Cyanogen hydrid

Hydrogen cyanide—Cyanogen hydride—Hydrocyanic add—iVuMte ON )... 

In this series, too, replacement of the N-methyl by a group such as cyclopropylmethyl leads to a compound with reduced abuse potential by virtue of mixed agonist-antagonist action. To accomplish this, reduction of 24 followed by reaction with tertiary butylmagnesium chloride gives the tertiary carbinol 27. The N-methyl group is then removed by the classic von Braun procedure. Thus, reaction with cyanogen bromide leads to the N-cyano derivative (28) hydrolysis affords the secondary amine 29. (One of the more efficient demethylation procedures, such as reaction with ethyl chloroformate would presumably be used today.) Acylation with cyclopropylcarbonyl chloride then leads to the amide 30. Reduction with lithium aluminum hydride (31) followed by demethylation of the phenolic ether affords buprenorphine (32).9... 

Nitrobenzene Aluminum trichloride Hydrochloric acid Cyanogen bromide Sodium hydride Calcium carbonate Ethanethiol... 

Acetone Alkali cyanides, hydrides, metals Aluminum borohydride, carbide, hydride nitride Benzoyl chloride Boron compounds Carbonyls Chlorine Cyanogen Cyanogen bromide Cyanogen chloride... 

Several Erythrina bases have been transformed into dibenzazonines. The first report, by Prelog et al. (63), described the transformation of dihydroerysotrine (80) to the simple dibenzazonine 81 by degradation with cyanogen bromide followed by reduction with lithium aluminum hydride. In a similar way, treatment... 

In connection with biosynthetic studies, compound (41) or (42) has been prepared, starting with OO-diacetyl-lycorine (37) (Scheme 6).13 Treatment of (37) with cyanogen bromide gave the cyanamide (38) in 80% yield this was not isolated but was directly oxidized to the aldehyde (39). Acetalization followed by reduction with lithium aluminium hydride gave the unstable amine (40), which upon hydrolysis gave a compound which, on the basis of its conversion into lycorine (37 OH in place of OAc) may be formulated as (41). This assignment is in doubt, since spectral evidence favours structure (42). 

Cyanobenzotriazole is readily prepared in 92% yield by treatment of benzotriazole with sodium hydride followed by cyanogen bromide. This solid and stable compound is a convenient reagent for introduction of the nitrile functional group into activated methylene compounds RCH2X, via lithiation <2007ARK5>. 

Cinchonine (CVI) can be transformed into dihydrocorynantheane (XV) by a series of reactions which first changes it into 9-benzoy]-2-oxyhexahydrocinchonine (CVII). The latter reacts with cyanogen bromide to give CVIII and this in turn under alkaline conditions suffers reduction and rearrangement to CIX, which on further reduction with lithium aluminum hydride followed finally by Oppenauer oxidation generates 3-epidihydrocorynantheane (CX). This can be isomerized by known means to dihydrocorynantheane (XV) (71). 

Complex metal hydrides Cyanides and cyanogen bromide Cycloserine... 

Acetyldemissidine (436b) reacted smoothly with cyanogen bromide in refluxing chloroform to give the bromocyanamide (442). When this degradation product (442) was treated with lithium aluminium hydride in refluxing tetrahydrofuran,... 

Treatment of diphenylacetonitrile in toluene with sodium amide and 2-chloro-pyrazine gave 2-(C-cyano-C,C-diphenylmethyl)pyrazine (1021), and 2-vinylpyrazine with phenylacetonitrile and sodium heated at 120-130° for 10 minutes gave 2-(3 -cyano-3 -phenylpropyl)pyrazine (731). 2-Amino-5-bromomethyl-3-cyano-pyrazine with sodium hydride and methyl cyanoacetate in tetrahydrofuran formed the dialkylated product (56) (1031). 2-Amino-3-mercapto-5,6-dimethylpyrazine in methanol with potassium hydroxide and chloroacetonitrile gave 2-amino-3-cyanomethyIthio-5,6-dimethylpyrazine (1229), and 2-carboxypyrazine refluxed with chloroacetonitrile and triethylamine in ethyl acetate for 45 minutes gave the cyanomethyl ester (1317). 2-Hydroxy 5-methyl-3-propylpyrazine with cyanogen halides in aqueous sodium hydroxide-dimethylformamide at 0-5° gave l-cyano-5-methyl-2-oxo-3-propyl-l, 2-dihydropyrazine (1123). 

In the second synthesis (77) isoconessimine (CXXIII was converted to its S-iV-formyl derivative, and the latter was treated with cyanogen bromide to yield the 20-iV-cyano derivative (CXXIV) which on reduction with lithium aluminum hydride afforded conessimine. 

This assignment was confirmed by the work of Kaneko (9). Tuberostemonine was converted to the lactam XX which was transformed by reduction with lithium aluminum hydride followed by cleavage with cyanogen bromide into XXI. Debromination by hydrogen over palladium followed by reductive removal of the cyano group gave XXII. The... 

The simplest and therefore most probable case of this association of two carbon atoms is that in which one unit of affinity of the one carbon atom is combined with one unit of affinity of the other. Of the 2x4 units of affinity of the two carbon atoms, two are used in holding the two atoms together there remain, therefore, six which may be held in combination by atoms of other elements. In other words the group of two carbon atoms, is hexatomic it will form a compound with 6 atoms of a monatomic element, or in general with that number of atoms that will make the sum of their chemical [affinity, TransL] units=6 (e.g. ethyl hydride, ethyl chloride, ethylene dichloride, l carbon tetrachloride [C2Cle, TransL] j acetonitrile, cyanogen, acetaldehyde, acetyl chloride, glycolide, etc.). 

Alkyl cyanates. Kauer and Henderson found that an alcohol such as neopentyl alcohol can be converted into the corresponding cyanate, if in low yield, by successive treatment with sodium hydride and cyanogen chloride. 1,4-Dihydroxybicyclo-[2.2.2]octane afforded the dicyanate, m.p. 155-156 , in reasonable yield. The... 

Desoxycodeine-E [xxx] pan be prepared by the lithium aluminium hydride reduction of codeine [n] p-toluenesulphonyl ester [17-18], Its structure is shown to be [xxx] by hydrogenation of the base to dihydrodesoxycodeine-D [xiii], degradation of the methiodide to desoxy-a-codeimethine [xxix], and isomerization of the latter to desoxy-/3-codeimethine [xxvin], production of cyanonordesoxy codeine-E [xxxi] by the action of cyanogen bromide on the base, and by the facts that desoxycodeine-E is neither a phenol nor an enol ether [17]. Desoxycodeine-E can be demethylated to desoxymorphine-E [62]. 

A new erythrina alkaloid, erythroculine, from Cocculus laurifolius has been shown to have the structure (167). The ester group may be reduced with lithium aluminium hydride and the acetyl ester of the resulting alcohol on treatment with cyanogen bromide affords the hindered diphenyl (168), with loss of hydrogen bromide and methanol. This on reduction to the secondary base, N-methylation, and successive Hofmann degradations affords an olefin that may be oxidised to the tricarboxylic acid (169).The base represents a novel structure in having the additional carbon atom linked to the ring system. 

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