Cyanide, benzoyl preparation

Benzoyl cyanide was prepared by heating a mixture of benzoyl chloride and cuprous cyanide, then 13.1 g purified benzoyl cyanide (O.lOmol), 11.67 g benzaldehyde (0.11 mol), and 100 mL dry ether were cooled in an ice bath and saturated with dry hydrogen chloride. The mixture was kept at 0°C overnight, then transferred onto 300 g crushed ice and extracted with ether (2 x 100 mL). The combined organic layers were washed with water, saturated NaHSOs, and water and dried over Na2S04. Upon removal of the solvent, the residue was recrystallized from acetone or an acetone/methanol mixture to give 15.34 g 2,5-diphenyl-4-chloro-oxazole, in a yield of 60%, m.p. 71-72°C. 

This method is an adaptation of that of Dengel. -Methoxy-phenylacetonitrile can also be prepared by the metathetical reaction of anisyl chloride with alkali cyanides in a variety of aqueous solvent mixtures by the nitration of phenylaceto-nitrile, followed by reduction, diazotization, hydrolysis, and methylation 1 by the reduction of ct-benzoxy- -methoxy-phenylacetonitrile (prepared from anisaldehyde, sodium cyanide, and benzoyl chloride) and by the reaction of acetic anhydride with the oxime of -methoxyphenylpyruvic acid. ... 

Campaigne et al. have used 3-thenyl bromide obtained by benzoyl peroxide-catalyzed, side-chain bromination of 3-methylthiophene with A -bromosuccinimide, as a starting material for 3-substituted thiophenes. - 22 3-Methylthiophene is now prepared commercially from itaconic acid. The reactive halogen in 3-thenyl bromide could be directly reacted with a variety of nucleophiles, such as cyanide, or malonate, to give more complex 3-substituted compounds. 3-Thenyl bromide was converted by the Sommelet reaction to 3-thio-phenealdehyde which, with silver oxide, was oxidized to 3-thio-... 

Ethyl benzoylformate has been prepared by the direct esterification of the acid 1 and by the action of oxides of nitrogen on an alcoholic suspension of indigo.2 The acid has been prepared by many different reactions but the most practical are the hydrolysis of benzoyl cyanide,3 the oxidation of acetophenone 4 and the oxidation of mandelic acid.5... 

R)-Benzoins and (/ )-2-hydroxypropiophcnonc derivatives are formed on a preparative scale by benzaldehyde lyase (BAL)-catalyzed C-C bond formation from aromatic aldehydes and acetaldehyde in aqueous buffer/DMSO solution with remarkable ease in high chemical yield and high optical purity (Eq. 8.112).303 Less-stable mixed benzoins were also generated via reductive coupling of benzoyl cyanide and carbonyl compounds by aqueous titanium(III) ions.304... 

Benzoyl cyanide can be prepared by the thermal decomposition of cj-isonitrosoacetophenone,5 from silver cyanide and benzoyl chloride,3 from anhydrous hydrogen cyanide and benzoyl chloride in the presence of pyridine,4 and by the thermal decomposition of phenylchloronitrocyanomethane.6 6... 

Bobek and FarkaS40 reported the preparation of crystalline 2,3,5-tri-0-benzoyl-/3-D-ribofuranosyl cyanide (82) from the corresponding bromide (81). Their work was based on initial experiences of Hel-... 

Aroyl cyanides, which have low stability in the presence of water, can be prepared under phase-transfer catalytic conditions in yields >60% [24], A major byproduct of the reaction with benzoyl chloride is a,a-dicyanobenzyl benzoate, resulting from reaction of the benzoyl cyanide with the cyanide ion and subsequent esterification. 

The synthesis of the basic skeleton of 1-benzylisoquinoline alkaloids has been reported by Uff et al. 15) starting from isoquinoline and benzyl chloride (Scheme 5). The preparation of Reissert compound iV-benzyl-l-cyano-l,2-di-hydroisoquinoline (4) was performed in a dichloromethane-water two-phase system with potassium cyanide and benzoyl chloride in about 64-69% yield. The deprotonation of 4 with sodium hydride in dimethylformamide solution, the subsequent alkylation with benzyl chloride, and the final alkaline hydrolysis could be performed as a one-pot reaction sequence to supply 1-benzylisoquinoline (25) in an overall yield of 75-84%. 

Reticuline (38), one of the most important intermediates in the biosynthesis of opium alkaloids, has been synthesized in racemic form (Scheme 7) (78). 6-Methoxy-7-benzyloxyisoquinoline (39), prepared from O-benzylisovanillin via a modified Pomeranz-Fritsch isoquinoline synthesis, was treated with benzoyl chloride and potassium cyanide to obtain Reissert compound 40. Alkylation of the anion generated from 40 with 3-benzyloxy-4-methoxybenzyl chloride gave the corresponding 1-substituted Reissert compound 41 which was hydrolyzed in alkaline medium to 1-benzylisoquinoline derivative 42. Quatemarization of 42 with methyl iodide followed by sodium borohydride reduction and debenzylation led to ( )-reticuline (38) in about 25% overall yield from 39. 

The formation of Reissert derivatives of the antineoplastic agent ellipticine (225) (Scheme 29) and their reactions have been extensively studied by Popp and co-workers 39,49-51). The ellipticine Reissert compound 226 could be prepared either with benzoyl chloride and potassium cyanide in a dichloromethane-water system or, better, with benzoyl chloride and trimethylsilyl cyanide in dichloromethane. In similar manner 9-methoxyellipticine and a number of 6-substituted ellipticines have also been converted to the corresponding Reissert compounds. 

In the case of pyrene, there are two sextets and two fixed double bonds similar to the phenanthrenic double bond. In agreement with this argument and with the result for phenanthrene, co-ozonolysis of pyrene with formaldehyde or acetyl cyanide afforded the expected normal ozonide 114 and the cross-ozonide 115 with an aldehydic group. In a separate co-ozonolysis of 115 with vinyl acetate, diozonides 116 were prepared. No cross-ozonide was obtained in the presence of benzoyl cyanide, which afforded only the normal mono-ozonide 114 (Scheme 36 and Table 15). 

Phenylethylamine has been made by a number of reactions, many of which are unsuitable for preparative purposes. Only the most important methods, from a preparative point of view, are given here. The present method is adapted from that of Adkins,1 which in turn was based upon those of Mignonac,2 von Braun and coworkers,3 and Mailhe.4 Benzyl cyanide has been converted to the amine by catalytic reduction with palladium on charcoal,5 with palladium on barium sulfate,6 and with Adams catalyst 7 by chemical reduction with sodium and alcohol,8 and with zinc dust and mineral acids.9 Hydrocinnamic acid has been converted to the azide and thence by the Curtius rearrangement to /3-phenyl-ethylamine 10 also the Hofmann degradation of hydrocinnamide has been used successfully.11 /3-Nitrostyrene,12 phenylthioaceta-mide,13 and the benzoyl derivative of mandelonitrile 14 all yield /3-phenylethylamine upon reduction. The amine has also been prepared by cleavage of N- (/3-phenylethyl) -phthalimide 15 with hydrazine by the Delepine synthesis from /3-phenylethyl iodide and hexamethylenetetramine 16 by the hydrolysis of the corre-... 

The conversion of aliphatic and aromatic acyl halides to a keto nitriles has been effected by heating the halides with dry metallic cyanides, of which cuprous cyanide has given the most satisfactory results (60-87%). The acyl bromides rather than the chlorides ate preferred, at least in the formation of aliphatic compounds. Thus, pyruvonitrile is prepared in 77% yield from acetyl bromide and cuprous cyanide whereas no product is obtained if acetyl chloride is employed. Benzoyl cyanide is made in 65% yield by heating the corresponding acyl chloride with cuprous cyanide. "... 

Another procedure consists in slowly adding pyridine to an ethereal solution of an acyl chloride and anhydrous hydrogen cyanide. This order of addition of the reactants is important in order to retard the formation of acyl cyanide dimers. In this manner, certain benzoyl cyanides as well as furoyl cyanide have been prepared (40-80%). 

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