Cyclo-butylamine

Cyclo-butylamine, for example, is converted to cyclo-butyl-ammoninm hydroxide, and this on distilling is decomposed into cyclo-butylene, trimethylamine and water 14... 

The effect of /3-methyl groups was investigated only for the cis-a-arylsulphonyl-j3-bromo- or /3-chloro-ethylenes. The 2-4- to 3-9-fold rate decrease with MeO- ion, as well as the 1-3- to 3-2-fold decrease for /3-bromo-a-p-nitrobenzenesulphonylethylene-di-n-butylamine and cyclo-hexylamine reactions, may point to a contribution of the elimination-addition route with these nucleophiles. When the elimination becomes more difficult, either for thep-methyl derivative or with a chlorine leaving group, a j8-methyl group decreases the substitution rate 20- to 84-fold with the same amines. With PhS- ion, for which other substitution routes are less probable, the rate retardation is higher (322- to 3100-fold). 

Compound 2 was chosen as a direct precursor to cyclo-Ci since it should lose three anthracene molecules in a retro-Diels-Alder reaction under thermal conditions (Scheme 13-1). The synthesis of 2 (Scheme 13-2) started with the Diels-Alder reaction of anthracene and tra 5-dichloroethene [10], followed by dehydrochlorination and subsequently bromination to 10. The latter conversion was best achieved by simply adding elemental bromine to a solution of the vinyl anion formed with n-BuLi [11]. Palladium-catalyzed alkynylation of 10 with trimethylsilylacetylene in n-butylamine followed by deprotection with aqueous KOH in MeOH gave the diethynyl derivative 11 as very unstable crystals, which in one case exploded spontaneously. 

The first examples of the 1,3-oxazete system (44) have been prepared by the sequence shown in Scheme 8. The first stable 4-imino-l,2-oxazetidines (45) have been obtained from [3 + 1] cycloaddition of isocyanides to N-neopent-ylidene-t-butylamine AT-oxide. Their chemistry is dominated by O—N bond cleavage for example, acid brings about rearrangement to amino-acid derivatives, and, in the presence of tetrahydroisoquinoline, cyclo-reversion to give imine and isocyanate can be detected. An unstable 1,3-oxazetidine is involved in the reaction of the imine (46) with the aldehyde (47) to give the imine (48). ... 

Cyclohexene added to a stirred soln. of mercuric acetate in N-methylaniline-tetrahydrofuran, stirred 16 hrs. at room temp., butylamine added, cooled to 0°, Li-powder added, and the product isolated after 16 hrs. N-methyl-N-cyclo-hexylaniline. Y 58%. - The reactions can be carried out at room temp., and the method is suitable for both sec. and tert. amines. F. e., also isolation of the intermediates, s. J. Barluenga, A. Ara, and G. Asensio, Synthesis 1975, 116 cf. H. Hodjat-Kachani, J. J. Perie, and A. Lattes, Chem. Lett. 1976, 409 2-amino-mercuration-demercuration of allenes cf. ibid. 1976, 405. 

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