Cyclobutyl bromide, reaction

To check this possibility we performed experiments with different concentrations of NaBr in the NaY zeolite. Table 2 presents the results. It can be seen that upon increasing the amount of NaBr impregnated on NaY, there is preference to formation of the cyclobutyl bromide over allylcarbinyl bromide, indicating that the relative position between the bromide ions and bicyclobutonium governs the product distribution. Hence, zeolites may act as solid solvent, favoring ionization of alkyl halides and nucleophilic substitution reactions. In contrast to liquid solvents, where solvation is mostly uniform, the zeolite surface seems to provide unsymmetrical solvation of the cations, leading to product distribution that is different from solution. 

Some variations of the method have been used to prepare cyclopropyl and cyclobutyl halides. Simultaneous addition of bromine and 3-bromocyclobutanecarboxylic acid to the suspension of mercuric oxide gives 1,3-dibromocyclobutane in good yield.7 Similarly, cyclopropanecarboxylic acid gives bromo-cyclopropane,9 and 3-(bromomethyl)cyclobutanecarboxylic acid gives 3-(bromomethyl)cyclobutyl bromide.10 In the latter reaction, it was found desirable to remove the water from the reaction as it is formed in order to obtain high yields. Another variation is the addition of a mixture of the acid and mercuric oxide to excess bromine in bromotrichloromethane.6... 

Cyclobutyl chloride does not react with Ph2P- ions in the dark or under photostimulation in liquid ammonia. On the contrary, cyclobutyl bromide (77) reacts with Ph2P ions in the dark (15 min, 42% of substitution product 78) as well as under photostimulation (83% of substitution) (equation 64). p-DNB does not affect the dark reaction while it partially inhibits the light catalysed one. In the latter case, the amount of product obtained is similar to that formed under dark condition151. 

This may all seem far-fetched, but it happens in laboratory reactions too Treatment of the simplest cyclopropyl alcohol with HBr gives cyclobutyl bromide by a similar rearrangement. 

Wurtz reaction. Wiberg and Connor1 noted that lithium amalgam is far more satisfactory than either sodium or lithium for conversion of 3-bromomethyl-cyclobutyl bromide (1) into bicyclo[l.l.l]pentane (2). When sodium metal was... 

A soln. of cyclobutyl-MgBr from cyclobutyl bromide and Mg in di-n-butyl ether treated with cooling below 50° during 30 min. with n-butyl alcohol —cyclobutane. Y 83%.—The use of di-n-butyl ether and n-butyl alcohol permits easy separation of the low-boiling reaction product. (J. Cason and R. L. Way, J. Org. Chem. 14, 31 (1949).)... 

The product of the reaction between the Grignard reagent of cyclobutyl bromide and 3-pentanone is an alcohol. Draw it. Are there distinguishing features in the proton NMR What features in the proton NMR might suggest a four-membered ring Can structural information be obtained from the mass spectrum ... 

Electroreductive cyclization of dimethyl 5-bromopent-l-ene-l,1-diearboxylate at —1.85 V (SCE) in dimethylformamide containing tetrabutylammonium bromide gave dimethyl cyclobutyl-malonate (19) in 65-80% yield.18 The mechanism of this electrochemical reaction is, however, unclear. 

Using a somewhat similar reaction sequence cw-l-bromo-2-vinylcyclopropane was reacted with various acid chlorides and transformed stereospecifically to 1-acyl-2-vinylcyclopro-panes. Very good yields were obtained thus, when the bromide was allowed to react successively with tert-butyllithium, phenylsulfanylcopper and cyclobutanecarbonyl chloride at — 78 °C, cyclobutyl d5-2-vinylcyclopropyl ketone (2a) was isolated in 93% yield. 

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