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 H I L I . , 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 .
2 , j-DIME'I'HYLBENZYL-2
5 . DIRIETHYLBENZAL.
1067
amount of a 4 per cent. sodium amalgam sufficient t o reduce the aldazine to its corresponding hydrazone. This was heated in a flask connected with a reflux condenser for from three t o four hours upon a water-bath. The solution, nearly colorless, was then filtered and the filtrate left in a freezing-mixture of salt, ice and water until the hydrazone crystallized out. T h e hydrazone was then filtered off, washed with water and recrystallized from alcohol. I t melted at 74"-78" (uncorr). The reaction takes place according to the following equation : (CH,),C,H,CH : N . N : C H C,H,(CH,), 3-H, = (CH,),C,H,CH, N H . N : CH.C,H,(CH,),. The analysis gave: C, 81.03;H, 8.21. Calculated: C, 81.2; H, 8.04. 2,~-Dimethylbenzyl-2,~-dimethylbenzal hydrazone is soluble in ether, chloroform, benzene, carbon bisulphide, toluene, ethyl alcohol, methyl and amyl alcohols. I t is insoluble in water. The hydrazone is very unstable and begins to decompose at once when exposed to the air.
Acrtyl ~,5-dimethylbenzyl-r,5-dimethylbenzalHydrazone, (CH,),C,H,CH,N(C,H,O)N : CHC,H,(CH,),. T o a concentrated alcoholic solution of the hydrazone was added a slight excess of acetic anhydride and the solution evaporated slo~vlp to dryness upon a water-bath. The residue was recrystallized from alcohol. I t gave long, white, satin-like needles which melted at 137'. The analysis gave 9.11 per cent. N. Calculated, 9.09 per cent. The acetx 1 derivative is soluble in benzene, toluene, ether, chloroform, carbon disulphide, acetic acid and in hot ethyl, methyl, and amyl alcohols. I t is insoluble in water. Bcirzoyl 2,5-dinzrt~ylbeizzy1-2,5-dinaet~~~lbe~izal Hydrazone, (CH,),C,H,CH,N(C,H,CO)N : CHC,H,(CH,),. A slight excess of benzoyl chloride was added to a concentrated alcoholic solution of the hydrazone and the solution evaporated to dryness upon a water-bath. The residue was recrystallized from alcohol. Long satin-like crystals formed which melted at 134'I 34.5O. The analysis gave 7.60 per cent. N. Calculated, 7.57 per cent T h e benzoyl derivative is soluble in benzene, toluene, ether,
1068
E Y E R H A R T P E R C Y H.kKDI?r'G.
chloroform, carbon tlisulphitle, acetic acid ant1 i i i hot ctli!.i, nicthyi, and amyl alcohols. It is itisoltible in water. Nitroso and picric acid derivatives are at presciit being prcpared.
PREPARATlON OF 2,4,6-TRIRETHYLBENZALDAZlNE; O F 2,4,6-TRIMETHYLBENZY L-2,4,6-TRIMETHYLBENZAL HYDRAZONE A N D SOME OF ITS DERIVATIVES. H Y E\'t:xii.iK'r I'I;RL'V €I 414r ) i \ i , iii.
~,~,6-T~i~~iatl~y1bCllialdll=ill(', CH.,
CHI
I /
\
CH:,\ /
/
---.\
>CH : X . S : C H C
\ 4
$H,.
\--4
I
I
CH, CH,, 2,4,6-Triiiiethylbenzaldazine was prepared by addiiig to a \veak alcoholic solution of 2,4,6-trimethylbenzaldehyde, which \vas prepared according to Gatterinann,l a solution of hytlrazine sulphatc~ containing the calculated amount of sulphate to prodtice the corresponding aldazine. The mixed solutions were \\-armed to 60"violently shaken for thirty minutes and allowed to stand for t\vo hours. The ~ ~ I I o wsubstance that separated formed spherulitic inasses which recrystallized from acetic acid in 1,eautiful li$t yello\v prisms which melted a t 167'. ~CH:J,C,H,CH:O ... .. $. H;N'N:H, . .. . I-.o;Hcc,H,(cH.,),, . , .(cH,~,c,H~.cH : ?;.x : C H . C , H , ~ C H These gave c). jy per cent. N. Calculatetl. 9.50 per cent. 2.4~3-Trimethylbenzaldazine is very soluble i n chloroform. I t is soluble in cold ether. benzene, toluene, acetone a i i d in hot acetic acid, ethyl, methyl and amyl alcohols. I t is insoluble i l l water. Like all known aldazines it is a very stable u ~ i i i p o ~ i i ~ ~ l . ~ . ~ . 6 - T ~ i 1 r 1 ~ ~ t l i y l b e ~ i ~ y l - - s , ~ , 6 - t ~ i t H?ltlix:zuiic,. ~~ctlzylbeii~cil (CH,).,C,H,CH,NHN : CHC,H,(CH Slore than the calculated amount of a 4 per cent. sodium anialganx 1
w. Graf :
Inaug. Diss.. Heidelberg, 1899.
