Acetic cyano

A concentrated solution of monochloroacetic acid is neutralised with sodium bicarbonate, and then heated with potassium cyanide, whereby sodium cyano-acetate is obtained ... 

A solution of 4% aq. H2SO4, (301) was heated to 50"C over 30-60 min. Nitrogen was bubbled through the solution during this time. 4-(Cyano-methyl)phenylhydrazine hydrochloride (1080g, 4.77 mol) was added as a solid to the heated mixture. After it had dissolved, A,A-dimethyl-4,4-dimethoxy-butanamine (965 g, 5.98 mol) was added over a period of 30 min. The mixture was then heated at reflux for 2 h. The reaction mixture was cooled and diluted with portions of 30%o aq. NH4OH (21 total) over 0.5 h at a rate to maintain the temperature at 25-30°C. The product was then extracted into isopropyl acetate (3 x 101). The solution was concentrated to 31 which led to a precipitate which was isolated by filtration and washed with cold isopropyl acetate to give 827.4 g (76%) of product. 

Diethyl malonate is prepared commercially by hydrolysis and estenfication of ethyl cyano acetate... 

Pyrethroid Esters of Benzene Acetate. These insecticides have more extensive stmctural optimization in both acid and alcohol moieties. Fenvalerate [51630-58-17, a-cyano-(3-phenoxyphenyl)methyl (+)-(2R,5)"Ct"isoprop5i-4-chlorophenylacetate (24) d 1.17, vp 1.4 p.Pa at 25°C), a mixture of four isomers, is soluble in water to 0.3 mg/L The rat oral LD q is 450 mg/kg. Esfenvalerate [66230-04-4] is the (+)-2-(i, 5)-isomer (mp 59°C). The rat LD qS are 75, 458 (oral), and the rabbit dermal LD q is 2000 mg/kg. These pyrethroids are widely used general-purpose insecticides for field, vegetable, and fmit crops. 

Two interesting syntheses of the base followed in 1956 the first involves a Principal Synthesis from ethyl 2-cyano-2-(tetrahydropyran-2 -yloxy)acetate and guanidine to give the tetrahydropyranyloxypyrimrdine (949) which undergoes gentle acidic hydrolysis to... 

Acetic acid, (4-chloro-2-oxobenzothiazolin-3-yl)- — see Benazolin Acetic acid, cyano-methyl ester... 

The reaction mixture is filtered through a Hirsch or Buchner funnel, and the bottle is rinsed with 50 ml. of benzene, which is also poured through the funnel. The filtrate is washed with two 50-ml. portions of 10% sodium chloride solution and three 2S-ml. portions of water (Note 4). The washings are extracted with three 10-ml. portions of benzene, and the combined benzene solutions are distilled under reduced pressure from a 250-ml. modified Claisen flask. The yield of ethyl -butylcyanoacetate, b.p. 108-109°/9 mm., is 79-81 g. (94-96%, based on the ethyl cyano-acetate used) (Note 5). 

The formation of ethyl cyano(pentafluorophenyl)acetate illustrates the intermolecular nucleophilic displacement of fluoride ion from an aromatic ring by a stabilized carbanion. The reaction proceeds readily as a result of the activation imparted by the electron-withdrawing fluorine atoms. The selective hydrolysis of a cyano ester to a nitrile has been described. (Pentafluorophenyl)acetonitrile has also been prepared by cyanide displacement on (pentafluorophenyl)methyl halides. However, this direct displacement is always aecompanied by an undesirable side reaetion to yield 15-20% of 2,3-bis(pentafluoro-phenyl)propionitrile. 

To minimize the gradual embrittlement that can occur on aging of cyanoacrylate adhesives, plasticizers are added. Some of the materials, which have been used as plasticizers, include phthalates, phosphonates, acyl esters, succinates, and cyano-acetates. The use of allyl, methallyl, and crotyl phthalates is also claimed to improve thermal resistance properties in addition to plasticizing the adhesive [23]. 

Cyano-3 -hydroxy-5a-pregnan-20-one A suspension of 5a-pregnane-3, 20-dione (2 g) in ethanol (90 ml) is treated with acetone cyanohydrin (4 ml) and three drops of triethylamine and stirred at room temperature until complete dissolution. After 3 hr, the solution is diluted with 200 ml of water, acidified with acetic acid and the crystalline precipitate is thoroughly washed with water and dried under vacuum to give 2.1 g (97%) of product mp 172-178° (dec). A sample recrystallized from ethyl acetate melts at 176-179° (dec) [a]p 86° (ethyl acetate). 

Cyano-17-(2 -tetrahydropyranyloxy)-androst-5-en-3j5-ol Acetate A solution of 10 g of 17-cyanoandrost-5-en-3j5,17-diol 3-acetate in 40 ml of 2,3-dihydropyran is treated at the boiling point with 0.2 ml of phosphorus oxychloride for 1.5 hr. The solution is then diluted with ether, washed with aqueous sodium carbonate, and then water, dried over sodium sulfate and distilled under reduced pressure. The oily residue is crystalhzed from petroleum ether to give 6.7 g of 17a-cyano-17j5-(2 -tetrahydropyranyloxy)-androst-5-en-3) -ol acetate mp 127-130° [a]o —92° (diox). The mother liquor when evaporated to dryness yields an oily residue of 7.1 g which resists crystallization attempts. Subsequent reactions (see below) indicate it to be 17jS-cyano-17a-(2 -tetrahydropyranyloxy)-androst-5-en-3jS-ol acetate. 

Despite the variability of yields often noted by various workers, the reaction is extremely simple to perform and remarkably insensitive to the presence of other functional groups. Thus, systems which do not interfere markedly include S-keto-A, S-keto-A , 3a- or 17a-hydroxy, ll-keto, 12-keto, 6-methyl,16-methyl, 16-methylene, 3-hydroxy-A , 16,17-epoxy, 3-keto-A -6-methyl, ll)5-hydroxy, and 10-cyano. In one instance, hydrolysis of a 3-acetate during the first step has been reported. ... 

An unprotected 3-hydroxyl group does not significantly lower the yield, but an 11 j5-hydroxyl has an adverse effect, and no product is obtained in the presence of a free 21-hydroxyl group. An isolated double bond at C-5 does not seriously interfere /,/-20-cyano-3,3-ethylenedioxy-21-hydroxypregna-5,17 (20)-dien-l l-one acetate gives 89% of the 17a-hydroxy-20-ketone. ... 

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