Propionitrile 2-chloro-3-

Since the exocyclic sulfur is more reactive in the ambident anion than in A-4-thiazoIine-2-thione. greater nucleophilic reactivity is to be expected. Thus a large variety of thioethers were prepared in good yields starting from alkylhalides (e.g.. Scheme 38 (54, 91, 111, 166-179). lactones (54, 160), aryl halides (54, 152. 180, 181), acyl chlorides (54. 149, 182-184). halothiazoles (54, 185-190), a-haloesters (149. 152. 177. 191-194), cyanuric chloride (151). fV.N-dimethylthiocarbamoyl chloride (151, 152. 195. 196), /3-chloroethyl ester of acrylic acid (197), (3-dimethylaminoethyl chloride (152). l,4-dichloro-2-butyne (152), 1,4-dichloro-2-butene (152), and 2-chloro-propionitrile (152). A general... 

Reduction of 3-benzyl-8-chloro-4-oxo-4//-pyrido[l,2- ]pyrimidine-2-carboxylate <2004W004/064741> and 2-methyl-4-oxo-4//-pyrido[l,2-tf]pyrimidine-3-carboxylate <2003T4123> with DIBAL-H afforded 2- and 3-formyl derivatives, respectively. Reduction of /V-(4-fluorobenzyl)-3-hydroxy-8-[methoxy(methyl)amino]-4-oxo-6,7,8,9-tetra-hydro-4//-pyrido[l,2- ]pyrimidine-2-carboxamide with Zn-dust in aqueous AcOH afforded the 8-methylamino derivative, which was acylated with AcOH in the presence of Hiinig s base, HOBt, and l-(3-dimethylaminopro-pyl)-3-ethylcarbodiimide-HCl <2004W004/058756>. 3-(Perhydropyrido[l,2- ]pyrimidin-2-yl)propylamine was obtained by catalytic hydrogenation of 2-(perhydropyrido[l,2- ]pyrimidin-2-yl)propionitrile over a Pt02 catalyst <2003FRP1275647>. 

Cycloadditions to a cyano group are comparatively rare. The high-temperature reactions of 1,3-dienes, e.g. butadiene, isoprene and 2-chloro-l,3-butadiene, with dicyanogen, propionitrile or benzonitrile result in formation of pyridines (equation 80)70. Sulfonyl cyanides 147, obtained by the action of cyanogen chloride on sodium salts of sulfinic acids, add to dienes to give dihydropyridines 148, which are transformed into pyridines 149 by oxidation (equation 81)71. 

Hydroxy-4-methyl-4-penten-2-one (1) was prepared from 3-chloro-mesityl oxide using a modified procedure from the literature [ref.4], A reference sample of 4-methyl-4-penten-2,3-dione (2) was prepared from using the copper acetate method [ref.2], 4-methyl-pentan-2,3-dione (3) was purchased from Wiley Co. 2-Hydroxy-4-methyl-4-penten-3-one (4) was synthesized in 30% yield from 2-propenyl-magnesium bromide and 2-hydroxy-propionitrile in tetrahydrofurane. The structures of all compounds were confirmed by H-. C-NMR- and mass spectroscopy [ref. 5],... 

De-2-methyl propionitrile or 2-amino-4-chloro-6-isopmpylamino-.v-triazine cyanazine Deethylsimazine... 

BENZIMIDAZOLINE-1 -PROPIONITRILE. 3- (1- (p-CHLORO-alpha-METHYLBENZYL) 4-PIPERIDYL) -2-0X0-. HYDROCHLORIDE... 

Synonym Bladex, 90DF, DW 3418, Fortrok, Fortrol, Payze, SD 15418, WL 19805 Chemical Name 2-(4-chloro-6-ethylamino-l,3,5-triazin-2-ylamino)-2-methyl-propionitrile... 

The photostimulated reaction of propionitrile anions with haloarenes in liquid ammonia has been studied as a synthetic route to a-arylpropionic acids32. Thus, 2-bromonaphthalene gave 76% yield of the product, whereas 2-bromo-6-methoxynaphtha-lene, p-bromobiphenyl and l-chloro-2-metoxynaphthalene yielded 81%, 52% and 52% of the substitution products, respectively. 

METHYL)ETHYLAMINO-s-TRIAZINE 2-(4-CHLORO-6-ETHYLAMINO-s-TRIAZINE-2-YLAMINO)-2-METHYL-PROPIONITRILE 2-(4-CHLORO-6-ETHYLAMINO-l,3,5-TRIAZINE-2-YLAMINO)-2-METHYLPROPIONITRILE ... 

Ethyl 3-ethoxy-a-nitroacrylate with 1,1-diphenylhydrazine in ethanol followed by heating has been shown to give l,4-bis(diphenylamino)-2,5-diethoxycarbonyl-l,4-dihydropyrazine (1586). A small amount of 2,5-dicyano-l,4-bis(dimethylamino)-1,4-dihydropyrazine was obtained from the reaction of 2-chloro-3-(2, 2-dimethyl-hydrazino)propionitrile [(Me)2NNHCH2CH(Cl)CN] with sodium hydride (1587). Hexaalkyl-l,4-dihydropyrazines and other 1,4-dialkyl-1,4-dihydropyrazines can be obtained by thermolysis of the products of reaction of a-(alkylamino)carboxylic acid esters with alkylmagnesium bromide. Thus the reaction of ethyl a-s-butyl-aminopropionate with ethylmapesium bromide, followed by heating in vacuo to 250-300°, gave 2,5-dimethyl-3,6-diethyl-l,4-di-s-butyl-l,4-dihydropyrazine (1588). 

Chloro-3-(/>-nitrophenyl)propionitrile 247 / -Nitroaniline (4.2 kg) is dissolved in a hot mixture of concentrated HC1 (91) and water (91), cooled to 30°, and treated with ice (24 kg). 30% Sodium nitrite solution (7.3 1) is run in within a few minutes with vigorous cooling. The diazonium salt solution is filtered and treated with a solution of acrylonitrile (1.76 kg) in acetone (15 1). CuCl2 (600 g) is then added and a short time thereafter at ca. 18° evolution of nitrogen begins. The temperature is kept below 30° by ice-cooling. 2-Chloro-3-(p-nitro-phenyl)propionitrile separates and after recrystallization from methanol has m.p. 110° (yield 5.3 kg). 

Schand in 1946 demonstrated that addition of hydrogen chloride to 2-chloronitriles yields the expected 1 1 adducts. For example, 2-chloro-propionitrile and hydrogen chloride combine easily to form j8-chloro-propionimidoyl chloride (XXXIX). 

Ether, 2-chloro-o,a,a-trifluoro-p-tolyl 3-ethoxy-4-nitrophenyl. See Oxyfluorfen Ether cyanatus. See Propionitrile Ether, decyl methyl. See Decyl methyl ether Ether, 2,4-dichlorophenyl p-nitrophenyl. See Nitrofen... 

Cyanopyridines have been reduced to aminoethylpyridines by a variety of methods, 2- And 4-cyanopyridine are reduced with sodium borohydride to 2-and 4-aminomethylpyridine, respectively. In acidic solutions, the polaro-graphic reduction of 4-cyanopyridine yields 4-aminomethylpyridine. Hydrogenation of 6-chloro-5-cyano-4-methoxymethyl-3-nitro-2-picoline over palladium-charcoal in aqueous hydrochloric acid gives 3-amino-5-aminomethyl-4-methoxymethyl-2-picoline hydrochloride. 3-Amino-5-aminomethyl-2,4-lutidine is prepared in good yield by the catalytic reduction (Pd—C in methanol) of 6-chloro-3-cyano-2,4-dimethyl-3-nitropyri-dine. The hydrogenation of 3-( S-pyridylmethoxy)propionitrile over Raney Nickel yields 3-[(3-aminopropoxy)methyl] pyridine. ... 

Nitriles condense with malonyl chloride to give 2-chloro4,6-dihydroxypyii-dines (MI-174) in 23 to 63% yield and/or the pyrimidones (XII-17S) or chloropyranooxazines (Section I.5.C.) depending on conditions. 5-Bromo-3-carbethoxy-2-chloro-4,6-dihydroxypyridine (XII-176, R = CO2C2H5) is prepared either by bromination of MI-174 (R = C02Et) or by cyclization of bromomalonyl chloride and ethyl cyanoacetate. Methylmalonyl chloride did not react with propionitrile. The product from acetonitrile and malonyl chloride, first described as 2-chloro-4,6-dihydroxypyridine (MI-174,R = H), is6-chloro-2-methyl-4-pyrimidone (XI-175, R = H). ... 

Chloro-2-methyl-2-butene added slowly below 10° with efficient stirring to a soln. of propionitrile in coned. H2SO4, allowed to warm to room temp, and stirred for 3 hrs. 2-etbyl-4,4-dimeibyl-5,6 dibydro-l,3-oxazine (startg. m. f. 655). Y 59%. A. I. Meyers, J. Org. Gbem. 25, 1147 (1960). 

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