1063
C O N D E N S A T I O N O F CHLORAL.
in the case of each of the oilv liquids obtained by the above methocls . Calculated for
Calculated for
NO? CoHi CHiCl
( N O ? ) & c H , CH?C1
............. .... 8.2 . . . . ..
Nitrogen Specific gravity at
27O
12.9
..
Found I1
I
8.7 8.6 1.333 1.332
I11 12.1
1.476
From the above it is evident that not only is the yield of p-nitrobenzyl chloride practically the same but that the byproducts are also the same, whichever of the two methods of preparing p-nitrobenzyl chloride is employed. The further investigation of the dinitrobenzyl chloride was not proceeded with as Cohn and Friedlander1 have recently obtained o-p-dinitrobenzyl chloride by an analogous method and have announced their intention of soon publishing the details of their work. r N I V E R S I T Y PLACE, N E B ,
June 16, 1902
[CONTRIBUTION FROM THE CHEMICAL OF
LABORATORY
O F THE UNIVERSITY
NORTH CAROLINA].
CONDENSATION OF CHLORAL WITH THE NITRANILINES. BY ALVIN S . W H E E L E R A N D H. R. W E L L E R . Keiei\ed luly 28, ~ g a i
CHLORAL forms condensation products readily with aromatic amines according to the equation CC1,CHO PRNH, = CC1,CH ( N H R ) , H,O. 0 . \i7allach2effected the condensation of chloral with aniline, the product being trichlorethylideiiediphenylamine, CC1,CH (NHC,H,),. In 1898 Eibner3 and Baskerville, working independently, carried out the condensation of chloral with p-nitraniline. Baskerville's results are incorporated in the present paper. O u r investigation shows that similar products are obtained with ortho- and metanitraniline. The melting-points of the condensation products form an ascending series as in the nitranilines. The chloral used was prepared by distilling chloral hydrate with concentrated sulphuric acid and the nitranilines were recrystallized until pure. Trichlorethylidenedi-o-nitroph enamine,
+
1 Bey. d. chem. Ges.. 35. 1266 ( 1 9 2 ) . * A n n . Chcm. (Liebig), 173, 278. 8 Zbid.,30a, 366.
+
I
064
A L V I N S. WHEELEK .\SI) H . R. WELLEX.
L'L'I {L'H( SHK( )2C,H,),. --Five
grains of o-nitraniline \vere sus1)r.iitletl i n 75 cc. of benzene and 5 grams of chloral lvere added. '1'n.o aiicl one-half grams of chloral are required hy theory. l'hc crystalliiie nitraniline was quickly converted into a flocculent imcipitate which melted at 162'. The benzene solution \vas evaporated down to a gummy inass 011 the ivater-bath, the residue was talxii up with lioilinc alcohol aiitl, iipon cooling, a beautiful yello\v crystalline precipitate settled out. The t\vo precipitates were recr!.stallized from hot alcohol until the melting-poiiit was raised to \ determination oi chlorine gave 26.ro per cent. CalcuI 7 1'. lritccl for (', $ H , , ),K,Cl:, ( 26.12 per cent. Tricliloretliylidenetli-o-nitl.ol)lieiianiiiic crystallizes from hot alcohol in yello\v transpareiit rcctaiig:ul:ir plates and melts at I 71 '. I t is iiisolul~lci i i ether ani1 ligroin hut soluble in acetone, chloroi c irni and bciizeiie. It iiia\. l)c pur-ifietl by dissolviiig in glacial :icc.tic acitl and precipitating \\it11 Xyiiter. 1t is not decomposed Iiy \vatcr aiitl is insoluble in hot hyclrochloric acid. The yield was ahout 45 per cent. of the theory. 'i'i~iri~lorctl~~~lin'circn'i-iii-iiif~~opltenanzii~r. C'C1::CH( ST3S(.)2CJ34) 2.-l:ivc grams ot' i/i-iiitraniliiie were s~~speiidetl i n 12; c c . I)ciizcne and 5 grains oi chloral were added. The iicedle cr\,stals o f ~~!-iiitraiiiline were quickly converted into tllicciilerit precii)itate. at first yellowish white but soon assuming ;L ricli flc4i color which \vas permanent. The crude substance dccomposed at 3 0 8 ~ . ( )n digestion with acetone the impurities \yere dissolved out and the tneltiiig-point was raised to 2 ~ 2 ' . .4 dctcriuination of chlorine gave 26.18 per cent. Theorj- requires ~ ( ~ per 2 2cent. Trichlorethylidenedi-m-nitrophenamie crystallizes iroiii alcohol i n rectangular plates of a rich flesh color. It melts ;it ? I ? ^ . I! is rcntlily soluble in alcohol and insoluble in ether, l i p o i n a i d lxiizeiic. It is decomposed by hot water and 1)y hydrochloric acid, chloral and rii-nitraniliiie being re-formed. The yield of the condensation product is ahout 30 per cent of the theory. Tlic reaction seenis to run a different cotirsc ii the matcrials are lmiled for some time under a reflux condenser. Under these circtimstaiices a body is obtained which, recrystalling once from alcnliol. melts at 89'. :I single analysis for chlorine showed
CONDENSATION O F CHLORAL.
I 065
presence of 32.3 pcr cent. This substance will be examined further. l‘~iclzlo~~thglzd~iie~~i-~-~iit~opheiiarii~iie, CC1,CH (NHNO,C,H,),.-Ten grams of p-nitraniline were suspended in 100 cc. benzene, and I j grams of chloral were added slowly. -4 heavy J ellow precipitate formed immediately. After heating for some tinie on the water-bath to complete the reaction, the precipitate was filtered off and dried. The melting-point of the crude substance was 210’. I t is extremely insoluble and by removing the impurities with small amounts of cold acetone the melting-point was raised to 216’. A determination of the chlorine gave 26.35 per cent. Calculated, 26.22 per cent. Trichlorethylidenedi-p-nitrophenamine is a yellow powder of very great insolubility. It is insoluble in water, alcohol, ether, ligroin and benzene. It is somewhat soluble in acetone and readily soluble in boiling nitrobenzene. T h e yield was 14.51 grams or nearly 54 per cent. of the theory. I t is slowly decomposed by hot hydrochloric acid. Its conversion by acetic anhydride into p-nitroacetanilide and by benzoyl chloride into benzoyl p-nitroanilide, asdescribed by Eibner, was carried out. Kcdiirfiorz of the Nitrouwtines.--We have tried to reduce these nitroamines with various reducing agents but so far without succe.ss. Ti the nitro-group could be reduced, the resulting amine might again react with chloral, forming a complex ring body. Interesting results were obtained when the nitroamines were boiled with ammonium sulphide in alcoholic solution. In each case a volatile substance condensed on the walls of the reflux air condenser in white cr!stals. In the case of the para-compound, thrse crystals melted at 120’ and were insoluble in water and alcohol. but dissolved readily in carbon distilphide. This group of hotlies \vi11 be studied further in this laboratory. In naming these compounds Eibner places the “di” after the “nitro” hut it seems preferable to 11s to place it before the “ p ” . Coi~stitzitioiz.--In the reaction between chloral and the nitranilines it might be possible for the oxygen to combine with hydrogen in the ring, leaving the amino groups iuitouched. But these substances do not possess any basic properties ; hence they are to be represented as follows : t;,e
1066 EVEKHART
PERCY H A R D I N G A N D EDGAR
m. R I C E .
cc1,
CCl,,
1
I
CH
NO,
CH /\
//
NH
'
\
"
/\ \
/ \/ NO>
/\
\
/ \/ NO,
CHAPEL HILI., N . C., July 24. 1 9 0 2 .
PREPARATION OF 2,s-DInETHY LBENZYL-2,S-DIMETHY LBENZAL HYDRAZONE A N D ITS BENZOYL A N D ACETYL DERIVATIVES. BY
EVERHART PERCYHARDISGA N D EDGAR W. R I C E . Received August
11.
,902.
r,5-Dimethylbeizzyl--.,5-diniethylbe}izal Hydrazone, CH,
CH,, ._ -
!
/-----~\
\ //
-:=
=:
\>CH,NH.N
\
: C H /\'
\ 4
\ . 4
I
I
4
CH,, CH, To an alcoholic solution of 2 ,j-dimethylbenzaldazine, prepared according to Curtius and Jay,' was added more than the calculated 1
J . p i a 4 l . Clrenr., 8 9 , 4 3 .
