Organic compounds -- part of the class 532-570 series – Organic compounds – Sulfur halides
Patent
1992-09-02
1995-07-25
Geist, Gary
Organic compounds -- part of the class 532-570 series
Organic compounds
Sulfur halides
562830, C07C30308, C07C30312, C07C30986
Patent
active
054363705
DESCRIPTION:
BRIEF SUMMARY
The invention relates to an improved process for the preparation of 3-nitrobenzenesulfonyl chloride in high yields by reaction of nitrobenzene with chlorosulfonic acid and subsequent action of an inorganic acid chloride.
3-nitrobenzenesulfonyl chloride is an important precursor, in particular for the preparation of dyes.
It is known (BIOS Final Report No. 1153, p. 38) that 3-nitrobenzenesulfonyl chloride can be prepared by sulfochlorination of nitrobenzene at temperatures of 60.degree. C.-105.degree. C. In this process, the nitrobenzene is added to 4 mol of chlorosulfonic acid, the temperature slowly rising to 60.degree. C. After addition is complete, the reaction mixture is slowly heated to 70.degree. C. and then up to 105.degree. C. and finally kept several hours at 105.degree. C. The yield in this process was given as 79% of theory, which is insufficient for a large-scale process. It is further known (C. M. Suter, "The Organic Chemistry of Sulfur", John Wiley & Sons Inc., New York/London, 1944, page 223), that on heating nitrobenzene with 2 mol equivalents of chlorosulfonic acid 3-nitrobenzenesulfonyl chloride is allegedly formed (which has been questioned again in more recent literature), violent decomposition of the reaction mixture occurring with the formation of SO.sub.2 on heating at 150.degree. C. for several hours.
The preparation of 3-nitrobenzenesulfonyl chloride by chlorination of 3-nitrobenzenesulfonic acid with chlorine/disulfur dichloride is likewise described (Chem. Abstr. 104 [1986] 68 593s). 3-Nitrobenzenesulfonyl chloride could also be prepared by a reaction of Na 3-nitrobenzenesulfonate with phosphorus oxychloride in sulfolane (Chem. Abstr. 98 [1983] 215 331 t).
Finally, the desired 3-nitrobenzenesulfonyl chloride could also be obtained in a yield of about 90% ( SU 1097613 [1982]) from the reaction of benzene with chlorosulfonic acid and a mixture of conc. nitric acid and conc. sulfuric acid.
There was therefore a need for an economically and ecologically advantageous process for the preparation of 3-nitrobenzenesulfonyl chloride in high yields.
It has now surprisingly been found that 3-nitrobenzenesulfonyl chloride can be advantageously prepared in high yields from nitrobenzene and chlorosulfonic acid by reacting nitrobenzene with chlorosulfonic acid at temperatures of about 90.degree. to about 120.degree. C. and allowing an inorganic acid chloride to act on the resulting reaction mixture at about 40.degree. to about 90.degree. C., preferably at about 60.degree. to about 80.degree. C.
In detail, the process is expediently carried out by initially introducing the chlorosulfonic acid at a temperature of about 90.degree. to about 120.degree. C., preferably of about 110.degree. to about 115.degree. C., and metering in the nitrobenzene. When the total amount of nitrobenzene has been added, the reaction mixture is advantageously kept for about a further 4 hours in the temperature ranges indicated and then allowed to cool to about 40.degree. to about 90.degree. C. The inorganic acid fluoride is then metered in in this temperature range, but preferably at about 60.degree. to about 80.degree. C. It is then advantageous to keep the reaction mixture for about a further 2 to 3 hours in this temperature range.
Phosphorus oxychloride, phosphorus trichloride or thionyl chloride, for example, can be employed as inorganic acid chlorides. Phosgene can also be used and should additionally be included by the term "inorganic acid chloride". The use of thionyl chloride is particularly preferred.
About 3.0 to about 10.0 mol, preferably about 3.5 to about 6.0 mol, particularly preferably about 4.0 to about 4.6 mol, of chlorosulfonic acid are employed in the process according to the invention per mol of nitrobenzene. If less than 3 mol of chlorosulfonic acid are used per mol of nitrobenzene, ranges are reached in which the reaction solution tends to decompose more easily. It is actually possible to employ more than 10 mol of chlorosulfonic acid, but less efficient, as in this case the excess of chlorosulfonic
REFERENCES:
patent: 3574739 (1971-04-01), Wei et al.
patent: 4166070 (1979-08-01), Blank
patent: 5136043 (1992-08-01), Meier et al.
"The Organic Chemistry of Sulfur, Tetracovalent Sulfur Compounds", Chester Merle Suter, Wiley & Sons, Inc., New York, p. 223.
BIOS Final Report No. 1153, "I.G. Farbenindustrie. The Manufacture of Miscellaneous Dyestuff Intermediates (Excluding Naphthalene Derivatives)", British Intellegence Objectives Sub-Committee, London, pp. 38-39.
Chem. Abstract No. 104:68593s of Czechoslovkia 219,703.
Chem. Abstract No. 98:215331t of JP 57/203,056.
Chemical Abstracts, vol. 101, p. 613; abstract 210737a, & Su, A, 1097613 (Voroshilovgrad machine Building-Institute, Rubezhnoe) (1984).
Chemical Abstracts, vol. 113, No. 9; abstract 77909n, & JP, A, 02108661 (EIWA Chemical Industrial Co., Ltd) (1990).
Meier Michael
Wagner Reinhard
Geist Gary
Hoechst AG
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