Synlett 2017; 28(17): 2281-2284
DOI: 10.1055/s-0036-1590811
letter
© Georg Thieme Verlag Stuttgart · New York

Base-Induced Cyclization of Active Methylene Isocyanides with Xanthate Esters: An Efficient Method for the Synthesis of 5-Alkoxy-4-(tosyl/ethoxycarbonyl)-1,3-thiazoles

Narasimhamurthy Rajeeva, Toreshettahally R. Swaroopb, Seegehalli M. Anila, Yadaganahalli K. Bommegowdaa, Kanchugarakoppal S. Rangappa*a, c, Marilinganadoddi P. Sadashiva*a, c
  • aDepartment of Studies in Chemistry, University of Mysore, Manasagangothri, Mysuru, Karnataka 570 006, India
  • bDepartment of Studies in Organic Chemistry, University of Mysore, Manasagangothri, Mysuru, Karnataka 570 006, India
  • cInstitution of Excellence, Vijnana Bhavan, University of Mysore, Manasagangothri, Mysuru, Karnataka 570 006, India   Email: mpsadashiva@gmail.com   Email: rangappaks@gmail.com
Further Information

Publication History

Received: 15 April 2017

Accepted after revision: 02 June 2017

Publication Date:
13 July 2017 (eFirst)

Abstract

Sodium hydride-induced cyclization of 1-[(isocyanomethyl)sulfonyl]-4-methylbenzene or ethyl isocyanoacetate with various xanthate esters gave 5-alkoxy-4-tosylthiazoles or ethyl 5-alkoxythiazol-4-ylcarboxylates, respectively, in good to excellent yields. The xanthate ester S-methyl O-phenyl dithiocarbonate gave 5-(methylsulfanyl)-4-tosyl-1,3-thiazole when treated with 1-[(isocyanomethyl)sulfonyl]-4-methylbenzene under similar conditions.

Supporting Information

 
  • References and Notes

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  • 30 O-Benzyl S-Methyl Dithiocarbonates 2a–g: General Procedure The appropriate benzylic alcohol 1ag (10 mmol) was added to a solution of NaOH (20 mmol) in THF (10 mL), and the mixture was stirred at r.t. for 10 mins. The mixture was then cooled to 0 °C, CS2 (10 mmol) was added, and the mixture was stirred for 10 min. MeI (10 mmol) was then added at 0 °C, and the mixture was stirred at r.t. for a further 2–3 h until the reaction was complete (TLC). Ice-cold H2O (25 mL) was added, and the mixture was extracted with EtOAc (2 × 25 mL). The organic layers were combined, washed with H2O (25 mL) and brine (25 mL), dried (Na2SO4), and concentrated under reduced pressure to give the crude product that was purified by column chromatography [silica gel, EtOAc–hexane, (1:9)]. O-Benzyl S-Methyl Dithiocarbonate (2a) Yellow viscous liquid; yield: 1.861 g (94%). IR (KBr): 622, 1051, 1185, 1203, 1609, 2920 cm–1. 1H NMR (400 MHz, CDCl3): δ = 2.57 (s, 3 H, SMe), 5.63 (s, 2 H, CH2), 7.24–7.40 (m, 5 H, Ar-H). 13C NMR (100 MHz, CDCl3): δ = 19.0, 75.1, 128.5, 128.6, 130.0, 134.7, 215.7. HRMS: m/z [M + H]+ calcd for C9H11OS2: 199.0000; found: 199.0173.
  • 31 5-Alkoxy-4-(tosyl/ethoxycarbonyl)-1,3-thiazoles (4ai) and 4-(Methylsulfanyl)-4-tosyl-1,3-thiazole (4j); General Procedure A mixture of the appropriate xanthate ester 2 (2 mmol) and active methylene isocyanide 3 (2 mmol) in DMF (1.5 mL) was added dropwise to NaH (60% suspension in paraffin; 4 mmol) in DMF (1.5 mL) at 0 °C. The mixture was stirred at r.t. for 10–20 min until the reaction was complete (TLC) then poured into sat. aq NH4Cl (20 mL). The mixture was extracted with EtOAc (2 × 20 mL), and the EtOAc layers were combined, washed with H2O (20 mL) and brine (20 mL), dried (Na2SO4), and concentrated under reduced pressure to give the crude product, which was purified by column chromatography [silica gel, EtOA–hexane (2:8)]. 5-(Benzyloxy)-4-tosyl-1,3-thiazole (4a) White solid; yield: 0.635 g (92%); mp 130–132 °C; IR (KBr): 626, 983, 1040, 1318, 1593, 2920 cm–1. 1H NMR (400 MHz, CDCl3): δ = 2.39 (s, 3 H, Ar-Me), 5.24 (s, 2 H, CH2), 7.26 (d, J = 8.0 Hz, 2 H, Ar-H), 7.37–7.41 (m, 5 H, Ar-H), 7.92 (dd, J = 6.8, 2.0 Hz, 2 H, Ar-H), 8.14 (s, 1 H, Ar-H). 13C NMR (100 MHz, CDCl3): δ = 21.6, 80.0, 127.9, 128.1, 128.8, 129.2, 129.6, 133.6, 135.0, 138.2, 140.3, 144.3, 163.7. HRMS: m/z [M + H]+ calcd for C17H16NO3S2: 346.0000; found: 346.0493.