Methyl dichlorophosphate

Trimethylphosphate Dimethylcyanamide, vinyl sulfone Methyl dichlorophosphate N-methy Iformamide Methyl methanesulfonate Trimethylphosphite... 

Methyl dichlorophosphate added dropwise to anhydrous pyridine, after 15 min. j -cyanoethanol added, stirred 1 hr., a soln. of 5 -0-tritylthymidine in pyridine added, allowed to stand 16 hrs., then treated with water pyridinium 5 -0-tritylthymidine-3 jS-cyanoethyl phosphate. Y 83%. Also dinucieoside phosphates s. M. Rubinstein and A. Patdiomik, Tetrahedron 31, 2107 (1975) f. method cf. F. Ramirez, J. F. Marecek, and H. Okazaki, Am. Soc. 97, 7181 (1975). 

Methyl dichlorophosphate I pyridine Mixed phosphoric acid diesters One-flask process... 

The submitters, working on a kilogram scale without purification of reagent or solvent and with no precaution against moisture, obtained 6,7-dimethoxy-l-methyl-3,4-dihydroisoquinoline hydrochloride,2 m.p. 202-203°, instead of the dichlorophosphate at this stage. The checkers obtained this hydrochloride by either treating the free base with... 

Treatment with dimethyl sulfoxide in the presence of phenyl dichlorophosphate or phosphoryl chloride converts ( + )-a-pinene (39) to (6/ ,4.S)-4-isopropenyl-l-methyl-6-chlorocyclohexene (51) in virtually quantitative yield, presumably also via the cyclobutylmethyl to pent-l-enyl cation rearrangement.164 Similarly, / -pinene (45) is converted to 4-isopropenyl-l-chloromethylcyclohexene (52), also in quantitative yield.164... 

A practical synthesis of a-amido 3-lactams uses a Dane salt (9) formed by the reaction of a methan-olic solution of the potassium salt of glycine with methyl acetoacetate (Scheme 9). The salt (9) readily reacts with a Schiff base in the presence of triethylamine and e.g. a chloroformate ester. Other activating agents such as phenyl dichlorophosphate - or phosphorus oxychloride - have also been successfully used. 

Amino-substituted )S-lactams are accessible by reaction of furfiirylimine 767 with the Dane salt 770 in the presence of phenyl dichlorophosphate. The resulting cis-p-lactam 771 is formed with a diastereomeric excess of 91%. Compound 772 is converted to methyl ketone... 

Phosphorochlorendic acid diphenyl ester. See Diphenyl chlorophosphate Phosphorodichloridic acid, phenyl ester. See Phenyl dichlorophosphate Phosphorodithioic acid s-((t-butylthio) methyl)-0,0-diethyl ester. See Terbufos Phosphorodithioic acid, S-((6-chloro-2-oxo-3(2H)-benzoxazolyl) methyl) 0,0-diethyl ester. See Phosalone... 

Esterification.—iVAWW -Tetramethylchloroformamidinium chloride, which is readily prepared from iVAWW -tetramethylurea and oxalyl chloride, is an efficient reagent for the esterification of carboxylic acids with alcohols yields of between 66 and 97% are obtained, and the method has also been applied to macrolide synthesis. A modified one-pot procedure for the esterification of carboxylic acids, using phenyl dichlorophosphate-dimethylformamide complex, has appeared. A simple method of activation of carboxylic acids, using methanesulphonyl chloride and triethylamine followed by addition of the alcohol and 4-dimethylaminopyridine, leads to esters in 57— 96% yield for thirteen examples. 0-Methylcaprolactim reacts with carboxylic acids to give methyl esters in 73—91 % yield for seven examples and 2-iodoethyl esters are prepared from acyl chlorides, ethylene oxide, and sodium iodide. Transesterification, catalysed by titanium(iv) alkoxides, provides an effective method for synthesis of esters. Diethyl trichloromethylphosphonate reacts with carboxylic acids to give ethyl esters via transesterification, in 52 to 98 % yield. ... 

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