Synthesis of 3,1-Benzothiazines by Cyclisation of 2- Thioformylaminodiphenylacetylenes

Synlett

Volumn , Issue 14, 2003, Pages 2231-2233

  Fernandes, Manuel A ^a   Reid, David H ^a  

^a UNIVERSITY OF THE WITWATERSRAND   (South Africa)

Author keywords

3,1 benzothiazines; Cyclisation; Sonogashira coupling; Thionation; X ray crystal structure

Indexed keywords

3,5 DICHLORO 2 THIOFORMYLAMINODIPHENYLACETYLENE; 4 BENZYLIDENE 6,8 DICHLORO 4H 3,1 BENZOTHIAZINE; ACETYLENE DERIVATIVE; BENZOTHIAZINE DERIVATIVE; INDOLE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL REACTION; CYCLIZATION; DRUG STRUCTURE; DRUG SYNTHESIS; ENVIRONMENTAL TEMPERATURE; HEATING; QUANTUM YIELD; SONOGASHIRA REACTION; STRUCTURE ANALYSIS; X RAY CRYSTALLOGRAPHY;

EID: 0242491554     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-2003-42078     Document Type: Article

References (27)

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14. 3N were removed at reduced pressure from the filtrates. The residual oil, which solidified rapidly, was dissolved in benzene (200 mL) and chromatographed on silica (12 x 3.2 cm) with benzene for elution. The eluates (800 mL) were concentrated to ca. 75 mL, hexane (200 mL) was added gradually, and the resulting voluminous precipitate was filtered off and washed with hexane to give the formamide 3b (12.5 g, 98% yield) as pale beige crystals, mp 117-118°C (cyclohexane-acetone). Also obtained: compound 3a, 96% yield, mp 99-100°C (benzene-hexane); compound 3c, 97% yield, mp 98-100°C(cyclohexane); compound 3d, 96% yield, mp 180-182°C (EtOH).
15. 10 (6.67 g, 15 mmol) was added portionwise over 1 min. The resulting mixture was boiled with stirring for 20 min. Diethyl ether (100 mL) and then benzene (50 mL) were added and the solid was filtered off and washed with diethyl ether (300 mL) and benzene (50 mL). The combined filtrates were washed with sat. aq NaCl solution (400 mL), dried, and the solvent was removed. The residue was extracted with boiling benzene (200 mL) and the cooled extract was chromatographed on silica (25 x 2.4 cm) with benzene for elution. The residue from the evaporated eluates (500 mL) was dissolved in acetone (40 mL) and cyclohexane (120 mL). The solution was concentrated to ca. 40 mL, cooled, and hexane (120 mL) was added, giving the thioformamide 4b (2.94 g, 54%) as very pale yellow crystals, mp 163-165°C. Also obtained: compound 4a, 48% yield, mp 102-103°C (MeOH); compound 4c, 55% yield, mp 102-105°C (cyclohexane-hexane); compound 4d, 80% yield, mp 156-159°C(cyclohexane).
16. 19 mp 191 °C). Fraction(ii) gave (4Z)-4-benzylidene-6-chloro-4H-3,1-benzothiazine(5b) (1.2 g, 75%) as yellow crystals, mp 82-84 °C (MeOH). Also obtained: compound 5a, 80% yield, orange oil; compound 5c, 82% yield, mp 63-65°C (MeOH); compound 6c, 3.7% yield, mp 182-184°C (cyclohexane); compound 5d, 69% yield, mp 140-142°C (cyclohexane).
17. Detailed crystallographic data for 4d and 5d (excluding structure factors) were deposited at the Cambridge Crystallographic Database (deposition number CCDC-205334 and CCDC-205335 respectively). Copies of this information can be obtained, free of charge, on application to CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK; fax: +44(1223)336033 ore-mail: deposit@ccdc.cam.ac.uk.
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24. 6): δ = 100.0 (C-3), 116.4 (C-5 or C-7), 118.2, 120.6, 123.9 (C-7 or C-5), 126.0 (C-3′ + C-5′), 128.2 (C-4′), 128.7 (C-2′ + C-6′), 130.9, 131.0, 132.7, 141.0 (C-7a).
25. 13C NMR: δ = 121.8, 123.2, 126.1, 128.3 (C-5 or C-7), 128.4 (C-3′ + C-5′), 128.6 (C-4′), 129.2 (C-2′ + C-6′), 130.2 (C-7 or C-5), 134.1, 134.3, 134.7, 137.0, (C-8a), 151.8 (C-2).
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