Org. Synth. 1959, 39, 52
DOI: 10.15227/orgsyn.039.0052
β-METHYL-β-PHENYL-α,α'-DICYANOGLUTARIMIDE
[Glutarimide, 2,4-dicyano-3-methyl-3-phenyl-]
Submitted by S. M. McElvain and David H. Clemens
1.
Checked by W. E. Parham, Perry W. Kirklin, Jr., and Wayland E. Noland.
1. Procedure
In a
2-l. Erlenmeyer flask fitted with a reflux condenser and arranged for magnetic stirring are placed
400 ml. of absolute ethanol (Note 1) and
11.5 g. (0.5 g. atom) of sodium added in small portions. After the
sodium has reacted
(Note 2), the clear solution is cooled to room temperature, and
42.0 g. (0.5 mole) of finely powdered cyanoacetamide (Note 3) is added with stirring over a period of 1 minute. Immediately thereafter
107.6 g. (0.5 mole) of ethyl (1-phenylethylidene)cyanoacetate (
p. 463) is added. After about 20 minutes, the mixture becomes homogeneous and is allowed to stand at room temperature for 2 hours. Water (650 ml.) is added, followed by
100 ml. of concentrated hydrochloric acid in 1 portion. The resulting suspension is stirred thoroughly with a
glass rod and placed in a refrigerator overnight. The product is then filtered by suction. The filter cake is sucked as dry as possible using a
rubber dam, stirred to a paste with a mixture of 150 ml. of water and
50 ml. of 95% ethanol, and sucked dry. This process is repeated using 200 ml. of water, and the product is dried to constant weight in an
oven at 45°. The yield is
114–116 g. (
90–92%) of the dicyanoglutarimide, m.p.
274–278° (dec.)
(Note 4).
2. Notes
1.
Commercially available absolute
ethanol is used without further drying.
2.
The checkers report that the
sodium ethoxide solution should be used promptly in order to avoid the formation of colored impurities.
3.
Eastman Kodak white label grade is used after grinding in a
mortar.
4.
Recrystallization from absolute
ethanol gives glistening plates melting at
286–287° (dec.).
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3. Discussion
β-Methyl-β-phenyl-α,α'-dicyanoglutarimide has been prepared in low yield by the Guareschi condensation of
acetophenone,
ethyl cyanoacetate, and
ammonia.
2
This preparation is referenced from:
Appendix
Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)
β-METHYL-β-PHENYL-α,α'-DICYANOGLUTARIMIDE
ethanol (64-17-5)
hydrochloric acid (7647-01-0)
ammonia (7664-41-7)
Acetophenone (98-86-2)
sodium (13966-32-0)
sodium ethoxide (141-52-6)
CYANOACETAMIDE (107-91-5)
Ethyl cyanoacetate (105-56-6)
ETHYL (1-PHENYLETHYLIDENE)CYANOACETATE
Glutarimide, 2,4-dicyano-3-methyl-3-phenyl- (6936-95-4)
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