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Synlett
Volumn , Issue 5, 2009, Pages 0731-0734
Synthesis of 3,6-divinyl-1,2,4,5-tetrazine, the first member of the elusive vinyltetrazine family
Author keywords

Azo compounds; Condensation; Cyclizations; Fused ring systems; Heterocycles
Indexed keywords

EID: 62349137370     PISSN: 09365214     EISSN: 14372096     Source Type: Journal    
DOI: 10.1055/s-0028-1087818     Document Type: Article
Times cited : (7)
References (53)
  • 6
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    • Konishi, K.; Kobota, J.; Kotone, A.; Nakane, Y. JP 7234499, 1972.
    • (f) Konishi, K.; Kobota, J.; Kotone, A.; Nakane, Y. JP 7234499, 1972.
  • 34
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    • Lithium aluminium hydride, sodium borohydride, or diisobutylaluminium hydride led to major decomposition regardless of the conditions used
    • Lithium aluminium hydride, sodium borohydride, or diisobutylaluminium hydride led to major decomposition regardless of the conditions used.
  • 38
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    • Simpkins, N. S. In Sulfones in Organic Synthesis, 10; Baldwin, J. E.; Magnus, P. D., Eds.; Tetrahedron Org. Chem. Series, Pergamon Press: Oxford, 1993.
    • (a) Simpkins, N. S. In Sulfones in Organic Synthesis, Vol. 10; Baldwin, J. E.; Magnus, P. D., Eds.; Tetrahedron Org. Chem. Series, Pergamon Press: Oxford, 1993.
  • 48
    • 62349107351 scopus 로고    scopus 로고
    • Ethyl 3-Phenylsulfanylpropionimido Ester Hydrochloride (2) A steady stream of gaseous HCl was bubbled at r.t. for 10 h through a stirred EtOH solution (7.3 mL, 0.125 mol) of propionitrile 1 (2.02 g, 12.3 mmol, A white powder gradually precipitated. The solvent was removed under vacuum, and the crude precipitate was triturated three times with anhyd Et2O and finally filtered leading to compound 2 as a white powder (94% yield, mp 74-75°C. 1H NMR (400 MHz, CDCl3, δ, 12.50 (s, 1 H, 11.60 (s, 1 H, 7.41-7.27 (m, 5 H, 4.56 (q, J, 6.9 Hz, 2 H, 3.30 (t, J, 6.6 Hz, 2 H, 3.06 (t, J, 6.6 Hz, 2 H, 1.44 (t, J, 6.9 Hz, 3 H, 13C NMR (100 MHz, CDCl3, δ, 177.0, 133.7, 130.9, 129.1, 126.4, 70.9, 33.4, 28.8, 13.4. IR (KBr, νmax, 3078, 2951, 1692, 1384, 975 cm-1. LC-MS AP, MeCN-H2O, 80:20, 2.67 min, 246.7 [M, 1] and 21
    • 15ONS [M - HCl]: 209.0874; found: 209.0875.
  • 49
    • 62349091053 scopus 로고    scopus 로고
    • General Cyclization Procedure Imidoester hydrochloride 2 (6.17 g, 25.1 mmol) was dissolved in EtOH (0.16 M) under a nitrogen atmosphere, and the solution was brought to -10°C. Then, Et3N and N 2H4·H2O (2.5 mL, 51.4 mmol) were successively added to the solution and the mixture was allowed to stir (conditions: see Table 1, The mixture was concentrated under vacuum, and the slightly pink crude solid obtained was further dissolved in EtOAc and washed with H2O. The aqueous layer was then extracted with EtOAc, and the resulting organic layer was washed with brine, dried over MgSO4, filtered, and concentrated under vacuum. Depending on reaction conditions the products could be obtained. Compound 5 was isolated after simple precipitation from cyclohexane, whereas 3, 4, and 6 were obtained after chromatography over SiO2 (cyclohexane-EtOAc, 7:1, N′-[1-Amino-3-phe
    • +]: 355.1051; found: 355.1043.
  • 50
    • 34648818845 scopus 로고    scopus 로고
    • Katritzky, A. R, Rees, C. W, Scriven, E. F. V, Eds, Pergamon Press: Oxford
    • Comprehensive Heterocyclic Chemistry II, Vol. 6; Katritzky, A. R.; Rees, C. W.; Scriven, E. F. V., Eds.; Pergamon Press: Oxford, 1996, 949.
    • (1996) Comprehensive Heterocyclic Chemistry II , vol.6 , pp. 949
  • 52
    • 62349096181 scopus 로고    scopus 로고
    • 6-Bis(2-phenylsulfonylethyl)-1,2,4,5-tetrazine (7) Tetrazine 6 (1.86 g, 5.25 mmol) was dissolved in CH2Cl2 (0.05 M, and the solution was cooled to -10°C. A solution of MCPBA (5.38 g, 21.8 mmol) in CH2Cl2 (0.25 M) was added over a period of 1 h (the temperature was kept below 0°C, after which TLC analysis indicated completion of the reaction [Rf(6, 0.37 (cyclohexane-EtOAc, 7:1, pink spot; Rf(7, 0 (cyclohexane-EtOAc, 7:1, pink spot, The mixture was successively washed with a solution of NaHSO3 (10, and a solution of NaHCO3 (10, The organic layer was then washed with sat. NaCl solution, dried over MgSO 4, and filtered. Product 7 was finally obtained as a pink powder (2.19 g, 100, after concentration under vacuum; mp 183-185°C. 1H NMR (400 MHz, DMSO-d6, δ, 7.92-7.88 m, 4 H, 7.74-7
    • +]: 419.0848; found: 419.0854.
  • 53
    • 62349105614 scopus 로고    scopus 로고
    • 6-Divinyl-1,2,4,5-tetrazine (8) To a stirred solution of s-tetrazine 7 (600 mg, 1.43 mmol) in dry THF (120 mL) was added KOt-Bu (307 mg, 2.73 mmol) at -20°C for 1.5 h. The reaction was followed by TLC analysis [Rf(7, 0.45 (cyclohexane-EtOAc, 4:6, Rf(8, 0.95 (cyclohexane-EtOAc, 4:6, The solution was finally diluted with 150 mL of cooled Et2O, filtered, and washed with a solution of NaHCO 3 (10, 2 x 100 mL, The organic layer was then washed with brine (150 mL, dried over MgSO4, and further concentrated under controlled vacuum because of its volatility. Product 8 was purified over a SiO 2 column (pentane-Et2O, 80:20; Rf, 0.96, obtained as a dark pink oil (81 mg, 42% yield, and kept in the freezer. 1H NMR (400 MHz, CD2Cl2, δ, 7.17 (dd, J, 10.8, 17.6 Hz, 2 H, 7.01 dd
    • +]: 134.0592; found: 134.0590.

* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.