Methyl triethylammonium hydroxide

CONVERSION OF PRIMARY ALCOHOLS TO URETHANES via THE INNER SALT OF METHYL (CARBOXYSULFAMOYL)TRIETHYLAMMONIUM HYDROXIDE METHYL n-HEXYLCARBAMATE... 

The above procedure describes the only known preparation of the inner salt of methyl (carboxysulfamoyl)triethylammonium hydroxide and illustrates the use of this reagent to convert a primary alcohol to the corresponding urethane.2 Hydrolysis of the urethane would then provide the primary amine. The method is limited to primary alcohols secondary and tertiary alcohols are dehydrated to olefins under these conditions, often in synthetically useful yields.2... 

Methyl (carboxysulfamoyl)triethylammonium hydroxide, inner salt (Burgess reagent). 

On treatment with (carboxysulfamoyl)triethylammonium hydroxide inner salt methyl ester (Burgess reagent), the adducts of ketones yielded 1-vinylcyclopropyl selenides, but the adducts of aldehydes, e.g. 4, rearranged to cyclobut-1-enyl selenides.176... 

The internal salt (Me0-C0 N-S02-NEt3), derived from methyl(carboxy-sulphamoyl)triethylammonium hydroxide, is effective in dehydrating alcohols (36) to give olefins (38), in anhydrous benzene at room temperature. " The cis proton is eliminated, apparently through an ion-pair mechanism (37). Tertiary... 

Lithio-l-cyclopropyl selenides (128) react with aldehydes and ketones to give ) -hydroxycyclopropyl selenides (129) which undergo dehydration and C3 - C4 ring expansion upon treatment with (carboxysulphamoyl)triethylammonium hydroxide inner salt methyl ester (Me02CH S02N Et3) (equation... 

Burgess, E. M., Penton, H. R., Jr., Taylor, E. A., Williams, W. M. Conversion of primary alcohols to urethanes via the inner salt of methyl (carboxysulfamoyl)triethylammonium hydroxide methyl n-hexylcarbamate. Org. Synth. 1977, 56, 40-43. 

When 1-phenylsulfanylcyclopropanols 66 were treated with either p-toluenesulfonic acid under anhydrous conditions or the methyl ester of (carboxysulfamoyl)triethylammonium hydroxide, inner salt (Burgess reagent) high yields of 1-phenylsulfanylcyclobutenes 67 were obtained. ... 

The mechanism of dehydration of alcohols by hexamethylphosphortri-amide , phosphorus oxychloride and thionyl chloride in the presence of bases , and sulfur tetrafluoride have been studied. Kirk and Shaw have shown that it is unwise to assume a r/-stereospecificity in dehydration with phosphorus oxychloride or thionyl chloride with basic catalysts. The stereoselectivity is greatly dependent upon the basicity and steric environment of the base. Various steroidal alcohols undergo stereoselective iy -elimination upon treatment with methyl (carboxysulfamoyl) triethylammonium hydroxide inner salt . 

URETHANES Methyl (carboxysul-famoyl)triethylammonium hydroxide inner salt. 

Burgess reagent (methyl carboxysulfiimoyl triethylammonium hydroxide inner sah)... 

E-2-bromomethyleneglutaric esters (>70%) have been obtained from the corresponding 2-bromo-2-bromomethylglutarates using a 25% excess tetra-n-butyl-ammonium fluoride in HMPA [24], A similar procedure converts dimethyl 2-bromo-2-bromomethylsuccinate into dimethyl Z-2-bromomethylenefumarate [25], whereas methyl 2,2-bis(bromomethyl)ethanoate yields the 2-bromomethyl-propenoate when reacted with aqueous sodium hydroxide in the presence of benzyl-triethylammonium chloride [26]. No hydrolysis of the ester is evident at 0°C, but becomes apparent at 25 °C. 

Phase-transfer catalysis has been used to prepare toluene-p-sulphonates. When sulphonation at the anomeric position of 2,3.5,6-di-O-cyclohexylidene-D-manno-pyranose was attempted using toluene-p-sulphonyl chloride-benzene-butyl-triethylammonium chloride, the a-mannosyl chloride and the a,a-iinked manno-disaccharide were obtained in addition to the desired product. Selective sulphonation of benzyl (or methyl) 4-0-benzyl-0 -L-rhamnopyranoside with toluene-p-sulphonyl chloride-aqueous sodium hydroxide-dichloromethane gave 65% 2-O-toluene-p-sulphonate. ... 

---