NEWCOMPOUNDS
Sept., 1942
cator over sulfuric acid the compound melted a t 276-278" (uncor.). Anal. Calcd. for CZZHI~SSOSN~: N, 9.96; S, 17.09. Found: N, 9.54; S, 16.85. CHEMO-MEDICAL RESEARCH INSTITUTE GEORGETOWN UNIVERSITY FILADELPO IRREVERRE M. X. SULLIVAN WASHINGTON, D. C. RECEIVED JUNE 25, 1942
2331
--C
Formula
NO.
CilHioONsClz C12H210NSClz ClsH2sONaC12 C1sHzrONsClz CizHilONsClz CISH~~O~ C~sHz602NzCIz
I I1 I11 IV V VI VI1
47.12 48.96 50.63 53.56 48.96 N 51.12 ~C~ 63.39
--
Analyses,
% '
H
C
H
6.84 7.20 7.52 8.13 7.20 ~7 . 7 3 7.77
47.38 48.67 50.67 53.45 49.05 51.27 53.02
6.61 7.27 7.80 8.04 7.51 7.75 7.62
Calcd.
Found
BURROUGHS WELLCOME & Co., U. S. A. RICHARD BALTZLY EXPERIMENTAL RESEARCH LABORATORIES WALTERS. IDE TUCKAHOE, NEWYORK JOHANNES S. BUCK Dimethylamine reacted with p-nitro-p-bromopropionRECEIVED MAY18, 1942 anilide t o form p-nitro-8-dimethylaminopropionanaide, m. p. of the hydrochloride, 200-20l0. A portion of this was transformed into the methochloride and both subSome New Quaternary Salts stances were reduced catalytically in alcohol containing Methylaniline and octadecyl iodide reacted to yield hydrogen chloride to give, respectively, p-amino-p-dimethylaminopropionanilide dihydrochloride (I), colorless methyloctadecylaniline, a yellow oil, b. p. (3 mm.), 234". felted needles, m. p. 218-219 ', and p-amino-p-dimethyl- This was treated in benzene solution with methyl iodide aminopropionanilide methochloride hydrochloride (11), forming octadecylphenyldimethylammonium iodide which crystallized in leaflets from ethyl acetate. hygroscopic crystals, m. p. 211-212". Cyclohexylethylamine (prepared from cyclohexylacetic N,N-Diethylethylenediamine,' prepared by the reduction (sodium and alcohol) of diethylglycine nitrile, reacted acid by the sequence: acid --j acid chloride -+amide -+ with p-nitrobenzoyl chloride, forming @- [p-nitrobenzoyl- nitrile +amine) was methylated by the Clarke-Eschweiler amidoethyl] -diethylamine hydrochloride, colorless needles method. The resulting tertiary amine reacted with benzyl melting a t 164-5". This substance and its ethochloride chloride in ether to give cyclohexylethylbenzyIdimethy1were reduced catalytically in alcoholic hydrogen chloride to ammonium chloride. Benzyl-@-bromoethyldimethylammonium bromide was @- [p-aminobenzoylamidoethyl]-diethylamine dihydrochloride (111), m. p. 176.5-178", and t o p-[p-aminobenzoyl- prepared from benzyldimethylamine and ethylene broamidoethyll-triethylammonium chloride, hydrochloride mide. Triethylamine and a-menaphthyl chloride (a-naphthyl(IV), which forms stubby prisms melting a t 228". Reduction of p-dimethylaminopropionitrile gave y- methyl chloride) yielded a-menaphthyltriethylammonium dimethylaminopropylamine, m. p. of the dihydrochloride, chloride. Data on these substances are presented in the 182-184' The base reacted with p-nitrobenzoyl chloride subjoined table.
Some Diamino Peptides
c
Formula
M .p., o c .
Composition
C
(n-C1&~,7)CeHSNMeJ (C6HnCHZCHZ) ( CsHsCHz)NMezC1 (CBHSCHZ) (BrCHzCH2)NMezBr (a-CioH7CH2)NEtaCl
93-94 906 dec. 174 197 dec.
CzsHasNI Ci7HzeNCI C11H11NBr2 CirH24NCl
82.25 72.44 40.87 73.49
to form y-[p-nitrobenzoylamidopropyl]-dimethylamine hydrochloride, m. p. 190-192". This was reduced catalytically in alcoholic hydrogen chloride solution to y-[paminobenzoylamidopropyl] -dimethylamine dihydrochloride (V), m. p. 184185". Reduction of the p-nitrophenylurethan of @-hydroxyethyltriethylammonium chloride yielded 6- [p-aminophenylcarbamatoethyl]-triethylammonium chloride, hydrochloride (VI), which forms irregular prisms melting a t 138139 '. By the reduction of @- [p-nitrobenzoyloxyethyl] -triethylammonium chloride, there was obtained @- [p-aminobenzoyloxyethyll-triethylammonium chloride, hydrochloride (VII), m. p. 214-215". This has been reported2 previously, but the synthesis used was not free from ambiguity. The salts described here were crystallized from absolute alcohol or from alcohol-ethyl acetate mixtures. The analytical data are in the table. (1) Ristenpart. Rer., as, 2526 (1896). (2) Einhorn and lThlfelder,A n n . , 871, 138 (1909).
Calcd.
Analyses, % '
Found
H
C
9 . BS 10.02 5.31 8.71
62.12 7 2 . 13 40.91 3 41
n 9.69 10.16 5.61 8.82
BURROUGHS WELLCOME & Co., U. S. A. EXPERIMENTAL RESEARCH LABORATORIES TUCKAHOE, NEWYORK RICHARDBALTZLY CLAYTON W. FERRY JOHANNES S. BUCK RECEIVED MAY18, 1942
Some Mono- and Disubstituted Guanidines The guanidines here described were all prepared by conventional methods. The S-methyl-isothiourea sulfate method (generally applicable with amines of moderate strength and water solubility) wyas used to prepare the five following : 6- [N-morpholinoethyl]-guanidinesulfate (from aminoethylmorpholine), @,p-diethoxyethylguanidine sulfate (from amino acetal), N,N-dicyclohexylguanidinesulfate (from dicyclohexylamine), N-benzyl-N-methylguanidine sulfate (from benzylmethylamine) and 6-phenoxybutylguanidine sulfate (from 6-phenoxybutylamine prepared by reduction of y-phenoxybutyronitrile) . In all these cases the salt was isolated by evaporation of the reaction mixture
