June, 1944
CLEAVAGE OF
(DIALXYLVINYL)-ALKYLCYANOACETIC ESTRRS BY SODIUM ALKOXDbES 881 TABLE I POLYRYDROXY AMIN E HYDRORALIDES Empirical formula
Compounds
M. p., OC.
uncor.
Halogen anal res % Calcd. %ouidb
(HOCHn)sCNHs*HCI' (HOCH&CNHvHBr" (HOCHa)8CNHCH2CHiNHC(CH20Hs).2HBr (HOCH&CNH(CH&NHC( CH*OH)s4HBr (HOCHz)sCNH(,CHt)rNHC(CHzOH)c2HBr (HOCHn)sCNHCHzCHOHCHnNHC( CHzOH)a*2HCI (HOCHn)sCNHCH~CHOHCH,"C( CHzOH)s.2HBr
CrHirOiClN 149-150 22.50 22.58 GH1208BrN 133-134 39.55 39.52 37.16 37.09 C~dIasosBrrN~ 205-206 35.98 35.25 CIIHZSO~B~~N 170-171 I 32.87 32.10 CirHsrOoBraNn 160.5-162 C~1HnaO~CIlNi 186-188 19.10 19.07 C11H&7Br2N~ 160-162 34.73 34.67 20.90 20.97 CiiHzsOsClzN2 98-100 (HOCHrCHz)zNCHzCHOHCHzN(CH:CH~0H)n~2HCl CiiHzsOsCliNt 139-141 19.96 19.55 (HOCH~CHz)zNCHzCHOHCHzNHC(CH~OH)s*2HCl Sirup 20.90 19.74 CliHnsOsClaNs fHOCHzCHz)(CzHs)NCHzCHOHCHiNH(CH,OH)r*2HCl HOCHzCHOHCHzNHC(CH20H)s.HCI C7Hl.g06CIN Sirup 15.31 14.90 HOCHzCHJ'iHC( CH20H)saHCI CeHlsOdYN Sirup 17.58 17.30 C7H1804BrN Sirup 30.72 30.18 HOCH1CH2CHzNHC(CH,OHh.HBr ClrHsr07Cl~N, Sirup 17.16 16.30 (HOCHa)aCNH(CHz)aO(CHZhNHCf CHzOH)&HCI Compounds given for reference. We are indebted to E. E. Bowden and Walter W. Haden for mast of the halogen analyses in this work. from the melting points. No &@'-bis-[tris-(hydroxy- The sirup, while hot, was placed in a vacuum desiccator. After two days of drying, a satisfactory analysis for methyl)-methylamino]-ethyl ether was isolated. 1,Z-Dihydroxy-3-tris-( hydroxymethy1)-methylaminopro- chloride was obtained. pane Hydrochloride, HOCHzCHOHCH2NHC(CHyOH)8. Similar procedures were used for the reaction of ethylene HCL-A mixture of 24 g. of ( A ) (0.2 mole) and 11 g. of chlorohydrin and trimethylene bromohydrin with (A) and glycerol monochlorohydrin (0.1 mole) was heated under for purification of the products formed. reflux with 50 ml. of alcohol for five hours. The resulting liquid was acidified with hydrochloric acid, while hot. Summary On cooling, crystals of (A).€€CIwere obtained and filtered A series of highly polar polyhydroxyamines off. More (A).HCl was obtained by concentration of the filtrate and treatment with dry acetone. This process have been made from tris-(hydroxymethy1)was repeated until no crystals were obtained. The solu- aminomethane. tion then was concentrated to a sirup which was completely miscible with absolute alcohol and dry acetone. RICHMOND, VA. RECEIVEDJANUARY 18, 1944
[CONTRIBUTION FROM
THE
CHEMICAL LABORATORY OF BRYN MAWRCOLLEGE]
The Cleavage of (Dialkylviny1)-alkylcyanoacetic Esters by Sodium Alkoxides' BY ELIZABETH hf. OSMANAND ARTHURC. COPE
More or less extensive cleavage of (dialkylvinyl)-alkylcyanoacetic esters to unsaturated nitriles has been observed to occur as a side reaction during condensation of the esters with urea in the presence of sodium alkoxides.* This paper reports an investigation of the cleavage reaction, and its use in the preparation of certain a,bunsaturated nitriles. The hydrolysis of the iiitriles to acids has also been studied. The products of cleavage are ethyl carbonate and an a,p-unsaturated nitrile R'CH=C( R')>
