P., 307. Kay, Francis William, and William Henry Perkin, jun., experiments on the synthesis of the terpenes. Part I. (continued). Direct synthesis of terpin from ethyl cyclohexanone-4-carboxyl- ate, T., 372. Kaye, John. See Thomas Stewart Patterson. Keane, Charles Alexander, and William Walter Scott Nicholls, the condens- ation of salicylamide with aryl alde- hydes, T., 264 ; P., 36. Keane, Charles Alexander. See also Hawy Burrows. Kenyon, Joseph. See Robert Howson Pickard. King, Percy Edgar. See Arthzw George Green. Kipping, Frederic Stanley, organic derivatives of silicon.Part 11. The synthesis of benzylethylpropylsilicol, its snlphonation, and the resolution of the dl-sulphonic derivative into its optically active components, T., 209 ; P., 9 ; discussion, P., 9. Kipping, Frederic Xtanley, organic derivatives of silicon. Part 111. &Ben z yline th yle thy1 propylsilirane and experiments on the resolution of its sulphonic derivative, T., 717 ; P., 83. Knight, Lottie ETniZy. See John Ken- neth Harold Inglis. L. sander, George Druce, mixed semi- ortho-oxalic compounds, T., 967 ; P. , 148. Lang, William Robert, and Thomas HoZes Allen, an improved form of apparatus for the rapid estimation of snlphates and salts of barium, T., 1370 ; F'., 187. Lapworth, Arthur, oxime formation and dezomposition in presence of mineral acids, T., 1133 ; P., 168.Lapworth, Arthur, and l l k a n Wechsler, the interaction of cyanodihydro- carvone, aniyl nitrite, and sodium ethoxide. Part I., T., 977 ; P., the interaction of cyanodihydrocarvone, anryl nitrite, and sodium ethoxide. Part 11. The constitution of the products, T., 1919 ; P., 252. Lapworth, Arthur. See also Ernest Barrett and Reginald William Lane Clarke. ' Lattey, Bobert Tabor, the vapour pres- sures of triethylamine, of 2:4:6-tri- methylpyridine, and of their mix- tures with water, T., 1959 ; P., 243. liquid tricthylamine, T., 1971 ; P., 243. Law, Herbert Drake, electrolytic reduc- tion. Part III., T., 748; P., 73; discussion, P., 74. Law, Herbert Drake, and Frederick Mollwo Perkin, preparation of chromyl dichloride, T., 191 ; P., 11. oxidation of hydrocarbons of the benz- ene series, T., 258 ; P., 11.action of metallic calcium on ketones, P., 308. Leach, Fyederick Peacock, pinene nitrol- amine, T., 1. a pseudosemicarbazide from pinene, T., 10. Le Bas, Gervaise, a relation between the volumes of the atoms of certain organic compounds a t the melting point and their valencies ; inter- pretation by means of the Barlow- Pope theory, T., 112. r37.INDEX OF AUTHORS. 2097 Le Bas, Gervaise, the relation between valency and heats of combustion ; preliminary note, P., 134. Lees, Frederic Herbert, researches on morphine. Part III., T., 1408 ; P., 200. Lees, Norman, and Jocelyn Field Thorpe, some derivatives of 2-phenyl-l:3- naphthglenedianiine. Part I., T., 1282 ; P., 189. Le Sueur, Henry Rondel, the action of heat on a-hydroxycarboxylic acids.Part 111. ad-Dihydroxysebacic acid and its diacetyl derivative, T., 1365; P., 196. dihydroxyadipic acids ; preliminary note, P., 196. Littlebury, William Oswctld. See Robert Howson Picka d. Lowe, Frank Harolk See James Codrington Crocker. Lowry, Thomas Martin, and Egbert Hockey Magson, studies of dynamic isomerism. Part VI. The influence of impurities on the mutarotation of nitrocamphor, P., 193 ; discussion, P., 194. studies of dynamic isomerism. Part VII. Note on the action of carbonyl chloride as an agent for arresting isomeric change, P., 260. Lnmsden, John Xcott, the liquid volume of a dissolved substance, T., 24. M. McBain, James William, adsorption formuh, T., 1683 ; P., 209. McCallum, James. See Arnold William (jiregory.McConnan, Jams, disalicylamide, T., 196 ; P., 18. McConnsn, James, and Morris Edgar Marples, benzoyl derivatives of N- methylsalicylamide, T., 193 ; P., 18. XcKenrie, Alemnder, and Hermann August Miiller, racemisation by alkali as applied to the resolution of r- mandelic acid into its optically active isomerides, T., 1814 ; P., 234. McKenzie, Alexatzder, and Herbert Bryan Thompson, measurements of the velocities of saponification of the E-menthyl and I-bornyl esters of the stereoisomeric manilelic acids, T., 789; P., 113. McKenrie, A lexander , and Henry Wren, studies in asymmetric syn- thesis. VI. The asymmetric synthesis of the optically active tartaric acids, T., 1215 ; P., 188. McMillan, Andrew. See Thomas Magson, Egbert Hockey. See Thomas Marples, Morris Edgar.See James Marsden, (illiss) Efie Gwendoline. See Marsh, James Ernest, and Robert de Jerscy Fleming Struthers, di-iodo- camphor, P., 119. some mercury derivatives of camphor, P., 246. Marshall, Hugh, and Alexander Thomas Cameron, succinic acid and its potass- ium salt, T., 1519 ; P., 214. Masson, [David] Orme, the action of hydrogen peroxide on potassium cyanide, T., 1449 ; P., 117. Meldola, Raphael, presidential address, T., 626 ; P., 101. the position and prospects of chemical research in Great Britain, T., 626 ; Xeldola, Zaphael, and James Gordon Hay, the diazotisation of dinitro- anisidines and related compounds, T., 1474 ; P., 211. Meldrum, Andrew Nornaan,and William Ernest Stephen Turner, the molecular weights of amides i l l various solvents ; preliminary note, P., 165.Micklethwait, (Miss) . Prances Mary Gore. See Gilbert TTioma@Xorgan. Mitchell, Rerbert Victor. See John Theodore Hewitt. - Moir, James, some derivatives'of diphenol (4:4'-dihydroxydiphenyl), T., 1305. estimation of halogen in organic substances, P., 233. the .so-caf?d " tetrabroniodipheno- quinone and the constitution of coerulignone, P., 308. Moodie, (Miss) Agnes Marion. See James Colqzchoun Irvine. Moody, Gerald Tattersall, the mechanism of the rusting of iron, P., 84 ; dis- cussion, P., 84. Moore, Tom Sidney, a method for the determination of the equilibrium in aqueous solutions of amines, pseudo- acids and -bases, and lactones, T., 1373; P;: 154. the " true ionisation constants and the hydration constants of piperid- me, ammonia, and triethylamine, T., 1379 ; P., 154.Morgan, Enwys. See Kennedy Joseph Previte' Orton. Morgan, Gilbert Thomas, and Edward Cahen, new cerium salts, T., 475 ; P., 74 ; discussion, P., 74. Stewart Patterson. Martin Lowry. McConnan. Edward Charles Cyril Baly. P., 101.2098 INDEX OF AUTHORS. Xorgan, Gilbert Thomas, and James Mortoit Hird, the diazo-derivatives of benzenevulphonylbenzidine, T., 1505 ; P., 209. Xorgan, Gilbert Thomas, and (Miss) Frances Mary Gore Micklethwait, infiuence of substitution on the formation of diazoamines and amino- azo-compounds. Part VI. The partially methylated 4:G-diamino- m-xylenes, T,, 360; P., 28 ; dis- cussion, P., 28. the interactions of aromatic amines and p-diazoimides, T., 1512 ; P., 209. Morgan, Gilbert Thomas, and William Ord Wootton, a series of coloured diazo-salts derived from benzoyl-l:4- naphthylenediamine, T., 1311 ; P., 180 ; discussion, P., 181.Morrell, Robert Selby, and Albert .Ernest Bellars, some compounds of guanidine with sugars. Part I., T., 1010; P., 87. Mouilpied, Alfred Theophilus dc. and AlGander Rule, tetriketopiperazine, Miiller, Hermann Auaust. See Alex- r r . , 17s ; P., 13. ander McKenzie. Yuller, Eugo, the occurrence of quercitol (quercite) in the leaves of Chamae- Tops humilis, T., 1766 ; P., 218. cocositol (cocosite), a constituent of the leaves of Cocos nucifera and Cocos plumosa, T., 1767 ; P., 219. inositol (inosite), T., 1780 ; P., 219. Xuir, Matthew Moncriefl Pattison, per- manganic acid, T., 1485 ; P., 195. N. Happer, Sidney Scrivener. See Robert X00gi, Paiichafian.See Prafulla Nicholls, William Walter Swtt. See Robertson. Chandra R&y. Charles Alexander b a n e . 0. Orton, Kennedy Joseph Previtd, Joseph Edward Coatee, [and, i n part, (Miss) Frances Burdett], the influence of light on diazo-reactions, T., 35. Orton, Kennedy Joseph Previtd, William Charles Evans, and Emrys Morgan, action of hydroxylamine on o-benzo- quinonediazides (o-diazophenols) ; 3 5 - dibromo-o-azoiminobenzoquinone (4:6- dibromo-2-hydroxyphenylazoimide) ; preliminary note, P., 167. Orton, Kennedy Joseph PrevitC, and Walter William Reed, isomeric change in benzene derivatives ; re- placement of halogen by hydroxyl in chlorobromodiazobenzenes, T., 1554 ; See also Walter FVillinm Reed and (Miss) Alice Emily Smith. P., 212. Orton, Kennedy Joseph Previtt?.P. Patterson, Thomas Stewart, Andrew Henderson, and Frank Walter Fsirlie, the influence of solvents on the rota- tion of optically active compounds. Part X. Effect of the coilfiguration aud degree of saturation of the solvent, T., 1838 ; P., 236. Patterson, Thomas Stewart, and John Raye, studies in optical superposition. Part HI., T., 705 ; P., 89. Patterson, Thomas Stewart, and An- drew IcMillan, the influence of solvents on the rotation of optically active compounds. Part IX. A new general method for studying intra- inolecular change, T., 504 ; P., 60. Patterron, Thomas Stewart, and David Thornson, the influence of solvents on the rotation of optically active com- pouuds. Part XI. Ethyl tartrate in aliphatic halogen derivatives, P., 263. Paul, David McLaren. See Thomas Purdie.Peachey, Stanley John. See William Jackson Pope. Perkin, Arthur George, constituents of natural indigo. Part II., T., 435 ; P., 62. methyl ethers of some hydroxyanthra- quinones, T., 2066 ; P., 288. the occurrence of isatin in some samples of Java indigo, P., 30. Perkin, Adhur George, and WilZiam Popplewell Bloxam, some constitu- ents of natural indigo. Part I., T., 279 ; P., 30. indican. Part I., T., 1715; P., 116, 218. Perkin, Frederick Mollwo, and Lionel Pratt, note on the action of metallic calcium on alcohols, P., 304. Perkin, Frederick Mollwo. See also Herbert Drake Law. Perkin, (Sir) William Henry, the magnetic rotation of hexatriene, CH2: CH *CH: CH *CH : CH,, and its relationship to benzene and other aromatic compounds; also its re- fractive power, T., 806; p., 110; discussion, P., 111.INDEX OF AUTHORS.2099 Perkin (Sir) William Henry, gift of bust of, to Society, P., 53. Perkin, William Henry, jun., some ex- periments on the oxidising action of hydrogen peroxide ; preliminary note, P., 166. Perkin, William Henry, jun., and Robert Robinson, brazilin and hzmatoxylin. Part VII. Synthesis of derivatives of hydrindene closely allied to brazilin and hzmatoxylin, T., 1073. some derivatives of y-pgranol allied to certain derivatives of brazilein and hematein ; preliminary communica- tion, P., 149. synthesis of brazilinic acid and the lactones of dihydrobrazilinic and dihydrohamotoxylinic acids, P., 291. Perkin, William Benry, jun., and John Lionel Simonsen, the action of tri- bromopropane on the sodium deriva- tive of ethyl nialonate.Part I., T., 816. the action of tribromopropane on the sodium derivative of ethyl malonate. Part 11. Formation of Aa<-heptadi- inene-6-carboxylic acid (4-m-toluio acid), (CH:C. CH,),C(CO,H),, T., 840. experiments on the synthesis of the terpenes. Part XI. Synthesis of 4-isopropylidenecyclohexanone and its derivatives, T., 1736 ; P., 197. Perkin, William Henry, jun., and George Tattersall, experiments on the syn- thesis of the terpenes. Part X. Syn- thesis of carvestrene and its derivatives, T., 480 ; P., 66. Perkin, William Henry, jun. See also Thomas Edward Gardner and Francis Williavz Kay. Perman, Edgar Philip, and John Hughes Davies, molecular weight of &naphthol in solution in solid naphthalene, T., 1114; P., 162.Philip, James Charles, influence of non- electrolytes and electrolytes on the solubility of sparingly soluble gases in water; the question of hydrates in solution, T., 711 ; P., 85 ; discussion, P., 86. Pickard, Robert Howson, and Joseph Kenyon, contributions to the chemistry of oxygen compounds. 11. The compounds of cineol, diphenyl- sulphoxide, nitroso-derivatives, and the carbainides with acids and salts, T., 896 ; P., 138. the resolution of sec. -octvl alcohol [methylhexglcarbinol ; octane-2-01], T., 2058 ; P., 286. Pickard, Robert Howson, and Joseph Kenyon, the reaction between organo- magnesium halides aud nitro-com- pounds, P., 153. Pickard, Robert Howson, and William Oswalcl Littlebury, studies on opti- cally active carbimides. Part V. The aryl esters and the amides of l-menthylcarbamic acid, T., 300 ; P., 30.the alcohols of the hydroaromatic and terpene series. Part I. Resolution of the alcohols into their optically active components and the prepars- tion of the borneols, T.,1973 ; P. ,262. Pickering, Spencer [Percival] Umfi-eville, note on the arsenates of lead and calcium, T., 307 ; P., 35. the interaction of metallic sulphates and caustic alkalis, T., 1981 ; P., 261. the chamistry of Bordeaux mixture, T., 1989; P., 261. emulsions, T., 3001 ; P., 266 ; discus- sion, P., 256. Pope, William Jackson, and Thomas Consta?itine Beck, resolution of tetra- hydro-p-tolnquinaldine into its opti- cally active components,T., 458 ; P.,15. Pope, William Jackson, and Charles Stanley Gibson, the alkyl compounds of gold, T., 2061 ; P., 245, 295.Pope, WiZliam Jackson, and Stanley John Peachey, a new class of organo- metallic compounds ; preliminary notice ; trimethylplatinimethyl hydr- oxide and its salts, P., 86 ; dis- cussion, P., 87. Pope, William Jackson, See also William Barlow. Power, Frederick Belding, and Arthur Henry Salway, the constituents of the essential oil of nutmeg, T., 2037 ; P., 285 ; discussion, P., 285. Power, Frederick Belding, and Frank Tutin, the constitution of hoinoerio- dictyo1.-A crystalline substance from Eriodictyon leaves, T., 887 ; P., 133, 243. Power, Frederick: Belding. See also Marmaduke Barrowcliff. Pratt, Lionel. See B-ederick Mollwo Perkin. Price, Thomas Xlater, depression of the freezing point of aqueous solutions of hydrogen peroxide by potassium per- snlphate and other compounds, T., 531 ; P., '75.Price, Thomas #later, and Douglas Frank Twiss, the electrolytic preparation of disulphides. Part I. Dibenzyl di- sulphide and diethyl dieulphide, T., 2021 ; P., 263.2100 INDEX OF AUTHORS. Prideaux, Edmund Brydges Rudhall, the atomic volumes of phosphorus, T., 1711 ; P., 207. Purdie, Thomas, and David McLaren Paul, the alkylation of d-fructose, T., 289 ; P., 33. Pyman, Frank Lee, calmatambin, a new glucoside, T., 1228 ; P., 183. Pyman, Frank Lee. See also flooper Albert Dickinson Jowe tt. R. Ramsay, (Sir) William, the chemical action of the radium emanation. Part I. Action on distilled water, T., 931 ; P., 132 ; discussion, P., 132. Ramsay, (Sir) William. See also Alex- nndey Thomas Cameron.Ramsbottom, John Edwin. See David Leonard Chapman. Raper, Henry Stanley, the condensation of acetaldehyde and its relation to the biochemical synthesis of fatty acids, T., 1831 ; P., 235. RPy, Prafulla Chandra, mercurous hyponitrite, T., 1404 ; P., 89. cupric nitrite, T., 1405 ; P., 117. the double nitrites of mercury and the alkali metals, T., 2031 ; P., 165. silver-mercuroso-mercuric oxynitrates and the isomorphous replacement of univalent mercury by silver, T., 2033; P., 165. M y , Prafulla Chandra, and Atul Chandra Gafiguli, the decornposi- tion of mercurous and silver hypo- nitrites by heat, T., 1399; P., 89. the decomposition of hyponitrous acid in presence of mineral acids, T., 1866 ; P., 184. Ray, Prafulla Chandra, and Pafichaiian Neogi, preparation of aliphatic nitro- compounds by the interaction of the alkyl iodides' and mercurous nitrite, P., 246.Reed, Walter William, and Kennedy Joseph Previttf Orton, the wandering of bromine in, the chlorination of bromo- anilines, T., 1543 ; P., 210. Reed, Walter William. See also Kennedy Joseph Previtt! Orton. Renouf, (Miss) Nora. See Arthur William Crossley. Report of the Council, T., 615 ; P., 95. Report of the International Committee on atomic weights, 1907, P., 2. Report as t o the nomenclature of the proteins, P., 55. Richardson, Arthur, the reactidn be- tween calcium carbonate and chlorine water, P., 118. Robertson, Robert, and Sidney Scrivener Napper, the estimation of small quantities of nitrogen peroxide, T., 761 ; P., 91. the evolution of nitrogen peroxide in the decomDosition of guncotton.T.. " , , 764 ; P., $1. Robinson, Robert. See William Henry Robinson, [Miss) Rona. See William Perkin, jun. Henry Bentley. Ruhemann, Siedried, the action of ethyl oxalate on thioacetanilide and its homologues, T., 797 ; P., 115. methyl dicarboxyaconitate, T., 1359 ; P., 195. Rule. Alexander. See Alfred Thswhilus de 'Mouilpied. 8. Sageman, Philip John. See John Ecdmes. Salwag, Arthur Henry. See Frederick Belding Power. Hand, Henry Julius Salmon, the rapid electroanaly tical deposition and separ- ation of metals. Part I. The metals of the silver and copper groups and zinc, T., 373 ; P., 26 ; discussion, P., 26. ganders, J a m s MeConnell, a simple gas generator for analytical operations, P., 232. Senier, AIfred, and Percy Corlett Austin, the condensation of aldehydes with mixtures of a-naphthol and a- naphthylamine ; synthesis of 7- aryl-iz$31>-dinaphthacridioes, T., 1233 ; P., 185. the synthesis of phenonaphthacridines ; trimethylphenonaphthacridines, T., 1240 ; P., 185.attempted synthesis of 1 -di- naphthacridine ; condensation of methylene chloride and l-substi- tuted-2-naphthylamines, P., 300. Senier, Alfred, and Arthur Compton, the synthesisof acridines and phenonaphth- acridines ; tetra- and hexa-methyl- acridines ; dimethylphenonaphthacrid- ines ; dixylylmethylenediamines, T., 1927; P. 247. B-N-B B-CH-BINDEX OF AUTHORS. 2101 Senter, George, displacement of halogens by hydroxyl. I. The hydrolytic de- composition of hydrogen and sodium monochloroacetates by water and by alkali, and the influence of neutral salts on the reaction velocities, T., 460; P., 6 0 ; discussion, P., 61.Sidgwick, New2 Vincent, and Henry Thomas Tizard, 011 the colour of cupric salts in aqueous solution, P., 305. Simon, Theodor. See Bernhard Flur- scheim. Simonsen, John Lionel, synthesis of terebic, terpenylic, and homoterpenylic acids, T., 184. Simonsen, John ,%Onel. See also William Henry Perkin, jun. Sirkar, Annoda Prasad. See Ernest George Hill. Blade, Boland Edgar, the reducibility of magnesia by carbon ; preliminary note, P., 152. Smedley, (Miss) Ida, synthesis of hexa- triene derivatives ; preliminary note, P., 162. the refractive power of diphenylhexa- Criene and allied hydrocarbons, P., 295. Smiles, Samuel, the nitrates of dimethyl- and methylethyl-thetine menthyl esters, P., 291.Smiles, Samuel, and Alexander William Bain, phenol p-snlphoxide, T., 1118 ; P., 161. Smiles, Sanmel, and Thomas Percy Hilditch, camphor-8-sulphinic acid and camphorylsulphonium bases, T., 5 1 9 ; P., 35. aromatic selenonium bases, P., 12. p-cresol sulphoxide and sulphide, P., 161. derivatives of S-phenylphenazothion- ium. Part I., P., 306. Smiles, Samuel. See also Thomas Percy Hi1 di tch . Smith, (Miss) Alice Emily, and Kennedy Joseph PrevitS Orton, transformations of highly substituted nitroaminobenz- enes. 11. s-Tribromo-l-nitroamino- benzene, T., 146 ; P., 14. Smith, Arthur Richard, and Jocelyn Field Thorpe, ethyl a-cyano-y-phenyl- acetoacetate, T., 1899 ; P., 249. Spencer, James Frederick, and Elmnor Marguerite Stokes, the direct inter- action of aryl halides and magnesium, P., 302; discussion, P., 303.Sprankling, Charles Henry Graham. See Herbert Henstock. Sprengel, Hermann Johann Philipp, obituary notice of, T., 661. Steele, Bertram Dillon, the velocity and mechanism of the reaction between iodine and hypophosphorous acid, T., 1641 ; P., 213. Stewart, Alfred Walter, the relation between absorption spectra and optical rotatory power. Part I. The effect of unsaturation and stereoisomerism, T., 199 ; P., 8 ; discussion, P., 8. the relation between absorption spectra and optical rotatory power. Part JI., T., 1537 ; P., 197. Stewart, Alfred Walter. See also Nor- man Thomas Mortiiner Wilsmore. Stokes, EZeanor Marguerite. See James Frederick Spencer. Struthers, Robert de Jersey Fleming. See James Ernest Marsh.Sudborough, John Joseph, and Ebenezer Rees Thomas, esterification constants of substituted acrylic acids. Part II., T., 1033; P., 146. audborough, John Joseph, and John Thomas, the addition of bromine to unsaturated compounds. Part I., P., 147. Sudborough, John Joseph, and Gwilym Williams, the addition of bromine to the a- and P-chloro- and broiiio-cin- namic acids and their methyl esters, P., 146. Sudborough, John Joseph. See also Thomas Campbell James. T. Tattersall, George. See William Henry Perkin, jun. Taylor, John. See Augustus Edward Dixon. Temperley, Claude Yazeille. See Wil- liam Henry Bentley. Thole, Ferdinand Bernard Theodore. See Albert Ernest Dnnstan. Thomas, Ebenezer Bees. See John Joseph Sudborough. Thomas, Frederick. See William Eenry Bentley.Thomas, John. See John Joseph Sud- borough. Thompson, Herbert Bryan. See Alex- ander McKenzie. Thomson, David. See Thomas Stewart Patterson. Thorpe, Jocelyn Field, a reaction of certain colonring matters of the oxaziue eries, T., 324 ; P., 32,2102 lNDEX OF AUTHORS. Thorpe, Jocelyn Field, the formation and reactions of imino-compounds. Part IV. The formation of 1:4-naphthyl- enediamine from ethvl r-imino-a- cyano-y-phenylbutyrat4 T., 1004 ; P., 151. Thorpe, Jocelyn Field. See also Ernest Francis Joseph Atkinson, Norman Leee, and Arthur Richard Smith. Tinkler, Charles Kenneth, studies of the perhalogen salts. Part I., T., 996 ; P., 137. Titherley, Arthur Walsh, phenylbenzo- metoxazone and related derivatives, T., 1419 ; P., 203. Tizard, %enry Thomas.See Nevi1 Vin- cent Sidgwick. Tuck, William Bradshaw, the constitu- tion of hydroxyazo-compounds, T., 449 ; P., 58 ; discussion, P., 59. Tuck, William Bradshaw. See also Edward Charles Cyril Baly and William Henry Bentley. Turner, William Ernest Stephen. See Andrew Norman Meldrum. Tntin, Frank, the constitution of umbel- luloce. Part 11. The reduction of umbellulonic acid, T., 271 ; P., 28. the reduction of hydroxylaminodi- hydroumbelluloneoxime, T., 275 ; P., 29. the interaction of methylene chloride and the sodium derivative of ethyl malonate, T., 1141 ; P., 158, 245. the melting point of d-phenylglucos- azone, P., 250. Tntin, Frank. See also Marmaduke Barrowcliff and Frederick Belding Power. Twius, Douglas Frank. See Thrnnas Slater Price. v. Veley, Victor Eerbert, the affinity con- stants of aminocarboxylic and aminosulphonic acids as determined by the aid of methyl-orange, T., 153. the affinity constants of aminosulph- onic acids as determined by the aid of methyl-orange, T., 1246 ; P., 179. the afinity constants of bases as de- termined by the aid of methyl- orange ; preliminary note, P.; 284. W. Walker, James, and Heather Henderson Beveridge, p - toluidine monohydrate, T.. 1797 ; P., 236. Walker, Norman. See John Theodore Hewitt. Wechsler, EZkan. See Reginald Wil- liam Lane Clarke and Arthur Lap- worth. Weir, John. See James Colquhoun Irvine. Weizmann, Charles. See William Henry Bentley and Arthur Friedl. Werner, Emil Alphonse. See William Caldwell. Whiteley, (Miss) Martha Annie, studies in the barbituric acid series. I. 1:3- Diphenylbarbituric acid and some colourecl derivatives, T., 1330 ; P., 180, 203. Williams, CTwilynt. See John Joseph Sudborongh. Wilsmore, Norman Thomas Nortimer, keten, T., 1938 ; P., 229 ; discussion, P., 230. Wilsmore, Norman Thomas Mortimer, and Alfred Walter Stewart, a note on certain pyrogenic reactions, P., 309. Wilson, Robert William. See Albert Ernest Dnnstan. Winmill, Thomas Field. See John Theodore Hewitt. Woolley, (Miss) Bertha Elizabeth. See Herbert Hens tock. Wootton, Hicbert Arthur. See Hum- phrey Owen Jones. Wootton, WilZiam Ord, aromatic amides and imides of camphoric acid, T., 1890 ; P., 250. Wootton, William Ord. See also Gil- bert Th>omas Morgan. Wren, Henry. See Alexander McKenzie. Wyler, Max. See Arthur Friedl. Y. Young, William John, the organic phosphorus compound formed by yeast-juice from soluble phosphates ; preliminary notice, P., 65.

ISSN:0368-1645    

DOI:10.1039/CT9079102091

出版商:RSC    

年代:1907

数据来源: RSC