PREPARATION OF CYANO COMPOUNDS

PREPARATION OF CYANO COMPOUNDS USING ALKYLALUMINUM INTERMEDIATES. III. 36-ACETOXY-5a—CYANOCHOLESTAN-7-ONE,... 

PREPARATION OF CYANO COMPOUNDS USING ALKYL-ALUMINUM INTERMEDIATES. I. DIETHYLALUMINUM... 

PREPARATION OF CYANO COMPOUNDS USING ALKYLALU-MINUM INTERMEDIATES. II. l-CYANO-6-METHOXY-3,4-DIHYDRONAPHTHALENE, 52, 96... 

Nagata, W., Yoshioka, M. Preparation of cyano compounds using alkylaluminum intermediates. I. Diethylaluminum cyanide. Org. Synth. 1972, 52, 90-95. 

Ethyl l-cyano-2-methylcyclohexanecarboxylate has been prepared by catalytically hydrogenating the Diels-Alder adduct from butadiene and ethyl 2-cyano-2-butenoate3 and by the procedure described in this preparation.4 8 This procedure illustrates a general method for the preparation of alicyclic compounds by the cyclization of <5-ethylenic carbon radicals l.6 Whereas the primary 5-hexen-l-yl radical 1... 

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%. 

Evidence forcoball(l) was first obtained from the electrolytic reduclion of cyano-compounds and some of the reduced species have been isolated. There arc also many cohaltfl) coordination compounds of Ihe organomelallic class carbonyl, isonitriles, and unsaturated hydrocarbon derivatives. The oxidation state cobalt(O) may be represented in the eyano-Lompound which has been formulated as Ks[Cu (CN)b. It has been prepared as an air-sensitive brown-violet compound by reducing a liquid ammonia solution of Kj Co(CN)f,l with an excess of K tnctal. The only other known coball(O) species arc organomelallic compounds. 

The preparation of cyano-substituted styryl and stilbenyl compounds can be achieved38,39 by using sodium methoxide at room temperature. In this way, o-tolunitrile has been reacted with the anil of 2-(/>-formyl-phenyl)benzo[6]furan and / -chloroaniline (52) to give 2-(2-cyano-stilben-4 -yl)benzo[6]furan (53). 

This methodology has been successfully extended to the preparation of cyano-fluoromethylene compounds. Thus the a-fluoro-a-cyano anion (10) generated in situ was trapped with RX [64], R2NCOCI [65], and allylic halide ]66] to afford the adducts in high yields (Scheme 11.42). 

The D phase had been found in only four compounds until recently (Paschke et al., 1994). The four compounds are the 16 and 18 members of the 4 -n-alkoxy-3 -nitrobiphenyl-4-carboxylic acids (AnBC) synthesized by Gray et al. in 1957 and the n = 16 and 18 members of the analogous ii -cyano compounds (ACBC) prepared by Goodby and Gray (1980). Detail experiments (Etherington et al., 1985, 1986) verified that the compound (CN 18) is of space group P23 or Pm3, and is optically isotropic with no apparent optical rotation. Recently, Paschke et al. (1994) found that the D phase appears in more members of the above series of cyano compounds with n = 15 to 22. The temperature range of the D phase becomes wider as n increases. 

Preparation and Synthetic Applications of Cyano Compounds, A. J. Fatiadi, 1983 This comprehensive book chapter (1236 references) deals with synthesis of nitriles and some of their reactions. Synthetic methods and reactions involving cyano substrates are also... 

Synthesis. The preparation of these compounds involved three steps. The first step was the synthesis of -cyano- -hy dr oxyb iphe ny 1 (jA) ... 

The use of unsaturated nitriles as Michael acceptors represents a facet of the synthetic utility of cyano-compounds that nicely complements the reactivity discussed above. Michael addition of 2-lithio-1,3-dithianes to a,B-unsaturated nitrile derivatives appears to be of use in the preparation of protected cyanoketones, although the method may be limited by the fact that reactions of substrates unable to stabilise the negative charge of the adduct before workup were difficult to achieve satisfactorily. 

Olah s original preparative nitrations were carried out with mixtures of the aromatic compound and nitronium salt alone or in ether, and later with sulpholan as the solvent. High yields of nitro-compounds were obtained from a wide range of aromatic compounds, and the anhydrous conditions have obvious advantages when functional groups such as cyano, alkoxycarbonyl, or halogenocarbonyl are present. The presence of basic fimctions raises difficulties with pyridine no C-nitration occurs, i-nitropyridinium being formed. ... 

An unusual method for the preparation of syndiotactic polybutadiene was reported by The Goodyear Tire Rubber Co. (43) a preformed cobalt-type catalyst prepared under anhydrous conditions was found to polymerize 1,3-butadiene in an emulsion-type recipe to give syndiotactic polybutadienes of various melting points (120—190°C). These polymers were characterized by infrared spectroscopy and nuclear magnetic resonance (44—46). Both the Ube Industries catalyst mentioned previously and the Goodyear catalyst were further modified to control the molecular weight and melting point of syndio-polybutadiene by the addition of various modifiers such as alcohols, nitriles, aldehydes, ketones, ethers, and cyano compounds. 

Unsaturated hydrazones, unsaturated diazonium salts or hydrazones of 2,3,5-triketones can be used as suitable precursors for the formation of pyridazines in this type of cyclization reaction. As shown in Scheme 61, pyridazines are obtainable in a single step by thermal cyclization of the tricyanohydrazone (139), prepared from cyanoacetone phenylhydrazone and tetracyanoethylene (76CB1787). Similarly, in an attempted Fischer indole synthesis the hydrazone of the cyano compound (140) was transformed into a pyridazine (Scheme 61)... 

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