1-Butylmagnesium bromide preparation

Ethoxy-5-methyl-3,4-dihydropyran added at ca. 90° to n-butylmagnesium bromide prepared in ether with subsequent partial replacement of the ether by toluene, and refluxed 1.5 hrs. at 85-90° l-(l-methyl-2-ethoxy-l-cyclobutyl)-l-pentanol. Y 90%. F. e. s. R. Quelet and J. d Angelo, Bl. 1967, 3390. 

Arnold reaction. frans-But-2-enyl mesitoate and ii-butylmagnesium bromide prepared from n-butyl bromide and ca. 5% excess Mg in ether stirred and refluxed 12 hrs. trans-oct-2-ene (containing 10% 3-methylhept-l-ene). Y 59%. —No c/s-isomer could be found. This method allows some fairly selective syntheses of hitherto difficultly accessible frans-trialkylethylenes. F. e. s. G. M. G. Higgins, B. Saville, and M. B. Evans, Soc. 1965, 702. 

A suspension of selenium dioxide in tetrahydrofuran added slowly at 20° to an ethereal soln. of n-butylmagnesium bromide prepared from 1-bromobutane and Mg, and stirring continued 1 hr. dibutyl selenide. Y 48-62%. F. e. s. A. Arase and Y. Masuda, Chem. Lett. 1975, 1331. 

The finely divided hydride produced by pyrolysis is pyrophoric in air, while synthesis from the elements produces a substantially air-stable product [1]. That prepared by reduction of butylmagnesium bromide with lithium tetrahydroalumi-nate is pyrophoric and reacts violently with water and other protic compounds [2], The hydride produced from magnesium anthracene has a very large specific surface area and is pyrophoric [3], In the context of use of the hydride for energy storage purposes, ignition and combustion behaviour of 100-400 g portions were studied, as well as the reaction with water [4],... 

This compound has also been prepared by reacting three equivalents of butylmagnesium bromide with tin-124 tetrachloride35 (equation 32). 

Di-n-butylcadmium was prepared by the rapid addition of cadmium chloride (50.4 g, 0.275 mol) to a cooled solution of n-butylmagnesium bromide formed from magnesium (12.15 g, 0.50 mol) and n-butyl bromide (75.4 g, 0.55 mol) in anhydrous diethyl ether (550 ml). Following the addition, the reaction mixture was stirred at 0°C for 2 h. The di-n-butylcadmium reaction mixture, including the precipitate, was then added to a stirred solution of phosphorus trichloride (85.9 g,... 

Butylmagnesium bromide was prepared from magnesium and butyl bromide in tetrahydrofuran at room temperature by a standard procedure Org. Synth. 1978, 58, 127), and titrated by the procedure of Eastham, et al. 

Figure 3. Meso (isotactic) dyad frequency (m) of polyfmethyl methacrylate), prepared at 250 initiated by t-butylmagnesium bromide, as a function of solvent composition. The meso-frequency m is indicated for each point. The solvent composition, given in terms of mole fractions of THF, XThf, of toluene, Xtoiimie and of monomer, , ore indicated by the scale on each median, with each apex corresponding to the pure component indicated.

The first detailed study of the stereochemistry of a mercury exchange reaction that was known to be bimolecular was carried out as follows.83 Di-j-butyl-mercury was prepared by reacting optically active j-butylmercuric bromide with racemic i-butylmagnesium bromide as shown in Equation 4.48. 

Apart from the oxidation of trihexylborane,16 1-hexanol has been prepared by a previous Organic Syntheses17 procedure involving the reaction of ethylene oxide with n-butylmagnesium bromide and alternate methods of synthesis are reviewed therein. 

Similar to the conjugate addition, the focus of the last decade has been put on the development of chiral copper catalysts for enantioselective S -substitutions of prochiral substrates.197,197a,197b 271,285 These represent a useful alternative for the preparation of those substitution products which cannot be obtained by anti-stereoselective copper-promoted or -catalyzed SN2 -substitution of chiral substrates (see Section 9.12.2.1.2). The first reported example for such a transformation is the reaction of the allyl acetate 333 with //-butylmagnesium bromide in the presence of 15 mol.% of the copper arenethiolate 334 which gave the substitution product 335 with exclusive y-selectivity and 50% ee (Equation (18)),286 286a... 

Butylmagnesium bromide was prepared from the corresponding butyl bromide and magnesium turnings in anhydrous ether.2... 

Aldol-Type Addition. Aldol-type addition of the magnesium enolate of (R)-(+)-7-butyl 2-(p-tolylsulfinyl)acetate, prepared with 7-butylmagnesium bromide, with aldehydes and ketones afforded, after desulfurization with Aluminum Amalgam, p-hydroxy esters in very high diastereoselectivity (eq Two chiral centers are created in the first step with very high diastereoselectivity (mainly one diastereomer is formed). A model M based on the structure of the sulfinyl ester enolate (determined by C NMR) and on electrophilic assistance of magnesium to the carbonyl approach, was proposed to explain and predict the absolute configuration of the two created chiral centers. ... 

Aldol-Type Condensation. The aldol-type condensation of the enolate anion of sulfinylpropionate, which was prepared as usual with the base t-butylmagnesium bromide, with aldehydes afforded after desulfurization with Aluminum Amalgam the corresponding 3-hydroxy esters in high yield (90%) and, with aliphatic aldehydes, high diastereoselectivity (eq 3). The amount of asymmetric induction was determined by transformation of the 3-hydroxy esters to the corresponding isopropyl-substituted alcohols. 

R. J. Ferrier, D. Prasad, A. Rudowski, and 1. Sangster, J. Chem. Soc., 3330(1964) Tri-n-butylphosphine, (n-C4H9)sP. MoL wt. 202.32, b.p. 240° (130°/20 mm.), pKa 8.4, colorless liquid with a garliclike odor, immiscible with water but miscible with most organic solvents. Prepared by reaction of n-butylmagnesium bromide with... 

Hatada, K. Ute, K. Yamamoto, M. Nishimura, T. Kashiyama, M. On-line GPC/NMR analyses of block and random copolymers of methyl and butyl methacrylates prepared with tert-butylmagnesium bromide. Polym. Bull. 1989,21, 489 95. 

Scheme 4 Preparation of the aglycone of OSW-1 (2). (a) PhsPEtBr, rm-BuOK, 78% TBDPSCl, 100%. (b) (CH2OX, Bp30Et2, 75%. (c) Dess-Martin periodinane, 86% 3-methyl-butylmagnesium bromide, 96%. (d) PDC, 83% HOCHjCHjOH, 96%. (e) TBAF, 95% TBSCl, 96%. (f) OSO4, 41%. (g) ClCOCOCl, DMSO, 78% NaBH CeCE, 93%.

SoUadid has introduced a-sulfinyl acetates as reagents for asymmetric aldol reactions.Compound (211) is prepared in good optical purity from the menthyl ester of p-tolylsulfinic acid. The magnesium enolate of (211), prepared by reaction of the sulfrnyl ester with r-butylmagnesium bromide, reacts with aldehydes and ketones to give diastereomeric mixtures of a-sulfinyl-3-hydroxy esters (Scheme 13). No... 

Di-w-butylcarbinol has been prepared by the action of M-butylmagnesium bromide upon m-valeraldehyde1 and upon ethyl formate.1,2 It has also been obtained by the catalytic hydrogenation of di- -butyl ketone in the presence of platinum.3... 

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