Bromide benzyl, reaction with amines

The chloride is usually (but not always) stabilised in storage by addition of aqueous alkali or anhydrous amines as acid acceptors. A 270 kg batch which was not stabilised polymerised violently when charged into a reactor. Contact of the chloride (slightly hydrolysed and acidic) with rust led to formation of ferric chloride which catalysed an intermolecular Friedel-Craft reaction to form polybenzyls with evolution of further hydrogen chloride. Contact of unstabilised benzyl chloride with aluminium, iron or rust should be avoided to obviate the risk of polycondensation. See Benzyl bromide Molecular sieve... 

Kinetics and Mechanism of Reactions of Bis (methyl-2,2 -dimercaptodiethyl-amine) dinickel(II) with Alkyl Halides. The rates of reaction of [Ni2 CH3N-(CH2CH2S)2 2], structure III, with methyl iodide, benzyl bromide, benzyl chloride, p-chlorobenzyl chloride, and p-nitrobenzyl chloride have been studied as functions of temperature and concentration in chloroform (3). Absorbance measurements were utilized to determine the rates. All experiments were conducted with excess alkyl halide (20 to 1000 times the initial concentration of complex). Jicha and Busch (18) were able to isolate alkylated complexes of the composition... 

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)... 

The effect of cyanogen bromide on acyclic tertiary amines is to remove the smallest w-alkyl group (up to w-hexyl) as alkyl bromide in reaction (a). This reaction usually leads to the alkyl bromide that most readily exchanges its bromine thus, when R is allyl or benzyl it readily appears as the bromide RBr, but when R is phenyl this is not so. The quaternary ammonium bromide is obtained as by-product, by reaction of the RBr with the tertiary amine used,... 

Heating A, Af -diphenylurea with amines (butylamine, cyclohexylamine, benzylamine, 2,6-diethylaniline or morpholine) in DMF in the presence of triethylamine yields unsym-metrical ureas, e.g. PhNHCONHBu from butylamine . High yields of isocyanates RNCO are obtained in the reactions of primary aliphatic amines, carbon dioxide and triethylamine with phosphorus oxychloride . Treatment of secondary amines with butylUthium, followed by carbon monoxide at —78 °C under atmospheric pressure, sulphur and an alkyl halide affords 5-alkyl thiocarbamates, e.g. Et2NC(0)SCH2Ph from diethylamine and benzyl bromide. The key step in the sequence is the generation of the lithium thiocarbamate shown in equation 112 . 

A rapid route to N-substituted trihydroxypiperidines (l,5-dideoxy-l,5-imino-pentitols) by nucleophilic opening of bis-epoxides derived from d- and L-ara-binitol, D-xylitol and related compounds has been reported. The 3-0-benzyl-Zn s-epoxides, generated by tosylation of the primary hydroxyl groups followed by treatment with sodium hydride and benzyl bromide, were treated with primary amines to yield piperidine/pyrrolidine mixtures, whose composition was found to be dependent on the nature of the alditol precursor, the amine and the reaction... 

Alkylphosphines (PR3) are analogs of the parent phosphine (PH3) in the same ways that alkylamines (NR3) are analogs of the parent ammonia (NHg). Phosphorus is directly beneath nitrogen in group 15 of the periodic table, so it is reasonable to expect that phosphines (PR3) should react similarly to amines (NR3). In most cases, this is a correct assumption, and phosphines react with alkyl halides by an mechanism in the same way as amines. In one example, benzyltriphenylphosphonium bromide (50) is formed by reaction of benzyl bromide with triphenylphosphine (49). This Sn2 reaction with phosphine and alkyl halides is sometimes called the Arbuzov reaction, named after Alexander Arbuzov (Russia 1877-1968). 

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