Allyl cyanides

2CuS04-l-4NaCN — 2CuCN + (CN)2 + 2Na2S04 CH2 = CHCH2Br+CuCN - CH2 = CHCH2CN+CuBr 

Preparation of Cuprous Cyanide. (Note i)—In a 6-1. round-bottom flask fitted with a stopper carrying a mechanical stirrer, a separatory funnel, and a gas exit tube leading to a good hood (Note 2), is placed a solution of 650 g. (2.6 moles) of crystallized copper sulfate in 4 1. of water. The flask is surrounded by an oil bath and heated to about 8o°. The stirrer is started and a solution of 255 g. (5.2 moles) of sodium cyanide (Note 3) in 650 cc. of water is added from the separatory funnel over a period of about one-half hour. Then the mixture is boiled until no more cyanogen gas is evolved. This requires about five to ten minutes. 

The cuprous cyanide, which begins to separate as a light tan precipitate as soon as any of the cyanide solution is added, is allowed to settle and the solution is decanted. The precipitate is filtered, then washed with water (r 1.) and finally with alcohol (500 cc.) and ether (300 cc.). After drying at no0 for about thirty-six hours, the product weighs 200-210 g. (85-90 per cent of the theoretical amount). 

Preparation of Allyl Cyanide.— In a i-l. round-bottom flask fitted with a condenser (Note 4) and a mechanical stirrer are placed 220 g. (1.83 moles) of allyl bromide (Note 5) and 170 g, 

The condenser is then set for distillation and the allyl cyanide is distilled from the flask by heating it in an oil bath with stirring (Notes 7 and 8). Upon redistillation the allyl cyanide is pure and boils at 116-121° with almost no loss. The yield is 98-I03 S- (80-84 Per cent of the theoretical amount). 

---

Allyl cyanide. Into a 1 5 litre three-necked flask (1), provided with a mercury-sealed stirrer and two long double surface condensers, place 293 g. (210 ml.) of freshly-distilled allyl bromide, b.p. 70-71° (Section III, 35) and 226 g. of dry cuprous cyanide (Section 11,50,3, Method 1), Remove the mercury-sealed stirrer and replace it by a tightly fitting... 

Vinylacetic acid. Place 134 g. (161 ml.) of allyl cyanide (3) and 200 ml. of concentrated hydrochloric acid in a 1-htre round-bottomed flask attached to a reflux condenser. Warm the mixture cautiously with a small flame and shake from time to time. After 7-10 minutes, a vigorous reaction sets in and the mixture refluxes remove the flame and cool the flask, if necessary, in cold water. Ammonium chloride crystallises out. When the reaction subsides, reflux the mixture for 15 minutes. Then add 200 ml. of water, cool and separate the upper layer of acid. Extract the aqueous layer with three 100 ml. portions of ether. Combine the acid and the ether extracts, and remove the ether under atmospheric pressure in a 250 ml. Claisen flask with fractionating side arm (compare Fig. II, 13, 4) continue the heating on a water bath until the temperature of the vapour reaches 70°. Allow the apparatus to cool and distil under diminished pressure (compare Fig. II, 20, 1) , collect the fraction (a) distilling up to 71°/14 mm. and (6) at 72-74°/14 mm. (chiefly at 72 5°/ 14 mm.). A dark residue (about 10 ml.) and some white sohd ( crotonio acid) remains in the flask. Fraction (6) weighs 100 g. and is analytically pure vinylacetic acid. Fraction (a) weighs about 50 g. and separates into two layers remove the water layer, dry with anhydrous sodium sulphate and distil from a 50 ml. Claisen flask with fractionating side arm a further 15 g. of reasonably pure acid, b.p. 69-70°/12 mm., is obtained. 

When the volume of liquid in the flask is small, it is advisable to arrange the apparatus for distillation under reduced pressure (water pump) in order to completely separate the allyl cyanide from the solid residue. The final tarry residue may be removed by treatment with concentrated nitric acid, followed by water. 

Some organosilicon compounds undergo transmetallation. The allylic cyanide 461 was prepared by the reaction of an allylic carbonate with trimethylsi-lyl cyanide[298]. The oriho esters and acetals of the o. d-unsaturated carbonyl compounds 462 undergo cyanation with trimefhylsilyl cyanide[95]. 

Allyl amine Allyl cyanide Allyl ether Allyl halide Amines... 

Allyl cyanide, OHj. CH CEI. ON. The analytical values of a frac-tiori amounting tc a Few grama, which passed over botw ui 190° and 123°, and which also coolained sulphur (d, O fi- iTO saponification number 47 7) pointed to the prolialile presi.-nce oF allyl cyanide. 

Allyl cyanide, CHg. CH CH. CN, occurs in some of the oils of the mustard type. It is a liquid of specific gravity 0 8365 boiling at 120° to 123°, and yields, on boiling with alcoholic potash solution, crotonic acid, melting at 72°. 

Toward the end of this distillation it is advisable to connect with the suction to remove the last of the allyl cyanide from the solid residue in the flask. 

Allyl cyanide has been found in oil of mustard 1 and has been prepared from allyl chloride and potassium cyanide,2 allyl bromide and potassium cyanide,3 allyl iodide and potassium cyanide4 and silver cyanide.5 The method described in the procedure is essentially that of Bruylants, who has shown that the yields are much better when dry cuprous cyanide is treated with allyl bromide.6... 

A Dry Ice trap, inserted between the oil pump and the apparatus, condenses 5-10 g. of unchanged allyl cyanide. The yield of crude acid, after allowing for the recovered nitrile, is... 

The only practical methods for the preparation of vinylacet.ic acid involve hydrolysis of allyl cyanide 6 carbonation of allylmag-nesium bromide 8 or the malonic acid synthesis.9... 

Allyl carbamide, al02 Allyl chloride, c236a Allyl cyanide, b482 Allyl glycidyl ether, a91 l-Allyl-2-hydroxybenzene, a94 Allyl iodide, i50... 

A subsequent publication by Blechert and co-workers demonstrated that the molybdenum alkylidene 3 and the ruthenium benzylidene 17 were also active catalysts for ring-opening cross-metathesis reactions [50]. Norbornene and 7-oxanorbornene derivatives underwent selective ring-opening cross-metathesis with a variety of terminal acyclic alkenes including acrylonitrile, an allylsilane, an allyl stannane and allyl cyanide (for example Eq. 34). 

The hydroformylation of unsaturated nitriles such as crotonitrile and allyl cyanide is a potential route towards chiral amino alcohols, which are building blocks in the synthesis of pharmaceuticals. The hydroformylation of acrylonitrile was studied in the early years [5], but lately the hydroformylation of allyl cyanide and crotonitrile have also been investigated [25,81]. 

The asymmetric hydroformylation of allyl cyanide has recently focused the interest of researchers because the iso-aldehyde derivative can be easily transformed into 2-methyl-4-aminobutanol, a useful building block, for instance for the asymmetric synthesis of tachikinin (58), a novel NK1 receptor agonist developed by Takeda [82], It should be noticed that this aldehyde is not accessible via the hydroformylation of crotononitrile. 

Table 5 Rh-catalyzed asymmetric hydroformylation of allyl cyanide with ligands 2, 5, 59-62 ...

---