Magnesium methyl carbonate preparation

Cyclohexanone added to magnesium methyl carbonate prepared from Mg, methanol, and COg in dimethylformamide (cf. Synth. Meth. 14, 709), refluxed 2 hrs. under Ng, treated at ca. 0° with satd. methanolic HCl, and allowed to stand overnight at room temp. dimethyl cyclohexanone-2,6-dicarboxylate. Y 44-45%. S. N. and M. Balasubrahmanyan, Org. Synth. 49, 56 (1969). 

Other Reactions. a-Nitroalkanoic acids or thek esters can be prepared (54—56) by treating nitroparaffins with magnesium methyl carbonate, or with triisopropylaluminum and carbon dioxide. These products are reduced readily to a-amino acids. 

The carboxylation of nitroalkanes with magnesium methyl carbonate followed by esterification gives a-nitro esters in 40-58% yield.14 Magnesium methyl carbonate is prepared by the saturation of a magnesium methoxide suspension in DMF with C02. More elegantly, sodium salt of nitroalkanes can he carboxylated by means of 1 -ethoxycarbonylbenzotriazole to give a-nitro esters in 55-80% yield (Eq. 5.7).15 Nitroacetic acids and its esters can serve as useful... 

Alkylation of 2,4-disubstituted-5(477)-oxazolones can be conveniently performed via phase-transfer catalysis. For example, the substrate and an alkyl halide are dissolved in an organic solvent and stirred with an aqueous sodium carbonate solution containing tetrabutylammonium bromide as a phase-transfer catalyst. 4,4-(Diarylmethyl)-2-phenyl-5(4/f)-oxazolones can be prepared in one-step by dialkylation of 146 using magnesium methyl carbonate and the corresponding... 

The magnesium etiolate is prepared from 2.1 equivalents of potassium ethyl malonate (16) by treatment w ith 2.0 equivalents of alkyl Grignard (usually methyl or ethyl since these are commercially available). The resulting dianion, shown in Scheme 6.4 as 17. has strong nuclcophilicity at the carbon. 

A new preparative method for allenes has appeared (Scheme 4). Several alk-2-ynyl carbonates (prepared by nucleophilic addition of magnesium and lithium acetylides to ketones or aldehydes followed by quenching with methyl chloroformate) were selectively hydrogenolysed with ammomium formate under palladium catalysis to give allenes in good yields. 

Methyl p-toluenesulphonate. This, and other alkyl esters, may be prepared in a somewhat similar manner to the n-butyl ester with good results. Use 500 g. (632 ml.) of methyl alcohol contained in a 1 litre three-necked or bolt-head flask. Add 500 g. of powdered pure p-toluene-sulphonyl chloride with mechanical stirring. Add from a separatory funnel 420 g. of 25 per cent, sodium hydroxide solution drop by drop maintain the temperature of the mixture at 23-27°. When all the alkali has been introduced, test the mixture with litmus if it is not alkaline, add more alkali until the mixture is neutral. Allow to stand for several hours the lower layer is the eater and the upper one consists of alcohol. Separate the ester, wash it with water, then with 4 per cent, sodium carbonate solution and finally with water. Dry over a little anhydrous magnesium sulphate, and distil under reduced pressure. Collect the methyl p-toluenesulphonate at 161°/10 mm. this solidifies on cooling and melts at 28°. The yield is 440 g. 

The properties of 1,1-dichloroethane are Hsted ia Table 1. 1,1-Dichloroethane decomposes at 356—453°C by a homogeneous first-order dehydrochlofination, giving vinyl chloride and hydrogen chloride (1,2). Dehydrochlofination can also occur on activated alumina (3,4), magnesium sulfate, or potassium carbonate (5). Dehydrochlofination ia the presence of anhydrous aluminum chloride (6) proceeds readily. The 48-h accelerated oxidation test with 1,1-dichloroethane at reflux temperatures gives a 0.025% yield of hydrogen chloride as compared to 0.4% HCl for trichloroethylene and 0.6% HCl for tetrachloroethylene. Reaction with an amine gives low yields of chloride ion and the dimer 2,3-dichlorobutane, CH CHCICHCICH. 2-Methyl-l,3-dioxaindan [14046-39-0] can be prepared by a reaction of catechol [120-80-9] with 1,1-dichloroethane (7). 

Preparation of 9a-Fluoro-110,17a,21-Trihydroxy-160-Methyl-4-Pregnene-3,2O-Dione 21-Acetate To a solution of 200 mg of 9(3,11(3-epoxy-1 7a,21-dihydroxy-16(3-methyl-4-pregnene 3,20-dione 21-acetate in 2 ml of chloroform and 2 ml of tetrahydrofuran in a polyethylene bottle at -60°C was added 2 ml of a 2 1 (by weight) mixture of anhydrous hydrogen fluoride and tetrahydrofuran. After 4 hours at -10°C the mixture was cooled to -60°C and cautiously added to a stirred mixture of 30 ml or 25% aqueous potassium carbonate and 25 ml of chloroform kept at -5°C. The aqueous phase was further extracted with chloroform and the latter phase washed with water and dried over magnesium sulfate. The residue on crystallization from acetone-ether gave pure 9a-fluoro-11(3,17a,21-trihydroxy-16(3-methyl-4-pregnene-3,20-dione 21-acetate. 

The stereospecific conversion of menthyl arenesulphinates into chiral aryl methyl sulphoxides may also be achieved by means of methyllithium . The reaction of methyllithium with diastereoisomerically or enantiomerically pure arenesulph-inamides 283 was found to give optically active aryl methyl sulphoxides 284 (equation 156). The preparation of optically active sulphoxides 285 and 286, which are chiral by virtue of isotopic substitution (H - D and - respectively), involves the reaction of the appropriate non-labelled menthyl sulphinates with fully deuteriated methyl magnesium iodide (equation 157) and with benzylmagnesium chloride prepared from benzyl chloride labelled with carbon (equation 158). 

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