HERMAN ALEXANDER BRUSON AND THOMAS w. RIENER
2850
Vol. 64
[CONTRIBUTION FROM ROAMAND HAASCo., INC., AND RESINOUS PRODUCTS & CHEM.Co.]
The Chemistry of Acrylonitrile. 11. Reactions with Ketones BY HERMAN ALEXANDER BRUSON AND THOMAS W. RIENER The powerful cyanoethylating action of acrylonitrile in the presence of strong bases upon organic compounds possessing labile hydrogen atoms' is strikingly evident with various types of keiones. Aromatic methyl ketones of the type R-COCHs as exemplified by acetophenone, P-methylacetophenone, p-methoxyacetophenone, p-chloroacetophenone, p-bromoacetophenone, p-acetyldiphenyl, and 2-acetylnaphthalene readily took up three molecular equivalents of acrylonitrile in the presence of strong alkali catalysts such as trimethylbenzylammoniurn hydroxide or po tassiuni hydroxide to form crystalline tri-cyanoethylation products (I). /CH&H2CN R-CO-C-CH~CHZCN (I) (R = Aryl nucleus) \CH~CH~CN
These are listed in Table I together with their physical and analytical data. Upon hydrolysis with aqueous sodium hydroxide or potassium hydroxide these tri-(cyanoethy1)-methyl aryl ketones yielded the corresponding aryl keto tricarboxylic acids R-CO--C (CH~CH~COOH)S. These are listed in Table 11. Even acetomesitylene which because of steric hindrance reacts sluggishly, gave a small yield (300/o) of the tri-cyanoethylation product (11). CHa
\CHz/ (VI) NCCH&HyCO\ NCCHzCHz
CHI
Propiophenone and desoxybenzoin which possess only two active hydrogen atoms contiguous to the carbonyl group, each took up two molecular equivalents of acrylonitrile to form 7benzoyl-ymethylpimelonitrile (111)and y-benzoyl-y-phenylpimelonitrile (IV), respectively. NCCH~CH-C-CHZCH~CN GH~--CO/\CH~ (111) NCCHzCHz-C-CH82H>CN G,H~--CO/\CJ~6 (IV)
Upon hydrolysis with aqueous sodium hydrox64 3 1 5 7 (1'?42), I
i P a t e n t 2,287,-
y\CHZCHzCN
Cyclohexanone itself as well as p-methylcyclohexanone, p-t-amyl cyclohexanone, 9-(a,a,y,ytetramethylbuty1)-cyclohexanone and p-cyclohexylcyclohexanone each took up four moles of acrylonitrile to yield crystalline 2,2,6,6-tetracyanoethylation products of the general type (VIII) in 80-95% yields (Table 111).
\c/co'\c(
N C C H ~ C HI ~ CHI
\CH/I
(11)
1
/CHzCHzCN
CHt-CHz (VI11
NCCHzCHz
CH~-
