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Although dimethyl sulfate is mostly known as a methylating agent, it can also act as a sulfonating agent. Sulfonation will occur either by slow release of SO3 by heating DMS or by attack at the sulfur end of the O-S bond.

Certain aromatic compounds that are highly reactive to electrophilic substitution can be sulfonated with DMS. Triphenylamine, diphenylmethylamine, anisole, and diphenyl ether give ring sulfonation on reaction with DMS at 150-190°C (302-374°F). Thallium (III) oxide or mercury (II) oxide catalyzes the DMS sulfonation of anthraquinone at 170°C (338°F).19 At 200°C (392°F) N-methyl-2-pyridones and related compounds sulfonate in the 5-position.20


Some pyrolysis reactions are catalyzed by the presence of dimethyl sulfate. An example is the formation of ketene from methyl acetate:21
Also, 1,3-dihydroxypropene ether and acrolein acetals are produced by heating 1,1,3-trihydroxypropane ethers at 200-450°C (392-842°F) in the presence of DMS.22

The alkylation of phenol with isobutylenes is promoted by the presence of catalytic amounts of DMS.23 DMS mixed with titanium or vanadium halides acts as catalyst for the low temperature polymerization of olefins.24 Telomers of ethylene and other polymerizable olefins are made by polymerization in the presence of DMS and a peroxide catalyst.25 Also, a combination of certain tertiary amines and DMS is reported to initiate vinyl polymerization.26

In some cases, the catalytic effect of DMS may be due to the slow release of sulfuric acid, either from hydrolysis or from heat. For example, DMS is a curing agent for furfuryl alcohol condensates, for which neutral DMS is considered a source of sulfuric acid when heated to 180°C (356°F).27


Some solvent uses of DMS have been reported. It has been used as a solvent in research on Lewis acid-aromatic hydrocarbon complexes.28 DMS has been used as an electrolyte in electroplating iron.29 It has served as an extraction solvent to separate phosphorus halide-hydrocarbon mixtures30 and aromatic hydrocarbons from aliphatics.31,32


Dimethyl sulfate is reported to be a stabilizer against thiophosphate and thiophosphonate insecticides. 33,34 Decomposition of DMS has been used with certain boron compounds to stabilize against polymerization of sulfur trioxide.35

It was reported that ground wood pulp has better brightness stability when the pulp is first treated with DMS before bleaching.36


As mentioned under "Catalyst," DMS can slowly release sulfuric acid. This property is useful in the separation of trivalent rare earths by a slow release into a solution of rare earth chelated with an ethylenediaminetetracetic acid and iodate anion. As the pH slowly decreases, each metal is released from the chelate in turn and precipitates as the iodate. The process yields better separations.37

A mixture of DMS and SO3 is thought to be dimethyl pyrosulfate. In reaction with chlorobenzene, 4,4-dichlorodiphenylsulfone is produced.38,39

19 Kirk-Othmer: Encyclopedia of Chemical Technology, 22, 3rd Edition, page 240, John Wiley & Sons, Inc. (1983).
20 German Pat. 597,452 (May 24, 1934) (to Chemische Fabrik von Heyden A.G.).
21 K.K. Georgieff, Can. J. Chem., 30, 322 (1952).
22 Brit. Pat. 695,789 (Aug. 19, 1953), R.H. Hall and E.S. Stern (to Distillers Co., Ltd.).
23 U.S. Pat. 3,116,366 (Dec. 31, 1963), J.L. Van Winkle (to Shell Oil Co.).
24 U.S. Pat. 3,389,128 (June 18, 1968), J.W. Bayer and W.C. Grinonneau (to Owens-Illinois, Inc.).
25 U.S. Pat. 2,478,390 (Aug. 9, 1949), W.E. Hanford and R.M. Joyce (to E.I. du Pont de Nemours & Co.).
26 T. Otsu and Y. Takemura, Bull. Chem. Soc. of Japan, 43, 567 (1970).
27 Ger. Pat. 911,659 (May 17, 1954), A. Scmidt (to Chemische Werke Huls A-G).
28 W.I. Aalbersbert et al., J. Chem. Soc., 3055 (1959).
29 V.Y. Tybkovskii, et al., Tr. Kishinev. S-Kh Inst., 123, 95 (1974); Chem. Abstr. 88, 80954 u (1978).
30 U.S. Pat. 2,801,957 (Aug. 6, 1957), G.C. Ray (to Phillips Petroleum Co.).
31 U.S. Pat. 2,776,327 (Jan. 1, 1957), A.W. Francis (to Socony Mobil Oil Co.).
32 P. Pascal and M.L. Quinet, Compt. rend., 211, 193 (1940); Chem. Abstr. 36 368 (5).
33 Brit. Pat. 937,762 (Sept. 25, 1963) (to Monsanto Chemical Co.).
34 U.S. Pat. 2,770,567 (Nov. 13, 1956), K. Wedemeyer et al. (to Farbenfabriken Bayer Aktiengesellschaft).
35 U.S. Pat. 3,160,474 (Dec. 8, 1964), W.G. Schnoor and A.W. Yodis (to Allied Chemical Corpage).
36 Can. Pat 810,571 (April 15, 1969), D.H. Andrews and R.P. Singh (to Canadian Industries Ltd.).
37 F.H. Firsching, et al., J Inorg. Nucl. Chem., 36, 1655 (1974).
38 U.S. Pat. 2,971,985 (Feb. 14, 1961), R. Joly, et al. (to UCLAF).
39 U.S. Pat. 3,335,497 (Nov. 28, 1967) E.G. Budnick (to Plains Chemical Development Co.).