Ethyl benzenesulfonate

A mixture of 58 g. (0.32 mole) of ethyl aminomalonate (p. 144), 50 ml. of pyridine, and 250 ml. of water is stirred while 48.5 g. (0.35 mole) of benzoyl chloride is added at such a rate that the temperature of the reaction mixture remains below 50°. The mixture is cooled to room temperature, and the white crystalline precipitate is collected by filtration and dried. The solid is recrystallized by dissolving in the minimum amount of hot benzene and slowly adding six times the volume of petroleum ether. There is obtained 92.4 g. (90%) of ethyl benzamidomalonate melting at 73-74°. 

A solution of 36 g. (0.2 mole) of benzenesulfonyl chloride in 100 ml. of dry pyridine is cooled to —8°, and 11.7 ml. (0.2 mole) of absolute ethanol (p. 142) is added slowly. The temperature is held in the range of —5 to —8° during the addition and for a total of 20-25 minutes. To the reaction mixture is added 250 ml. of 5 N sulfuric acid which has been cooled to 3°. The mixture is also cooled during this operation. The mixture is then extracted with chloroform, and 

---

Synthesis. Ethylation of morphine with ethyl benzenesulfonate (E. Merck, 1902 Ehrhart and Ruschig, 1972 Kleemann et al., 1999). 

Esters having two a-hydrogen atoms give poor yields of alkylated product partly because of their greater tendency for self-condensation to /3-keto esters (method 211). Ethyl isovalerate, however, has been ethylated in 33% yield by treatment with sodium triphenylmethide and ethyl benzenesulfonate. ... 

Esters of aliphatic and aromatic sulfonic acids are conveniently prepared in high yields from alcohols and sulfonyl halides. A basic medium is required. By substituting sodium butoxide for sodium hydroxide in butanol, the yield of n-butyl p-toluenesulfonate is increased from 54% to 98%. Ethyl benzenesulfonate and nuclear-substituted derivatives carrying bromo, methoxyl, and nirro groups are prepared from the corresponding sulfonyl chlorides by treatment with sodium ethoxide in absolute ethanol the yields are 74-81%. Pyridine is by far the most popular basic medium for this reaction. Alcohols (C -Cjj) react at 0-10° in 80-90% yields, and various phenols can be converted to aryl sulfonates in this base. "... 

CjHioOjS, Ethyl benzenesulfonate.. . . 145 CsHioS, 3-Phenylethyl mercaptan. 172 CsHiiClNaS, S-Benzylisothiuroiiium... 

The rates of solvolysis of cyclopropylcarbinyl derivatives are strongly enhanced. Thus, the ethanolysis of cyclopropylcarbinyl benzenesulfonate 488), Ar=Phenyl, is 500 times as fast as that of ethyl benzenesulfonate (4S9)383. The rate acceleration of 488), Ar=j3-Naphthyl, is 1220 in methanol, and 139000 in acetic acid384. Electron supply by the cyclopropyl group increases with increasing electron demand at the cationic center.The p+ value for the cyclopropyl derivatives 491), -2.78, is consider-... 

Ethyl ester. CsHl0O3S, ethyl benzenesulfonate. Colorless to slightly yellow, almost odorless liq. bpu 156°. d 1.219. Slightly sol in water misc with ale, benzene, chloroform, elher. 

TV-Alkylated heterocyclic compounds can be built up in one operation by treating diol bissulfonates with primary amines. For instance, 1-cyclohexyl-piperidine, b.p. 234°, is obtained in 81% yield from 1,5-pentanediol bis-(benzenesulfonate) and cyclohexylamine, and 4-benzylmorpholine, b.p. 79°/ 2 mm, from 2,2 -oxybis(ethyl benzenesulfonate) and benzylamine.852... 

The positive- and negative-ion mass spectra of ethyl benzenesulfonate have been reported48. In the positive-ion mode, the parent radical cation either eliminated ethyl radical and neutral S02 sequentially or rearranged with loss of S02, formally yielding the radical cation of phenol. In the negative-ion mode, the molecular anion underwent loss of C6H5 or C2HsO. 

Water-soluble organic compounds are selectively oxidized by aqueous solutions of platinum salts [22]. For example, p-toluenesulfonic acid undergoes stepwise hydroxylation to the corresponding alcohol and aldehyde while p-ethyl-benzenesulfonic acid is functionalized at both the benzylic and methyl positions. Ethanol affords a variety of products (about 50% of the substrate is converted into products) ... 

---