摘要:

402 STUART AC'I'IOX OF XXX1.-Actiofa of Phosphorus Pentachloride on Xalicylaldehyde, By CEARLES M. STUART M.A. Fellow of St. John'g College, Cambridge, IT is stated by Henry (Ber. 2 1.35) that the action of phosphorus pentachloride on salicylaldehyde first produces dichlororthocresol, CC12H.C6H4*OH but that the further action of the pentachloride dis-places the hydroxyl-group by chlorine giving rise to orthochloro-benzalchloride C,H,CI*CCI,H; by the action of water on this at 1 i O " orthochlorobenzaldehyde C,HdCl*COH may be prepared. (See 1Yatt.s' Dictionttry 8 302.) On attempting t o prepare orthochlorobenzaldehyde in 'chis way I found t h a t if the mixture of phosphorus pentachloiide and salicyl PHOSPHORUS PENTACHLORTDE ON SALICYLALDEHYDE. 403 aldehyde was heated it was entirely carbonised whilst if it were poured into water the product always contained phosphorus ; I there-fore undertook a more complete examination of this reactim.Salicylaldehyde was added to phosphorus pentachloride in mole-cular proportion care being ta.ken to keep the mixture cool ; on pour-ing the product into water the water became heated by the decom-position of the phosphorus oxychloride and a pink oil sepamted ; on cooling this became semi-solid and after being mashed with potash and crystallised from alcohol it formed tufts of white needles melting at 78". On analysis-0.4944 gram gave 0.0984 gram Mg2P,07. 0.4058 , 0 6518 , CO,. 0.1014 , H,O. 0.5287 gram required 54-95 C.C. 2 AgNO sol., 10 corresponding to-Theory for C2,H,,C1GPO,.C . 43.80 43.74 H . 2.77 2-61 P 5.55 5.37 C1 36-89 37-06 Its constitutional formula is PO(O*C6H1~CCl2H),. The first action of phosphorus peutachloride is to displace the oxygen of the COH-group by C1 giving dichlororthocresol but this is at once acted on by the phosphorus oxychloride produced this reaction taking place according to the equation-POCl + 3CGHk(HO).COH = PO(O.C,H,.CCl,H) + 3HC1. I n this way phosphate of dichlororthocreaol is formed just as tri-plienyl phosphate is by the action of phosphorus pentachloride on phenol. Pbosphate of dichlororthocresol is not altered by boiling with a 10 per cent. solution of caustic potash; and even with a saturated solution it is not entirely decomposed the solution containing a little chloride and phosphate only.On treating its alcoholic solution with alcoholic potash however, potassium chloride at once separates but no phosphate was obtained on boiling. I n this respect i t resembles triphenyl phosphate which is not saponified by boiling with potash. It now seemed of interest t o ascertain what would take place in this reaction if the hydrogen of the nydroxyl-group were already dis 404 WERNER RESEARCHES ON CHROM-ORGA NIC ACIDS. placed by some radicle and for this purpose methyl salicylaldehyde was chosen. Methyl salicylaldehyde was added to phosphorus pentachloride in molecular proportion ; the phosphorus oxychloride produced was dis-tilled off under diminished pressure and the residue shaken up with ether and a solution of acid sodium sulphite; the ethereal solution was then dried with calcium chloride and the ether distiiled off; the residual oil distilled a t 231".On analysis 0.3285 gram gave 0.6065 gram GO and 0.11'79 gram H,O. Thpory. Found. C,H,OCl2. C . 50.33 50.26 €3. 3.98 4.18 It is therefore orthomethoxybenzalchloride C,H,( OCK,).CCl,H, podiiced by the displacement of the oxygen of the COH-group in riiethyl salicylaldehyde by Cl,. It is extremely unstable and is a t once decomposed by warm water yielding methyl sxlicylaldehyde ; it decomposes slowly in moist air and in preparing it any rise of tem-perature or prolonged contact with water must be avoided. I think i t worth remarking that when the bydroxylic hydrogen of dichlor-orthocresol is displaced by methyl the CC1,H-group is decomposed by water whereas i f the satne hydrogen is displaced by phosphoric acid the CCI2H-group is not altered by boiling with potash

ISSN:0368-1645    

DOI:10.1039/CT8885300402

出版商:RSC    

年代:1888

数据来源: RSC

摘要:

404 WERNER RESEARCHES ON CHROM-ORGA NIC ACIDS. XXXT1.-Researches o n Ch-om-organic Acids. Part 11. Certain C h ~ o nz oxalat es. Bed lSer ies. B*y EMrL A WERNER Assistant in the Chemical Laboratory Trinity College University of Dublin. Tim first member of the red series of chromoxalates was discovered by Crofts in 1842 (Ph;Z. Mag. 21 197) but has hitherto been little studied. Salts of this series are in all cases constant products of the reduction of dichromates by oxalic acid the compounds of the blue series which are formed under conditions described in the first part of this paper (Trans. 51 383) being the result of the direct addition of oxalic acid or an oxalate to the red salt. Regarded as anhydrous compounds the salts of the blue and red series are represented respectively by the formultx M’&h,( C,O,) and 31 ,Cl*,(C,O,), WERNER RESEARCHES ON CHROM-ORGANIC ACIDS.405 The potassium salt was prepared by the interaction of potaasium dichromate (1 mol.) and oxalic acid (7 mols.) both in aqueous solution ; tbe composition of the purple-red crystals which separate from the concentrated liquid and to which Crofts assigned the formuia K,Cr,(C20~)d,12H20 I find to be correctly represented by the formula KzCr,(C204)4,10H,0. The method of analysis was the same as that adopted in the case of the blue chromoxalates. Pound. 7-7 Theory. I. 11. K2 . . . . . 10.92 p. C. 11.08 p. C. 11.26 p. C. Cr . . . . . . . . 14.56 , 14.19 , 14.34 ,, (CZO4)i . . . . 49.29 , 49.17 , 49.21 ,, (HzO),o . . . . 25.21 , 22.72 , 25.19 (by diff.).-99.98 97.06 100~00 The apparent deficiency in the water-determination of the first analysis-the result of direct experiment-is due to the fact that the last 2 mols. HzO in this salt are only expelled a t an exceptionally high temperature. The behaviour of the water in this salt has such an important bearing on its constitution that I append the experi-mental results obtained during the dehydration of the compound. TVeig7~t taken 1.153 gram. Time. 2 hrs. ,* 9 4 hrs. > 150" 2 hrs. Y 180 2 hrs. Y 7 4 hrs. ) 200-235 2 1113. > 9 4 hre. Heated to 110-120" C. , 180-200" C. 2 lirs. H,O. Loss = 0 *1865 grain = 16 e l 7 , = 0.1865 , - ,, NO further loss -Loss = 0 *2145 gram = 18.60 , = 0.2255 , = 19.55 , = 0.2415 , = 20.94 , = 0'2535 , = 21-98 , = 0.2621 , = 22.72 -Molecules.6 -33 Y ? -'7 '37 7 9 4 8 *29 8 -70 8.99 The loss of the first 6 mols. H,O is accompanied by a change of colour from red to bluish-grey and after 8 mols. have been lost the salt commences to become green ; at the time that the above analyses were made the appearance of the latter colour mas thought to be due to decomposition but I have since found that the salt may be heated to a temperature approaching 300" without decomposition. 0943 gram heated cautiously until the whole mass assumed a deep green colour lost 0.062 gram = 25.51 per cent. of total water. Calc. 25.21 per cent. When strongly ignited with access of air this compound leaves a, ' O L . L I t I . 2 406 WERNER RESEARCHES ON CHROM-ORGANIC ACLDS.residue of chromic oxide and potassium chromate the decomposition taking place according to the equation-2K,Cr2(C201)4,10H20 + 110 = 2KzCr04 + Cr203 + 10H20 + 16C02. which represents a residue = 37.81 per cent. or 36 per cent. if the salt contained 12H20 ; 0.4897 gram left residue = 0.1848 gram, corresponding with 37.72 per cent. My formula therefore is the correct one. When the decahydrated salt is exposed over sulphuric acid in a desiccator it continues to lose water for several weeks but the loss ceases when the compound has the composition K2Cr2( C2OJ4,4H,O. This also represents the composition of the salt dried at 110-120" ; if however the aqueous solution of the salt is evaporated to dryness on the water-bath it leaves a green amorphous residue which has the composition K2Cr2 ( C2O,),,2H,0.Crofts considered this compound to be a double salt of potassium oxalate and chromic oxalate thus K2C,04 + Cr2(C,04)3 differing simply from Gregory's compound by 2 mols. KaCZO4 since on boiling its solution with the latter Gregory's blue salt is produced thus :-K2Cr2(C204)4 4- 2K2C204 = I(6cr2(c20~)6. This view of the constitution of these salts as I have already pointed out is quite untenable and its inconsistency with their peculiar properties is particularly recognised in this somewhat rern arkable compound. With the exception that their solutions are not precipitated by either calcic chloride or ammonia the salts of the red series differ remarkably in their properties from the blue ; they do not yield cor-responding salts by double decomposition.The only oiher compounds of the series hitherto described are the complete sodium and ammonium salts (Warington Phil. >lag. 21,202). I have succeeded in producing the potassium ammonium compound, K(NH4) Cr2( C,O,)JOH,O, by the following reaction :-KNH4Cr207 + 7H,Cz0 = K(NH,)Cr,(C2OJ4 + 6C0 + i H 2 0 . This salt is of interest in proving that the simplest formula for these compounds must. contain at least 2 atoms of chromium. This com-pound forms small pnrple-red monoclinic prisms ; they are more freely soluble in water than the potassium salt itself which in every other respect they resemble closely. A remarkable property of the salts of this series is the readines WERNER RESEARCHES ON CHROM-ORGANIC ACIDS.407 with which they form addition products. With ammonium oxalate Croft's salt yields the compound K,(NH,)4,Cr,(C,04)6,6H20 ; it also combines with the oxalates OE the different types of organic bases, yielding in some cases beautifully crystallised compounds. The com-binations of these red salts are not restricted to oxalates but extend also to salts of certain other organic acids yielding i n each case products in which the new acid radicle can no longer be detected by the m u d reagents. The effect of alkalis and particularly of ammonia on the red salt' is very peculiar if t o the rich red solution of the latter an alkali be added the colour of the liquid will immediately change t o green ; on adding an acid in excess the original red colour of the liquid is restored.This colour change is very delicate the green solution being sensitive even to carbonic acid. I n the case of the fixed alkalis, decomposition of the green liquid with separation of chromic hydr-oxide takes place after 5 to 6 mols. of alkali have been added for each mol. of the red salt. In an experiment 7.14 grams of the red salt required at the boiling temperature 2-20 grams NaOH for decom-position corresponding to 5.5 mols. This behaviour with alkali seemed entirely in favour of a view regarding the constitution of the red salt which had already been suggested to me by Dr. Emerson Reynolds on his consideration of my results obtained on heating the compound to the very high temperature at which it lost the last 2 mols. of HzO; namely that in this compound there were at least two but more probably four hydroxyl-groups in the molecule.Looking upon it as a derivative of chromic hydroxide the constitu-tion of Croft's salt may be expressed by the following structural formula :-These compounds will be described in another paper. i n which the hydrogen-atoms of four of the hydroxyls have been displaced. According to this formula the componnds would contain the hydroxyls in two distinct positions whereby two would be basic and two acidic tending to neutralisation; as a matter of fact the acidic property predominates in the red salt as the feeble basic powers of chromic hydroxide? would naturally indicats. The existence of the compound K,Cr,( C,OJ,(OH), obtained in the following way is strong evidence in favour of the above constitution ascribed to the red salt.A quantity of the latter in aqueous solution was mixed with 3 mols. of caustic potash and the greenish-red solution precipitated with alcohol ; the mixture was then warmed on the water-bath which caused the precipitate to quickly coagulate and attach itself to the sides and bottom of the flask from which afte 405 TTERNER RESEARCHES ON CHROBI-ORGANIC ACIDS. decanting the mother-liquor and heating in the air-bath it was easily removed. When dry it forms a dull greenish-red dichroic powder which on heating a t 110" to expel H,O gave the following results on analysis :-0.3854 gram gave 0.091 gram Crz03. 0.3854 gram gave 0.206 gram &SO,. (I) 0.346 gram gave 0.188 0.2399 gram (C2O4).gram (Cz04) ; (11) 0.441 gram gave From which the following percentage composition is obtained. Found. 7- -7 Theory. I. 11. - Kd 24.14 p. C. 24.00 p. c. C r 2 . 16.10 , 16.22 ,, (C,O,)a. . 54.48 , 54.39 , 54.42 p. c. (0H)z 5.26 , 5.39 (by diff.) --- -99.98 100~00 This compound as indicated by its constitution possesses a feeble alkali~ze reaction. When ignited it leaves a residue of potassium chromate the decom-position taking place according to the equation-K4Cr2(C204)4(0H)2 + 7 0 = 2K,Cr04 + 8C02 + H,O, which requires a residue = 60.06 per cent. ; 0.3854 gram ignited with free access of air left a residue = 0.931 gram corresponding to 59.93 per cent. Heated to a temperature approaching :-lOOo this compound loscs its reddish tint leaving a pure green residue of the corresponding anhydride thus :-(OH) Cr( O*C,Oz*OK) Cl*( O*C202*OK), I = O/I + HZO.(OH) Cr(O*C,O,*OK)2 'Cr(O-C,02*0K), In t'he same way the original red salt near 300" yields its corre-sponding anhydride by loss of 2 mols. H,O. With ammonia the chromoxalates of the red series react in a peculiar manner ; when it is added to the red solution of the potash salt WERNER RESEARCHES ON CHROX-ORGANIC ACIDS. 409 a deep-green liquid is formed as in the case of the fixed alkalis and when all free ammonia has been expelled by boiling 2 mols. are still retained for each mol. of red salt employed corresponding to the compound K,(NH&,Cr2(C20&. If ammonia gas be passed to saturation into the green solution or better if the finely-powdered red salt be treated with strong aqueous ammonia it dissolves after a short time yielding an intense claret-coloured liquid which on boiling becomes green.Alcohol added in excess to the red ammoniacal liquid throws down a dull red crystalline precipitate which after drying by a gentle heat gave results on analysis which lead to the formula KzCr2 ( G O ) J 6NH3,6Hz0. (I) 0.4535 gram gave 0.0629 gram NH ; (11) 0.334 gram gave 0.043 gram NH,. 0.328 gram gave 0.15417 gram (C,OJ radicle. (I) 0.3472 gram gave 0.0865 gram K,SOI; (11) 0.3175 gram gave 0-0774 K,SO,. 0.3175 gram gave 0.0636 gram Crz03. Calculated percentage composition :-Found. r-J- 7 Theory. I. 11. 10.48 p. c. Cr, . . . . . . 13.97 ). 13.75 , -(C,Oi)r . . . . 47.31 ) 47.00 ,) -R .. . . . . . . 11-04 p. c. 10.82 p. c. (NH3)G . . 13.71 , 13.87 , 13-88 ,, (H,0)6 14.51 :7 14.34 (by diff.) -99-98 100~00 It readily loses ammonia on heating. chromic oxide thus :-When ignited it leaves a residue of potassium chromate and 2KzCr2(CzOr)~,6NRS,6H20 + 130 = 2K,Cr04 + Cr,03 + 16C02 + 12NH + 12Hz0, corresponding to 36.29 per cent. ; 0.1715 gram left a residue weighing 0.063 gram = 36.67 per cent. If the salt (NH,),H2Cr2(C,04)r(OH)2* be treated with ammonia solution in place of Croft’s salt alcohol precipitates the compound Cr,(CzOa)a,6NH3,6H10 ; as deduced from the following analysis :-* Warington’s ammonium salt represmted as a hydroxyl compound. VOL. LIII. 2 ‘4 1 O WERNER RESEARCHES ON CHROM-ORGANIC ACIDS. 0.2372 gram gave 0.0546 gram CrzOs; 0.2267 gram gave 0.0351 0.396 gram gave 0.2087 gram (C204) radicle.gram NH,. Theory. Found. (NH,),. . 15.31 p. c. 15.49 p. c. Cr 15.61 , 15.81 ,, (C,O,)j. 52.85 , 52-77 ,) (H,O) . 16.21 15.93 (by diff.) - -99.98 100*00 When heated this compound readily loses part of its ammonia. On ignition it leaves a residue of chromic oxide; 0.2372 gram left a residue weighing 0.0546 gram = 23.01 per cent. Theory 22.82 per cent. The addition of calcic chloride to solutions of these compounds produces an immediate precipitate of calcium oxalate ; hydrochloric acid added to warm concentrated solutions causes the separation of osalic acid on cooling together with small red crystals of the corre-sponding chloride. From these reactions it will be seen that these two compounds are no longer chromoxalates but appear to be the oxalates of a peculiar class of chromammonium base.In an experiment with a view to displace the two hydroxylic hydrogen-atoms in the compound K,Cr,( CZO4),( OH) by potassium by the direct action of potash (4 mols.) on the red salt, and precipitation of the solution with alcohol a compound was obtained belonging to st new class of chromoxalates containing 4 atoms of chromium in the niolecule apparently resulting from the condensation of 2 mols. of the di-hydroxyl compound with elimination of oxalic acid. The nature of this reaction has not yet been sufficiently studied for inter-pretation and is being investigated. I here take the opportunity of acknowledging the receipt of a paper from Professor F. W. Clarke containing a communication made t o the American Chemical Society some years ago on the blue series of chromoxalates. In this paper Professor Clarke has assigned to these compounds a constitution similar to that independently adopted by me in my former paper. Professor Clarke’s paper completely escaped my notice a t the time. University Laboratory, Trinity Cbllege Dublin

ISSN:0368-1645    

DOI:10.1039/CT8885300404

出版商:RSC    

年代:1888

数据来源: RSC

摘要:

411 XXXIIL-The Action of Isothiocyanates on the Aldehyde-amnzonias. By AUG. E. DIXON M.D. Assistant Lecturer in Chemistry Trinity College University of Dublin. Acetaldehyde-ammonia is known to combine with certain of the “mustard-oils; ” thus R. Schiff (Ber. 9 565) has described corn-pounds obtained by the action of the former on ethyl- allyl- and phcnyl-thiocarbimides respectively. Some time ago happening to have in my possession a quantity of benzylthiocarbimide I tried its action on acetaldehyde-ammonia ; with the result that the two substances readily combined under the following conditions :-1 mol. of benzylthiocarbimide dissolved in a small quantity of strong alcohol was mixed with a concentrated alcoholic solution of 2 mols. of aldehyde-ammonia. The mixture was gently warmed on the water-bath and in a few minutes solid matter began to separate ; on removing the dish from the water-bath the contents almost immediately set to a white crystalline mass.This was drained on +he filter-pump and pressed between filter-paper. It was then shaken up with cold spirit and again drained and pressed. On care-fully recrystallising the product from hot absolute alcohol a woolly mass of white shining needles was obtained which was dried over sulphuric acid under the air-pump receiver. The substance is sparingly soluble in cold alcohol; it dissolves tolerably freely in boiling alcohol by which however it is gradually decomposed with evolution of ammonia and aldehyde. It is insoluble in water sparingly soluble in ether and bisulphide of carbon more easily in chloroform.Benzene when hot dissolves it moderately but when cold very sparingly. It melts at 175” with browning and copious evolution of gas. The alcoholic solution is slowly desulphurised by boiling with alkaline lead tartrate ;* wit,h excess of silver nitrate a white precipitate separates which on standing quickly blackens. Ammoniacal silver nitrate gives a yellow precipitate which blackens on boiling. The substance was found to contain carbon hydrogen nitrogen, and sulphur. On analysis the following data were obtained :-0.2192 gram burnt with lead chromate gave 0.1507 H,O and 0.4966 coz, or C = 61.78 H = 7.66. f Described by Emerson Reynolds Trans. 1884 162. 2 F 412 DIXON THE ACTION OF ISOTHIOCYAKATES 0.2230 gram gave 0,5042 GO (hydrogen lost), 0.3344 gram burnt with soda-lime gave 0.4208 Pt, 0.2492 gram fused with EazC03 + KC103 gave 0.2358 BaS04, or C = 61-65.or N = 18.13 per cent. or S = 13.01 per cent., from which the formula G121817N3S is deduced. ~~ ~ 421 143.64 . H, 17-00 . N3 42.03 . S 31.98 . 234 *65 Theory. -61 -21 7 -24 17 -91 13 *62 99.98 -~ Experiment. I. 1 11. i- -I - -The reaction may be represented thus :-C,H7*NCS + 2CzH40,NH3 = C12HI7N3S + 2HzO. This decomposition recalls the observation made by Nencki (Bey. 7, 162) that thiocarhamide and aldehyde-ammonia unite with elimina-tion of water and NH3 :-CS(NH,)2 + 2C,H,O,NH = CsHiIN3S + NH3 + HZO. Nencki considers the compound C5Hl,N3S to be an ammonia-derivative of diethylidenethiocarbamide CS (N C2H4), and writes its formula- cs C2H,)N2,NHs0 CzH4 J From the mode of formation of this compound we may suppose group to exist in i t ; and the decomposition may be the represented thus :-‘X< .. . . . . . . -in ,/ sc + . . ‘ H N< :H + 2H,O + NH3 ON THE ,4LDEHYDE-AMMONIAS. 413 We may suppose now that in the case of benzylthiocarbimide the NH3 which 2 mols. of aldehyde-ammonia can afford (as above), instead of being evolved is fixed by the thiocarbimide forming, perhaps for the moment benzylthiocarbamide which then reacts with the aldehyde-ammonia residue-+ Thus the compound of benzylthiocarbimide with aldehyde-ammonia would be a benzylated derivative of Nencki's " DGthytiden-t hio hams tofa mrnoniak.'' The first question now was-can homologues of methyl be substi-tuted for the methyl-groups ? The answer was obtained as follows :-1 mol. benzylthiocarbimide dissolved in spirit was added to a spirituous solution containing 2 mols. of ordinary (hydrated) iso-valeraldehydc-ammonia. Crystals soon began to separate and the mixture was exposed freely to the air (at ordinary temperature) till most of the liquid had evaporated. The crystalline mass was drained, and pressed on the filter-pump washed lightly with spirit and dissolved in hot absolute alcohol. The latter somewhat decomposed the substance,-valeraldehyde and ammonia being evolved,-but on cooling beautiful snow-white silky needles separated forming a felted mass which retained much mother-liquor.It was thrown on the filter-pump washed repeatedly with cold alcohol and dried over sulphuric acid in a vacuum. The substance is insoluble in water soluble easily in hot sparingly in cold alcohol soluble in chloroform ether and bisulphide of carbon, and easily soluble in warm benzene. It melts at 161-162" with decomposition. Silver nitrate gives a finely granular white pre-cipitate which blackens gradually on standing or instantly on addition of ammonia. The alcoholic solution is slowly desulphurised by boiling with alkaline lead solution. The following data were obtained on analysis :-0.2313 gram burnt with lead chromate gave 0.5764 CO and 0.1932 &O, or C = 67-96 per cent. ; H = 9.28 per cent. or C = 67.92 per cent. ; H = 9.20 per cent. 0.2264 gram gave 0.5639 CO and 0.1875 HzO 414 DIXON THE ACTION OF ISOTHIOCYANATES 0.2564 gram burnt with copper oxide gave 29 C.C.N at 9" C. and 755 mm., or 13.50 per cent. N. 0.3042 gram evaporated to dryness with sodium hydrate in a nickel crucible and fused with potassium nitrat,e,* gave 0.2170 BaS04, or S = 9.80 per cent., which agreev wit'h the formula CIeH,,N3S. 67-65 9.10 C18 215.46 . H, 29-00 . N3 42.03 . S 31-98 . 318.47 S'i.96 6'7.92 - I 9.28 9.20 - -Experiment. Theory. I 1 11. 1 111. 1 IT. 13.19 -10.04 1 -- 13.50 -- - 9 *80 -____-____-- I - 1 - 1 - 1 -The reaction may be represented thus :-C,H,*NCS + 2CH(CH,),*CH,*COH,NH3 = C,H,gN,S + 2H20, and the provisional formula ascribed is-This compound is accordingly homologous with that previously described butyl-groups being substituted for the metlhyl-groups.The next question was Can other radicles be substituted for the benzyl-group ? To this an affirmative answer was also obt,ained. (a.) Ethylthiocarbinzide and A1dehyde-arnmonia.f-Warm concentrated alcoholic s o h tions of ethylthiocarbimide (L mol.) and aldehyde-ammonia (2 mols.) were mixed. On cooling, crystals separated which were collected and pressed. After two recrystallisations from spirit they were found to melt-though not without decomposition-at 135-136". At a few degrees higher they decompose completely with evolution of gas. * This is the method now regularly used by Professor Reynolds for the determi-nation of sulphur (and halogens) in suitable thio-compounds ; it gives very satisfac-tory results.j- By the action of aldehyde-ammonia on ethylthiocarbimide R. Schiff obtained results which will be referred to later on. The details will probably be published shortly ON THE ALDEHYDE-AMMONIAS. 415 C 83 5'9 . H, 15-00 . . . . . . . . . . . . . . . . . N 42.03 . S 31-98 . . . . . . . . . . . . . . . . . 172 -80 Analytical data :-0.2419 gram burnt with lead chromate gave 0.4315 CO and 0.1911 HZO, or C = 48.64; H = 8.77. 0.2534 gram burnt with copper oxide gave 54.1 C.C. N at 10" C and $42 mm., or N = 24.94 per cent. 0.3394 gram evaporated to dryness with sodium hydrate solution and fused with nitre gave 0.4484 gram BaS04, or S = 18.16 per cent. This agrees with the formula C7HI5K3S. 48 -49 8-68 24.32 18.50 ---1 Theory.Experiment. 11. ' 111. I - I -The structural formula may be provisionally written-Allylthiocarbimide and Aldehyde-am;izonia.* The ally1 compound was prepared similarly to the preceding. It formed white woolly masses of needles which after two recrystal-lisations from spirit melted a t 108-109". Analytical data :-0,2057 gram burnt with lead chromate gave 0.3913 CO and 0.1621 HZO, or C = 51.87; H = 8.75. 0.2465 gram burnt with copper oxide gave 47.6 C.C. N at 12' C. and 767 mm., or N = 23.13 per cent. * See note under ethylthiocarbimide j ante 416 DIXON THE ACTION OF ISOTHIOCYANATES Theory. I____-51.83 8.11 22-75 17.30 0.1423 gram evaporatled to dryness with sodium hydrate solution, and fused with nitre gave 0.1820 BaS04 from which the formula C8Hl,N3S is deduced.or S = 17.58 per cent., I. 11. 111. 51 * 87 - -8 -75 - -- 23 '13 - ___-- 17 '58 --~ I I Experiment. C 95.76 . N3 42.03 . S 31.98 . HlS 15.00 . which may be represented-(C,H,)*cH<;% . S%H - C H < ~ ~ , ( b . ) Phenylthiocarbimide and Aldehyde-anarnonia.* Warm concentrated alcoholic solutions of 1 mol. thiocarbimide and 2 mols. aldehyde ammonia were mixed. The mixture " set " instantly to a yellowish-white paste. This was freed from the mother-liquor, which it obstinately retains by squeezing in a cloth. The mass was recrystallised three times from warm alcohol and the product dried over sulphuric acid in a vacuum. The pure substance thus obtained crystallises in fine silyer-white needles which melt at 148-149" with browning and copious evolution of gas.The substance is insoluble in water but decomposed by boiling with it ; sduble in alcohol ether and chloroform. The alcoholic solution is freely desulphurised by warming with alkaline lead solution. Silver nitrate in excess gives a white precipitate which rapidly blackens, even in a freezing mixture. Results of analysis :-0.2020 gram burnt with lead chromate gave 0.4405 GO2 and 0.1331 HtO, or C = 59.46 per cent. ; H = 7.32 per cent. or C == 59.43 per cent.; H = 7.43 per cent. 0.2188 gram gave 0.4769 CO and 0.1465 H20, 0.2070 gram burnt with copper oxide gave 32.6 C.C. X at 9" C. and 777 mm., or N = 19.36 per cent. * See note under ethyl thiocarbiniide ante ON THE ALDEHYDE-AMMONIhS.417 11. I 111. ____--59-43 -7'43 -- 19-36 - -0.4600 gram evaporated to dryness with sodium hydrate solution and fused with nitre; gave 0.4943 gram BaS04, or S = 14.77 per cent., from which the formula C,,H,,N,S is deduced. IV. ---14 -77 Theory. C, 131 -67 . H15 15'00. N 42.03. S 31.98 . 59 -66 6-79 19.04 14.49 The structural formula (provisional) is-A homologue of the latter was next obtained. ( c . ) Phenylthiocarbimide and Valeraldehyde-ammonia. Alcoholic solutions were mixed ; on warming a precipitate separated which was drained and pressed. The mass was twice recrystallised from alcohol Fine snowy-white needles were thus obtained which when dried over sulphuric acid in a vacuum melt with decomposition at 152-153".The dry substance becomes SO electrical on slight friction that the particles fly about. The following data were obtained :-0.2057 gram burnt with lead chromate gave 0.5036 CO and 0.1780 &O, or C = 66.76 per cent.; H = 9.61 per cent. 0.2043 gram burnt with copper oxide gave 23.4 C.C. N at 7" C. and 77 mm., or N = 14-07 per cent. 0.2988 gram treated with sodium hydrate and nitre (see above) gave 0.2330 BaSOj, or S = 10.72 per cent., which agrees with the formula C17H27N3S 418 DIXON THE ACTION OF ISOTHIOCYANATES C, 2G3-49 . S 31.98 . H,; 27.00 . N 42'03 . Experiment. Theory. ' 66 -83 66 -76 A 13 -80 14 -07 10 -50 8 -86 9.61 The structural formula may be written-N(C6Hs)4H<$Eg s c < ~ ~ - ~ ~ < c 1 9 (d.) Orthotoly 1 t hiocarbimide and Aldehyde- ammonia.These substances unite at once when waym alcoholic solutions are mixed the contents of the vessel " setting '' to a snow-white mass. The yield is large-over 90 per cent. of the theoretical but as this substance like all the preceding is decomposed by hot alcohol the final yield of pure substance is small. The crude compound was recrystallised three times from warm alcohol thus were obtained short white prisms insoluble in water and melting a t 158-159" w i t h decomposition and evolution of gas. The substance dried over sulphuric acid in a vacuum gave the following results on analysis :-0.2264 gram burnt with lead chromate gave 0.507'5 CO and 0.1548 H20, or C = 61.13; H = 7.59. 0.2930 gram burnt with copper oxide gave 45.1 C.C.N at 10" C. and o r N = 18-30 per cent. 0.3250 gram treated with sodium hydrate and nitre gave 0.3236 755 mm., Bas04 or S = 13.68 per cent., from which the formula C12HI,,N3S is deduced ON THE ALDEHYDE-AMMONIAS. 419 ----143 '64 . Hi 17-00 . 42-03 . 2 31.98 . Theory. 61.21 7 '24 17'91 13-62 Experiment. I. 61-13 7 -59 - -11. 111. ----- --18 '30 - - 13.68 The reaction may be formulated as in the case of the isomeric benzyl compound and the structure represented thus :-Reference bas been made in the early part of this paper to the fact that R. Schiff (Bey. 9 565) has also obtained compounds by the union of aldehyde-ammonia with certain " mustard oils." As his method of operating was essentially the same as that which I have described above whilst on the other hand the resulting compounds were quite different I must indicate briefly the nature of his result,s.(I.) CGHBeNCS + CJ€,O,NH,. By the action of these substances upon one another in alcoholic solution Schiff obtained a compound to which he assigns the formula C,,H,,N,O,S,. The structure he considers may be expressed by the following formula which though not proved " accords perfectly with the mode of formation and reactions." I NH The melting point of this substance is given at 148" ; the compound which I obtained from the same materials melts at 148-149' 420 DIXON THE ACTION OF ISOTHIOCYANATES c H . . . . . N . 8 . O . For the purpose of comparison I here tabulate the analytical results obtained by Schiff and by myself together with the values calculated for the respective formulae C22H3JY502Sz and C11H15N3S.57.22 5'7'53 6-73 7-05 15.21 15'30 13-89 14.42 6.95 -C22H31N502S2 (Schiff) . Experiment. 57.26 6-95 ---I Theory* I-, C H . N . . s 59-66 6-79 19-04 14-49 59-46 7-32 19-36 14-77 ~ CIIH,,N,S (Dixon). i Experiment. Theory. ~ I I. (11.) C3H6*NCS + C2H40,NH3. The compound obtained by the union of these compounds is described as having a similar constitution t'o the preceding. Em-pirical formula C,H3,N5S20 ; m. p. 107-108". The compound similarly obtained by mysslf has the empirical formula C,H,,N,S ; I append as before a table of analytical results with corresponding m. p. 108-109".calculated values. ~ --c . H . N . 8 . 0 . C,H,,N3S (Dixon). I C16H3,N5S202 (Schiff). 49'30 51-82 51 '8'7 7 -98 18 -03 16 *46 17 '58 - I 8.23 1 (111.) CZH5*NCS + CZH,O,NH,. The compound of ethylthiocarbimide with aldehyde-ammonia obtained similarly to the two preceding compounds is described as having an analogous composition and to it a similar structure is assigned. The melting point is given as 118-119". Empirical formula C14H3,N5S202. The compound obtained by me correspond ON THE ALDEHYDE-AMRIONIAS. 421 ~ with the description ‘‘white silvery needles” given by Schiff to the ethyl-compound; but its melting point is as already stated, 135-136” and its empirical formula C7H15N3S. As before I give a table of comparative data. C7HljN3S (Dixon).c . H . N . . . s . 0 . Theory. Experiment. I- I -c H . N S 4 - 4 9 48.64 8.68 8 -77 24-32 24 -94 18.50 18.16 45 -97 8 -50 19 * 21 17 *54 8 -78 I Theory. I Experiment. 46 -30 8 -50 - --As I have directly determined all the constituent’s of each of the substances I obtained and the analyses add up fairly satisfactorily i t is obviously impossible to admit that my compounds contain oxygen ; yet their characters agree in the main with those described by Schiff. In his paper he states that experiments directed with a view to determine whether hydroxyl-groups (whose existence he assumes) were present led to no result. I f the substances I obtained are really identical with Schiff’s compounds I can only conclude that he did not obtain them in a sufficiently pure state for analysis. The structural formulae given by myself are only provisional but I hope shortly to be in a position to make a further communication in which the constitution of these cornpounds shall be dealt with. Chemical Laboratory, University of Dddin, March lst 1888

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DOI:10.1039/CT8885300411

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年代:1888

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422 XXXIV.-A New Jlethod of Estimating Nitrites either crlone 01' in presence of Nitrates and Chlorides. By T. CUTHBEKT DAY. JN most text-books on chemistry a method is given for the prepara-tion of nitrogen by heating a mixture of potassium nitrite and ammonium chloride the change being represented by the equation-K02K + NH4C1 = KC1 + 20Hz + NZ, which niay be simplified by saying that ammonium nitrite when heated splits u p into nitrogen and water thus :-NO,*NH = N2 + OH, the quantity of nitrogen produced being exactly double of that present as nitrous acid in the nitrite. The method here given consists in applying this well-known reac-tion quantitatively. I have never seen any mention of the use of this reaction for quantitative purposes and I scarcely think that a method, based on its use would have been omitted in any work on analytical chemistry if accurate results had been obtained by its means.I n order t o test the accuracy of the method I have devised I pre-pared a quantity of pure silrer nitrite NO,Ag and determined the amonnt of nitrogen it contained comparing the results obtained with that required by the known composition of the salt. The process is conducted in the following way :-The FIG. 1. solution containing the nitrite is introduced into the flask A (Fig. 1) (about 75 C.C. capacity) and an excess of solid ammonium chloride is then added till the solution is thoroughly saturated. It is important that the solution should be concentrated otherwise considerable di€Ecultr will be found in driving off the last traces of nitrogen.The flask is closed by a cork carrying the capillary tube DAY A NEW METHOD OF ESTIMATING NITRITES. 423 and the delivery tuk)e C of somewhat wider bore 1.5 t'o 2.0 mm. Carbonic anhydride generated from white marble and hydrochloric acid in the apparatus shown in the figure is then allowed to flow through the flask until all the air is removed. The small U-tube n, is filled with glass beads moistened with a little weak potash solution, and is intended to intercept any acid spray which may be carried over by the current of gas. As soon as it is considered that the whole of the air in the flask is displaced by carbonic anhydride the screw-tap E is closed and the flask disconnected from the carbonic anhydride apparatus. The end of the delivery tube C is now brought under the graduated absorp-tion-tube F which contains mercury and a few C.C.of strong potash solution to absorb the carbonic anhydride. The solution in the flask is now heated till it boils. As long as any nitrogen is given off the boiling liquid effervesces freely but as soon as the last traces have been expelled the boiling assumes the peculiar bumping character noticed in water free from dissolved gas. The boiling is continued till all the nitrogen produced in the reaction has been carried over by the steam and collected in the absorption-tube. The screw-cock E may now be opened while the liquid is still boiling and the flask removed. The absorption-tube containing the collected gas is removed to aJ vessel full of water the mercury is allowed t o fall out.and the volume of nitrogen obtained is measured after standing a few hours. The observed volume of nitrogen when due allowance has been made for temperature pressure and tension of aqueous vapour is halved its weight calculat'ed and we have then all the data necessary for calcu-lating the amount present in the nitrite under analysis. The following experiments will show the degree of accuracy attain-able by this method :-The weighed quantity of silver nitrite was in each case dissolved in hot water and decomposed by a solution of sodium chloride. The solution was filtered through a small filter into the flask A and the precipitated silver chloride washed repeatedly with small quantities of hot water adding the washings to the solution in the flask :-Gram N. P. c. N. N02Ag. Gram N02Ag. Half vol. P. c. N. Theory. P. c. Expt. 1. 0.1364 gave 0.012136 = 8.90 9.02 Loss 0.12 , 2. 0.1700 , 0.0155'79 = 9.12 9 9 Gain 0.10 , 3. 0.1712 , 0.015452 = 9.02 9 9 Exmt. I repeated the determinations in presence of excess of potassium About 0.5 gram of this salt was added to the solution i n nitrate. each experiment : 424 RUREMANN AND CARNEGIE THE ACTION OF ACETONE Gram N. P. c. N. N0,Ag. Gram N0,Ag. Half vol. P. c . N. Theory. P. c. Expt. 1. 0.1716 gave 0.015455 = 9.12 9-02 Gain 0.10 , 2. 0.1808 , 0.016556 = 9.16 7 7 Gain 0.14 The results of these two experiments show that the presence of the nitrate does not affect the accuracy of the determinations

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DOI:10.1039/CT8885300422

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年代:1888

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424 RUREMANN AND CARNEGIE THE ACTION OF ACETONE XXXV.-The Action of Acetone 0% Ammonium Salts of Fatty Acids in presence of Dehydraticng Agents. By DF. S. RUHEMANN and D. J. CARNEGIE. SOME years ago Zanoni (Bey. 15 528) investigated the action of phosphoric anhydride on a mixture of acetamide and glycerol and obtained P-picoline as a product of the reaction. Afterwards Hesekiel (Ber. 18 511 and 3091) more thoroughly studied the reaction and found that it involves the previous formation of acraldehyde whilst the acetamide acts merely as a convenient source of ammonia which, combining with the acraldehyde under the influence of the dehydrating agent yields P-picoline in accordance with the following equation :-2C.3H.40 + NH = CsH,N + 2HZO. Hesekiel extended this reaction t o the formztion of the higher members of the pyridine series using aldehydes instead of glycerol.Acetic aldehyde for instance he found to be first transformed by phosphoric anhydride into crotoiiic aldehyde which in turn con-densing with the ammonia derived from the acetamide forms methyl-ethylpyridine. This transformation of the aldehydes of the fatty series into the homologues of pyridine induced us to investigate analogous methods involving ketmes instead of aldehydes. Briefly stated our experimental method consisted in heating mix-tures of acetone and ammonium salts of fatty acids with dehydrating Agents. In o u r first experiments dehydration was effected by heating the mixture with zinc chloride in sealed tubes at a temperature of 250" for about four hours; but the pressure of the gases evolved under these conditions was so great as to cause much inconvenience.I n our later experiments phosphoric anhydride was substituted for zinc chloride and the reaction was allowed to proceed in ordinary flasks fitted with reflux condensers. The charge for each flask was ON AJIYONIUM SALTS OF FATTY ACIDS. 485 30 grams of acetone, 40 grams of ammonium salt, 35 grams of phosphoric anhydride. After 24 hours' heating on the sand-bath the contents of each flask were submitted t o distillation in a current of steam in order to separate the hydrocarbons which are always formed in this reaction ; excess of solid potash was then added t,o each flask care being taken t o keep the temperature low the while and the resulting strongly alkaline liquid subjected to a second distillation with steam.The preater part of the base formed appeared as an oily layer floating on the surface of this second distillate. To liberate that portion of the base which i8 dissolved in the water of the distillate solid potash was added thereto since the base though fairly soluble in water is insoluble in concentrated potash solution. The base was finally dried over solid potash and fractionally distilled through the temperature interval 80-200". Tl e second fraction (161-163') on treatment with hydrochloric acid and platinic chloride gave a platinochloride but at the same time an oil, undoubtedly a hydrocarbon rose to the surface of the liquid. The platinochloride was purified in the usual way by repeated decompo-sition by hydrogen sulphide followed by repeated precipitation with platinic chloride.It was dried at loo" and burnt in a stream of oxygen. As will be seen from the appended numbers the analysis undoubtedly proved it to have the composition (CgH,5N)2,H,PtC1,. The first fraction (80-160") did not give a platinochloride. Theory. Found. P t 28.4 28.3 C . . 31.6 3 1.4 H . 4.68 4.7 N . 4.06 4.07 Each of the fractions (165-167") (1 TO-l80") (180-185"), gave platinum salts which were purified by recrystallisation from water. In all cases the analyses qf these salts gave a mean of 28.3 per cent. of platinum; hence it is clear that the chief product of the reaction of acetone on ammonium acetate in the presence of phos-phoric anhydride is the base CgHI5N ; but that other bases of higher boiling point are also present in small quantity is evident from the behaviour of the liquid during distillation.The mixture of hydrocarboris formed along with the base C,H,,N in this reaction was also examined and was found to consist chiefly of mesitylene (b. p. 165-167') mixed with small quantities of hydro-VOJ,. LIII. 2 426 RUHEMANN AND CARNEGIE THE ACTION OF ACETONE carbons of higher boiling points. The analysis of the fraction 165-167" gave the following result :-Theory for mesitylene. Found. c . 90.0 89.:3 H . 10.0 10.2 I t should in this connection be noted that when zinc chloride is used to dehydrate much more hydrocarbon and much less base is formed than when phosphoric anhydride is used. Experiments similar to the foregoing were now made with ammo-nium formate and ammonium butyrate ; and from the analyses of the platinochlorides we found that the bases formed in each case aye identicaI with the base C,H,,N already prepared from ammonium acetate :-Analyses of Pt salt Analpsis of Pt salt of base from of base from Theory for H*COONH,.C,H,.COONK,. (CgH,,Pi),,H2PtCl,. Pt 28-42 28.6 28.4 The mixture of hydrocarbons formed in the case of ammonium formate undoubtedly consisted largely of mesitylene as before. I n the case of ammonium butyratre the bye-product distilled over almost complet.ely at 110-113". As it could not possibly be mesitylene an analysis was made. The appended numbers show that the substance was not as we had anticipated a hydrocarbon but the ethyl salt of butyric acid -Theory for C,H7.COOC2H,.Found. C 62.0 61.68 H . . 10.3 10.28 The identity of the compound was further proved by the fact that the product of its hydrolysis gave the iodoform reaction. From these experiments i t follows that in all. cases only the ammonia of the salts plajs a part in the formation of the base C9H15N. This base is identical in all its properties with that isolated by Heintz (Annalen, 174 167 and 183 276) from the products of the reaction of ammonia and acetone and which was called by him dehydrotri-acetonamine, Canzoneri and Spica (Ber. 18 51 and 331) obtained it as chief product on heating a mixt'ure qf acetone and acetamide with zinc chloride a t 135-140". They also studied the action of reducing agents on the base and found that it was thus transformed into methylated piperidines.From these observations we may conclude that dehydrotriacetonamine is a hydrogeiiised pyridine-derivative. Accordingly we now tried the action of mild oxiclising agents on th ON XJfMONIUM SALTS O F FATTY ACIDS. 427 base C,H,,N in the hopes that we might by this means dehydrogenise it and so obtain some well-defined member of the pyridine series. Some of the base (boiling a t 161-163') was treated with a filtered solution of bleaching powder ; the mixture became wai-m and a pre-cipitation of calcium hydrate took place. After allowing it to remain for an hour the mixture was heated for some time on the water-bath, and t>hen distilled with steam. In this way we obtained an oil differing from the original base in its very pungent odour and also in the fact that it was heavier than water.We had merely succeeded, however in chlorinating the base not in reducing it. The chlorinc-derivative obtained was exceedinglj unstable ; on attempting to distil it sudden decomposition took place at 80" and chloroform distilled over in large quantity. An analysis of the unpurified substance was made but no conclusions could he drawn from the result viz. 27.7 per cent. C1. Again in the hopes of obtaining a pyridine-derivat'ive we treated the chlorine-derivative with alcoholic potash and then distilled in a current of steam. On saturating the distillate with potash a fair quantity of a light oil was obtained. This was separated dried over solid potash and distilled.It distilled over almost completely between 78" and 79". Three analyses and three vapour-density determinations were made which showed that tlie action of alcoholic potash on the chlorine-derivative does not simply remove hnloid acid, and give a pyridine-derivative as we had hoped but that a more deep-seated decomposition takes place resulting in the formation of large quantities of an isopropyl alcohol hydrate of the formula C3H30,H20. Appended are the results of analysis :-Found. 7 Theory for r-A-C,Hi,O:. I. 11. 111. C 46.15 46-48 46-36 45.91 H 12.82 12.6 12-67 13.7 Theoretical vapour-density of C,H1,O2 referred to hydrogen. Found. 39 39.5 Hydrates of isopropyl alcohol have already been observe& b u t so far as we are aware the known hydrates do not include the one above referred to. Erlenmeyer (Anxaleiz 126 308) describes a hydrate of the formula 2C,H80,H,0 ; whilst Linnenian (AnnaZen 136 40) has isolated hydrates having the compositions 3C3H80,2H20 arid 3C3H80,H20. U?& emity Laboratory Cmn b ridge. 2 G

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DOI:10.1039/CT8885300424

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年代:1888

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428 XXXVI.-Ca?.boxyl-derivativRs of Benxoquiiaone. By J. U. NEF.* CHLORO- bromo- hydroxy- nitro- and amido-derivatives of benzo-quinone have long been known but attempts to obtain carboxyl-derivatives have hitherto been unsuccessful. The following experiments undertaken with the intention of filling up this gap were carried out at the suggestion of Prof. v. Baeyer, and it is an especial pleasure to the author t o have this opportunity of expressing his gratitude to Pi-of. v. Baeyer for the kindness and interest shown him during his stay in Muiiich. Durene was chosen as the startinq-point f o r the experiments on account of the especial interest attaching t o the production of quinono-tetracarboxylic acid C,oH,O, = C,O,( COOH), which has the same percentage composition as croconic acid C5H305 one of the products obtained by Gmelin (Qmelin Handbuch 4 Aufl.5 478) from the explosive bye-product formerly obtained in the preparation of potas-sium. The Russian chemist Basaroff (Dict. de Chemie par WZrtz, 2 1363). expressed the opinion that croconic acid and quinone-tetracarboxylic acid were identical but very recently Nietzki and Benckiser (Bey. 19 293 772) by a series of remarkable experiments, have shown that croconic acid has the formula C5H305 thus render-ing i t impossible that it can be identical with a derivative of benzene. The following synthesis of ethylic quinonetetracarboxylate confirms the conclusion that the two compounds are totally differem. A close investigation of etliylic quinonetetracarboxylate has led to the discovery of a series of compounds which stand in a remarkably close relation to ethylic succinosuccinate and its derivatives.A study of durylic-acid-qninone C,O,(CH,),COOH has shown that carboxylated quinones are very unstable substances and that the carboxyl-group which is usually so stable in benzene-derivatives. can easily be displaced by other groups ; the nitro-group for example. On the whole however they exhibit the general chemical reactions charactmising other quinone-derivatives On reduction they take up two atoms of hydrogen forming colourless quinols which on oxida-tion yield the original quinone. A very noteworthy fact is the existence of many carboxyl-pamdi-hydroxy-derivatives of benzene which cannot under any conditions be oxidised to the corresponding quinones.The oxidation to a * Compare Annalen 237 1 NEF CARBOXTL-DERIVATIVES OF BENZOQUINONE. 4 I 9 quinone can only be accomplished in the case of hexa- substituted benzene-derivat,ives which in this respect exhibit a much greater stability than other incompletely substituted derivatives of benzene. The durene used was obtained from the chemical factory of Lang-feld and Reuter Bramom near Rostock an2 was made from mono-bromopseudocumene C,H,(CH,),Br [I 2 4 51 (m. p. 71") by Fittig's method. It was nut pure as the boiling point ranged from 185" to 220", and contained moreover a liquid boiling a t about 170° and a solid compound melting a t loo" and boiling at 240". D u r j l i c acid was prepared from pseudocumidine CsH,( CH,).N.H2 [l 2 4 51 by Sandmeyer's method of displacing the amido- by the cyanogen-group (Hdler Ber.18 93). Although the yield of durotiitrile is poor (10-15 per cent.) arid the preparation of the acid therefore wearisome this is by far the best method of making durylic acid and the product obtained is pure (m. p. 149'). As pseudo-cumidine is now much used in the colour industry in making azo-dyes and therefore easily procurable I have recently tried to better the yield of duronitrile by modifjing Sandmeyer's method somewhat. Cnprous cyanide was used the solution in potassic cyanide being kept boiling over a flame while the diazo-pseudocumene solution was added. After extracting with ether washing the ethereal solution with dilute sodic hydrate and sulphuric acid and distilling off the ether the nitrile was distilled over with steam.It was thus obtained pure fusing a t 57.5". It can be saponified quantitatively by heating it with concentrated hydrochloric acid (1.18) in a sealed tube at 160-170". The yield thus obtained was about 50 per cent. which is far better than that afforded by the usual method. The course pursued in the iitvestigation was the fo€lowing :--The durene was converted by the usual methods into duroquinone, C60,( CH,),. As attempts to oxidise the methyl-groups to carboxyl-groups were unsuccessful the durene was used solely to make durylic acid which on nitration gives dinitrodurylic acid ; this acid was then converted into durylic-acid-quinone and pyromellithic-acid-quiiione. I. Duroquinone from Dureize.Dinitro-durene was made according to Jannasch and E'ittig's method (Zeit. f. Chem. 1870 161). The durene (5 grams) was added slowly to pure fuming nitric acid (1*49) 40 c.c. kept at a tempe-rature below 0". The substance rotates rapidly and then dissolyes with a passing deep-brown coloration. After allowing the mixture t o remain for two hours it is poured on to ice when the dinitro-durene separates out as a white flocculent precipitate. By crystal-lisation from alcohol i t can be separated from an oily bye-product 430 NEF CARBOSTL-DERIVA'I'IVES OF BESZOQUISONE. nnd obtained in colourless prisms melting a t 205". It has all the properties ascribed to it by Jann,zsch and Fittig; it dissolves easily in benzene and ether sparingly in hot and very little in cold alcohol.I t sublimes without decomposition in needles and volatilises with steam. It is unusually stable in the presence of oxidising agents; dilute nitric acid or a mixture of 1 vol. glacial acetic acid 1 vol. concent~ated nitric acid and 1 vol. of water (in which the substance dissolves) not having the slightest action on it. Dinitrodurol is best reduced as follows :-A hot solution of the substance in acetic acid is treated with zinc-dust until it no longer gives any turbidity on addition of water. The zinc is then precipitated from the diluted solution with sulphuretted hydrogen and the filtrate concentrated. On addition of sodic hjdrate diamidodurene is pre-cipitated in colourless pearly plates ; this was not analysed but con-verted directly into duroquinone.It is easily Roluble in chloroform and alcohol ; less so in ether. When exposed to the air in solution, or in a moist condition it turns green. Thc hydrochloride of the base in sparingly s o h ble in concentrated hydrochloric acid. An aqueous solution thereof treated i n the cold with ferric chloride, platinic chloride or sodic nitrite is oxidised to duroquinone. I n the case of platinic chloride the addition of nlcoliol precipitates am-monium platinochloride wliilst duroquinone remains in solution, (NH4),PtCl6 + 2HC1 + H,O. A similar easy elimination of the amido-groups with formation of a quinone was also observed in the case of diamidodurylic acid. The duroquinone was made by treating a solution of diamido-dcrene in hydrochloric acid with an excess of ferric chloride in the cold.A temporary deep-green coloration is noticed and then the solution becomes yellow and the quinone crystallises out in yellow needles. The yield is almost quantitative and the product obtained is pure. If the diarnidodurene is not isolated after the reduction with zinc-dust and the ferric chloride is added directly to the acetic acid solution (from which the zinc has been removed) the quinone is obtained in small quantity as a very dark-coloured impure product. nuroquinone was obtained by cryst:illisation from light petroleum ill beautiful long yellow needles melting a t 111". 0.1220 gram substance dried in a vacuum gave 0.3259 gram CO, and 0.0815 H,O. Cti(CH,),(NH,Cl)? + HzPtC1 + 2HZO + 0 = Ctj(CH,),O + CtLlculilted for c (GI3 3) 4 0 2 .Found. C . 73-18 72-86 H . 7-32 7.42 The quinone is volatile with steam and sublimes at 100" in needles NEB' CBRBOXYL-DERIVATIVES OF CENZOQUINONE. 43 I which possess a feeble but distinct odour characteristic of quinone. It is very easily soluble in alcohol ether chloroform and in hot light petyoleum ; insoluble in water or alkalis. It was not possible under any condition to oxidise the methylated side-chains to carboxyl ; oxidising agents in alkaline neutral or acid solution decomposed the benzene ring compietely. Worthy of note is the great stability of duroquinone in tlie presence of concentrated nitric acid (1*4) in which it dissolves with ease but even after long heating on a water-bath remains in great part unchanged. Treated with zinc-dust and acetic acid the quinone is reduced and on adding water a colourless substance melting at about 210" is pre-cipitated.Oxidising agents such as ferric chloride or nitric acid, oxidise it again to duroquinone. It is probable that the substance is dihydroxydurene but want of material has prevented me from obtain-ing the product in amount sufficient for an analysis. IT. Dinitrodurylic Acid out of Durol. DtwyZic A c i d C,H,(CH,),*COOH.-Jannasch (Zeit. f. Chem. 1870, 449 and 1871 33) has shown that durene heated for a loiig time wibh dilute nitric acid yields in about equal amount two acids one of which durylic acid C6H,( CH3),-COOH is volatile with steam ; the other cumidic acid,* C6HL(CH3)2(COOH)2 is not volatile with steam. I n my experiments however the great object was to obtain as much of the durylic acid as possible.When durene is heated with dilute nitric acid for three or four hours only and the acid formed is then separated froni unchanged durene I find that durylic acid alone is formed. Durylic acid is also the sole oxidation-product obtained on treating a solution of durene in acetic acid with the calculated amount of chromic acid also dissolved in acetlic acid. The yield in this case is however not so good as when the following method is employed. 20 grams durene is heated for three to four hours with 500 C.C. dilute nitric acid (1 V G ~ . concentrated nitric acid sp. gr. 1.4 to 3 vols. water) taking care t o add a few pieces of porous porcelain to pre-vent bumping. After filtering from the nitric acid the product is treated with dilute sodium carbonate solution aud the unchanged durene heated agaiu with nitric acid as above.After the second and third treatment with sodium carbonate an insoluble yellowish oil remains which can easily be separated from the soda solution by means of ether. On distilling off the ether an oil is left which cou-tains nitrogen and undergoes little change on further heating with nitric acid.? * This has recently been shown to consist of two isomeric acids (Schnapituff, Be? 19 2510). + The oil has a peculiar camphor-like odour and is very easily soluble in ether 432 NEF CARBOXYL-DERIVATIVES O F BENZOQUISOSE. On adding hydrochloric acid to the mixed sodium carbonate solu-tion impure durylic acid separates as a flocculent precipitate.It is first treated in acetic acid solution with zinc-dust to get rid of the nitro-products possibly formed and then distilled with steam. As the whole is volatile with steam there can be no bibasic cnmidic acid formed. The durylic acid thus driven over with steam is pure, melting a t 149" and has all the properties assigned to it by Jannasch (Z'eit. f. Chem. 1870 449). It is very sparingly soluble even in boiling water and volatilises with steam without melting. The yield obtained by the above method was 15-20 grams of impure durylic acid and 20-22 grams of oily bye-product from 40 grams of durene. I n the further experiments, the impure durylic acid obtained on adding hydrochloic acid to the soda solutions was used. (2.) Dinitrodurylic Acid C6(N0,),(CH,),GOOH.-The nitration of durylic acid according to Gissrnann's method was not found advan-tageous as the reaction is too violent.The following process gives a quantitative yield :-20 grams finely pulverised durylic acid (dried at lOO0) is dissolved in pure concentrated sulphuric acid and the solution cooled down to - 10" or - 15" by means of a freezing mixture. A solution of 28 grams potassic nitrate in concentrated sulphuric acid is now added as quickly as possible-taking care to stir well and to keep the temperature below 5". A deep brown colour appears at first which changes finally to light yellow while dinitrodurylic acid partly separates. After allowing the mixture to remain a t the ordinary temperature for four or five IIOUTS o r over night the solution is poured cwefully on to ice.The nitro-acid separates out as a flocculent yellowish precipitate which is collected and well washed. If pure durylic acid is used the product thus obtained is sufficiently pure; if however the impure acid is employed the nitro-derivative must be purified by means of its calcium salt. The crude product is heated with water and finely pulverised marble until the reaction is neutral ; on filtering and concentrating the calcium salt crystallises out in colourless radiating needles. When lieated on platinum-foil it explodes violently. An analysis of the oil as well as of a solid product obtained therefrom by cooling below Oo and pressing between filter-paper (melting point 35-40") gave figures agreeing with those required by mononitrodurene.The oil however does not yield dinitrodurene on treatment with fuming nitric acid and it is lherefore more proba-ble that the oil is a nitrate of a trirnetliylated bcnzyl alcohol. This i the more probikble as by oxidation with potassium permanganate in soda solution acids are obtained which contain no nitrogen. I n this way I succeeded in isolating an acid possessing all the prbperties of pyromellitic acid and the analp3is of the silver salt gave figures which are exactly those required by C,II,(COOAg),. (Gissmann Annalen 216 20s. NEF CARBOSYL-l)ERIVATIVES OF BENZOQUINONE. 433 0.3155 gram substance dried a t 180" gave 0.0760 gram CaS04 = 7.10 per cent. calcium ; calculated 7.32 per cent. The free acid obtained by the addition of hydrochloric acid t o the purified calcium salt is a yellowish amorphous powder melting a t about 205".It has all the properties mentioned by Gissmann The potassium salt is sparingly soluble in cold water and crystal-(loc. cit.). lises in colourless lustrous needles. 111. Bury lic Acid Quiraone f r o m Dinitrodurylic Acid. (1.) Diarnidodurylic Acid Cs(NH,)2(CH3),*COOH.-A solution of dinitrodurylic acid in acetic acid (50 per cent,.) is treated with zinc-dust in small portions; a violent reaction takes place at first and finally the soliltion becomes colourless. Sfter filtering hot from the excess of zinc-dust the solution is diluted wit'h about 4 volumes of water and allowed to cool when the diamidodurylic acid crystallises out almost completely i n colourless silky needles.The small portion remaining in solution is recovered by precipitating khe zinc concen-trating the a,mmoniacal solution and adding dilute acetic acid. The yield is almost quantitative. For analysis the substance was crystallised from water several times, and then dried carefully a t 110". 0.1642 gram anhydrous substance gave 0.1105 gram H,O and 0.0950 gram anhydrous substance gave 12 C.C. nitrogen a t 15' and 0.371 gram CO,. 723 mm. Calclrlated for CloH,,h',02. Found. C . 61.85 61.62 H . 7.22 7.48 N . 14.48 14.10 The figures obtained for carbon were a t first always about 1 per cent. too low because the substance sticks together on healing and it is difficult to remove the last trace of water of crystallisation. Diamidodurylic acid forms salts with bases and with mineral acids.The compounds with hydrochloric acid and with snlphuric acid are easily soluble in water. On adding platinic chloride to a solution of the hydrochloride in the cold ammonium platinochloride separates and dui-ylic-acid-quinone is formed. The oxidation to the quinone also takes place with equal ease on treatment with ferric chloride or sodic nitrite. Diamidodurylic acid is sparingly solable in cold alcohol or water ; much more soluble in hot; it is insoluble in ether. It melts at 221 434 NEF CARBOXYL-DERIVATIVES OF BENZOQUINONE. with decomposition. When heated wit,h acetic anhydride for several hours at 140" an acetyl-derivative was formed. After getting rid of the acetic anhydride the substance was dissolved in ammonia and pre-cipitated therefrom by hydrochloric acid; in this way i t was pre-cipitated in colourless quadratic plates melting at about 275".When heated in a test-tube the substance loses carbonic anhydride and a compound sublimes in colourless needles ; it is insoluble in alkalis. 0 CH /\ COOH (2.) Durylic-acid-quiriowp .-This compound the CH3 (2 CH3 first carboxylated qninone-derivative known is formed quantitatively on adding an excess of ferric chloride to a solution of pure diamido-durylic acid in hydrochloric acid and allowing the mixture t o remain for about half an hour. No colour reactions are noticed but the yellow solution bas a faint but distinct quinone-like odour. If the solution is sufficiently concentrated part of the acid crjstallises out in yellow rhombohedrons.The solution is extracted three or four times with ether and the ether dried with calcium chloride ; after distilling off part of the ether and allowing the remainder to evaporate spontaneously the quinone acid remains as a dark-yellow crystalline pubstance having a distinct quinone odour. I f the above directions are carefully followed it is only necessary to wash away the traces of adhering ferric chloride with a little water in order to obtain a perfectly pure product. On heating with ferric chloride or on trying to convert dinitrodurylic acid directly into the quinone without isolating the diamido-compound a very impure yellow oily product is obtained. The c r j stals obtained from the ethereal solution are radiating flat needles of a deep yellow colour.Heated in a capillary tube they become red a t 127-129" and decompose at 130" with brisk evolution of gas. I. 0.1340 gram substance dried in a vacuum gave 0.3038 gram CO, 11. 0.1540 gram substance dried in a vacuum gave 0.346 gram GOz and 0.065 gram H,O. and 0.076 gram H,O. Calculated for Cs02(CH,),.COOH. C 61-85 H 5.15 Durylic-acid-quinone dissolves easily solvents except light petroleum. It Found. r---7 I. 11. 61.83 61-68 5.40 5.52 in alcohol and in other organic is sparingly soluble in col XEF CARBOSYL-DERIVATIVES OF BEKZOQUIXONE. 4315 water more soluble in hot water (the quinone odour is then especially noticeable) but does not crystallise out well on cooling. It dissolves in benzene in the cold unchanged but on heating t8he yellow solution changes to an intense dark red.Durylic-acid-quinone difl'ers from other quinones in being lion-volatile and easily decomposed. Being ail acid it decomposes soluble carbonates in the cold and dissolves in alkalis and in ammonia with a deep yellow colour. The alkaline solutions can be partly evaporated without change. In other respects, the quinone acid resembles the other paraquinone compounds of benzene; thus for example it can be reduced in alkaline or acid solution to the corresponding quinol or paradihydroxy-compound which on oxidation yields the original quinone compound again. An intermediate compound corresponding to quinhydrone was not noticed. Like quinone itself the above quiiione acid reacts with phenol and resorcinol forming dark-red compounds.On allowing a dilute alcoholic solution of the quinone acid to stand for two days with an excess of hydroxylamine hydrochloride a yellow unstable compound containing nitrogen is formed ; this is probably the quinoneoxime. Of the salta of durylic-acid-quinone the silver salt was prepared by adding silver nitrate to a concentrated solution of the neutral animoninm salt. It was thus obtained in yellow needles little soluble in cold water more so in hot. It is unstable towards heat and light, and explodes when heated quickly on platinuni foil. 0.146 gram substance dried in a vacuum gave 0.041 gram H,O, 0.2125 gram COz and 0.0525 gram Ag. Calculated for C6 02(CH,) - co Odg . Found. c 39.87 39-70 H 2.99 3-12 Ag 35.88 35.96 A concentrated solution of the ammonium salt of durylic-acid-quinone treated with lead acetate gives the lead salt as an insoluble yellow amorphous precipitate.Bark chloride gives the barium salt as a yellow crystalline precipitate dissolving on heatii1,g. Copper sulphate gives the copper salt as a pale-yellow sparingly soluble granular precipitate. ( 3 . ) Dihydrox y dury l ic Acid C (OH) *( CH,) 3*C 0 OH .-Dury lic-aci d-quinone can be redaced quantitatively in alkaline or acid solution to dihydroxydurylic acid. I n my first experiments I used zinc-dust and sodic hydrate. A dilute solution of the substance in sodic hydrate was treated in the cold with zinc-dust added in small portions a t 436 NEF CARBOXYL-DERIVATIVES O F BESZOQUINOSE. time. The solution turns green then violet and finally becomes colourless ; it is then acidified with concentrated hydrochloric acid, and extracted with ether.On distilling off the ether a wliite amor-phous mass remains having a characteristic sweet sniell. This method of reduction is uncertain on account of the instability of dihydroxydurylic acid in alkaline solution and it is much better to reduce with sulphurous acid which a t once gives a pure product. On adding a concentrated cold aqueous solution of sulphurous acid to finely pnlverised durylic-acid-quinone and shaking the whole mass is converted into dihydroxydurylic acid without dissolving ; in order t o obtain a colourless product the mixture is heated in a sealed tube a t 100" for two to three hours and then repeatedly crystallised out of water containing sulphurous acid.Dihydroxydurylic acid is thus obtained in colourless spheres made up of very fine radiating needles ; i t melts at 210" with decomposition. I. 0.1432 gram substnnce dried a t 110" gave 0.3208 gram CO, 11. 0-1556 gram substance dried a t 110" gave 0.3485 gram CO, and 0.084 gram H,O. and 0.089 gram H,O. Found. Cidcnlated for r-7 C (OH) 2 (C H3) 3.C 0 OR. I. 11. C 61.27 Gl.l.0 61.08 H . 6.13 6-52 6.36 This quinol dissolves easily in alcohol and ether sparingly in benzene and chloroform. Ferric chloride added to a dilute alcoholic solution oxidises it with passing green coloration t o the quinone. The colourless alkaline solution of the acid is unstable when exposed to the air changing quickly to a yellow red red-violet and filially to a deep violet.An ammoniacal solution of the acid reduces silver nitrate in the cold. Lead acetate added t o a solution of the ammo-nium salt gives a colourless amorphous precipitate. (4.) 13thyZ quinonedumjhte C6O,(CHr,),.CO0C,H5 was made by allowing the sili-er salt of durylic-acid-quinone to stand for 24 hours with a dry ethereal solution of ethyl iodide. The ethereal solution, filt)ered from the silver iodide was washed with sodic carbonate and dried by means of calcic chloride. After distilling off the ether cz yellow oil remained which on rubbing with a glass rod solidified readily to yellow radiating needles. On recrystallisation from hot light petroleum it was obt~~iried in long yellow needles melting a t 51".0.12% gram substance dried in a vacuum gave 0.0706 gram H,O and 0.2902 gram CO, NEF CARBOSYL-DERIVATIVES OF BENZOQUINONE. 43 7 Calculated for C6O9 (CH,) ,*COOC,H+ Found. c 64.86 64-61 H 6.31 6.40 The ethereal salt unlike the free acid is odourless. Like other quinones it sublimes with ease and without decomposition. It is easily soluble in alcohol and ether ; insoluble in water or alkalis. It is saponified when heated with sodic hydrate. (5.) Ethyl Dihyclroqdzwy Zate C6(OH),(CH,),*C00C?Hs.-on heating ethyl quinonedurglate with a concentrated aqueous solution of sulphurous acid it is reduced and on cooling ethyl dihydroxydnrylate crystallises out in needles. The substance may be purified by dis-solving it in alcohol and adding water containing sulphurous acid t o the hot alcoholic solution.It is thus obtained in colourless broad needles melting a t log" and having a characteristic sweet smell. 0.0935 gram substance dried i n a vacuum gave 0.2183 gram CO, Calculated for and 0.06 gram H,O. C,(OH),(CH,),.COOC,H~. Found. c 64.29 63.73 H . 7.14 7.13 The ethereal salt is soluble in alcohol and other organic solvents except light petroleum. It is somewhat soluble i n cold water ; much more so in hot. It dissolves in sodic hydrate forming a colourless solution ; on heating however hydrolysis occurs and the colour of the solution changes to deep violet. In alcoholic solution ferric chloride oxidises it to the quinone with passing green coloration. Nitric acid (sp. gr. 1.4) also oxidises it to the quinone.An intermediate product corresponding to quinhydrone was not noticed. (6.) Action o,f Concentrated Nitric Acid on Dury1ic-acid-quinone.-Durylic-acid-quinone dissolves without change in nitric acid (sp. gr. 1*4} in the cold. On heating on a water-bath however a strong evolution of gas is observed. The addition of water now pre-cipitates a beautiful Fellow crystalline substance which is insoluble in alkalis and therefore no longer an acid. Further investigation has shown that the carboxyl-group of durylic-acid-quinone has been displaced and in fact quantitatively by a nitro-group according to the reaction :-Cp,O,(CH,),*COOH + HNO = c6o,(cH,),*NO + H,O + CO,. The resulting conipound nitropseudocurnoquinono is one of the most stable of quinone compounds 438 NEF CARBOSPL-DEKIVATIVES OF BENZOQTJINONE.By heating durylic-acid-qixinone with alcoholic a,mmonia in a sealed tube a t loo" the elements of carbon dioxide are removed and a deep-red solution is obtained. Want of material has prevented me thus far from investigating the product more closely. These observations aye in harmony with those of Hermann (Annalen 211 343) in the case of paradihydroxyterephthalic acid. The latter when treated with concentrated nitric acid gives no tere-phthnlic-acid-quinone but 2 mols. CO are eliminated in the cold with formation of nitrnnilic acid. All these facts go to show that the carboxyl-group i n carboxylated quinoce-compounds is very loosely bound. 0 heating durylic-acid-quinone on a water-bath for about half an hour with nitric acid (sp.gr. 1.4) until the erolution of carbonic anhydride ceases. On adding water the quinone separates out completely and crystallises in yellow plates melting at 113". 0.1485 gram substance dried in a vacuum gave 0.3023 gram CO and 0.230 gram substance dried in a vacuum gave 15 C.C. nitrogen at 0.0655 gram H,O. 16" and 710 mm. Calculated for C692(CH,),.N02. Found. (3 55.38 55.52 H . 4.62 4.9 N . 7-18 7.09 This substance is vei-y stable. It sublimes easily and without decom-position. Heated on a water-bath for hours with concentrated nitric acid it remains in great part unchanged. On cry~tallisation from nitric acid light petroleum or especially from dilute alcohol it is obtained in yellow plates melting a t 113" and possessing a faint but distinct quinone-likc odour.(7.) Nitropseudocurno~lsilzol C6( OH),( CH,),*NO,.-This was ob-tained by treating nitropseudocumoquinone in a sealed tube at 100" with a concentrated solution of sulphurous acid in 25 per cent. alcohol. On cooling the tube is filled with long broad yellow needles which are quite pure and remain unchanged on repeated treatment with sulphurous acid solutions. For analysis the substance was crystallised from ether when it was obtained in flat yellow needles melting a t 106" NEF CARBOSYL-DERIVATIVES O F BESZOQUINONE. 439 0.1797 gram substance dried in a vacuum gave 0.3592 gram CO,, and 0.0908 gram H,O. Calculated for C,(OH)?(C'HJ,.NOp Found. C . . 54.82 54.52 H 5.58 5-58 Nitropseudocumoquinol is easily soluble in chloroform ether and alcohol.It is somewhat soluble in hot water crystallising therefrom in flat needles. Sodic hydrate colours i t bluish-violet and it then dissolves with a pale greenish-yellow colour. Ferric chloride or con-centrated nitric acid oxidiaes it to the corresponding quinone. On treating a solution of the quinone or of the quinol in acetic acid with zinc-dust reduction takes place and finally a colourless solution is obtained which on exposure to the air soon becomes deep red-violet. On neutralising with sodic carbonate after precipitation of the zinc as zinc sulphide ether extracts a deep red substance which with hydrochloric acid forms a colouriess hydrochloride crystallising in needles and sparingly soluble. IV. Corwersion of D i n i t r o d w y lic Acid i n t o E t h y l Quinonetetracar-b oxy 1 ate.(1.) Diniti.o~yro?nelZitic A c i d C,(NO,)?( COOH),*.-The oxidation of the three methyl side-chains in dinitrodurylic acid to carboxyl was carried out by means of potassium permanganate and gave an almost quantitative yield. 20 grams of dinitrodurylic acid (dried a t 100') and 50 gr:i.ms of anhydrous potassic carbonate were dissolved in 2 litres of water and heated on a water-bath. To this a solution of 72 grams of potassic permanganate was slowly added. A t first oxidation takes place rapidly, but towards the end very slowly and is finished after four or five days. The manganese dioxide formed was filtered off and the filtrate concentrated. After acidifying with concentrated hydrochloric acid and dilute sulphuric acid the solution was extracted four times with ether ; on distilling off the ether a white mass remained behind con-sisting of a mixture of the tribasic and the tetrabasic acid.After many trials the following method of separation was found to be exceedingly sharp. The mixture was dissolved in water and heated * The direct nitration of pyromellific acid seems to be impossible. This acid can be heated with a mixture of concentrated sulphuric acid and potassic nitrate for 10 hours in a sealed tube at 150" without the slightest change. The application of Burkhardt's method by which as is well known terephthalic acid has been nitrated (Beviehie 10 145) was in this case entirtlj fruitless 440 NEE' CARBOXTL-D ERIVATIVES O F BENZOQUISONE. on a water-bath with finely pulverised marble until the reaction WRS neutral and alcohol (about 2 volumes) was then added to the concentrated filtrate until no further precipitation took place.In this way the calcium salt of the tetrabasic acid is precipitated com-pletely in pale-yellow needles while the calcium salt of the tribasic acid remains in solution and in fact cannot be precipitated at all by addition of more alcohol. The tribasic acid was then converted into the tetrabasic acid by renewed treatment with potassic permanganate. The l a s t methyl-group in the tribasic acid is attacked by oxidising agents with great difficulty so that it takes from four to five days to oxidise 10 grams. The yield was excellent; 20 grams of dinitro-durylic acid gave from 20 to 23 grams of pure anhydrous dinitro-pyromellittic acid.The abovementioned calcium salt of dinitropyromellitic acid was purified by dissolving it in water and precipitating by addition of alcohol. It crystallises in pale-yellow needles. When heated in an air-bath a t 180" it loses its wat'er of crystallisation and becomes deep golden-yellow. I. 0-1260 gram salt dried a t 180" gave 0.0802 gram CaS04. 11. 0.1602 ,? 9 , 0.1022 , 9 , Found. Calculated for (--A- 7 c (NO,) 2 (CO 0) 4Caz. I. 11. Ca 19.05 18-73 18.i6 To obtain the acid the purified calcium salt was dissolved i n water, and the strongly acidified solution extracted three or four times with pure ether. On distilling off the ether and drying at loo" pure dinitropyromellitic acid is left. The acid is colourless has a very strong acid smell and decomposes marble in the cold with violent evolution of carbonic anhydride.It crystallises from ether or water in long silky needles. It is easily soluble in cold water still more so in hot water and deliquesces in ether vapour. It is also readily soluble in alcohol and acetic acid but insoluble in chloroform benzene, and light petroleum. With the exception of the silver lead and barium salts the salts of this acid are easily soluble in water and most of them are precipitated from their aqueous solutions by alcohol. The barium salt is easily soluble in hot water much less so in cold water. A separation of the tribasic and tetrabasic acids can also be accomplished by means of their barium salts as the salt of the tribasic acid is much more easily soluble.When heated in a capillary tube dinitropyromellitic acid loses water (100-160") and becomes slightly yellow. Above 160° i NEF CARBOXYL-DERIVATIVES OF BENZOQUINONE. 441 becomes gradually deeper and deeper yellow and decomposes with violent evolution of gas between 208" and 225" according as the tem-perature rises slowly or quickly. If heated in an air-bath at 140" for several hours the acid decomposes and is converted into a deep-yellow substance. When dried at loo" the acid is colocrless and anhydrous as was deduced from the precipitation and analysis of the silver salt. I. 10.2 grams acid gave 22.5 grams silver salt. Calculated 22.88 , 9 7 11. 21.3 grams acid gave 47% 9 7 7 , Calculated 47.77 , 7 , The silver salt was prepared by adding a neutral solution of the ammonium salt of the acid to a hot solution of silver nitrate.It forms a stable amorphous yellow precipitate quite insoluble in water For analysis it was dried at loo" and as it explodes on heat-ing it was carefully mixed with the copper oxide. I. 0.3954 gram substance gave 0.2278 gram CO and 0.0210 H,O. II. 0.4115 gram substance gave 0.2340 gram GO2 and 0.0120 H20. 0.223 gram substance gave 0.1650 gram AgCl or 0.1242 Ag. 0.5668 gram substance gave 18.75 C.C. nitrogen at 7" and i14 mm. Found. Calculated for (----C6 (NO,),(COOAd 4 I. 11. Ag 55.96 55.70 -C 15.55 15-71 15-51 H - 0.59 0.52 N 3-63 3.73 -It is not possible to convert dinitropyromellitic acid into the noymal ethereal salt by the ordinary methods An alcoholic solution saturated with gaseous hydrogen chloride and allowed to stand for two days did not yield it and the acid heated with alcohol and a few drops of concentrated sulphuric acid for two days on a water-bath remained in great part unchanged.With reducing agents the acid shows a very characteristic reaction ; all reducing agents whether applied in neutral acid or alkaline solu-tion produce a deep red coloration. Ether extracts from acid soluiions a red substance ; the deep red ethereal solution has a very m-arked yellowish-red fluorescence. The red substance remains unchanged even when heated wit'h reducing agents for a long time; it is un-doubtedly as will be seen below from results obtained with the ethereal salt free diamidopyromellitic acid.The reduction takes a VOL. LIII. '2 I 442 NEF CARBOXPL-DERIVATIVES OF BENZOQUINONE. different course when granulated zinc and dilute sulphuric acid are used in the cold. In this case a yellow solution is produced from which ether extracts a yellow substance. The yellow ethereal solu-tion has a marked green fluorescence. The tribasic acid methylparadinitrotrimellitic acid, c,(No,),(cH~)(cooH)~, which is obtained along with dinilropyromellitic acid on oxidising dinitrodurylic acid forms a deliquescent calcium salt. With basic lead acetate it gives a fine yellow basic lead salt. The silver salt comes down after long heating with silver nitrate in sparingly soluble yellow plates. The acid itself is easily soluble in hot water ; much less so in cold.It dissolves with the greatest ease in alcohol and ether. It is obtained in long colourless needles by crystallisation from water containing hydrochloric acid. (2.) Ethy 1 DinitropyromeZZitafe C,(NO&( COOC2H5)4.-The ethyl salt of dini tropyromellitic acid was prepared in considerable quantity by treating the silver salt with ethyl iodide. The neutral silver salt can be precipitated quantitatively as follows :-A solution of 20 grams of dinitropyromellitic acid carefully neutralised with ammonium hydrate is added slowly to a warm (50') solution of 50 grams of silver nitrate. The silver salt was dried a t 100" and then allowed to stand over night with ethyl iodide (l$ times the calculated amount) and dry ether ; to complete the reaction t'he mixture was heated for five or six hours on a water-bath.The ethereal solution was now filtered from the silver iodide washed with dilute sodic carbonate and then dried with calcic chloride ; after distilling off the ether the solid ethyl salt, was left suffic.iently pure for farther work. For analysis it was crys-tallised twice from alcohol when it formed long colourless needles melting a t 130". 0.1155 gram substance gave 0.2006 gram GOz and 0.0465 gram Calculated for H20. c6 (N02)2 (C00C!2H5)4- Found. c 47.37 47-38 H . 4.39 4-47 It is easily soluble in benzene chloroform acetic acid and acetone ; less so in ether. By crystallisation from hot alcohol or light petroleum, i t is obtained in beautiful needles. It dissolves in alcoholic ammonia with a fugitive red colour.The yield was seldom over 60 per cent. of the theoretical. (3.) EthyZ Diamidopyromellitate c& NH&( COOC2H8,)4.-Ethyl di NEF CXRBOXYL-DERIVATIVES OF BENZOQUINONE. 443 nitropyromellitate on reduction with zinc-dust and acetic acid gives a beautiful red compound which I long regarded as ethyl azopyro-mellitate. It was found impossible in spite of repeated efforts to reduce this substance further with elimination of the nitrogen. I thought therefore that it might possibly be an inner azo-compound as it sublimes without decomposition like a quinone. I tried to ascertain its molecular weight by means of a vapour-density determination, using Victor Meyer's method but withoutJ success. Nevertheless the analytical figures obtained did not agree sharply ; the hydrogen especially was always too high.Later when I had larger quantities of the substance in my hands and analysed a product purified with especial care I obtained figures agreeing exactly with those required by ethyl diamidopyromellitate. Finally the formation and isolation of a colourless diacetyl-derivative by treating it with acetic anhydride is a convincing proof that the red substance is actually a diarnido-compound. The deep red colour of the diamido-compound is now no longer remarkable as v. Baeyer (Beq 19 430) has recently shown that ethyl paradiamidoterephthalate has the colour of potassic dichro-mate. For reducing ethyl dinitropyromellitate the following method was found most advantageous and gave an almost quantitative yield.The substance was Grst dissolved inacetic acid and to the hot solution a little water and then zinc-dust in small portions at a time were added. When the addition of more zinc-dust no longer produced a violent reaction and the red colour had changed to yellow the solution was filtered hot from the zinc-dust and poured slowly (stirring well) into a dish containing water. The diamido-compound then separated completely in yellow flakes which soon changed to a red crystalline precipitate. For purification the substance was dissolved in ether, washed with dilute sodic carbonate and the ethereal solution dried with calcic chloride was then allowed t o evaporate over sulphuric acid ; the diamido-compound crystallised out in beautiful deep red four-sided prisms.For analysis the large crystals were mechanically picked out and dried at 100". They melted at 134" and sublimed without decomposi-tion and without leaving any residue. When melted and allowed to solidify again the substance has exactly the appearance of sealing-wax. I. 0.1231 gram substance gave 0.2447 gram GO and 0.0675 gram 11. 0.1774 gram substance gave 0.3554 gram CO and 0.1044 gram HZO. HZO. 2 H 444 111. Dr. NEF CARBOXYL-DERIVATIVES OF BENZOQUINONE. 0.1842 gram substance gave 0.3681 gram COz and 0.1036 gram 0.29'70 gram substance gave 20.3 C.C. nitrogen a t 19" and Found. H,O. 723 mm. Theory for v- 7 C,(NH2)2(COOC2H,) 4' I. 11. 111. c 54-55 54.20 54-64 54.50 H 6.06 6.09 6.54 6.25 N . . 7.47 - - '7.07 Ethyl Diamidopyl.on~ellitate.W. Muthmann examined the above cryst,als of ethyl diamido-pyromellithate in the mineralogical laboratory of P. Groth- in Munich, and reports as follows :-Monoclinic system /3 61" 17'. a b c = 0.66964 1 0.62686. Planes .m = (110) = mP. = (001) = OP; o = (111) = +P. = (010) = wywo; 12 = (110) = my;?. b The majority of the crystals showed only the ci-j-stal faces w c, and b. Found. Calc dated. ( n o ) (iio) = *60° 50' - -(110) (001) = *65 31 - -(010) (in) = *60 55 - -(iio) (111) = 53 39 53" 35' (110) (120) = 19 7 19 10 (010) (001) = 90 3 90 NEF CARBOXYL-DERIVATIVES OF BENZOQUINONE. 445 Colour reddish-orange (Radde's International colour scale). The plane of the optic axes is parallel to the plane of symmetry. One bisectrix lies i n the acute angle of the crystallographic axes and forms with the vertical one an angle of 154".An optical axis comes out very nearly perpendicular to (001). From these data the axial angle is found to be approximately 85-90'. The crystals are very soft and possess a remarkably perfect cleavage in the direction (001). Ethyl diamidopyromellitate has feeble basic properties. On adding to it concentrated hydrochloric acid it becomes colourless ; and on diluting with an equal volume of water and heating the colourless salt dissolves and crystallises out again in needles on cooling. More water decomposes the salt and the free base separates out in beautiful rhombic plates. The diamido-compound dissolves in concentrated sulphuric acid with a pale-yellow colour ; water precipitates the free base again unchanged.The substance dissolves easily in alcohol ether and acetic acid. The ethereal solution is red and shows a very marked yellowish-red fluorescence. On saponification with alcoholic potash and acidifying, ether extracts from the solution a red substance identical with that obtained by the reduction of dinitropyromellitic acid. On treating a hot alcoholic solution of the ethereal salt of the diamido-compound with sulphuric acid (1 H,SOa to 1 of water) and zinc-dust it is easily reduced and on adding water a colourless substance crystallising in needles separates out. This was found to contain no nitrogen and it was therefore supposed to be ethyl pyro-mellitate. A close study however of the substance after v.Baeyer had observed that ethyl paradiamidoterephthalate is converted by reduction into ethyl succinosuccinate has shown that it is identical with ethyl paradiketohexamethylenetetracarboxylate described below. On converting this product into ethyl quinoltetracarboxylate and into ethyl quinonetetracarboxylate the last doubt about the complete identity of the two substances vanished. Ethyl diamidopyromellitate is therefore reduced hy means of zinc-dust and sulphuric acid according to the following reaction :-C I O C2H5OOC*i /\ Y.COOC2H2 C H 5 0 0 C - H 6 'CH.COOC2H5 + H2 + 2E20 = C2H5OOC.C C400C2H5 CZH5OOC.HC CH.COOC2Hh I / \/ c:o \c/ I + 2NH3. NH2 Ethyl paradiketohexmethylene-tetracarboxylate 446 NEF CARBOXYL-DERIVATIVES OF BENZOQUINONE. Oxidising agents such as ferric chloride platinic chloride or sodic nitrite in acid solution do not convert the ethereal salt of the diamido-compound iato the corresponding quinone chromic acid in acetic acid solution as well as potassic dichromate and sulphuric acid decompose it entirely.Concentrated nitric acid however oxidises it to the quinone. (4.) Ethyl Diacetyldiamido~yromellitate.-This was obtained by heating the diamido-compound with excess of acetic anhydride at 140" for four or five hours ; on adding alcohol the new compound was in great part precipitated. After getting rid of the excess of acetic anhydride the substance was purified by crystallisation from alcohol ; it forms colourless lustrous rhombic plates melting at 149". 0.1161 gram substance gave 0.2342 gram CO and 0.0614 gram HZO.Theory for C6(COOC,H,)4(NHAc),. Found. C 55.00 55.01 H 5.83 5.88 The acetyl-derivative dissolves easily in acetone chloroform and in warm alcohol. It cannot be again resolved into its components by treating with sodium hydrate or hydrochloric acid. The same is true of many other acetyl-derivatives of aniido-acids. (5. ) Ethyl QuinonetetracarBoxybte or Ethyl Quinonepyrornel1itate.-On heating ethyl diamidopyromellitate with concentrated nitric acid, or with sulphuric acid and potassic nitrate it is oxidised to the corresponding quinone. The presence of nitrous acid is detrimental, giving rise to oily bye-products. The best yield (50-55 per cent.) was obtained by the following method 5 grams of the substance were dissolved in 40 C.C.pure concentrated nitric acid (sp. gr. 1.4) and allowed to stand in the cold for two hours. The subst,ance dissolves at first with yellow colour and without change ; soon however the solution becomes much darker and the quinone begins to crystallise out i n yellow needles. A slow and constant evolution of gas is noticed after the end of the first hour. It is therefore well to stir from time to time. On pouring into wafer the quinone separates out com-pletely in yellow needies. For analysis it was crystallised twice from alcohol when it was obtained in long yellow needles melting at The results of the analysis agreed with the formula C,O,( CO0CzH5),. 0.1375 gram substance gave 0.2756 gram CO? and 0.0662 gram 148-149". HZO. Theory. Found. c 54.55 54.66 H 5-15 5.3 NEF CARBOXYL-DERJTATIVES OF BENZOQUINONE.447 The substance is of quinone-yellow colonr ; it is odourless ; it sub-limes readily without decomposition and unquestionably belongs to the class of true (para) quinone compounds. It is very stable in the presence of concentrated nitric acid in which it easily dissolves. The solution even when heated a long time undergoes little change and the quinone separates again completely on adding water. It is but little soluble in cold alcohol or ether ; much more so in warm. Hydroxylamine hydrochloride in neutral or acid solution reduces it almost immediately to the quinol compound. It is insoluble in cold potassic hydrate ; on heating gently however it liquefies turns dark-red and then goes into solution.By using the calculated amountl of potassic hydrate it was saponified and strangely enough the product obtained was dihydroxypyromellitic acid. On saponifying in acid solution with acetic acid and concentrated sulphuric acid dihydroxy-pyromellitic acid also was obtained and not as was expected pyro-mellitic-acid-quinone. ( 6 . ) Ethyl Dihlldroxypyromellitate or Ethyl Quinoltetracarboxylate. -On treating ethyl quinonetetracarboxylate with zinc-dust and acetic acid it is reduced with great ease to the corresponding quinol-compound C,(OH)2(COOC2H5)~ [l 4 2 3 5 61. This as will become evident from what follows bas a most remarkable resem-blance in chemical as well as physical properties to Herrmann’s (Annalen 211 327) so-called ethyl quinonedihydrodicarboxylate ; the latter according to recent results obtained by v.Baeyer (Ber. 19, 4281 is to be regarded as ethyl quinolparadicarboxylat,e, C,H,(OH),(COOC,H,)2 [l 4 2 51. Of especial interest moreover is the action of redncing agents on ethyl quinoltetracarboxylate. It is converted in a manner analogous to the conversion of ethyl quinoldicarboxylate t o ethyl succino-succinate-to a hexnmethylene-derivative or hexahydrated derivative o€ benzene-that is from a tertiary t o a secondary bound ring (v. Baeyer ‘‘ Ueber Nomenclatur,” Ber. 19 160). H 0 C I O /\ + H = I I \ / COOC2H5-HC CH-COOCZHS COOC,H,-HC CH*COOCzH, c-; 0 Ethyl quinoltetracarboxylate. Ethyl paradike1;ohexametliylenetetra-The resulting compound ethyl paradiketohexamet hylenente tracar-boxylate (Ber.19 160) has a remarkably deceptive resemblance in all respects to ethyl succinosuccinate. By means of bromine in carbon carboxylate 448 NEF CARBOXYL-DERZVATIVES OF BENZOQUINONE. bisulphide solution it can be reconverted to ethyl quinonetetracar-boxylate. I n order to reduce ethyl quinonetetracarboxylate it is dissolved in acetic acid and zinc-dust added in small portions. The yellow solu-tion immediately become colourless with a beautiful blue fluorescence. On adding water the quinol compound separates out in almost colour-3ess needles having a marked bluish tinge. For purification it is dissolved in acetic acid and precipitated again by addition of water. I. 0.1280 gram substance gave 0.2564 gram CO and 11. 0.1475 gram substance gave 0.2934 gram GO and H,O.HZO. Found. Theory for F--T C6(0H)2(C00C2H5)4* I. 11. 0.0676 gram 0.0752 gram C 54.27 54-62 54-25 H 5-53 5-86 5.66 Ethyl quinoltetracarboxylate crystallises in pale-yellow needles having a bluish tinge. It has no sharp melting point 127-129'. When carefully heated between two watch-glasses it sublimes without decomposition. It dissolves easily in alcohol ether and acetic acid and tlhe solutions show a very marked beautiful blue fluor-esence. On adding a drop of ferric chloride to an alcoholic solution of the substance a bluish-green coloration is produced. I f heated with concentrated nitric acid it dissolves and is oxidised quantitatively to the quinone. It remains unchanged when exposed to an atmosphere of bromine for several days.It dissolves un-changed with yellow colour in dilute sodic hydrate or sodic carbonate. Concentrated sodic hydrate precipitates a deep cin-nabar-red sodium salt which is also obtained on adding sodic ethylate to a dry ethereal solution of the quinone. On heating the sodium hydrate solution hydrolysis takes place and the sparingly soluble sodium salt of dihydroxypyromellitic acid separates out in yellowish prisms, Ethyl quinoneparadicarboxylate also forms a similar coloured sodium salt and gives bluish-green coloration with ferric chloride. The solution of the substance in ether also shows the same marked blue fluorescence. An investigation of the physical properties of ethyl quinoltetra-carboxylate has shown still further the remarkable resemblance existing between these two compounds.The study of the physical properties OF this substance-which certainly is one of the mos NEF CARBOXYL-DERIVATIVES OF BENZOQUINONE. 449 remarkable substances physically in chemistry-was begun during the last Easter vacation in the new chemical crystallographical laboratory of Professor P. Groth. Dr. W. Muthmann reports thereon as follows :-Et hy 1 &&no 1 tetracarboxy late. Modification I. Monoclinic system p = 64" 36'. a b c = 2.3875 1 3.0601. Planes c = (001) = OP. p = (101) = -I&. r = (ioi) = +Pm. nt = (110) = a?. Elongation in the direction of the axis b ; often in thin needles. The base never predominates but always appears as a small plane. Found. Calculated. (110) ( i i o ) %go 45' - -(001) (101) '36 46 - -(001) (TOl) *68 45 - -(110) (101) 68 10 68" 29' (iio) ( i o i ) 73 13 73 27 The plane of the optic axes lies in the plan of symmetry.An optical axis appears very nearly perpendicular to (101) and as a consequence no total reflection is noticeable on this face. In (101) pretty strong dichroism-dark-yellow and light-yellow-noticeable ; this was not perceptible in ( i O l ) , Colour greenish-yellow, Modification 11. Monoclinic system /3 = 81" 53'. a b c = 1.7896 1 3.3206. Planes c = (001) = OP. 0 = (111) = -P. a = (100) = mpm. Of= (111) = +P 450 NEF CARBOXTL-DERIVATIVES OF BENZOQUINONE. Thick plates in direction (001). In many of the crystals the corre-sponding opposite planes were not quite parallel owing to disturbances in their growth.The angles used in the calculation of the axial ratios &c. are the mean of 20-25 angle measurements on eight of the best crystals. (111) (111) (111) (111) (111) (111) (100) (001) (001) (111) (001) ( i n ) (100) (111) (loo) (111; Found. 56" 43' 111 44 117 53 81 57 71 25 78 45 59 40 63 21 2alculatecl. .- -- -81' 53' 71 28 78 55 59 49 63 28 Colour pale-yellow. Dichroism-coloudess and bright-yellow-noticeable in (001). In the summer transparent crystals of the first modification alone were obtained from carbon bisulphide solution. These on heating become turbid and seem to undergo a transformation. The change begins at 111" and is complete at 115". The product then melts on higher heating sharply at 133.2-133-6".In the colder months (April) at a temperature of about -5", crystals of the second modification were obtained side by side with the first modification from a solution in carbon bisulphide. Modifica-tion I1 becomes transformed at 63-5-64' into a different modification. On cooling this does not change back t o the original again. The modification thus obtained at 64" shows a peculiar fusing point. It begins to melt at 123-124" and thereupon a part of the substance becomes solid again a8nd the whole melts entirely at 128.5". On cooling and reheating the same phenomena again appear. Besides these two modifications a third was observed t o crystallise from the carbon bisulphide solution at very low temperatures. The The total reflection in (001) exactly diagonal NEF CARBOXYL-DERIVATIVES OF BENZOQUINONE.451 amount of material on haud has up to the present time been in-sufficient for the closer study of this peculiar modification. The modifications I and I T described are undoubtedly totally different from one another and it is not possible by heating or fusing t o convert either one into the other. There is first of all a remarkable difference in colour I is green; 11 pale-yellow. On fusing and cooling I appears dark-yellow ; 11 bright-yellow. One modification crystallises in needles the other in plates so that it is an easy matter to separate them mechanically. When either modification thus sharply separated is dissolved in carbon bisulphide the mixture of the two modifications side by side like two substances totally dis-tinct from one another is again obtained.I f these are carefully separated mechanically and the operation repeated the same result is invariably obtained showing a mixture of the two modifications side by side. The substance therefore on being dissolved in carbon bisulphide (the same result is obtained on using pure dry ether) must undergo some transformation. The molecules of the substance must either possess a very peculiar tendency to arrange themselves always in two definite states of equilibrium corresponding to the two totally different crystalline forms or what is equally probable certain atoms of the molecule of the substance itself must be in a perpetual unstable equilibrium and the two modifications observed would then corre-spond each t o a different molecular structure.Certain it is the solutions of the two modifications have exactly the same colour. The absorption-spectrum of each modification dissolved in dilute sodium carbonate solution was quantitatively determined for all parts of the spectrum and found in both cases to be exactly the same. The data &c. will be given later in connection with a study of the absorp-tion-spectra of various other closely allied substances. On oxidation with concentrated nitric acid both modifications I and I1 give the same perfectly homogeneous substance the quinone melting sharply at 149" whilst on treatment with zinc-dust and hydrochloric acid in alcoholic solution both give the same colourless and perfectly homo-geneous substance-the diketone compound melting at 144".It is worthy of note that quinol and many other derivatives of quinol or paradihydroxybenzene as well as paradiicmido-deriratives of benzene are dimorphous. It may be noted now that Dr. Muthmann has discovered two entirely distinct modifications of ethyl para-diamidoterephthalate (Ber. 19 430) and measured the crystals bf both forms only one modification has as yet been found of tbe very closely allied ethyl paradiamidopyromellitate. The fact that so many of the paradihydroxy-derivatives of benzene are dimorphous naturally leads one to suspect that this dimorphis 4-52 NEF CARBOXYL-DERIVATIVES OF BENZOQUINONE. may be due to a difference in the molecular constitution of these substances. It might be supposed that one modification corresponds to the real paradihydroxy-derivative of benzene e.g., H 0 C // \.Xc cx (X = H COOC2H5 or any I )I other atom o r group of xc cx atoms). 0 H and that the other modification corresponds t o the pseudo- or ketone form e.g., co I XHC CX atoms). The transference of the hydrogen-atoms to adjacent carbon-atoms which is assumed here is analogous for instance to what takes place in the case of carbostyril isatin pyridone and phloroglucin (Ber. 19, 159). In all these instances t,he chemical behaviour of these sub-stances necessitates the assumption of pseudo-forms or of the migra-tion of the hydrogen-atom to an adjacent carbon- or nitrogen-atom. These compounds however have never been obtained in two different physical modifications.If the dimorphism of the quinol compounds is due to a difference in chemical constitution i t must be possible to prove this by chemical means; the experiments thus far carried out however have been insufficient to settle this question. A short time ago Nietzki and Kehrmann (Ber. 20 613) found that quinol reacts with hydroxylamine giving a compound C6H6N,O2. If the above theory is correct this compound ought to have the formula C,H,N,O (that is contain two more hydrogen-atoms). These experiments were repeated but the analysis of the substance confirmed the formula given by Nietzki and Kehrmann which seems to show that quinol is first oxidised to quinone and then acted on by the hydroxylamine. The study of the action of hydroxylamine on ethyl quinoltetracar NEF CARBOXYL-DERIVATIVES OF BENZOQUINONE.453 boxylate as well as on tetrachloroquinol has n o t as yet given any positive results. Dr. Muthmann and myself have joined to make a combined chemical and physical study of this subject. We have decided to publish here the results thus far obtained because Hantzsch and his pupils (Hantzsch and Zeckendorf Ber. 20 1308 2796; Hantzsch and Hermann Ber. 20 2801) in their study of ethyl quinolparadi-carboxylate and its derivatives have found the same peculiar di-morphism t o exist. Hantzsch has gone further and puts especial stress on the colour of the modifications. If the modification is colourless he says this corresponds to the true paradihydroxy-compound of benzene as all true compounds of benzene must be colourless (?).I f the modifica-tion is coloured it corresponds t o the ketone or quinone form because all ketones or quinones me coloured (?). The question of colour is it seems to us purely arbitrary and does not prove anything whatever. More has hitherto been considered necessary in settling the constitution of a chemical compound. It is very difficult to see for instance why ethyl quinolparadicarb-oxylate which according to Hantzsch is a ketone in its two most stable modifications does not under any circumstances act chemically like a ketone but invariably like a dihydroxy-compound of benzene. Hermann’s argument (Ber. 19 2229 2235) that ethyl quinolpara-dicarboxylate forms isomorphous mixtures with ethyl succinosuccinate seems a much more powerful argument for its ketone form.On the other hand it must be remembered that ethyl succinosuccinate acts like a dihydroxy-compound as well as like a diketone so that it is more logical to conclude that in the isomorphous mixtures the dihydroxy modification of ethyl succinosuccinate is present. (7.) Dihy droxypyyomellitic Acid OT Quinoltetracarboxylic Acid.-On heating ethyl quinoltetracarboxylate with potassic hydrate it is easily saponified ; the product dihydroxypyromellitic acid resembles very closely paradihydroxyterephthalic acid (Awnalen 211 335). 2 grams of the ethereal salt were heated with twice the calcu-lated amount of potassic hydrate (4 grams) on a water-bath ; a dark-yellow solution with a green fluorescence was obtained. After neutralising with acetic acid the lead salt was precipitated by means of lead acetate ; the precipitate was collected carefully washed and then decomposed with sulphuretted hydrogen.After filtering hot from the lead sulphide and concentrating the yellowish solution a pale-yellow substance crystallised out almost completely on cooling in four- and six-sided prisms. The substance purified by recrystal-lisation from water was found nofi to be free from ash. On adding concentrated hydrochloric acid to a hot concentrated solution pur 454 NEF CARBOXYL-DERIVATIVES OF BENZOQUINONE. dihydroxypyromellitic acid separates out slmost completely in pale-yellow broad flat needles. The acid dried on an air-bath a t loo" mas found to contain 1$ mols. H,O. 0.1227 gram substance gave 0.1706 gram CO and 0.0339 gram H,O.Theory for C6(OH)2(COOH)4 -t- 1+H20. Found. C 38.34 37.92 H 2-87 3-07 Heated to a higher temperature (150") the substance not only lost its water of crystallisation but was further changed. Dihydroxypyroineilitic acid dried at 100" is of a pale-yellow colouT and dissolves sparingly in most solvents. The yellow solutions shorn a characteristic green fluorescence. It dissolves easily in hot water and is precipitated therefrom by mineral acids. The aqueous solution is coloured deep blue on the addition of a few drops of ferric chloride. The colour remaiiis unchanged for days even when a great excess of ferric chloride is added. When heated in a test-tube it melts at a very high temperature, losing water and then sublimes without leaving any residue the subli-mate which is probably the dianhydride of the acid crystallising in yellow flat needles.It dissolves in dilute alcohol with yellowish-red colour and reddish-yellow fluorescence. On shaking the solution with air a peculiar violet tinge is noticed on the sides of the test-tube. On standing or more quickly on heating the colonr of the solution changes to the yellow tint and green fluorescence of dihydroxypyro-mellitic acid again. The salts of this acid are yellow and in solution exhibit a characteristic green fluorescence. The silver salt was more closely studied and analysed. It was obtained by adding a solution of the neutral ammonium salt to a neutral solution of silver nitrate in the cold. It separates out as a lemon-yellow flocculent precipitate.When dry it is stable a t ordinary temperature. Heated quickly on platinum foil it explodes; if heated slowly a volatile yellow substance sub-limes. 0.2283 gram substance dried over sulphuric acid in a vacuum gave 0.0562 gram substance gave 0.0338 gram silver. 0-1394 gram CO and 0.0114 gram H,O. Theory for C6(0H)2(C00Ag) 4. Found. C 16.80 16.65 H . . 0.28 0.55 Ag 60.51 60.1 NEF CARBOXYL-DERIVATIVES OF BENZOQUINONE. 455 Lead acetate throws down the lead salt as a light-yellow floccu-lent precipitate ; baric chloride gives the barium salt as a granular, pale-yellow precipitate. The sodiuni salt is especially characteristic. On heating the free acid with sodium hydrate the sodium salt sepa-rates out in pale-yellow prisms which are very sparingly soluble even in boiling sodium hydrate.The oxidation of dihydroxypyromellitic acid to pyromellitic-acid-quinone C60z(COOH)4 presented unexpected difficulties. Con-centrated nitric acid has i n the cold no effect on dihydroxypyro-mellitic acid ; on heating gently however the substance dissolves with a violent evolution of carbonic anhydride and as it would seem is completely decomposed. When heated gently with a solution of chromic acid a violent evolution of gas is noticed. Potassium permanganate oxidises the acid in neutral or acid solution in the cold but although as much as three times the calculated amount of the oxidising agent was used much unchanged dihydroxypyromellitic acid was the only product obtained. A solution of the acid allowed to stand in the cold for days with a great excess of ferric chloride retained the beautiful blue coloration unchanged and much unchanged acid was found t o be present.It may he mentioned here again that ethyl quinonetetracarboxylate on hydrolysis in acid or in alkaline solution invariably gives dihydroxypyromellitic acid and not the quinone. A similar resistance towards the formation of the qninone from a paradioxy-compound was observed in the case of paradihydroxy-benzoic acid C,H,( OH),*COOH and its ethyl salt. Repeated attempts were made to oxidise these substances to quinones varying the con-ditions in every conceivable way. Paradihydroxybenzoic acid was found to evolve carbonic anhydride even on heating gently with such a mild oxidising agent as ferric chloride.Ethyl paradihydroxy-benzoate when treated with oxidising agents either remained un-changed or was entirely decomposed. Similar negative results were obtained by Brunner (Monats. Chenh., 1881 464) in the case of toluquinolcarboxylic acid, C,Hz( CH j (OH) 2C OOH, and its ethyl salt. Hantzsch and Loewy (Bey. 19 26) could not convert ethyl quinol-paradicarboxylate into the corresponding quinoneterephthalate, although they succeeded in obtaining mother oxidat;ion product. (8.) Etli y 1 Paradiketohexamethy lenetetra cai-boa y late.-The conversion of ethyl quinoltetetracarboxylate into a derivative of hexahydroben-zene or hexamethylene-that is from a tertiary t o a secondary chain of six carbon-atoms-can readily be accomplished by v.Baeyer’ 456 NEF CARBOXYL-DERIVATIVES OF BENZOQUINOXE. method (Bey. 19 432). To a very concentrated hot alcoholic solu-tion of the substance (2 grams) zinc-dust (10 grams) was added and then concentrated hydrochloric acid. The change takes place almost instantly and quantitatively. On adding water to the filtrate a colourless substance separates out in needles this when purified by dissolving in a little alcohol and precipitating with water was ob-tained in long colourless needles. The substance contains water of crystallisation and melts therein at 94". Heated in an air-bath at 110" it loses its water of crystallisa-tion and a hard granular mass remains fusing a t 144". 0.1312 gram substance dried a t 110" gare 0.2500 gram CO and 0.0720 gram H,O.Theory for C1sH24010. Found. C 54-09 53.84 H . . 6-00 6.10 The anhydrous substance is very sparingly soluble in alcohol ether, and carbon bisulphide. It separates from hot carbon bisulphide solu-tion in beautiful colourless needles. The solutions show a very faint but distinct blue fluorescence. The substance containing water of crystallisation on the other hand is easily soluble in alcohol and ether. On adding sodium ethylate to a dry ethereal solution of the di-ketone compound a colourless salt separates out at first but on adding more sodium ethylate this changes to a rose-coloured salt. Ethyl succinosuccinate gives exactly the same reaction. Potassic hydrate colours the substance yellow ; on diluting with water it dissolves forming a yellow solution from which the substance is precipitated unchanged on the addition of an acid.A drop of ferric chloride added to an alcoholic solution produces a cherry-red coloration. By treatment with bromine in carbon bisul-phide solution the substance is reconverted quantitatively into ethyl quinolt e tracarbox yl ate. That the compound has free ketone-groups is proved by the ease with which it reacts with phenylhydrazine hydroxylamine and am-monic acetate. Heated over a flame with ammonic acetate a yellow substance is obtained which dissolves in ether with a marked green fluorescence. It contains nitrogen and melts between 115" and 120". It is not however converted by treatment with bromine and concen-trated sulphuric acid into ethyl diamidopyromellitate as might be expected from a di-imido-derivative (Rer.19 429). On further treatment with ammonic acetate products melting a t higher tempera-tures (180-200") were obtained ; these also could not be converte NEF 0-AHBOXYL-DERIVATIVES O F BESZOQUISOSE. 457 irito ethyl diamidopyromellitate. It was therefore considered pro-bable that the ethylated carboxyl-groups as well as the ketone-groups, were attacked by the ammonic acetate. On heating an alcoholic solution of ethyl paradiketohexamethylene-tetracarboxylate with phenylhydrazine (twice the calculated amount) for 10 hours a t a temperature of 110-120" in small amount a sub-stance crystallising in red needles is formed ; as it is quite insoluble in alcohol it is readily obtained pure. The chief products of the reac-tion are soluble in alcohol and form a red granular mixture ; want, of material has thus far prevented me from obtaining them in quantity sufficient to purify them for analysis.The red product insoluble in alcohol shows all the properties of dip heiiy ldi pyrrazohexahy drobenzene (Bey. 17,55 1,205 5) a compound which Knorr obtained by the action of phenylhydrazine on ethjl succinosuccinate. It dissolves in alkalis with purple-red colour ; also in concentrated mineral acids but is precipitated in yellow flakes on the addition of waker. On treatment with sodium nitrite in acetic acid solution a blue insoluble dye is formed. The same blue compound is produced on adding sodium nitrite to an alkaline solution and then acidifying with dilute sulphuric acid. The above facts suffice to show the very great resembIaiice between ethyl paradiketohexamethylenetetracarboxylate and eChyl succinosucci-nnte.This is not surprising when one reflects that the former com-pound is simply the ethereal salt of a dicarboxylated derivative of succinosuccinic acid. They all contain nitrogen. co co Hzi /\ rH*COOC2H5 COOC,H,.Hd bH.COOC,H, COOC2Hb.HC CH COOC,H,.HC CH*COOC2H5 l l \co/ \/ co Ethyl succinosuccinate. Ethyl paradiketohexamethylene-tetracarboxylate. To show the great resemblance between the derivatives obtained from ethyl succinosuccinate and those obtained from ethyl diamido-pyromellitate the following tables (pp. 458 459) are added showing the chief reactions of tjhe difFerenh compounds. The experiments on durylic-acid-quinone and pyromellitic-acid-quinone will be continued.VOL. LIII. 2 Name. I---- I--I-I- --Properties. I----Ferric chloride. Solutions. J3Eth;l succinosucci-nate Etrhyl psrarliketohexa-methylenetetracarb-oxylate Sodium ethylate. colourless needles, m. p. 126-127" -_---coloudess needles, in. p. 144' faint blue fluores-cence cherry - red coloration colourless, then rose-coloured salt, - -colourless, t,hen rose-coloured salt fa.int bluc 5uores-cence cherry - red colorat ion Name. Ethyl pamdihydroxy-tvrephthalate Properties. -----______:_____-Par:diliytlrox;r tere- yellow plates plithalic acid - ~ - -marked blue fluor-escence -___.--yellowish - green, with green fluor-escence ---yellow with green fluorescence - - ~ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Dihydroxypyromellitic light-yellow flat nee-acid 1 dles bluish-green coloration intense blue coloration intense blue co I oration Ferric chloIide. Solut,ions. rnellitate --_________ marked blue fluor- ~ bluisli-green escence ~ coloration dles m. p. 133.5'; light-yellow plates, m. p. 128'5' Sodium ethylate. deep red-coloured salt -deep red-coloured salt ---Name. Ferric Sodium I chloride. 1 ethylate. solutions. Properties. brown with gold-yellow fiuores-cence -red with yellowish-red fluorescence --------^__-____-Ethyl 'diamidopyro-mellitate fire-red prisms m. p. 134' weak bas

ISSN:0368-1645    

DOI:10.1039/CT8885300428

出版商:RSC    

年代:1888

数据来源: RSC

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460 XXXVI1.-Researches on the Constitution of Azo- and Diazo-derivatives. I I I . Compounds of the Naphthalene @-Series. By RAPHAEL MELDOLA F.R.S. and F. J. EAST Introductory. WHEN diazo-salts are allowed to act on naphthalene-derivatives of the p-series such as &naphthol or 6-naphthylamine azo-compounds are readily formed the pu’,-group generally entering the a- (ortho) posi-tion with respect to the P-substituent. That the displaced hydrogen-atom has a t least in the majority of compounds hitherto investigated, the above-mentioned position is now placed beyond doubt by the work of numerous chemists and there is no occasion to restate the evidence for what is now a generally received view. The azo-compounds of the naphthalene @series which comprise a large pro-portion of the azo-dyes met with in commerce differ however in so many of their properties from the other azo-compounds that it has been lately called in question whet,her tbey belong to the same class of derivatives.Thus the azo-derivatives of a-naphthol show by their phenolic character the undoubted presence of hydroxyl whereas the corresponding p-naphthol-compounds have until recently given no distinct evidence of the presence of the hyciroxyl-group. Similarly with respect to the azo-derivatives of P-naphthylamine it was pointed out by one of the authors four years ago (Trans. 1884 117) that these differed in many ways from the corresponding a-naphthylamine-derivatives a fact which has since received ample corroboration from the researches of Zincke and his pupils.Among the points in which the azo-derivatives of P-naphthylamine differ from the corresponding a-compounds is the difference in the facility with which the two classes of compounds can be diazotised. The P-derivatives in fact appeared a t one time t o have been con-sidered as being incapable of diazotisation and this was especially the case with respect to the compounds obtained by the action of the diazotised nitranilines on P-naphthylamine investigated by one of the authors (see the paper referred to Trans. 1884 116). For the reason just stated i l was supposed that the derivatives in question did not contain an amido-group and a formula was therefore sug-gested for these compounds i n accordance with which they were represented as related to the azimido-compounds of Griess.An analogous view with respect to the azo-6-naphthol-compounds was about the same time put forward by Lieberrnann (Ber. 1883 2858) THE COXSTITUTION OF AZO- AND DIAZO-DERIVATIVES. 4Gl who concluded from the circumstance that benzeneazo-@-naphthol is insoluble in aqueous alkali that these oxyvazo-@-derivatives did not contain hydroxyl. The two formulae thus proposed as alternative to the generally received views were the following :-(4 (4 (PI (B) clOH6<f;:>N*x Cl0H6 < ;g>N*x. Zincke who had previously been investigating the action of phenyl-hydrazine on the naphthaquinones shortly afterwards put forward the view that the oxyazo-@-compounds were constructed on the type of hydrazides (Ber. 1885 3135 ; 1886 1461 ; and 1887 1169).This view of the constitution of the compounds in question appears to be maintained by Zincke (Bey. 1887 2903) and in accordance therewith the formule would be written-0 NH CIOH6/ 1 ClOH8 I \N-NH.X \N.NH.X' The conclusion arrived a t by one of the authors with respect to the absence of the amido-group in the p-naphthylamine azo-compounds was as already stated based upon negative evidence that is the non- diazotisable character of para- and meta-nitrobenzeneazo-p-nnphthylamine. In 1886 however the generality of this conclusion was shaken by the discovery by Niefzki and Go11 (Ber. 1886 1281) that amidoazo-P-naphthalene could be converted into oxyazo-F-naphthalene by means of the diazo-reaction. This fact although strongly suggestive of the presence of NH in the compound in ques-tion could not be taken as it complete proof Rince the reaction may also be interpreted in accordance with the formula proposed by one of the authors o r with that of Zincke.It is in fact not inconceivable that the NH-group and nitrous acid may interact according to either of the equations :-NH 0 ClOH6' I + O:N*OH = C10H/I + Nz -I- HZO. 'N*NH-X \N-NH.X The diazo-salt$s of benzeneazo-P-naphthylamine have however been since isolated by Zincke and Lawson (Bey. 1887 Z896) and it is diE-cult to see how this result can be interpreted in any other way tllan by admitting the presence of an amido-group in the original compound 462 MELDOLA AND EAST THE CONSTITUTION OF It was suggested by one of the authors in 1884 (Chern. News, December 5th) that much light would be thrown on the constitution of these and other azo-compounds by investigating the products of reduction of their acetyl- or alkyl-derivatives.This method has already been extensively applied to the investigation of the constitu-tion of the diazoamido-compounds in the series of papers communi-cated to the Chemical Society by one of the authors in conjunction with Mr. F. W. Streatfeild (Trans. 1886 625 ; 1887 102 and 434 ; B e y . 1886 3239). The investigation of the diazoarnido-alkyl-derivatives is still in progress and much work has yet to be done in this direction as the first result of the application of the method has been the discovery of a new and quite unexpected class of cases of isomerism about which me shall have more to say shortly.I n the meantime the formation of an acetyl-derivative of azirnidotoluene by the action of nitrous acid on acetyl-orthotoluylenedinmine observed by Roessneck (Ber. 1886 1757) shows that the constitution of the azimido-compounds as pointed out by one of the authors (Phil. Ma,g. June 1857 525) is more probably that assigned by Kekul6 and Ladenburg :-This conclusion has been recently confirmed by Niilting and Abt, (Ber. 1887 2999) by the method of alkylation so that another formula, for the azo-derivatives of the naphthalene-&series thus becomes; possible :-With respect to the oxyazo-P-naphthalene-compounds it has been recently shown by Weinberg (Be?-. 1887 31 71) that benzeneazo-/3-napht,hol forms an ethyl-derivative which on reduction furnisheti diamidoethoxpap hthylphenyl -NH,*CJL*CioH,O[ CJ35(P)].NJ&(a).Weinberg justly concludes from this circumstance that the ,B-oxy-azo-compounds contain hydroxyl. While the present research was in progress a paper has appeared in which P. Jacobson (Ber. 1888, 414) gives additional evidence in favour of the older view of the con-stitution of benzeneazo-@naphthol. This summing up of the present position with reference to the con-stitution of the naphthalene-p-azo-compounds will render it evident that the question as to the presence of hydroxyl and amidogen in these derivatives has been practically reopened Sy the expwimental results recentJy obtained. These results must certainIy be regarded as oppose AZO- AKD DIAZO-DERIVATIVES. 463 to the azimido-formula as well as t o the hydrazide-formula of Zinckc.Two years ago further experiments in the direction indicated in 1884 (the method of acetylation and alkylation) were commenced by one of the authors and Mr. F. W. Streatfeild but the work was temporarily interrupted in order to carry on other investigations. The chief con-clusion arrived at in these first experiments was that the compounds obtained by nitriting the nitroazo-derivatives of p-naphthylamine in acetic acid were not as had been at first aupposed nitroso-derivatives, although the products thus formed had neither the characters of the original compounds nor the corresponding oxyazo-compounds nor of diazo-compounds so that it was evident that some distinct reaction had occurred. In order to gain further insight into the course of t8his reaction the research has been recently resumed and at the same time other P-naphthaleneazo-compounds which appeared likely to throw light on the question of the constitution of these derivatives have been comprised in the investigation the results of which we now submit t o the Society.The Action of Nitrous Acid in the Presewe of Acetic Acid on the Azo-conzpounds obtained by the Action of Diaxotised Para- and Meta-nitraniline on 6-naphthylarnine. The first experiments mere made with metanitrobenzeneazo-p-naph-thylamine m. p. 182" (Trans. 1884 116).* The action of nitrous acid on this compound dissolred in glacial acetic acid varies according t o the conditions of the experiment. If the substance is dissolved in a sufficient quantity of acetic acid to keep it in solution in the cold a diazo-compound is first formed when the necessary quan-tity of sodium nitrite is added to the solution.On boiling nitrogen is evolved and on distilling off the acid or on diluting with water, metanitrobenzeneazo-/3-naphthol (Trans. 1885 668) separates out. This compound was identified by its melting point (194") and by the following analyses :-I. 0.1058 gram gave 0.2558 gram CO and 0.0374 gram H,O. 11. 0.2204 , 0.5284 , 77 09753 79 9, 111. 0.2298 ,, IV. 0.0998 , 12 , , 13.3" C. , 749 ,, 27.4c.c. N at 15.5" C. and 759.7 mm. bar. Calculated for Found. - - C . . 65-52 65.93 65.38 H 3-73 3-92 3-79 N 14.33 - 13.92 13-96 - -* In the paper above referred to the melting point is erroneously given as 177' 464 MELDOLA AND EAST THE CONSTITUTION OF In effecting this reaction,it is necessary to use a very large quantity of acetic acid owing to the sparing solubility of the azo-compound in this solvent one part of the nitrobenzeneazo-p-naphthylamine requiring about 140-150 parts of glacial acid to keep it in solution in the cold.The same reaction takes place at once if one-third of this quantity of acid is used and the nitrite is added to the solution raised to just its boiling point. The results obtained on working by either of these methods show that the reaction is in this case quite normal and analogous to the conversion of benzeneazo-/?-napht h y lamine into benzeneazo- {J-naph tho1 (Zincke Ber. 1887 2898). The chief point of interest in connec-tion with the present method of carrying out the reaction is that it takes place in the absence of any strong mineral acid.By repre-senting the free diazo-conipound as the first product the reaction may be regarded as the following :-We may add that the diazo-salts of metanitrobenzeneazo-p-naph-thylamine are extremely unstable and no attempts have as yet been made to isolate them. If instead of working in the manner just described a much smaller quantity of acetic acid is used and the temperature is kept below 70" during the whole operation the reaction takes an entirely different course. Cnder these circumstances nitrogen is given off as before, and a substance crjstallising in beautiful orange-brown scales gradually separates. After purification by crystallisation from acetic acid and then from alcohol this compound was obtained in the form of red filamentous needles melting at 161-162" and giving the following results on analysis :-J.0.1512 gram gave 0.3598 gram COz and 0.0535 gram H,O. 11. 0.1445 , G.3416 , , 0.0530 , ,, 111. 0-1883 ,, The formula deduced from these numbers showed that the sub-staolce was the ncetyl-derivative of metanitrobenzeneazo-&naphthol :-19.1) C.C. N at 11.5" C. and 779.1 mm. bar. Calculated for Found. 7 N2*C,jH,*NO9 (.-.-C10H6<C).C,H,0 ' I. 11. 111. c 64.44 64.89 64-47 -H 3-93 4.07 - 3.85 N 12.53 - - 12.82 The following are the details of the method of performing the re AZO- AKD DIAZO-DERIVATIVES. 465 action :-One part of the nitroazoamido-compound is heated with about 70 parts of glacial acetic acid till completely dissolved and the solution then allowed to cool down to 60-70".The theoretical quantity of sodium nitrite is then added in the solid state in small quantities at a time the Oemperature of the solution not being allowed to rise above 70". The contents of the flask are well shaken after each addition of nitrite and each quantity of the latter is allowed to dissolve before adding more. When all the nitrite has been added the solution is set aside to cool and the crystalline acetyl-derivative can be collected after 6-8 hours. From the foregoing result it will be seen that when metanitro-benzeneazo-/I-naphthylamine is treated with sodium nitrite in the presence of acetic acid under the conditions specified the acetic acid takes part in the reaction :-It is of course possible that an unstable diazo-compound is formed as an intermediate product this compound immediately undergoing decomposition in presence of the acetic acid according to the follow-ing scheme :-/N,.C6H,.NO cIoH,\;N ; ,.;OH! :.-" " ' i H.10 .C,H,O 1.. That the acetyl-derivative has the constitution assigned to it was shown by cohobating the compound with one molecular proportion of potassium hydroxide dissolved in alcohol when the acetyl-group was easily removed and metanitrobenzeneazo-p-naphthol (m. p. 194') was obtained. The yield of acetyl compound is practically quantitative, and as the reaction promises to be widely applicable for the synthesis of phenolic acetates and other ethereal salts it is proposed to extend the investigation in this direction and to make a special study of the conditions which determine the displacement of amidogen by the C,H,O*O-group by means of the diazo-reaction.It will be of interest here to point out the analogy of this reaction to that in which phenolic alkyl-ethers are formed by the action of diazo-salts on alcohol :-(Fittica Ber. 1878 1209; G. Schultz Ber. 1884 and 475; Haller, Ber. 1884 1887 ; Hofmann Ber. 1884 1917 ; Wroblewsky Ber. 466 JIELDOLA AND EAST THE COSSTITUTIOS OF 1884 2703; Remsen Bey. 1885 65; and Amer. Chern. J. 8 243 and 9 387). Paranitro benzeneazo-P-naphthylamine (Trans. 1883,430) undergoes a similar decomposition when treated with sodium nitrite in the presence of acetic acid.One part of the nitroazo-compound was dissolved in 140-150 parts of the glacial acid and the necessary quanity of sodium nitrite added to the solution the temperature of the latter not being allowed to rise above 70". Paranitrobenzeneazo-/3-naphthgl acetate crystallises out on cooling in beautiful red flat-tened needles having a slight violet reflexion. The melting point is 192-193". After crystallisation from alcohol in which the sub-stance is soluble only with great difficulty it was obtained in the form of flat orange needles having the same melting point. The following analyses were made by Mr. Streatfeild :-I. 0.1484 gram gave 0.3510 gram CO and 0.0523 gram H,O. 11. 0.1988 , , 0.4694 , , 0.0724 9 9 I Calculated for Found. N2.OcH.j *NO2 '1oH6<() .C,H,O * I.11. c 64.44 64.50 64-39 H . 3.85 3-91 4-04 The acetyl-derivative like its metanitro-isomeride is readily de-composed by boiling for a short time with one molecular proportion of potassium hydroxide dissolved in alcohol the acetyl being removed and paranitrobenzeneazo-@naphthol rn. p. 249" (Trans. 1885 662), being formed. Acetylation of Oxyazo-P-Naphthalene Compounds. I n order to ascertain whether acetyl-derivatives could be obtained by direct acetylation as well as by the diazo-reaction with acetic acid, metanitrobenzeneazo-6-naphthol (m. p. 194') was boiled for about 12 hours with acetic anhydride and anhydrous sodium acetate. The product after being washed with water and crystallised from alcohol, proved to be identical with the acetyl-derivative of m.p. 161-162" obtained in the manner described in the foregoing part of this paper. The acetylation of the nitroazo-compound could not be effected in less time than that specified. Benzeneazo-P-naphtli y l acetate.-In order to prepare this compound, benzeneazo-P-naphthol was boiled with acetic anhydride and dry sodium acetate for 24 hours the acetylation not being completed in less time. The product after being washed with water and crystal-lised two or three times from alcohol was obtained in the form o AZO- Ah'D DIAZO-DERIVATIVES. 467 deep orange-coloured scales melting at 117". numbers on combustion :-It gave the following 0.1520 gram gave 0.4130 gram CO and 0.0679 gram H,O. 0.2463 , , 20 C.C. N at 14.5" and 772.4 mm. bar. Calculated for NO'C6H5 '10I16 < 0:C2H30' Found.C . 74-48 74.1 6 H . 4-82 4.93 N . 9.65 9-68 It follows from these results that the azo-derivatkes of p-naphthol contain one atom of hydrogen capable of being displaced by acetyl, and the experiments of Weinberg already referred to have show-n that these compounds are also capable of being ethylated. I n order to clear up the constitution of these derivatives i t is only necessary to ascertain whether the acetyl- or alkyl-group is attached to oxygen or nitrogen that is to find out whether the displaced hydrogen-atom is imidic or hydroxylic. That the latter is the case is shown by the conversion of metanitrobenzeneazo-p-naphthylamine into metanitro-benzeneazo-/I-naphthyl acetate by means of the diazo-reaction with acetic acid as described in the present paper.This acetate is identical with that produced by the direct acetylation of netanitro-benzeneazo-&naphthol and is converted into the latter by hydrolysis. We have not yet succeeded in converting benzeneazo-P-naphthyl-amine into benzeneazo-/3-naphthyl acetate by the diazo-reaction with acetic acid,* but since Zincke has shown that this reaction in the presence of water converts the amido-6-azo-compound into the corre-sponding benzeneazo-@naphthol the chain of evidence is so far com-plete. The direct proof of the Constitution of these P-azo-derivatives of naphthalene will however be only forthcoming when the products of complete reduction have been studied. We have already made a large number of experiments in this direction but have met with so many practical difficulties that we prefer to withhold the results for the present. We may state in conclusion that the whole of the evidence thus far obtained points distinctly to the existence of hydroxyl and amidogen respectively in the p-oxyazo- and /I-amidoazo-compour,ds of naphthalene but we refrain from offering any opinion upon the constitution of these derivatives until more experimental evidence has been obtained. Finsbury Technical College, .March loth 1888. * Acetic anhydride cannot be used in this reaction as it acts so energetically on benzeneazo-,8-naphthylamine that complete decomposition with the formation of resinoue products takes place

ISSN:0368-1645    

DOI:10.1039/CT8885300460

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年代:1888

数据来源: RSC

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X x x v I r r . - CONTRIBUTIONS FROM THE LABORATORY O F GONVILLE AND CAIUS COLLEGE CAMBRIDGE. NO. XII.-The action of j n e l y divided metals on solutions of Fer& Salts and a rapid method for the titration of the latter. By DOUGLAS J. CARNEGIE B.A. Demonstrator in Chemistry Gonville and Caius College. 1. I T is universally admitted in text-books that of existing methods for converting ferric salts into ferrous salts prior to titration with potassium permanganate the safest and best though by far the slowest method is to boil the acidified ferric solution with zinc in an inert atmosphere. The more rapid methods (excluding the stannous chloride method, which is not applicable if permanganate titration be employed) are hampered by the facts that in their employment it is difficult to deter-mine the point of exact reduction and excess of the reducing agent is as fatal as defect.It seemed to me that the safest method might be so modified as a t the same time to make it a rapid one by increasing the effective surface of the zinc through the employment of zinc-dust in the place of the usual granulated zinc. While experimenting in this direction I found that zinc-dust instantly reduces ferric to ferrous salt and this even in 7ieutraZ solufions. At the same time if the solction is neutral iron is precipitated partly as ferrous partly as ferric hydroxide. I n acid solutions no iron is precipitated but the reduction is less rapid the more free acid there is present. In every case zinc goes into soh-tion. 2. Very rapid and accurate estimations of ferric solutions are realised by the following method :-The bottom of a dry and narrow beaker is covered with zinc-dust, which has been sifted through fine muslin.A known volume of ferric solution previously nearly neu tralised by ammonia is now delivered into the beaker and shaken briskly with the zinc-dust. Finally a known volume of dilute sulphuric acid is added and the contents of the beaker are once more shaken. It is essential for rapid reduction that the above order be observed ; the nearly neutral ferric solution must Jirst be added to the zinc then the acid. I n order to withdraw for titration a definite volume of the ferrous solution free from particles of undissolved zinc I make use of the " reversed filter," figured in which n is a glass tube ; c miislin ; d filter-paper, held in position by an india-rubber ring b.When this filter i CARNEGIE THE ACTION OF FINELY DIVIDED METALS. 469 25 C.C. of an acidulated ferric chloride solution reduced by iron-free magne-Fium required 15.3 C.C. of a decinormal permanganate solution. immersed in the beaker the clear ferrous solution rises in it to the same level as the liquidin the beaker and may then be withdrawn by 25 C.C. of same solution reduced as above required 15.2 C.C. of same perman-ganate solution 470 CARNEGIE THS ASTPON OF FINELY DIVIDED METALS tried the action of the volatilised zinc crystals on ferric chloride. Their reducing power was unimpaired ; hence I had to seek for a new explanation. It is well known that ferric chloride in aqueous solution is in a state of partial dissociation as is roughly represented in the equation-Fe2C1 + (n + 3)H20 Z (Fe,,O,nH,O) + FeaCl + 6HC1.It might be urged that on adding zinc-dust to such a system the hydrochloric acid would be removed from the sphere of action with formation of zinc chloride and hydrogen and that the nascent hydrogen would reduce the ferric chloride existing as such while the soluble hydrated iron oxide might in virtue of this upsetting of the mobile equilibrium be simultaneously transformed into an insoluble hydrated form. According to this explanation it would follow that more iron hydroxide would be precipitated the higher the temperature at which reduc t'ion takes place €or the dissociation of ferric chloride increases with the temperature.And indeed experiment proved that about twice as much iron is precipitated as insoluble hydroxide when the reduction is effected a t 100" as when it takes place a t ordi-nary temperatures. But according to this explanation one would predict the improbability of reduction i f absolute alcohol were substi-tuted for water as the medium of the change ; whereas experiment shows that even under these conditions reduction readily takes place with great rise of temperature. 4. I am thus driven to the conclusion that the zinc acts merely as a &chlorinating agent much as stannous chloride acts -Fe2C!6 + Zn = ZnC1 + Fe,Cl,, and that the precipitate of iron hydroxides which occurs in neutral solutions is partly due to .the zinc oxide which is always present in the dust to the extent of about 50 per cent.partly to the zinc hydroxide formed during the reduction by the action of water on the finely divided zinc. Zinc-dust merely effects instantaneously the dechlorinat,ion which I found zinc-foil required several hours to effect. The change represented above is an exothermic one; the heat of formation in aqueous solution of ZnC1 [112,840] is greater than the negative thermal change in the passage from the system Fe2Cl,,Aq to the system FezS14,Aq [55,540]. 5. If this explanation of direct dechlorination be valid it seemed probable that all those metals whose chlorides have a heat of forma-tion in aqueous solution greater than 55,540 gram-units would in the finely-divided state reduce ferric solutions.I have made many experiments in this direction and I find that the following metals i ON SOLUTION3 OF FERRIC SALTS. 47 1 a finely-divided state reduce ferric solutions with varying degrees of rapidity :-iron mercury silver aluminium and copper as well as zinc. Sometimes the metals were employed in the shape of foil [aluminium copper silver] sometimes in the state of fine division in which they are precipitated from boiling alkaline solutions of their formates or from hot solutions of any of their salts by means of zinc-dust followed by repeated digestion with dilute acids suited to the occasion. I n the cases of aluminium and silver it was definitely proved that no precipitation of a salt of iron occurred. This without doubt would be the case with all metals M” where M” + H,O = M”O + H represents an endothermic change.Platinum and gold do not reduce ferric soliitions. Now with the exception of the last two named the heats of formation of the chlorides of all the fore-going metals are greater than 55,540. Nevertheless the rapidity of reduction by a metal- does not appear to be a function of the energy which runs down i n the formation of its chloride thus [AP Cl‘ Aq] = 475,650 whilst [Zn CP Aql = only 112,840; yet zinc reduces instantaneously whilst aluminium reduces the most slowly of all the metals experimented with. But experiment showed it to be undoubtedly the case that those metals reduce the quickest which are the most readily attacked a t ordinary temperatures by dilute chlorine-water. It is of interest to note that galena in a finely-divided state also reduces ferric chloride solution whereas antimony sulphide has not this power.6. From the whole of my experiments I conclude that zinc-dust is practically the best reducing agent for the purpose in hand. True it is that zinc-dust may sometimes contain a little iron and that titra-tion with permanganate cannot be conducted in an acid solution containing zinc but that the latter must be first removed. But in the first place zinc-dust contains so little iron and so slight a solution of zinc takes place before titration by my method that any error arising from this source is negligible. However in the attempt to elaborate a method which would preclude any uncertainty on this point I prepared zinc-dust free from zinc oxide as recom-mended by Sabatier by means of repeated digestion with dilute acid and also by what I found to be a more rapid method viz.by digestion with solutions of ammonium chloride and ammonia in both cases finally drying the product on porous tiles in a vacuum. This purified zinc was shaken up with a standard ferric chloride solution without the addition of any acid; the ferrous solution was filtered off, acidified and titrated; but the iron was not fully accounted for in the filtrate so rapidly does water attack the finely-divided zinc with formation of hydrogen and zinc hydroxide ; the latter precipitating solutions of iron salts in contact with it. I n fact i n solutions o 472 CARNr(:GIE THE ACTION OF FINELY DIVIDED METALS several metallic fialts MgClZ AL(S04)3 Co(NO,), MnS04 &c , finely-divided zinc very soon causes a precipitate either of the hydroxides or of basic salts of the metals present.I n the second place even when the reduction is effected by metals which can easily be obtained absolutely free from iron which are not oxidised by water and which do not evolve hydrogen with dilute acids separation from the finely-divided metal musf always precede titrntion; for even silver and aluminium are attacked i n feebly acid solutions bv permanganate. 7. Mitscherlich ( Z e d . anal. Chem. 2 72) has stated that in the reduction of ferric solutions it is absolutely necessary that the whole of the zinc shmld be dissolved before titration ; the reason adduced being that iron is precipitated on the surface of the zinc and does not dissolve until the last traces of the zinc themselves disappear.If this statement be accurate objection may be taken to my method detailed above ; but I much doubt its accuracy. Experiment showed that the titre of an acidulated iron solution was independent of the time it had remained i n contact with the zinc-dnst. This might be explained iu this special case by supposing the finely divided zinc to be practically enveloped in a protecting layer of hydrogen but other experiments would lead me to believe that such a supposition is unnecessary. Examination of pieces of granulated zinc free from iron removed either before or after complete reduction of both hot and cold ferric solntions always failed to give evidence of iron. Beebe’s method of reducing ferric solutions (Chem.News 53 269) would also be untrust-worthy were Mitscherlich’s statement correct. Wit’hout doubt the zinc in all cases becomes coated with a black deposit which as Rodwell Vogel and others have shown contains in addition to the iron present originally in the impure zinc iself zinc combined with lead sulphur aiid carbon. 8. After the work of which this paper is a short account was finished I casually came across a reference in Fremp’s EmyclopBdie to a paper by Brown on the reduction of ferric compounds b; zinc. I Jiare procured the paper referred to ( I r o n 1878 361) and find that E ~ o w ~ ’ s method consists in reducing iron ores directly by fusion with ~ Z V P T ~ S ~ ~ zinc (Hobson and Sylvester had shown that a t a temperature of 205” zinc becomes so brittle that i t may be powdered in a mortar).Brown has also used this pulverised zinc to reduce ferric salts in acid solutions ; but that his method is founded as is the current one on the reducing action of nascent hydrogen and not on the direct reducing. powers of the zinc is obvious from the following quotation :-“ There should be but a very small excess of sulpburic acid present so that at the end of an hour or fwo only about half the zinc will be dissolved.” Brown is also of opinion that the whole of the zinc must be dis ON SOLUTIONS OF FERRIC SALTS. 4 i 3 solved before titration but he does not state his grounds for that opinion. I prepared some pulverised zinc by Hobson and Sylvester's met.hod, but with three different specimens of zinc. I uniformly found that they did not become brittle at 205" but at higher temperatures and also that it was impossible thus to obtain anything approaching the fice division of zinc-dust. The pulverised zinc obtained reduced neutral ferric solutions but slowly. In conclusion I would express my thanks to Mr. Pattison Muir for the kindly suggestive interest he has taken in the work detailed, VOL. Lcrr

ISSN:0368-1645    

DOI:10.1039/CT8885300468

出版商:RSC    

年代:1888

数据来源: RSC

摘要:

ANNUAL GENERAL MEETING, March 28th 1888. W. Crookes F.R.S. President in the Chair. I n accordance with our bye-laws it be-omes my duty to lay before you the usual Annual Report on the state of the Society duriug the past twelve months. As regards the number of B’ellows I am happy to state t’hat there is no sign of falling off. The following table shows the present state of the Society :-Number of Fellows (March 31st 1887) . 1477 Since elected and paid admission fees 109 1586 Deceased 11 Withdrawn 11 Removed on account of arrears 30 - 52 Present number of Fellows 1534 Increase 57 Deceased (J. B. Boussingault) Newly elected. . 7 Present number of Foreign Fellows . Number of Foreign Members (March 31st, 1887) . 31 1 30 __ -37 Our losses by death which include several well-knon n names are :-Professor C.L. Bloxarn; J. B. Boussingault (foreign member), Patrick Duffy; J. J. Field; A. M. Graham; Dr. T. S. Humpidge; James Millar A. Muter ; H. H. MacMunns; W. B. Ritchie; Dr. Arthur Phillips ; G. €3. Sweeting ; and A. E. Wilson. 11 Fellows have withdrawn :-L. M. Deane ; H. W. Eve ; G F. Dowdeswell; G. Gladstone; Hugh R. Mill; Ed. Pnckard; T. A. ltickard ; B. 31. F. Rogers ; C. A. Stitt ; J. E. Tuit ; and J. C. Wright. The following Fellows have been removed on account of arrears :-TIarry Allen; A. W. Bickerton ; G. B. Barker ; Dr. H. C. Bartlett ; Benjamin Browning; G. E. Basu; C. N. Betts; T. J. Barr; R. L) ANKUXL GEKERAL MEETIKG. 473 Courtney ; Thomas Donnelly ; W. T. H. Elsey ; H. W. Fenner ; Wm, Fox ; Thos.Gibbs ; G. A. George ; Chas. Gillett ; W. E. Heathfield ; E. A. Harris; Edwin Lapper; R T. Matkhews; Alexr. Noble; Arthur Ness; 0. Davies Owen; 3. A. Ogilive; Thos. Palmer; Matthew Percy ; J. Schweitzer ; Sidney Trivick ; Rev W. G. Whittam ; and Wm. Wilson. There are 88 original papers in the Journal this year (1887), occupying 871 pages as against 85 papers of 865 pages last yeai-. The Abstracts this year occupy 1159 pages as against 1088 in 1886. The number of Abstracts is 2277 as against 2164 the average of the five years preceding. 108 Pampers have been communicated to the Society during the session-10 fewer than in the previous session; but if we look through the Proceedings we see that not a few of the papers have been of exceptional interest and value and that a number of im-portant qnestions have been brought forward for discussion during the year.This view is confirmed by the fact that the Trmsac-tious contain a greater number of papers than any previous years. It is again our agreeable duty to make the triennial award of the medal founded by our highly esteemed friend and Fellow Dr. Longstaff. Most gentlemen here present are aware that according to the stipulations of the giver this medal is intended as a mark of recogni-tion of the labours of men engaged in chemical research. Before divulging the name of the distinguished chemist to whom the Council propose the medal this year should be awarded you will I am sure, cordially join with me in congratulating Dr. Longstaff that although so near the eve of his 89th birthday he is still hale and hearty and in expressing the hope that he may long be spared to our Society.The medal this year is conferred on Dr. W. H. Perkin F.R.S. a past President of our Society. Doubtless you are ail aware that Dr. W. H. Perkin has devoted a great portion of his life to an interesting and delicate department of industrial chemistry and that he has gallantly upheld our character for indomitable scientific enterprise. He has now ret<ired from active business but with no intention of resting on his oars. He carries into his private laboratory the same undaunted spirit of inquiry and devotes his well-earned leisure to diligent and difficult research. It is not often that an opportunity such as that which has fallen to DF.Perkin's lot is so fully made use of and that one who has been engaged in industrial pursuits undertakes a research of such magnitude as that of which Dr. Perkin first gave an account to the 2 E 476 ANNUAL GENERAL MEETING. Society in 1884 (Trans. pp. 421-579) and which it is known has since wholly engaged his attention. Dr. Perkin,-I feel it a privilege that to my lot it has fallen to present to you the Longstaff Medal in recognition of your interesting and important researches “ On the Magnetic Rotary Polarisation of Compounds in Relation to their Chemical Constitution.” I hope that further examples of your investigations on this subject are in store for us, and that your example may stimulate us all and especially the younger Fellows of the Society to increased zeal and devotion in the exten-sion of our Science.Our library thanks in great measure to the Library Committee, has had many additions to its shelves during the year. The subjoined table shows the increase. Additions in Present 1887-8. state. Volumes of systematic works. 169 2,780 Volumes of journals . 172 5,119 Pamphlets. 12 1,411 0 Volumes of duplicate journals for cir-cnlation 42 941 -395 10,250 The expenditure under this head for the current year is $129. The following are the titles of the papers which have been com-municated to the Society since April 7th 1887. Papem con,tributed to the Chemical Society between March 30th 1887, and March %th 1888. April 7th. I. “Researches on the Constitution of Azo- and Dinzo-derivn-tives.11. Diazoamido-compounds (continued) :” by R. Meldola F.R.S. and F. W. Streatfeild. 11. “ Conjugated Sulphates and Isomorphous Mixtures of the Copper-magnesium-group :” by P. C. Roy B.Sc. 111. “Suboxide of Silver Ag40:” by G. H. Bailey and G. J. Fowler. IV. “Action of Trimethylene Bromide on the Sodium Corn-pounds of Ethylic Acetoacetate Renzoylacetate Para-nitrobenzo~lacetate and Acetonedicarboxylate :” by W. H. Perkiti Jun. P1i.D ASKUAL GENERAL MEETING. 477 April 21st. V. “The Atomic Weight of Gold :” by T. E. Thorpe F.R.S., and A. P Laurie B.A. VI. “ The Atomic Weight of Silicon :” by T. E. Thorpe F.R.S., and J. W. Young B.A. VII. “Note on Substitution in the Benzene Nucleus :” by H. Foster Morley. VIII ‘& Reply to the Foregoing Note :” by Henry E.Armstrong, F.R.S. May 5th. 1X. “ A Contribution to the Study of Well Water :” by R. Warington F.R.S. X. “Crystals in Basic-Converter Slag:” by J. E. Stead and C. H Ridsdale. XI. “Note on the Influence of Temperature on the Heat of Dissolution of Salts in Water :” by William A. Tilden, D.Sc. F.R.S. XII. “The Distribution of Lead in t,he Brains of two Factory Operatives Dying Suddenly :” by A. Wynter Blyth. XIII. “ Researches on Silicon Compounds and their Derivatives. A New Chloi-ohroniide of Silicon :” by J. Emerson Reynolds M.D. F.R.S. May 19th. XIV. “ The Formation of Hyponitrites :” by W. R. Dunstan and T. S. Dymond. XV. “ Ozone from Pure Oxygen :” by W. A. Shenstone and J. Tudor Cundall. XVI. “The Volumetric Relations of Ozone and Oxygen A Lecture Experiment :” by W.A. Shenstone and 5. Tudor Cnn dall . XVII. ‘‘ The Thermal Phenomena of Neutralisation and their bearing on the Nature of Solution and the Theory of Residual Affinity :” by S. U. Pickering. XVIII. “The Action of Metallic Alkylates on Mixtures of Ethereal Salts and Alcohols :” by T. Purdie Ph.D. B.Sc. June 2nd. Reynolds late R.E. and Professor W. Ramaay. XIX. “ The Equivalent of Zinc ” by Lieut.-Colonel H. C. XX. “ The Magnetic Rotation produced by Chloral Chlora 478 ANNUAL GENERAL MEETING. Hydrate and Hydrated Aldehyde :” by W. H. Perkin, Ph.D. F.R.S. XXI. “ Note on a New Class of Voltaic Combinations in which Oxidisable Metals are replaced by Alterable Solutions :” by C. R. Alder Wright and C.Thompson. XXII. ‘‘ The Composition of Prussian Blue and Turnbull’s Blue :” by Edgar F. Reynolds. XXIII. ‘‘ Phlorizin :” by E. H. Rennie D.Sc. XX1V. “Further Notes on the Chemical Action of Bacterium XXV. ‘‘ Note on the Cellulose formed by Bacterium xyZinurn :” XXVI. “The Oxidation of Ethyl Alcohol in the Presence of aceii :” by Adrian J. Brown. by Adrian J. Brown. Turpentine:” by C. E. Steedman. June 16th. XXVII. “ A Study of the Thermal Properties of a Mixture of Ethyl Alcohol and Ethyl Oxide :” by W. Ramsay Ph.D., and Sydney Young D.Sc. XXVIII. “ Derivatives of Hydrindonaphthene and Tetrahydro-naphthalene :” by W. H. Perkin J u n . Ph.D. XXIX. “ The Synthetical Formation of Closed Carbon-chains in the Aromatic Series :” by F. S. Kipping B.Sc.Ph.D. XXX. “The Product of the Action of Ethylene Bromide on Ethylic Acetosodacetate :” by P. C. Freer Ph.D. and W. El. Perkin Jun. Ph.D. XXXI. “ Derivatives of Pentamethylene :” by H. G. Colnian, B.Sc. and W. H. Perkin Jun. Ph.D. XXXII. “ The Synthesis of Hexamethylene-iieriva]tives :” by P. C. Preer Ph.D. and W. H. Perkin Jun. Ph.D. XXXIII. “ An Attempt to Syuthesise Heptamethylene-deriva-tives :” by P. C. Freer Ph.D. and W. H. Perkin Jun., Ph.D. XXXIV. “ The Composition of Shale-spirit :” by A. K. Miller, Ph.D. and T. Baker B.Sc. XXXV. “ The Magnetic Rotatory Power of the Ethyl Salts of Maleic and Citraconic Acids and their Isomerides :” by W. H. Perkin Ph.D. F.R.S. XXXVI. “ The Temperature at which various Sulphates undergo Decomposition :” by G.H. Bailey D.Sc. XXXVII. “ The Reaction between Sulphites and Nitrites of Metals other than Potabsium :” by Edward Divers M.D., F.R.S. and Tamemasa Haga F.C.S ANNUAL GENERAL MEETING. 479 XXXVIII. " The Action of Acetyl Chloride on Acetoximes :, by Victor Meyer and A. W. Warrington B.Sc. XXXIX. " Sulphinic Compounds of Carbamide and Thiocarb-amide :'7 by George McGowan. XL. " Anacardic Acid :" by Dr. S. Ruhemann and S. Skinner, B.A. Received during the recess and Printed in the Transactions. XLI. " Note on an improved form of Apparatus for the Separa-tion of Iodine Bromine and Chlorine:" by &I. Dechan, F.C.S. XLII. '' Notes on Anhydro-bases. I. Ethenyltriamidonophtha-lene:" by R. Meldola F.R.S. and F. W. Streatfeild F.I.C. XLIII. " Dibenzyl Ether :" by C.W. Lowe. XLIV. " On Aluminium in the Ashes of Flowering Plants :,' by Hikorokuro Yoshida F.C.S. XLV. " Some Ethereal Salts of the Vanadium Acids :,' by John A. Hall. XLVI. " The Compounds of Ethyl Alcohol with Water :" by D. Mendel8eff. XLVII. " Isomeric Change in the Phenol Series. (Second Notice) :" by Arthur R. Ling. XLVIII. " The Effects of Dilution and the Presence of Sodium Salts aud Carbonic Acid on the Titration of Hydroxyl-amine by Iodine :, by Tamemasa Haga. XLIX. " The Action of Light on the Hydrides of the Halogens in Presence of Oxygen " by Arthur Eichardson Ph.D. L. "Note on the Influence of Liquid Water in promoting the Interaction of Hydrogen Chloride and Oxygen on Exposui e to Light :'7 by Henry E. Armstrong F.R.S. LI. '' The Synthetical Formation of Closed Carbon-chains.Part I (cmztiimed). Trimethylenedicarboxylic Acid 7 ' by W. H. Perkin Jun. Ph.D. November 3rd. LTI. " Note on the Atomic Weight of Gold :" by T. E. Thorpe, LIII. "The Int,eraction of Zinc and Sulphuric Acid:" by M. M. LIV. " Note on Safety Taps 7 7 by W. A. Shenstone. LV. " Note on Guthrie's Compound of Amylene with Nitrogen F.R.S. and A. P. Laurie. Pattison Muir and R. H. Adie. Peroxide :' by A. K Miller Ph.D 480 ANNUAL GENERAL MEETING. LVI. “ The Dehydration of Metallic Hydroxides by Heat wit,h Special Reference to the Polymerisation of the Oxides and to the Periodic Law :” by Professor Carnelley D.Sc., and Dr. .James Walker. LVLI. “ The Bromination of Naphthalene p-Sulphonic Acid :” by 0. Stallard.LVIIT. “ The Constitution of the Three Isomeric Pyrocresols :” by W. Bott Ph.D. LIX. “ Preliminary Note on certain Products from Teak :” by R. Romanis. November 17th. LX. ‘‘ Zinc-copper and Tin-copper Alloys :” by A. P. Laurie. LXI. “ The Halogen Substituted Dei-ivatives of Benzoylmalonic LXII. “ Note on a Modification of Traube’s Capillarimeter :” by LXIII. “ The Formation of Hyponitrites a Reply:” by Edward LXIV. “ Reply to the foregoing Note :” by W. R. Dunstan. Acid :” by C. M. Stuart M.A. H. S. Elsworthy. Divers M.D. F.R.S. December 1st. LXV. “ The Alleged Existence of a Second Nitroethane :” by W. R. Dunstan and T. S. Dymond. LXVI. “ An Extension of Mendeleeff’s Theory of Solution to the Discussion of the Electrical Conductivity of Aqueous Solutions :” by Holland Crompton.LXVII. ‘‘ Note on Electrolyti.~ Conduction and on Evidence of a Change in the Constitution of Water:” by Henry E. Armstrong F.R.S. LXVIlI. “ Bismuth Iodide and Bismuth Fluoride :” by B. S. Gott and M. M. Pattison Muir. LXIX. “ The Action of Hydrogen Sulphide on Arsenic Acid :” by B. Brauner Ph.D. and F. TomiGek. LXX. “Note on the Constitution of Mairogallol :” by C. S. S. Webster. December 15th. LXXT. “ An Apparatus for Comparison of Colonr-tint,s :” by LXXII. “ The Alloys of Copper and Antimony and of Copper Alfred W. Stokes. and Tin :” by E. J. Ball Ph.D ANNUAL GENERAL MEETING. 481 LXXIII. “ The Constitution of the so-called mixed dzo-com-pounds :” by Francis R. Japp F.R.S. and Felix Klinge-mann Ph.D. LXXIV.“ The Interpretation of Absorption-spectra :” by G. H. Bailey. LXXV. ’‘ The Rednction of Potassium Dichromate by Oxalic Acid ” by C. H. Rothamley. LXXVI. L L The Reduction of Chlorates by the Zinc-copper Couple:” by C. H. Rothamley and G. R. Thompson. LXXVII. “ Preliminary Notice on the Oxidation of Oxalic Acid by Potassium Dichromate :” by Emil A. Werner. LXXVIII. “ Isomeric Change in the Naphthalene Series. No. 1 :” by Henry E. Armstrong F.R.S. LXXIX. “ Isomeric Change in the Naphtha.lene Series. No. ‘2. Ethoxy naphthalenesulphonic Acid :” by E. G. Amphlett and Henry E. Armstrong F.R.S. No. 3. p - Chloronaphthalenesulphonic Acids :” by Henry E. Armstrong F.R S. and W. P. Wynne. No. 4. oc - Haloidnaphthalenesulphonic Acids :” by Henry E. Armstrong F.R.S.and 8. Williamson. LXXXII. “ The Sulphonation of Naphthalene :” by Henry E. Armstrong F.R.S. and W. P. Wynne. LXXX. “Isomeric Change in the Naphthalene Series. LXXXI. “Isomeric Change in the Naphthalene Series. January 19th 1888. LXXXIII. “ Morindon :” by T. E. Thorpe F.R.S. and W. J. Smith M.B. LXXXIV. (‘ Manganese Trioxide :” by T. F. Thorpe F.R.S., and F. J. H-ambly. LXXXV. “Note on Chatcard’s Process for the Estimation of Small Quantities of Manganese :” by T. E. Thorpe F.R.S., and F. J. Hambly. LXXXVI. “ Contributions to the Theory of the Vitriol-chamber Process :” by G. Lunge Ph.D. February 2nd. LYXXVII. LECTURE. “ The Range of Molecular Forces :” by A. W. Riicker M.A. F.R.S. LXXXVIII. “ A New Method of obtaining Monohydraxides of a-Diketonea :” by F.R. Japp F.R.S, and F. Klingemann, Ph.D 488 ANNUAL GENERAL MEETING. LXXXIX. “ The Formation of Dihydrazides of a-Diketones :” by F. R. Jspp F.R.S. and F. Klingemann Ph.D. XC. ‘‘ The Action of Phenylhydrazine on an Unsaturated yDi-ketone :” by F. R. Japp F.R.S. and G. N. Huntly. XCI. “The supposed Identity of Rutin and Quercitin by E. Schunck Ph.D. F.R.S. XCII. “ The Composition of Bird-lime :” by E. Divers M.D., F.R.S. and M. Kawakita M.E. F.C.S. February 16th. XCIII. “ Chemical Investigation of Wackenrzder’s Solution and Explanation of the Formation of its Constitnents :” by H. Debus Ph.D. F.R.S. XCIV. “ Potilizin’s Law of Mutual Displacement of Chlorine and Bromine:” by T. E. Thorpe F.R.S. and J. W. Rodger. XCV. “ A Gasometric Method of Determining Nitrous Acid :,’ by P.F. Frankland Ph.D. XCVI. “ The Action of some Specific Micro-organisms on Nitric Acid:” by P. F. Frankland Ph.D. XCVII. “ The Action of Phosphorus Pentachloride on Salicyl-aldehyde :” by C. 31. Stuart MA. XCVIII. “ Some Interactions of Nitrogen Chlorophosphuret :” by Ward Couldridge B.A. XCIX. “Action of Alcohols on Ethereal Salts in presence of small quantities of Sodic Alkglate :” by T. Purdie Ph.D., B.Sc. and W. Marshall B.Sc. C. “Note on the Densities of Cerium Sulphide Solutions :” by B. Brauner Ph.D. March 1st. CI. “The Origin of Colour and the Constitution of Colouring CII. “ Researches on Chromorganic Acids. Part 11. Certain Matters :” by H. E. Armstrong F.R.S. Chromoxalates of the Red Series :” by E.A. Werner. March 15th. CIII. “ Note on Benzyldithiourethane :” by A. E. Dixon. CIV. “The Nature of Solutions as elucidated by the Heat evolved on their Dilution. Part I. Calcium Chloride :” by S. U. Pickering ANNUAL GENERAL XIEETING. 483 CV. " The Action of Thiocyanates on Aldehyde Amrnonias :" by CVI. " Carboxy-derivatives of Quinone :" by J. U. Nef. CVTI. " The Action of Acetone on Ammonium Salts of Fatty Acids in presence of Dehydrating Agents :" by S. Ruhe-mann and D. J. Carnegie. CVIII. " A Method of Est,iniating Nitrites either alone or in presence of Nitrates and Chlorides :" by T. Cuthbert Day. A. E. Dixon. The condition of the Journal during the past year as compared with the previous four years is shown in the following table :-General and Physical Chemistry.. Inorganic Chemistry. . Mineralogical Chemistry Organic Chemistry . Physiological Chemistry. Chemistry of Vegetable Physio-logy and Agriculture. . Analytical Chemistry . Technical Chemistry Tota.1 . 1 1883. 205 189 204 739 73 163 195 212 1980 1884. 237 189 192 939 118 324 256 286 254 1 1885. -331 191 201 1047 142 218 337 280 2i47 -1886. 235 223 223 1056 100 160 289 66* -2352 -1887. -271 242 180 1045 100 123 316 - -2277 ~~ Papers in Transactions 63. 57. 85. 85. I now turn to a subject of no small practical importance. the past year the cost o f oiir Journal amounted to the very large sum of 322116. It is to be expected that as the number of Papers offered to the Society multiplies-as it surely will-and as the number of Papers to be abstracted augments the cost will become even greater.Our publication is of such supreme importance to chemical science in this country that the Society is not likely to shrink at necessary expenditure. But I am impelled to refer to a question which ere long must be seriously considered not only by us but by scientific societies generally viz. how far it is desirable that the same Paper should be published in more than one Journal. Our bye-laws only provide that authors shall not be at liberty save by permission of the Council to publish in EqZish papers they have communicated until such Papers, or abstracts of them have either appeared in the Journal of the Society or have been returned to the writer.It must be taken for granted in this time of culture that a paper published in English French or German is thus made known to the 88. During * The Technical Division was discontinued after the April number 1886 484 ANSUAL GENERA4L JIEETISO. entire scientific world and in the case of a Paper published in f u l l in one of these three languages it is unnecessary to give triple repeti-tions ; an abstract of the essential facts observations and conclusions would be all sufficient. Some such curtailment will probably find favour not only as a means of diminishing the cost of publication to individual societies but also because it will put an end t o the grievance undoubtedly felt by subscribers to scientific journals of paying more than once for the same set of facts.With this suggestion I leave the special concerns of the Chemical Society of London’ and turn to the general position of Chemical Science. On occasions like the present not a few of my predecessors have laid before the Society able and instructive surveys of hhe progress of chemical research discovery and invention. For two reasons I find myself debarred from following their example. Of late we have been favoured with such plentiful summaries of advances in every department of Science that I feel unwilling to add to the number lest I might be accused of producing an IZias post Homer urn. And secondly although a great quantity of sound and useful work has indeed been done since our last anniversary yet with two excep-tions-I fear I must say incomplete exceptions-me have not witnessed the dawn of any epoch-making far-reaching discovery which opens out new and tempting prospects of truth.The two exceptions which I have ventured to call partial or incomplete, because they have not yet been fully verified are the researches of Messrs. Kriiss and Nilson on the so-called rare earths and the inves-tigations of Professor Griinwald of Prague. The result reached by Professor Griinwald in his mathematical discussion on certain spectral revelations seems at least to foreshadow the conclusion that hydrogen oxygen carbon and magnesium are not simple bodies but compounds. If the phenomena he records admit of no other explana-tion and if no unexpected source of error is detected we may con-sider ourselves to be within measurable distance of a truly “new chemistry.” B u t here time must decide.Objections already have been raised to the conclusions of Professor Griinwald and we are forewarned we must not allow ourselves to be carried away by our hopes and our sympatliies. To one event I must beg to draw particular attention,-the tardy justice accorded to Mr. J. A. R. Newlands the painstaking discoverer of the periodic law of the Chemical Elements. Of the importance of this law it is utterly needless to enlarge. It has been universally accepted as a most valuable generalisat’ion as the grandest step in theoretica AXXUAL GESEIthL MEETING:. 485 chemistry within the last quarter of a century. Mr. Newlands formulated and published this law in all its main features as early as 1864 and 1865 and was only ridiculed for his pains ; yet four or five years later when Professor MendeGeff announced the same idea it WRS received as an original discovery.Original it was in the sense that Professor MendelBeff was perfectly ignorant of what had been done by Newlands. The strangest thing in this curious history is the fact that in 1882 the Royal Society awarded “ Davy Medals ” to Professors Mendelkeff and Lot har Meyer wholly ignoring the prior claims of Mr. Newlands. By degrees however the truth became known; and the prior claim of Mr. Newlands was admitted in Miller’s Elements in 1878 whilst Dr. Tilden accepted it in his Cheinical Philosophy in 1880 and Dr. Gladstone in his Presi-dential Address to the Chemical Section of the British Association in 1883.Mr. Newlands reprinted his original papers on this subject in 1884 giving the date of each paper. At length in November last, better late than never he received from the Royal Society the well-earned award of the Davy Medal. It would be nnpardonable to over-look the energetic action of Professor Frankland in bringing about the recognition of Mr. Newlands’ claims. He drew up a lucid and compact statement of the case with all the necessary evidence and appended the opinions published and written of many of the most eminent chemists. Now this episode in the history of chemical discovery appears to me to convey a lesson worth noting. We see that it is possible for an important discovery even after full and formal publication to be so thoroughly overlooked and forgotten that when the same idea some years later is evolved by another and independent inquirer i t passes as a striking and novel revelation.Other 0ccupant.s of the chair I now have the honour to fill have of late years discussed the position and prospects of scientific technical, and especially of chemico-technical education. This is doubtless a, most weighty subject. Seeing the multitude of chemical manuals we have produced the schools and colleges and classes we have opened, and in particular the examinations we have instituted we may fairly ask whether our returns of chemical discoveries and inventions are commensurate with all this stir and activity. Our chemical industries, we admit are by no means in n satisfactory position.We know what systems of training prevail in the countries whose competition we have most cause to fear. We are perfectly aware in what respects these systems differ from our own. But I may ask what probability is there after gleaning hints from our rivals that we shall lay aside, or even modify the plans we have taken up and so doggedly follow. I cannot help quoting here the opinion of an eminent writer in th 45 G -4 YXUAL GENERAL MEETISG. Guardian :-“ Aiicl yet man who is so wise and good that he is a1 ways saying. like King Alphonso of Castile ‘ Had we been consulted on t!Je creation of the world we could have arranged things better,’ has invented competitive examination which means suffering and pain for all without even a compensatory ‘survival of the fittest’ or im-provement of the race.’’ I must notice an unsat’isfactory feature in our schools and colleges, to which Mr.Goschen has recently called attention in his inaugural address as Lord Rector of the University of Aberdeen. It is not a flaw in our curriculum or in our methods of teaching but something. more deeply seated and less easily remedied. It is the little intel-lectual interest taken by the students in their studies. MI Goschen tells us of the abusive epithets applied in our schools and colleges to pupils who “ not content with doing their work commit the heinous offence of being absorbed in it.” Now in this country we have scientific men unequalled in the pure, devoted love of truth to whom discovery is its “ own exceeding great reward.” Among the general run of our pupils and students there is, however little of this enthusiastic temper and it is perhaps on this very account that English educationists think it necessary to offer the stimulus of prizes and certificates together with other accessories of the competitive system.But do not all these dei-ices tend in the long run to increase that lack of intellectual interest wliich Mr. Goschen deplores and are they not sorry substitutes for enthusiasm ? In close connection with the point just discussed there is another subject to which attention may usefully be drawn. I mean the degree of public estimation which chemistry a t present enjoys. I n his late Presidential Address delivered before the British Association Sir Henry Roscoe remarked that science was less respected in Britain than in other civilised countries.A variety of facts lead me to suspect that chemistry in this sense is exceptionally unfortunate. For instance, until lately two of thc subjects for the matriculation examination at the University of London were “ Natural Philosophy and Chemistry.” Recently by one of those odd alterations so often made in the cnrri-culum of our institutions of higher education this is changed. The subjects now demanded are-mechanics which is compulsory for all, and at option one of three subjects chemistry or one of two depart-ments into which physics is divided. Thus chemistry is no longer deemed indispensable ! It is to be regretted also that in the course adopted somewhat recently by certain of the licensing bodies of the medical profession with regard to the requirements of preliminary training in natural science the candidate is now no longer required to study these branches in a college or school with recognised facilities for chemica ANNUAL GENERAL MEETIYG.437 or other natural science teaching but may obtain that instruction from any person. At first sight this m9,y appear to be a broad and liberal measure but on reflection it is easy to see how such action on the part of licensing bodies is a direct encouragement of the pernicious system of “ cram.” It is well known t<hat some of our public schools had be m n t o introduce physics and chemistry into their ordinary courses and that other schools were preparing to follow their example.But no incon-siderable check has been given t o this reasonable mwement by certain changes introduced at the Military School of Sandhurst and by others about to be adopted in the school for the Royal Engineers and Artillery at Woolwich. According to the new code whilst as many as 3000 marks each can be earned in Latin French and German and in “ compulsatory ” and “ opt)ional ” mathematics the utmost possible number to be gained in physics and chemistry which rank as “ second class,” is 2000 each! Hence the study of these subjects which are not made compulsory is heavily handicapped. Even youths possess-ing exceptional taste and ability for physical science if they select such subjects must either fail altogether or come out lower in the successful list than if they they had confined themselves to languages and mathematics.Hence physics and chemistry are much more rarely taken up. The public schools which prepare boys for the admission examinations at Sandburst and Woolwich will of course pay less attention t o chemistry and physics, and may not impossibly feel inclined to drop them altogether. AR Nature puts i t :-“ Good work in science pays less well than medio-crity in other subjects. The new regulations lower the standard of school work by constantly withdrawing from the science classes a, large proportion of the best students.” If the new regulations should he introduced at Woolwich as is threatened it will be somewhat farcical to speak of the Engineers and the Artillery as the “ scientific branches ” of the Rervice.Nor does the mischief end here. ELEMENTS AND META-ELEMENTS. Permit me gentlemen now to draw your attention for a short time to a subject which concerns the fundamental principles of chemistry, a subject which may lead us to admit the possible existence of bodies which though neither compounds nor mixtures are not elements in the strictest sense of the word;-bodies which I venture to call “ me ta-elements ” To explain my meaning it is necessary for me to revert to our con-ception of an element. What is the criterion of an element ? Where are we t o draw the line between distinct existence and identity 458 ANNUAL GENERAL MEETING. No one doubts that oxygen sodium chlorine sulphur are separate elements ; and when we come to such groups as chlorine bromine, iodine &c.we still feel no doubt although were degrees of " elemen-ticitg " admissible-and to that we may ultimately have to come-it might be allowed that chlorine approximates much more closely to bromine than to oxygen sodium or sulphur. Again nickel and cobalt are near to each other very near though no one questions their claim t o rank as distinct elements. Still I: cannot help asking what would have been the prevalent opinion among chemists had the respective solutions of these bodies and their compounds presented identical colours instead of colours which, approximately speaking are mutually complementary. Would their distinct nature have even now been recognised ? When we pass further and come to the so-called rare earths the ground is less secure under our feet.Perhaps we may admit scan-dium ytterbium and others of the like sort to elemental rank ; but what are we to say in the case of praseo- and neo-dymium between which there may be said to exist no well-marked chemical difference, their chief claim to separate individuality being slight differences in basicity and crystallising powers though their physical distinctions as shown by spectrum observations are very strongly marked? Even here we may imagine the disposition of the majority of chemists would incline towards the side of leniency so that they would admit these two bodies within the charmed circle. Whether in so doing they would be able to appeal to any broad principle is an open question. If we admit these candidates how in justice are we to exclude the series of elemental bodies or meta-elements made known to us by Rriiss and Nilson ? Here the spectral differences are well marked, whilst my own researches on didymium show also a slight difference in basicity between some a t least of these doubtful bodies.In the same category must be included the numerous separate bodies into which it is probable that yttrium erbium samarium and other '' elements "-commonly so-called-have been and are being split up. Where then are we to draw tho line ? The different groupings shade off so imperceptibly the one into the other that it is impossible to erect a definite boundary between any two adjacent bodies and to say that the body on this side of the line is an element whilst the one on the other side is non-elementary or merely something which simulates or approximates to an element.Wherever an apparently reasonable line might be drawn it would no doubt be easy at once to assign most bodies to their proper side as in all cases of classification the real difficulty comes in when the border-line is approached. Slight chemical differences of course are admitted and up to a certai ANNUAL GENERAL MEETING. 489 point so are well-marked physical differences. What are we to say, however when t'he only chemical difference is an almost imperceptible tendency for the one body-of a couple or of a group-to precipitate before the other P Again there are cases where the chemical differ-ences reach the vanishing point although well-marked physical differences still remain.Here we stumble on a new difficulty in such obscurities what is chemical and what is physical ? Are we not entitled t o call a slight tendency of a nascent amorphous precipitate to fall down in advance of another a " physical difference ?" And may we not call coloured reactions depending on the amount of some particular acid present and varying according to the concentration of the solution and to the solvent employed " chemical differences ?" I do not see how we can deny elementary character t o a body which differs from another by well-marked colonr- or spectrum-reactions, whiht we accord it to another body whose only claim is a very minute difference in basic powers. Having once opened the door wide enough to admit some spectrum differences we have now to enquire how minute a difference qualifies the candidate to pass ? I will give instances from my own experience of some of these doubtful candidates.1. Two closely allied bodies" differ slightly in basic powers and more decidedly also in their spectrum reactions; are they distinct entities ? Probably yes. 2. Two bodies? have no distinct spectimm reaction and differ in basicity so slightly that their separation has hitherto proved to be impossible ; but they differ decidedly in the colour of their oxides. Are they different ? 3. Two bodies1 obtained from different minerals have no recog-nisable chemical difference but there is st strong line in the phos-phorescent spectrum of one which is absent in the other. What are we to say in this case ? 4.An earths separated with enormous difficulty from its associates has a certain very definite phosphorescent spectrum. The addition of another body greatly intensifies one or more of the lines of the spec-trum of the earth so separated while upon the other lines in the I should in this case also say " yes." * Erbium and holmium ; erbium and yttrium ; samarium and didymium &c. t The white and yellow components of cerium (PhiZ. Trans. 176 (1885) 704). $ Yttrium from samarskite gives the S6 line whilst in that from gadolinite this line is absent (Proc. Roy. Soc. 40 (1886) 502-509). The reputed Y a of M. de Marignac contains all the phosphorescent lines of the old yttrium spectrum except the line of 8 6 (P,roc. Roy. SOC. 40 (1886) 236).3 The phosphorescent spectra of yttrium and samarium are modified by the addition of various earths in the way here mentioned. Samarium affects the alumina spectrum in a similar manner (Proc. Roy. Soc. 42 (1887) 111-131). VOL. LIII. 2 490 ANNUAL GENERAL MEETING. spectrum of the same earth it has no action. Is the basis of this earth simple or compound? 5. An earth* showing no difference on fractionation has a phos-phorescent spectrum not materially modified by the admixture of another earth ; but the residual glow of one part of the spectrum as seen in the phosphoroscope is suppressed while that of the other is not affected. Are we not here also dealing with more than one sort of molecule ? 6. Earths,? apparently the same from different minerals behave alike chemically and spectroscopically with the exception that a certain line in the spectrum of the one is a little brighter than the corresponding line in the spectrum of the other.If an immediate decision were required and a poll of the chemists in this room demanded we should probably find the dividing lines placed in all positions among these seven cases. But to have only one rank in the elementary hierarchy t o class these obscure and indefinite bodies in the same rank with silver and chlorine and oxygen and sulphur is as manifest an absurdity as i t would be to put a speck of meteoric dust upon a level with the planet Jupiter because both may be called distinct members of the solar system. Must we either make the elementary examination so stiff that only some 60 or 70 candidates can pass or must we open the examination doors so wide that the number of admissions is limited only by the number of applicants ? The real difficulty we encounter by unlimited multiplication of elements arises from the Periodic theory.That theory has received such abundant verification that we cannot lightly accept any inter-pretation of phenomena which fails to be in accordance with it. But if we suppose the elements reinforced bay a vast number of bodies slightly differing from each other in their properties and forming if I may use the expression aggregations of nebulae where we formerly saw or believed we saw separate stars the periodic arrangement can no longer be definitely grasped. No longer that is if we retain our usual Conception of an element.Let us then modify this conception. For " element " read " elementary such elementary groups taking the place of the old elements in the periodic scheme,-and the difficulty falls away. Again where are we to draw the line? Is there no way out of this perplexity? * Calcium sulphate and many other bodies behave in this manner in the phos-+ Yttrium from different minerals shows great variations of intensities in all its GC appears in greater quantity in samarskite tliari it does in gadolinite phoroscope (Proc. Roy. Soc. 42 (1887) 120). lilies. (Chem. News 54 (1886) 157) ANNUAL GENERAL MEETING. 491 In defining an element let us not take an external boundary but an internal type. Let us say e.g. the smallest ponderable quantity of yttrium is an assemblage of ultimate atoms almost infinitely more like each other than they are to the atoms of any other approximating element.It does not necessarily follow that the atoms shall all be absolutely alike among themselves. The atomic weight which we ascribe to yttrium therefore merely represents a mean value around which the actual weights of the individual atoms of the " element " range within certain limits. But if my conjecture is tenable could we separate atom from atom we should find them varying within narrow limits on each side of the mean. The very process of fractionation implies the existence of such differences in certain bodies. Until lately such bodies passed muster as elements. They had definite properties chemical and physical ; they had recognised atomic weights.If we take a pure dilute solu-tion of such a body yttrium for instance and if we add to i t an excess of strong ammonia we obtain a precipitate which appears per-fectly homogeneous. But if instead we add very dilute ammonia in quantity sufficient only to precipitate one half of the base present we obtain no immediate precipitate. If we stir up the whole thoroughly so as to ensure a uniform mixture of the solution and the ammonia, and set the vessel aside for an hour carefully excluding dust we may still find the liquid clear and bright without any vestige of turbidity, After three or four hours however an opalescence will declare itself, and the next morning a precipitate will have appeared. Now let us ask ourselves what can be the meaning of this pheno-menon ? The quantity of precipitant added was insufficient to throw down more than half the yttria present therefore a process akin to selection has been going on for several hours.The precipitation has evidently not been effected at random those molecules of the base being decom-posed which happened t o come in contact with a corresponding mole-cule of ammonia for we have taken care that the liquids should be uniformly mixed so that one molecule of the original salt would not be more exposed t o decomposition than any other. If further v e consider the time which elapses before the appearance of a precipitate, we cannot avoid coming t o the conclusion that the action which has been going 013 for the first few hours is of a seZective character.The problem is not why a precipitate is produced but wlzat determiiies or directs some atoms to fall down and others to remain in solution. Out of the multitude of atoms present what power is it trhat directs each atom t o choose the proper path ? We may picture t o ourselves some directive force passing the atoms one by one in review selecting one for precipitation and another for solution till all have been adjusted. 2 L 492 ANNUAL GENERAL MEETING. I n order that such a selection can be effected there evidently must be some slight differences between which it is possible to select and this difference almost certainly must be one of basicity so slight as to be imperceptible by any test at present known but susceptible of being nursed and encouraged to a point when the difference can be appre-ciated by ordinary tests.FIG. 1. Let us follow our atoms through another stage of fractionation. The ammonia has divided them into two groups one of which displays just the minutest possible suspicion of greater basicity than the other. Let us repeat the first experiment again with these two groups. Again we obtain from each a precipitate and a solution so that we have now two precipitates and two xolutions. It is evident that whereas the precipitate from the original salt was slightly less basic t,han that which remained dissolved the second precipitate from the first precipitate must have its basic character still further diminished, while at the same time the second solution from the first solution must contain selected atoms of a slightly higher degree of basicity.The least basic at one end and the most basic at the other end are thus two removes each from the original ; and treating them in the same way for a third time we obtain two groups of atoms which are three removes from the centre. (The intermediate groups need not be her ANNUAL GENERAL MEETING. 493 discussed. By systematic rnixings they can be made to contribute their quota to the end groups.) By repeating this operation not once or twice but many hundreds of times those atoms having a tendency t o come down first always going one way and those having a tendency to remain dissolved always going the other way we so to speak, educate the atoms adding to them no fresh properties but drawing out and giving free scope to properties that already existed but that were previously masked.A similar absence of absolute homogeneity may possibly yet be traced in many of the “elements” if once the right reagents are selected and if laborious chemists are to be found willing to devote years to researches barren to outward seeming. That this deviation from absolute homogeneity should mark the constitution of these molecules* or aggregations of matter which we designate elements will perhaps be clearer if we return in imagination to the earliest dawn of our material universe and face to face with the great secret try to consider the processes of elemental evolution. Going back to the “ fire-mist,” the “ ur-stoff ” of the German philo-sophers or the “ protyle,” as after Roger Bacon I have ventured t o call it we see an infinite number of immeasurably small ultimate or rather ultimatissimate particles gradually accreting out of “ formless stuff ,” and moving with inconceivable velocity in all directions.We find those particles which approximately hare the same rate and modes of movement beginning to heap themselves together by virtue of that ill-understood tendency through which like and like come together-that principle by virtue of which identical or approximately identical bodies are found collected in masses in the earth’s crust instead of being uniformly distributed. One of the first results of this massing tendency is the formation of certain nodal points in space between which occur approximately voidintervals.How such nodes and spaces come to be formed we shall be better able to understand by a very few simple illustrations, choosing in the first instance instead of ultimate atoms living men and women. If we take any very frequented street in London say Fleet Street, at a time when the animated current runs pretty equally in two direc-tions and if o u r rate of walking is somewhat greater than the mean speed of the other foot passengers we shall observe that the throngs on the footways are not evenly distributed but consist of knots or groups-we might almost say blocks-with comparatively open inter-vening spaces. The explanation of this unequal agglomeration of * Clerk-Maxwell defines a molecule as “ a material system the parts of which me connected in some definite way.” (“ Atom,” Encyclopcedia Britannica 9th Ed., 3 43.494 ANNUBL QENERAL MEETING. individuals is simple. Some two or three persons whose rate of walk-ing is slower than the average somewhat retard the movements of other persons whether travelling in the same or in the opposite direc-tion. I n this manner a slight temporary obstruction is created, The persons behind catch up to the obstruction and so increase it, while those in front of the obstruction hurrying on unhindered a t their former rate leave a comparatively free and open space until they too find themselves delayed further on by another little group of loiterers. The same process may be observed with vehicles in the carriage-way of much frequented streets. Thus we find that differences in rate of movement ase sufficient to arrange 8 multitude of moving bodies into a series of knots arid gaps.In a crowded thoroughfare like Fleet Street with two opposing human currents much regularity in the sequence of these knots and voids is not to be expected ; but if the observer happens to be walking with a crowd whose constituents are travelling in the same direction, the regularity becomes more apparent ; and if as is sometimes the case, a lit'tle rhythm is infused into the steps by an accompaniment of music, the knots and gaps become so orderly that the distance between one block andanother measured in yards will be found not to differ very greatly from one end of the road to the ot'her. If instead of men and women we experiment with little grains of substances of approximately equal size but differing in specific gravity and mixing them in a horizontal tube with water we set them in movement by rhythmical agitation similar phenomena will occur and the heavy and light powders xi11 sort themselves in a very regular manner.* Descending to a lower degree of minuteness we all know what occurs when an induction current is passed through a rarefied gas.Here the particles being exempt from free will or caprice implicitly obey the law I have attempted to illustrate and out of infinite disorder under the influence of the electric rhythm, sort themselves into beautiful forms of st,ratifications. Let us now return to our ultimate atoms where the case though much more complicated is of the same character.We will suppose certain points in space where the first step in differentiation has been achieved. The ultimate particles have commenced to vibrate in their Jc. " The atoms run like t o like as you may see either in the case of seeds which are being wirnowed in a Fieye or in the case of pebbies on the sea shore; for on account of the whirling of the sieve beans are separated and go with beans barley with barley and wheat with wheat ; and on account of the motion of the waves, the longish pebbles are driven to the same spot as the longish ones and the round with the round."-Democritus in a fragment given in Sextus Math. (vii 116 seq.). '' The Atomic Theory of Luci-etius," by John Mssson. 1884 p. 66 ANNUAL GENERAL MEETING. 495 new born enei'gy in all directions and with velocities ranging from zero to infinity.* The law which we have traced from animated beings and coarse powders down to the molecules of a rarefied gas, still holds good a t this transcendental stage of matter and the imagi-nation can picture knots and voids gradually forming there as well as in Fleet Street.The slower particles will obstruct the quicker the more rapid will rush up to the laggards in front and we shall soon have groups forming in different parts of space. The constituents of each group whose rate of vibration is not in accord with the mean rate of the bulk of the components of that group will work to the outside and be thrown off to find other groups with which they are more in harmony. In time therefore a conditiorr of stability is esta-blished between the various groups and we may call these the mole-cules of our present system of elementary bodies.With regard t,o the place where atoms come into existence it seems to me almost certain that if their existence has had a beginning, it has begun at the very edge of ihe protyle or the confines of the ponderable Universe and that their subsequent migrations have always been inwards. In dynamical language every new position into which an atom can glide must be from a position of higher t o a position of lower potential. If the atom has had a beginning it must therefore have been where the potential is highest Le. on the confines of the ponderable Universe, and if i t comes t,o an end it must be where the potential is lowest Le., in the centre of ovei*grown stars ; so that the extinction of the central part of a star when it becomes overgrown is that which puts R iimit t o the size a star can attain by attracting t o itself surrounding matter.This assigning of the places where chemical atoms have their origin and where they meet with extinction seems the only-or almost the only-conclusion we can yet with confidence advance.? Q Maxwell " Atom," Encyclopczdia Britannica (9th Ed.) 3 40. For this fruitful suggestion and for other valuable criticism and zdvice on parts of this address I am indebted to my friend G. Johnstone Stonep M.A. F.R.S. Mr. G. Johnstone Stoney has given in the Times of April 4th the following explanation of this passage :-"There is nothing more certain in physical science than that if atoms of ponderable matter are generated by any process of nature they will inevitablj thenceforth gravitate inwards towards the rest of the ponderable matter of the universe and that therefore they must have come into existence at a position further out than those through which they subsequently pass.It may further be stated that some at least must have been formed at or beyond the limits now occu-pied by any ponderable matter. And it is also certain that their extinction if it arrives a t all must overtake them in the position of lowest potential which they can reach and that the position of lowest potential is a t the centre of the largest star. " You regard a limit to the universe as having been gratuitously invented for thi 496 ANNUAL GENERAL MEETING, From the above illustrations it will be seen that) the constituent atoms of these molecules originally may not have been gifted with exactly the same speed or amplitude of vibration.I n the molecule of a certain group let the form of energy which has for a factor what we call atomic weight be represented by the figure 35.5 ; it follows, from the foregoing exposition-which I have endeavoured to make clear-that whilst the great bulk of its component ato-ms have this theory. But have you not here overlooked what we are taught by the other sciences which along with chemistry bring us our knowledge of Kature ? The lesson to which astronomy points is that the universe is limited. We know that the stars which constitute our Miiky Way our sun and all the stars we see of a clear night form a detached group.It is certainly possible and the facts that are known about the nebula in Andromeda make it probable that there exist other groups of stars as numerous as we see in the Milky Way and scattered over our sky. The spectroscope indicates that that great nebula consists of stars although their great distance precludes their being seen separately by any telescope and their aggregate brightness is about the same as that of the Milky Way ; in other words they present very much the appearance which our great group of stars would bave if seen from an equal distance. Moreover a star outburst appeared among them as has from time to time happened in our part of the universe. From these facts we may with probability infer that this nebula is a group of stars comparable to our great group.But that there are not an infinite number of such groups seems almost certain. It is a familiar theorem in optics that if stars in unlimited numbers sent us their radia-tions we should have 200,000 times as much light and heat as we actually receive, unless the radiations are absorbed or intercepted on the way to such an extent that only one two-hundred-thousandth part reaches us. This is so improbable that the alternative conclusion that the uniTerse is limited is with some emphasis declared by astronomy. It was not therefore invented for the exigencies of the chcmical hypothesis. Nor is a limited unirerse necessary for the statement madc by Mr. Crookes. Whether limited or not the ponderable universe consists of detached stellar groups that of our Milky Way that of the great nebula in Andromeda and perhaps some others.The vast celestial spaces between these groups are beyond the confines of the universe in the sense required by Mi Crookes’s statement,-they are outside the universe of ponderable matter. “Astronomy again comes to our aid with reference to the locality where atoms may become extinguished. Stars are not of all sizes. There is a distinct limit beyond which they cannot be ascertained to grow. The variety of their dimensions is like that found among the pebbles of a gravelled walk. There are none among them which in comparison are mountain masses or even boulders. There is tliere-fore some cause in nature which puts this limit to their growth. And if chemical elements anywhere meet with extinction this limitation of the size of stars is fully accounted for On dynamical principles the extinction of an atom can only occur when it reaches its position of lowest potential and the position of lowest potential is a t the centre of the greatest star.“ It has always appeared to my mind a great recommendation of the hypothesis that there are processes in nature which convert radiant energy into the energy stored up in ponderable matter that it relieves us from the T-astly greater improbability of the only alternative hypothesis viz. that the entire universe mill become motionless and inert through the equable distribution or complete dissipation of its energy. ANNUAL GENERAL MEETING. 497 atomic weight a small percentage may vary from this figure to the extent of a decimal place while a few others may stray as much as a whole number or two on one side or the other of the mean.The ultimate atoms whose rates are not exactly 35.5 but a little higher or lower than 35.5 will congregate around the 35.5 nucleus forming a group whose average value will be 35.5. In like manner similar groups will be formed having the average rates of 80 and 127 whilst intermediate spaces will be cleared the ultimate atoms which occupied these lone spaces being attracted to the chlorine bromine, and iodine groupings. These groupings represent what at present we call elements but which I conjecture may possibly consist each of an element and of a certain number of meta-elements or each may be formed of a whole group of meta-elements none of which greatly preponderates over the remainder.On the threshold we encounter an objection very clearly stat’ed by Clerk-Maxwell in his Theory of Hea.t (1871). “ I do not think,” says this eminent physicist “ t h a t the perfect identity which we observe between different portions of the same kind of matter can be explained on the statistical principle of the stability of the averages of large numbers of quantities each of which may differ from the mean ; for if of the molecules of some substance such as hydrogen, some were of slightly greater mass than others we have the means of producing a separation between molecules of different masses and in this way we should be able to produce two kinds of hydrogen one of which would be somewhat denser than the other.As this cannot be done we must admit that the quality which we assert to exist be-tween the molecules of hydrogen applies to each individual molecule, and not merely to the average of groups of millions of molecules.” “ The molecules of the same substance are all exactly alike but different from those of other substances. There is not a regular gradation in the mass of molecules from that of hydrogen which is the least of those known t o us to that of bismuth ; but they all fall into a limited number of classes o r species the individuals of each species being exactly similar to each other and no intermediate links are found to connect one species with another by a uniform grada-tion. ’ ’ “ I n the case of molecules however each individual is permanent ; there is no generation o r destruction and no variation or rather no difference between the individuals of each species.” “ Our molecules are unalterable by any of the processes which go on in the present state of things and every individual of each species is of exactly the same magnitude as though they had all been cast in the same mould like bullets and not merely selected and grouped according to their size like small shot.498 ANNUAL GENERAL MEETING. I think it evident that the statements here quoted some of which involve no small amount of assumption no longer accord with facts, for we actually do find variations behween the properties of certain molecules which heretofore had been pronounced identical with each other.It had its definite atomic weight ; it behaved in every respect as a simple body an element to which we might indeed add but from which we can not take away. Yet this yttrium this supposed homogeneous whole on being submitted to a certain method of fractionation is resolved into portions not abso-lutely identical among themselves and exhibiting a gradation of properties. Or take the case of didymium here was a body betraying all the recognised characters of an element. It had been separated with much difficult<y from other bodies which approximated closely to it in their properties and during this crucial process it had undergone very severe treatment and very close scrutiny. I n short until 1atel-y we might have said of it just what Clerk-Maxwell says of hydrogen that the equality which we assert to exist between the molecules of didymium applies to each individual molecule and not merely to the average of groups of millions of molecules.But then came another chemist who treating this assumed homogeneous body by a peculiar process of fractionation resolved it into the two bodies praseodymium and neodymium between which certain distinctions are perceptible. Further we even now have no certainty that neodymium and praseo-dymium are simple bodies. On the contrary they likewise exhibit symptoms of splitting up. Now if one supposed element on proper treatment is thus found to comprise dissimilar molecules we are surely warranted in asking whether similar results might not be obtained in other elements, perhaps in all elements if treated in the right way? We may even ask where the process of sorting-out is to stop? a process which of course presupposes variations between the individual molecules of each species.And in these successive separations we naturally find bodies approaching more and more closely to each other. Dr. Auer von Welsbach the discoverer of neodymium and praseodymium remarks that these bodies “ approximate more closely to each other than any two supposed simple bodies yet known.” Thus we approach nearer and nearer either to a regular gradation in the molecules or to the recognition of those intermediate links which I have named “ meta-elements ” o r elementoicls. A suggestion here occurs that it may be to the presence of these meta-elements that so many of the chemical elements whilst approching closely in their atomic weightts the values required by Prout’s law deviate from it by a small but measurable Take the case of yttrium ANNUAL GENERAL MEETINU.499 amount. We can scarcely regard their approximation as purely accidental. We now come to the last objection pertinently put forth by Clerk-Maxwell to the hypothesis that the elements are not absolutely homogeneous. He writes :-" It is difficult to conceive of selection and elimination of intermediate varieties for where can these elimi-nated molecules have gone to if as we have reason to believe the hydrogen he. of the fixed stars is composed of molecules identical in all respects with our own ? '' I n the first place we may call in question this absolute molecular identity since we have hitherto had no means for coming to a con-clusion save the means furnished by the spectroscope whilst it is admitted that for accurately comparing and discriminating the spectra of two bodies they should be examined under identical states of temperature pressure and all other physical conditions.We have certainly seen in the spectrum of the sun rays which we have not been able to identify. We have supposed the cosmic cycle re-entering in successive periods during a fall of temperature the same region-say for in-stance where chlorine bromine or iodine have been formed. I f most of the atoms present approximate more or less closely to 35.5 80 or 127-the atomic weights of these three bodies-they will be in consequence easily disposed of.But there may be besides a few intermediate atoms having say atomic weights of between 36 and $9 and between 81 and 126. These atoms will be attracted t o the masses onone side o r the other of the cyclical track. We can even imagine spa,rse atoms scattered so far from the centre line of track as to be midway between chlorine and bromine or between bromine and iodine ; these wanderers likewise will be slowly picked up and will gravitate to chlorine bromine or iodine; and being thus accounted for none need be eliminated. It is not impossible moreover that the elementary atoms them-selves are not the same now as when first generated. For if an atom has commenced its existence at a certain epoch and may go through such vicissitudes that it will cease to exist it seems at least probable that i t may undergo inward change.These vicissitudes probably directly affect only the primary motions wbich constitute the existence of the atom but they indirectly and only in a slight degree affect those secondary motions which produce all the effects we can observe-chemical effects heat effects electrical and so on. Thus while the life of an atom may be waning away under the various experiences to which it is subjected it may and probably does appear to us the same as a t first. But perhaps not quite so that atoms originally alike taken from different minerals collected a t widel 500 ANNUAL GENERAL MEETING. separated stations on the earth may have had sufficiently different past histories to have come to be markedly different in regard to the primary motions which elude our observation and through the very slight influence which changes in the primary motions have OLL the secondary motions may be just perceptibly different under our experi-ments.From this point of view a rare element like a rare plant or animal is one which has failed to develop in harmony with its surroundings. This view lends itself very naturally to the facts we encount,er in our fractionation experiments. Where all the ultimate atoms have precisely identical rates of vibration any fractionation is impossible. Where such rates are not identical the process proves successful ; and all the more easily the wider the differences among the vibration-rates of the ultimate atoms. The bodies thus split off necessarily very closely approximate to each other and the further we push our frac-tionations the less marked are the differences.But as we review the series of elements arranged on the curve I adopted from Professor Emerson Reynolds to illustrate my address on the “ Genesis of the Elements ” delivered before the Chemical Section of the British Association (Birmingham Meeting) we cannot fail to be struck by a consideration which a t first sight appears absolutely fatal to the notion of the production of the elements from a series of “ knots,” as just described. I f the element which we call aluminium has been formed from ultimate atoms having rates of vibration of the rate 27 or a little more or less so as to give a niean of 27 and if the atoms between aluminium and the next element in the series have in this manner been sorted out to the one hand or the other leaving a void between we should expect that their properties would not differ very widely from each other or at least that they would present con-siderable analogies.Now to a certain extent trhis is actually the case. Upon aluminium follows silicon. We may perhaps conceive these two elements as springing from the differentiation of a nearly homo-geneous swarm of ultimate atoms. But if we pursue the curve onwaads what elements follow ? Phosphorus sulphur and chlorine, bodies heterologous with each other and heterologous with silicon. We can scarcely imagine original atoms so to speak in doubt whicli of two aggregations they should join the one being silicon and the other phosphorus.Kor can we conceive of anything being split off from sulphur which should make even the slightest approximation to chlorine. It appears to me however that these difficulties are more apparent than real. In the Birmingham Address already referred to I asked my audience to picture the action of two forces on the original protyle one being time accompanied by a lowering of temperature ANXUAL GENERAL MEETING. 501 the other swinging to and fro like a mighty pendulum having periodic cycles of ebb and swell rest and activity being intimately connected with the imponderable matter essence or source of etiergy we call etectricity. Now a simile like this effects its object if it fixes in the mind the particular fact it is intended to emphasize but it must not be expected neccssarily to run parallel with all the facts.Besides the ebb and flow of temperature with the periodic ebb and flow of electricity positive or negative requisite to confer on the newly born elements their particular atomicity it is evident that a third factor must be taken into account. Nature does not act on a flat plane ; she demands space for her cosmogenic operations and if we introduce space as the third factor all appears clear. Instead of a pendulum which though to a certain extent a good illustration is impossible as a fact let us seek some more satisfactory way of representing what I conceive may have taken place. Let us suppose the zigzag diagram not drawn upon a plane but projected in space of three dimensions.What figure can we best select to meeh all the conditions involved ? Many of the facts can be well explained by supposing the projection in space of Professor Emersdn Reynolds's zigzag curve to be a spiral. This figure is however inadmissible inasmuch as the curve has t o pass through a point neutral as to electricity and chemical energy twice in each cycle. A figure of eight or lemniscate will foreshorten into a zigzag just as well as a spiral and it fulfils every condition of the problem. Such a figure will result from three very simple simultaneous motions. First a simple oscillation backwards and forwards (suppose east and west) ; secondly a simple oscillation at right angles to the former (suppose north and south) of half the periodic time i e .twice as fast; and thirdly a motion at right angles to these two (suppose downwards), which in its simplest form would be with unvarying velocity.* If we project this figure in space we find on examination that the points of the curves where chlorine bromine and iodine are formed come close under each other; so also will sulphur selenium and tellurium ; again phosphorus arsenic and antimony and in like manner other series of analogous bodies. It may be asked whether this scheme explains how and why the elements appear in this order ? Let US ima'gine a cyclical translation in space each revolution wituessing the genesis of the group of elements which I previously represented as produced during one complete vibration of the pendulum. Let US suppose tbat one cycle f Put into their simplest mathematical dress the first of these motions is repre-sented by z = a.sin (mt) the second by y = 6. sin (2 mi) and the third by z = c. t. We must therefore adopt some other figure 502 ANNUAL GENERAL MEETING. has thus been completed the centre of the unknown creative force in its mighty journey tbrough space having scattered along its track the primitive atoms the seeds if I may use the expression which presently are to coalesce and develop into the groupings now known as lithium beryllium boron carbon nitrogen oxygen fluorine, sodium magnesium aluminium silicon phosphorus sulphur and chlorine. Were it, strictly confined to the same plane of temperature and time the next elementary groupings to appear would again have been those of lithium and the original cycle would hare been eternally repeated, producing again and again trhe same fourteen elements.The condi-tions however are not quite the same. Space and electricity are as a t first ; but temperature has altered and thus instead of the atoms of lithium being supplemented with atoms in all respects analogous with themselves the atomic groupings which come into being when the second cycle commences form not lithium but its lineal descendant potassium . Suppose therefore the uis generatrix travelling to and fro in cycles along a lemniscate path as above suggested while simul-taneously temperature is declining and time is flowing on (variations which I have endeavoured t o represent by the downward sink) ; each coil of the lemniscate track crosses the same vertical line at lower and lower points.Projected in space the curve shows a central line neutral as far as electricity is concerned and neutral in chemical pro-perties-pobitive electricity on the north negative on the south. Dominant atomicities are governed by the distance east and west from the neutral centre line monatomic elements being one remove it diatomic two removes and so on.* As the mighty focus of creative energy goes round we see i t in successive cycles sowing i n one tract of space seeds of lithium potassium rubidium, and caesium; in another tract chlorine bromine and iodine; in a third sodium copper silver and gold ; in a fourth sulphur selenium, and tellurium ; in a fifth beryllium calcium strontium and barium ; * I n the model curve Fig.2 the elements are supposed to follow one another at equal distances along the lemniscate spiral. The vertical scale is divided into 240 equal parts on which the atomicweights are plotted from H = 1 t o Ur = 239. Each ball representing an element is accurately on a level with its atomic weight on the vertical scale. Metallic elements are silvered ; it will be seen that with one or two exceptions all the metals are on the north side. Missing elements are repre-sented black. A few doubtful elements :-didymium samarium erbium holmium, and thulium,-are inserted in the positions required by the atomic weights nsually assigned to them ; a glance however will show that they have no riglit to the places they occupy. What is most probably the form of track now pursued ? I n every successive coil the same law holds good ANNUAL GENERAL MEETING.503 in a sixth magnesium zinc cadmium and mercury ; in a seventh, phosphorus arsenic antimony and bismuth ; in other tra,cts alnm-FIG. 2. inium gallium indium and thallium ; silicon germanium and tin ; carbon titanium and zirconium ; whilst a natural position near the neutral axis is found for the three groups of elements relegated by Professor Mendelheff to a sort of hospital for incurables-his 8th family. We have now traced the formation of the chemical elements from knots and voids in a primitive formless fluid. We have shown the possibility nay the probability that the atoms are not eternal in existence but share with all other created beings the attributes of decay and death.We have shown from arguments drawn from the chemical laboratory that in matter which has responded to every test of an element there are minute shades of difference which ma 504 ANNUAL GENERAL MEETING. admit of selection. We have seen that the time-honoured distinction between elements and compounds no longer keeps pace with the developments of chemical science but must be modified to include a vast array of intermediate bodies-" meta-element's." We have shown how the objections of Clerk-Maxwell weighty as they are, may be met; and finally we have adduced reasons for believing that primitive matter was formed by the act of a generative force, throwing off at intervals of time atoms endowed with varying quantities of primitive forms of energy.If we may hazard any conjectures as t o the source of energy em-bodied in a chemical atom we may I think premise that the heat radiations propagated outwards through the ether from the ponder-able matter of the universe by some process of nature not yet known t o iis are transformed at the con6nes of the universe into the primary -the essential-motions of chemical atoms which the instant they are formed gravitate inwards and thus restore to the universe the energy which otherwise would be lost to it through radiant heat. If this conjecture be well founded Sir William Thomson's startling prediction of the final decrepitude of the universe through the dissipation of its energy falls to the ground. In this fashion gentlemen it seems to me that the great question of the elements may be provisionally treated.Our slender knowledge of these first mysteries is extending steadily surely though slowly. Whilst certain ardent chemists are testing the commonly received view of the homogeneity of the elements by methods of fractiona#tion, others by means of the spectroscope are carrying on another form of assault; each worker bent on the one idea of undermining the secret. I earnestly recommend such researches. However success-fully pursued they cannot I know lead directly to any results capable of being turned to industrial account. If however we consider the small but firm foothold we have gained in pursuit of this line of investigation I venture to think there is reasonable ground t o hope that these researches may tend to place chemistry upon a new founda-tion by penetrating down through loose superficial matter to the solid rock.The application of tjhe luminous principle of evolution has re-modelled and vivified many branches of biology ; and philosophers are eagerly invoking its aid in other departments of science ; I would fain hope that I may not be deemed unduly sanguine in believing that the application of this regenerating principle t o chemistry will produce far-reaching effects on its harmonious and progressive development. Dr. Gladstone then moved that thanks be given t o the Presiden ANNUAL GENERAL IIIEETIXG. 503 for his address and that he be requested to allow it to be printed. The motion was seconded by Dr. Atkinson and carried with acclama-tion.The President having replied tlhe Treasurer Dr. Russell gave an account of the financial condition of the Society. The receipts by admission fees and subscriptions had been $3158 ; by sale of Journal, $351 11s. I d . ; by dividends on invested capital $317 12s. 9d. ; the whole income being GI896 29. 1.0d. The expenses on account of the Journal had been %?I16 10s. 4d.; on account of the Abstracts of Proceedings 2140 15s. 5d. ; on account of the Library $365 7s. 10d. ; the total expenditure being $3194 Is. 4d. $300 had been invested in Metropolitan Board of Works 3$ per cent. stock and there was a balance in hand of GI672 19s. 3d. Dr. T. Stevenson moved that the thanks of the Society be tendered to the Treasurer for his services during the past session; Mr.J. A. R. Newlands seconded the motion. Dr. Russell acknowledged the vote. A vote of thanks to the auditors was proposed by Professor Ramsay, seconded by Mr. Friswell and acknowledged by Professor Dunstan. My. Heaton proposed a vote of thanks to the Officers and Conncil ; the vote was seconded by Professor Dunstan and acknowledged by Dr. Armstrong. Professor Clowes moved that the thanks of t)he Society be tendered t o the Editors Abstractors and Librarian for their important services during the year. Dr. Plimpton seconded the motion. hlr. Groves and Dr. Thorne replied. Messrs. Heron and Jackson having been appointed scrutators a hallot was taken and as result the following were declared elected as Officers and Council for the ensuing session :-President W.Crookes F.R.S. Vice-Presidents who have-filled the ofice of President Sir F. A. Abel, C.B. D.C.L. F.R.S.; Warren de la Rue D.C.L. P.R.S.; E. Prank-land D.C.L. F.R.S.; J. H. Gilbert Ph.D. F.Rl.S.; J. H. Gladstone, Ph.D. F.R.S.; A. W. Hofrnann D.C.L. F.R.S.; H. Miiller Pli.D., F.R.S.; W. Odling M.B. P.R.S.; W. H. Perkin Ph.D. F.R.S.; Sir Lyon Playfair Ph.D. K.C.B. F.R.S. ; Sir H. E. Roscoe LL.D., P.R.S. ; A. W. Williamson LL.D. F.R.S. Vice-Pcresidents G. Carey Foster F.R.S. ; David Howard ; J. W. Mallet M.D. F.R.S.; H. McLeod P.R.S. ; Ludwig Mond; C. Schor-lemmer Ph.D. F.R.S. Secretaries H. E. Armstrong Ph.D. F.R.S. ; J. Millar Thomson, F.R.S.E. E’oreign Secretary P. R. Japp M.A. Ph.D. F,R.S. Treasurer W. J. Russell Ph.D. F.R.S. TOL.LIII. 2 DR . THE TREASURER IN ACCOUNT WITH THE CHEMICAL SOCIETY FROM MARCH 21. Expenses 071 Account Salary of the Rditor . Salary of the Sub-Editor . Miscellaneous Expenses of Editors Distribuiion of Jouriial . Expenses on Account Salary of Librarian Library Attendant Rooks and Periodicals . Binding Catalogue Cards. Boxes for Printing Authors' Copies . I'roccedings of Royal Society Distrihution of Proceedings of Royal Printing and Distribution of Abstracts Miscellaneous Printing . Post Card Accwnt . Inhabited House Duty and Income-Stationery . Furniture and Repairs Collector's Commission on Subscriptions Treasurer's Stqrnps and Drafts Jvbilee Expenses Address to Queen dilly Fund (+lo) . House Expemes Providing Refreshments .Lighting Fees to Abstractors . Printing of Journal . Heating the Building . Cleaning Petty House Expenses . Wages of House Porter . Balance at Bank March 21st. 1887 . in hands of Treasurer . ,, 25 Life Compositions . 110 Admission Fees 3 Subscriptions for 1884 . 20 , , 1885 . ) 1886 . 3;; : , 1887 715 , , 1888 . 1 ) , 1889 Subscriptions for Proceedings of Royal Society Sate of Journal and Index . . , , from Institute of Chemistry from Society of Public Analysts 1 , ? Chemical industry (for 5 years) Dividends on Consols . Metropolitan Board of Works 3+ pel Cent . Stock London and North Western Railway Debenture Stock ,, ,, Assets . d 8 . d . Balance at Bank 1. 6i2 12 0 Three per Cent . Consols 4. 000 0 0 Lolidoti and North Western Railway Ikhcnture Stock .788 0 0 Metropoliian Board of Works 3+ per cent . Stock . 5. I00 0 0 in hands of Treasurer . 0 7 3 % s . d . 1. 297 3 0 4 7 3 500 0 0 440 0 0 5 0 0 38 0 0 141 0 0 634 0 0 1. 398 0 0 2 0 0 2 s . d 1. 301 10 %. 158 0 ( 351 11 1 38 0 ( 6 5 ( 4 4 ( 21 0 ( 116 10 ( 170 11 C 30 11 I -. 198 3 I Treasurer's Petty Cash Disbursements Balance at Ennli . Purchase of 2300 MetropolitanBoard , in hands of Treasurer . Muarch 24th. 1888 D R. TRKASUREB OF T E E CHEMICAL SOClETY IN A C C O u X WlTH RESEARCB FROM MARCH 21ST 1887 TILL MARCH 21ST, 1887. .S s. d. Mar. 21. Balance at Bank 23’7 5 6 Bug. 9. Subscription from Drapers’ Company 105 0 0 38 per cent. Stock 134 1 6 Dividends on Metropolitan Board of Works Dividend on North British Railway Stock .. 38 14 5 g515 1 5 - . -Assets. d3 s. d . North British Railway 4 pel* cent. Stock . . 1,000 0 0 Metropolitan Board of Works 3 per cent. Stock 4,000 0 0 Balance at Bank 309 11 5 -25,309 11 5 Grants made Stock Purchase of $100 Stock Balance at Audited with vouchers to be correct 1 Narch 24th 1808 508 ANNUAL GENERAL MEETING. Ordinary Members of Co.unciZ Messrs. T. Carnelley D.Sc. ; A. H. Church; Frank Clowes D.Sc.; Wyndliam Dunstan; P. F. Frank-land Pb.l). ; R. J. Friswell; Charles W. Heaton; E. Kinch; H. F. Morley M.A.; R. T. Plimpton Ph.D.; Thomas Purdie B.Sc.; W. Ramsay Ph.D. 0 B I T U A R Y N 0 T 1 C E S. CHARLES LOUDON BLOXAM was born on the 23rd March 1831 a t Meriden IVarwickshire where his father had a medical practice.Dr. Bloxam subsequently came to London and in 1812 his son Charles was sent to King’s College School. Charles Bloxam remained there for two Sears and in 1845 he was entered as one of the earliest students a t the Royal College of Chemistry under Professor Hofmann. His progress under that teacher was very rapid and in 1849 he was appointed Assistant a t the College. After occupying this post for a year he resigned and obtained a considerable private practice as an analyst and teacher at his laboratory in Duke Street Grosvenor Square. During this time in conjunction with Mr. now Sir Frederick Abel he wrote the Handbook. of Chewzistny which was first published in their joint names in the year 1853.Professor Bloxam’s forte however lay in his power as a teacher, and feeling this he became a candidate for the post of Demonstrator of Chemistry in King’s College London when a vacancy occurred in 1854. At that time the Chair was divided Dr. William Allen Miller being Professor of Theoretical Chemistry and Mr. John Bowman of Practical Chemistry. On the death of the latter in 1856 Nr. Bloxam was appointed to conduct t,he classes in Practical Chemistry, and in 1870 on the death of Dr. Miller the Council combined the two chairs appointing Professor Bloxam as the sole occupant. Besides the different posts which Professor Bloxam held in connec-tion with King’s College he was also connected with the Royal Military Academy and the Royal Artillery College Woolwich.He succeeded Sir F. Abel as Lecturer on Chemistry a t the former estab-lishment in 1855 and afterwards held the joint Lecturership of Chemistry and Physics until 1882 and the Lecturership on Chemistry at the Artillery College from 1864 until his death. Professor Bloxam was beyond doubt one of the most successful teachers i n experimental science of his time. The great pains whic AXXUAL GENERAL MEETING. 509 he took in the direction of making his lectures explicit and interesting both by clear reasoning and good experimental illustration left him little time for original research. Although he gave 13 lecturer; a week for nine months of the year for nearly 20 years he almost invariably wrote fresh lecture notes for each course ever attempting to consider the matter in some clearer light and to impart fresh interest to the subjects of his lectures by new experimental illustrations.His text-book Chemistry Inorganic and Organic was first published in 1866 and the sixth edition had just gone through the press when he died. His Laboratory Teaching first appeared in 1869, and Professor Bowman's Practical Chemistry has also been edited through the last six editions. Professor Bloxam was elected a Fellow of the Chemical Society in 1854 and has contributed various papers to the Society chiefly on Mineral and Analytical Chemistry besides publishing numerous smaller communications in the Chemical News. Unfortunately the state of his health prevented him from appearing in the world outside King's College and his lecture rooms at Woolwich.He suffered of late years from extreme delicacy of the lungs which obliged him to exercise great care and it was to this disease that he ultimately succumbed on the 28th November 1887, at the comparatively early age of 56. JEAN BAP'IWTE JOSEPH DIEUDONN~ BOGSSINGAULT was born in Paris on February 2nd 1802. He received his scientific education at the School of Mines of St. gtienne ; and in the laboratory of that institu-tion he conducted his fiist investigation-on silicides of platinum-the results of which were published in 1821. Shortly afterwards he was appointed tjo a Professorship in the School of Mines of BogotA, in Colombia South America. But the South American War of Independence broke o u t soon after his arrival and Boussingault attached himself to Bolivar the leader of the insurrection whose aide-de-camp he became.After the war he accepted the post of manager of some mines for an English company in Colombia. He remained there for about ten years and during that period found time to publish some 50 scientific memoirs chiefly on metallurgical or mineralogical subjects. But before leaving Europe he had received valuable suggestions as to the points deserving observation from A. Humboldt whose notice he had already attracted and to whom, in the form of letters many of his afterwards published communica-tions were made. Notwithstanding the direction given t o liis energies by his technical education and engagements his natural bent soon showed itself and we find him making observations on the meteorolog 510 ANNUAL GENERAL JIEETISG.and the vegetation of the regions he visited. In regard to his con-tributions to science while in South America Humboldt speaks of liim as having enriched chemistry meteorology astronomy and geography with a number of precious works. On his return to France Boussingault was appointed Professor of Chemistry a t Lyons where he conducted an investigation on the composition of the atmosphere. He married the sister of a former fellow student a t St. ktienne &I. Le Be1 ; and by his marriage became joint proprietor with his brother-in-law of the now famous estate of Bechelbronn in Alsace which besides a large farm included a mine of bitumen. M. Le Bel besides being a chemical manufacturer was also a very intelligent practical farmer who was accustomed to use the balance for the weighing of manures crops and cattle.Here, then was associated “ practice with science,” and i t was under these favourable not to say indispensable conditions that the first laboratory on a farm was established and the firbt agricultural experimental station was founded. From this time forward Boussingault generally spent about half the year in Paris and the other half in Alsace. His first important con-tribution to agricultural chemistry was made in 1836 when he pub-lished a paper on the quantity of nitrogen contained in different foods and on the equivalents of the foods founded on the amount of nitrogen they contained which he determined in a large series of such foods; and he compared the estimates so arrived a t with the results of others founded on actual experience.Althoiigh his original conclusions have probably undergone some modification the work itself marked a great advance on previously existing knowledge and modes of viewing the subject, I n 1837 Boussingault published papers on the aniount of gluten in different kinds of wheat on the inflnence which the clearing of forests exercises in diminishing the flow of rivers and on the meteorological influences affecting the culture of the vine. In 1838 he published the results of an elaborate research on the pi-inciples underlying the ralue of a rotation of crops. He determined by analysis the com-position both organic and mineral of the manures applied to the land and of the crops harvested ; and in his treatment he evinced a clear perception of the most important problems involved in such an inquiry some of which even with the united labours of‘ himself and many other workers have scarcely yet received an undisputed solu-tion.Thus i n the same year he published the results of an investi-gation on the question whether plants assimilate the free nitrogen of the atmosphere ; and although the analytical methods of the ciay were inadequate to the decisive settlement of the point his conclusions were in the main those which much subsequent work of his own ANXUhL GENERAL MEETING. 511 and much of others also has served to confirm. As a further element in the question of the chemical statistics of a rotation of crops, Boussingault determined the amount and composition of the residues of crops.He also ascertained the amount of constituents consumed in the food of a cow and a horse as against the amount yielded in the milk and excrements of the cow and in the excrements of the horse. Here agxin the exigencies of the investigation he undertook were beyond the reach of the known method3 of the time. Indeed rude as the art of ngricul ture is generally considered to be the scientific eluci-dation of its practice requires the most refined and varied methods of research dealing as the subject does with the chemistry of the atmosphere of meteoric and other waters of the soil of vegetation, and of animal life ; and a characteristic of the work of Boussixigault may be said to be that he has frequently had t o devise methods suited to his purpose before he could grapple with the problems before him ; and in t,his way he has made valuable contributlions t o analytical chemistry.I n 1839 chiefly in recognition of his important contributions to agricultural chemistry Boussingault was elected a member of the Institute. Thns already be€ore 1840 the date of the first appearance of Liebig’s memorable work Boussingault hsd canvassed much of the ground and there can be no doubt that many of the important facts established by his researches served as the basis for many of Liebig’s brilliant generalisations. This led to the publication in 1841 by Dumas and Boussingault jointly of an essay which was afterwards translated into English and published in this country under the title of “The Chemical and Physiological Balance of Organic Nature.” I n 1843 Boussingault published a larger work, which embodied the results of many of his own previous original investigat,ions.This also was translated and published in this country under the title of “ R’ural Economy i n its Relations with Chemistry Physics and Meteorology.” A second edition of this book, Zconomie RuraZe appeared in. France in 1857 but was not translated into English. Although Boussingault’s attention ha5 been by no means limited to subjects bearing on agriculture by far the greater number of his researches have had relation to the problems which it suggests. Thus the amount and condition of the combined nitrogen in the atmosphere, in the aqueous depositions from i t in rivers and springs and in the soil have been investigated by him.The amounts of nitrogen phos-phoric acid &c. in different manuring substances have been deter-mined and their comparative VitlueS estimated accordingly. The question of whether or I;ot plants assimilate the free nitrogen of the air has again and again been taken up the weight of the evidenc 512 ASXUAL GEXERAL MEETISG. always serving to confirm the conclusion that they do not. In a letter to Dr. Gilbert written in 1876 he says “ If there is one fact perfectly demonstrated in physiology it is this of the non-assimila-tion of free nitrogen by plants; and I may add Fy plants of an inferior order such as mycoderms and musbroorns.” And in conver-s-ttion with Dr. Gilbert a t Liebfrauenberg in 1883 he still emphati-cally maintained the same view.Recent’ly he made experiments in regard to some functions of the leaves of plants. Lastly in the sphere of animal chemistry he from time to time devoted himself to the elucidation of important points such as the sources in the food of the fat of the fattenirig animal the assimilation of mineral con-stituents the question whether any of the nitrogen of the food of the animal is exhaled and so on. In 1844 Boussingault was elected a member of the Conseil d’Hiygi6ne Publique and in this capacity carried out numerous inves-tigations on questions both of general hygiene and of the special hygiene of various chemical industries. In 1848 Boussingnult who was in politics a moderate Republican, was elected a member of the Assemblhe Nationale and he was for a s1iort time member of the Conseil d’6tat.I n 1851 however he was on account of his political opinions dismissed hy the Government from his position of Professor a t the Conservatoire des Arts et XBtiers ; but on the representation of scientific friends of emineiice and authority and the threat of his colleagues to resign in a body, he was reinstated. When in the commencement of the Franco-German War the Crown Prince of Prussia had crossed the Rhine into Alsace some of the soldiers bivouacked in the woods of Bechelbronn and some of the officers were quartered in Boussingault’s house the old convent of Liebfrauenberg. Some time afterwards Boussingault received R letter from one of those officers saying that finding in whose house they were and having the highest respect for its scientific owner he had done his best he hoped successfully to prevent any injury from being done especially to the laboratory.He further expressed a hope that Boussingault would find nothing missing except a thermometer, which he had himself presumed t o take as a memorial. Boussingault’s first scientific contribution appeared in 1821 and in the ‘‘ Royal Society Catalogue of Scientific Papers ” there is given a list of 150 papers published by him from that date to 1873 inclusive. Almost the whole if not the whole of Boussingault’s investigations relating to agricultural chemistry will be found recorded in his work, entitled Agrononzie Chim ie AgricoZe et PhysioZogie published in seven yolumea the first of which appeared in 1860.Boussingault was elected a Foreign Member of the Chemica ANNUAL GENERAL MEETING. 513 Society in 1840 and received the Copley Medal of the Royal Society in 1878. He died at Paris on May 1 1 t h . 1887 in his eighty-sixth year. Mr. PATRICK DUFFP F.L.S. F.C.S. was born in 1829 and edncated at the High School Monaghan. In 1848 he obtained an appointment i n the Inland Revenue Department and two years later attended University College London for a course of instruction in chemistry, with the view of detecting adulterations in articles subject to the duties of Customs and Excise. Under Professors Graham and Williamson he diligently and most successfully pursued his studies and in 1831 obtained the Gold Medal for Chemistry.He also made great ndvance-ment in other subjects particularly in the German language and literature. On leaving University College his official duties occiipied B considerable portion of his time but he continued to devote himself to the study of chemistry and botany. Amongst his contributions to science was a paper on the trans-formation &c. of fats which is of considerable importance and was published in the Qnarterly Journal of the SociAtA Chirniqne de Paris. He received great praise from scientific men for the irdustry and patience shown in the preparation of this work particularly from the late Professor A. Wurtz of Paris. I n 1856 he was again in London and in that year obtained the University College Senior Gold Medal for Botany. About this time he distinguished himself by the detection of adulterations in taxed commodities.He was afterwards stationed at Kilkenny for some years as Supervisor of Inland Revenne and in spite of his multifarious duties, contributed many interesting meteorological notices to the ICiZkermi/ Moderator and did work in connection with the Irish Historical and Archzological Society of which he was a member for many years. Although a mail of considerable scientific attainments and a good linguist few of his papers have appeared in print. He was constantly a t work on some subject and availed himself of every available opportunity t o obtain information in coniiection with scientific and social matters. During his visits to the Continent he collected valuable particulars respecting the cultivation of hops &c.the inanufacture of beer and other alcoholic liquors and articles on which duties were levied. I n his travels he obtained numerous botanical specimens of which he had a considerable collection. He died very suddenly on the 27th May 1887. THOXAS SANUEL HUMPIDGE was born a t Gloucester on July 23rd, 3853 and received his early training a t the Crypt Grammar School i n that town. Whilst at school he won a number of prizes and VOL. LIII. 2 514 ANNUAL GENERAL MEETIKG. already showed a strong inclination towards those sciences the study and furtherance of which later on formed the great aim of his life-Vnfortjiinately the necessity of earning a livelihood compelled him to leave school a t the age of fourteen when he entered the employment of a Gloucester corn merchant with whom he remained for seven years.While thus engaged he had little spare time and conse-quently did not make such rapid progress in his scientific studies as he would have done under more farourable circumstances; the time he could get to himself however he devoted to science attendifig many of the classes a t the Science and Art Schools. Mr. Walter Jeffery then at the head of the science department of these schools, recogiiised the ability of his young student and did all he could to foster it. At this time youiig Humpidge obtained permission to appropriate a loft in his father’s house and this he gradually converted into a rough laboratory in which to supplement his work a t the Science Schools. I n after life he looked back with pleasure to his connection with these Schools and always retained a loving and grateful remem-brance of his first science teacher and friend whilst on the other hand Mr.Jeffery (who survives his former pupil) followed the latter’s career with the warmest interest. To show what good use he made of his spare time it may be mentioned that in one year he sat for examination in seventeen branches of science at the May examina-tions passing successfully in thirteen or fourteen thereof. I n 1873 he obtained from the Science and Art Department the silver medal for geology receiving a t the same time the offer of free lectures and laboratory work a t the Royal School of Mines and $50 a year for two years. Though unable t’o avail himself of this offer at the time he accepted i t when renewed in the following year.His strictly scientific training may thus be said to have begun in the autumn of 1874 when he ent’ered a t the Royal School of Mines making chemistry his chief subject. Here he obtained a bronze medal and in 1875 was nominated to one of the three Jodrell travelling scholarships founded a t that time. Whilst studying here under Professor Frankland he carried out a valuable research on “The Coal-gas of the Metropolis,” the results of which were pub-lished in this Journal. I n the same year he passed the Intermediate B.Sc. a t London gaining the second place in the first class in Honours and an exhihition of 240 a year for two years. I n 1876 Humpidge went to Heidelberg where for two years he studied under Bunsen and became an ardent and enthusiastic dis-ciple of that great chemist.During this time he devoted his energies to the investigation of the rare earths :rnd in 1879 in conjunction with his friend and fellow student Mr. W. Burney communicated the results obtained to this Society ANNUAL GENERAL MEETIXG. 515 At Heidelberg he took the degree of Ph.D. (sumrn& cum luude) and about the same time passed his final B.Sc. examination. In the spring of 1878 he removed to the Fellenberg Institute, Hefwyl near Berne where he had been appointed Science Mastfr; here he was very successful i n his teaching and soon won the love and esteem of both pupils and colleagues. In September 1879 he was elected to the Chair of Natural Science in the University College of Wales Aberystwyth which post he retained till his death.At the time of his appointment the resources of the Science De-partment of the college were very limited and for the first five terms of his tenancy of the chair he was single-handed being responsible for tshe whole of the science teaching of the college and having but poor laboratory accommodation and a scanty supply of apparatus. Not-withstanding he threw his whole heart into the work and the present successful position of the Science Department there is undoubtedly due in large measure to Professor Humpidge's enthusiasm and devotion, and its gradual growth and development was a constant source of the keenest enjoyment t o him. A lecturer in Biology and subsequently one in Physics were added to the college staff and Dr.Humpidge was thus enabled t o devote his whole energies to the teachiiig of chemistry. Naturally under tlhese circumstances his powers were severely taxed by the duties of t,ha chair but he still managed to work in his favourite fields of chemical research though it is to be feared a t considerable sacrifice of health. Whilst at Aberystwyth he devoted himself to the determination of the atomic weight and the position in the atomic system of the rare element-ber.yllium. This problem he attacked from two points of view namely by the determination of the specific heat of the element and by the det'ermination of the vapour-densities of its compounds. It is not necessary to dilate here on the diffi-culties of such work which are sufficiently well known to Fellows of' this Society.His first specific heat determinations led him to adopt the atomic weight 13.6 and his early attempts to determine the vapour-densites of the haloid salts proved abortive owing to the high tem-perature at which they me volatile their easy decomposition and their corrosive action on glass. When after long laborious and careful wcrk he was ready iii the spring of lS84 to renew his experiments in platinum vessels and under more favourable conditions he heard that the two well-known Swedish ct~emists-Nilson aiid Pettersson-were a t work on the same subject and about to publish their results. Great as was the temptation to hurry on his work lie would not permit his private research to interfere in the least with the duties of his chair and SO quietly allowed his experiments to lie i n abeyance till the long vacation though he well knew that this 2 N 51 6 ANNUAL GENERAL MEETING.would entail loss of priority of publication. But love of the truth was his great aim and incentive and he was content to finish and publish his experiments as independent confirmation of his friendly rivals' results. Not by any mmns the least pleasing feature of this incident was the friendly spirit existing between Dr Humpidge and the two Sedwish chemists and the letters which passed between them and the references to one another in their respective papers are very pleasant reading and in very welcome contrast to the bitter rancour but too often found between rival investigators. The results of his determinations of the vapour-densities of beryllium chloride and his new determinations of the specific heat of the metal were communi-cated from time to time by Dr.Rumpidge to the Royal Society in four papers of which one was published in the Philosophical Trans-uf'fions and three in the Proceedings; the results obtained fully con-firmed and established the atomic weight of beryllium as 9.1. Towards the expense of his work on beryllium the Royal Society made from tke Research Fund two grants of $50 each and one of $20 and with the elaborate and accurate calorimeter which he had thuq been enabled to construct fo" his specific heat determinations o€ beryIlium Dr. Humpidge intended to make a series of redetcrmi-nations of this important physical factor with other elements.With this object he had prepared very pure specimens of copper magne-sium and tin and was preparing others when the sad fire of JnlF, 1885 occurred by which the college was almost wholly destroyed and in which Dr. Hurnpidge not only lost his apparatus and materials but also valuable notes of much work already completed. The terrible night of .the fire in which Humpicige but narrowly escaped death undoubtedly greatly injured his health ; but with his usual ardour he a t once decided to forego his much-needed vacation devoting it to the arrangement of Cemporary science premises. He continued the duties of his chair during the follow-ing session and also reconstructed his calorimeter &c. 'but towards the end of the session his health began to give way and the long vacation did not bring the hoped-for improvement so that in September 1886 he had to oktain leave of absence from his Profes-sorial duties.He spent the winter in Nice and San Remo and the spring seemed to bring renewed vigour. So much was this the case, that Professor Humpidge returned to Aberyatwyth in August 1887, with the full intention of resuming work a t the commencement of the autumn session. A relapse however again occurred and after a painful illness he died of cerebral deterioration on November 30th. His friends did not wish an ostentatious Rinertzl but the unanimous desire of colleagues and students to pay a last tribute of esteem to a valued and loved friend and teacher was not denied. The buria ANNUAL GENERAL MEETING.517 therefore took place with academic honours representatives of the staff having the mournful pleasure of acting as pall-bearers at the house whilst students had the privilege of performing the same duties in the pretty churchyard of Llangoewen (about two miles from Aberystmyth) where his body was laid in the grave. The funeral cortege as it wound slowly over the hills preceded by the whole of the college staff of students in their sombre academic garb, formed a touching and picturesque though mournful scene which will long remain in the memory of those who took part in or witnessed it. The ceremony a t the grave was simple and touching, and when as the coffin was lowered into the grave the whole of those present sang reverently the quaint but solemn Welsh Resurrection hymn “ Bydd myedd o ryfeddodan,” many an eye was moist.During the last year of his work at the college Dr. Humpidge gave great care and thought to the elaboration of the plans for the new laboratories and this resumed as soon as his strength began to return on the sunny shores of the Mediterranean was continued to the last. After his return to Aberystwyth (when the work of re-building had already begun) it was Professor Humpidge’s greatest pleasure to lie a t his study window and watch the steady progress of the buildings of which to the end he fondly spoke as (‘my labora-tory.” As a teacher he very soon won the regard of his students a t Aberystwyth and there are not a few of them who are now making their way in the scientific world who would freely admit the en-tliusiasm and ardour of their old teacher to have given them their first stimulus to a scient’ific career.By his colleagues he was equally esteemed as a friend as a teacher and as a fellow councillor in the deliberations of the Senate. But his influence on the scholastic world was not confined to Aberystwyth. His translation of Kolbe’s Inorganic Chemistry rapidly won favour as a text-book and a new edition had been called for and almost perfected at the time of Professor Humpidge’s death. Shortly after he went to Aberystwyth Dr. Humpidge married Fraulein Johanna Ruder of Oldenburg whose acquaintance he had made whilst at Hefwyl. He leaves two bcys of the tender ages of five and three respectively. Owing to the heaviness of his college duties and to the difficulty of access of Aberystwyth his face was seen at the Society’s meetings with much less frequency than he or his friends could have wished.But there are still many among us who will feel they have lost in him a valued aiid true friend and fellow worker and many more to whom, though personally unknown his work has made him no stranger 57 8 ANR’UAL GENERAL JIEETIBG. Amongst the obituary notices of deceased Fellows issued in 1886, the name of Mr. W. Sykes Ward occurred. A s no further informa-tion was supplied to the Society a t that time no hicgraphical notice could be given. But the exceptional circumstances of Mr. Ward’s early association with the Chemical Society and the retention of that connection for about 38 years make it desirable briefly to supply the omission.Mr. W. SYRES WARD of Leeds was a solicitor whose tastes always inclined him in the direction of physical science and he was able to devote both leisure and means towards such pursuits. I n Vol. I of the Quarterly Journal of the Chemical Society a paper by Mr. Ward L‘ On a Balance Galvanometer,” is mentioned as the fourth in order read before the Chemical Society (on December 4, 1S48) which a t that period only published “ a t irregular intervals ” communications made to it. In Vol. I1 (1850) this paper is printed, and the presentation of the galvanometer to the Society is acknow-ledged. The suggested method for the measurement of an electrical current was ingenious and differed from that put forward by Becquerel in 1837 which probably was unknown to Mr.Ward. Mr. Ward was an early explorer in such fields as telegraphy atmo-spheric railways photography &c. and his inventions were the subject of several patents. He was an enthusiastic student of music in its higher aspects. For about 30 years Mr. Ward was one of the Honorary Secretaries of the Leeds Philosophical and Literary Society whose operations were most congenial to the great versatility of his tastes for science. Owing to failing health Mr. Ward spent the last few years of his life in retirement continuing however his scientifjc pursuits. The larger part of his considerable collection of scientific apparatns has been transferred by his family to the Physics Department of the Yorkshire College at Leeds

ISSN:0368-1645    

DOI:10.1039/CT8885300474

出版商:RSC    

年代:1888

数据来源: RSC

摘要:

519 XXXIX.-The Constitution of certain so-cdled ‘‘ Mixed Azo-compounds.” By FRANCIS R. JAPP LL.D. F.R.S. aird FELIX KLINGEMANN Ph.I). PART I. INTRODUCTORY AND THEORETICAL. UETWEEN three and four years ago Dr. Ludwig Landsberg mentioned to one of us that he had obtained by the action of sodium methoxide and methyl iodide on benzene-azo-acetone* a coiourless feebly basic cornpound melting at 64’ which he had not further examined. Dr. Landsberg stated that he did not inkend to continue the investigation of this compound and very kindly allowed us to take up the subject. Analysis showed us that as was to be expected the cornpound had been formed from benzene-azo-acetone by the substitution of a methyl-group for hydrogen. Adopting the usually accepted formula for benzene-azo-acetone, CH,*CO*CH,*N:N*C,H,, the most probable supposition was that the methyl had displaced a hydrogen-atom of the methylene-group-a view which w9 put forward in a preliminary note on the subject (Ber.20 3398). By the action of acetic anhydride on benzeue-azo-acetone we also pre-pared an acetyl-derivative to which we assigned (Zoc. cit.) an analogous constitution. We shall show in the present communication, that the above formula for benzene-azo-acetone does not correctiy express its constitution and that the formuh which we ascribed to the two derivatives just mentioned must be correspondingly modified. As the yield of the methyl-derivative obtained by Dr. Landberg’s reaction was very small,? we endeavoured t o prepare the compound by splitting off carbon dioxide from benzene-azo-methacetoacetic acid, a method which would at the same time prove its const,itution.We had hoped to obtain ethylic benzene-azo-methacetoacetate by tbe action of diazobenzene chloride on ethylic sodio-methacetoacetate, following the analogy of the reaction described by V. Meyer (Ber., 10 2075) for the preparation of ethylic benzene-azo-acetoacetate from ethylic acetoacetate and diazo-salts ; but we found that the benzene-azo-group could only be introduced into the molecule of ethylic * Benzene-azo-acetone first described by v. Richter and Munzer (Ber. 17,1928), was discovered independently by Dr. Landsberg in the Chemical Laboratory of the Noi*mal School of Science about the time referred to; but the investigation was ttbandoiied after the publication of v.Richter and Miinzer’s memoir. t A relatively advantageous method of carrying out the reaction is described later on 520 JAPP AND KLIKGERIANN THE COXSTITUTIOK OF methncetoacetate with simultaneous elimination of the acetyl-group : thus-CH,.CO*CKa(CH,>*COOC,H + C,H,*N,Cl + H,O = C11Hl,N202 + C2Ha02 + NaCl. To t'he " ester " thus formed we a t first assigned the formula-CH,*CH*COOC,H, (Ber. 20 2942) regarding it. as the ethyl salt of benzene-a-azopro-pionic acid-the first representative of a new class of benzene-azo-fatty acids. The acid CgH,,N,02 was obtained by hydrolysis; and we also prepared a number of homologous " esters '' and acids under the impression that we were dealing with a new class of compounds. The supposed benzene-azo-propionic acid CgHlnN2O2 yielded by treatment with sodium amalgam belLxene-hy~razopl.opionic acid, N:N*C6H5 CH,*(I K*COOH NH-NHCeH,' which proved to be identical with E.Fischer and Jourdan's " phenyl-hydrazinepropionic acid " (Ber. 16 2244) a fact which however, eseaped our notice at the time of our first publications on the subject (Ber. 20 2943 and 3284). Fischer and Jourdan obtained their acid by reduction of phenylhydra,zonepyrnvic acid,* C H,*C.C 0 0 H N*NHC,H * On comparing our " benzene-azo-propionic acid " with phenyl-hydrazonepyruvic acid we found that these two acids were also identical. It was therefore necessary to ascertain whether the acid had the constitution of a hydrazone as assumed by Fischei. and Jourdan and indicated by its formation from phenylhydrazine and pyruvic acid; or that of an azo-compound as we had all along supposed.The fact that in the reaction discovered by us the diazo-salt expels simultaneously sodium and acetyl from tlhc moleciile of ethylic sodio-methacetoacetate might it appeared to us be interpreted in favour of the hydrazone formula since in this process the bivalent group CH,*C.COOC,H, would be formed; on the other hand the possibility of regenerating the acid by the action of an ammoniacal solution of a cupric salt on benzene-hydrazopropionic acid as observed * Jn the nomenclature of componnds formed bv the action of phenylhydrazine on carbonyl-compounds we have followed the recently published suggestion of Emil Fischer (Ber. 21 984) CERTAIN SO-CALLED MIXED AZO-COJIPOUSDS.521 by Fiecher and Jourda.n indicated rather the constitution of a n azo-compound. The problem we pointed out was of the same order as that involved in distinguishing between an isonitroso- and a nitroso-compound ( B e y . 20 3285). Of course the quest,ion also arose as t o whether benzene-azo-acetone itself was an azo-compound or a hydrazone ; and it appeared likely that in the case of this compound a study of the alkyl-deriva-tives obtainable by Landsberg’s react’ion might furnish a ready solution of the problem. If benzene-azo-acetone was an azo-com-pouiid the alkyl-derivative would have the formula-C H3.C 0 * CHR’. N :N*C,H ; whereas if it was a hydrazone (derived from pyruvic aldehyde) the alkyl would more probably athach itself to nitrogen thus-By the action of nascent hydrogen an alkyl-derivative of the first formula ought to yield aniline ; one of the second formula an alkyl-miline.I n either case the other half of the molecule would probably yield a ketine. The method of attacking the problem was therefore analogous to that employed by Victor Meyer and Ceresole in ascertaining the constitution of the isoni troso-compounds (Bey. 15 3071). We preferred however to introduce instead of a alkylm-group the group *CH2*COOH into the molecule of benzene-azo-acetone. The resulting compound would thus yield on reduction instead of a mixture of two bases a. base and an acid in this way greatly facilitat-ing the separation of the products ; whilst in order to ascertain the constitution of the compound ik was only necessary to distinguish between aniline on the one hand and anilidoacetic acid on the other, instead of between aniline and an alkjl-aniline.Benzene-azo-acetone was accordingly heated with sodium ethoxide and ethylic chloracetate in alcoholic solution. The resulting ‘‘ ester ” was converted into the acid which pi,ored t o have the expected formula CIIH,,N,O,. On reduction this acid yielded anilidoacetic acid but no aniline. I t has therefore the formula-and “benzene-azo-acetone” is not an azo-compound at all but a h j drazone of the formula-CH3.C O.CH:N*NHC,H, 522 JAPP AND KLINGEMBKN THE CONSTITUTION OF -an “ aldehydrazone ” of pyruvic aldehyde as distinguished from the “ ketohydrazone ”* derivable from the sitme compound.This view was confirmed by the fact that “ benzene-azo-acetone ” Fielded with phenylhydraziiie a compound-CH,.C:N.NHC,H, identical with the 0sazone-f- of pyruvic aldehyde (met,hylglyoxal) pre-pared by v. Pechmann. T t appears therefore that when diazo-salts act on ethylic aceto-acetate and its analogues o r on their mono-alkylated derivatives, hydrazones are formed. R. Meyer (Ohem.-Zeit. 1887 836) has sliown that the compound obtained from ethylic malonate and diazo-benzene chloride is identical with the phenylhydrazone of ethylic mesoxalate but draws the opposite conclusion to that arrived a t by us believing that the hydrazone undergoes transformation into an azo-compound. CH:N-NHC R,’ * These names are formed on the analogy of “ aldoxime” and “ketoxime.” ‘‘ Aldehydrazone ” is a contraction for (‘ aldehydehydrazone.” t “Osazone” is the term introduced by Fischer to denote the dihydrazone of a n a dicarbonyl-compound.$ This preliminary communication in the Chemiker-Zeitung had unfortunately escaped our notice at the time we published our first note on the identity of our ‘. benzene-azo-propionic acid ” with Fischer and Jourdan’s plieiiylliydrazonepyriiric acid . Our views on the constitution of the above “ mixed azo-compounds,” were first published together with a brief account of the experimental proofs in the Proceedings of December 15 1887 and somewhat later in the Berichte (20, 3284 and 3398). Professor Victor Meger who arrived independently a t the same conclusions published a paper later still in the Berichte (21 ll) in which he dis-cusses the theoretical question very fully but does not contribute any fresh experi-nrental material although he suggests various experiments some of which we had alrcady described in our paper.After his paper had been sent to the Berichte (date of reception 30th December 1887) Professor Victor Meyer received the number of the Proceedings containing the account of our work and despatched to the Berichte an addendum (4th January 1888) in which he says “ Ich gestatte mir darauf hinzuweisen dass ich uber das Thema am 13. December in der Gottinger chemischen Gesellschaft vorgetragen habe.” We believe that in the above sentence Professor Victor Meyer has unintentionally conveyed the impression that he read a paper before the Gottingen Chemical Society on December 13.VSTe understood the words in this sense and therefore tiwned to the account of the meeting in question given in the Chemiker-Zeitung (1837 11 1584) but found no mention of any such paper. Later however on January 8 in the number of the Chemiker-Zeitung following that i n which an account of our work had been published there appeared a second and “ supplementary ’) notice of the above meeting of the Gottingen Chemical Society in which it was stated that in a discussion which followed on the reading of a paper by P. Jacobsen, Professor Victor Meyer had made certain remarks on the constitution of mixed azo CERTXIS SO-CALLED MIXED AZO-COJIPOUKDS. 523 The bivalent hydrazone-group :N*NHC,H, thns corresponds with the bivalent isonitroso-group :N*OH.The isonitroso-compounds as Victor Meyer has shown are formed either by the action of hydroxyl-amine on a carbonyl-compound or by the action of ‘nitrous acid on a compound containing the group CH2 or CHR’ att,ached to two electro-negative radicles R’ being a readily displaceable radicle (acetyl or carboxyl). Substituting in the foregoing statement “ phenyl-hydrazine ” for “ hydroxylamine,” and “ diazo-componnd ’’ for “nitrous acid,” it describes the modes of formation of the hydr-azones. The analogy between the action of hydroxylamine and phenyl-hydrazine on carbonyl-compounds needs no illustaration. The analogy between the action of nitrous acid and diazobenzene-compounds 0x1 ethylic acetoacetate acetoacetic acid and their monalkyl-derivatives, is exemplified in the following equations in which for the sake of simplicity free diazobenzene is employed instead of its salts :-1.With ethylic acetoacelate the reactions may be expressed as follows :-2. I n the case of monalkyl-derivatives of ethylic acetoacetate the acetyl-group is expelled :-CEJ322>CH*COOC,H + HNO = CH,-C*COOC2H + C2HJ0,, N*OH compounds. The views embodied in these remarks were we niny say identical with those put forward by us and to this extent we were forestalled by Professor Victor Meyer. Two criticisms suggest themselves on the foregoing. In the first place as regards the general question although a discussion made before a learned Society may embody valuable remarks yet if this discussion is not reported in the ordinary course along with the other work of the Society i t would be hardly fail.to outsiders to regard such remarks as equivalent to publication. Secondly on the present and personal matter if we had chosen to take the same course as ProPessor Victor Mejer and publish our theoretical views first leaving the experimental confirmation for later we might have considerably anticipated the date of December 13 on which he lays so much stress 524 JAPP AXD KLINGEMANN THE COSSTITUTION OF 3. When nitzous acid acts on free acetoacetic acid or its monalkyl-derivatives instead of on their ethyl salts the carboxyl-group is eliminated and isonitroao-ketones are formed. We find that. in this case also diazobenzene behaves in an analogous manner. Thus with acetoacetic acid we have-whilst methacetoacetic acid yields with diazobenzene the compound CH,.CO*C (CH,) :N.NHC,H (the monohydrazone of d iacetyl already prepared by v.Pechmann from diacetyl and phenylhydrazine) ; a n d ethauetoacetic acid yields the corresponding compound of the formula CH,*CO.C (C,H,):N.NHC,€€,. The so-called azo-ketones are thus monohydrazones of a-dicarbonyl-compounds. We also discovered in the course of the present investigation the following curious mode of formation of osazones (dihydrazones of a-dicarbonyl-compounds). ILL heating phenylhydrazonepyruvic acid at 180-190° until it had ceased to evolve gas we obtabed along with oily matters a crystal-line substance of the formula CIGKIBN1 ( B e y . 20 2943). We after-wards found that this compound was identical wit'h the osazone of diacetyl since prepared by v.Pechmann. Its formation from plienylhydrazonepyruvic acid may be expressed by the equation-2C9K,,N20 = C,,H,,N + 2C0 + H,; but we believe that it is in reality formed in a secondary reaction. E. Fischer and Jourdan have shown (Be, 16 2242) that phenyl-hydrazonepyruvic acid breaks up on heating with evolution of carboii dioxide and formation of aldehydrazone (ethylidenephenylhydr-azine)-CSH,N,Oz = C,EI,,N + GO,. I n fact this is the chief reaction the oily subshance which we obtained consisting mainly of aldehydrazone whilst the osazone is formed only in small quantity. We therefore heated aldehydrazone a t 180-190" and found that the osazone of diacetyl was formed. The following equation shows t lie reaction : CERTAIN SO-CALLE t) MIXED AZO-COhlPOUICDS.525 PART 11. EXPERIMENTAL. 1 . Introductim of Momd Radicle.? into the Molecule of Yyruualdehydr-azone (L' Beraene-azo-acetone "). The pyruvaldehydrazone (to give the compound the name denotinq the coustitution to which the following experiments point) was prepared by a modification of v. Richter and Miinzer's method (Bey., 17,1928). The crude product of the action of diazobenzene chloride on ethylic sodacetoacetate wa9 first hydrolysed by warming for a few minutes with alcoholic caustic soda. Instead however of continuing the heating until the sodium salt thus formed was converted by the action of the caustic alkali into pyruvaldehydrazone and sodium carbonate we added watei. acidified with hydrochloric acid so as partially to precipitate the organic acid added sodium carbonate so as to redissolve the precipitate and then heated the liquid on a water-bath for several hours.I n this way the pyruvaldehydrazone was not exposed to %he deoomposing action of the caustic alkali and was obtained in a purer condition. It separated from the 'hot liquid in large plates which were filtered off and the liquid was heated afresh until 1 1 0 further separation occurred. The latter portions were less pure. The compound is most convenientlg purified by recrystallisat,ion from hot benzene or methyl alcohol. As regards its physical properties, we have nothing to add to v. Richter and Munzer's description. We have described the foregoing method because it was trhat8 by which the material employed in this investigation was obtained but later on we g5ve a method by which the compound can be much more readily prepared namely by the action of diazobenzene chloride on acetoacetic acid.Action of Acetic Anhyd&ie.-PFruvaldehydrazone was boiled with excess of acetic anhydride for several hours after which the solution was poured into water- An oil separated which speedily became crystalline. By recrJ-stallisation from boiling light petroleum the compound was obtained in colourless needles melting at 93". From a benzene solution it is deposited in thick well-furmed crystals appa-rently quadratic. Analysis agreed with the forniuls CllH12N202. Substance. co,. HzO. . I. 0.2 150 0.5105 0.1151 11 0-2265 0.5375 0.1202 111. 0.1110 gram burnt with oxide of copper in a vacuum gave 22-63 C.C.of a mixture of nitrogen and nitric oxide measured dry at 19.5" and under 459 mm pressure. After absorption of the nitric oxide there remained 22.63 c.c of dry nitrogen at 19.5" and under 434 mm. pressure 52 6 JXPP AND KLISGEMZANN THE COSSTlTUTION OF Found. 7 Calculittctd for r-h-C,IH1,N20,. I. 11. xIr. C 64-70 64.i5 64.72 H . . . . . . 5.88 5.91 5.89 -N 13.73 - 14.05 0 15.69 10o.c 10 --- - I -The compound is therefore acetylp!jri~valiZehydI-~xone, CH,.CO.CH:N.N(C,HI,O)CGH,. At the time when we first prepared this compound we were under the impression that the acetyl-group had displaced hjdrogen in thp '' methylene-group of benzene-azo-acetone " and that the compouri'l was therefore a diketone.We consequently heated i t with an excess of phenylhydrazine in alcoholic solution biit even at 200" only oy,e oxygen-atom was displaced by the phenylhydrazone-group. The phenylhydrazone which in reality has the formula, CH:N-?L'(C,H,O)CGH, C H,.C:N*NHC,H 9 crystallises in pale-yellow needles melting at 329" readily soluble in hot sparingly soluble in cold alcohol. 0.1013 gram burnt with copper oxide in a vacuum gave 22.63 C.C. of a niixtnre of nitrogen and nitric oxide measured dry a t 15.5" and under a pressure of 548 mm. After absorption of the nitric oxide, there remained 22.63 C.C. of dry nitrogen a t 15.5" and under 543 mm. pressure. Calculated for C17"18N 0 Found. N in 100 parts 19.04 19.06 A c h n of Methyl Iodide.-By heating together in methyl alcoholic solution equimolecular proportions of pyruvaldehydrazone sodium methoxide and methyl iodide only a very small proportion of the pyruvaldehydrazone was converted into the methyl-derivat,ive.This is due to the fact that the sodium methoxide and methyl iodide inter-act in great part by themselves as if no pyruvaldehJdrnzone were present. We then tried whether an increase in the proportion of sodium methoxide and methyl iodide would render the conversion more complete ; but the result was still unsatisfactory. The follow-ing slight modification of the process however by which the presence of any but a very small proportion of sodium methoxide during the progress of the reaction is avoided gave an excellent yield. A solution of 1 mol.proportion of pyruvaldehydrazone with 4 mol CERTAIN SO-CALLED MIXED AZO-COMPOUN DS. 527 proportions of methyl iodide in methyl alcohol was boiled with a reflux condenser ; a solution of 4 atomic proportions of sodium in methll alcohol was allowed to drop gradually into the boiling liquid so that the process extended over several hours; and the boiling was continued for a short time after the whole of the methoxide had been added. On pouring the contents of the flask into excess of water an oil separated which speedily solidified ; this substance was purified by recrystallisation from boiling light) petroleum. It forms colourless, flat needles melting at 64" very soluble in alcohol ether and benzene, somewhat less soluble in light petroleum. It is a weak base dis-solving i a concentrated hydrochloric acid but is reprecipitated by water.Analysis showed that it had the formula C,,H,,N,O :-Substance. co,. HsO. I-. . 0.2180 0.5450 0.1344 IL 0-2039 0.5098 0.1260 111. 0.1088 gram burnt with copper oxide in a vacuum gave 22.63 C.C. of nitrogen measured dry at 18.2" and under 500 nim. pressure Nitric oxide was not present. Found. -3 Calculated for r-h-ClOH,,"A). I. 11. 111. C 6818 68.18 68.18 H . . . . . . 6.82 6.85 6.86 -N 15.91 - 16-12 0 9\09 --- - --100~00 The compound has the constitution CH,*CO*CH:N*N<:g. That the methyl-group has not displaced hydrogen attached to carbon is shown by the fact that the compound is distinct from the hydrazone of diacetyl ( u i d e infka). When heated with phenylhydrazine in alcoholic solution it yields a compound, CH:N*X(CH,)C6H, which crystallises in faint-yellow needles melting a t 151-1 52", sparingly soluble in alcohol readily soluble in ether.0.0770 gram burnt with copper oxide in a vacuum gave 22.63 C.C. of a mixture of nitrogen and nitric oxide measured dry at 15.4" and under a pressure of 471 mm. After absorption of the nitric oxide, there remained 22.63 C.C. of dry nitrogen at 15.6" and under 460 mn]. pressure. C H,. C N N €l C H 528 JAPP AND KLINGEMAXN THE CONSTITUTJON OF Calciilxted for Cltal8N.l. Found. N in 100 parts 21.05 21.4 Action qf Ethyl Iodide.-Pyruvalde hydrazone reacted in an analogous manner with sodium ethoxide and ethyl iodide yielding the compound C H3.CO*CH:N.N(C2H5) C6H5 which crystallised from light petroleum in thin prisms melting at 5.5".The substance had a faint reddish tinge doubtless due to impurity. 0,1942 gram gave 0.4923 gram CO and 0.1277 gram H,O. Calculated for CIIH,,N,O. Found. c . 69.47 69-1 3 H . 7-37 7.30 N. 14.74 0 - 8.42 100~00 -Action qf Ethylic Ch1omcetata.-The pyruvaldehydTazone together with four times its molecular porportion of ethylic chloracetate was dissolved in alcohol and a solution of 4 atoms of sodium in alcohol was gradually added t o the boiling liquid conducting the operation as in the preparation of the methyl-derivative. Caustic soda was then added and the solution was boiled so as t o hydrolyse the "ester" which had been formed in the reaction. After expellinq part of the alcohol by heating water was added the liquid was filtered and the new acid was precipitated with hydrochloric acid.I n order to purify the substance it was dissolved in a cold solution of sodium carbonate, reprecipitated with hydrochloric acid and repeatedly recrystallised from boiling water. It formed yellow needles which melted with decomposition about 161-1 62". Analysis agreed with the formula CH3.C CbCH:N*N( CGH,) C HZ*COOH. I. 0.2128 gram gavet0.4671 gram CO and 0.1070 gram H,O. 11. 0.1067 gram burnt with coppel. oxide in a vacuum gave 22.63 c.c- of a mixture of nitrogen and nitric oxide measured dry a t 16" and under 405 mm. pressure. After absorption of the nitric oxide there remained 22.63 C.C. of dry nitrogen at 16' and under 395 mm. pressure.Found. Calculated for rL- 7 C,,H*2N2O3* I. 11. C 60.00 59.86 H 5-58 - 245 N 12-73 - 13.25 0 21.82 -- -100~0 CERTAIN SO-CALLED MlXED AZO-COMPOUNDS. 529 Action of Nascent Hydrogen on the Acid CIIH,,N203.-The acid was dissolved in alcohol and treated with excess of tin and hydrochloric acid. The tin was then precipitated with sulphuretted hydrogen the solution evaporated to dryness the residue extracted with ether,* and the substance remaining on evaporation of the ether recrystallised from hot water. The aqueous solution on cooling deposited small crystals with a slight brownish tinge melting at 126-1227'. (M. p. of anilidoacetic acid 126-127"; P. Meyer). I n all its properties, excepting the slight brown colour it was indistinguishable from ft specimen of anilidoacetic acid prepared from bromacetic acid and aniline.As the quantity was too small for further purification we analysed it direct. 0.0926 gram burnt with copper oxide in a vacuum gave 22-63 C.C. of a mixture of nitrogen and nitric oxide measured dry at 15" and under 253 mm. pressure. After absorption of the nitric oxide there remained 22-63 C.C. of dry nitrogen at 15" and under 246 mm. pressure. Calculated for 9.27 NH(C,HJ *CH,.COOH. Found. N in 100 parts. . . . . . . 9-54 Anilidoacetic acid was also obtained by reducing the acid CllHI2N2O3 with sodium amalgam in aqueous solution. No aniline was formed; but a strong smell of a ketine was perceived. We reduced simultaneously isonitrosoacetone with sodium amalgam and perceived the same smell.The acid CH,*CO*CH:N*N( CsH5)*CH2*COOH is therefore broken up by the nascent hydrogen with separation of the nitrogen-atoms, one-half of the molecule yielding milidoacetic acid the other a ketine. The formation of anilidoacetic acid from this acid proves that the latter has the constitution here assigned to it and thus indirectly, that the so-called '' benzene-azo-acetone " is pymvaldehydrazone. 2. Action of Pheny lhydrazine o n $ome Ketonic Compounds containing the Phenylhydraxone-group. Action on Ethylic Pheyiy lhydrazone-acetoglyozylate (" Benzene-azo-ucetoacetafe") .-lo grams of ethylic yhenylhydrazone-acetoglyoxylate and 5.5 grams of phenylhydrazine were heated with glacial acetic acid in a sealed tube for an hour at 120-130". On cooling the tube * As the substance here extracted was anilidoacetic acid we would point out that Sellwebel's statement (Be?.10 2046) that this acid is insoluble in ether is incorrect. Michaelson and Lipprnann the discoverers of anilidoacetic acid say (Annulen 139, 236) c c It is fairly soluble in water less soluble in ei her." This is correct. The statement as to its insolubility in ether has passed into Beilstein's Handbuck VOL. LIII. 2 530 JAPP AND ELINGEMANN THE CONSTITUTION OF was found to be filled with red needles with a characteristic blue reflex ; these after crystallisation from glacial acetic acid melted at 155". These properties pointed to the identity of the compound with Knorr's (l)-phenyl-(3)-methy7pyrazoZone-(4)-azobentene ( A n n a l e n , 238 183) which this author obtained by the action of diazobenzene salts on phenylmethylpyrazolone and to which he assigns the consti-tution-CGH5.N A N CO II I CH3.C -CH*N:N*C,H5.In the present case it is formed according to the equation-CH,*CO*C*COOC,H + C,Hj*NH*NH2 = Ci,H,,N,O + C2HGO + H2O. N*NHC,H, A nitrogen determination gave the following result :-0.0967 gram burnt with copper oxide in a vacuum gare 22.63 C.C. of a mixture of nitrogen and nitric oxide measured dry at 18" and under 556 mm. pressure. After absorption of the nitric oxide there remained 22.63 C.C. of dry nitrogen at 18" and under 550 mm. pressure. Calculated for CMHl,N,O. Found. N in 100 parts . . . . 20.14 20.06 Although ethylic phenylhydrazone-acetoglyoxylate must be regarded as a hydrazone we should not like positively t o affirm the same of the pyrazolone-derivative obtained from it in the foregoing reaction.It is quite conceivable that in the formation of this compound the hydrazone-group is transformed into an axo-group ; and indeed the extremely pronounced colour of Knorr's compound would rather indi-cate the occurrence of such a change.* p he n y 1-hydrazone-acetoglyoxylic acid is warmed with phenylhydrazine in alcoholic solution osazone-acetoglyozy lic acid-Action on P h en y Ih y drazone- acet og ly oxy 1 ic Acid .-When *CH3* C :N zHC,H, C:NzH CsH5, COOH separates almost immediately in slender yellow needles melting at 209". This acid was obtained by Knorr (Annden 238 195) by the action of phenylhydrazine on rubazonic acid.Knorr gives the melting point at 212". * Compare also Bernthsen Bev. 21 743 CERTAIN SO-CALLED MIXED AZO-COMPOUNDS. 531 0.1048 gram burnt with copper oxide in a vacuum gave 22.63 C.C. of a mixture of nitrogen and nitric oxide measured dry at 15.8" and under 572 mm. pressure. Aftel. absorption of the nitric oxide there remained 22.63 C.C. of dry nitrogen at 16" and under 555 mm. pressure. Calculated for CltJH16N402* Found. N in 100 parts 18.92 19.00 When heated with acetic acid this compound part@ with the ele-ments of 1 mol. H20 and yields the foregoing phenylmethylpyrazo-lone-azobenzene melting at 155O.* Action o n Pyrucalde lay d raz one.-Pyruvaldeh y drazone and phen yl-hydrazine when heated together in alcoholic solution react yielding the compound-C H3*C :N,HC,H, CH:N2HCsH; I t is deposited from hot alcohol in which it is only sparingly soluble, as a yellowish crystalline powder melting a t 145".It dissolves in concentrated sulphuric acid in the cold with an olive-green colour, which speedily changes to slate-blue and finally after standing for some hours to violet. A drop of the blue or violet solution poured into a porcelain basin and breathed upon becomes first green and afterwards yellow. 0.0889 gram burnt with copper oxide in a vacuum gave 22-63 C.C. of a mixture of nitrogen and nitric oxide measured dry a t 16.2" and under 561.5 mm. pressure. After absorption of the nitric oxide there remained 22.63 C.C. of dry nitrogen at 16.5" and under 551 mm. pressure. Calculated for C15H16N4.Found. N in 100 parts 22.22 22-08 Assuming that the above formula is correct the compound should be identical with the osazone of pyruvaldehyde (methylglyoxal) obtained by v. Pechmann by the act<ion of phenylhydrazine on pyruv-aldehyde and also by heating isonitrosoacetone with phenylhydrazine in acetic acid solution (Ber. 20 2543). We therefore prepared the * After the above was alceady in type we received No. 6 of the Berichte 1888 in which Knorr describes the formation of phenylmethylpyrazolone-azobenzene from osazone-acetoglyoxy1ic acid and points out its identity with phenylhydrazone-phenylmethylketopyrazolone (Ber. 21 1203). Knorr is of opinion that the compound is a hydrazone. Knorr converts the osazone into the pyrazolone-compound by dissolving it in caustic alkali and precipitating with acetic acid.2 0 532 JAPP AND KLINQEMANN THE CONSTITUTION OF compound by the latter method and found that it agreed in all its properties with that above described. 3. Action of Diazo-salts on Monalkyl-deriratives of Eth ylic Acetoacetate : Form ation of Hydrazones of u- Ketonic Acids. Ethylic Methacetoacstate a n d Diazobenzene Chloride.-An aqueous solution of diazobenzene chloride was gradually added in equimole-cular proportion to an alcoholic solution of ethylic sodiomethaceto-acetate cooling during the process. The liquid became deep red, and towards the end of the operation a dark-red oil i;eparated. Water was then added to complete the precipitation after which the oil generally solidified. When this did not occur the oil was washed with water in a separating funnel and then mixed with alcohol which caused it to become solid and crystalline.The solid substance was iwxystallised several times first from alcohol afterwards from light petroleum by which means it was obtained in yellow needles melting at 117". Analysis led to the formula CI,H,,N20 :-I. 0.2050 gram gave 0.4820 gram CO and 0.1255 gram H,O. 11. 0.1123 gram burnt with copper oxide in a vacuum gave 22.63 C.C. of nitrogen measured dry a t 17*S0 and under 438 mm. pressure. Nitric oxide was not present. Po nnd . Calculated for -7 CllH14N202. I. 11. - C 64-08 64.12 H 6.80 6.80 N 13.59 - 1370 0 15.53 100~00 -- -The acid was readily obtained by warming the '' ester " with an alcoholic solution of caustic soda and precipitating with hydrochloric acid.It crystallises from hot benzene in yellowish needles melting with evolution of gas at 185". It dissolves in cold concentrated sul-phuric acid with a yellow colour which soon changes to a deep-red. On allowing a drop of the concentrated red solution to flow about in a porcelain baoin and breathing on it the colour changes t o blue. Analysis gave figures agreeing with the formula C,H,,N,O :-I. 0.2202 gram gave 0.4893 gram CO and 0.1126 gram H,O. 11. 0*1102 gram burnt with oxide of copper in a vaciium gave 22-63 C.C. of nitrogen measured dry a t 23.4" and under 501 mm. pressure. Nitric oxide was not present CERTAIN SO-CALLED MIXED AZO-COMPOUNDS. 533 Found. Calculated for r-- 7 CISH1ON302.I. 11. C 60.67 60.60 H 5.68 I 5-62 N 15.73 - 15.68 0 17-98 -- -This acid proved as already mentioned to be identical with E. Fischer and Jourdan's phen ylhydyazonepyruvic acid, CH,*C*COOH N*N HC8HI' (Ber. 16 2241). Fischer and Jourdan give the melting point of their acid at 169" ; but later Fischer (Ber. 17 578) stated that this was a misprint for 192" which he gives as the true melting point of the acid.* We therefore carefully purified specimens of acid prepared both by our method and by that of Fischer and Jourdan but in * In an earlier communication on this subject (Ber. 20 3283) me unfortunately overlooked Fischer's correction and stated that Fischer and Jourdan had given the melting point " much too low." Our attention was called to the oversight by V.Meyer (Ber. 21 18). Fischer's correction appears to have escaped notice in another quarter thus Sandmeyer in a paper emanating from the laboratory of the Zurich Polytechnic (Ber. 20 641) identifies pyruvic acid by means of its phenyl-hydrazone which according to him " after dissolving once in dilute ammonia and precipitating with hydrochloric acid showed the correct melting point of 169"." Since the foregoing was written Professor Fischer has alluded to the subject of the melting point of phenylhydrazonepyruvic acid (Ber. 21 987). After pointing out that the acid as a substance which decomposes in melting will show too low a melting point unless rapidly heated he adds :-" It was evidently from this cause that Messrs. Japp and Klingemann who have overlooked both my correct,ed statement as to the melting point " [i.e .that 169" was a misprint for 192"] " and my remarks on the mode of heating found the melting point of the compound first at 182" and afterwards a t 185"." We stated (Ber. 20 3285) that in our first communication the melting point of the compound " was erro-neously given a t 182" instead of a t 1 8 5 O . " Professor Fischer somewhat hastily concludes that " erroneously given " is synonymous with '' erroneously found.'' As a matter of fact the error in question was an error in transcribing although we did not specify this at the time imagining that the cause of such an error-whether il misprint as in Professor Fischer's case or otherwise-could be of interest to no one save the authors.We have already expressed our regret that we overlooked Professor Fischer's correction. As regards the other oversight-of Professor Fischer's " remarks on the mode of heating"-we would point out that we expressly stated that the com-pound decomposed in melting and we are under the impression that the precaution to be taken in determining the melting point of substances of this character was There is a point here which calls for correction 534 JAPP AND KLISGEXANN THE COSSTITUTION OF neither case could we succeed in raising the melting point above 185" which we must therefore regard as the correct melting point. Both acids on heating yielded a crystalline compound of the formula C,F,H,,N1-diacetylosazone (vide supra)-together with oily matters. We also found that Fischer and Jourdan's acid gave the above characteristic colour reaction with concentrated sulphuric acid.Fischer and Jourdan give the melting point of the ethyl salt of their acid a t 114-115". We found f o r the ethyl salt prepared as above described the melting point 117". The metallic salts appear to be very unstable and could not be obtained in a state fit for anadysis. We reduced the acid obtained by the above method with sodium amalgam. By moderate reduction of the sodium salt in aqueous solution wiih sodium amalgam a hy drazo-acid was obtained which was precipitated on acidifying with hydrochloric acid avoiding an excess which was found to redissolve the hydrazo-acid. It crystnllised from methyl alcohol in slender colonrless needles which on exposure to air become yellow especially when moist.We found the melting point at 170° but had not sufEcient substance for further recrystalli-sation; the true melting point is 172'* (see later on). The sub-stance evolves gas in melting. Analysis gave figures agreeing with the formula C9H12N202 :-I. 0.1910 gram gave 0.4207 gram CO and 0.1174 gram H,O. 11. 0.0978 gmm burnt with copper oxide in a vacuum gave 22-63 C.C. of a mixture of nitrogen and nitric oxide measured dry a t 16.8" and under 433 mm. pressure. After absorption of the nitric oxide there remained 22.63 C.C. of dry nitrogen at 16.9" and under 430 mm. pressure. Found. Calculated for r-A--7 C9H,2N202* I. 11. c 60.00 60.07 H 6.67 6.83 -N 15-55 - 15.58 0 17.78 -. . . . . . . . . . - -known before Professor Fischer illustrated it in the case of the hydrazones.We made a point of heating as rapidly as is practicable. Professor Fischer's explanation will hardly account €or the fact that in the case of the corresponding hydrazo-acid-also a compound which decomposes in melting -we found the melting point 20" higher than he did. * The melting point (162") given in our first publication on this subject (Ber., 20 2943) is too low. The substance had not been sufficiently purified CERTAIN SO-CALLED MIXED AZO-COMPOUNDS. 535 This acid would be benzene-3-hydrazopropionic acid, CH,. CH-COOH N H-NH C,H,' Fischer and Jourdan (Ber. 16 2244) obtained this acid by the re-duction of phenylhydrazonepyruvic acid but assign to it the melting point 152-154".We therefore prepared phenylhyrazonepyruvic acid from phenylhydrazine and pyruvic acid and reduced it with sodium amalgam. The hydrazo-acid thus obtained was identical with the foregoing and after repeated recrystallisation from methyl alcohol had a constant melting point of 172". Aniline is always formed in this reduction as observed by Fischer and Jourdan. We therefore endeavoured to isolate the other product which would be formed by the breaking up of the niolecule of the hydrszo-acid by reduction-alanine. A quantity of phenylhydr-azonepyruvic acid was dissolved in dilute caustic soda and treated with excess of sodium anialgam on the water-bath. The aniline which was formed was then extracted with ether; the alkaline aqueous solution was slightly acidified with hydrochloric acid thus precipitating a small quantity of the hydrazo-acid which was removed by filtration ; the filtrate was evaporated to dryness and the residue treated with boiling absolute alcohol to extract the alanine hydrochloride which remained as a crystalline residue on evaporating the alcohol; t h i s residue was boiled with water and litharge; the filtered solution containing the lead salt of alanine, was precipitated with sulphuretted hydrogen ; and the filtrate from the lead sulphide was evaporated to a small bulk and then mixed with an excess of alcohol.Alanine separated in slender white needles. The alanine thus obtained had a sweet taste; sublimed above 200" and gave on analysis :-C. H. N. Calculated for C,E,NO? 40.45 7.86 15.73 per cent.Found 40.38 8.03 15-61 ,, E t h y l i c Methacetoacetate and o-Diazotoluene Chloride.-The re-action was conducted as in the former case. The " ester " was ob-tained as a red oil which did not solidify even in a freezing mixture : it was therefore hydrolysed by heating with caustic soda and alcohol. The acid was precipitated with hydrochloric acid and purified by recrystallisation from benzene. It formed small yellowish laminae, melting with evolution of gas a t 156". It is identical with Raschen's o-tolylh ydyazorzepyr.uz;ic acid (Annalen 239 228)' which we prepared from pyruvic acid and 0 . tolylhydrazine hydrochloride for the purpose of comparing it with our compound. Raschen give 536 JAPP AND KL~NGEMANN THE CONSTITUTION OF the melting-point at 158-159'.gave the following figures on analysis :-The acid prepared by our method I. 0.2214 gram gave 0.5051 gram COz and 0.1221 gram H,O. 11. 0.0988 gram burnt with copper oxide in a vacuum gave 22.63 C.C. of a mixture of nitrogen and nitric oxide measured dry at 15.7" and under 412 mm. pressure After absorption of the nitric oxide there remained 22.63 C.C. dry nitrogen at 16" and under 408 mm. pressure. Found. Calculated for +- -7 C,oH,&z02. I. 11. C 62 22 - 62.50 H 6.13 - 6-25 N 14-58 - 14.67 0 16.67 - -100~00 The hydrazo-acid which had not hitherto been prepared was obtained by reducing tbe acid from 0-diazotoluene and ethylic meth-acetoacetate with sodium amalgam. The acid was precipitated by careful addition of hydrochloric acid and recrystallised from methyl alcohol.It formed tufts of small colourless needles meltiiig at 143". This melting point is possibly too low as the quantity of substance was iiisufficien t for further recryatallisation. Substance. co,. H20. I 0.1911 0.4506 0.1262 11 0.2048 0.4617 0.1331 IIT. 0.0998 gram burnt with copper oxide in a vacuum gave 22-63 C.C. of nitrogen measured dry at 20" and under 412 mm. pressure. Nitric oxide was not present. Found. Calculated for I---- 7 CloHI,N?O?. I. 11. 111. C 61-86 61.45 61.48 -IT. 7.33 7.22 - 7-22 N . . 14.43 - - 14-39 0 . 16-49 100~000 - - -The acid is consequently the expected o-toluenehydmzopropionic acid, CH,*C H* C 0 OH NH.NHCsHa*CH,( 1 2). o-Toluidina was regenerated during the reduction CERTAIN SO-CALLED MIXED AZO-COVPOUNDS.537 Ethylic Jfethacetoacetate and p-Diazotoluene Chloride.-In this case, the " ester," when precipitated with water solidified. It was deposited in yellowish laminse from light petroleum and in needles from alcohol melting at 106". C. H. N. Calculated for C12H,,N,02 . . 65.45 7-27 12.73 per cent. B'ound 65.64 7.33 13.05 ,, The " ester " was hydrolysed with alcoholic caustic soda. The pre-cipitated acid was recrystallised from benzene from which it was deposited in yellow laminae melting at 162" with evolution of gas C. H. N. Calculated for C,,H12N,02 . . 62.50 6.25 14.58 per cent. Found. 62.48 6.28 14.54 ,, This acid is identical with Raschen's p-tolylhydraaonepyrucic acid (Annalen 239 224) which we prepared for comparison.Raschen gives the melting point of the acid at 158-160" ; that of the ethjl salt at 106-107". The hydrazo-acid was not prepared. Ethylic Ethacetoacetate and Diazobenzene Chloride.-In this case, diazobenzene chloride was added to the molecular proportion of ethylic ~~ sodethacetoacetate dissolved in alcohol. The new " ester," when precipitated with water did not solidify and was therefore hydro-lysed with alkali. The acid precipitated with hydrochloric acid, was purified by recrystallisation from benzene which deposited it in yellow needles with a silky lustre melting with decomposition at 152'. I. 0,1984 gram gave 0.4543 gram CO and 0,1139 gram H,O. 11. 0.0927 gram burnt with copper oxide in a vacuum gave 22.63 C.C. of nitrogen measured dry at ltjO and under 384 mm.pressure. Nitric oxide was not present. Found. Calculated for r---7 C,oH*2pJ,~2* I. 11. C 62.44 - 62-50 H 6-37 - 6.25 N 14-58 - 14-63 0 16.67 100-00 - --The acid is phen,ylhydrc~xonepr~p~onylformic acid, CH,*CH,.C*COOH N.NHC,H, 538 JAPP AND KLIKGEM-4NN THE CONSTITUTION OF I n the preliminary account of these reactious which we published (Bey. 20 2943) we described this acid regarding it however as " benzene-a-axobutyric acid." Later W. Wislicenus and E. Arnold (Ber. 20 3395) described an acid obtained from propionylformic acid and phenylhydrazine which ought to be identical with the fore-going. They state that it crystallises from dilute alcohol in lamine melting a t 144-145". By reduction of the sodium salt of the above acid in aqueous solu-tion with sodium amalgam benz ene-a- hy draxo but yric acid, CH,*CH,*CH.COOH NH-NHGH: was obtained.The hydrazo-acid precipitated by hydrochloric acid, avoiding an excess and recrystallised from methyl alcohol formed small colourless needles. The compound exhibits a peculiar be-haviour on heating. At 165" it softens without distinctly melting, and a substance which colours the sulphuric acid in the melting-point bulb violet distils out of the capillary tube; then the contents of the tube again become solid; and before the temperature of 245" is reached a t which a slight residue still left in the capillary tube melts, nearly everything has sublimed out of the tube. The substance was dried over sulphuric acid for analysis.Substance. cop H,O. I . 0.2098 0.4763 0.1395 I1 . 0-2047 0.4645 0.1337 111. 0.0970 gram burnt with copper oxide in a vacuum gave 22.63 C.C. of a mixture of nitrogen and nitrous oxide measured dry at 20" and under 406 mm. pressure. After absorption of the nitric oxide there i-ernained 22.63 C.C. of dry nitrogen at 20",and under 402 mm. pressure :-Found. Calculated for f--- -7 C10H14N202. I. 11. 111. C 61.86 61-91 61.88 -7-39 7-25 - H 7.22 N . . 14.43 - - 14-51 0 16-49 100.00 - - --4. Action of Diazo-salts on Ketonic Acids Formation of Monohydrazones of a-Dicarbonyl-conapou~d~. Acetoacetic Acid atad Diazobenzene Chloride.-65 grams of ethylic acetoacetate were dissolved in a solution of 30 grams of causti CERTAIN SO-CALLED MIXED AZO-COMPOUNDS.539 potash in 1120 grams of water and allowed to stand for 24 hours, after which the solution was acidified with hydrochloric acid in order to liberate the acetoacetic acid. A solution of the molecular propor-tion of diazobenzene chloride (from 47 grams of aniline and 35 grams of sodium nitrite) containing a slight excess of hydrochloric acid was then added. The acid solutions remain clear when first mixed; then a separation of pjruvaldehydrazone (" benzene-azo-acetone "), C H3.C 0.C H :N.NH*C6H5 cornm ences accompanied by an evolution of carbou dioxide ; but the reaction takes place very slowly and is not quite complete even at the end of eight hours. It is therefore better to add to the acid solution after mixing an excess of a solution of sodium acetate ; the reaction then takes place rapidly and an almost quantitative yield of a practically pure product is obtained.I n both cases the pyruvaldehydrazone separates in a crystalline form. It is probably advisable to use rather less diazo-salt than the theory requires. After recrystallising twice from benzene the pyruvaldehydrazone showed the proper melting point 149-150". It yielded a phenyl-hydrazine-derivative melting a t 14.5" which gave with concentrated sulphuric acid the characteristic colour reaction (p. 531). The above is both as regards yield and purity of the product, by far the best method as yet known of preparing pyruvaldehydr-azone. Methacetoacetic Acid and Dinxobenzene Chlo~ide.-The operation was conducted as in the foregoing experiment substituting 72 grams of ethylic methacetoacetnte for the ethylic acetoacetate.On adding sodium acetate to the hydrochloric acid solution of methaceto-acetic acid and diazobenzene chloride diacety Zkydrazone, CH,*C:N*NHCsH, CH,*CO 3 separated in minute needles with evolution of carbon dioxide. The crude product was treated with sodium carbonate to remove any yhenylhydrazonepyruvic acid that might have been formed from unhydrolysed ethylic methacetoacetate and then reci-ystallised from hot benzene which deposited it in yellow tabular crystals mostly grouped staircase-fashion melting a t 133". 0.2350 gram gave 0.5847 gram CO and 0.1414 gram H,O. Calculal ed for ~lOH,,N,O. Found. C . 68-18 67.85 per cent. H 6.82 6.68 ,, The monophenylhydrazone of diacetyl has been prepared from diacetyl and phenylhydrazine by v.Pechmann (Ber. 20 3164) wh 540 JAPP AND KLINGEJIANN THE CONSTITUTION OF gives the melting point at 133" with which our determination exactly agrees. On pouring a concentrated aqueous solution of phenylhydrazine hydrochloride into a hot alcoholic solution of the above nionohydr-line powder melting a t 243". v. Pechmann (Zoc. &.) gives 242" as the melting point of diacetylosazone which we also prepared from diacetyl and phenylhydrazine and found identical in all its proper-ties with the compound obtained by us. A nitrogen determination was made with our compound :-0.1074 gram burnt with copper oxide in a vacuum gave 22.63 C.C. of a mixture of nitrogen and nitric oxide measured dry a t 11" and under 627 mm.pressure. After absorption of the nitric oxide, there remained 22.63 C.C. of dry nitrogen a t 11" and under 621 mm. pressure. Calculated for C,,H,*NI. Found. N in 100 parts 21.05 20.88 Diacetylosazone gives a colour-reaction with concentrat'ed sulphuric acid. It dissolves in the cold with a brown colour ; but this speedily changes to a claret-red which in thin layers appears green. E'tlzacetoacetic Acid and Diazobenzene Chloride.-The experiment was performed as in the preceding cases exceptl that the ethylic ethnceto-acetate required longer shaking with the caustic potash solution to make it dissolve and owing to the greater difficulty with which it is hydrolysed it was allowed to stand in alkaline solution for 48 hours instead of for 24.In this case the propionylacetylhydrazone C2H5'c:N'NHCsH5 separated as a red oil on the addition of sodium CH3.CO acetate to the hydrochloric acid solution of ethacetoacetic acid and diazobenzene chloride. On dissolving this oil in a small quantity of alcohol the new compound was deposited in a solid form. The product was treated with sodium carbonate to remove any acid. From concentrated solutions in hot beiizene it crystallised in yellow needles or prisms radiating from a point ; from dilute solutions in large transparent plates. I n spite of the apparent purity of the substance the carbon was found to be 1 per cent. too low on analysis and the hydrogen was also too low. Only after repeated recrgstallisatior~ from benzene were numbers obtained agreeing fairly well with the theory :-It melted a t 116-117".8 ubatance. cop HZO. I . 02669 0-6762 0.1748 11. 02333 0.5908 0.150 CERTAIN SO-CALLED MIXED AZO-COMPOUNDS. 541 Found. 7 Calculated for T-h-C,,H,4N,O. J. 11. C 69-47 69-09 69.06 H 7-36 7.28 7.17 We suspect, therefore that the substance was contaminated with a small quantity of pyruvaldehydrazone which would be formed if the ethylic eth-acetoacetate contained as it very easily might unchanged ethylic acetoacetate. We find that propionylacetylhydrazone and pyruv-aldehydrazone crystallise together. Possiblya small quantity of the same impurity formed in the same way was present in the specimen of diacetylhydrazone which we analyaed (ante) in which the hydrogen was also found too low. Even in these analyses the hydrogen is too low.C!2H5.C:N'NHC6H5 was obtained The osazone of propionylacetyl CH,.C:N.NHC,H5, by heating an alcoholic solution of the foregoing compound with phenylhydrazine hydrochloride a i d sodium acetate. It crystallises from benzene in yellow needles melting at 162" which give with concentrated sulphnric acid exactly the same colour-reaction as the osazone of diacetyl (p. 540) .* 0.1012 gram burnt with copper oxide in a vacuum gave 22.63 C.C. of a mixture of nitrogen and nitric oxide measured dry at 14" and under 557 mm. pressure. After absorption of the nitric oxide there remained 22.63 C.C. of dry nitrogen at 14" and under 553 mm. pressure. Calculated for C17H20N4' Found. N in 100 parts 20.00 19.51 5. Action of Heat o n Hydrazones of Ketonic Acids and o n Alclehydrazorbes Formation of Osaxones.Action of Heat on Phenylhydrazonepyruvic Acid.-A quantity of phenylhydrazonepyruvic acid was heated in an oil-bat]h at 180-190" until gas ceased to be evolved. From the dark-coloured oil thus obtained a crystalline substance separated on adding alcohol. It was * No. 6 of the Berichte received after the above was in type contains an account of the hjdrazones of propionylncetyl by v. Pechmann. The author prepared these compounds by the direct action of phenylhydrazine on propionylacetyl. He finds that the monohydrazone obtained in this way is distinct from our compound and he therefore assigns to i t the formula-C2HS * C 0 CH3.C N*NHC,jH,' For the osazone he finds the melting point a t 161-162.5' agreeing wit11 our deter-mination 542 JAPP AND KLINGEMANN THE CONSTITUTION OF washed with hot alcohol in which it is only sparingly soluble and dried for analysis.It formed a yellow crystalline powder melting at 238". Analysis led t o the formula C,,H,,N,. I. 0,1717 gram gave 0.4536 grain CO and 0.1041 gram H,O. 11. 0.1047 gram burnt with copper oxide in a vacuum gave 22.63 C.C. of a mixture of nitrogen and nitric oxide measured dry at 14.7" and under 617 mm. pressure. After absorption of the nitric oxide there remained 22-63 C.C. of dry nitrogen at 15" and under 610 mm. pressure. Found. Calculated for r---7 C16H1RN4. I. 11. C 72.18 72.04 -H 6.77 6.73 N 21.05 - 20.78 -100*00 The compound was soluble in cold concentrated sulphuric acid with a brown colour changing afterwards t o a claret-red which in thin layers amppeared green.The formula and the colour-reaction with sulphuric acid are there-fore those of diacetylosnzone (p. 540) with which the compound is indeed identical. The difference in the melting point-238" instead of 242"-is due to the fact that the substitiice owing to the smallness of the quantity available was not recrystallised. The yield is very small. The formation of the osazone of diacetyl in the above reaction may be expressed thus :-CH3*C:N,HC,Hj I CH,*C:N2HC,H, Action of Heat on AZdehydrazone.-As already mentioned Fischer and Jourdan have shown (Zoc. cit.) that the oil which is obtained on heating phenylhydrazonepyruvic acid mainly consists of aldehydr-azone (ethylidenepheny1hydrazine)-CH3*C:N,HC,Hj = CH3*CH:N,H.CsH + CO,.COOH It therefore seemed possible that the osazone of diacetyl had been formed from the aldehydrazone in a secondary reaction according to the equation CERTAIN SO-CALLED MIXED AZO-COMPOUNDS. 54 3 We therefore heated aldehydrazone wit,h a reflax condensing- tube for three hours. On adding alcohol to the liquid product the ex-pected osazone separated as a crystalline powder. I t was identified by its melting point (237-238") and by the reaction with sulphuric acid. The yield is very small but may be somewhat increased by passing air through the aldehydrazone during the heating process. The osazone obtained by the above methods was carefully compared with a specimen prepared from diacetyl arid phenylhydrazine.Action of Heat on the Tolylh~clrcnzolzepyr~~vic Acids.-o-Tolylhydr-azonepyruvic acid when heated f o r some time at its melting point, yielded in like manner diacetyl-o-toZy ZosazolLe, CE3~C:N2H*C6H4~CH3 CH,-C:N,H.C,H,*CH (17 2)9 which separated from the oily product of the reaction on adding alcohol. It formed a yellow crystalline powder melting at 198", sparingly soluble in alcohol. The sulphuric acid reaction is not characteristic; the compound dissolves in the concentrated acid with a brown colour which afterwards changes to a reddish-brown. The same compound was obtained by heating an aqueous solution of diacetyl with o-tolylhydrazine hydrochloride and sodium acetate. I. 0.0827 gram burnt with copper oxide in a vacuum gave 22-63 C.C.of a mixture of nitrogen and nitric oxide measured dry at 15.5" and under 448 mm. pressure. After absorption of the nitric oxide there remained 22.63 C.C. of dry nitrogen at 15.5" and under 444 mm. pressure. 11. 0.0754 gram burnt with copper oxide in a vacuum gave 22.63 C.C. of a mixture of nitrogen and nitric oxide measured dry at 14" and under 402 mm. pressure. After absorption of nitric oxide there remained 22.63 C.C. of dry nitrogen at 14" and under 400 mm. pressure. Found. r. Calculated for C18H22N4. I. N in 100 parts . . . . . . . 19.05 19-08 18.92 Analysis I was made with a preparation obtained from 0-tolyl-hydrazoriepyruvic acid ; analysis I1 with a preparation from diacetyl and o-tolylhydrazine. p-Tolylhydrazonepyruvic acid yields when heated diacety Z-p-toty Zos- -azone " ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ (1 4).It was separated like the foregoing compounds of this class and formed a yellow crystalline powde 5-14 SHENSTONE AND CUNDALL INFLUENCE OF TEMPERATURE melting a t 229-230". It dissolves in cold concentrated sulphuric acid with a brown colour which changes through yellow and greenish-yellow to green. 0*1101 gram burnt with copper oxide in a vacuum gave 22.63 C.C. OE a mixture of nitrogen and nitric oxide measured dry a t 11" and under 585 mm. pressure. After absorption of the nitric oxide there remained 22-63 C.C. of dry nitrogen a t 11" and under 580 mm. pressure. Calculated for c 1 8H22N4. Found. N in 100 parts . . . . . . . . 19.05 19-02 The same compound was obtained by the action of free p-tolyl-hydrazine on diacetyl in ethereal solution. Curiously enough when we attempted to prepare the compound like its ortho-isomeiide, by heating an aqueous solution of diacetyl with p-tolylhydrazine hydrochloride and sodium acetate only the mono-y-toZyZhydrazone, CH3*c:N2H'C6H4*CH3 (l' was formed. It crystallises from benzene CH,*CO in slender yellow needles melting at 161". A nitrogen determination gave 14-91 per cent. Calculated N 14.73 per cent. Normal School of Xcience, South Kensington

ISSN:0368-1645    

DOI:10.1039/CT8885300519

出版商:RSC    

年代:1888

数据来源: RSC