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Synlett 2010(9): 1345-1350  
DOI: 10.1055/s-0029-1219828
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Silver-Catalyzed Tandem Ammonolysis-Cyclization of 2-Alkynylbenzenamines with Tetraalkylthiuram Disulfides to 4-Methylene-4H-benzo[d][1,3]thiazin-2-amines

Ri-Yuan Tanga, Pei-Song Luoa, Xing-Guo Zhanga, Ping Zhongb, Jin-Heng Li*a
a College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035, P. R. of China
Fax: +86(577)88368607; e-Mail: jhli@wzu.edu.cn;
b Oujiang College, Wenzhou University, Wenzhou 325035, P. R. of China
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Publication History

Received 18 January 2010
Publication Date:
15 April 2010 (online)

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Abstract

In the presence of AgBF4, the ammonolysis-cyclization tandem reactions of various 2-alkynylbenzenamines with tetraalkyl­thiuram disulfides afforded the corresponding 4-methylene-4H-benzo[d][1,3]thiazin-2-amines in moderate to good yields.

Key words

silver - tandem reaction - 2-alkynylbenzenamine - tetra­alkylthiuram disulfide - 4-methylene-4H-benzo[d][1,3]thiazin-2-amine

    References and Notes

  • 1a McReynolds MD. Dougherty JM. Hanson PR. Chem. Rev.  2004,  104:  2239 
    Google Scholar
  • 1b Chivers T. Chem. Rev.  1985,  85:  341 
    Google Scholar
  • 1c Lewis NJ. Inloes RL. Hes J. Matthews RH. Milo G. J. Med. Chem.  1978,  21:  1070 
    Google Scholar
  • 1d Potts KT. McKeough D. J. Am. Chem. Soc.  1972,  94:  6215 
    Google Scholar
  • 2a Matysiak J. Bioorg. Med. Chem.  2006,  14:  2613 
    Google Scholar
  • 2b Su Y, Guo Q, Wang G, and Guo S. inventors; Faming Zhuanli Shenqing Gongkai Shuomingshu Patent  1683349.  ; Chem. Abstr. 2006, 145, 124577
  • 2c Gauthier JA, and Asselin AA. inventors; Canadian Patent  1212396.  ; Chem. Abstr. 1987, 106, 176409
  • 2d Kluge S, Leistner S, Wagner G, Schuster G, Lohmann D, and Laban G. inventors; DE  293713.  ; Chem. Abstr. 1992, 116, 53664
  • 2e Dreikorn BA. inventors; US  4001227.  ; Chem. Abstr. 1977, 86, 155674
  • 2f inventors; Fr. Patent  7359.  ; Chem. Abstr. 1971, 75, 151817
  • 2g Umio S, Kariyone K, and Kishimoto T. inventors; JP  45037020.  ; Chem. Abstr. 1971, 74, 76433
  • 2h Umio S, Kariyone K, and Kishimoto T. inventors; JP  45015030.  ; Chem. Abstr. 1970, 73, 45525
  • 3a Csomós P. Fodor L. Bernáth G. Sinkkonen J. Salminen J. Wiinamäki K. Pihlaja K. Tetrahedron  2008,  64:  1002 
    Google Scholar
  • 3b El-Desoky SI. Kandeel EM. Abd-el-Rahman AH. Schmidt RR. J. Heterocycl. Chem.  1999,  36:  153 
    Google Scholar
  • 3c Beilenson B. Hamer FM. J. Chem. Soc.  1942,  98 
    Google Scholar
  • 4a Nishio T. Tetrahedron Lett.  1995,  36:  6113 
    Google Scholar
  • 4b Nishio T. J. Org. Chem.  1997,  62:  1106 
    Google Scholar
  • 4c Gimbert C. Vallribera A. Org. Lett.  2009,  11:  269 
    Google Scholar
  • 5a Deck LM. Turner SD. Deck JA. Papadopoulos EP. J. Heterocycl. Chem.  2001,  38:  343 
    Google Scholar
  • 5b Dean VL. Lindamood BS. Papadopoulos EP. Synthesis  1984,  68 
    Google Scholar
  • 5c Dean WD. Papadopoulos EP. J. Heterocycl. Chem.  1982,  19:  1117 
    Google Scholar
  • 5d Abaev VT. Tsiunchik FA. Gutnov AV. Butin AV. Tetrahedron Lett.  2006,  47:  4029 
    Google Scholar
  • 5e Butin AV. Abaev VT. Stroganova TA. Gutnov AV. Molecules  1997,  2:  62 
    Google Scholar
  • 5f Tárraga A. Molina P. López JL. Tetrahedron Lett.  2000,  41:  4895 
    Google Scholar
  • 5g Hari A. Miller BL. Org. Lett.  2000,  2:  3667 
    Google Scholar
  • 5h Ding Q.-PWJ. J. Comb. Chem.  2008,  10:  541 
    Google Scholar
  • For recent reviews on Ag-catalyzed reactions, see:
  • 6a Álvarez-Corral M. Muñoz-Dorado M. Rodríguez-García I. Chem. Rev.  2008,  108:  3174 
    Google Scholar
  • 6b Yamamoto Y. Chem. Rev.  2008,  108:  3199 
    Google Scholar
  • 7 Pi S.-S. Zhang X.-G. Tang R.-Y. Li J.-H. Synthesis  2009,  3032 
    Google Scholar
  • 8a Qiu J.-W. Zhang X.-G. Tang R.-Y. Zhong P. Li J.-H. Adv. Synth. Catal.  2009,  351:  2319 
    Google Scholar
  • 8b Guo Y.-J. Tang R.-Y. Li J.-H. Zhong P. Zhang X.-G. Adv. Synth. Catal.  2009,  351:  2615 
    Google Scholar
  • 8c Jiang T.-S. Zhang X.-G. Li J.-H. Synthesis  2009,  3029 
    Google Scholar
  • 8d Du H.-A. Zhang X.-G. Tang R.-Y. Li J.-H. J. Org. Chem.  2009,  74:  7844 
    Google Scholar
  • 8e Guo Y.-J. Tang R.-Y. Zhong P. Li J.-H. Tetrahedron Lett.  2010,  51:  649 
    Google Scholar
  • For selected papers on the synthesis of tetraalkylthiuram disulfides, see:
  • 9a Watanabe Y. Yuzurus Ishimura Y. J. Org. Chem.  1988,  53:  2120 
    Google Scholar
  • 9b Karimi B. Hazarkhani H. Zareyee D. Synthesis  2002,  2513 
    Google Scholar
  • 9c Liang F. Tan J. Piao C. Liu Q. Synthesis  2008,  3579 
    Google Scholar
10

The crystal structure of compound 3 has been deposited at the Cambridge Crystallographic Data Centre and allocated the deposition number CCDC 769763.

11

General Procedure for the Silver-Catalyzed Tandem Reaction
A flame-dried Schlenk tube with a magnetic stirring bar was charged with 2-alkynylbenzenamine 1 (0.5 mmol), tetraalkylthiuram disulfide 2 (0.5 mmol), AgBF4 (0.05 mmol), and DMSO (1 mL). The reaction mixture was stirred at 80 ˚C for 36 h. After the reaction was finished, the mixture was poured into EtOAc, washed with brine (3 × 10 mL), and extracted with EtOAc. The combined organic layers were dried by anhyd Na2SO4 and evaporated under vacuum. The residue was purified by flash column chromatography (hexane-EtOAc) to afford the desired product.
4-Benzylidene- N , N -dimethyl-4 H -benzo[ d ][1,3]thiazin-2-amine (3) Z/E = 90:10; pale yellow solid, mp 68.9-72.6 ˚C (uncorrected). ¹H NMR (300 MHz, CDCl3): δ = 7.51-7.46 (m, 3 H), 7.43-7.38 (m, 2 H), 7.29-7.25 (m, 2 H), 7.21-7.17 (m, 2 H), 7.08-7.07 (m, 2 H), 3.21 (s, 0.6 H), 3.16 (s, 5.4 H). ¹³C NMR (75 MHz, CDCl3): δ = 153.3, 145.0, 136.0, 129.6, 129.4, 128.1 (2 C), 127.2, 126.0, 125.5, 124.2, 123.4, 120.0, 38.2. IR (KBr): 2924, 1560, 1187, 756 cm-¹. LRMS (EI, 70 eV): m/z (%) = 280 (100) [M+], 236 (78). ESI-HRMS: m/z calcd for C17H17N2S [M + H]+: 281.1107; found: 281.1104.
3-[2-(3,3-Dimethylbut-1-ynyl)phenyl]-1,1-dimethyl-thiourea (22) Pale yellow solid, mp 88.1-89.3 ˚C (uncorrected). ¹H NMR (300 MHz, CDCl3): δ = 8.34 (d, J = 8.3 Hz, 1 H), 7.77 (br, 1 H), 7.37 (d, J = 7.7 Hz, 1 H), 7.28-7.26 (m, 1 H), 7.05-7.02 (m, 1 H), 3.41 (s, 6 H), 1.34 (s, 9 H). ¹³C NMR (75 MHz, CDCl3): δ = 180.3, 140.3, 131.8, 127.8, 123.5, 121.9, 115.1, 105.7, 75.0, 41.2, 31.1, 28.3. IR (KBr): 3367, 2963, 1530, 1335, 755 cm-¹. LRMS (EI, 70 eV): m/z (%) = 260 (29) [M+], 245 (37), 200(18), 88 (100), 88. ESI-HRMS: m/z calcd for for C15H21N2S [M + H]+: 261.1420; found: 261.1419.
( E )-1,1-Dimethyl-3-(2-styrylphenyl)thiourea (23) Pale yellow solid, mp 211.3-214.1 ˚C (uncorrected). ¹H NMR (300 MHz, CDCl3): δ = 7.52-7.49 (m, 1 H), 7.35 (d, J = 7.7 Hz, 2 H), 7.31-7.29 (m, 2 H), 7.28-7.25 (m, 4 H), 7.07-6.99 (m, 2 H), 3.30 (s, 6 H). ¹³C NMR (75 MHz, CDCl3): δ = 183.3, 137.6, 137.1, 133.2, 131.5, 128.7, 128.1, 128.0, 127.3, 126.8 (2 C), 126.4, 123.7, 41.8. IR (KBr): 2924, 1524, 1332, 758 cm-¹. LRMS (EI, 70 eV): m/z (%) = 282 (100) [M+], 249 (27), 237 (100), 204 (32), 88 (78). ESI-HRMS: m/z calcd for C17H19N2S [M + H]+: 283.1263; found: 283.1260.