Synthesis of 2,3-dihydronaphtho[2,3-d][1,3]thiazole-4,9-diones and 2,3-dihydroanthra[2,3-d][1,3]thiazole-4,11-diones and novel ring contraction and fusion reaction of 3H-spiro[1,3-thiazole-2,1'-cyclohexanes] into 2,3,4,5-tetrahydro-1H-carbazole-6,11-diones

Lidia S Konstantinova; Kirill A Lysov; Ljudmila I Souvorova; Oleg A Rakitin

doi:10.3762/bjoc.9.62

Synthesis of 2,3-dihydronaphtho[2,3-d][1,3]thiazole-4,9-diones and 2,3-dihydroanthra[2,3-d][1,3]thiazole-4,11-diones and novel ring contraction and fusion reaction of 3H-spiro[1,3-thiazole-2,1'-cyclohexanes] into 2,3,4,5-tetrahydro-1H-carbazole-6,11-diones

Beilstein J Org Chem. 2013 Mar 19:9:577-84. doi: 10.3762/bjoc.9.62. Print 2013.

Authors

Lidia S Konstantinova¹, Kirill A Lysov, Ljudmila I Souvorova, Oleg A Rakitin

Affiliation

¹ N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospect, 47, 119991 Moscow, Russia.

Abstract

Treatment of N-substituted 2-(methylamino)naphthoquinones 3 and -anthracene-1,4-diones 4 with S2Cl2 and DABCO in chlorobenzene gave the corresponding 2,3-dihydronaphtho[2,3-d][1,3]thiazole-4,9-diones 1 and 2,3-dihydroanthra[2,3-d][1,3]thiazole-4,11-diones 2 by triethylamine addition, in high to moderate yields. The DABCO replacement for N-ethyldiisopropylamine in the reaction of anthracene-1,4-diones 4 led unexpectedly to the corresponding 2-thioxo-2,3-dihydroanthra[2,3-d][1,3]thiazole-4,11-diones 10. The reaction of 3H-spiro[1,3-thiazole-2,1'-cyclohexanes] 1d, 2d with Et3N in chlorobenzene under reflux yielded 2,3,4,5-tetrahydro-1H-carbazole-6,11-diones 15, 16, i.e., ring contraction and fusion products. A plausible mechanism was proposed for the formation of the products.

Keywords: 1H-carbazole-6,11-diones; anthracene-1,4-diones; fused thiazoles; fusion reaction; heterocycles; naphthoquinones; ring contraction; sulfur–nitrogen.