Methyl magnesium chloride

Iododesilylation, 41 of aryltrimethylsilanes, 42 Iodomethyltrimethylsilane, 27 4-Iodophenylalanine, 42 Ionic hydrogenation, 136 Ireland-Claisen rearrangement, 112-14 ftwtf-2 Isocyanocyclohexanol, 137 Isophorone, 52 Isophorone dienol ether, 135 (Isopropoxydimethylsilyl)methyl magnesium chloride, 58... 

C11H14O2, Mr 178.23, exists in cis (mp 35-36 °C) and in Irans mp 86°C) forms. The trans isomer has a sweet vanilla-like odor. Propenylguethol can be prepared from isosafrole by reaction with methyl magnesium chloride or by ethylation of isoeugenol followed by selective demethylation with alkali [169]. 

To a solution of 4.2 gm (0.0276 mole) of JV-methyl-A -phenyldiimide dioxide in 50 ml of anhydrous ether is added 185 ml of a 0.21 N solution of methyl magnesium chloride in anhydrous ether (0.0389 mole) over a 3 hr period while maintaining the reaction mixture at 20°C. Then the reaction mixture is cautiously heated with 100 ml of a saturated aqueous solution of ammonium sulfate. At this point 37 mg of an unidentified deep-red solid (m.p. 126°-127C C dec.) after recrystallization, m.p. 140.5°C dec., separates. This material is removed by filtration and discarded. 

Chen, Y. Wang, T. Helmy, R. Zhou, G.X. etal., Concentration determination of methyl magnesium chloride and other Grignard reagents by potentiometric titration with in-line characterization of reaction species by FTIR spectroscopy /. Pharm. Biomed. Anal. 2002, 29, 393 04. 

Chlorobutanoyl chloride Phosphorus tribromide Methyl magnesium chloride ALIQUAT (phase transfer catalyst) Phosphorus oxychloride Benzoyl chloride... 

Methyl 2-(2-iodophenyl)propanoate Tetrabutylammonium chloride Diethyl 1,1-cyclopropanedicarboxylate Vinyl magnesium bromide Methyl magnesium chloride Borane-tetrahydrofuran complex Diisopropylethylamine Methanesulfonyl chloride... 

Methyl magnesium chloride (3.0 Molar solution in THF, 790 mmol) was added dropwise over 30 min to the CeCI3 slurry at 0°C. After stirring 2 hours, the mixture was cooled to -5°C and a toluene (600 mL) solution of the ethyl 2-(3(S)-(3-(2-(7-chloro-2-quinolinyl)ethenyl)phenyl)-3-hydroxy-propyl)benzoate (152 mmol) was added dropwise over 1 hour. The reaction mixture was stirred another hour before the addition of 2 M HOAc (600 mL) and toluene (600 mL). The organic layer was washed with saturated aq. NaHC03 and with brine. Concentration in vacuo and purification of the residue by flash chromatography (30% EtOAc in toluene) gave 63.48 g (91%) of the 2-(2-(3(S)-(3-(2-(7-chloro-2-quinolinyl)ethenyl)phenyl)-3-hydroxypropyl)phenyl)-2-propanol. 

Fiirstner and coworkers revealed a competition between the Brook rearrangment and the Peterson olefination. The adducts of aroylsilanes 161 with (trimethylsilyl)methyl-magnesium chloride 162 underwent a Brook rearrangement and then a Peterson elimination affording vinylsilane 163 (equation 98). On the other hand, the reaction of cycloalkylcarbonylsilane 164 with 162 gave vinylsilane 165 via the direct Peterson elimination (equation 99)228. 

Commercially available organometallics methyllithium (MeLi) methyl magnesium chloride, bromide, and iodide (MeMgX)... 

Reaction of the enone with methyl magnesium chloride gave rise to the tertiary alcohol 127 (which is a double racemate). 

Methyl magnesium chloride (3 M) in THF was added to copper(I) bromide-dimethyl sulphide dissolved in 45 ml THF at — 20°C and after 20 minutes treated dropwise with the Step 1 product (0.014 mol) dissolved in 20 ml THF over 10 minutes. The mixture was stirred 2.5 hours and then quenched with saturated NH4C1 solution. The layers were separated and the aqueous portion extracted with diethyl ether. The combined organic phases were washed with 1M HC1, 5% aqueous NH4OH, dried with MgS04, concentrated, and the product isolated in 88% yield as a white solid. 

V- Methyl magnesium chloride, dodecylbenzene sulfonic acid, THF... 

The product from Step 4 (0.9 grams) was dissolved in 20 ml THF, cooled in a dry ice/acetone bath, 9 ml 1M methyl magnesium chloride added drop wise over 15 minutes, and the mixture stirred for 2 hours and at 0°C. Once warmed to ambient temperature, it was poured into a 50 ml ice water mixture, 20 ml diethyl ether added, and the layers separated. The aqueous layer was extracted twice with 20 ml diethyl ether, the organic portions combined, and concentrated. The residue was dissolved in 50 ml toluene containing 2 drops of dodecylbenzene sulfonic acid, refluxed 2 hours, cooled, and 0.73 g product isolated. 

The Petasis reagent, dimethyl titanocene (4.93) can also be used for the methylenation of carbonyl compounds. The Petasis reagent (4.93) is prepared by the reaction of methyl magnesium chloride or methyllithium with titanocene dichloride (Cp2TiCl2). Carbonyl compounds on heating with 4.93 at 60-65° C in a toluene solution give the corresponding alkenes or enol ethers. 

The reaction vessel used in the preparation of methyl-magnesium chloride is a 2-1. round-bottomed flask with a 30-cm.-long 20-mm.-o.d. glass column sealed to its bottom. The flask is fitted with a two-hole rubber stopper which bears 6-mm. glass inlet and outlet tubes for the methyl chloride gas. The inlet tube extends to the bottom of the glass column, and the outlet tube is fitted with a silica gel drying tube to prevent moisture from entering the system. 

The first alkyl derivative, the Tr-allylmethylnickel, IX, was prepared by treating TT-allylnickel bromide with methyl magnesium chloride at —100°C. (3, 4). TT-Allylmethylnickel, the first transition metal compound having a TT-allyl and a a-alkyl group as ligands, is a violet crystalline compound stable only below — 80°C. 

The synthesis of terminal alkenes entails addition of either (trimethylsilyl)methyl-magnesium chloride (Me3SiCH2MgCl) or (trimethylsilyl)methyllithium (Me3SiCH2Li) to an aldehyde or a ketone to yield the corresponding P-hydroxysilane, which undergoes base- or acid-mediated elimination to furnish the alkene, as exemplified below. " ... 

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