Methane esters

Hydroxy-phenyl-methan- -diphenylester XII/1, 477 aus Phosphorigsaure-chlorid-diphenylester, Benzaldehyd und Eissessig XII/1, 496 Hydroxy-phenyl-methan- -dipropylester XII/1, 478 Hydroxy-phenyl-methan- -ester E2, 318 1-Hydroxy-3-phenyl-2-propen- -dimethvlester XII/I, 480... 

Docusate Calcium. Dioctyl calcium sulfosuccinate [128-49-4] (calcium salt of l,4-bis(2-ethylhexyl)ester butanedioic acid) (11) is a white amorphous soHd having the characteristic odor of octyl alcohol. It is very slightly soluble in water, and very soluble in alcohol, polyethylene glycol 400, and com oil. It may be prepared directly from dioctyl sodium sulfo succinate dissolved in 2-propanol, by reaction with a methan olic solution of calcium chloride. 

Carbanioas derived from the other above mentioned methane derivatives react with alkylboranes, bornic, and boronic esters, providing rich possibihties for the preparation of siagle-carbon iasertion products. Thus 2-aLkyl-l,3,2-dithiaborolanes are converted iato acids or thioacetals by trichloromethyllithium (335). 

On dehydration, nitro alcohols yield nitro-olefins. The ester of the nitro alcohol is treated with caustic or is refluxed with a reagent, eg, phthaUc anhydride or phosphoms pentoxide. A mil der method involves the use of methane sulfonyl chloride to transform the hydroxyl into a better leaving group. Yields up to 80% after a reaction time of 15 min at 0°C have been reported (5). In aqueous solution, nitro alcohols decompose at pH 7.0 with the formation of formaldehyde. One mole of formaldehyde is released per mole of monohydric nitro alcohol, and two moles of formaldehyde are released by the nitrodiols. However, 2-hydroxymethyl-2-nitro-l,3-propanediol gives only two moles of formaldehyde instead of the expected three moles. The rate of release of formaldehyde increases with the pH or the temperature or both. 

An aiyl methane- or toluenesulfonate ester is stable to reduction with lithium aluminum hydride, to the acidic conditions used for nitration of an aromatic ring (HNO3/HOAC), and to the high temperatures (200-250°) of an Ullman reaction. Aiyl sulfonate esters, formed by reaction of a phenol with a sulfonyl chloride in pyridine or aqueous sodium hydroxide, are cleaved by warming in aqueous sodium hydroxide. ... 

Other methods for the preparation of cyclohexanecarboxaldehyde include the catalytic hydrogenation of 3-cyclohexene-1-carboxaldehyde, available from the Diels-Alder reaction of butadiene and acrolein, the reduction of cyclohexanecarbonyl chloride by lithium tri-tcrt-butoxy-aluminum hydride,the reduction of iV,A -dimethylcyclohexane-carboxamide with lithium diethoxyaluminum hydride, and the oxidation of the methane-sulfonate of cyclohexylmethanol with dimethyl sulfoxide. The hydrolysis, with simultaneous decarboxylation and rearrangement, of glycidic esters derived from cyclohexanone gives cyclohexanecarboxaldehyde. 

The benzyloxycarbonyl-L-proline thus obtained (180 g) is dissolved in a mixture of dichloro-methane (300 ml), liquid isobutylene (800 ml) and concentrated sulfuric acid (7.2 ml). The solution is shaken in a pressure bottle for 72 hours. The pressure is released, the Isobutylene is allowed to evaporate and the solution is washed with 5% sodium carbonate, water, dried over magnesium sulfate and concentrated to dryness in vacuo, to obtain benzyloxycarbonyl-L-proline tert-butyl ester, yield 205 g. 

Ben2yloxyindolyl-3)-Q -acetvlamino-Q -methylthiopropionic acid methane-thiol ester Hydrogen Sulfuric acid... 

A solution of 27.6 g (0.16 mol) of freshly distilled ethyl 7-aminoheptanoate in 40 ml of nitro-methane was added all at once and with mechanical stirring to a suspension of 26.2 g (0.08 mol) of 5,8-dichloro-10-dioxo-11 -methyldibenzo[c,f] thiazepined, 2) in 1 20 ml of nitro-methane. The whole was heated to 55°C for 30 minutes, the solvent was then evaporated in vacuo and the residue was taken up in water. The crude ester was extracted with ether. After evaporation of the ether 36 g of crude ester were obtained, and 30 g (0.065 mol) thereof were treated under reflux with a solution of 2.8 g (0.07 mol) of sodium hydroxide in 75 ml of eth-... 

The only other esterification method which rivals the present procedure in convenience, mildness of conditions, selectivity, and yield js the preparation of methyl esters wdth diazomethane [Methane, diazo-] 10 Esterification with trialkyloxonium salts, however, allows... 

Diazomethane [Methane, diazo-], 62 Diethyl sulfate [Sulfuric acid, diethyl ester], 48... 

Mesitylene [Benzene, 1,3,5-tnmethyl-], 86 Z Met Gly Gly OEt [Gly cine,V-[Ar-[A-[(phenylmethoxy)carbonyl] -L-methionyl] glycyl] -, ethyl ester], 9 3 Methane, iodo-, hazard note 127 Methyl chlonde polystyrene [Benzene, diethenyl-, polymer with ethenyl-benzene, chloromcthylatcd], 96 Methyl iodide [Methane, iodo-], 79 Methyl mercaptan [Methanethiol], 73 Moffat oxidation, 99... 

Malonic acid, amino-, diethyl ester, HYDROCHLORIDE, 40, 24 Malonic acid, bts(hydroxymethyl)-, DIETHYL ETHER, 40, 27 Malonitrile, condensation with tetra-cyanoethylene, 41, 99 2-Mercaptopyrimidine, 43, 6S hydrochloride of, 43, 68 Mercuric oxide in preparation of bromo-cyclopropane, 43, 9 Mesityl isocyanide, 41,103 5-Methallyl-l,2,3,4,5-pentachlorocyclo-pentadiene, 43, 92 Methane, dimesityl-, 43, 57 Methanesiileinyl chloride, 40, 62 Methanesulfonic acid, solvent for making peroxybenzoic acid from benzoic acid, 43, 93... 

HydTOX5 proline-derived polyesters are usually readily soluble in a variety of organic solvents (benzene, toluene, chloroform, dichloro-methane, carbon tetrachloride, tetrahydrofuran, dimethylformamide, etc.) As expected, the solubility in hydrophobic solvents increased with increasing chain length of the N protecting group, while the solubility in polar solvents decreased. For example, poly(N-hexanoyl-hydroxyproline ester) is slightly soluble in ether but easily soluble in acetonitrile, while poly(N-palmitoylhydroxyproline ester) is readily soluble in ether but virtually insoluble in acetonitrile. 

Nitrene addition to alkenes can be aided by the nse of a transition metal, such as copper, rhodium, ruthenium, iron, cobalt, etc. NHC-Cu catalysts have been used in nitrene addition. For example [Cu(DBM)(IPr)] 147 (DBM = dibenzoyl-methane) was successfully employed in the aziridination of aliphatic alkenes 144 in presence of trichloroethylsulfamate ester 145 and iodosobenzene 146 (Scheme 5.38) [43]. 

Early work by Strassner and co-workers showed that the chelating bis-NHC Pd complexes 32a and 32c were capable of promoting the oxidation of methane, whilst the iodo-analogues 32b and 32d were inactive under the same reaction condition [45], Indeed, in a mixture of TEA and TFAA, in the presence of potassium peroxodisulfate under 20-30 bar of methane, trifluoroactic acid methyl ester is produced, using 32a or 32c as catalyst (Scheme 10.14). hi a more recent work, the authors disclosed the use of pyrimidine-NHC Pd complexes for the same reaction. A shghtly better catalytic activity was obtained with the unexpected cationic complex 34 [46],... 

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