HERMAN PLAUT WITH
4076
[COSTRIBUTIONFROM
THE
JOHN
J. RITTER
Vol. 73
CHEMICAL LABORATORY O F NEW YORK UNIVERSITY ]
A New Reaction of Nitriles. VI. Unsaturated Amides1 BY HERMAN PLAUT~ WITH
JOHN
J. RITTER
The amide synthesis from nitriles and alcohols or olefins has been extended to include unsaturated nitriles and aldo-cyanhydrins. A number of N-alkyl acrylamides, methacrylamides, cinnamamides and lactamides are described.
Previous publications in this series3 have described the reaction of nitriles with olefins or alcohols to yield N-substituted amides and the application of this synthesis to form t-carbinamines and N-benzoylamino acids. This paper records the extension of this novel synthesis to produce N-alkyl unsaturated amides. For example CH2=CH-CN
H' + HOC--(CHa)a --+
self was considered and found to go when the time of reaction was extended to one week. As no case of addition to the terminal carbon has ever been found in this type of reaction, the polymer is represented as propagating through the a-carbon; no experimental evidence is available. CH2=CH-CN + CH+=C13-C0-
0
I1
CH2=CH-C-NH-C(
NH-(211-CO-
[
CHI
CHg).q
I.
NH-CH-CS &Ha
Reaction of the N-alkyl acrylamides with nitriles could not be achieved; even under the most Table I lists the reactants used and the products obtained, together with yields, physical properties, drastic conditions only the original N-alkyl acrylanalyses and the melting points of the dibromo-de- amides were recovered unchanged. rivatives. Experimental One of us, with another collaborator, has previPreparation of Materials.-Certain of the tertiary and ously reported the reaction of acrylonitrile and tsecondary alcohols were obtained by Grignard reactions. amyl but the subject was not then further Acrylonitrile and lactonitrile were kindly supplied by the investigated. American Cyanamid Corporation and used without further The N-alkyl acrylamides and methacrylamides purification. Methacrylonitrile was prepared by pyrolysis are of interest as components of polymeric systems. of acetone cyanhydrin acetate. The preparation of cinis described below. None of the cinnamamides prepared in this study, namonitrile reactions with olefins and tertiary alcohols were carried however, could be made to polymerize or copoly- outThe in glacial acetic acid. Concentrated sulfuric acid was merize with other acrylic monomers in the presence the solvent employed for the condensations of the secondary of peroxides. The study of the polymerization of alcohols. Liquid products were distilled in vacuo after ether extraction and drying. Traces of acid these materials is under investigation in this Labo- neutralization, caused violent polymerization on heating. Solid products ratory. were recrystallized from benzene, hexane or combinations An alternative preparation of these N-alkyl of the two. Some cinnamamides required preliminary reacrylamides by the pyrolysis of the respective crystallization from aqueous methanol. Analyses were performed in the Laboratory of Micro a-acetoxy N-alkyl propionamides as made Chemistry at New York University. Nitrogen determinathrough the amide synthesis from lactonitrile was tions were by the Kjeldahl method. investigated; the products were identical with those Cinnamonitrile.-A warm solution of 66 g. (0.5 mole) of derived from acrylonitrile Via the amide synthesis. freshly distilled cinnamaldehyde in 200 ml. of 95% ethanol mixed with a solution of 41.7 g. (0.6 mole) of hydroxylTable I1 lists the data relative to the reactions of was amine hydrochloride in 50 ml. of water. Sodium hydroxide, lactonitrile. The various relationships are shown 30 g. (0.75 mole), in 40 ml. of water was then added with agiin Fig. 1. tation. The solution was set aside for 3 hours after which the oxime was precipitated by adding 250 g. of crushed ice and rapidly saturating with CO1. Filtered and air-dried, the Amide I I yield was 71 g., 97%. OH synthesis OH The oxime was mixed with 100 ml. of $Amide synthesis &(cHaCo),o acetic anhydride and gently warmed tu initiate the dehydration, the mixture res fluxed for 0.5 hour after the violent re4-CHa-cH-coxHR action subsided, auenched in 300 E. of CHa=CH-CONHR I ice, the oil lay& separated, washed-free OOCCHB of acid, dried (Na2S04) and distilled, b.p. Fig. 1. 134-136' (12 mm.); yield 45 g., 70%, based on aldehyde. Reaction of Nitriles with Olefins and Tertiary Alcohols.Acetone cyanhydrin could not be made to react unThe following procedure is typical of that used throughout der the same conditions in the amide synthesis. the work. A solution of 5.3 g. (0.1 mole) of acrylonitrile, The possibility of reaction of the nitrile with it- 50 ml. of acetic acid and 7.4 g. (0.1 mole) of t-butyl alcohol cooled in an ice-bath was treated with 10.1 g. (0.1 mole) of (1) Based in part on the thesis submitted by Herman Plaut in parconcd. sulfuric acid with stirring so as to keep the temperatial fulfillment of the requirements for the degree of Doctor of Philosoture below 40' during the addition and subsequent reaction phy. (1 hour). The reaction mixture was poured onto 200 g. of ( 2 ) Vegetable Oil Products Company, Inc., Los Angel-, CPlif. ice, the product filtered and air-dried; yield 10 g. (80%), (3) (a) J. J. R i t t u and P. Paul Minieri, THIS JOURNAL, 70, 4045 m.p. 124'. An additional 0.7 g. could be obtdned by neu(1948); (b) J. J. Ritter and Joseph Kalish, ibid., 70, 4048 (1948); trdization and ether extraction of the filtrate. The analyti( c ) F. R. Benson and J. J. Rftter, ibid., 71, 4128 (1949); (d) I,. W. Hartzel and J. J. Ritter, dbid., 71, 4130 (1949); (e) R. M. Lusskin and -cal sample (from - benzene) melted at 126.8'. CH3=CH-CN
f--
C H 2 - c ~ - c ,~- .
J. J . Ritter, dbid., 72, 5577 (1950).
CH~-CH-CONHR
(1'
€'~-nri
-1iii'
389 1 1 7 (181'2)
A
Sept., 1951
NEW
REACTION O F NITRILES : UNSATURATED rhIDES
3077
TABLE I AMIDESFROM ACRYLONITRILE CH-CH-CO-NHR
Vzh'
Alcohol or olefin
Crude yield
%'
Formula
Nitrogen, % Calcd. Found
Diisobutylene t-Amyl alcohol &Butyl alcohol 3-Pentanol Isopropanol 2-Methylhexanol-2
83" 91-99 126-128 63 62' 60
71 78 80 77 45 70
C11H21NO CsHlsNO C7H18N0 CoHi7NO CaHiiNO CiaHigNO
7.64 9.92 11.02 9.02 12.38 8.28
7.56 9.87 10.94 8.94 12.29 8.18
Cyclohexanolf
112-113
72
coHi6NO
9.14
9.19
57
CllHZINO Cl&llpNO CgH17N0 CIrH15N0 CgHlrNO C,HlaNO C7H12NOCl
7.64 8.28 9.02 6.63 9.02 11.02 8.67
7.62 8.23 9.08 6.72 8.91 11.12 8.71
Amides from cinnamonitrile CsH6-CH=CH-CONHR t-Amyl alcohol 141 73 CidHIgNO 6.45 t-Butyl alcohol 143 70 CiaHirNO 6.89 Diisobutylene 118-120 77 C ~ ~ H S ~ N O 5.28 2-Methylhexanol-2 96 CisHzsNO 5.71 125-126 2,4-Dimethylhexanol-2 137-138 73 C17H~6N0 5.28 3-Methylhexanol-3 140-141 61 CieHzsNO 5.71 2,4-Dimethyloctanol-4 108-109 67 ClgHzpNO 4.87 2,3-Dimethylbutanol-2 , 122-123 6.06 86 C16HnN0 2-Methylpentanol-2 151-152 69 C16Hg1N0 6.06 4-Methyloctanol-4 90-91' 74 CisHziNO 5.12 2,3-Dimethylhexanol-3 69 Ci7Hz6NO 5.28 97 4-Methylundecanol-4 79 GiHsrNO 4.48 89
6.31 6.79 5.23 5.78 5.38 5.74 5.02 6.11 5.95 5.17 5.39 4.33
2,4-Dimethylhexanol-4 3-Methylhexanol-3 2,3-Dimethylbutanol-2 2.4-Dimethyloctanol-4 2-Methylpentanol-2 s-Butyl alcohol Methallyl chloride
88-89 71-72 91-92 79-80 56-57 26' 93-94
82 71 36 71 76 92
Dibromoderivative m.p., "C.6
132 dec 171 174-175dec. 165-166 dec. 119-120 105-106 170 119 dec. 193-194dec. 158-159 dec.
. .. . . . . . .
124 133 dec. 149 dec.
188 dec. 187 dec. 168-169 dec. 167 dec.
. .. .. ....
193-194 dec. 186-187 dec. 181 dec. 175 dec. 158-159 dec.
.. .
. . ..
161 dec.
Amides from methacrylonitrile CHZ=C( CHa)-CO-NHR B.p., "C. Mm.
t-Butyl alcohol 57.5 55 Cd3isNO 9.92 9.92 87 15 t-Amyl alcohol 26 78 CoHi7NO 9.03 8.95 106-108 15 Diisobutylene 44 60 Ci2HzaNO 7.10 6.98 12C-123 14 All melting points uncorrected. B.p. 140-142' (20 mm.). Ritter and Minieri; 3a reported M.p. in sealed tube. Reaction run a t 60' for 1 hour. * Reaction From cyclohexene the yield was 66%. 93". e B.p. 110-115" (15 mm.). run a t 70" for 1 hour. B.p. 125-130" (20 mm.). 3 Recrystallize from 70% ethanol below 70". Above 70" an oil sepaHeyboer and Steveman, Rec. trao. chim., 69, 787 (1950), give b.p. 111-112' (43 mm.), m.p. 59'. rates.
*
TABLE I1 AIUDESFROM LACTONITIULE CHiCH( 0H)CONHR R
M.P., 'C.
-C( CHr )a -C(CHs)rGH5 -C( CHa)2CHlrC(CH,)a
53 23 88
QC.
B.p.,
1147122 128-135
. . .. .
Mm.
15 13
..
Yield,
%
Formula
40
GHI'NQ C&17NO, CiiH*:NOn
35 65
Anal. Calcd. for C7HlJNO: N, 11.02. Found: N, 10.94. The dibromo-derivative was prepared by addition of bromine to a carbon tetrachloride suspension of the air-dried amide to a permanent excess of bromine. The carbon tetrachloride and excess bromine were removed by evaporation and an analytical sample obtained by recrystallization (charcoal) from hexane, m.p. 174-175' dec. in a sealed tube. Anal. Calcd. for C7HlsBrzNO: N, 4.88. Found: N, 4.85. Secondary alcohols were treated in the same way except that 20-25 ml. of concd. sulfuric acid was substituted for the acetic acid. The self condensation of acrylonitrile was accomplished in a mixture of 1:1 acetic acid; concd. sulfuric acid a t 30"
Nitrogen, % Calcd. Found
M.p., OC. benzoate
9.65 8.80 6.96
143 121-122
9.63 8.87 7.03
.....
M.p., OC. acetate
84-85 77-78 74
for 7 days. The product is a pasty resinous mass that swells in water alkaline to litmus. No analysis was obtained.
Preparation of N-t-Butylacrylamide from the Lactamide .-
N-&Butyl lactamide was prepared from lactonitrile and tbutyl alcohol in acetic acid solution as described above. The oil formed on hydrolysis was taken up in ether, dried (Na&04), the ether removed and the residue refluxed for 1 hour with twice its volume of acetic anhydride. The acetate crystallized on dilution with HIO; recrystallized from hexane, m.p. 84-85', It was pyrolyzed by dropping an ether solution of the acetate into a flask kept at 500-550° by a Wood's metal-bath. The distillate was recrystallized from hexane, m.p. 126". Mixed m.p. with an authentic sample of N-t-butylacrylamide showed no depression. HOLLYWOOD, CALIF.
RECEIVED FEBRUARY 12, 1951
