摘要:

PRIEDEL AND CRBFTS’ REACTION. PART I. 1335 CXLIII.-Mochjkation and Extension of the Friedel and Crafts’ Reaction. Part I. By JNANENDRA NATH RAY. RADZIEWANOVJSKI (Ber. 1895 28 1139) suggested some modifi-cations of the Friedel-Crafts’ reaction in one of which he used a mixture of aluminium powder and mercuric chloride. He pre-pared ethylbenzene in small yield but did not obtain any tri-phenylmethane in the condensation of chloroform and benzene. Von Gulewitsch (Rer. 1904 37 1560) studied the interaction of mercuric chloride and aluminium in benzene and isolated a com-pound C,H6,A1C1,,RgC1. A similar compound was formed with toluene. It was thought that i f this double compound were employed as a catalyst t,he secondary changes that rendered Radziewanowski’s reaction unsuccessful might disappear.This expectation has been amply realised. Von Gulewitsch showed t8he course of the reaction to be C6H6 + A1 + 2HgC1 -+ C6H6,A1C1,,HgC1 + Hg. The mercury liberated as above forms an amalgam with the unchanged aluminium but when an excess of mercuric chloride is employed this tendency to amalgamate is reduced inasmuch a 1336 RAY MODIFICATION AND EXTENSION OF THE the whole of the aluminium is utilised in reducing mercuric to mercurous chloride. The success of the reaction depends on the non-formation of the amalgam as otherwise it acts concurrently with the double compound. Some interesting products have been isolated in the condensation of the hydrocarbons with chloroform carbon tetrachloride benzyl-idene chloride etc. Thianthren has been prepared in an 80 per cent.yield from benzene and sulphur. This compound was obtained in small amount along with phenyl niercaptan phenyl sulphide and phenyl disulphide by Friedel and Crafts ( A n n . Chim. Pliys. 1888 [vi] 14 438) in the condensation of benzene and sulphur wit9h aluminium chloride whilst Genvresse ( 7 3 u I I . SOC. chim. 1897 [iii] 17 599) observed the formation of thianthren and isothianthren in the same reaction. 9 10-Diphenyl-9 10-dihydrosnthracene is formed by the con-densation of benzene and chloroform whilst in the ordinary Friedel-Crafts' reaction (Annalen 1878 194 254 ; 1885 227, 107) triphenylmethane cliloroarylmethanes and t'etraphenyl-ethane (h'er. 1893 26 1952) are the products. The same compound is obtained by the interaction of benzylidene chloride and benzene.Carbon tetrachloride and benzene give 9 9 10 10-tetmphenyl-9 1 0-dihytZroanthrace~ze which is also obtained from benzotri-chloride and benzene whilst in the usual reaction triphenyl-methane chloroarylinethanes ( A nnnlen 1878 194 254) and tetra-phenylethylene (Ber. 1893 26 1952) are obtained. Similarly dimethyl-9 10-ditol~l-9 10-tlilaydroan thracene has been obtained from chloroform and toluene. In this condensation, using aluminium chloride Schwarz ( R e r . 1881 14 1530) pre-pared tet~atolylet~hane which has ilhe same melting point ( 2 1 5 O ) and empirical formilla hiit a niixture of the two melts at, 20G-208°. Renzylidene chloride and toluene yield dimethy!-9 10-diphcnyl-9 3 O-diJiyilron,ntJ~raceiie.Finally chloropicrin and benzene under the action of the reagent, furnish w-nitrotriphenylmethane previously obtained by the direct addition of nitrogen peroxide to triphenylmethyl (Schlenk Mair and Bornhardt BPT. 1911 44 1172). Boedtker (BUZZ. Sot. chim. 1908 [iv] 3 726) states however that all aliphatic nitro-compounds lose their nitro-groups under the influence of aluminium chloride arid obtained triphenylmethane and some triphenylcarbinol in this reaction FRIEDEL AND CRAFTS' REACTION. PART I. 1337 E x P E R I M E N TAL. To a mixture of 20 C.C. of dry benzene and 20 grams of mercuric chloride contained in a flask with reflux condenser 1 gram of aluminium powder was added gradually and the flask vigorously shaken. The heat of the reaction caused the benzene to boil and the flask was occasionally cooled in an ice-bfth.A green crystal-line mass eventually separated and the reaction was completed by immersing the flask in tepid water for half an hour. The mercury liberated in the reaction was reiiioved and the preparation of the catalyst was coi~plete. In all the reactions described below the components were well agitated by a mechanical stirrer. Acetophenone.-The calculated amount (I niol.) of acetyl chloride was added through the condenser in small quantities a t a time the mixture allowed to reiilain for two hours a t the ordinary temperature and then heated t,o 400 for an hour. On cooling i t was decomposed with water and the oil extracted with benzene, the benzene solution being dried and finally fractionated.The yield of acetophenone was GO per cent. of the theoretical whilst by Friedel and Crafts' method i t is 55.5 per cent. p-Tolyl iMethyl Ice tone.-Following an almost identical method, from 33 C.C. of toluene 2.5 grams of aluminium and 45 grams of mercuric chloride 16.1 grams of this ketone were obtained. 9 Thianthren C,H4<s>C,H,.-The cat'alyst was prepared from 2.5 grams of aluminium 45 grams of mercuric chloride and 30 C.C. of benzene; I0 grams of flowers of sulphur were added and the mixture was heated on the water-bath until hydrogen sulphide was no longer evolved. The product on cooling was decomposed with ice filtered and the residue repeatedly extracted with chloro-form from which the substance was obtained on concentration. When crystallised from acetone i t melted a t 160O.The yield was 14 grams (Found C=66*1; H=3.8; S=28*5. Calc. CI~66.6 : H=3*7; S=29*6 per cent!.). 9 10-Diphenyl-9 lO-diltydroniLtlzmcene.-The catalyst was pre-pared from 1 gram of aluminium 20 grams of mercuric chloride, and 15 C.C. of benzene. Six C.C. of chloroform were added drop by drop through the condenser and the flask was allowed to remain a t the ordinary temperature for two hours and then heated for an hour a t 40° and then for another hour a t 40-50°. On cool-ing the product was decomposed with ice and filtered. There separated from the filtrate a deep red oil from which some un-changed benzene was evaporated. The residue was extracted wit 1335 RAY MODIFICATION AND EXTENSION O F THE boiling acetic acid containing a little water from which the com-pound separated on cooling.After being crystallised from dilute alcohol and then repeatedly from dilute acet,one the compound melted at 159O (Linebarger Amer. Chem. J. 1891 13 556 gives 164.2') (Found C=93*2; H=6-7. Calc. C=93*9; H=6*1 per cent.). The same compound was obtained by the interaction of 3 C.C. of benzylidene chloride 8 C.C. of benzene 0.5 gram of aluminium, and 10 grams of mercuric chloride the reaction being completed a t 50-55O. The product was isolated as described above (Found: C =34.0; €1=6*39. Calc. C= 93.9; H=6*1 per cent.). A solu-tion of 1 gram of the substance in acetic acid was oxidised with an acetic acid solution of chromium trioxide and the product poured into water. The resinous mass was dried and then sublimed and the sublimate was proved to be anthraquinone by the method of mixed melting points.The diacetyl derivative was prepared by heating 1 gram of the substance with 10 C.C. of acetic anhydride and four drops of pyridine under reflux for an hour. The product was poured into water and neutralised with sodium carbonate. The viscous mass solidified and after being fractionally crystallised from dilute alcohol melted a t 9 2 O (Found C=85*3; H=7*4. C28H2402 requires C=85-7; H=6-8 per cent.). condensa-tion was performed as in the preceding case the catalyst being prepared from 1 gram of aluminium 20 grams of mercuric chloride, and 15 C.C. of toluene. Chloroform (1 mol. for 2 niols. of toluene) was added through the condenser and finally the reaction was completed a t 70°.The oily product obtained after the decompasi-tion of the mixture with ice after being freed from chloroform and toluene solidified when kept in a vacuum desiccator and when crystallised from dilute acetic acid melted a t 2 1 5 O (Found: C=92*0; H=7-9. catalyst , prepared from 8 C.C. of toluene 0.5 gram of aluminium and 10 grams of mercuric chloride was treated with 4 C.C. of benzyl-idene chloride the reaction being completed by heating at 60-70° for two hours. The oily product obtained after the usual treat-ment was dried and distilled under diminished pressure when some oily matter passed over and the residue solidified. This was extracted with hot alcohol and on concentration a product was obtained which after crystallisation from acetic acid melted a t 1 8 5 O (Found C= 92.8 ; H = 7.0.C&H2* requires C = 93-3 ; H = 6.7 per cent.). Dimethyl-9 10-ditolyl-9 10-dihydr0anthracene.-This C,H2 requires C=92.7; H=7.3 per cent.). Dime t hyl- 9 10 -dip heny l-9 1 0-di hydroaltt hracene .-Th FRIEDEL AND CRAFTS' REACTION. PART I. 1339 9 9 10 10-Tetraykenyl-9 lO-dih?/cEroulLthrucenf:.-Eight C.C. of carbon tetrachloride were added to the catalyst prepared from 20 C.C. of benzene 1 gram of aluminium and 20 grams of mercuric chloride and the whole was kept a t 50-60° for two hours and then at TOo for an hour. After decomposing the product with ice and filtering the dried residue was extracted with carbon disulphide from which some of the tetraphenyl derivative was obtained.The filtrate separated into two layers and the benzene layer on evaporation gave a further quantity of the substance, which when crystallised from dilute acetone melted a t 159' (Found C=94.0; H=6*8. C,H requires C=94*2; H=5*8 per cent.). The same compound was obtained by adding 5 C.C. of benzotrichloride in the course of half an hour to the catalyst pre-pared from 15 C.C. of benzene 1 gram of aluminium and 20 grams of mercuric chloride. The product isolated as above melted at 169O (Found C=94*02; H=5.1. Calc. C=94-2; H=5*8 per cent.). o-Nitrotriphen?/lmethane .-Five C.C. of chloropicrin were used with 20 C.C. of benzene. The mixture was warmed first in a tepid-water bath and then for a few hours at 45O. The product was decomposed with ice distilled in a current of steam and the resi-due filtered dried and extracted with much boiling alcohol. This, on concentration deposited o-nitrotriphenylmethane which on recrystallisation from alcohol melted and decomposed a t 145' (Found C=78*49; H=5.54; N=4.5. Calc. C=78*8; H=5*1; N = 4.8 per cent.). I n conclusion I wish t o express my best thanks t o Sir P. C. Rgy for the interest he has taken in the work and to Mr. M. L. Dey for his criticisms and suggestions. CHEMICAL LABORATORY, COLLEGE OF SCIENCE, UNIVERSITY OF CALCUTTA. [Received May 216t 1920.

ISSN:0368-1645    

DOI:10.1039/CT9201701335

出版商:RSC    

年代:1920

数据来源: RSC

摘要:

1340 SIDGWICK THE FREEZING POINT OF WET BENZENE, CXL1V.-The Fyeezing Point of Wet Benzene and the Injihence of Drying Agents. By NEVIL VINCENT SIDGWICK. DURING the purification of benzene by freezing for cryoscopic purposes irregularities were observed in the freezing points of successive fractions which were found to be due to traces of water absorbed from the air. This suggested the determination of the maximum depression of the freezing point of benzene by water. I n a previous paper (T. 1915 107 675) it was stated that this depression amounts to 0*042O but later work has shown that the readiness with which benzene absorbs water from the air had been underestimated and that the original benzene was not really dry. If proper precautions are taken to dry the benzene its freezing point is lowered 0*1000 by the addition of excess of water." This affords a convenient method for determining the efficiency of various drying agents.I f the wet benzene is shaken with 8 solid dehydrating agent which is insoluble in it until a constant freezing point is obtained the ratio of the depression observed in the presence of the drying agent to that produced by pure water is a measure of the lowering of the vapour pressure of the water by the latter and hence of the efficiency of the drying agent This efficiency must be the same (at temperatures near 5 O ) for a solution in any solvent in which the drying agent is insoluble. E X P E R I M E NTAL. Two samples of benzene each about a litre were used one ( A ) was kindly given me by Dr.Hewitt and Mr. W. J. Jones; it was of English origin and had been purified by them. The other ( B ) was Kahlbaum's purest. Neither gave more than the faintest trace of the hdophenine reaction. I n the later stages irregularities of several hundredths of a degree were observed in the freezing points which disappeared when the measurements were made in the presence of potassium carbonate. When the freezing points appeared to be constant the benzene * After this work was finished a paper appeared by Richards Carver and Schumb ( J . Amer. C h ~ m . SOC. 1919,41 2024) in which two experiments are described on the depression of the freezin? point of pure benzene by water, giving th? values 0.093' and 0'096" mean 0.095". This is in satisfactory agreement with the value 0*100" adopted in the present paper.These were further purified separately by repeated freezing AND THE INFLUENCE OF DRYING AGENTS. 1341 was still further purified by the method described by Richards and Shipley ( J . Amer. Chem. SOC. 1914 36 1825) and by Richards and Barry (ibid. 1915 37 993). It mas boiled for some hours with clean sodium (previously washed with the benzene) in a flask with a bent reflux condenser and drying tube. The condenser was then inclined downwards and connected to the side-tube of a carefully dried Beckmann apparatus. A steady stream of dried air was passed into the apparatus through the sheath of the stirrer, which was expanded into a bulb in the usual way to prevent moist air from being drawn in when the stirrer was raised.It is essential that the access of moist air should be prevented; in one experiment the condenser tube was accidentally separated from the Beckmann apparatus for a minute and this caused a drop in the freezing point of several thousandths of a degree. To the condenser tube between the water- jacket and the freezing-point apparatus a rather narrow side-tube was sealed so as to point downwards when the condenser was in position for distillation. The first runnings escaped through this tube which was then closed by attaching a test-tube to it with an air-tight cork. The tube then filled up with liquid and the rest of the distillate ran straight into the freezing-point apparatus. Several readings of the freezing point having been taken two or three drops of water were added the tube was warmed with the hand and well stirred and the freezing point again observed.This gave the difference between the freezing point of pure benzene and that of benzene saturated with water (the triple point solid benzene-liquid benzene-water). Then about half a gram of dry, powdered potassium carbonate was added and thoroughly stirred, and the freezing point again taken. A smaller quantity of the salt was then added in the same way and if this raised the freez-ing point another small quantity was added; more than three additions were never required. This gives the temperature of the quadxple point solid benzene-solid potassium carbonate-benzene solution-saturated aqueous solution of potassium carbonate. These operations were performed with successive frozen-out fractions of the purified benzene and the results are given in the following table.The temperatures are referred to the arbitrary zero of the Beckmann thermometer which remained constant during the experiments; each is the mean of several concordant readings, corrected for the temperature of the emergent stem. The fractions marked A are the English benzene B the German; the index number following this shows the number of times it had been frozen out; thus A 7 is the fraction obtained by freezing out the English beqzene seven times 1342 SIDGWIUK THE JFREEZING POINT OF WET BENZENE, 111. I. 11. Wet with Dried by With potassium Fraction. sodium. wet,er. carbonaDe. I.-11. 111.-11. A 7 ............ 3.120" 3.021' 3-080' 0.099" 0.059" A 7 ............3.121 3-02 1 3.081 0.100 0.060 ............ 0.060 A S - 3-023 3.083 - ............ - 0.098 - A 9 3.119 3.021 B 6 ............ 3.115. 3.015 3.075 0.100 0.060 ............ 0.061 B 7 - 3.020 3-08 1 -B8 ............ 3.121 3.022 - 0.099 -............ 0.061 B S - 3.022 3.08 1 -Means A.... 0.099 0.060 B.... 0.100 0-061 The freezing point is thus lowered O*lOOo by saturation with water. If the molecular weight of the dissolved water is 18 its solubility at 5.4" (assuming the cryoscopic constant 51O) must be 0.035 gram per 100 grams of benzene. Groschuff (Zeitsck. EZektrochem. 1911 17 348) found that 100 grams of benzene a t 3O dissolve 0.030 gram of water and a t 23O 0.061 which would mean about 0.032 gram a t 5*4O agreeing with the observed depression for a molecular weight of 18.The value 0.24 gram in 100 grams at 22" given by Herz (Ber. 1898 81 267) is presumably erroneous. On the addition of potassium carbonate water is withdrawn from the benzene t o form a saturated solution of the salt the vapour pressure of which is lower than that of pure water; the concentration of the benzene solution diminishes and its freezing point rises by 0'061" being 0.039O lower than that of pure benzene. Other dehydrating agents were then examined in the same manner. Carefully dried and powdered specimens of sodium sulphate copper sulphate and calcium chloride were used and also powdered sodium hydroxide and pure phosphoric oxide ; this last blackens rapidly in impure benzene but remains quite colourless in the pure liquid.All these compounds differ from potassium carbonate in forming hydrates with the water and it is perhaps for this reason that some of them especially copper sulphate act more slowly and must be stirred with the liquid for some time before their full effect appears. In these experiments the benzene was not in each case distilled over sodium but a mixture of the fractions A 9 and B8 which had been so treated was saturated with water and aEter its freezing point had been measured it was dried with the saIt and the rise of freezing point so produced was observed AND THE INFLUENCE 0%' DRYING AGENTS. 1343 Drying agent. None ........................... Sodium sulphate ............ Potassium carbonate ...... Copper sulphate ............ Calcium chloride ............Sodium hydroxide.. .......... Phosphoric oxide ............ Elevation of freezing point.. 0.024" 0.061 0.089 0.091 0.098 0.100 -Depression by water + agent. o*looo 0.076 0.039 0.01 1 0.009 0.002 0-000 The removal of water by phosphoric oxide seems to be quite complete. The middle column in the above table gives a measure of the relative efficiency of the drying agents examined. If water in benzene solution is unimolecular its concentration in the solution is proportional to the pressure of its vapour and hence the depression given in the last column is directly proportional to the vapour pressure of the system drying agent-lowest hydrate (or saturated solution in the case of potassium carbonate)-vapour . The last column in the following table gives the values of the tension of aqueous vapour calculated on this hypothesis. The pre-ceding column gives the actual freezing points based on the revised value given by Richards Carver and Schumb (see foot-note on p. 1340) for pure benzene. System. pure ........................... saturated with water ... wet + sodium sulphate ... , + potassium carbonate ,) + copper sulphate ... ) + calcium chloride ... y +sodium hydroxide , + phosphoric oxide . Freezing point. 5493" 5.393 5.420 5.454 5.482 5.484 5-491 5.493 Tension ?f aqueous vapour in mm. 6.73 5.11 2.62 0.74 0.61 0.13 0.00 -The relative efficiency of these substances is of course the same for drying solutions in any other solvents in which they do not dissolve. ORGANIC CHEMISTRY LABORATORY, OXFORD. [Received August 13thy 1920.

ISSN:0368-1645    

DOI:10.1039/CT9201701340

出版商:RSC    

年代:1920

数据来源: RSC

摘要:

1344 ROWE AND DAVIES: CXLV.-Studies in the Acenaph thene Se'vies. Part I. me Conversion of o- A'itroamines into isoOxadiuxole Oxides. By FREDERICK MAURICE ROWE and JOHN STANLEY HERBERT DAVIES. IN four previous communications (T. 1912 101 2452; 1913 103, 897 2023; 1917 111 612) one of us has shown that many o-nitro-amines in the benzene and naphthalene series are converted into f uroxans (furazan oxides or isooxadiazole oxides) when oxidised in alkaline solution with sodium hypochlorite. I n order further to test the generality of this reaction we have now carried out similar experiments in the acenaphthene series. Sachs and Mosebach (Ber. 1911 44 2852) have shown that whilst the direct nitration of acenaphthene yields a dinitro-derivative which contains the nitro-groups in the 3 4- or peri-position the reduction of 3-nitro-acenaphthene followed by acetylation nitration and hydrolysis of the resulting nitroacetylaminoacenaph thene gives rise to 2-nitro-3-aminoacenaphthene.The latter compound which contains the nitro- and amino-groups in the ortho-position with respect to one another has now been submitted to the hypochlorite oxidation. It is interesting to note that although the yield of the oxidation product was low the methylene groups of the acenaphthene ring remained unaffected and acenaphthene-2 3-isooxadiazole oxide was obtained. The corresponding compounds in the benzene and naphthalene series possess a charact'eristic almond odour and are readily volatile with steam but this compound is odourless and non-volatile.It is reduced by hydroxylamine to acenaphthene-2 3-quino?zediozime which may be converted into acenaphthene-2:S-isoozadiazole in the usual manner although the yield is not good. An attempt to reduce 2-nitro-3-acetylaniinoacenaphthene to the corresponding nitroso-compound in a similar manner to that used by one of us for the preparation of o-nitrosoacetanilide (Zoc. c i t . ) , in order to prepare acenaphthene-2 3-isooxadiazole from it by the alkaline hypochlorite oxidation proved unsuccessful. o-Quinoneclioximes are readily converted into isooxadiazole oxides by oxidation in alkaline solution with sodium hypochlorite, and consequently it was t o be expected that the oxidation of acenaphthene-7 I 8-quinonedioxime in this manner would yield an isooxadiazole oxide derivative of acenaphthene of a different typ STUDIES IN THE ACENAPHTHENE SERIES PARTI.1345 from that already described. This in fact proved to be the case, and acenaph thene-7 8-isooxadiazole oxide was obtained. On the other hand acenaphthene-7 8-quinonedioxime resisted all attempts to convert i t into acenaplithene-7 8-isooxadiazole by the removal of water. It remained unaffected by prolonged boiling with aqueous sodium hydroxide and when heated with aqueous sodium hydroxide in a sealed tube decomposition occurred with the form-ation of acenaphthenequinone and ammonia whilst no better result was obtained by heating with water in a sealed tube. Moreover, treatment of the diacetyl derivative of acenaphthene-7 S-quinone-dioxime with sodium hydroxide merely resulted in hydrolysis with no dehydration.This failure to dehydrate acenaphthene-7 8-quinonedioxime suggests that this coinpound most probably has the structure of a P(anti)-dioxime (I). The failure of this compound 0-0 HO*N:C-C:N*OH N 5 .. .. C-C! to give a nickel salt when treated with ammoniacal nickel solutions, as described by Atack (T. 1913 103 1317) in an investigation of the three stereoisomeric henzildioximes further supports this view. The preparation of acenaphthene-7 8-isooxadiazole oxide was of interest in view of the fact that Francesconi and Pirazzoli (Gazzetta 1903 33 i 36) prepared a compound by boiling acenaphthene-7 8-quinonedioxiine with aniyl nitrite to which the peroxide formula (TI) was provisionally assigned.This compound is described as forming reddish-brown crystals decomposing a t 90° and melting a t 1 4 0 O . It is soluble in organic solvents with decom-position forming a black substance which does not melt a t 260O. We therefore prepared a quantity of this compound in order to determine whether it was identical or not with acenaphthene-7 8-isooxadiazole oxide. After repeated crystallisation it was obtained finally in small brown needles decomposing at 190° and melting a t 206*5O and when pure it was not decomposed by organic solvents. This substance possesses quite different properties from those of acenaphthene-7 8-isooxadiazole oxide ; for example the former dissolves in cold aqueous sodium hydroxide with a pale yellow colour whilst the latter is quite insoluble in alkali hydr-oxides and moreover is readily reduced to acenaphthene-7 8-quinonedioxinie by hydroxylamine.J t is evident that the tw 1346 ROWE AND DAVIES: compounds are not identical and Francesconi and Pirazzoli’s com-pound was not examined more closely but in view of its properties, it seemed doubtful whether it possesses the peroxide formula assigned to it by these authors. When the present investigation was commenced the literature contained no reference to nitro-derivatives of acenaphthenequinone, and it was decided to fill in this blank. After the necessary experi-ments had been carried out however these compounds were described by Mayer and Rauffmann (Ber. 1920 53 [B] 296). The product of moiionitration is 3-nitroacenaphthenequinone melting a t 218O (M.and K. give 1 9 9 O ) which forms a monophenyl-hydrazone melting a t 234-235O (M. and K. give 186O) and the product of dinitration is 3 4-dinitroacenaphthenequinone melting and decomposing above 300° which forms a monophenylhydrazone darkening a t 260° and melting at 287O. I n conclusion ii appeared of interest t o ascertain whether the nitro-derivatives of acenaphthenequinone could be prepared by the oxidation of the nitro-derivatives of acenaphthene as the pre-paration of a substituted acenaphthenequinone by the oxidation of the corresponding derivative of acensphthene has been effected only in one instance namely by Graebc ( i l 9 ? n d e n 1903 327 7 7 ) , who found that 5-bromoacenaphthene was oxidised either to bromo-acenaphthenequinone or bromonaphthalic acid according to the conditions used.Experiments were made with S-nitroace-naphthene using a series of oxidising agents under a variety of conditions but i t was found that this compound either remained unaffected or was oxidised t o 4-2iitronaphthalene-1 8-dicarboxylic acid melting as anhydride at 229-230° (Graebe gives 220°) and in no case could we isolate any 3-nitroacenaphthenequinone . E X P E R I M E N T A L . The 2-nitro-3-aminoacenaphthene required was obtained by Sachs and Mosebach’s method (Zoc. cit.). Acenaphthene (m. p. 96O) was nitrated in glacial acetic acid suspension and the product extracted with light petroleum (b. p. goo) in which any dinitro-derivative formed simult.aneously is insoluble. The yield of 3-nitroacenaphthene7 yellow needles melting a t 101-102° was 89 per celntl.(S. aad M. give 84 per oemt.). The r d u d i m od th STUDIES IN THE ACENAPHTHENE SERIES. PARTI. 1347 nitro-compound is best effected in aqueous-alcoholic solution with sodium hyposulphite. The yield of 3-aminoacenaphthene almost colourless silky needles melting a t 104-1Oti0 was 71 per cent. (S. and M. give about 77 per cent. of an almost pure product). The monoacetyl derivative is best prepared with acetyl chloride. After repeated crystallisation from methyl alcohol 3-acetylamino-acenaphthene glistening needles melting a t 238O was obtained in a yield of 92 per cent. The melting point of this compound is greatly affected by traces of impurities; thus Quincke (Ber. 1885, 21 1457) gives 176O Graebe (Aniznlen 1903 327 77) gives 1 8 6 O , and Sachs and Mosebach (Zoc.cit.) give 1 9 2 O . A number of nitra-tions were carried out but the yield was always low owing to oxidation ; 2 - nitro - 3 - acetylaminoacenaphthene golden-yellow needles melting a t 255O was obtained in a yield of 35 per cent. (S. and M. give 253'; yield about 54 per cent.). When hydro-lysed with alcoholic' hydrochloric acid 2-nitro-3-aminoacenaphthene, blunt red prisms with a green lustre melting at 222O was obtained in an almost t,heoretical yield (S. and M. give 85 per cent.). The oxidation of 2-nitro-3-aminoacenaphthene was best effected by the addition of an excess of alkaline sodium hypochlorite to a hot alcoholic solution of the nitroamine. The mixture was boiled for a short time cooled diluted with water and the precipitate collected.When crystallised from alcohol or acetic acid, acenaphthene-2 3-isoozadiazole oxide forms pale brown needles melting a t 177-178O. The compound is odourless non-volatile with steam and when heated with zinc dust ammonia is evolved and naphthalene formed (Found N = 13.32. A yield of 50 per cent. was obtained. C12FI,02N2 requires N = 13.2 per cent.). This cornpound was formed by the reduction of acenaphtheae-2 3-isooxadiazole oxide with an excess of hydroxylamine (at least four molecular proportions). It was difficult t o isolate owing t o the ease with which it was converted into acenaphthene-2 3-iso-oxadiazole. The best results were obtained by dissolving the isooxadiazole oxide in alcohol and adding an aqueous solution of hydroxylamine hydrochloride after which the mixture was rendered alkaline with sodium hydroxide a t 50° and heated for twenty minutes on the water-bath at 60°.The brown solution was cooled acidified with acetic acid and diluted with water. Th 1348 ROWE AND DAVIES: precipitate was extracted with dilute sodium hydroxide filtered, and the filtrate precipitated with acetic acid. The quinone-dioxime separates as a colloidal precipitate which it was not found possible to crystallise. When dry it forms a brown amorphous powder which decomposes when heated and does not melt below 280° sparingly soluble in organic solvents but dissolving readily in alkali hydroxides with a brawn colour. On oxidation with sodium hypochlorite i t is reconverted into acenaphthene-2 3-iso-oxadiazole oxide and on heating with sodium hydroxide it is converted into acenaphthene-2 3-isooxadiazole (Found N = 13.34.CI2H,,O,N2 requires N = 13.08 per cent .) . CH,*CH . . A cenaphthene-2 3-isooxaditsxole, Acenaphthene-2 3-quinonedioxime was dissolved in dilute sodium hydroxide and distilled in a current of steam. The product after recrystallisation from acetic acid forms yellow needles melting a t 143-144O. It is only slightly volatile with steam and the yield is low owing to the formation of a large proportion of a black, non-volatile decomposition product (Found N = 14.45. C,,H,ON, requires N = 14.28 per cent.). 0 . . A cennphthene-7 8-isoozadiazole Oxide C = W /\I \/\/ The acenaphthene-7 8-quinonedioxime required was obtained by Francesconi and Pirazzoli's method (Zoc.cit.). Five grams of powdered acenaphthenequinone (m. p. 259O) were suspended in 450 C.C. of boiling alcohol and 3.8 grams of hydroxylamine hydro-chloride dissolved in the minimum quantity of water added. The mixture was boiled for one hour under reflux and the major por-tion of the alcohol removed by distillation. The product colour-less needles melting and decomposing a t 220° was obtained in almost theoretical yield. An excess of alkaline sodium hypochlorite was added to a solu-tion of acenaphthene-7 8-quinonedioxime in dilute sodium hydr STUDlES IN THE ACENAPHTHENE SERIES. PARTT. 1349 oxide and the mixture boiled. A yellow precipitate separated, which changed in colour through red to pale pink and boiling was coiitinued until no further colour change occurred.After crystal-lising twice from alcohol the compound forms pale pink needles melting a t 199'. Acenaphthene-7 8-isooxaddazole oxide is reduced by liydroxyl-amine to acenaphthene-1 2-quinonedioxime (Found N = 12.96. C,,H,O,N requires N = 13.30 per cent.). co-co 3-hTitroacenaphthenequinone, Ten grams of acenaphthenequinone dissolved in 50 C.C. of con-centrated sulphuric acid were nitrated in the cold with one mole-cular proportion of nitric acid (D 1-51) mixed with twice its volume of concentrated sulphuric acid. A t the end of the addition, the mixture was warmed for one hour a t 30° and poured on ice. The yield was 92 per cent. Purification by immediate crystallisa-tion proved unsatisfactory and the best results were obt'ained by a mild oxidation which removed the impurities without affecting the nitroquinone.The product (11.5 grams) was dissolved in glacial acetic acid the solution filtered and 5 grams of powdered sodium dichromate were slowly added to the filtrate. The mixture was heated on a boiling-water bath for a quarter of an hour and poured into water. After repeated crystallisation from acetic acid, 3-nitroacenaphthenequinone forms yellow needles melting a t 218O. It dissolves in sodium hydrogen sulphite with a red colour and dissolves in dilute alkali hydroxides with a brown colour whilst it is converted by hot concentrated aqueous sodium hydroxide into 2(or 3)-nitronaphthaldehydic acid as described by Mayer and Kauffmann (Zoc.cit.). 3-Nitroacenaphthenequinone is oxidised by sodium dichromate and acetic acid to 4-nitronaphthalene-1 8-dicarboxylic anhydride, almost colourless needles melting a t 229-230° identical with the product obtained by a similar oxidation of 3-nitroacenaphthene. When distilled with lime a-nitronaphthalene is obtained (Found : N=5*93. Calc. N=6*17 per cent.) i\? \/\ NO, A cold glacial acetic acid solution of 5 grams of 3-nitx-m acenaphthenequinone was mixed with a cold glacial acid! solution of 2.4 grams of phenylhydrazine and the dark red mixture was left a t the ordinary temperature for half an hour with frequent shaking. The monophenylhydrazone separates as a maroon-coloured precipitate. After several crystallisations from pyridine, the product forms reddish-brown needles melting a t 234-235O (Found N= 13-22.Calc. N = 13.25 per cent.). co-co Q' \/ 3 4-DinifroacenaphtrfLen.eyui7Lone, 0% KO, Ten grams of acenaphthenequinone dissolved in 150-206 C.C. of conoentrated sulphuric aoid were nitrated by the addition of a mixture of 7 C.C. of nitric acid (D 1-51> and 20 C.C. of concen-trated sulphuric acid. The mixture was cooled a t first then warmed to 80° and poured on ice. The product after extraction with very dilute sodium carbonate crystallised from nitric acid in orange-yellow needles melting and decomposing above 300O. It. dissolves with a red colour and is soluble in alkali hydroxides with a reddish-brown colour. 3 4-Dinitroacenaphthenequinone is oxidised by sodium di-chromate and acetic acid to 4 5-dinitronaphthalene-l 8-dicarb-oxylic anhydride almost colourless needles melting and decom-posing above 310° identical with the product obtained by the oxidation of 3 4-dinitroacenaphthene.No dinitronaphthalene is obtained when distilled with lime as 1 €Ldinitronaphthalene decomposes below its boiling point (Found N = 10.17. Calc. : N = 10.29 per cent.) DIETHYLENETRIAMINE AND TRIETHYLENETETRAMINE. 1351 3 4-DinitroacenaphtherLeyuinone-7-.znonophen~lh~dra~one, i /\ r\l I \/\/ 0,s NO, An acetic acid solution of 2 grams of phenylhydrazine was added to an acetic acid solution of 5 grams of 3 4-dinitroacenaphthene-quinone a t 50° and the mixture allowed to remain for one hour a t the ordinary temperature. On dilution with water the product separated as a reddish-yellow precipitate. It crystallises from acetic acid in brown glistening plates darkening above 260° and melting a t 287O (Found N = 15.57. C,,H,,O,N requires N=15.47 per cent.). I n conclusion we desire to express our thanks to Messrs. Hardman and Holden Ltd. who have kindly supplied us with the acenaph thene required in this investigation. DYESTUFFS RESEARCH LABORATORY, MUNICIPAL COLLEGE OF TECHNOLOGY, MANCHERTER. [Received October 8th 1920.

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年代:1920

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DIETHYLENETRIAMINE AND TRIETHYLENETETRAMINE. 1351 CXLWI.-Diethylenetriamane and l'ricthylenetetramirle. By ROBERT GEORGE FARGHER. THE interaction of ethylene dichloride and a large excess of ammonia has been investigated by Kraut (Annalen 1882 212, 253) who considered that it led almost entirely to ethylenediamine, although the reaction of the alcohol-soluble portion of the mixed hydrochlorides with potassium bisniuth iodide indicated that a small proportion of piperazine was formed. The author had occasion to prepare several kilograms of ethylene-diamine essentially by Kraut's method and it was thought to be of interest to investigate in more detlail the other products of the reaction. The hydrochlorides obtained by evaporation of the product were converted into the corresponding bases and fraction-ally distilled.The portion of' higher boiling point consisted mainly of diethylenetriamine whilst there was also produced although in much smaller quantity triethylenetetrainine. The intermediat 1352 FARGHER DIETHYLENETRXAMINE cyclic bases piperazine and triethylenetriamine appeared to be absent. Of the two bases isolated the former was first obtained by Hofmann (Proc. Roy. Soc. 1860 10 619) admixed with triethylenetriamine by the action of ammonia on ethylene dibromide and was separated by the more sparing solubility of its platinichloride; the second base he obtained by the interaction of ethylenediamine and ethylene dibromide (Zoc. cit.) ethylene dibromide and alcoholic ammonia (Zoc. cit .) and ethylenediamine and ethylene dichloride (Ber.1890 23 3712). For purposes of identification and characterisation a number of derivatives of both have been prepared. . It is of interest to record that the direct union of ethylene with chlorine utilised in the preparation of the ethylene dichloride required in the present experiments shows that electrolytic chlorine from a freshly charged cylinder is considerably more active under identical conditions than that prepared from bleach-ing powder. This is in accordance with the view that chlorine is activated by exposure to an electric discharge (compare Kellner, Zeitsch. Elektrochem. 1902 8 500 ; RUSS Jfonutsh. 1905 26, 627 ; Briner and Durand Zeitsch. Elektroclhenz. 1908 14 706), and that chlorine prepared by electrolysis is more active towards hydrogen (Chapman and MacMahon T.1909 95 135). Contrary to the experience of Russ (Chem. I n d . 1908 31 131)) the increased activity is not lost by heating or by contact with water or solutions of such salts as calcium chloride or potassium chlorate. As an example the fractionation of the products of two experiments may be cited the results being representative of many others. In the first using chlorine from bleaching powder 92 per cent. of the product distilled between 8 4 O and 8 8 O only 4 per cent. passing over a t a higher temperature. In the second using chlorine from a freshly charged cylinder only 7 per cent. distilled between BOO and 90° 25 per cent. passing over between 90° and looo 50 per cent. between looo and 120° and 14 per cent. above that temperature.As an alternative to the Kraut process the reduction of amino-acetonitrile was investigated. The catalytic reduction with hydrogen under pressure in the presence of nickel suboxide had already been claimed to yield ethylenediamine (Brit. Pat. 21383 of 1914). Reduction with sodium and alcohol zinc and hydro-chloric acid and iron and hydrochloric acid also yielded ethylene-diamine although as hydrolysis of the nitrile proceeded simultaneously the yield never exceeded 33 per cent. of the theoretical AND TRIETHYLENETETRBMINE 1353 E x I' E R I M E N T A L. Separation of the Bases. The bases obtained by distilling the mixed hydrochlorides with solid sodium hydroxide preferably under somewhat diminished pressure were freed from water by means of solid sodium hydr-oxide" and then distilled first under the ordinary pressure t o remove most of the ethylenedianiine hydrate and then under 20 mm.There was first obtained a small fraction boiling below 100° which consisted almost entirely of ethylenediamine and after this most of the remaining oil passed over between looo and 120'. The temperature then rose to 155O without remaining constant at any intermediate point and a fraction was collected boiling between 155O and 165O/ZO mm. The first fraction proved to consist almost entirely of diethylenetriamine which distilled at 109O/20 mm. The second fraction on redistillation boiled a t 157O/ 20 mm. and proved t o be triethylenetetramine. Diethylenetriarnine and its Derivatives. Diethylenetriamine dissolves in water with the evolution of heat and apparent formation of a hydrate.The aqueous solution of the base gives copious white precipitates with potassium mercuri-iodide mercuric chloride or phosphotungstic acid soluble in excess of the base but no precipitate with tannic acid. It reduces silver nitrate on warming. The alcoholic solution yields an insoluble carbonate when treated with carbon dioxide. Attempts to titrate the base with standard acid using methyl-orange Congo-red, litmus or cochineal as indicator proved unsuccessful as no definite end-point could be obtained. For analysis it was finally distilled over a little solid sodium hydroxide and was afterwards kept out of contact with moisture or carbon dioxide (Found: C=46*3; €1=13*1; N=40*3.Calc. C=46*6; H=12*7; N=40.75 per cent.). The trihydrochloride (1 Iofmann Proc. Roy. Soc. 1862 11, 420) separates from aqueous alcohol containing excess of hydrogen chloride in bunches of feathery needles which melt at 233O (corr.), sintering from 225O (Found Cl=50*1 50.2; N=19*6. Calc. : C1= 50.1 ; N = 19.8 per cent.). The tripicrate is sparingly soluble even in boiling water and crystallises in glistening flattened prisms which melt and decom-* It is n u t sufieieni; simply to distil over sodium hydroxide. VOL. CXVII. 31 1354 FARGHER DIETHYLENETRIAMINE pose a t 2120 (corr.) (Found N-21.5. C4H,,N,~3C,H30,N, requires N = 21.3 per cent.). The oxaZute crystallises from water in which it is readily soluble, in flattened prisms containing 4H,O. After drying a t l l O o it melts and effervesces a t 1 8 3 O (corr.) (Found loss a t 110°=13*0.2C4Hl3N3,3C2R2O4,4H,O requires H20 = 13.1 per cent. I n dried substance N = 17.5. 2C4H,,N,,3C2H,04 requires N = 17.6 per cent .) . The citrate is practically insoluble in alcohol ether or chloro-form but readily so in water from which it separates in well-defined rhombic prisms containing lH,O. After drying a t l l O o , it melts and effervesces a t 206O sintering from ZOOo (Found loss a t l l O o = 6.3. C,Hl,N,,C6H,07,H,0 requires R,O = 5.8 per cent.). In dried substance N = 14.4. C,H13N,,C6H,07 requires N = 14.2 per cent .). The triacetyl derivative is practically insoluble in alcohol or light petroleum but very readily soluble in water. It separates from 70 per cent.alcohol as a felted mass of needles which in contact with the solvent change to well-defined prisms melting at 220° (corr.) (Found N = 18.0. Cl,H,,03N3 requires N = 18.3 per cent .). The tribenzoyl .derivative is very sparingly soluble in ether, or light petroleum but readily so in water or alcohol. From chloroform it separates in small flattened prisms containing one molecule of the solvent which is gradually lost on exposure t o the air but regained on keeping over chloroform in a desiccator. After removal of the solvent of crystallisation it melts a t 166O (corr.) (Found CHC1,=21.9. After forty-eight hours this had diminished to 16.1 per cent. In dried substance C=71*9; H=6*1; N=10.1. C,H,03N3 requires C=72.2; H=6-1; N=10.1 per cent .) . Triethylenetetramine and its Deriuartivcs.Triethylenetetramine behaves very similarly to diethylenetri-amine in its reactions dissolving in water with evolution of heat, forming an insoluble carbonate when carbon dioxide is passed through its alcoholic solution and giving precipitates with pot,assium mercuri-iodide mercuric chloride and phosphotungstic acid. For analysis it was finally distilled over solid sodium hydroxide (Found C = 48.8 ; H=12*7; N=38.0. Calc. C=49*3; H=12*4; N=38.3 per cent.). The tetrahydrochloride seprates from 70 per cent. alcohol con-taining excess of hydrogen chloride in minute needles (Found: Cl=48*0. It reduces silver nitrate on warming. Calc. C1=48*5 per cent. AND TRTETHYLENETETRAMINE. 1355 The tetrapicrate is very sparingly soluble even in boiling water, from which it separates in fern-like clusters of minute rhombic prisms melting and decomposing a t 240° (corr.) (Found N = 20.7.C,H,8N,,4C,H,Q,N3 requires N = 21.1 per cent.). The hydrogen oxalate is sparingly soluble in water and separates in glistening needles which effervesce a t 243O (corr.) and contain lH,O (Found loss a t 110"=3-0. 1€&0 requires 3.2 per cent. In dried material C = 33-3 ; H = 5.5 ; N = 10.9. C6H,,N4,4C,H,O, requires C=33*2; H=5*2; N = l l * l per cent.). The tetrabenzoyl derivative dissolves sparingly in water or alcohol but readily in chloroform. It separates from a mixture of chloroform and alcohol in fine powdery crystals melting a t 2 3 8 O (corr.) .(Hofmann Ber. 1890 23 3717 gives 228-229O) (Found C=72.8; H=6-5; N=9.9.Calc. C=72*55; H=6*1; N = 10.0 per cent.). Methyleneaminoacetonitrile and Aminoacetonatrale. Methyleneaminoacetonitrile was prepared substantially by the process described by Klages (Ber. 1903 36 1511). It was found, however that the time of addition of the cyanide could be materially decreased without detriment to the yield so long as the temperature was maintained below 100 during the first half of the addition and below 1 5 O during the second. It was readily converted into aminoacetonitrile hydrochloride by shaking with the calculated quantity of N-alcoholic hydrogen chloride the yield amounting t o 90 per cent. of the theoretical. Reduction of A ininoacetonitrile Hydrochloride. W i t A Sodium and Alcohol .-Twenty grams of the hydrochloride were added to 60 C.C.of alcohol in which 5 grams of sodium had previously been dissolved 80 grams of sodium were added and, after the first violent reaction had ceased the mixture was heated on the water-bath 250 C.C. of alcohol being gradually added. After about an hour most of the alcohol was removed by distilla-tion a little 90 per cent. alcohol added to ensure that the sodium was all used water added and the mixture transferred to a copper flask and distilled to dryness under somewhat diminished pressure. The distillate was boiled to remove ammonia neutralised with hydrochloric acid and concentrated to crystallisation. The yield of ethylenediamiae dihydrochloride varied from 25 to 33 per cent. of the theoretical. W i t h Iron and Hydrochloric Acid.-Five grams of aminoaceto-3 ~ 1356 WERNER AND FEARON: nitrile hydrochloride were dissolved in 100 C.C.of water 16 grams of iron filings added and 50 C.C. of hydrochloric acid added slowly during an hour with shaking. At the end of the reaction the product was evaporated to dryness distilled from a copper flask with sodium hydroxide and the base in the distillate isolated as hydrochloride. The yield amounted to 10 per cent. of the theoretical. With Zinc and Bydrochloric Acid.-To a solution of 6.8 grams of the hydrochloride in 100 C.C. of water 30 grams of zinc were added and 70 C.C. of concentrated hydrochloric acid added as above the product being then treated as in the previous reduction. The yield of ethylenediamine dihydrochloride amounted to 25 per cent. of the theoretical. I n conclusion the author would thank Messrs. R. R. Baxter and J. A. Goodson for assistance in tJhe preparat>ion of the ethylene dichloride and ethylenedianiin e which formed' the basis of the investigation. WELLCOME CHEMICAL RESEAECH LABORATORIES, LONDON. [Received Septembar 30th 1920.

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DOI:10.1039/CT9201701351

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年代:1920

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1356 WERNER AND FEARON: CXLVl I.-The Constitut iort of Chdamides. Part X I I L .The Constitution of Cyanic Acid and the Rorrzzation of Ureu from the Interaction of Ammonia and Cyanic Acid at Low Temperatures. . By EMIL ALPHONSE WERNER and WILLIAM ROBERT FEARON. THE theory which has been pub forward by one of us to explain the constitution of urea and the mechanism of its formation from ammonium cyanate (T. 1913 103 1013 2276; 1918 113 84) is based primarily on the conception that cyanic acid whether in the static condition or in solution is an equilibrium mixture, represented thus : Promoted by rise of t". (enol-form) I-lC).CN + HN:CO (keto-form). Promoted by fall of t". temperature. temperature. Stable only at low Stable at high Since cyanic acid is a6 all times very unstable the stability Permanent stability is only referred to above is only relative THE CONSTITUTION O F CARBAMIDES.PART XIII. 1357 attained by polymerisation with the production of cyanuric acid from the keto-form and of cyamelide from the enol-form of the bcid (Zoc. cit.). Now the ease with which aixmoniuni cyanate is changed to urea Es indicative of a close similarity in structure and hence the con-stitution of cyanic acid is s question of paramount importance in solving the problem of the relation which exists between the two isomerides. There are two reasons why previous investigators have given either little or no consideration to this important question namely, the apparent uncertainty which has been assumed to exist as regards the nature of cyanic acid and the general acceptance of the '' carbamide '' formula which has all along masked the true relationship between urea 2nd ammonium cyanate.As a matter of fact tho constitution of cyanic acid is clearly indicated by ( a ) its polymerisation and (6) its hydrolysis and behaviour towards ammonia at low temperatures. (a) Po?!ymerisation of Cymzic A cid. Seniar and TValsh (T. 1902 81 290) showed that the spontaneous polymerisation of cyanic acid yielded a product which contained in round numbers 70 per cent. of cyanuric acid and 30 per cent. of cyanielide. This was the result of a single experi-ment in which no particular effort was made to control the temperature a t which polymerisation took effect. If the theory of the polymerisation of cyanic acid which was propounded by one of us is sound (T.1913 103 1016),* and if cyanic acid is an equilibrium mixture as indicated above it follows that its composition a t any particular temperature will be revealed by the relative proportions of the two polymerides formed. This inference which was predicted when the theory was put forward, has now been verified by analyses of the products formed when liquid cyanic acid polymerised a t different temperatures. At zero the acid was stable for about four hours provided it was not agitated and it polymerised slowly. I n order to obtain a reasonable control of the temperature a t which polymerisation took place only very small quantities of the acid were dealt with in each experiment (see experimental part). The results were as follows: * For the sake of brevity the theory is not reproduced here ; in order to appreciate the significance of the result,s obtained it is necessary to consult the paper on the mechanism of the polymerisation of cyanic acid to which reference is made 1358 WERNER AND FEARON: Temperature of Weight polymerisation of (approximate).polymeride. 0" 0.53 gram. 5 0.42 ,, 10 0.105 ,, 20 0.24 ,, TABLE I. Percentage composition of C y anuri c polymeride. acid v-0.216 gram 59.25 40.75 0.174 , 58.58 41-42 0.045 , 57.27 42.73 0.136 , 42.92 57-08 found. Cyamelide. Cyanuric acid. I n several experiments where the acid polymerised when the containing vessel was plunged into water at 20* the temperature rose suddenly to about 70° and the proportions of cyanuric acid formed were from 70 to 80 per cent.Since the latter acid is almost the sole product found when polymerisation takes place a t high temperatures as for example when urea is heated above its melt-ing point ( 1 3 2 O ) (T. 1913 103 2276) it follows that under such conditions cyanic acid is liberated in the keto-form Liquid cyanic acid on the other hand must be an equilibrium mixture, the composition of which is a function of the temperature; thus, at O" it may be represented as approximately HO*CN HXCO 60 per cent. 40 per cent. (b) Hydrolysis of Cyanic A c i d a d its Reaction with Ammonia at Low Temperatures. Whenever urea is formed in a reaction where cyanic acid and ammonia are concerned it has always been assumed that it must originate from the transf orination of ammonium cyanate produced in the first instance.Since the difference between the two isomerides is nothing more than that of the products of the union of ammonia with the enol- and keto-forms respectively of cyanic acid it is obvious that the above assumption is superfluous. A quantitative study of the hydrolysis of cyanic acid has sup-plied convincing evidence that both isomerides are simultaneously formed when ammonia reacts with the acid a t low temperatures. Not less than six consecutive changes are involved during the pro-gress of this reaction and these are conveniently divided into two groups as follows: Primary changes : (1) (HOCN t BNCO) + H20 = CO + NN,. (2) HOCN + NH = NH4*OCN. (3) HN:CO 4- NH = HN:C <xH3 THE CONSTITUTION OP CARBAMIDES.PART XIII. 1359 Secondary changes : (4) NH3 + CO + H,O = NH4HC03. (5) Formation of biuret from interaction of urea and HNCO. (6) Production of cyamelide. The main question was to prove the validity of reaction (3). This was successfully accomplished when an approximately N / 4-solution of cyanic acid was allowed to hydrolyse a t Oo. Under such conditions the secondary changes were almost completely suppressed up to the point a t which the primary changes were completed. A solution of cyanic acid was prepared by the addi-tion of the theoretical amount (62.5 c.c.) of N-nitric acid to 5-05 grams of pure potassium cyanate dissolved in 187.5 C.C. of water. The solution (250 c.c.) was prepared a t Oo and maintained a t this point during all the analyses.The following results were obtained with 25 c.c. taken at intervals of fifteen minutes (Expt. 11). TABLE Ir. Time in minutes. 15 30 45 60 75 90 1230 -Cyanic acid present (free and as NH,OCN). Gram. 0.230* 0. i C6 0.165 0.129 0.109 0.101 0.094 0-061 Urea formed (theoretical). Gram. 0.024 0.090 0.094 0.118 Urea found. Gram. 0.018 0.038 0.063 0.081 0.087 0.089 not estimated. -* 0.267 Gram is the theoretical amount from the weight of potassium cyanate taken. The deficiency found a t the outset was due to (a) lose by volatilisakion-the solution had a very pungent odour ; ( b ) time elapsed during addition of nitric wid and impossibility of avoiding t o a small extent the change HOCN + H20 + HNO =NH,NO + CO,.The theoretical values for urea formed were calculated from the amounts of cyanic acid which had disappeared after each interval on the basis 2HNCO -+ CON,H,. It will be seen that under the conditions stated the hydrolysis of cyanic acid was comparatively slow; thus about ninety minutes were required before all free acid had disappeared. At this stage the three primary reactions had been completed hence there was no object in estimating urea formed beyond this point since it could only then arise from the slow transformation of ammonium cyanate as a result of its hydrolytic dissociation thus: NH,OCN = NH3 + HOCN HNCO 1360 WERNER AND FEARON: This is strikingly shown by the last result where in the interval between 90 and 1230 minutes only 0.033 gram of cyanic acid (as ammonium cyanate) had been removed and when this is considered in connexion with the fact that in 75 minutes from the commence-ment of the change 0'313 gram of urea was formed there can be no doubt that the latter can only have been produced as the direct result of reaction (3).Now after 75 minutes when the 'disturb-ing effects of reaction (4) were just noticeable,* half of the solution (125 c.c.) had been used that is 1.15 grams of cyanic acid capable of yielding 0.8 gram of either urea or ammonium cyanate had taken part in the completion of reactions (l) (2) and (3). Hence (0-8-0.313) 0.487 gram of ammonium cyanate was formed which shows that cyanic acid in aqueous solution at Oo had reacted with ammonia as a mixture of HOCN=60-9 per cent.and of HNCO= 39.1 per cent. a result almost identical with that arrived a t from the study of the polymerisation of the anhydrous acid a t the same temperature. As regards the secondary changes the production of biuret con-firms reaction (3) since it must be a sequence of it (compare Werner T. Zoc. cit.; P. 1914 30 262) and whilst its format,ion does not affect the above result as regards the proportion of cyanic acid which reacted as HN:CO its presence was mainly responsible for the low values found for urea formed in the early stages of the reaction. I n agreement with theory the formation of biuret was largely confined to this period. The production of a trace of cyamelide in these esperiments proves that cyanic acid was liberated in the enol-form since the generation of this polymeride takes effect from the change HOCN -+ HNCO.When a solution of ammonia in pure ether a t -80 was gradually added to a similar 'solution of cyanic acid, the crystalline product which immediately separated was found to be a mixture of ammonium cyanate and urea in the proportion of 6 to 2-6 respectively. Note on the XanthhydroZ Test for Urea. The use of xanthhydrol for the detection and estimation of urea depends on the formation of a very sparingly soluble condensation product. Posse (Compt. rend. 1907 145 813; 1913 156 1938) recommends pure acetic acid as the solvent in applying the test. This introduces certain limitations and where the detection of a * For this reason 75 minutes must be taken as the limit up to which the change had proceeded undisturbed in accordance with the primary reactions THE CONSTITUTION OF CARBAMIDES.PART XIII. 1361 trace of urea in a relatively large volume of water is desired the process is tedious. As a matter of fact xanthhydrol is not a test for “free” urea; thus in alcoholic solution no reaction was effected even after heating a t 100. in a sealed tube for several clays. After the addi-tion of one drop of concentrated hydrochloric acid the condensa-tion product was precipitated and its formation was completed within ten minutes. The solubility of dixanthylurea in pure alcohol a t 1 5 O was equal t o 0.009 gram in 100 C.C. A salt of urea must be formed in order to bring about the necessary configuration of the urea molecule before it can react with xanthhydrol and in accordance with this view the test can be applied as follows.A saturated aqueous solution of xanthhydrol (containing 0.13 gram in 1000 C.C. at 15.) is readily prepared by adding the reagent, previously dissolved in 2 C.C. of alcohol to a litre of boiling water. The cold solution (filtered if necessary) when added in consider-able excess (not less than 6 vols. to 1) to an aqueous solution con-taining urea to which a few drops of hydrochloric acid have been added will reveal 1 part in 10,000 within fifteen seconds whilst 1 part of urea in 800,000 can be detected in about ten minutes. The solution of xanthhydrol loses its sensitiveness after about a week on account of gradual oxidation to xanthone.EX P E R I M E N TAL. I Polymerisation of Cyanic Acid.-The results given in table I were obtained as follows cyariic acid was prepared from pure, dry cyanuric acid which was heated electrically in a hard glass tube so arranged that the heating could be continued right up to the neck of the receiver. The construction of the latter was such that liquid cyanic acid collected in the narrow space between an inner and an outer vessel each of which was kept a t Oo. A relatively large surface of the acid was thus maintained a t a constant temperature and by careful avoidance of agitation which was found to be a great promoter of the change polymerisation was allowed to proceed as slowly as possible. The ice in the outer vessel only was displaced by water a t the temperature a t which it was desired to bring about polymerisation; in this way only was it possible to control within reasonable limits the temperature a t which the change took effect.A weighed quantity of the polymeride was extracted with hot water; the cyanuric acid present was estimated by titration with N / 10-so.dium hydroxide using phenolphthalein as indicator. 3 D 1362 FARMER AND INGOLD: Whilst it was necessary to prepare small portions of cyanic acid for each experiment the values given represent the mean of many more experiments than are recorded. 11. Formation of Urea at Oo.-Cyanic acid was estimated by precipitation with an excess of silver nitrate and the silver cyanate dissolved in dilute nitric acid was titrated by Volhard's method. The filtrate freed from the excess of silver was rendered just alkaline by addition of pure lime and after the removal of all traces of ammonia urea was estimated in the residue by ( a ) the '' hypobromite " method ( b ) decomposition by urease and (e) precipitation with xanthhydrol. The presence of biuret was proved by the copper test. Part of the expense of this researoh was defrayed by the Mackinnon Research Studentship of the Royal Society granted to one of us (W.R.F.). UNIVERSITY CHEMICAL LABORATORY, TRINITY COLLEGE DUBLIN. [Received September 22nd 1920.

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DOI:10.1039/CT9201701356

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年代:1920

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1362 FARMER AND INGOLD: CXLVII1.-The Chemistry of PoZycycZic Structures in Belation to tlzei?. Homocyclic UnsatuT-ated Isomerides. Part I. Some Derivatives of cyclo-Pentene and dicy clo Pentane. By ERNEST HAROLD FARMER and CHRISTOPHER KELK INGOLD. PERKIN and Thorpe (T. 1901 79 729) showed that when ethyl aa’-dibromo-~&dimethylglutarate is condensed with ethyl malonate in the presence of an excess of sodium ethoxide there is formed a remarkable yellow sodium compound to which hitherto the formula I has been ascribed. Numerous derivatives of this sub-stance were prepared both by hydrolysis and by alkylation and subsequent hydrolysis and many of the products so obtained were subjected to oxidation and reduction. Much more recently one of us in conjunction with Prof.J. F. Thorpe prepared from ethyl ad-dibromocyclohexane-1 1-diacetate a second rather similar yellow sodium compound (11). This also yielded a large number C(CO,Et)*Q:C(ONa) *OEt CMe4(Co2Et)- c THE CHEMISTRY OF POLYCYCLIC STRUCTURES ETC. 1363 of hydrolytic products analogous broadly speaking to those of the gem-dimethyl series but exhibiting a number of very striking differences which were studied in some detail (T. 1919 116 320) and correlated in a definite manner to the constitutions of the substances concerned. I n the course of neither of these investigations has there been discovered any fact which could reasonably be regarded as casting doubt on the bridged structures assigned to these sodium com-pounds and to their more immediate derivatives.On the contrary, much evidence confirming these structures has been accumulated. The principal item consists of course in the mode of formation of the sodium compounds. Thus when e thy1 aa'-dibromo-@/3-di-methylglutarate is treated with two molecular proportions of ethyl sodiomalonate there is formed the sodium compound of an ester, which as it can readily lie alkylated cannot but have the structure 111. This structure is quite inevitable and is strictly analogous to that of ethyl ethoxycaronate (IV) which is formed by the action of sodium ethoxide on the dibromo-ester. The ester (111) on being treated with sodium in xylene or with an excess of alcoholic sodium ethoxide loses one molecule of ethyl alcohol and is converted into the yellow sodium compound which therefore must have either formula I or formula V.Of these the former alone is capable of C( CO,Et)*CH(CO,Et) y( C@,Et)*OEt CMe2<bH.C0,Et CMe2<CH*C0,Et (111.) ( IV. ) C- -C(CO,Et) :C(ONa)*OEt CMe,/ \GO C?O,Et int,erpreting t,he many decoinpositions of the substance. Quite recently doubt has been cast by Toivoaen (,4nnulen 1919, 419 176) on the bridged constitution which has hitherto been assigned to these compounds. When the sodium compound (I) is hydrolysed by acids it yields first a dibasic acid (VI) and finally, a monobasic acid (VII). This monobasic acid was obtained by \c/ (V.) (CO,Et)*F:C(GNa)*OEt CMe,< C(CO,H)*YH*CO,H CMez<&CO,Et)*CO CH-- co (VII.) 3 D" 1364 FARMER AND INGOLD: Toivonen in the course of some experiments on the oxidation of isodehydrofenchoic acid and as a result of his investigations he formed the opinion that not only this acid but all the compounds of the series including the yellow sodium compound itself were unsaturated substances containing the cyclopentene and not the dicycZopent,ane ring system.Thus according to Toivonen the sodium coinpound would be represented by the formula VIII the dibasic acid by IX and the monobasic acid by X. Toivonen found + C(CO,Et)====~*OO,Et C(CO,H)=FH CMc2<C[ C( ONa) *OEt]*CO -+ CMe"cH(co2H)*co that the oxidation of isodehydrofenchoic acid by alkaline per-manganate proceeded in two stages. I n the first place a diketonic acid (XI) was produced. This then underwent internal condensa-tion under the influence of the alkali and gave Perkin and Thorpe's acid with the elimination of one molecule of water.Toivonen represents this reaction as follows : (XI. 1 (X.1 We therefore have two methods of formation of one and the same substance which are exceedingly difficult to reconcile with one another. I n fact one must either assume that the conversion of the ester (111) into the yellow sodium conipouiid instead of being a simple Dieckniann condensation is a remarkable change involving the rupture by alcoholysis of t,he cyclopropane ring, possibly as in the following scheme: C( CO,Et)*CH( CO,Et) C( C0,Et) (OEt)*CH( C0,E t)z @Me2<bH*c*,Et * c'Te2<CH,*C02Et C(C0,Et) (OEt)* 7 K*C02Et ~ CH (C0,Et)--CO -+ CMe,< C(C0,Et) =y*CO,Et CMe~<CH(CO,Et)*CO or regard t'hc iiit.erna1 coiiilcnsal ioii of di~netJ~yldiket~ohesoic acid (XI) as taking place in two st,agcs.111 the first place t,here mus THE CHEMISTRY OF POLYCYCLIC STRUCTURES ETC. 1365 be formed a cyclic aldol condensation product (XII) which is then dehydrated across the cyclopentane ring : (VII.) Both alternatives appear almost equally extraordinary. The subject therefore obviously required fresh investigation and some months ago we were asked by Prof. J. F. Thorpe to under-take this work and there have now been obtained r3sults which show unquestionably that for the series of compounds with which we are here concerned the bridged and not the unsaturated, constitution is correct. Turning first to the facts which have already been placed on record one observes two reasons why the formula suggested by Toivonen cannot be regarded as adequate.The first concerns the dibasic acid the bridged formula for which is VI the double-bonded formula IX. That the alternative formulze XIII and C( CO,H)*QH G(CO,H):F*CO,H CMe < C(CO,H)*CO cMe~<CH2-C0 (XIII.) (XN.) XIV are incorrect is proved by the fact that the acid is a tauto-meric substance ; it readily gives a coloration with ferric chloride, and its ester can be alkylated. Now an acid of the formula IX, in which as an examination of structural models shows the carboxyl groups are actually further apart than is the case with such compounds as trans-hexahydroisophthalic acid or cis-hexahydro-terephthalic acid would not be expected to form an anhydride. Actually however the acid does form an anhydride with the greatest of ease a fact which is in full accordance with the bridged-ring formula (VI).The second point arises in connexion with the ester produced by methylating the yellow sodium compound with methyl iodide. The bridged and unsaturated structures for this substance are shown in formulae XV and XVI. On treating with alcoholic potassium hydroxide there is formed the lactone of a hydroxy-tribasio acid the produotlioln of which izlvoilves (a) the hydrolysis of all three carbethoxyl groups to carboxyl; ( b ) the loss of one carboxyl group by elimination of carbon dioxide; ( c ) fission with the addition of water in the immediate neighbourhood of th 1366 FARMER AND INGOLD: ketone group which thus becomes a carboxyl group; (d) a further fission with the addition of water.Now whether formula XV C(C0,Et) *C)Me*CO,Et C(CO,Et)==$WO,E t CMe,< C(CO,Et)*CO I C~xe2<cMe(C0,Et)*C0 (XV.) (XVI.) or formula XVI is adopted process ( a ) can only take place in one way process ( b ) in two ways and process ( c ) in two ways. I f one adopts the structure XV the addition of a further molecule of water process (d) must involve the fission of one of the cyclo-propane bonds. On the other hand if formula XVI be accepted the addition must take place a t the double bond since the product is fully saturated. This might occur in two ways. On considering the combinations of these possibilities one observes that as many lead to the same formulz there are but six possible structures for such a hydroxy-tribasic acid derived from an ester of the constitution XV and six from an unsaturated ester of the constitution XVI.The proper-ties of the lactone (Toc. cit.) show however that in the correspond-ing hydrolxy-acid (a) the hpdroxyl group is in the y-position with respect to one of the three carboxyl groups; (6) that no two carboxyl groups are attached to the same carbon atom; (c) that the two carboxyl groups other than that to which the hydroxyl group is in the y-position are attached to two carbon atoms directly united. These conditions reduce the number of possible formulze derived from the structure XV t<o three one of which is the accepted one and the number from XVI to one only namely, XVII. It will be seen that this differs from the customary formula This could take place in six ways.C(C0,H)*CH,*C02H CMe,/ C! Me, \ Z . c O * O (XVIT. ) (XVIII.) (XVIII) only in the position of the single methyl group. The difference however is an important one as the lactonic acid was found to exist in two forms namely a cis- and a trans-form (or meso- and racemic) each of which yields its own anhydride that of the trans-lactonic acid passing on distillation into that of the cis-lactonic acid. This property is characteristic of substances of the type of s-dimethylsuccinic acid and clearly proves that there exists in the molecule of the lactonic acid a free open-chain succinic acid residue in which both the carboxyl-bearing carbon atoms are asymmetric. This condition is fulfilled by formula XVIII but formula XVII is obviously incorrect as it lacks one of the necessary asymmetric carbon atoms in the succinic acid group.One mus THE CHEMISTRY OF POLYCYCLIC STRUCTURES ETC. 1367 therefore conclude that the unsaturated structure XVI for the methylation product of the yellow sodium compound is incapable of interpreting the properties of the products obtained by hydrolysis. Toivonen however was more deeply impressed with the behaviour of the monobasic acid on oxidation. Perkin and Thorpe had shown (Zoc. cit.) that when treated with alkaline perman-ganate it was converted into aa-dihydroxy-88-dimethylglutaric acid (XXII). Toivonen proved that the reaction could be carried out a t the ordinary temperatures and as it is capable of being easily explained along conventional lines if the unsaturated struc-ture be assumed he saw in it conclusive confirmation of this method of formulation.The successive stages are as follows: (XX.) (XXI.) GMo2<C(OH)2*CO2H + ~ae,<C02H C H,*C02H CH,*CO,H (XXII.) (XXIII.) I n practice between four and five atoms of oxygen are taken up, and the product is a mixture of dihydroxydimethylglutaric acid (XXII) and as-dimethylsuccinic acid (XXIII) . I n spite of the apparent simplicity of this explanation the issue is not in reality quite so clear. For as was shown in the paper by Ingold and Thorpe (Zoc. c i t . ) the bridge-bond in such dicyclo-pentane systems is in a condition of great strain and may become -in fact in certain circumstances it undoubtedly does become-the most unstable part of the molecule giving rise to reactions the similarity of which with the reactions characteristic of unsaturated compounds is very striking.This state of strain owes its origin t,o the fact that in both the rings to which the bridge-bond is common, the internal angles are considerably less than the normal angle at which two free valencies are inclined (Ingold and Thorpe Zoc. cit.). The case of carone is very different. Here the internal angles between the valencies in the two rings separated by the bridge differ in opposite ways from the normal angle of inclination of carbon valencies. There is therefore a mutual accommodation existing between the strains which react on the carbon atoms terminating the bridge rendering the latter stable to a consider-able degree."he theory of the matter may readily be placed o 1368 FARMER AND INGOLD: a quantitative basis by a simple calculation on lines indicated elsewhere (Zoc. c i t . ; note this vol. p. 603). Therefore Toivonen’s argument that because carone dimethyldzcycloheptanone (XXXI, p. 1370) can be oxidised by permanganate to a cyclopropane deriv-ative namely caronic acid (XXXII p. 1370) the acids derived from dimethyldicyclopentanone should behave similarly with this reagent cannot be regarded as being in the least degree convincing. On a priori grounds i t might be very difficult to discover an oxidising agent capable of attacking the four-membered ring at the carbonyl group and yet leaving the somewhat unstable bridge-bond intact. On the other hand should such a substance as caronic acid be obtainable by oxidation under special and care-fully regulated conditions the circumstance could not but be regarded as the clearest possible proof of the dicyclic constitution of this series of compounds.This proof we have now been able to The general plan pursued in our experiments was its follows. If the alternative formulz VI and I X for the dibasic acid and the two formulm XV and XV1 for the methylation product of the yellow sodium compound be examined it will be noticed that in the one case a carboxyl group and in the other a methyl group, is in a different position relative to the gem-dimethyl group in the two alternative formulz. It should be possible to ascertain the true positions of these groups by oxidation. Thus for example, whilst the ester (XV) after hydrolysis and oxidation might perhaps yield some derivative of PP-dimethylglutaric acid an ester the formula of which is XVI should give derivatives not of PP-dimethylglutaric acid but of aflfl-trimethylglutaric acid.There are similar differences in the oxidation products t o be expected from dibasic acids having the structures V I and IX. A number of interesting results have already been obtained in this field but it has become apparent that an extended investigation is necessary both in the series with which we are here concerned and in other related ones. It is therefore our desire to place on record a t the present time only a limited number of experiments on the oxida-tion of the dibasic acid (VI) which however supply singularly convincing evidence regarding its structure.I n the first place when an aqueous solution of t,he dibasic acid is titrated with cold alkaline permanganate a sharp end-point is reached after three atoms of available oxygen have been taken up. The resulting solution contains aa-dihydroxy-B8-dimethylglutaric acid and oxalic acid the reaction supply. CgH1O0 + 3 0 + 2HZO = C,H,,O + C,H,O, being apparently quantitative. The behaviour of the dibasic aci THE CHEMISTRY OF POLYCYCLIC STRUCTURES ETC. 1369 with permanganate is therefore very similar to that of the mono-basic acid (VII). The remarkable fact regarding the product'ion of this dihydroxydimethylglutaric acid by the action of cold alkaline permanganate on these acids is that the fission of the bridge-bond is not due to oxidation but is of a purely hydrolytic character.There is therefore no analogy to fission of the double bond in unsaturated substances by permanganate the first stage of which involves the addit'ion of two hydroxyl groups. The fission of the bridge must be assumed to be due to the addition not of ZOH but of H-OH otherwise it is not possible to account for the structure of the product. The oxidation for example of the dibasic acid is therefore to be represented as follows: C(OH),-CO,H ' C(OH),*CO,H Cnle2<C H,*CO* CH(OH)*C02H * cMe2<CH2*CO*CO* CO,H (XXV.) (xxvr . + CMe,<c(oH)2*Co2H CH,*CO,H + CO,H*CO,H (XXII.) If the process is conducted with care no dilnethylsuccinic acid is formed. A precisely analogous scheme involving an intermediate hydrolytic product similar to XXIV and two intermediate oxida-tion products like XXV and XXVI may be considered as repre-senting the course of the oxidation of the monobasic acid-only in this case four atoms of oxygen are t,aken up as the final product., which replaces oxalic acid in the scheme outlined above is not formic acid but carbon dioxide.The formation of oxalic acid along with dihydroxydimethyl-glutaric acid when the dibasic acid is oxidised affords an interest-ing confirmation of the existence originally of the bridged struc-ture. For if the double-bonded formula IX for the original acid were correct the production of oxalic acid as a main product would be impossible. Four and not three atoms of oxygen would be taken up the successive changes being represented as follows : C(C0,H) =QH C( OH) (CO,H)-$XC-OH Cn4e~<CH(C02a)-C0 -+ CMe2<CH (GO,*)--CO -3 (XXVII.) C(OH),-CO,H C( OH),* CQ H (XXVIII.) (XXIX.) C(OH),*CO,H C(OH),*CO,H CMe,<CH(CO,H) -+ CMe2<CH,*C0, 1370 FARMER AND INGOLD: I n this method of representation the intermediate products XXVII to XXX are strictly analogous to the substances XIX to XXII which figure in the corresponding scheme (p.1367) for the oxidation of the monobasic acid whilst the direct elimination of a carboxyl group as carbon dioxide from the acid XXX appears to be the only method of accounting for the unsubstituted methylene group in the final product. We are unable to see any plausible alternative mechanism whereby the f orniation of oxalic acid along with dihydroxydiniethylglutaric acid by the oxidation of an unsaturat,ed substance having the formula IX might be explained.Owing to the curious hydrolytic action on the bridge-bond to which reference has just been made it does not appear possible to obtain cyclopropane derivatives by oxidation with perman-ganate. We have experimented with many other oxidising agents under a variety of conditions and have discovered two reagents by means of which it is possible to produce caronic acid from the dibasic acid which therefore must have the bridged structure VI. These are hydrogen peroxide and potassium ferricyanide. I n the former case the conditions necessary in order to obtain a good yield of caronic acid appear rather difficult to determine but with cold ferricyanide the oxidation proceeds very smoothly and if a little of the reagent is added each day is complete in rather more than a week when an excellent yield of trans-caronic acid can be extracted from the solution.The direct comparison wit'h the case of carone asked for by Toivonen now becomes possible: (XXXI.) (Carone.) C(CO,H)*~H*CO,E co CH-- CMo,< I K3WCNk (XXXII.) (Caronic acid.) -i If this experiment places as we believe i t does the bridged constitution beyond doubt there appears to be no alternative to accepting the mechanism proposed on p. 1365 for the internal con-densation of Toivonen's dimethyldiketohexoic acid (XI). Such a reaction is not however entirely without precedent for the inter-mediate aldol-condensation product (XII) is a cyclic pinacoline alcohol very similar in constitution to the dimethylcy clohexanol (XXXIII) the dehydration of which has been investigated by Meerwein (Annulen 1914 405 129) who found it to take place across the ring the final product being isopropylcyclo THE CHEMISTRY OF POLYCYCLIC STRUCTURES ETC.1371 pentene (XXXV). pound (XXXIV) is formed : We assume that intermediately a bridged com-(XXXV. ) The difference between this case and that with which we are con-cerned lies in the fact that the hydroxy-compound (XII) owing presumably to the presence of the ketone and carboxyl groups, undergoes dehydration spontaneously or a t any rate under very mild conditions. For the same reason the reaction stops a t the first stage the presence of the carboxyl group makes the analogous isomerisation impossible.Although no reaction resembling this isomeric change has been observed amongst the derivatives of gem-dimethyldicydopentarie there has been noticed (Ingold and Thorpe Zoc. cit.) in the cyclohexanespirodicyclopentane series a hydrolytic decomposition showing a considerable degree of similarity. The connexion is best exhibited by means of the forniulz expressed below and from these it will be seen that both stages of the above scheme for the dehydration of dimethylcyclo-hexanol have their counterpart. The cyclohexylcyclobutanolone acid (XXXVII) is obviously incapable of eliminating the elements of water and passing into a cyclobutene derivative as the strict analogy requires. TXII.) (VII.) C( CO,H) Q H CO,H+ C,H,,, CH*F(CO,H)--?H, C”H’~:C<k(CO,H)*CO C(CO,H)(OH)*CO (XXXVI.) (XXXVII.) The above considerations have an obvious implication regarding the internal condensation of other diketones and i t is hoped in the future to devote attention to this and similar questions. EXPERIMENTAL. Oxidation of Dimeti~yZdicyclope1Ltanonedicar~oxylic Acid (VI p. 1363) by Cold Alkaline Permanganate Formation of aa-Dihydroxy-&3-dime t hylglutaric Acid and Oxalic Acid. Two grams of the dicyclopentanone acid were dissolved in a small excess of aqueous potassium carbonate and carefully titrah 1372 THE CHEMISTRY OF POLYCYCLIC STRUCTURES ETC. in the cold with a 3 per cent. solution of potassium permanganate. When Chree atoms of oxygen had been taken up the perman-ganate ceased to be decolorised.The solution was then treated with a current of steam and filtered the precipitate of manganese dioxide being extracted with boiling water. The combined filtrates were acidified with hydrochloric acid boiled for a few minutes, and then rendered alkaline with ammonia. On adding calcium chloride to this solution there was obtained a precipitate of calcium oxalate which was collected and washed with dilute acetic acid in order to remove any traces of admixed calcium carbonate. The filtrate from the calcium. oxalate was evaporated to a small bulk, acidified with hydrochloric acid and exhaustively extracted with pure ether. On drying and evaporating the extract there was obtained a nearly quantitative yield of aa-dihydroxy-PP-dimethyl-glutaric acid.The acid prepared in this way melted a t 83-84O, and after recrystallisation from chloroform at 84O (Found : C-44.20; H=6*37. Further proof of the identity of the acid was obtained by means of a direct comparison with a specimen prepared from the hydrogen ester of aa-dibromo-PP-dimethylglutaric acid (Perkin and Thorpe, Zoc. cit. p. 757). Both preparations as well as a mixture of the two melted a t 84O. aa-Dihydroxy-PP-dimethylglutaric acid may also be obtained from the dicyclopentanone acid by oxidation with sodium manganate. Calc. C=43*7; H = 6 - 3 per cent.). Oxidation of Dimethyldicyclopentaizonedicarbozylic Acid (VI p. 1363) 7jy Cold Ferricyanide Formation of trans-Caroimc Acid. Thirty-three grams of potassium ferricyanide and 8 grams of potassium carbonate were dissolved in 140 C.C.of water and one-fifth of this solution was added daily to 2 grams of the dicyclo-pentanone acid dissolved in a slight excess of aqueous potassium carbonate. After the addition of the reagent was finished the mixture was allowed to remain for another period of five days and was then acidified and extracted repeatedly with pure ether. On drying and evaporating the ether there remained a crystalline residue which after washing with chloroform and recrystallising from water melted at 213O [Found C=53*13; H=6-41. Calc. : C=53.1; H=6*4 per cent. 0.0435 required 40.7 C.C. of 0-0135N-Br(OH),. C,H,(CO,H) requires 40.8 c.c.]. There can be no doubt that this substance is trans-caronic acid. It was identified with a known specimen of this acid by direc A NEW TYPE OF COMPOUND CONTAINING ARSENIC.1373 comparison and by the method of mixed melting point. I n addi-tion i t was converted by nieans of hydrobromic acid and by hydro-chloric acid into terebic acid which was similarq identified by comparison with a known specimen and by a mixed melting-point determination. Before we were aware that the product of this oxidation was trans-caronic acid we recrystallised the crude residue from the ether from concentrated hydrochloric acid. This treat-ment caused a considerable degree of conversion into terebic acid. Consequently after several recrystallisations we obtained pure terebic acid apparently as the sole crystalline oxidation product. The extraordinary ease with which this reaction takes place does not appear t o have been noticed previously (compare Beasley, Ingold and Thorpe T. 1915 107 1080). A search for cis-caronic acid amongst the residues of the oxidation proved fruitless. trans-Caronic acid may also be obtained by oxidising the original acid with cold alkaline hydrogen peroxide. We have to thank the Chemical Society for a Research Grant which has defrayed a considerable portion of the cost of this investigation. THE IMTERIAL COLLEGE OF SCIENCE AND TECHNOLOGY, SOUTH KENSINGTON. [Received October 6th 1920.

ISSN:0368-1645    

DOI:10.1039/CT9201701362

出版商:RSC    

年代:1920

数据来源: RSC

摘要:

A NEW TYPE OF COMPOUND CONTAINING ARSENIC. 1373 CXL1X.-A New of Compound containing Arsenic. By GEOEGE JOSEPH BURROWS and EUSTACE EBENEZER TURNER. HITHERTO our knowledge of additive compounds formed from arsines has been restricted to those of the cacodyl series and the compounds in question are of the co-ordination type and contain such elements as platinum mercury and copper. The authors have found that many arsines of the type R,R,R,As where R1, R, and R may be similar or dissimilar alkyl or aryl groups, combine readily with methyldi-iodoarsine and with the corre-sponding ethyl and phenyl derivatives to give brightly-coloured substances varying in shade from pale yellow to deep orange and of the general type R,R,R,As,RAsI,. They are completely dis-sociated into their parent substances 011 dissolving in benzene but evaporation of such solutions gives the pure additive compoun 1374 BURROWS AND TURNER: once more.They react in benzene solution with methyl iodide, with precipitation of the methiodide of the arsine the alkyl- or aryl-di-iodoarsine remaining in solution. The solid additive com-pounds cannot be said to be unstable remaining unchanged indefinitely under ordinary conditions but they crystallise only with difficulty from some solvents apparently owing to the retard-ing influence of the latter on the rate of addition of the two substances giving rise to the additive compound. The authors hesitate without further experimental work to suggest definite formula for the additive compounds. These may evidently be simple '' molecular compounds '' or compounds analogous to those formed between arsines and methylene iodide, and of the type R,R,R,IAs*AsRI.I n support of this structure can be cited the fact that as a rule an additive compound is paler than the di-iodoarsine from which it is formed and the further fact that iodine attached to arsenic in the quinquevalent condition has no chromophoric properties. Against the structure given above however is the fact of ready dissociation in benzene solution. Phenyldimethylarsine phenylmethylethylarsine and phenyldi-ethylarsine in their behaviour towards di-iodoarsines illustrate well the subject under discussion and the melting points of the various substances involved are tabulated below : MeAsI PhAsI EtAsI (30"). (19).(-9"). PhMe,As (liquid) ......... 94" 69" 44" PhMeEtAs (liquid) ...... 84 55" -PhEt,As (liquid) ......... 79 - -I n each of the nine cases allowed for by this table combination undoubtedly occurred since on mixing the pair of substances in quest'ion heat was evolved. Only six compounds were actually isolated and from the melting-point regularities this fact can no doubt be attributed to the low melting points of the three com-pounds which could not be isolated. Attention should perhaps be drawn to the isomerism of the additive compounds PhMeEtAs,MeAsI and PhMe2As,EtAsI,. On the other hand certain arsines show no tendency t o form additive compounds with di-iodoarsines no heat being evolved on mixing the substances in question. Thus diphenylmethylarsine, triphenylarsine and other aromatic arsines could not be caused to combine with di-iodoarsines under a wide range of experimental conditions.Phenyldichloroarsine has also been found to form an additive compound with the most reactive of the arsines in our possession A NEW TYPE OF COMPOUND CONTAINING ARSENIC. 1375 namely phenyldimethylarsine. The compound is strictly analogous to t)he iodo-compounds just described and the effect of heat on chloro-additive coinpounds generally if they can be pre-pared will be investigated since some light might thus be thrown on the interaction between say triphenylarsine and arsenious chloride which proceeds in a very irregular manner and is greatly influenced by temperature (compare Michaelis and Loesner Ber., 1891 27 294 etc.).The iodo-derivatives of arsenic have been found to be the most suitable for the preparation of the various types of arsines. They react almost quantitatively with Grignard reagents giving the expected arsines in all cases so far studied. The use of arsenious chloride or bromide (Auger and Billy C’ompt. rend. 1904 139, 597; Hibbert Ber. 1906 39 160) is t o be avoided as very low temperatures are necessarily involved. EX P E R I M E N TAL. Methyldiiodoarsine. This substance was prepared by Auger’s method (Compt. rend., 1906 142 1151) and was purified by distillation under diminished pressure. It boiled without decomposition at 128O/16 mm. and gave on cooling a bright yellow solid melting a t 30° (Auger, loc. c i t . gives 25O). On one occasion 320 grams of arsenious oxide converted into sodium methylarsinate by the method described by Klinger and Kreutz (Annalen 1888 249 149) gave more than 500 grams of pure redistilled methyldi-iodoarsine (Found M.W.[by cryoscopic method in benzene] = 331 340. Calc. M.W. = 344). In view of certain results obtained in other directions i t is considered possible that in other solvents methyldi-iodoarsine may be associated although a t present no direct evidence can be put forward in connexion with this point. The ease with which methyldi-iodoarsine may be prepared renders this substance a very convenient starting material for the preparation of arsenic deriv-atives. I n this connexion it is of interest to note that whereas methyl iodide reacts almost quantitatively in the course of a few hours with sodium arsenite in aqueous-alcoholic solution ethyl iodide reacts much more slowly a 57 per cent.conversion of sodium arsenite into ethyldi-iodoarsine (see below) being the maximum so far obtained. E thcyldi-iodoarsine . The product obtained (compare McKenzie and Wood this vol., p. 408) by the reduction of ethylarsinic acid was dried ove 1376 BURROWS AND TURNER: calcium chloride and the sulphur dioxide present removed by gentle warming under diminished pressure the whole of the liquid finally being distilled under the same conditions. Ethyldi-iodo-arsine was obtained in this way as a reddish-yellow oil boiling a t 1 2 6 O / 1 1 rnm. and setting to a pale yellow crystalline solid (m. p. -9") on cooling in solid carbon dioxide.Ph eny Zdi-iodoarsine . A mixture of phenyldichloroarsine (34 grams) 90 grams (a large excess) of finely powdered sodium iodide and 100 C.C. of absolute alcohol was shaken for three hours in the cold filtered and the filtrate evaporated to dryness under diminished pressure. The residue was extracted with qhloroform and the filtered extract evaporated under diminished pressure until quite free from chloro-form. A brownish-red oil in amount corresponding with an almost theoretical conversion of dichloro- into di-iodo-arsine was obtained and was purified by crystallisation from alcohol using solid carbon dioxide as an external refrigerant. In this way pure phenyldi-iodoarsine was obtained in lemon-yellow clusters of needles melting (after remaining in contact wiih porous porcelain a t a low temperature) a t 1 5 O (Found 1=62-9." M.W.[by cryo-scopio method in benzene] = 393 401. C,H,I,As requires I= 62.6 per cent. M.W. =406). Phenyldi-iodoarsine resembles the corresponding methyl and ethyl derivatives in odour and physiological properties. It under-goes slight decomposition when distilled under diminished pressure, boiling a t 190°/12 mm. The effect of heat on the product obtained by Michaelis and Schulte ( B e y . 1881 14 913) by the action of hydriodic acid on phenylarsenious oxide shows that this product was even before heating a mixture of several substances. Dime thyliodoarsine . The difficulty of obtaining derivatives of cacodyl has now been removed by the discovery that Auger's method for the reduction of methylarsinic acid to methyldi-iodoarsine (Zoc.cit .) may be applied to the conversion of dirnethylarsinic (cacodylic) acid into dimethyliodoarsine (cacodyl iodide). A solution of 250 grams of cacodylic acid and 800 grams of potassium iodide in 1 litre of water was saturated with sulphur dioxide dilute hydrochloric acid (500 C.C. of concentrated acid and * All these compounds in which iodine and arsenic are directly combined (whether the arsenic be ter- or quinque-valent) react quantitatively with silver nitrato in alcoholic solution A NEW TYPE OF COMPOUND CONTAININU ARSENIC. 1377 500 C.C. of water) being added from time to time. Reduction pro-ceeded rapidly with the separation of dimethyliodoarsine as a yellow oil the end of the process being indicated by the separation also of sulphur.The oily layer was separated dried over calcium chloride and distilled when pure dimethyliodoarsine (380 grams, corresponding with a 90 per cent. conversion) was obtained as a yellow liquid boiling a t 154-157O and freezing to a pale yellow, crystalline solid at about - 3 5 O . From . dimethyliodoarsine cacodyl oxide chloride etc. may readily be prepared without the production of intermediate com-pounds which are spontaneously inflammable. Phenylmethyliodoarsiize and Phenylmethylchloroarsine. By a similar reduction process phenylmethylarsinic acid (Bertheim Ber. 1915 48 350) has been converted into phenyl-met h y liod oarsin e . The plienylarsenious oxide required was prepared by treating phenyldichloroarsine with excess of powdered sodium hydrogen sulphite in the presence of a little water.On removing the inorganic matter by repeated extraction with hot water the pure oxide was left behind and when cold could be ground up and was then used without further purification for conversion int'o phenylmethyliodoarsine. Phenylarsenious oxide (50 grams) was dissolved in a solution of 30 grams of sodium hydroxide in 240 C.C. of rectified spirit and 60 C.C. of water the solution cooled and treated with 30 C.C. of methyl iodide. A vigorous reaction set in and was allowed to complete itself overnight. The mixture was acidified freed from alcohol by distillation treated with 50 grams of potassium iodide, and saturated with sulphur dioxide. The dark oil formed was separated dried over calcium chloride and distilled when 54 grams of phenylmethyliodoarsine a yellow oil boiling a t 138-140°/ 12 mm.were obtained (Found 1=43*7. C7H81As requires I = 43.2 per cent.). It is interesting t o note that in this preparation sodium hydr-oxide gives better results than potassium hydroxide. The preparation of the corresponding chloro-arsine is readily effected by treating the iodo-compound with the calculated amount of sodium hydroxide washing the oily oxide so obtained with water and subsequently shaking repeatedly with small quantities of concentrated hydrochloric acid. The oil after being dried over calcium chloride distils a t 113.5'/14 mm. (Found C1= 17.6. C7€18C1As requires C1= 17.5 per cent.) 1378 BURROWS AND TCTRNER: Plzenylme thykhloroarsine is a pale yellow liquid resembling phenyldichloroarsine in appearance and physiological properties.The so-called Bart reaction (D.R.-P. 250264) for the preparation of arsinic acids is unsatisfactory in the case of phenylmethylarsinic acid and therefore of its reduction products although a small quantity of phenylmethyliodoarsine was prepared in this manner, benzenediazonium chloride being combined with methylarsenious oxide in alkaline solution. The ethylation of phenylarsenious oxide proceeds very much more slowly than the methylation and is only partial under con-ditions that allow of quantitative methylation. Pheny Zdime thylamine. This arsine was obtained in 75 per cent. yield by Winmill (T., 1912 101 722) by the action of magnesium methyl iodide on phenyldichloroarsine in the presence of light petroleum.The following method gave even more satisfactory results. A Grignard reagent made by the interaction of 19 grams of bromobenzene 2.9 grains of magnesium and 50 C.C. of ether was gradually treated with a solution of 23.2 grams of dimethyliodo-arsine in 50 C.C. of ether. A vigorous reaction accompanied each addition of iodo-compound and after allowing the mixture to remain a t the ordinary temperature for two hours ice and dilute hydrochloric acid were added the ethereal layer separated and dried over anhydrous sodium sulphate. The ether was evaporated and the residue distilled under diminished pressure when 16 grams of phenyldimethylarsine were obtained as a colourless oil boiling a t 85O/14 mm.and possessing the properties ascribed to the arsine by Michaelis and Link ( A ~ ~ n a l e n 1881 207 205). The methiodide melted a t 2500 (Michaelis and Link Zoc. c i t . give 244O). The ethiodide is obtained a t water-bath temperatures and crystallises from alcohol in colourless needles melting a t 142O ; mixtures with the methiodide of phenylmethylethylarsine melted a t the same temperature indicating the identity of the two substances. The benziodide is readily formed and crystallises from a mixture of acetone and ether in colourless needles melting at 115-116O (Found I=31*5. Phenyldimethylarsine combines energetically with equimolecular quantities of certain halogenated arsines. Compound PhMe,As,MeAsI .-This compound is formed from the arsine aod methyldi-iodoarsine when the two substances are C,,H,,IAs requires 1=31.8 per cent.) NEW TYPE OF COMPOUND CONTAINING ARSENIC.1379 mixed in equimolecular quantities. Heat is generated and after a few moments the whole becomes solid. The product crystallises from a mixture of acetone and ether in lemon-yellow needles melt-ing a t 93-94O (Found I=48*3. M.W. [by cryoscopic method in benzene] = 259 264. C,IP,,I,As requires I = 48.3 per cent. The compound is theref ore completely dissociated into phenyl-dimethylarsine and methyldi-iodoarsine in benzene solution a t concentrations up to 5 per cent. M.W. =526). Action of Methyl Iodide on the Compound PhMe,As,MeAsI,. A solution of a small quantity of the compound in benzene, mixed with an excess of methyl iodide deposited after some hours, slender colourless needles which melted a t 243O without purifi-cation a mixture with pure phenyltrimethylarsonium iodide melt-ing a t 248O.The additive compound is quantitatively converted by methyl iodide into the methiodide of the arsine originally used. Compound PhMe,As,EtAsT2.-Phenyldimethylarsine combines readily with ethyldi-iodoarsine to give a yellow solid which when crystallised from alcohol melts a t 44O (Found 1 ~ 4 7 . 2 . M.W. [by cryoscopic method in bemenel= 364 266. C,,W,,I,As requires I=47*0 per cent. M.W. ~ 5 4 0 ) . Compound PhMe,As PhAsI,.-This compound prepared by mixing the arsine and iodo-arsine in calculated quantities crystal-lises from alcohol or acetone in orange-coloured prisms melting a t 69" (Found I = 43.3.M.W. [by cryoscopic method in benzene] = 286 287. C,,€11612A~L requires 1 ~ 4 3 . 2 per cent. M.W. ==588). This compound is of a deeper shade than those of the corre-sponding compounds from alkyldi-iodoarsines. Compound P hMe,As,PhAsCl,. -P henyldimethylarsine com bines readily with phenyldichloroarsine to give a colourless solid crystal-lising from alcohol in colourless needles melting a t 36O (Found: C1 17.7. M.W. [by cryoscopic method in benzene] = 215 212. C,,H,,Cl,As requires Cl = 17.5 per cent. M.W. = 405). Phenyldiet hylarsine. Michaelis and La Coste (Annalen 1880 201 212) first obtained this arsine from zinc diethyl and phenyldichloroarsine in ethereal solution Winmill (loc. cit .) subsequently showing that the reac-tion proceeded more satisfactorily in the presence of light petroleum.We have now by the following method eliminated the difficulty attached to these methods of preparation. A Grignard reagent prepared from 26.2 grams of ethyl bromide 1380 BURROWS AND TURNER: 5.8 grains of magnesium and 40 C.C. of ether was gradually treated with a solutioii of 22.3 grams of phenyldichloroarsine in 100 C.C. of benzene the mixture finally heated to boiling for two hours, and the ether allowed to distil off slowly. The resulting mixture was decomposed with ice and dilute sulphuric acid the benzene layer separated dried and evaporated and the residue distilled under diminished pressure when 12 grams of pE enyldiethylarsine were obtained as a colourless oil boiling a t 111-115°/14 mm. a further 3 grams of slightly less pure arsine distilling a t 115-120°/ 14 mm.The arsiiie possessed the properties ascribed t o i t in the literature. The methiodide was described by Michaelis (Annalen 1902, 328 296) as melting a t 1 2 2 O . We have been unable to confirm his statements our results being as follows. When phenyldiethylarsine and methyl iodide are mixed heat is evolved and a dark oil separates which only becomes crystalline after a considerable time or after scratching vigorously. This substance after thorough purification by repeated crystallisation from alcohol in the presence or absence of ether was obtained as a colourless crystalline solid melting a t 75-770 (Found I = 36.1, C,,H,,PAs requires T = 36.1 per cent.). The ethiodide and the methylene iodide additive compound were found to possess the propert,ies ascribed to them by Michaelis Cornpound PhEtl,As,Me Ad,.-This was formed readily and crystallised from alcohol or acetone in bright yellow needles melt-ing a t ‘78-79O (Found I=45*4.M.W. [by cryoscopic method in benzene]=271 27.3. C,,H,,T,As2 requires 1-45.8. M.W. =544). (ZOC. cit.). Phenylmethylethylarsine. Phenylmethyliodoarsine or the corresponding chloro-compound reacts vigorously with magnesium ethyl bromide to give the desired mixed arsine. Phenylmethyliodoarsine (19 grams) dissolved in 50 C.C. of benzene was gradually added to a Grignard reagent prepared from 7.8 grams of ethyl bromide 1.7 grams of magnesium and 20 C.C. of ether. When the whole of the iodo-compound had been added the mixture was heated to boiling for two hours decom-posed and worked up in the usual manner when 8 grams of phenylmethylethylarsine were obtained as a colourless oil boiling at 97O/12-13 mm.(Found [by Ewins’ method] As=37-8. C,H13As requires As = 38.3 per cent.). The arsine as might be expected possesses physical and chemica A NEW TYPE OF COMP0U;ND CONTAINING ARSENIC. 1381 properties intermediate between those of the dimethyl- and diethyl-arsine. The methiodide is readily formed and crystallises froni alcohol in colourless needles melting a t 142O (Found I = 37.5. C1,H161As requires I = 37.6 per cent.). Contpozcnd PhMeEtAs,MeAs12.-This compound crystallises from alcohol in yellow needles melting a t 84O (Found I=46.8. C,,,H1612As2 requires I = 47.0 per cent.).Compound PhMeEtAs,PhAsI,.-This substance separates from alcohol in orange-yellow prisms melting a t 55O (Found I = 42.3. M.W. [by cryoscopic method in benzene]=315 322 327. C,,H,,I,As requires I = 42.2 per cent. M. W. = 602). DZ~F.en~lmethylarsirLe. The preparation of this arsine by the action of zinc dimethyl on diphenylchloroarsine (Michaelis and Link Zoc. cit.) is less satis-factory than the following. A Grignard reagent prepared from 34.6 grams of bromobenzene, 5.4 grams of magnesium and 80 C.C. of ether was gradually treated with 34 grams of methyldi-iodoarsine after removal of unchanged magnesium by decantation. The product was worked up in the usual manner and gave 17.5 grams of diphenylmethyl-arsine boiling a t 163-1'iOO / 15 mm. and possessing the properties described in the literature.This arsine possesses only to a slight degree the property of forming additive compounds and so far 110 compounds have been obtained with alkyl- or phenyl-di-iodoarsines. The benziodide melts a t 1 9 3 O (Found I=27*5. C,,H,,IAs requires I = 27.5 per cent.). a-Naplz thyldime t hylarsin e . Dimethyliodoarsine (46.4 grains) was gradually added to a Grignard reagent prepared from 50 grams of a-bromonaphthalene, 5.34 grams of magnesium and 200 C.C. of ether (if small quantities of ether are used the magnesium a-naphthyl bromide separates out as a crystalline solid) 1,he reaction allowed to become complete by heating to boiling for an hour and the cooled product decom-posed and worked up in the usual manner. I n this way 37 grams (instead of the theoretical quantity of 46 grams) of a-naphthyl-dimethylarsine were obtained boiling at 163-165O/ 13 mm.The medkiodide is formed very readily and crystallises from alcohol in colourless needles melting at 330° (Found I = 33.7. Cl3HI6IAs requires I= 34.0 per cent.) 1382 A NEW TYPE OF COMPOUND CONTAINING ARSENIC. The ethzodzde is formed a t 90-looo and crystallises from alcohol in colourless leaflets melting a t 2 1 8 O (Found I=32.5. C',4H,81As requires I= 32.7 per cent.). Compound C,,H7*Me,As,MeAs12.-This compound is readily formed and crystallises from alcohol in yellow needles melting a t 76-77O (Found I = 44.0. C,3H,,12As2 requires I = 44.1 per cent.). Triphenytarsine , Although triphenylarsine is readily prepared by the action of sodium on a mixture of chlorobenzene and arsenic chloride the following method has been found to be the most convenient for the preparation of small quantities.More than 90 per cent. of the theoretical conversion can be effected and the arsine requires very little purification. Powdered arsenic iodide (22 grams) was gradually added with shaking to a Grignard reagent prepared from 26 grams of bromo-benzene 4 grams of magnesium and 50 C.C. of ether. The vigorous reaction having abated the mixture was heated to the boiling point for half an hour and then decomposed etc. the more volatile products beiog removed by heating finally to 200' under 12. mm. pressure. The residue practically pure triphenyl-arsine when once crystallised from alcohol melted correctly a t 5 8 O .No additive compounds could be obtained between the arsine and any of the di-iodoarsines a fact which falls in line with the difficulty of preparing the methiodide. Tri-o-tolytarsine. Arsenic iodide (22.8 grams) was added gradually to a Grignard reagent prepared from 26 grams of o-bromotoluene 3.7 grams of magnesium and 80 C.C. of ether the reaction completed by heating for a short time and the product worked up as in the case of triphenylarsine. Ten grams of tri-o-tolylursine were obtained and were crystallised from alcohol when colourless needles were formed melting at 9 8 O (Found As = 20.9. C,,H2,As requires As = 21.5 per cent.). The methiodide crystallises from water in colourless needles melting a t 1 6 6 O . Owing to the small quantity of matmerial avail-able for analysis the determination of iodine was unsatisfactory (Found I =24*2.C,,H,,IAs requires I= 25.9 per cent.) DERIVATIVES OR PHENYLDIHYDRORESORCIN. 1383 Di-o-tolylinethylarsine. A Grignard reagent was prepared from 22 grams of o-bromo-toluene 3.2 grams of magnesium and 50 C.C. of ether. A solution of 18 grams of niethyldi-iodoarsine in 100 C.C. of benzene was gradually added the reaction completed by heating under reflux, and the product decomposed with ice and dilute sulphuric acid. The separated ether-benzene layer was washed with aqueous sodium hydroxide to remove unchanged methyldi-iodoarsine dried over calcium chloride evaporated and the residue distilled under diminished pressure. In this way 8 grams of a very pale yellow oil were obtained boiling a t 178-18Z0/12 mm. and setting on cooling to a solid melting a t 4 2 O (Found As=27.3. C,,H17As requires As=27*6 per cent.). The methiodide is formed readily and crystallises from water in colourless needles melting a t 195O (Found I =31*2. Cl,H,oIAs requires I = 30.7 per cent.). TETE UNIVERSITY CE~EMIIYAL LABORATORIES, SYDNEY. [Received September 27th 1920.

ISSN:0368-1645    

DOI:10.1039/CT9201701373

出版商:RSC    

年代:1920

数据来源: RSC

摘要:

DERIVATIVES OR PHENYLDIHYDRORESORCIN. 1383 CL.- Derivatives of Yheny ldihy droresorcin . By ALEXANDER JOHN BOYD PERCY HERBERT CLIFFORD and MAURICE ERNEST PROBERT. THE following is a brief account of some experiments commenced by one of us (A. J. B.) in 1914 a t the suggestion of Professor A. W. Crossley the work was interrupted and could not be resumed until October 1919 and although we (P. H. C. and M. E. P.) cannot now coniplete the original plan it is thought advisable briefly to place on record such results as have been obtained. The original object of the work was twofold; first more fully t o examine certain derivatives of phenyldihydroresorcin because some of them notably phenylcyclohexanol had been encountered in the course of other experimental work then in progress (com-pare Crossley and Renouf T.1915 109 GOB) and secondly to investigate the influence and behaviour of aromatic groups such as phenyl in hydroaromatic hydrocarbons. Phenyldihydroresorcin was therefore converted into phenylcyclohexane by a series of reactions which had been successfully employed in previous case 1384 BOYD CLIFFORD AND PROBERT : (Crossley and Renouf T. 1905 87 1488). The dihydroresorcin (I) when treated with phosphorus trichloride readily yields chlorophenylcyclohexenone (11) which on reduction with sodium in moist ethereal solution gives phenylcyclohexanol (111). CHPh CHPh CHPh H,C/\CH - H,C/\CH -+ Cld Ico \/ H0-d ICO CH CH, \/ CH (1.) (11.) (111.) UHPh CHPh Hydrogen bromide converts the alcohol into bronLophenylcyclo-hexane (IV) in which substance the bromine is readily displaced by hydrogen under the influence of zinc dust in aqueous-alcoholic solution giving rise t o phenylcyclohexane.The hydrocarbon is easily obtained in about 74 per cent. of the theoretical amouiit, and has all the properties previously ascribed to it by other workers. Certain other derivatives of phenyldihydroresorcin were of necessity isolated in the course of the work and they are described in the experiirental part of this communication. EXPERIMENTAL. Phenyldihydroresorcin was prepared from ethyl malonate and styryl methyl ketone (benzylideneacetone) using the conditions described by Crossley and Renouf (T. 1915 107 608). The latter was obtained from benzaldehyde and acetone as described by Claisen and Ponder (Annalen 18'84 223 139) but it was found that two vacuum distillations did not remove entirely the unchanged benzaldehyde and the following procedure was there-fore adopted to purify the ketone.The crude product was dis-tilled once in a vacuum and the distillate which crystallised on cooling was broken up spread on a porous plate and exposed to the air for two days. This caused oxidatmion of the benzaldehyde to benzoic acid which was removed by washing with dilute sodium hydroxide solution. After further washing with water the ketone was dried and crystallised from light petroleum (b. p. 60-8OO) DERIVATIVES OF PHENYLDIHYDRORESORCIN. 1385 Action of Bromine on P~enyldihydroresorcin.-~ive grams of phenyldihydroresorcin (1 mol.) were suspended in 50 C.C.of dry chloroform and a solution of 4.3 grams (2 atoms) of bromine in dry chloroform was gradually added with constant shaking when the resorcin gradually dissolved. On further addition of bromine, much hydrogen bromide was evolved and a bulky white solid separated which was collected washed with chloroform dried on a porous plate and crystallised from aqueous alcohol (Found: Br = 29-95 CI2H1,O2Br requires Br = 29-96 per cent.). 4-Bromophenyldi?tydroresorcin CHPh<C,:.-,O>CHBr CH *co crystal-lises from aqueous alcohol in compact clusters of short glistening needles melting a t 177O with rapid evolution of gas. (If heated sufficiently rapidly the melting point may be found as high as 1 8 9 O . ) It is soluble in alcohol acetone or ethyl acetate sparingly so in chloroform or benzene on boiling but insoluble in ether or light petroleum.Oxidation of PltenyEdihydroresorcin .-Five grams of the resorcin were suspended in 125 C.C. of water and treated with a 4 per cent. solution of potassium permanganate until the latter was no longer decolorised the whole being continuously mechanically shaken. About five hours were required for the completion of the oxida-tion. The product worked up in the usual way gave 3.8 grams of a solid fro& which were isolated by repeated recrystallisation from dilute hydrochloric acid two acids A and B . The acid A melted a t 139O nor was this melting point lowered on admixture with a specimen of pure P-phenylglutaric acid prepared for purposes of comparison (see p.1387). The acid B melted a t 166.5-167° and its melting point was not lowered when mixed with phenylsuccinic acid (see p. 1386 for the proof of the identity of this acid). Owing to the great similarity in solubility of 15-phenylglutaric acid and phenylsuccinic acid it was not found possible to separate the whole of ,4 and B but there was no evidence of the presence of another compound in the remaining mixture. Action of Phosphorus Trichloride on Phenyldikydrores0rcin.-Sixty grams (3 mols.) of phenyldihydroresorcin were heated with 22 grams (1.5 mols.) of phosphorus trichloride and 240 grams of dry chloroform on a water-bath for three hours. After distilling off the chloroform the residue was poured into cold water and extracted four times with ether the ethereal solution thoroughly washed with sodium hydroxide solution (4 per cent.) then with water dried over calcium chloride and the ether evaporated.The oily residue which readily solidified on cooling was crystallised V O t . CXVLT. 3 1386 BOYD CLIFJ?ORD AND PROBERT : twice froiii light petroleum (b. p. 60-80O) (Found C1= 17.00. CI2H,,OC1 requires C1= 17.19 per cent.). 5 -Chloro-1-phe nyl-A4-cycloh c~cn-3-on e CHPh<CH CH IeCC1>CH -GO , L the yield of which is about 65 per cent. of the theoretical crystal-lises in colourless transparent plates melting a t 63.5-64O. It possesses a rather pungent odour is somewhat sternutatory and has an irritating effect on the skin. It is soluble in alcohol ether, chloroform acetone benzene or ethyl acetate and in light petroleum on boiling.When boiled with absolute alcohol and the solution allowed to remain in a moist atmosphere for several days, the ketone reverts to phenyldihydroresorcin. There is evidence that the ethyl ether of phenyldihydroresorcin (Vorlander and Erig, Annalen 1897 294 304) is an intermediate product but the change has not been fully investigated. The oxime crystallises from alcohol in almost colourless short needles melting and decomposing a t 1570 (Found N = 6 . 5 . C,2H,20NC1 requires N = 6.32 per cent.). The semicarbasone prepared in the usual manner crystallises from alcohol in rosettes of small colourless needles. When heated in a capillary tube it softens a t 150-5* melts a t 153*5O and decomposes a t 191O. It is insoluble in the usual organic solvents, with the exception of ether benzene and light petroleum in which it is only very sparingly soluble even on boiling (Found: N =.15.91.C13H,,0N3C1 requires N = 15.94 per cent.). Oxidation of Chlorophenylcyclohexenone .-Twenty grams of the chloro-ketone were suspended in 500 C.C. of water and treated with a 4 per cent. solution of potassium permanganate until the latter was no longer decolorised the whole being continuously shaken mechanically. Oxidation took place slowly requiring twenty hours for completion. The product worked up in the usual way, gave 13.5 grams of solid from which were isolated by repeated recry stallisation from dilute hydrochloric acid solution A an acid melting a t 167O; B an acid melting a t 138*5-139*5°; and C a small quantity of an acid melting a t 121-121.5° which was obtained by extraction of the above mixture with cold benzene and recrystallisation of the residue obtained on evaporation of the solvent.The acid ( A ) yielded an anhydride melting at 53-54O and an anilic acid melting a t 169-170° when treated according to the directions given by Hann and Lapworth (T. 1904 85 1366) for the preparation of these derivatives of phenylsuccinic acid. The fact that these data coincide with those given by Hann and Lapworth proves the acid ( A ) t o be phenylsuccinic acid DERIVATIVES OF PHENYLDIHYDRORESORCIN. 1387 The melting point of the acid B was not lowered on admixture with pure P-phenylglutaric acid (m. p. 138-140O) prepared for t'he purposes of comparison ( B e y .1899 32 1879). On treating its silver salt with methyl iodide in dry ethereal solution an ester resulted melting a t 83*5-84*5OY nor was this melting point lowered on admixture with a specimen of the pure dimethyl ester of P-phenylglutaric acid (m. p. 84-85O) prepared for the purposes of comparison (Ber. 1898 31 1828). Only a very small quantity of the acid C was obtained after recrystallisation froin water. On admixture with pure benzoic acid the melting point was not lowered appreciably and although the amount of the acid was too small to admit of further purifi-cation or preparation of derivatives its odour and behaviour towards various solvents support the supposition that it is benzoic acid. Reduction of Clzloroyl~enylcycloiLezenone.-Q~zantities of 20 grams of the chloro-ketone were treated with twice the calculated quantity of sodium in moist ethereal solution as described by Crossley and Renouf (T.1905 87 1494). When all the sodium had dissolved the ethereal solution was separated washed with water until no longer alkaline dried over anhydrous potassium carbonate and the ether evaporated. The residue was submitted to steam distillation until a test portion of the distillate gave no turbidity on adding potassium carbonate. The distillate contained a solid in suspension crystallising in colourless needles which were collected and crystallised from light petroleum (b. p. 80-looo) (Found C=81*60; H=9*36. C,,H,,O requires C=81*76; H=9.16 per cent.). 1-Phenylcyclohexan-3-01 C H P ~ < ~ ~ ~ ~ * C H ( ~ ~ ~ > C H ~ was pre-pared although not fully described by Crossley and Renouf (T., 1915 107 608) for comparison with a by-product obtained in the reduction of phenyldihydroresorcin.It is obtained in 50-53 per cent. of the theoretical amount and crystallises in fine colourless needles melting a t 79.5-80.5° and possessing a pleasant odour soniewhat resembling that of geranium. It is soluble in the usual organic solvents but only sparingly so in cold light petroleum. When dissolved in absolute alcohol and the solution gradually treated with concentrated sulphuric acid it gives a greenish-yellow colour slowly changing to brown with a green fluorescence. The ace t y l derivative prepared in the usual manner crystallises from a small quantity of alcohol in stout transparent oblong plates melting a t 43-44O and is readily soluble in all the usual organic solvents.It can be distilled in air without decomposition 3 3 1385 BOYD CLIFFORD AND PBOBERT and boils a t 300° (Found C = 77.05 ; H = 8-69. CT,,H,,O requires C = 77.01 ; H = 8-32 per cent.). The benzoyl derivative is readily obtained in quantitative yield. It crystallises from ethyl or methyl alcohol in rosettes of colourless prisms melting a t 6S0 and is readily soluble in all tho usual organic solvents on boiling (Found C = 81-28; H = 7-36. C,,EImO2 requires C = 81.39 ; H = 7.19 per cent.). The o-nitrobenzoyl derivative was prepared by allowing mole-cular proportions of o-nitrobenzoyl chloride and the alcohol t o react in pyridine solution. It crystallises from dilute solution in ethyl or methyl alcohol in rosettes of minute needles melting a t 70* (Found N=4*49.Action of Bydrogen Bromide on .Pl~enylc~clohexan-3-ol.-Quantities of 5 grams of the alcohol were sealed up in small soda-water bottles with 25 C.C. of fuming hydrobromic acid saturated a t Oo and heated in a water-bath for one hour. The resulting liquid which was in two layers was poured into excess of cold water and the lower oily portion dissolved in ether. The ethereal solution was washed with water then with dilute sodium carbonate solution finally again with water dried and the ether removed, the residue being distilled under diminished pressure (Found : Br = 33.49. C,,H,,Br requires Br = 33-42 per cent.). 3-Bromo-l-phenyZcycloliezane the yield of which is almost quantitative is a clear colourless liquid boiling a t 186-187O/ 40 mm.with a pleasant odour resembling that of geraniol yet somewhat reminiscent of the odour of oranges. A c t ion of 2 inc D zis t on 3-Bromo-1 -p henylcycloh e xnne .-Twenty-four grams of bromophenylcyclohexane were mixed with 75 C.C. of 90 per cent. alcohol and sufficient absolute alcohol to form a clear solution to which were added 38.5 grams of zinc dust mixed with an equal volume of sand and the whole was heated on the water-bath for ten hours. The resulting liquid was poured into a large excess of water the mixture extracted with ether the ethereal solution washed with water dried and the ether evaporated using a fractionating column. The resulting oil, which was nearly colourless was heated over metallic sodium for two hours and then distilled when 13 grams passed over a t 232-233" and after one further distillation from sodium 11-9 grams (yield 74 per cent.of the theoretical) were obtained boiling constantly a t 233-234O/ 755 mm. It readily solidified when cooled to just below Oo and melted at 6.5O. These properties agree closely with previous descriptions of the properties of phenylcyclo-hexane (Willstaitter and Lessing Rer. 1901 34 506 ; Eijkman, Cl9HI9O,N requires N=4.31 per cent.) DERIVATIVES OF PHENYLDIHYDRORESORCIN. 1389 Chem. Weelcblad 1903 1 7 ; Rleerwein and Kremers Anmale,n, 1919 419 121). In order further to establish its identity with phenylcyclo-hexane 6 grams of the substance were treated with fuming nitric acid (D 1.50) until the addition of acid caused no further visible change (about 10 C.C.of acid were used).‘ The mixture was poured into water and the heavy oily layer dissolved in ether and worked up in the usual manner. On evaporation of the ether 7.9 grams of a yellow oil were obtained which on cooling gave a crystalline deposit weighing 3.8 grams after drying on a porous plate. I t crystallised from aqueous alcohol in large colourless lustrom leaflets melting a t 57-5-580 (Kursanov Annalen 1901 318, 309 gives the meltipg point of p-nitrophenylcyclohexane as 5 7-5-5 ~ - 5 0 ) . Preparation of Ph enylcyclo hexan- 3 -one CH Ph< CH,*CH2 CB~-CO>CH,. -Fourteen grams of phenylcyclohexan-3-01 were added to 126 grams of Beckmann’s chromic acid mixture [60 grams (1 mol.) of potassium dichromate and 50 grams (2.5 mols.) of sulphuric acid in 300 C.C.of water] the whole being well shaken. The tempera-ture rose to 45O when a reaction set in which was soon complete. The mixture was then kept a t 50-55O for thirty minutes with constant shaking extracted with ether the ethereal solution worked up in the usual way and dried. After evaporating the ether the residual colourless oil was distilled under diminished pressure when 12.7 grams passed over a t 1.69-169*5°/18 mm. (Found C = 82-52 ; H = 8.42. C,,H,,O requires C = 82.72 ; H=8*10 per cent.). l-Phenylcyclohe~an-3-one the yield of which is practically quantitative is a colourless liquid boiling a t 169-169.5O118 mm. and 28?-288O/736 mm. which does not solidify when cooled to - loo.With alcoholic sulphuric acid it gives a reddish-yellow solution with a green fluorescence. The semicar bazone prepared in the usual manner crystallises from alcohol in radiating clusters of glistening prisms melting a t 167O. It is soluble in methyl or ethyl alcohol chloroform or ethyl acetate and in acetone benzene or light petroleum on boiling, but only very sparingly so in ether (Found N=18*22. C,,HI70N3 requires N = 18.18 per cent.). The oxime crystallises from alcohol in colourless ill-defined plates which melt a t 128-129O but begin to shrink a t about 12O0. It is insoluble in light petroleum and only sparingly soluble in ether but dissolves readily in the other usual organi solvents especially on warming (Found N = 7.34. C,,H,,ON requires N = 7-41 per cent.). The authors desire to express their sincere thanks to Professor Crossley for originally suggesting the work and for the help given by him during it,s progres‘s. ORGANIC RESEARCH LABORATORY, KING’S COLLEOE STRAND W.C. 2. [Eeccived October 6thy 1920.

ISSN:0368-1645    

DOI:10.1039/CT9201701383

出版商:RSC    

年代:1920

数据来源: RSC

摘要:

CLL-The Electrical Conductivity of Potassium Sodiuni, and Barium Chlorides in Mixtures of Pyyidine and Water. By JNANENDRA CHANDRA GHOSH. IN previous papers (T. 1918 113 449 627) it has been shown that in solutions of strong electrolytes the increase in molecular conductivity with dilution is given by the following equations : for univalent binary electrolytes and for uni-bivalent electrolytes where N is Avogadro’s number E the absolute charge on an ion ’Ir the molecular dilution and D the dielectric constant of the solvent. Equations (1) and (2) contain the term pN the molecular conductivity a t infinite dilution which cannot be determined experimentally. They can however be easily put in the following forms which contain no unknown magnitudes whatsoever : an The present investigation was carried out with the object of testing the validity of tho above relation between the dielectric constant of the solvent and variation of molecular conductivity with dilution.It has already been shown that the extensive experimental data of Walden on the molecular conductivity of tetraethylammonium iodide in various solvents can be accounted for (with the exception of the aldehydes) on the assumption that tetraethylammonium iodide a t first undergoes polymerisation and then the double mole-cule dissociates as a uni-bivalent electrolyte. The experimental difficulties in determining molecular conductivity in pure non-aqueous solvents are very great. The data of different observers do not very often agree a t all and it was therefore concluded that the agreement between the observed and calculated value of niole-cular conductivity was within the limits of experimental error.I n the present investigation only the chlorides of potassium, sodium and barium were used which unlike the iodide have very little tendency to complex-formation. Binary mixtures of pyridine and water were selected as they are completely miscible in one another and offer a very wide range of dielectric constants varying from 12 to 80. Preparation of Materials. Chemically pure pyridine was distilled several times over solid potassium hydroxide and the fraction distilling a t 115-116a was collected. This fraction was then allowed to remain overnight over pieces of metallic sodium as recommended by Hopkins (this vol.p. 280). Gas bubbles were evolved showing that moisture was present. The dry substance was distilled directly into a dry flask protected from moisture by a calcium chloride tube. The specific conductivity a t 1 8 O was 0.2 x 10-6 mho and the boiling point 115.6O. Water was purified by distillation from acid and alkaline per-manganates a block-tin condenser being used. It was finally distilled from a quartz distillation apparatus and stored in quartz flasks. The specific conductivity of the water was 1.2 x 10-6 mho a t 1 8 O . The mixtures of pure pyridine and water were also stored in quartz flasks. The salts were crystallised twice from pure samples and dried by heating in a platinum crucible. For experiments a t Oo a bath containing finely powdered ice was used jacketed by a second vessel containing ice.The tempera-ture varied from O0 to 0 . 0 5 O . For experiments a t 18O a thermostat was used the extreme variation of temperature being 0.02O. Fo 1392 GHOSH THE ELECTRICAL CONDUCTIVITY OF POTASSIUM, dilutions below 1000 litres a closed conductivity cell made of Jena resistance glass was used and for higher dilnt'ions a closed quartz cell made by the British Silica Syndicate. The bridge wire was carefully calibrated and the resistances were National Physical Laboratory standards of 1 10 100 and 1000 ohms. Dielectric Constants of Mixtures of Pyridine and Water. The Nernst method was employed as modified by Turner (Zeitsch. physikal. Chem. 1900 35 385). A Wehnelt interrupter was used in the primary circuit of the secondary coil; it consisted of two thin platinum wires dipped in dilute sulphuric acid.The anode could be raised up and down by means of a rack and pinion arrangement and a sharp fine tone obtained a t 16 volts by careful adjustment. The dielectric constant of pure pyridine a t Oo with chemically pure benzene as the liquid for comparison was found to be 12.5 from the equation S-S so -D = (Do - l)-s + 1, where Do is the dielectric constant of the known substance s the number of scale divisions the condenser plate has to be moved when the vessel is empty so the number for the substance of known dielectric constant and S for the unknown substance. For binary mixtures of water and pyridine pure pyridine was used as the comparison liquid and the dielectric vessel consisted of a platinum crucible and a platinum disk attached to the end of a platinum rod passing through a hole in the ebonite cover of the crucible.Although pure pyridine and pure water have themselves very little specific conductivity the conductivity of the binary mixture increases with increasing proportion of water and for a mixture containing 90 per cent of water it is as high as 10 x 10-6 mho a t 18O. The data for the dielectric constants of the mixtures contain-ing a large proportion of water are therefore not' very accurate as it is very difficult to get a sharp sound mininium in the telephone. Percentage by weight of pyridine in water. 96.0 93.8 so-0 67.0 60.0 40.0 30-0 TABLE I. Dielectric constant at 0". 13.0 15.3 22.9 27-7 40.0 56.4 68.3 Dielectric cons tmt at 18".12-5 16.0 21.0 25.1 37.0 52-3 64-SODIUM AND BARIUM CHLORIDES ETC. 1393 Jlolecidar C'onductiuity of Salts in Mixtures of Pyridine and 'CVater. Mixtures containing 80 or 60 per cent. by weight of pyridine do not dissolve the chlorides of barium potassium and sodium easily. A definite amount of salt was therefore first dissolved in a given quantity of pure water and pyridine then added. Barium chloride is not very readily soluble in these mixed solvents. Even in the case of N/40-solutions crystals generally separate on keep-ing overnight. The state of supersaturation can however be easily maintained for the few hours necessary for taking a complete set of readings a t various dilutions.The molecular conductivity of the solutions is rather small and hence the correction for the conductivity of the solvent becomes quite appreciable when the dilution is 80. The accuracy of the data for higher dilution depends on this solvent correction and it was therefore necessary to determine the specific conductivity of the solvents every few hours. In tables 11 111 IV V VI and VII are given the observed values of equivalent conductivities a t Oo and 18O. They are compared with those calculated from the observed value of A,, from equation (3) in the case of uni-TABLE 11. t=O0. Solvent containing 40 per cent by weight of pyridine. Salt. T7 = 10. 40. 80. 640. NaCl X obs. .................. 22.1 24.6 25.5 27.6 cdc. from A,, obs. = 56.3 22.5 24-8 25.6 27.4 'KCI X obs................... 25-6 28-3 29.3 31.4 X calc. from A,, obs. = 30.0 25.9 28.2 29-2 31-1 BaCl Xobs. .................. 20.0 23.6 - 27-7 X calc. from X,,,obs. = 36.1 19.6 23.4 - 28.0 TABLE 111. t = O 0 . Solvent containing 60 per cent. by weight of pyridine. 2560. 28-6 28.1 32-2 31-8 29.0 29.3 Salt. V = 10. 20. 40. 80. 640. 2560. NaCl X O ~ S . .................... 12.7 - 14.8 - 17.3 18.0 Xcalc. from XIGo obs. = 16.1 13-9 - 14.8 - 17.0 17.5 RCl Xobs.. . . . . . . . . . . . . . . . . . . . - 14.55 15.7 16.5 16-3 19.1 Xcalc. from h16 obs. = 17.2 - 14.80 13.7 16-5 18-2 18.8 13~C1 Xobs.. . . . . . . . . . . . . . . . . . . . 10.3 - 13-9 - 16.1 17-0 Xcalc. from hlGO obs. = 14-8 9.9 - 12.7 - 16.3 17.3 3 E 1394 GHOSH THE ELECTRICAL CONDUCTlVITY OP POTASSIUM, TABLE IV.t =oo. Solvent containing 80 per cent. by weight of pyridine. Salt,. V == 20. 40. SO. 640. 5170. NaCl Xobs . . . . . . . . . . . . . . . . . . . . . . . . . . . b.9 10.1 - 13.5 15.2 hCalC. from A,, obd. Z= 12.1 .... 9.4 10.4 - 13.2 14.4 X calc. from Xle0 obs. = 11.9 .... - 10.3 11.1 13.1 14.3 KCl Xobs ........................... - 20.1 10.8 13.8 15.5 TABLE V. t = 18'. Solvent containing 40 per cent. by weight of pyridine. Salt. V = 10. 40. 80. 640. 2560 NaCl Xobs.. ......................... 4G.4 44.6 46.5 50-1 51-S hcalc. from A160 obs. = 47.9 . . . . 40.9 45.1 46.7 49.8 51.1 KCI Xobs ........................... 46.8 51.8 53.8 57.8 59.4 Aca!c. from A,, obs. = 55.6 . . . . 47.4 52.3 54.1 57.8 59.2 BaCl hobs........................... 38.2 44.2 - 53.5 55.6 hcalc. from A,, obs. = 50-1 .... 37.5 44.8 - 53.8 56.2 TABLE VI. t = 18O. Solvent containing GO per cent. by weight of pyridine. Salt. V = 10. 20. 40. 80. 640. 2560. NaCl Xobs.. . . . . . . . . . . . . . . . . . . . 25.1 - 29.4 - 34.1 35.2 X cnlc. from XI, o h . = 32.0 25.6 - 29.5 - 33.6 34.7 KCl Xohs ..................... - 28.6 31.0 32.3 55.8 37-6 hcalc. from h,,o obs. = 34.1 - 29-4 31.3 32.5 35.9 37.3 BaC1 hobs.. ................... 19.6 - 24.9 - 31.4 33-2 hcalc. from A,, 011s. = 28.7 19.1 - 24.5 - 31.7 33.8 TABLE VII. t = 180. Solvent containing 80 per cent. by weight of pyridine. Salt. 17 == 20. 40. 80. 640. 6120 N&l lobs.. ......................... 17.2 19.5 - 26.3 29.9 Xcalc. from X16 obs.= 23.4 .... 18.1 20.1 - 25.5 27.9 KCl Aobs ........................... - 19-1 21.0 250 28.9 Xcalc. from obs. = 22.7 .... - 19.5 21-2 25.2 27.3 univalent salts and from equation (4) in the case of barium chloride. I n the tables V is the equivalent dilution in litres and A the equivalent conductivity SODIIJiVl AND BARIUM CHLORIDES BTC'. 1395 It will be noticed froni the above tables that the agreement between the observed and calculated values of equivalent con-ductivities are within the limits of experimental error except in the case of the solvent .containing 80 per cent. by weight of pyridine. Here the extreme deviations between the observed and calculated values are as much as 7 per cent. Perhaps in the mixed solvent rich in pyridine there is a slight complex-formation.Hartley Thomas and Applebey (T. 1908 93 538) have deter-mined the molecular conductivity of lithium nitrate in mixtures of varying proportions of pyridine and water. It appears interest-ing to exaniine whether their experimental data agree with those calculated from equation (3). The observed values of molecular conductivity in table V I I I are taken from their paper. TABLE VIII. t = 2 5 O . Salt Lithium Nitrate. Mol. per cent. of ppridine in solvent.. V = 16. 33. 64. 128. 256. 512. 1024. 133.98 XObS.. ............. 20.1 24.4 27.5 32.1 35.4 38.3 -15.8 ............ 19.3 23.3 27.5 31.9 36.1 40.1 - Xcak from obr;. = 73.76 hobs.. ............. 23.1 26.6 30.3 33.2 35.9 38.1 40.5 19.1 ............ 22.9 26.5 30.3 33.8 37.0 39.6 41.6 Xcdc.from obs. = 46.67 Xobs.. ............. 24.9 27.4 29.5 30.7 32.2 33.2 -21.5 ............ 24.4 26.6 28.4 30.0 31.2 31.9 -hcelc. from A obs. = 31-28 Xobs.. ............. 27.5 29.4 31.0 32.4 33.5 34.4 -25.2 ............ 27.4 29.1 30.4 31.4 32.2 33.5 -Xcalc. from A obs. = 5-71 Xobs.. ............. 60.8 63.1 64.9 66.3 67.5 68-5 69.5 58.1 ............ 61.0 63.3 65.1 66.7 67.6 68.2 68.5 X calc. from X obs. = It will be a t once seen that' the agreement between the observed and calculated values of molecular conductivity is quite satis-factory. It is peculiar that in the solvent containing a 46.67 molecular percentage of pyridine which is equivalent t o 79 per cent. by weight of pyridine the observed values of equivalent conductivity for lithium nitrate agree with the calculated values within the limits of experimental error.It is strange thai; tho simpler salts like potassium and sodium chlorides should show greater deviations. 3 E* 1396 THE ELECTRICAL COND UCTlVITY 04' PO'I'ASSIUAS ETC. Viscosity of Xixtures of Yyridinc U I L ~ Itrater. Nartley Thomas and Applebey (Zoc. cit.) and Dunstan and Thole (T. 1907 91 1728) have determined the viscosity of mixtures of pyridine and water a t Oo and 2 5 O . No simple relation like that discovered by WaIden between the molecular conductivity and viscosity of the solvent in solutions of tetraethylammonium iodide exists here. Following the lead of Bousfield Hartley, Thomas and Applebey conclude from the comparison of viscosity and conductivity data of lithium nitrate in mixtures of pyridine and water that there is a change in the size of the solvent atmo-sphere attached to the ions as the composition of the solvent changes.Although speculations in this field do not lead to tangible results it was thought advisable t o complete the investi-gation by determining the viscosities of the mixed solvents used in this invesstigation a t 18". For this purpose a Dunstan and Thole type of viscosimeter was used. The results are given in table IX. TABLE IX. Percentage of pyridine in the solvent mixture. relative to water at 18". 80 2.375 60 2.572 40 2.153 Viscosity of the solvent mixture It will be observed that the conductivity of the salts continually increases as the percentage of pyridine in the solvent diminishes from 80 to 40. The viscosity of the mixture of pyridine and water, however passes through a maximum when the percentage by weight of pyridine is approximately 65. Conclusion, The molecular conductivity of the chlorides of potassium sodium, and barium in mixtures of pyridine and water was studied. The dielectric constants of the solvents varied from 12 to 68; the experimental data confirm the hypothesis of complete ionisation of strong electrolytes as developed by the author. My best thanks are due t o Prof. F. G. Donnsn F.R.S. for his kind interest and help in providing the apparatus necessary for this investigation and to my friend Mr. J. N. Mukherjee. CHEMICAL LAB ORATORY, UNIVERSITY COLLEGE, LONDON

ISSN:0368-1645    

DOI:10.1039/CT9201701390

出版商:RSC    

年代:1920

数据来源: RSC

摘要:

THE SYSTEM BENZENE-ETHYL ATLX3HOTr-\VATRR ETC. 1397 CLII .-The System Benzene-Et hy 2 A I cohol- Water between c 25" and - 5". By NEVIL VINCENT SIDGWICI~ and WILLIAM JAMES SPURRELL SEVERAL investigations have been made on parts of this system at various temperatures but no complete study has yet been published of the conditions of separation of solid benzene from a mixture of the three components. This question is of general theoretical interest and also of some practical importance in view of the use of mixtures of benzene and alcohol as motor fuel. Considering first the two-component systems involved the system water-benzene is soon disposed of. The mutual solubilities a t any temperatures with which we are concerned are very small. A t 23O the solubility of water in benzene is 0.061 per cent.* (Groschuff, Zeitsch.Elektrochem. 1911 17 348); a t 1 5 O that of benzene in water is 0.15 per cent. (Moore and Rolaf Proc. Roy. SOC. 1905 [B], 77 96). If we assume that the solubilities change1 with temperature in the same proportion as the vapour pressures their values near t'he triple point (5-4O) will be water in benzene 0.082 benzene in water 0.092 per cent. The temperature of the triple point solid benzeneliquid benzene-water has been found to be 5.39O (Sidg-w i d tlhis voll. p. 1340)-0ne-tenth of a degree below the freezing point of benzene; that of the triple point ice-water-benzene is by calculation -O*OIGo the solubility of the benzene a t this temperature being 0.069 per cent. The freez-ing-poinh curve of solutions of water in alcohol has been measured (for example by Pickering T.1893 63 1015); a 10 per cent. solution freezes a t about -4*6O but the solubility of benzene in such a solution is so small that we did not investigate the ice curve. The system benzeneethyl alcohol is of much greater importance. The freezing-point curve has been examined by several observers. Our own results (extrapolated for anhydrous alcohol) are nearest to those of Piclcei-ing (Zoc. cit. p. 1019) with whom Viala (BUZZ. SOC. chim. 1914 [iv] 15 5) and R6zsa (Zeitsch. Elektrochem., 1911 17 934) also agree fairly closely. McIntosh ( J . Physical Chem. 1896 I 4-80) who also measured this curve states that his * All solubilities in this paper are expressed in grams of solute per 106 gram5 of solution.The system water-alcohol also scarcely concerns us alcohol may have contained water; from our results i t seems that it must have contained about 4 per cent. The three-component system has been examined by McIntosh (Zoc. cit.) Taylor ( J . PJhysicaZ C’Jwm. 1896 1 301 461) Lincoln (ibid. 1900 4 176) Bonner (ibid. 1910 14 779) and R6zsa (Zoc. c i t . ) . McIntosh investigated the freezing point of the benzene and drew attention to the remarkable fact that the freez-ing point of benzene containing alcohol is raised by the addition of water; he correctly explained this as being due to the increase of the vapour pressure of benzene on addition of a component in which it is insoluble but his numerical results are vitiated by the presence of water in his original alcohol.Taylor Lincoln and Bonner examined the two-liquid equilibrium between loo and 2 5 O , and determined the composition of the conjugate solutions (tie-lines). R6zsa investigated the system both above and below the freezing point; his results are difficult to understand as he does not define his concentrations but on the most probable hypothesis they are roughly in agreement with ours. These results taken together give an incomplete account of the behaviour of the system in the neighbourhood of the freezing point of benzene. We have endeavoured to extend and complete them. E X P E R I M E N T A L . The method adopted was to prepare mixtures of alcohol and water of known strength; these were mixed with various known proportions of benzene and the temperature was determined a t which the liquid separated into two layers or the benzene crystal-lised out.The concentrations are always expressed in grams of component per 100 grams of solution. The alcohol was obtained by distilling ordinary “ absolute ” alcohol with lime; the percentage of water in it was determined from the density using the tables given in the last edition of Beilstein’s “ Handbuch der Organischen Chemie.” From this the requisite aqueous mixtures were prepared gravimetrically . The purest alcohol used (99.5 per cent.) was obtained from this by redistillation after treatment with anhydrous copper sulphate. The benzene was freed from thiophen by sulphuric acid and frozen out seven times; it was then distilled over sodium. The apparatus consisted of an ordinary Beckmann tube with air-jacket thermometer and stirrer.A known weight of one of the liquids was placed in it and successive amounts (usually 1 c.c.) of the other added through the side-tube from an accurate pipette, which had been carefully graduated by weight with the particula ALCOIIOL-WATER BETWEEN -1 25" AND - 5'. 1399 liquid to be used in it. The tube was warmed or cooled by a bath of water ice or ice and salt. The thermometers had been compared with an instrument standardised a t the Reichsanstalt and were checked by redeter-minations of the ice-point. The readings were corrected when necessary for the emergent stem. At high concentrations of benzene the method of supercooling could be used as the amount of solid benzene separating did not seriously affect the proportions.At lower concentrations the point was observed at which the last TABLE I. Alcohol 99.5 per cent. Benzene. Per cent. 92-42 80.29 75-32 70.92 67.05 62.05 57.85 54-16 50.95 Alcohol, 95.20 93.09 91.12 86-86 81-82 77.15 69.23 65.56 58.76 53.30 50.55 45.30 Tenip. + 2-95' 1.26 0.50 -0.14 - 0.86 - 1-94 - 2.94 -4.16 - 5.42 98.0 per cent. + 3.50 3-10 2-76 2-22 1-62 1-08 0.03 - 0.72 -2.16 - 3.90 - 4.62 -5.72 Alcohol 95.76 per cent. 94-50 + 3.48 89.60 2.84 81.15 1.86 77.51 1.48 65.70 0-12 59.35 - 1.04 55-46 - 1.92 52.04 - 2.75 49-02 - 3.62 46.34 - 4.42 43.94 - 5-34 Alcohol 90.06 per cent. 89.18 +30*7 (A) 87.55 26.1 (L) 86.88 23.9 (L) Alcohol 90.06 per cent.-contcl. Benzene. Per cent. Temp. 85.24 16.1" (L) 84-30 11.0 (L) 83.15 5.2 (L) 82.54 2.0 (L) 81-19 2.51 74.22 2-1.3 68-33 1.78 59-42 0.95 55.60 0-42 49.31 - 0.51 46.62 - 0.91 42.09 - 1.97 37.65 - 3.54 35.76 - 4.30 34.05 - 5.14 Alcohol, 73-89 72-81 71-63 70.35 65.93 67-38 Alcohol, 63-52 61.66 57-41 50.55 47-14 44.19 44-19 39-24 33-03 30.64 26.78 86.0 per cent. +28-3 (L) 22.7 (L) 17.6 (L) 12.9 (L) 8.5 (L) 4.5 (L) 80.10 per cent. $39-2 (L) 32.1 (L) 19.6 (L) 9.2 (L) 5.2 (L) 1.6 (L) 2-45 3-00 0.96 0.30 - 1.12 Alcohol 74-45 per cent. Benzene. Per cent. 44.43 35-23 35.12 3 1-02 28.90 27.04 27-04 24-03 18.64 17-65 15-96 Temp.+29-5" (L) 20.3 (L) 15.2 (L) 3.00 (L) 7.75 (L) - 1.25 (L) $- 2.30 + 1.20 - 2.25 - 3.10 - 4.85. Alcohol 69.08 per cent'. 27-67 +25*3 (L) 24.31 17.3 ( L ) 25.88 21.2 (L) 22.91 21.67 '20.55 19.06 18-20 17.15 15.37 13.72 -12.37 11-81 Alcohol, 10.53 10.05 9.25 8-56 8-27 8-27 6-66 6.34 13.5 (Li 6.5 (L) 3-30 1-52 0.02 1.34 9.9 (L) 1-95 (L) - 3.02 - 3.70 57-66 per cent. +154 (L) 12.15 ( L ) 7-1 (L) 2.3 (L) - 0.40 (L) -+ 2-15 - 2.92 - 4.20 25.18 - 2.02 23.76 - 2.97 Alcohol 39 p e ~ cent 32-50 - 3-75 Less than 21.36 - 4.67 1.0 f-350 ( L 1400 SIDGWICK AND SPURRELL THE SYSTEM BENZENE-ICTIIWTJ crystals remained in equilibrium with the liquid. For the two-liquid equilibria the point was taken a t which the liquid on slow cooling became sufficiently turbid to obscure a bright object placed behind it.The temperature is in every case the mean of two or three concordant observations; these in the solutions containing more benzene did not differ by more than 0.lo but in the weaker solutions differences of as much as 0 - 2 5 O could not always be avoided. Each series in the table was carried out with alcohol of the strength stated a t the head; the percentage of benzene given in the first column is the number of grams in 100 grams of the result-ing mixture. The points marked ( L ) are those in which the separation was into two liquids; in all other cases they are the freezing points of the benzene. One or two solutions gave points of both kinds a higher (stable) solid and a lower (metastable) liquid point.From the curves the values for a series of round temperatures were interpolated and these are collected in table 11. The first column gives the temperature the second the freezing points of mixtures of benzene and anhydrous alcohol from the results of Pickering (Zoc. cit.); the other columns are from our own experi-ments. The two-liquid points are distinguished by an asterisk. The total composition of any liquid is of course obtained thus: the percentage of benzene is that given in the table; the per-centage of water or alcohol is obtained by multiplying the difference between this and 100 by the proportion of water or alcohol (from the figure a t the top of the column) in the aqueous alcohol used.At the foot of each column is given the percentage of benzene and the temperature a t the triple point solution I-solution 11-solid benzene. The results are plotted for temperatures from +5" t o - 5 O in Fig. 1 the full lines representing two-liquid and the dotted lines liquid-solid equilibria. The results are given in table I (p. 1399). Discussion of Results. The equilibrium of a three-component system can be expressed only by a solid diagram; this can take the form of a triangular prism the isothermal curves being represented on a series of triangles. Each of the curves obtained by adding varying quanti-ties of benzene to aqueous alcohol of a definite strength (which are plotted in Fig. 1) represents a section of this solid diagram by a plane which contains the temperature axis passing through th TABLE 11.the percentage of benzene in the liquid a t equilibrium. The first line gives the percentage of alcohol in the mixture of alcohol Alcohol per cent. 100 Pic kering - 25" .................. 15 .................. -5 .................. 99.48 4 .................. 97-57 3 .................. 93.82 3 .................. 2 .................. 87-00 2 .................. 1 .................. 80.89 1 .................. 0 .................. 74.08 0 .................. - 1 .................. 67.79 - 2 .................. 63-87 - 3 .................. 59.10 - 4 .................. 55.56 - 5 .................. 52.60 --I -............... -99.5 -__ --92-65 85.28 78-36 71.87 66.45 61.70 57.54 54-49 51-85 -----98.0 95.76 -_ _-02-52 91.22 85-06 82.64 76.58 72.78 69.25 65.03 63.93 59.48 59.62 55.07 56.00 51.17 52.71 47-82 49.90 44-81 96-76 - -- -- -- -- { +4.10" 90.06 87-22" 85.05" 83.05" 82-95" 82.76" 71-90 82*55* 59.80 82*35* 52.01 82*10* 46-39 42.00 39.00 37.48 34.45 82.62 f-2.55" I 80.10 69.41 55.00" 46.92" 46-45-39.24 44.50" 33.15 43* 29.85 43.08" 27.34 25.40 23.52 22.21 21.00 44.95 + 2.50" 1402 SIDGWICR AND SPURRELL THE SYSTEM BENZENE-ETHYL benzene edge of the prism and cuts the opposite side along a vertical line corresponding with the particular mixture of alcohol and water employed.The isothermals for three temperatures, namely +25O +3O and -so are plotted on the triangle in Fig.2. A t 2 5 O there is of course only the two-liquid equilibrium represented by the innermost curve. The dotted tie-lines giving 5" 3" . I " B 2 0" u F c -11" - 3" - 5" FIG. 1. 100 8 0 60 40 20 Benzene. Weight per cent. Full lines Liquid-liquid equilibria. Dotted lines liquid-solid ,, the compositions of the two liquids in equilibrium with one another are taken from Taylor's measurements (Zoc. c i t . ) . At telmpelratares below 5*49O sollid benzeaa is prelsent at B (pure, benzene) and extends further along BA as the temperature falls. At + 3 O for example the solid is in equilibrium with a mixture of benzene and alcohol containing 6.18 per cent.of the latter. I f water is added to this mixture the freezing point of the benzene is raised because the water being insoluble in the benzene ATL'OTTOL-WATER BETWEEN -k 25" AND - 5". 1403 increases its vapour pressure. I n order therefore to remain in the 3 O isotherm if water is added alcohol must also be added; the solid-liquid curve (the dotted line) will thus incline to the right. Our results show that when it has reached the point a a second FIG. 2. Water. W Benzene. Alcohol. $25" Isotherm -0- + 3" Isotherm Solid-liquid - - - x - - -Liquid-liquid -@--$ Isotherm - - - . _ - -Dotted tie lines Taylor 25". Full tie lines Sidgwick and Spurrell at 3". I 1 liquid phase appears; we have now reached the triple line solid benzene-solut'ion I-solution I1 (conveniently written S-L,-L,) .This new liquid is the conjugate solution the composition of which is given by the point b which is a t the other end of the tie-line ab ; being in equilibrium with the first liquid it must have th 1404 TITE SYSTEM BENZENE-ETHYL ALCOHOL-WATER ETC. same pressure of benzene vapour and so must also freeze a t 3 O . Thus at 3 O the L,-L2 part of the curve is confined to the part ccb; a t b the solid curve begins again passing between the two-liquid curve and the side AW. The triple line that is the curve joining the whole series o€ triple points S-L,Tl for all mixtures of alcohol and water on addition of benzene will begin on the line BTV (no alcohol) a t 5*39O (tlriple point, watler-benzene liquid-benzene solid) atl tmo point,s corresponding re'spectivdy with 99.97 and 0.092 per celnt.of benzene. As successive quantities of alcohol are added the temperature of the triple points will fall but a t any given tempera-ture (not too low) there will be two triple points corresponding with two conjugate solutions joined by a tie-line; these points will move towards one another with a fall in temperature as the alcohol increases but more rapidly from the water than from the benzene side (owing to the position of the tie-lines) until they finally meet a t the plait-point where the tie-lines vanish. The temperature of this point is the lowest a t which two liquid phases made up of water alcohol and benzene can co-exist. Our results show that this temperature is +2-50° and the composition of the liquid about 80 per cent.of benzene and 2 per cent. of water; a t 2 5 O Taylor found a t the plait-point 80.2 per cent. of benzene. The solid benzene curve has the form of the outer dotted line; somewhere near the water end it must meet the ice-curve which a t - 5 O starts on A'CV a t 91 per cent. of water but the solubility of benzene in this region is so small that it could not be investigated. One point of practical importance may be mentioned in view of the use of these mixtures for motor fuel. I f a fourth com-ponent (another hydrocarbon) were added the freezing point of the benzene would be proportionately lowered (some 5O for 10 per cent.) but; if a paraffin were used for this purpose it would certainly increase the tendency of the liquid to separate into two layers. The solubility of paraffins in alcohol containing water is extraordinarily small. The system hexane-alcohol-water has been examined a t Oo by Bonner (loc. cit. p. 777); the heterogeneous area occupies nearly the whole triangle. For example whilst 90 pelr clelntl. aqueloas alcolhoJ will dissollve up to1 f o a r timels itls weight of benzene it will only dissolve a third of its weight of hexane. At -5O no second liquid can exist. ORUANIC CHRXISTRY LABORATORY, OXFORD. [Received Septembcr 6th 1920.

ISSN:0368-1645    

DOI:10.1039/CT9201701397

出版商:RSC    

年代:1920

数据来源: RSC