Chlorosulfonation of some crisscross cycloadducts from isocyanates and diaryl azines

Article abstract of DOI:10.1080/10426500008042109

Reaction of chlorosulfonyl isocyanate (1) with arylaldehyde azines (7) gave the 2:1 crisscross adducts (8); attempts to prepare a disulphonamide of 8a gave only a mixture of the monosulfamide 9 and the diureide 10. The latter with trichloromethanesulfenyl chloride afforded the derivative 12a, and with chlorosulfonic acid hydrazinodicarbonamide (11). The azine 7a with benzoyl isocyanate (2) gave the expected crisscross adduct 13. With thiobenzoyl isocyanate (3) however, both 7a and 7d gave the 1:1 adducts (14), whereas 7c gave a different 2:1 adduct (15). Treatment of 14a with 1 gave the ureide 16. With both methyl isocyanate (4) and phenyl isocyanate (5), 7a gave the expected crisscross adducts (17a and b), and 7c with 5 similarly gave 17c. When 7a was treated with 1 followed by aqueous potassium iodide, the diureide (10) was formed; concentrated nitric acid converted 10 into the triazolenone (18). Treatment of 18 with chlorosulfonic acid-thionyl chloride gave the sulfonyl chloride (19) which was characterised as the sulfonamides (20 a-d). Diarylsulfamoyl azines (21 a-f) with 1 and potassium iodide, gave the diureides 22 a-f. 4-Methoxy-3-sulfamoylbenzaldehyde azines (23 a-c) reacted with 3 to give the 1:1 adducts 24 a-c, while 4-chlorosulfonylphenyl isocyanate (6) with benzaldehyde azine (7a) gave the bis-chlorosulfonyl adduct (25a), characterised as the diethylsulfonamide 25b. Attempted chlorosulfonation of the tetraphenyl cycloadduct 17b did not give the tetrasulfonyl chloride (although the reaction was successful with the more reactive methoxy adduct 17c); the tetrasulfonyl chloride (26a) was converted into 3 sulfonamides (26 b-d). The unsymmetrically-substituted diaryl azines (27) reacted with 1 and potassium iodide to yield the diureides 28 a-f. Analogous cycloadditions of 1 with several keto azines were unsuccessful. Selected compounds will be screened for medicinal and pesticidal activity: compounds 9, 10 and 12a showed fungicidal activity against barley powdery mildew.

Full text of DOI:10.1080/10426500008042109

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Phosphorus, Sulfur, and Silicon
and the Related Elements
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CHLOROSULFONATION OF SOME
CRISSCROSS CYCLOADDUCTS
FROM ISOCYANATES AND DIARYL
AZINES
Richard J. Cremlyn a , Richard M. Ellam a & Sultan
Farouk a
a Division of Chemistry, Depurtment of Physical
Sciences , University of Hertfordshire , Hurfield,
Hertfordshire, AL10 9AB, England, UK
Published online: 04 Oct 2006.
To cite this article: Richard J. Cremlyn , Richard M. Ellam & Sultan Farouk (2000)
CHLOROSULFONATION OF SOME CRISSCROSS CYCLOADDUCTS FROM ISOCYANATES AND
DIARYL AZINES, Phosphorus, Sulfur, and Silicon and the Related Elements, 161:1,
213-238, DOI: 10.1080/10426500008042109
To link to this article: http://dx.doi.org/10.1080/10426500008042109
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