Esters diethyl sulfate

Ethylisothiazolium salts 76 were prepared by N-alkylation of isothiazoles 74 with alkyl iodide, sulfonate esters, diethyl sulfate and triethyloxonium tetrafluoroborate. In Table 4 are given N-ethylated salts 76 (Scheme 21). 

Ethoxymethylene malonic acid diethyl ester Diethyl sulfate... 

The most successful of these products contain high ratios of VP to DMAEMA and are partially quatemized with diethyl sulfate (Polyquaternium 11) (142—144). They afford very hard, clear, lustrous, nonflaking films on the hair that are easily removed by shampooing. More recendy, copolymers with methyl vinyl imidazoliiim chloride (Polyquaternium 16) (145) or MAPTAC (methacrylamidopropyltrimethyl ammonium chloride) (Polyquaternium 28) have been introduced. Replacement of the ester group in DMAEMA with an amide analog as in Polyquaternium 28 results in a resin resistant to alkaline hydrolysis and hence greater utility in alkaline permanent-wave and bleach formulations (see Quaternary ammonium compounds). 

Various alkylating agents are used for the preparation of pyridazinyl alkyl sulfides. Methyl and ethyl iodides, dimethyl and diethyl sulfate, a-halo acids and esters, /3-halo acids and their derivatives, a-halo ketones, benzyl halides and substituted benzyl halides and other alkyl and heteroarylmethyl halides are most commonly used for this purpose. Another method is the addition of pyridazinethiones and pyridazinethiols to unsaturated compounds, such as 2,3(4//)-dihydropyran or 2,3(4//)-dihydrothiopyran, and to compounds with activated double bonds, such as acrylonitrile, acrylates and quinones. 

The starting material may be produced by reacting 6-amino-2-methylthiopyrimidine with ethoxymethylene malonic acid diethyl ester. The intermediate thus produced is converted by boiling in diphenyl ether to 6-ethoxycarbonyl-2-methylthio-5-oxo-5,B-dihydropyrido-[2,3-d]pyrimidine. That is hydrolyzed by sodium hydroxide to cleave the ethoxy group and then ethylated with diethyl sulfate to give the starting material. 

Ethyl thioglycolate and ethyl cyanoacetate are first reacted in the presence of sodium ethylate to give 4-oxo-thiazolidin-2-ylideneacetic acid ethyl ester. That is reacted with diethyl sulfate and then with piperidine to give piprozolin. 

Amino-2-methylthiopyrimidine Ethoxymethylenemalonic acid diethyl ester Sodium hydroxide Diethyl sulfate Pyrrolidine... 

Ethoxy-3-hydroxybenzaldehyde (isobourbonal) has been prepared in good yield (84%) by ethylation of 3,4-dihydroxybenzaldehyde [Benzaldehyde, 3,4-dihydroxy-] with diethyl sulfate [Sulfuric acid, diethyl ester] in dimethylformamide.2... 

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

Synonyms Diethyl monosulfate ethyl sulfate sulfuric acid diethyl ester diethyl tetraoxosulfate... 

Diethyl sulfate Highly toxic cancer suspect agent Sulfuric acid, diethyl ester (8,9) (64-67-5)... 

Phenanthridones and benzophenanthridones undergo ready alkylation on treatment with dialkyl sulfates in alkali.113, 126 As in the case of other, similar, ambident nucleophiles, V-alkylation normally predominates, although with diethyl sulfate 2-nitrophenanthridone gives a significant amount (27%) of 6-ethoxy-2-nitrophenanthri-dine,126 and, more recently, O-methylation has been observed in the reactions between both the methyl ester and the pyrrolidine amide of phenanthridone-4-carboxylic acid with methyl iodide in the presence... 

Diethyl phosphite Phosphonic acid, diethyl ester (762-04-9), 75, 22 Diethyl sulfate Sulfuric acid, diethyl ester (64-67-5), 77, 153 Diethyl tartrate, 76, 93 Diethylzinc Zinc, diethyl- (557-20-0), 76, 89... 

It was found in the early alkylation work that various olefin esters could be used in place of olefins to alkylate isobutane with a strong H2SO4 catalyst. It was also known that diethyl sulfate was an accepted ethylating agent in the chemical industry. 

Monoalkylation of malonic ester proceeds much more readily than alkylation of simple esters. The enolate is formed from diethyl malonate and alcoholic sodium ethoxide solution. Alkylation is effected in good yield by the use of primary bromides, diethyl sulfate, or ethyl p-toluene-sulfonate. In addition to the simpler primary alkylmalonates listed in Table 51, many higher members have been prepared. The list includes substituted malonates made from diethyl malonate and the following... 

Thus the reaction of sodium eugenoxide with various alkyl iodides in dry alcohol solution was shown to be in accord with second-order kinetics.1 The reaction of sodium ethoxide with optically active 2-bromo or 2-chlorooctane proceeded with complete inversion,2 and etherification of ethanol containing O18 with diethyl sulfate and alkali indicated that the ethyl group came from the sulfuric ester and that the alkoxide fragment was derived from the alcohol.8... 

The reagent is recommended as the base for alkylation of amines and for dehydro-halogenation (see Ethyidiisopropylamine). It has been used as proton acceptor in the reaction of carboxylic acids with phenacyl bromide in acetone to form the phenacyl esters. Unlike triethylamine, usually used for this purpose, the hydrochloride of the reagent is soluble in acetone and other water-miscible solvents. In the presence of ethyldicyclohexylamine, dimethyl and diethyl sulfate convert carboxylic acids into their esters in high yield. The commercially available hindered amine tris(2-hydroxypropyl)amine, [CH3CH(OH)CH2]sN, Eastman s 1,1, 1-nitrilotri-2-propanol, can be used but is somewhat less satisfactory. 

Grignard reaction, other examples n-Butyl borate (see Phenylboronic add). r-Butylhydro-peroxide. /-Butylperbenzoate. Dibromodifluoromethane. Diethyl sulfate. Ester synthesis (see 3-Dimethylaminopropylamine). Ethoxymethyleneaniline. Ethyl chloroformate. Ethylene dibromide (entrainment). Ethylene oxide. Ethyl formate. Ethynylmagnesium bromide. Sulfur. Triethyl orthoformate. Trimethylene oxide. See also Dichloroformoxime. 

Solvent effects [I, 279, after citation of ref. 14], Phenols and carboxylic acids are converted in high yield into the methyl ethers and methyl esters, respectively, by treatment with dimethyl sulfate and potassium carbonate in DMF solution. It is possible to esterify a carbonyl group selectively in the presence of a phenolic hydroxyl group. DMF is probably not involved as a reagent since the reaction with diethyl sulfate gives only the ethyl ether or ester.142... 

Esterification. Carboxylic acids can be converted into methyl esters in high yield with dimethyl sulfate in the presence of this base as the proton acceptor (10-20% excess amine).1 Ethyl esters can be prepared in the same way using diethyl sulfate. Dicyclohexylethylamine is equally elfective but is not available commercially. The method is simple and rapid and is useful when strongly acidic conditions must be avoided. 

Gasser described in 19S2 the acaricidal properties of the ethyl and isopropyl esters of 4,4 -dichlorobenzylic acid (6) and (7 respectively. The first was intr uced under the name chlorobenzilate, the latter under the name chloropropylate, as nonsystemic acaricides, mainly effective against adult mites. Chlorobenzilate is prepared by the alkylation of 4,4 -dichlorobenzylic acid with diethyl sulfate, while chloropropylate is obtained by esterification of the dichlorobenzylic acid with isopropanol (Haflinger, 1951). 

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