Magnesium,chloro methyl

Trimethylsilylmethylmagnesium chloride Magnesium, [chloro[(trimethylsilyl)methyl -(8,9) (13170-43-9)... 

Boron trifluoride etherate Ethyl ether, compd. with boron fluoride (1 1) (8) Ethane, 1,1 -oxybis-, compd. with trifluoroborane (1 1) (9) (109-63-7) (Trimethylsilyl)methylmagnesium chloride Magnesium, chloro[(trimethylsilyi)methyl]-... 

Metalation. Benzene reacts with alkaH metal derivatives such as methyl or ethyUithium ia hydrocarbon solvents to produce phenyUithium [591 -51 -5], CgH Li, and methane or ethane. Chloro-, bromo-, or iodobenzene will react with magnesium metal ia ethereal solvents to produce phenyHnagnesium chloride [100-59-4], C H MgCl, bromide, oriodide (Grignard reagents) (32). 

A mixture of 3.4 parts of 7-chloro-4-fluorobutyrophenone, 4 parts of 1-(4-piperidyl)-2-benzimidazolinone hydrochloride, 6 parts of sodium carbonate and 0.1 part of potassium iodide in 176 parts of 4-methyl-2-pentanone is stirred and refluxed for 48 hours. The reaction mixture is cooled and 120 parts of water is added. The separated organic layer is dried over magnesium sulfate and the solvent is evaporated to leave an oily residue which is dissolved in dilute hydrochloric acid and boiled. The acidic solution is filtered and cooled at room temperature whereupon there crystallizes from solution l-<1-[ y-(4-fluorobenzoyl)-propyl]-4-piperidvl>-2-benzimidazolinone hydrochloride hydrate melting at about 134°-142°C. 

The residue was dissolved in 75 ml of tetrahydrofuran, treated with charcoal, and sodium sulfate and filtered. This solution was added to a solution in 250 ml of tetrahydrofuran of phenyl magnesium bromide prepared from 17.7 ml (0.17 mol) of bromobenzene. This mixture was stirred and heated under reflux for 1 hour. It was then cooled and diluted with 400 ml of ether and sufficient 3N hydrochloric acid to make it acidic. The aqueous phase was separated, adjusted to pH 8 with 3N sodium hydroxide and extracted 3 times with 200 ml of ether. The ether extracts were combined, washed with water and dried over sodium sulfate. The residue left on removal of the ether in vacuo was crystallized from petroleum ether to give 3.3 g of 7-chloro-2,3-dihvdro-1-methyl-5-phenvl-1 H-1,4-benzodiazepine, according to U.S. Patent 3,624,703. 

Preparation of Intermediate Compound 4-Chloro-5-Sulfamyl-N-Acetylanthranilic Acid To a hot solution (80°C) of 366 g (1.482 mols) of magnesium sulfate (Epsom salts) in 2.8 liters of water was added 130 g (0.495 mol) of powdered 5-chloro-2-methyl-4-sulfamyl-acetanilide. With stirring and maintaining the temperature at 83°C, 234 g (1.482 mols) of potassium permanganate was added portionwise over a period of 2 hours. The mixture was then kept at 85°C with stirring for an additional 3 hours. By this time the pink color of the permanganate had been discharged. 

A synthetically useful diastereoselectivity (90% dc) was observed with the addition of methyl-magnesium bromide to a-epoxy aldehyde 25 in the presence of titanium(IV) chloride60. After treatment of the crude product with sodium hydride, the yy -epoxy alcohol 26 was obtained in 40% yield. The yyn-product corresponds to a chelation-controlled attack of 25 by the nucleophile. Isolation of compound 28, however, reveals that the addition reaction proceeds via a regioselective ring-opening of the epoxide, which affords the titanium-complexed chloro-hydrin 27. Chelation-controlled attack of 27 by the nucleophile leads to the -syn-diastereomer 28, which is converted to the epoxy alcohol 26 by treatment with sodium hydride. 

Tributyl(3-methyl-2-butenyl)tin was prepared according to the preceding procedure from 1-chloro-3-methyl-2-butene, tributyltin chloride, and magnesium. 

Interestingly, even methyl 2-bromo- or 2-chloro-2-cyclopropylideneacetate reacts cleanly with various Grignard reagents in a 1,4-addition without any chlorine-metal exchange side reactions (equation 35). These in situ generated magnesium enolates are particularly reactive with aromatic aldehydes . 

Hydroxy-4-methyl-4-penten-2-one (1) was prepared from 3-chloro-mesityl oxide using a modified procedure from the literature [ref.4], A reference sample of 4-methyl-4-penten-2,3-dione (2) was prepared from using the copper acetate method [ref.2], 4-methyl-pentan-2,3-dione (3) was purchased from Wiley Co. 2-Hydroxy-4-methyl-4-penten-3-one (4) was synthesized in 30% yield from 2-propenyl-magnesium bromide and 2-hydroxy-propionitrile in tetrahydrofurane. The structures of all compounds were confirmed by H-. C-NMR- and mass spectroscopy [ref. 5],... 

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