Reactions of halogenoquinolizinium bromides with aniline,isopropylamine and liquid ammonia

The reactions of quinolizinium bromide ( QB ) and its four monobromo derivatives with aniline, isopropylamine and liquid ammonia have been investigated. With aniline 2- and 4-bromo QB undergo substitution, whereas 1- and 3-bromo QB do not react at all. With liquid ammonia all bromo derivatives and the parent compound react with ring opening. This diversity in the reaction course is explained in terms of the HSAB principle. 2-BromoQB reacts with isopropylamine under formation of 2-isopropylamino QB . Two molecules of isopropylamine are involved in this substitution, as we isolated an intermediate: 1-isopropylamino-4(2-pyridyl)-3-isopropyliminio-1-butene bromide ( 13 ). The structure of the latter compound was confirmed by X-ray analysis.     

Reactions of selenium bromides with butyl vinyl ether

Russian Journal of Organic Chemistry -     

Reactions of benzofurazan oxide with amines—I : Reduction with diethylamine

The reactions of benzofurazan oxide with diethylamine gave a complex mixture from which quinoxaline-1,4-dioxide (10–15%), o-benzoquinone dioxime (5%), benzofurazan (5–10%), 1-hydroxy-2-methyl-benzimidazole-3-oxide (3%), o-nitrosoaniline (5%), o-nitroaniline (<3%), 3-methylbenzotriazine (5%), 3-methyl-benzotriazine-4-oxide (10%), and o-nitrophenyl-N,N-diethyl hydrazine (10%) were isolated.The formation of these products seems to have a common pathway that involves the reduction of benzofurazan oxide and the oxidation of diethylamine.     

Reactions of aryl bromides with cobaloxime(I). Reductive arylation

Successful arylations of both cobaloximes(I) and hydridocobaloximes with aryl halides with electron-withdrawing substituents have been demonstrated. The scope, utility and possible mechanisms of these useful synthetic reactions are discussed.     

Reactions of 6-diazopenicillanates with allylic sulphides,selenides, and bromides

6-Diazopenicillanates react with allylic sulphides, selenides and bromides, to give 6,6-disubstituted penicillanates $\text{via}$ [2,3]-sigmatropic rearrangements.     

Reactions of ortho oxy-substituted benzyl and phenacyl bromides in dimethyl sulphoxide

o-Acetoxy- and o-benzoyloxy-benzyl bromides and tosylates oxidatively rearrange in moist dimethyl sulphoxide to o-hydroxybenzyl esters; o-acetoxy- and o-benzoyloxy- phenacyl bromides rearrange to mixtures of 2-hydroxycoumaran-3-ones and o-hydroxyphenacyl esters; o-hydroxyphenacyl bromides also yield 2-hydroxycoumaran-3-ones, together with o-hydroxyphenacyl alcohols. 2-Acetoxybenzaldehyde is reductively rearranged by sodium borohydride to o-hydroxybenzyl acetate.     

Reactions of substituted phenacyl bromides with various bases: p-methyl- and p-methoxyphenacyl bromide. II

The products obtained from the reaction of p-methyl- and p-methoxyphenacyl bromide with various bases are described.     

Reactions of substituted phenacyl bromides with various bases. o- and p-nitrophenacyl bromide. I

The products obtained from the reaction of o- and p-nitrophenacyl bromide with various bases is described.     

Reactions between a superoxide anion and alkyl bromides in dimethyl sulfoxide

The activation parameters of the reactions between a superoxide anion (O₂^·−) and alkyl bromides are measured. An ab initio study of the transition states for various mechanisms of this reaction is performed. The mechanism of radical separation in a polar solvent becomes competitive upon an increase in the number of alkyl groups in an alkyl bromide molecule and depends on their arrangement relative to a reaction center.     

Reactions of the electrochemically generated dianion of [60]fullerene with bulky secondary alky bromides

Reactions of the electrochemically generated dianion of [60]fullerene (C₆₀^2?) with bulky secondary alkyl bromides exhibit different reaction behaviors. Reaction of C₆₀^2? with diphenylbromomethane gives rise to 1,2-C₆₀HR or 1,4-C₆₀R₂ (R?=?CHPh₂) adducts, while reaction of C₆₀^2? with diethyl 2-bromomalonate unexpectedly affords methanofullerene C₆₀?>?CR₂ (R?=?CO₂Et). Plausible reaction mechanisms have been proposed to explain the formation of the observed products.     

Reaction of perfluorinated vinyl ethers with diethylamine

Russian Journal of General Chemistry -     

Gas-phase reaction of phenyl cation with diethylamine

Reactions of phenyl cations generated by the beta-decay of tritium in tritiated benzene were studied by a radiochemical method. Identified labeled products are ethylphenylamine (72%), diethylamine (15%) and diethylphenylamine (13%). A reaction mechanism is proposed and the relative yields of products are rationalized taking into account the energy estimates of plausible products by the B3LYP method.     

Reactions of lithium tributyl heteroaryl borates with allylic bromides in the presence of copper(I) cyanide

The reaction of various lithium tributylheteroarylborates with allylic bromides in the presence of copper(I) cyanide furnished the regioselective allylation at the heteroaryl ring.     

Flourination of halogeno alcohols with 1,1,2,3,3,3-hexafluoropropyl diethylamine

Fluorination of halogeno alcohols with 1,1,2,3,3,3-hexafluoropropyl diethylamine (PPDA) was investigated. 2-Bromo-l-fluorobutane was obtained from the reaction of PPDA and 2-bromo-l-butanol (yield 50 %). Similar results were obtained from other aliphatic and aromatic halogeno alcohols. However, the corresponding 2,3,3,3-tetra-fluoropropionate esters were obtained from the reactions of PPDA and α-halogeno cycloalkanols, such as 2-chlorocyclohexanol.     

Interaction of adenosine with alkyltrimethylammonium bromides

The interaction of adenosine with alkyltrimethylammonium bromides, C_mH_2m+1N(CH₃)₃Br(m=16, 14, 12, 10, 8, and 6), has been studied by 1 H NMR spectroscopy. When surfactants exist as monomer units, the adenine ring of adenosine preferentially associates with the middle portion of the alkyl chain of the surfactants. The interaction is less specific with surfactants of shorter alkyl chains. When surfactants form micelles, no specific interaction between the adenine ring and the alkyl chain of the surfactant can be detected. A coordination of the cationic part of the surfactants with the adenine ring is suggested. The degree of association was evaluated from association constants. Similar results were obtained for purine and alkyltrimethylammonium bromide.