618 RUHEMANN AND BLXCKMAN : BESZOPHENYLHTDRAZISE,

LX.- Benzophemy 1 hy draaine.

By S. RUHEMANN, Ph.D., K A , , and F. F. BLACKMAN, B.Sc.

IN a recent number of this Journal (this vol., p. 242) one of ns pulslished a n investigation on the action of chloroform and alcoholic potash on some hydrnzines, and showed horn compounds were formed which contain a closed r ing of four nitrogen and two carbon-atoms. I n turn, that investigation led to the experiments, the results of which form the subject of the present cominunication.

Doebner (Annulen, 210, 267) acted on plithalanil with bensoyl chloride in the presence of zinc chloride, and obtained phthalyl-

benzoanilide, C,Kj.CO.C,H,*~<,,>C,H,, co which by alooholic pot-

ash is transformed into amidobenzophenone, o r benzoaniline, C,Hj*CO.CsH,*NH,. This base was regarded by i t s discoverer as a para-amidobenzophenone, since he was able to transform it- into paroxybenzoic acid by converting i t into oxybenzopheiioiie, and then fusing the latter with potash, Froehlich ( B e y . , 17, 2673), how- ever, showed that a benzophenone- derivative could be obtained from pseudocumidine by a metliod perfectly analogous to Doebaer’s. But since the constitution of 9-cumidine i s expressed by the formula

C,H,.CH,*CH,.CH,.NH,, the bemoyl-group cannot here enter into the para-position, this led him to consider the possibility of benzoaniline being an ortho-compound. I n support of this view he adduces the fact tha t by the action of melted potash molecular t’ransforniations take place; and i t may be tha t salicylic acid is the first product of the fusion of the oxybenzophenone t’rorn benzoaniline, and tha t paroxybenzoic acid results from i ts subsequent transformation. Bu t the experiments of R. Geigy and W. Koenigs (Ber., 18, 2700) have siiice proved that Doebner’s view of the constitution of benzo-

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RUHEMANN AND BLACKNAN : BENZOPHESTLHYDRAZINE. 61 3

aniline is correct, arid that this base is in reality para-amidobenzo- phenone.

W e have prepared this compound according to Doebner’s method, in order to convert i t into benzophenylhydrazine, with the object of characterising the latter and applying the isonitrile reaction to it.

Benzopheny lhydrazine,

The transformation of benzoaniline into the hgdrazine was effected by the reduction of the diazo-compound with stannous chloride. For this purpose 20 grams of the paramidobenzophenone were mixed with 400 grams of hydrochloric acid, and the calculated quantity of sodium nitrite (9 grams) dissolved in water, was gradually added to the well-cooled mixture ; an interval sufRcient foy the nitrous smell to disappear being allowed after each addition. When the diazotisation is complete, the solution is filtered and the filtrate poured into a cold solution of 90 grams of stannous ohloride in 200 grams of hydro- chloric acid. The pale yellow precipitate, which immediately appears, is collected on a linen filter and dried on porous plates ; during the drying it gradually becomes orangc in colour. To obtain this hydrazine hydrochloride in a state of purity, the orange powder is treated with hot water and the solution filtered, when a con- siderable quantity of a yellow, insoluble, organic tin-compound is left on the filter. The water used must not be quite a t the boiling point, o r the hydrazine will be slightly decomposed. When concentrated hydrochloric acid is added to the warm filtrate, faintly colourecl needles of the pure hydrazine hydrochloride are deposited, which, after drying in a vacuum, gave on analysis numbers corresponding to the

formula C6H4< (q--NK.NJ& - (1) -c 0 * (’6H5 ,H(-i1 .-

Found. Calrulated for r-A-- 7

C13H,:jN20Cl. I. 11. 111. N ...... 11.27 11-68 11.55 - CI.. , . . . 14-28 - - 13.98

The hydrochloride reduces Fehling’s solution, dissolves readily in warm water and in alcohol, but is insoluble in hydrochloric acid. The hydrazine sulphate may be prepared by the addition of dilute sulphuric acid to an ethereal solution of the base, when it separates out in white needles, easily soluble in water, but readily decomposed by boiling.

The hydraziiLe itself can only be prepared satisfactorily by the addition of a cuncentrated solution of sodium acetate to the slightly

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6 1 d RUHEIIANN AND BLACKJIAN : BENZOPI~ENPLHTDRAZISE.

warm solution of the liydrocliloride, when i t crystallises out in yellow needles. If the acetate be added to the very hot, o r boiling solution of the hydrochloride, the base is then precipitated in a more or less resinous state. The hydrazine is fairly stable a t ordinary tempera- tures, but a t 100" C. it gradually darkens, with slight decomposition. It melts a t 127", is very soluble in alcohol, ether, and benzene, but on evaporating the solut,ions i t is left behind as a resin. The crystals of the hydrazine obtained as above were prepared for analysis by washing with water and drying in a vacuum over sulpliuric acid.

The formnla C , t I , < ) : i ) ~ ~ ~ ~ ~ , requires :-

Found. Theory for r--J- v CI3HIP N,O. I. 11. 11 r. c 73.74 - - ...... 73.53

H 5*i2; -- - ...... 5.36 N ...... 13.20 - 13.52 13.23

Acetylbenxophenylli ydrazine.-Acetic anhydride acts on the hydrazine with evolution of heat. The reaction is completed on the water-bath, the crystalline product purified by treatment with animal charcoal, and recrystallised from hot watw. It forms white needles, melting a t 154+-155O, and easily soliible in alcohol ; i t gave on analysis values

(1 j-CO*C,H, (4 j-NH-NHCO.CH,' corresponding to the formula Cs&<

Found. Theory for r---L-- 7 C16tllJ20.. I. 11.

C .......... 70.87 70.72 - H . . ........ 5.51 5.80 N .......... 11.02 - 11-14

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Ben.zophenylseinical.baziJe is formed by adding an aqueous solutioa of potassium cyanate to a solution of the hydrazine hydrochloride. The resnlting precipitate crystallises from boiling water, in which i t is difficultly soluble, in slightlp coloured c r~s ta l s , which melt a t 21 5aq5" with decomposition and reduce Fehling's solution.

Analpis gave numbers corresponding t o the formula

(l)-CO*C,:H, C6H4< (4) -N H-NH-CO .NH;

Found. 7 Theo1.y for (----L--

C14H13N301. I. 11. C 66.10 - .......... 65-88 H .......... 5.10 5.37 N .......... 16.47

- 16.68 -

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REHEJIANN ABD BLACKMAN : BENZOPHENYLHYDRAZISE. 615

Bsnxophe~i~l-phenyls~ic~hosemica~ba~ide.--Ry adding phenyl mustard oil to an ethereal solution of the bydrazine, a sulphosemicarb-

xzide of the formula c6&< (4)--NH.NH.CS.NH.C,H5 is obtained.

This, after a short time, separates out in yellow crystals difficultly soluble in hot alcohol, from which on cooling they crystallise in plates melting a t 203" with decomposition.

(I)-CO*C,H5

They gave on analysis the following results :-

Pound. Calculated for -7 C,,Hl,N,OS. I. 11.

N .......... 12.10 19.31 S .......... 9.22 9.47

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Benzopheny 1-tenzaldehy de hy lhaz ine , c6H4< (l)--CO*C,H, (4)--NH,N:CH.C,H,,

is obtained by adding to a warm solution of benzophenylhjdrazine hydrochloride a concentrated solution of sodium acetate and benzalde- liyde. Alcohol is subsequently added and the solution allowed to stand for some time, when orange crystals separate out ; these dis- solve with difficulty in hot alcohol, and crystallise from i t in yellow glittering plates which melt a t 188". They gave on analysis-

Found. Theory for f-----7

€I 1 sN2O. I. 11. C .......... 80.00 $0.20 H.. 5.52 .- ........ 5.33 N .......... 9.33 - 9.27

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( 1)-C O*C,H5 Benzophenylacetone hydraxifie, c6H4< (4)--NH.N:C(CH,),, is pre-

cipitated from a solution of the hydrazine hydrochloride by the addi- tion of acetone and a conceritrated solution of sodium acetate. The precipitate is dissolved in hot dilute alcohol, which, on standing, deposits plates melting a t 125", and easily soluble in alcohol a n d acetone. This substance decomposes after being kept €or a few days a t ordinary temperatures.

A nitrogen determination of this compound dried in a vacuum gave-

Calculated for C16H16N20* Pound.

N ............ 11-11 11.09

(1)-co'c6H5 Acstophenone- benzoplieny Lhydrazine, C&< H.N:C < CH, , is

c6H5

prepared in a way quite analogous to that given aboye for the acetone

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6 16 RUHEMANN AND BLACKMAN : BESZOPHENYLI-IYDRAZINE.

compound. a t 140-141". mination.

It crystallises in bundles of yellow needles which melt Its composition was confirmed by a nitrogen deter-

Theory for C21H1BN20' Found.

N ............ 8.937 9.08

When pyruvic acid is added to a warm aqueous solution of the liydrazine hydrochloride, a lemon-yellow, flocculent precipitate of this substance is a t once thrown down. It is soluble in dilute alcohol and crystallises from i t in tuftjs of curved needles which melt at 210" with decomposition.

The following numbers correspond to the formula C,H,4N203 :-

Found. 7-- 7

Theory. I. 11. 111. C ...... 68-08 68.31 67.75 - H. . . . . . 4.96 5.90 5.19 - N . . . . . . 9.93 - - 10.14

This acid is easily soluble in alcohol, in alkalis, and ammonia. The barium salt is dissolved by hot water and crystallises from it in yellow needles. The silver salt is thrown down as a yellow precipi- tate on adding silver nitrate to ah ammoniacal solution of the acid. This salt rapidly decomposes and blackens on warming with water.

The ethyl suZt of this acid is easily formed by heating together on a water-bath, for 1-2 hours, nine parts of absolute alcohol, one part of concentrated sulphuric acid, amd one part of the pyruvic acid compound in a flask connected with an inverted condenser. The ethereal salt is then precipitated by the addition of water, washed with dilute ammonia to remove any unaltered pyruvic acid compound, and recrystallised from alcohol. The yellow needles thus obtained melt at 145" without decomposition. On analysis they gave numbers

(l)-CO*C,H5 (4)--NH*N:C <gFo C2H, corresponding to the formula CsH4<

Found. Theory for ---7

C,H,,N203. I. 11. C .......... 69.68 69-73 - H .......... 5-80 6.08 -

........ 9.29 N . . 9.09 -

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RUHEMANN ASD BLACKMAN : BESZOPHEKYLHTDRAZINE. 61 7

BenzoincEoZecarboxyZic acid, C6H5*CO*C,H,<,H>C*COOH, C H is pre-

pared by heating the finely powdered ethereal salt of benzophenyl- hydrazine-pyruvic acid with an equal weight of freshly fused zinc chloride at a temperature of 220" in an oil-bath. The mixture melts, darkens, and froths briskly after two or three minutes, at the end of which time the reaction is complete. When cool, the resulting brown mass is powdered and warmed with very dilute hydrochloric acid to remove the zinc chloride. The dark-coloured substance that remains is, with the exception of a little resin, all dissolved by repeated extrac- tion with ether. The ethereal solution is then shaken with dilute soda, from which, on subsequent addition of hydrochloric acid, the indolecarboxylic acid is thrown down as a yellow precipitate. TO purify this, it is dissolved in ammonia, and the solution boiled with animal charcoal; on addition of hydrochloric acid, it yields a less coloured precipitate which readily dissolves in alcohol and crystallises out in yellowish needles. The acid may be obtained perfectly white, though with a considerable loss of material, by boiling its alcoholic solution with animal charcoal, filtering and concentrating the filtrate. The pure acid melts at 284-285" with decomposition.

The formula C,sH,,N03 requires-

Theory. Found. C ............. 72.45 72.23 H ............. 4.15 4.34

This acid is only slightly soluble in boiling water, but dissolves readily in alcohol and in ammonia. The addition of silver nitrate to the latter solution throws down the silver salt as a, yellowish, flocculent precipitate. When heated at a temperature between 280-290", it gives off carbonic acid and is transformed into benzo- indole. The latter was obtained in the form of neai-ly white needles melting at 144-145", by dissolving the melted product in alcohol and decolorising the alcoholic solution by animal charcoal. When dissolved in alcohol, i t colours pine shavings moistened with hydro- chloric acid, violet, and when acidulated with hydrochloric acid, it is coloured red by potassium nitrite.

We intend t o pursue the investigation of this compound. A small quantity of the ethyl salt of the benzoindolecarboxylic

acid is contained in the ethereal solution of the product of the zinc chloride condensation, and may be obtained as a yellow residue by evaporating the ether after the free acid has been removed by agitation with sodium hydroxide solution. This residue, dissolved in alcohol, boiled with animal charcoal, and then concentrated, yields

VOL. LV. 2 x

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618 DISON: FURTHER STUDY OF THE THIOCARBIMIDES.

slender needles which melt at 160-161". The quantity obtained was, however, too small to admit of verification by analysis.

Act ion of Chloroform and Alcoholic Potash o n Benzophenylhydrazine.

It was expected that chloroform and alcoholic potash would act on this hydrazine in a manner analogous to that of their action on phenylhydrazine and its homologues, leading to the formation of a tetrazine, as has been shown before (Zoc. c i t . ) and as will be further seen from a communication shortly to be made to the Society. But the desired compound could not be obtained. When an alcoholic solution of the hydrazine is treated with these agents, it becomes first green and then deep-red in colour. The ethereal extract of the latter, when shaken with dilute sulphuric acid and then evaporated, yields a red resin from which boiling water extracts a small quaiitity of a crys- talline compound, probably formylbenzophenylhydrazine, which is easily decomposed when boiled with water; the same compound appeared also to be formed by heating the hydrazine with formamide a t 140" till ammonia ceased to be evolved, but owing to its easy decom- position it could not be recrystallised. All attempts to obtain a crystalline substance from the red resin left after extraction with water entirely failed.

University Laboratory, Cambridge.

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