Cyanoethylation, of aniline

Creosol, 33, 17 Crotonaldehyde, 33, IS 34, 29 diethyl acetal, 32, 5 Cupric acetate monohydrate, 36, 77 Cuprous oxide-silver oxide, 36, 36, 37 Cyanamide, 34, 67 36, 8 Cyanoacetamide, 32, 34 Cyanoacetic acid, 31, 25 Cyanoacetylurea, 37, 16 >-Cyanobenzaldehyde, 30, 100 >-Cyanobenzaldiacetate, 36, 59 3-Cyano-5,6-dimethyl-2(l)-pyridone, 32,34 N-2-Cyanoethylaniline, 36, 6 N-2-Cyanoethyl- -anisidine, 36, 7 Cyanoethylation, of aniline, 36, 6 of ethyl phenylcyanoacetate, 30, 80 N-2-Cyanoethyl-m-chloroaniline, 36, 7 Cyanogen, 32, 31 Cyanogen iodide, 32, 29 Cyanogen iodide, complex with sodium iodide, 32, 31... 

N-2-Cyanoethylaniline, 36, 6 N-2-Cyanoethyl-/>-anisidine, 36, 7 Cyanoethylation, of aniline, 36, 6 of o-chloroaniline, 38,14 of ethyl phenylcyanoacetate, 30, 80 N-2-Cyanoethyl-ftt-chloroaniline,... 

The submitters have found that other arylamines may be employed in a similar manner in place of aniline. Thus N-2-cyanoethyl-/)-anisidine was obtained in 76% yield as plates,... 

Synthetic Method 9 N-[8-bis(2-cyanoethyI) -9-[4- (phenylsulfonyl) -benzoyl]-9, 10-dihydro-1 0-phenyl-2-phenazinyl]-4-phenylsulfonylbenzamide (53) (procedure from US. Patent 4,889,932).18 A 3-liter round-bottom flask fitted with a mechanical stirrer was loaded with 16.6 g (0.066 mol) of 4-[di(2-cyanoethyl)amino]aniline in 800 ml of deionized water. A 10% excess of aniline (13.56 g, 0.1456 mol) and 100ml of deionized water were added to the mixture. The mixture was cooled to 0°C in an ice bath, and... 

The commercially available monohydrate form of cupric acetate was used. Anhydrous cupric acetate gives the same results. From 2% to 5% of catalyst by weight of the amine employed gives good yields of cyanoethylated products from a variety of anilines. 

Cupric acetate is an efficient catalyst for the cyanoethylation of all but nitro-substituted aromatic amines. It is particularly effective with anilines which give poor yields by known methods,... 

Other known catalysts for cyanoethylation of aromatic amines include acetic acid,5 6 acetic acid-cuprous chloride mixtures,7 8 aniline salts,9 and choline.10 3-Anilinopropionitriles may also be prepared by an exchange reaction between the aniline hydrochloride and diethylaminopropionitrile.2 4... 

Cyanoethylation. Reaction of a primary or To favor formation of the mono-substituted a secondary aromatic amine with acrylonitrile aniline, a large excess of aniline is used. 

The melt is cooled to 0°, 50 ml. of 10% aqueous sodium hydroxide solution is added, and the mixture is extracted with four 50-ml. portions of chloroform. The combined chloroform extracts are washed with two 25-ml. portions of water, and these in turn are extracted with 10 ml. of chloroform. The organic layers are combined and dried partially over anhydrous sodium sulfate. The solvent is removed by distillation on the steam bath, and the residue is distilled at reduced pressure from a 50-ml. distilling flask. After a fore-run of about 4 g. (Note 3), b.p. 60-70°/ 1.5 mm. (bath temperature taken up to 125°), the cyanoethyl-aniline is collected at 115-120°/0.01 mm. The product solidifies in the form of colorless plates, m.p. 48-51° (Note 4). The yield is 10.5-11.4 g. (72-78%) (Note 5). 

N-2-cyanoethylaniline has been prepared (accompanied by much of the N,N -bis-2-cyanoethyl compound) by heating aniline, acrylonitrile and acetic acid either in an autoclave, or at refluxing temperature for 10 hours in the presence of various inorganic catalysts. The substance has also been obtained, free of the N,N -bis-2-cyanoethyl compound, from aniline salts and /3-diethylaminopropionitrile. ... 

Pyridylethyl derivatives of 2 are formed by reaction of a- or y-vinyl-pyridine with 2.107 Treatment of 1 or 2, as well as the 5-arylidene derivatives, with acrylonitrile in the presence of pyridine results in formation of 84 by cyanoethylation on the ring nitrogen (Scheme 2) however, cyanoethyla-tion of 5-aryl-2-iminothiazolidinones involves the exocyclic nitrogen.108 Aminoalkylation (Mannich reaction) of 2 or 2-aryl-4-thiazolidinones with formaldehyde and amines in warm alcoholic solvents affords the desired 3-alkylated product 85 (Scheme 2),109,110 whereas 3-aryl-2-iminothiazoli-dinones react with substituted anilines and aliphatic amines and formaldehyde to give the 2-arylaminomethyl derivatives 86 [Eq. (25)].111... 

Reductive cyclization of V-() -chlorobutyryl)-V-l-(cyanoethyl)aniline afforded diazocine 9 (64FRP1378964 66USP3247206). 

A 4-methylanilidoplatinum(ii) complex with a PGP pincer-type ligand 615 reacts with acrylonitrile to form an alkylplatinum complex 616 via insertion of the G=G bond into the Pt-N bond (Scheme 86). Protonation of the complex releases A-(2-cyanoethyl)-4-methylaniline. The Pt complex also catalyzes addition of the aniline to the G=G bond of acrylonitrile. 

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