Benzyl cyanide hydrogenation

CfiHjCHjCN (benzyl cyanide) Hydrogenation of 14.3.7.1.1. CH3C6H4CN (p-tolunitrile) Hydrosilylation of 14.4.5.2. CgH7NO... 

P-Phenylethylamine is conveniently prepared by the hydrogenation under pressure of benzyl cyanide with Raney nickel catalyst (see Section VI,5) in the presence of either a saturated solution of dry ammonia in anhydrous methyl alcohol or of liquid ammonia the latter are added to suppress the formation of the secondary amine, di- P phenylethylamine ... 

Diethanol methylamine Sodium amide Sulfuric acid Hydrogen chloride Thionyl chloride Benzyl cyanide Ethanol ... 

Hydroxyimino-2-phenylacetonitrile has been prepared from benzyl cyanide by reaction with nitrous acid, with isoamyl nitrite and sodium ethoxide, and with butyl nitrite and hydrogen chloride." ... 

Benzyl alcohol, 23, 14 BeNZYLAMINE, a-METHYL-, 23, 68 Benzyl carbamate, 23, 14 Benzyl chloride, 21, 99 Benzyl chloroeormate, 23, 13 Benzyl cyanide, 23, 71 Bisulfite compound, use for purification of an aldehyde, 23, 78 use for purification of a ketone, 23, 79 Blood, defibrinated, 21, 53 Booster pump, use of, for hydrogenation, 23, 69... 

In a 2-1. bomb are placed 1 kg. (8.55 moles) of pure (Note 1) benzyl cyanide and 1 tablespoon of Raney nickel catalyst (Org. Syn. 21, 15). After the cap is securely fastened down, 150 cc. of liquid ammonia is introduced (Note 2). Hydrogen is introduced until the pressure is about 2000 lb. The bomb is then heated to 120-130° and shaking is begun. The reduction is complete well within an hour (Note 1). The bomb is cooled, opened, and the contents are removed. The bomb is rinsed with a little ether, and the combined liquids are filtered from the catalyst. The ether is removed, and the residue is fractionated under rfeduced pressure. The yield is 860-890 g. (83-87 per cent of the theoretical amount) of iS-phenylethylamine, b.p. 90-93°/15 mm. (Notes 3, 4, and 5). 

With phenols either the phenolic nr nuclear hydrogens can react lo give benzylaryl ether or benzylated phenols. Reaction with NaCN gives benzyl cyanide (phenylacelonitrile) with aliphatic primary amines the product is (he N-alkylbenzylamine. and with aromatic primary amines N-benzylaniline is formed. Benzyl chloride is converted 10 butyl benzyl phlhalatc plasticizer and other chemicals. 

Hydrogen selenide does not combine with aliphatic nitriles, thio-aeetamide, thiobenzamide or benzyl cyanide. 

Cognate preparation. Ethyl phenylacetate. Place 75 g (74 ml, 0.64 mol) of benzyl cyanide (Expt 5.157), 125 g (153 ml) of rectified spirit and 150 g (68 ml) of concentrated sulphuric acid in a round-bottomed flask, fitted with an efficient reflux condenser. Reflux the mixture, which soon separates into two layers, gently for 8 hours, cool and pour into 350 ml of water. Separate the upper layer. Dissolve it in about 75 ml of ether (1) in order to facilitate the separation of the layers in the subsequent washing process. Wash the ethereal solution carefully with concentrated sodium hydrogen carbonate solution until effervescence ceases and then with water. Dry over 10 g of anhydrous calcium sulphate for at least 30 minutes. Remove the solvent by flash distillation and distil the residue from an air bath. The ethyl phenylacetate passes over at 225-229 °C (mainly 228 °C) as a colourless liquid the yield is 90 g (86%). Alternatively, the residue after removal of ether may be distilled under diminished pressure collect the ester at 116-118°C/20mmHg. 

The following procedure removes the isocyanide and gives a stable water-white compound. Shake the once-distilled benzyl cyanide vigorously for 5 minutes with an equal volume of warm (60 °C) 50 per cent sulphuric acid (prepared by adding 55 ml of concentrated sulphuric acid to 100 ml of water). Separate the benzyl cyanide, wash it with an equal volume of saturated sodium hydrogen carbonate solution and then with an equal volume of half-saturated sodium chloride solution. Dry with magnesium sulphate and distil under reduced pressure. 

Nitriles (acetonitrile, benzonitrile, tolunitrile, benzyl cyanide) absorb nitrogen, the last three by direct addition without giving off another element, while acetonitrile gives hydrogen and some methane. 

The other type of carbamoyllithiums IIIc can also be prepared by reaction of CO with (V-lithioketimines, resulting from the addition of rert-butyllithium to aryl cyanides 10477,102. These intermediates 105 underwent selective cyclization to give 177-isoindole derivatives 10677 and six- (107)102 or seven-membered (108)102 cyclic products (Scheme 27). Compounds 107 result either by insertion of the carbene structure into the benzylic carbon-hydrogen bond, as in the case of carbamoyllithiums96, or by intramolecular protonation. 

In addition to malonic, acetoacetic, and cyanoacetic esters, compounds furnishing the active hydrogen atom are nitro paraffins,benzyl cyanide, malononitrile, cyanoacetamide, sulfones, methyl-pyridines, and ketones. ... 

Compounds containing active hydrogen atoms (pK = 11-25) could be brominated when DBU was added dropwise into a mixture of substrate (phenylacetylene, diethyl butylmalonate, indene, or fluorene) and BrCClj in benzene (78CL73). Compounds with lower acidity (pK 29) exhibited no reaction. With more acidic derivatives (diethyl malonate and benzyl cyanide), oxidative dimerization also occurred. Oxidative dimerization also took place when BrCClj was added dropwise into a solution of active methylene compound and DBU in benzene. The ratio of the reaction products depended on the ratio of DBU and BrCCIj. 

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