Process for producing azasulfonium salts and rearrangement there

Chemistry of carbon compounds – Miscellaneous organic carbon compounds – C-metal

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2602948D, 2602948E, 260465E, 260470, 260479R, 260551S, 260574, 260575, 260577, 260578, C07D21338, C07D21342

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039857565

ABSTRACT:
Preparing ortho-substituted anilines by reacting an N-chloroaniline with a non-carbonylic di-hydrocarbon sulfide to form an azasulfonium chloride, reacting the azasulfonium chloride with a strong base to form an aniline substituted in the 2-position with a hydrocarbon-S-hydrocarbyl thio-ether group. The ortho-substituted thio-ether compounds can be reduced with a de-sulfurizing reducing agent such as Raney nickel or the like to form the ortho-alkylated aniline. The aniline may be an amino-pyridine. The azasulfonium salt and thio-ether intermediate products can be isolated and recovered. If desired, the thio-ether compounds can be reduced to form ortho-alkylated aniline products which are useful as intermediates for a wide variety of purposes, including their uses in making dyes, herbicides, and the like.

REFERENCES:
kharasch, Organic Sulfur Compounds, vol. I, Pergamon Press (1961).
Kharasch, Organic Sulfur Compounds, vol. II, Pergamon Press (1966).
Gassman et al., Tetrahedron Letters, No. 6, Pergamon Press, pp. 497-500 (Feb. 1972).

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