Cyanogen reactions with amines

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... 

Cyanoethylation, 5, 2 Cyanogen bromide, reactions with tertiary amines, 7, 4... 

The 1,3,6-benzotriazocine ring system was first synthesized by Hornyak, Lempert, and co-workers, who found that N-tosyl-o nitroanilines could be haloalkylated and then aminated to yield compounds 234 (R = H, Me R = H, Me, OMe). Hydrogenation of 234, followed by reaction with orthoesters, R2C(OAlk)3, produced compounds 235 (R = R2 = H, Me R1 = H, Me, OMe). If cyanogen bromide was used instead of orthoesters, triazocines 235 (R2 = NH2) resulted. Reduction of 234 (R = R = Me), followed by condensation with diethyl carbonate, gave urea 234 (R = R = Me, X = O). A similar reaction starting with 234... 

Generation of benzomorphan secondary amines, for conversion to appropriate N-substituted derivatives, usually requires N-demethylation of the corresponding tertiary amine. This may be effected by the von Braun reaction with cyanogen bromide or by the use of alkyl-, halogenated alkyl-, and arylchloroformates or diethylazodicarboxylate. Methods for N-demethylation in the series have been summarized by Rice.(62) Removal of an N-benzyl substituent affords an alternative path to norbenzomorphans and is exemplified by Michne and co-workers(63) and Kametani and Aoyama.(s4)... 

Cyanogen chloride reacts with sodium sulfide, Na2S, to form sodium thiocyanate, NaSCN. An extension of this involves the reaction of thiolate anions, RS, with CICN to form thiocyanates, RSCN. Similarly, the reaction of phenols produces aromatic cyanates (Kaupp et al., 1998). In such reactions, 3° amines are used to trap hydrogen chloride. 

CHLORCYAN (506-77-4) CNCl C-N-CL Noncombustible gas. Violent polymerization can be caused by chlorine or moisture. Violent reaction with alcohols, alkenes, and alkynes (violent exothermic reaction) acids, acid salts, amines, strong alkalis, olefins, strong oxidizers. Contact with acid forms toxic hydrogen cyanide gas. Mixtures with benzene or cyanogen halides yield hydrogen chloride. In cmde form, this chemical trimerizes violently if catalyzed by traces of hydrogen chloride or ammonium chloride, forming cyanuric chloride. Alkaline conditions will convert this chemical to... 

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