Reactions with butyl chloride

The reaction of CIO- with methyl chloride can only proceed via the Sn2 process. An inverse KIE of 0.85 is measured (Table 10.3). The reaction with /-butyl chloride presumably proceeds via an E2 mechanism (since Sn2 attack on the Cl substituted carbon is blocked) and the observed KIE of 2.31 (Table 10.3) is consistent with that conclusion. The isotope effects for both species are nearly the same as the effects measured in the condensed phase (compare Tables 10.3 and 10.4) and measure the relative contributions of the two paths. The results indicate that the E2 pathway becomes the dominant channel as the substrate becomes more sterically hindered. 

The decomposition rates of butyl chlorides decreased in the following order tert > sec > //-butyl chloride. It is highly plausible that the formation of butene is caused by both the decomposition of butyl chloride over the copper surface and by the decomposition of zwitterion intermediate formed by the reaction of silylene on the surface of the silicon-copper contact mass with butyl chloride.80,81 From the reaction with //-butyl chloride, sec-butyldichlorosilane is also obtained as a minor product along with /z-butylchlorosilanes.80... 

Although hydrolysis of the reaction mixture from phenylsodium and P produced no simple compounds, reaction with butyl chloride gave over 70% total yield of mixed tertiary phosphines. These results indicate the presence of structural units having two phenyl groups bonded to phosphorus. But the presence of alkali diphenylphosphides is unlikely since they would hydrolyze cleanly to diphenylphosphine. 

Alkylation of pyrrole magnesium bromide and chloride with y-chloro-butyronitrile gives 2- and 3-cyanopropylpyrrole (2 >3). The isomer distribution is similar to those observed in reactions with butyl chloride, heptyl chloride and 8-methoxybutyl chloride. It is concluded that the constitution of pyrrole magnesium chloride is the same in tetrahydrofuran as in ether s. 

Hydrazoic acid reaction with cyclobu-tanecarboxyhc acid, 47, 28 Hydrogenation of t butylazidoacetate to glycme ( butyl ester, 46,47 Hydrogen bromide 46, 43 reaction with y butyrolactone, 46, 43 Hydrogen fluoride anhydrous, precautions in use of, 46, 3 in preparation of mtromum tetra-fluoroborate 47, 57 reaction with benzoyl chloride, 46,4 with boron tnfluonde in conversion of p cymene to m cymene, 47, 40 in bromofluorination of 1 heptene, 46, 11... 

The reactions of tri-ATZ-butylplumbyllithium with various phosphorus chlorides have been investigated. For example, reaction of the lithium compound with diphenylchlorophosphane afforded hexa-tert-butyldiplumbane and tetraphenyldiphosphane as the isolated products. Analogous reactions with -butyl-substituted phosphorus chlorides yielded (tri-A, 7-butylplumbyl)di- -butylphosphane or tri- z -butylplumbyl(amino)-, t -butylphosphane. These and other molecules were characterized by multinuclear magnetic resonance spectroscopic studies.24... 

When sodium ethoxide is used in place of sodium hydroxide in the carbonylation reaction of benzyl halides with dicobalt octacarbonyl, ethyl esters are produced instead of the acids [15], Esters are also produced directly from iodoalkanes through their reaction with molybdenum hexacarbonyl in the presence of tetra-/i-butylammo-nium fluoride [16]. Di-iodoalkanes produce lactones [16]. The reaction can be made catalytic in the hexacarbonyl by the addition of methyl formate [16]. t-Butyl arylacetic esters are produced in moderate yield (40-60%) under phase-transfer catalytic conditions in the palladium promoted carbonylation reaction with benzyl chlorides [17]. 

Butoconazole Bntoconazole, l-[4-(4-chlorophenyl)-2-[(2,6-dichlorophenyl)thio]butyl]-IH-imidazole (35.2.12), is synthesized from 4-chlorobenzylmagnesium bromide, which is reacted with epichloridrine to make 4-(4 -chlorophenyl)-l-chlorobutan-2-ol (35.2.10), which is reacted with imidazole in the presence of sodium to make 4-(4 -chlorophenyl)-l-(lH-imidazolyl)butanol-2 (35.2.11). The hydroxyl group in the last is replaced with a chlorine atom npon reaction with thionyl chloride, which is then by the reaction with 2,6-dichlorothiophenol bntoconazole [27,28], is obtained. 

A series of pyrido[2,3-rf pyrimidine-2,4-diones bearing substituents at C-5 and/or C-6 were synthesized using palladium-catalyzed coupling of uracil derivative 417 with vinyl substrates or allyl ethers to give the regioisomeric mixtures of 418/419 and 420/421, respectively. The ratio of the isomeric structures was dependent on the substituent R. In the case of the reaction with -butyl vinyl ether, only the product 419 was obtained. However, the reactions with acrylonitrile, ethyl acrylate, 2-trifluoromethylstyrene, and 3-nitrostyrene afforded only 418. Also, reaction with allyl phenyl ether gave only 420. The key intermediate 417 was prepared by the reaction of 6-amino-l-methyluracil with DMF-DMA (DMA = dimethylacetamide), followed by N-benzylation with benzyl chloride and vinyl iodination with iV-iodosuccinimide (NIS) (Scheme 15) <2001BML611>. 

Methoxyphenyl isocyanide, 41, 103 Methyl crotonate, reaction with -butyl Grignard reagent and cuprous chloride, 41, 63... 

Acetylbenzo[6]tellurophene is also formed in isolable quantities. Benzo[6]selenophene is converted into 2-acyl derivatives by reaction with acid chlorides in the presence of aluminum chloride, whereas similar Friedel-Crafts acylation of benzo[6]thiophene yields 3-substituted products. When the 2-position is blocked, formylation can be directed into the 3-position. Thus treatment of 2-bromobenzo[6]selenophene with dichloromethyl butyl ether (Cl2CHOBu) and titanium tetrachloride yields the 3-formyl derivative (72BSF3955). If the 2- and 3-positions of benzo[6]selenophene are blocked with methyl groups, acylation under Friedel-Crafts conditions occurs in the 6-position (78CR(C)(287)333>. 

REACTIONS OF BUTYL CHLORIDE AND BIPHENYL CATION RADICALS WITH... 

A global electrophilicity index of common benzylating and acylating agents has been established from MO calculations and it shows a quantitative linear correlation with the experimental substrate selectivity index from a series of benzylation and acylation reactions.21 The values of relative rate coefficients predicted from the index may be accurate to within 10%. The reaction of /-butyl chloride with anisole catalysed by /Moluenesulfonic acid in supercritical difluoromethane has been subject to kinetic analysis.22 The proportions of substitution at the ortho -position and disubstitution increase at lower pressures, attributed to the decrease in the hydrogen-bonding ability of the solvent. 

Butyl chloride, 44, 102 rec-Butyl dnnamate, 41, 62 ree-Butyl crotonate, 41, 60 reaction with -butyl Grignard reagent, 41, 61... 

A successful procedure for the formation of 2,5-di-/-butylfuran involves reaction of the parent heterocycle with /-butyl chloride in the presence of iron(III) chloride and iron(III) oxide. 

Three reactions, which were known from the literature to be catalyzed by Lewis acids were selected as test reactions. A, was the Reetz alkylation of silyl enol ethers with -butyl chloride for which titanium tetrachloride is known to be useful [52]. B, was the Diels-Alder reaction between furan and acetylenedicarboxylic ester for which aluminium trichloride is a good catalyst [53]. C, was a Friedel-Crafts acylation for which aluminium trichloride is the preferred catalyst [54]. The reactions are summarized in Scheme 6. 

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