1- 2- methylmagnesium chloride

Fig. 2. Preparation of 1,1-diphenylethanol from methylmagnesium chloride and ben2ophenone, phenylmagnesium chloride and acetophenone, or...

What effect does the solvent have on the structure, charges and reactivity of Grignards Compare geometries, atomic charges and electrostatic potential maps of the diethyl ether complex to that of methylmagnesium chloride itself. How does solvent-magnesium bond formation affect the reactivity of the methyl group Explain. 

Electrostatic potential map for methylmagnesium chloride-diethyl ether complex shows negatively-charged regions (in red) and positively-charged regions (in blue). 

Only a single example is as yet known of an organomagnesium compound involving the side chain, namely (3,5 dimethylisoxazol-4-yl)methylmagnesium chloride. ... 

Methyllithium, electrostatic potential map of, 37, 143 polar covalent bond in. 37 Methylmagnesium chloride,... 

Methylmagnesium chloride has been added to various d-(4-substituted-phenyl) <5-oxo esters 15 (X = H, Cl 13, F, Cl, Br, OC11,) which provides the diastereomeric -lactones 1642. The electronic properties of the phenyl 4-substituent have no significant influence on the diastereoselectivity. Except for the 4-methoxyphenyl compound, which is unreactive even at 60 °C, a ratio of ca. 40 60 in favor of the anti-Cram product is observed at 60 "C in tetrahydrofuran as reaction solvent. Lowering the reaction temperature to 0 °C slightly increases the anti-Cram selectivity in the case of the 4-fluoro-, 4-chloro-, and 4-bromo-substituted compounds. On the other hand, a complete loss of reactivity is observed with the <5-phenyl- and <5-(4-methylphenyl)-substituted h-oxo esters. 

The monolithium salt of 4-hydroxy-4-(phenylethynyl)-2.5-cyclohexadienone (12), prepared in situ by the addition of lithium acetylide to /7-benzoquinone, was treated with methylmagnesium chloride in l HF-TMEDA or in THF —DMPU. The syn-, 4-addition adduct 13, derived from intramolecular delivery of the carbon nucleophile by the hydroxy oxygen, as well as the <7s-1,4-diol 14, obtained via intermolecular 1,2-addition, were obtained in varying amounts depending on the conditions. The selectivity on 1,4- to 1,2-addition increased by the addition of cation chelating agents such as DMPU, TMEDA, and 15-crown-5. Although the 1,4 to 1,2... 

The difference in stereochemical outcome between methylmagnesium iodide and methylmagnesium chloride has been attributed to the formation of dimethylmagnesium by the former reagent at low temperature9- 0. 

The enantiomeric purity of the ( + )-(/J)-adduct was increased by using lithium tetramethylalu-minate (90% ee), triisopropoxy(methyl)titanium (91 % ee) or methylmagnesium chloride (98-100 % ee, 93 % yield). 

Such methodology can be seen in the construction of the nucleophilic hydroxymethylating reagents (isopropoxydimethylsilyl)methylmagnesium chloride (1) (8) and (allyldimethylsilyl)methylmagnesium chloride (2) (4) ... 

Note. The related reagent (diisopropoxymethylsilyl)methylmagnesium chloride (9) has been used similarly to hydroxymethylate organic halides and mesylates. 

Allenyl Silyl enol ethers, 86 Allyl alcohol trimethylsilyl ether, 84 Allyl carbonates, 114-15 9 Allyl-ay 2 octalone, 34-5 2-Allyl-2 methylcyclohexanone, 106 (Allyldimethylsilyl)methyl chloride, 58, 59 (AUyldimethylsilyl)methylmagnesium chloride, 59... 

After stirring at room temperature for 1 hour, methylmagnesium chloride (1.0 M THF solution, 112mL) was added at 0°C over 30 minutes. The reaction mixture was stirred at room temperature for 1 hour. To this solution, borane-THF complex (1.0 M, 70 mL) was added at 0 °C, and the mixture was stirred at the same temperature for 1 hour. 

Methyl isovalerate, azeotropic mixtures with butyl alcohols, 4 395t Methyl ketones, acetic anhydride used in synthesis, 1 148 Methyllithium, 14 249 15 147 Methylmagnesium chloride, 16 319 (R)-(—)-Methylmandelic acid chloride, chiral derivatizing reagent, 6 76t Methyl mercaptan production, 15 17 3-Methylmercaptopropionaldehyde (MMP), intermediate in methionine synthesis, 1 268, 269, 276... 

Methylmagnesium chloride can react with 2,3-allenamide 553 to give the /3-methyl-/3,y-unsaturated enamide 554 [256]. 

When using methyllithium instead of methylmagnesium chloride for the alkylation of 12, the product is obtained in good yield (70%) however the dia-stereoselective ratio drops to 5 1 in favour of alcohol 13. 

Methyltrichlorosilane is produced by the Grignard reaction of silicon tetrachloride and methylmagnesium chloride (structure 17.24). Dimethyldichlorosilane, used in the synthesis of polydimethylsiloxane, is obtained by the reaction of methylmagnesium chloride and methyltrichlorosilane (structure 17.25). 

Clemastine Clemastine, 2-[2-[l-(4-chlorophenyl)-l-phenylethoxy]ethyl]-l-methylpyrroli-dine (16.1.4), is synthesized by reacting l-(4-chlorophenyl)-l-phenylethanol (16.1.3) with 2-(2-chlorethyl)-2-methylpyrrolidine using sodium amide as a base. The starting l-(4-chlorophenyl)-l-phenylethanol (16.1.3) is synthesized either by reacting 4-chloroben-zophenone with methylmagnesium chloride, or by reacting 4-chloroacetophenone with phenylmagnesium bromide [6-8]. 

Methylmagnesium chloride Magnesium, chloromethyl- (8, 9) (676-58-4) Chloromethyltitanocene Titanium, chlorodi-Ti-cyclopentadienylmethyl- (8) Titanium, Chlorobis(Ti -2,4-cyclopentadien-1-yl)methyl- (9) (1278-83-7)... 

Methylmagnesium chloride in tetrahydrofuran was purchased from Aldrich Chemical Company, Inc. 

With unsubstituted 5-iodouracil 336, a trimagnesiated species 337 can be formed by sequential treatment with methylmagnesium chloride and isopropylmagnesium chloride, and reaction with various electrophiles then selectively gives 5-functionalized uracil derivatives 338 <20070L1639>. The same procedure was also successfully applied to the functionalization of 6-iodouracils, including the synthesis of Emivirine and l-[(2-hydroxyethoxy)methyl]-6-(phenylthio)thymine (ElEPT) precursors <20070L1639>. 

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