Butylmagnesium chloride in THF

Variable yields of azo compounds were also obtained from reactions of Grignard reagents with diazonium salts, but benzenediazonium tetrafluoroborate gave acceptable yields from arylmagnesium bromides or t-butylmagnesium chloride in THF [19] ... 

Yamamoto [16] also reported that when (E)-2-decenyl-l-diphenylphosphonate is treated with n-butylmagnesium chloride in THF at O C, a 91 9 mixture of 8n2/8n2 products is obtained in moderate yield (32%). 

To a mixture of 2.0 g benzonitrile (19.4 mmol), 10.7 mL 2 M tm-butylmagnesium chloride in THF (21.4 mmol) and 40 mL THF, was added 50 mg CuBr (0.34 mmol), and the mixture was refluxed under nitrogen for 14 h. After cooling to 0-5°C (ice water bath), the nitrogen inlet tube attached to the condenser was replaced by a soda lime trap... 

The crude tosylate obtained after evaporation of the diethyl ether was dissolved In 150 ml of THF. After addition of 1 g of CuBr the solution was cooled to -10°C and a solution of tert.-butylmagnesium chloride in 250 ml of THF, prepared from 0.40 mol of -butyl chloride and magnesium (see Chapter II, Exp. 4) was added... 

Temperature effects on the equilibrium between monomeric complexes have also been documented. An H-NMR investigation of r-butylmagnesium chloride in either THF or diethyl ether showed that low temperature shifts the equilibrium toward the dialkyl complex [18]. 

A 2.15A/ solution of freshly prepared t-butylmagnesium chloride in dry THF (0.462 mL, 1 mmol) is added under nitrogen to a solution of 3 -0-acetylthymidine or 3 -0-(t-butyldimethylsilyl)-2 -0-deoxy-ribonucleoside (1 mmol) in anhydrous pyridine (1.0 mL). To the resulting suspension of 5 -hydroxyl-activated nucleoside (25% molar excess), a solution of individual [Rp]- or [Sp]-isomer of suitable monomer 2 (0.75 mmol) in anhydrous pyridine (2.0 mL) is added after 15 min. The reaction mixture is stirred for 4 h at room temperature, and then left overnight without access to moisture. The reaction is quenched with water (20.0 mL), and the product is extracted with CHCI3 (2 x 20 mL). 

To a solution of phosphorus trichloride (6.4 g) in dry tetrahydrofuran (20 mL) was added tert-butylmagnesium chloride (1.0 M THF solution, 52 mL) at —78°C under an argon atmosphere over a period of 2 hours. 

Addition of RMgBr to nitriles. Grignard reagents react with nitriles slowly if at all, but even r-butylmagnesium chloride will add to nitriles in refluxing THF when catalyzed by a copper(I) salt. The adduct can be converted to a ketimine by anhydrous protonation, to a primary amine by reduction (Li/NH,), or to a ketone by hydrolysis. The actual reagent may be a cuprate such as R3Cu(MgX)2. 

Bromo-2-chloro-3-hexylthiophene (0.0355 mol) was added over a period of 30 minutes to a mixture consisting of 75 ml of 2-methyltetrahydrofuran, magnesium (0.0355 mol), and 0.15 ml of IM t-butylmagnesium chloride solution in THF at 60°C to 70°C. The mixture was stirred for 90 minutes at 70°C. It was then cooled to 60°C and treated with a suspension of l,2-bis(diphenylphosphino)ethane nickel(II) chloride (0.177 mmol) in 12.5 ml of 2-methyltetrahydrofuran for over 30 minutes. The mixture was stirred an additional 3 hours at 80°C and further treated with triethylphosphite (3 mmol) and stirred for 30 minutes at 80°C. The mixture was then concentrated and the residue dissolved in 10 ml of toluene. This solution was poured into 100 ml of EtOAc, which created a suspension, and the suspension was stirred for 30 minutes at 80°C. The cooled suspension was filtered, the residue washed twice with 20 ml of EtOAc, and the product isolated in 81% yield having a Mn of 19,543 daltons with a of 224°C. 

Reactions which have rale-determining FT have transition slates with charge development and should be accelerated in the more polar solvent THF. Since the various coordination equilibria existing in the reaction mixtures are seriously shifted, reactivity changes have to be carefully analysed. Although the FT reaction with azobenzene is accelerated in Till, the F.T reaction between t-butylmagnesium chloride and di-r-hulylperoxide is extremely slow in THF 1441... 

The two diastereoisomers of (134) can be readily resolved by column chromatography and react in THF with a 3 -0-acetylnucleoside in the presence of r-butylmagnesium chloride to give a dinucleoside methylphosphonate in about 65% yield with inversion of configuration (Scheme 22). When the reaction was repeated in pyridine a higher yield (- 80%) was obtained, but a considerable amount of epimerisation was observed. 

Yields of products obtained by electrochemical methods are comparable with those reported in the literature for similar alkylations of aromatic compounds in the presence of chemical oxidants. In spite of experimental difficulties, we have succeeded to alkylate dinitrobenzene. The reaction has to be carried out in THF (highly resistant medium) because DMF undergoes decomposition in the presence of butyl lithium. Use of butyl lithium provides higher yields of the target alkylation products, than butylmagnesium chloride. Also equivalent amounts of reactants, nitroarenes and organometallic reagents, have been found to be essential to provide the best yields of the reaction products. 

In a dry and argon-flushed flask, the respective transition metal catalyst (0.025 mmol) and the allylic diphenylphosphate 126 (194 mg, 0.50 mmol) are dissolved in THF (4 mL). The solution is cooled to -78 °C and -butylmagnesium chloride (1.0 mmol, 1 mL, 1 m in THF) is added dropwise. The reaction mixture is stirred for 1 h at -78 °C and then quenched with saturated aqueous NH4CI. Standard workup and purification by column chromatography (hexane) afford the above indicated mixtures of coupling products 127 and 128. The Sn2/Sn2 ratio is determined by GC analysis. ... 

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