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Volumn , Issue 9, 2007, Pages 1470-1472

A simple synthesis of 2-methyl-1,3-dithiolium and related cations

Author keywords

1,3 dithiolium cations; Heterocycles; Meldrum's acid; Sulfur

Indexed keywords

2 METHYL 1,3 DITHIOLIUM; ACETIC ANHYDRIDE; BORIC ACID; DITHIOL DERIVATIVE; FLUOROBORIC ACID DERIVATIVE; N,N DIMETHYL 2 (1,3 DITHIOL 2 YLIDEN)ETHYLIDENIMINIUM; N,N DIMETHYLFORMAMIDE; UNCLASSIFIED DRUG;

EID: 34250727116     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-2007-980362     Document Type: Article
Times cited : (8)

References (41)
  • 3
    • 34250731005 scopus 로고    scopus 로고
    • Schaumann, E, Ed, Thieme: Stuttgart
    • (c) Schukat, G.; Fanghänel, E. In Science of Synthesis, Vol. 11; Schaumann, E., Ed.; Thieme: Stuttgart, 2002, 191.
    • (2002) Science of Synthesis , vol.11 , pp. 191
    • Schukat, G.1    Fanghänel, E.2
  • 6
    • 10344244501 scopus 로고    scopus 로고
    • (c) Fabre, J. M. Chem. Rev. 2004, 104, 5133.
    • (2004) Chem. Rev , vol.104 , pp. 5133
    • Fabre, J.M.1
  • 15
    • 34250733198 scopus 로고    scopus 로고
    • 6b
    • 6b
  • 16
    • 34250711533 scopus 로고    scopus 로고
    • Thione 1a is commercially available,
    • (a) Thione 1a is commercially available,
  • 17
    • 0000132833 scopus 로고    scopus 로고
    • Compounds 1b and 1c were prepared according to: Haley, N. F.; Fichtner, M. W. J. Org. Chem. 1980, 45, 175.
    • (b) Compounds 1b and 1c were prepared according to: Haley, N. F.; Fichtner, M. W. J. Org. Chem. 1980, 45, 175.
  • 18
    • 34250780178 scopus 로고    scopus 로고
    • Compound 1d was prepared according to: Steimecke, G.; Sieler, H.-J.; Kirmse, R.; Hoyer, E. Phosphorus Sulfur Relat. Elem. 1979, 7, 49.
    • (c) Compound 1d was prepared according to: Steimecke, G.; Sieler, H.-J.; Kirmse, R.; Hoyer, E. Phosphorus Sulfur Relat. Elem. 1979, 7, 49.
  • 19
    • 37049161214 scopus 로고    scopus 로고
    • Compound 2a: Challenger, F.; Mason, E. A.; Holdsworth, E. C.; Emmott, R. J. Chem. Soc 1953, 292.
    • (a) Compound 2a: Challenger, F.; Mason, E. A.; Holdsworth, E. C.; Emmott, R. J. Chem. Soc 1953, 292.
  • 20
    • 0026062219 scopus 로고    scopus 로고
    • Compounds 2b-d: Moore, A. J.; Bryce, M. R. Synthesis 1991, 26.
    • (b) Compounds 2b-d: Moore, A. J.; Bryce, M. R. Synthesis 1991, 26.
  • 22
    • 34250724612 scopus 로고    scopus 로고
    • 2) in the case of 3c.
    • 2) in the case of 3c.
  • 23
    • 34250701857 scopus 로고    scopus 로고
    • Some of these isopropylidene malonates had already been prepared under different conditions than those described here, but their reported melting points3c are lower than those measured by us. Therefore, full characterization data for compounds 3 follow: Compound 3a: yield 69, mp 244-245°C (lit.3c 235-237°C, IR (Nujol, 1651 cm-1. 1H NMR (400 MHz, DMSO-d6, δ, 7.97 (s, 2 H, 1.66 (s, 6 H, 13C NMR (100 MHz, DMSO-d 6, δ, 182.0, 161.1, 1284, 103.8, 93.4, 26.3. MS (EI, m/z, 244 (60, Compound 3b: yield 76, mp 219-220°C (lit.3c 208-210°C, IR (Nujol, 1665 cm-1. 1H NMR (300 MHz, CDCl3, δ, 2.30 (s, 6 H, 1.70 (s, 6 H, 13C NMR (100 MHz, CDCl3, δ, 179.4, 162.1, 132.7, 104.2, 93.4, 26.9, 13.1. MS (EI, m/z, 272 70, Compound 3c: yield 68
    • 3): δ = 179.4, 161.6, 135.2, 104.6, 26.9, 19.2. MS (EI): m/z (%) = 336 (95).
  • 27
    • 34250765019 scopus 로고    scopus 로고
    • 2O, dried, and optionally recrystallized from AcOH. In the case of 4d we have not been able to completely purify the desired salt.
    • 2O, dried, and optionally recrystallized from AcOH. In the case of 4d we have not been able to completely purify the desired salt.
  • 28
    • 34250757836 scopus 로고    scopus 로고
    • Compound 4a: yield 82, mp 109-110°C. 1H NMR (300 MHz, CF3COOD, δ, 8.92 (s, 2 H, 3.43 (s, 3 H, 13C NMR (75 MHz, CF3COOD, δ, 204.3, 145.1, 20.6. MS (MALDI, dithranol, m/z, 117 [C4H5S2, Compound 4b: yield 87, mp 50-51°C (dec, 1H NMR (300 MHz, CDCl3, δ, 3.28 (s, 3 H, 2.69 (s, 6 H, 13C NMR (100 MHz, CDCl3, δ, 193.9, 151.4, 19.5, 14.3. MS (MALDI, dithranol, m/z, 145 [C6H9S2, Compound 4c: yield 84, mp 129-132°C. 1H NMR (300 MHz, CF 3COOD, δ, 8.73 (s, 1 H, 7.69-7.52 (m, 5 H, 3.40 (s, 3 H, 13C NMR (75 MHz, CF3COOD, δ, 202.0, 135.9, 135.2, 132.6, 129.9, 20.6. MS (MALDI, dithranol, m/z, 193 [C 10H9S2, Compound 4d: 1H NMR 400 MHz, C
    • 4].
  • 29
    • 0001093961 scopus 로고    scopus 로고
    • 3N: (a) Wadsworth, D. H.; Detty, M. R.; Murray, B. J.; Weidner, C. H.; Haley, N. F. J. Org. Chem. 1984, 49, 2676.
    • 3N: (a) Wadsworth, D. H.; Detty, M. R.; Murray, B. J.; Weidner, C. H.; Haley, N. F. J. Org. Chem. 1984, 49, 2676.
  • 36
    • 34250761108 scopus 로고    scopus 로고
    • 2O, dried, and recrystallized from AcOH if necessary.
    • 2O, dried, and recrystallized from AcOH if necessary.
  • 37
    • 34250737595 scopus 로고    scopus 로고
    • Compound 5a: yield 59, mp 161-162°C IR (Nujol, 1625 cm -1. 1H NMR (400 MHz, DMSO-d6, δ, 8.38 (d, 1 H, J, 11.8 Hz, 7.57 (s, 2 H, 6.91 (d, 1 H, J, 11.8 Hz, 3.41 (s, 3 H, 3.19 (s, 3 H, 13C NMR (100 MHz, DMSO-d6, δ, 181.9, 157.8, 125.8, 99.1, 46.4. MS-FAB: m/z, 172 [C7H10NS2, Compound 5b: yield 65, mp 193-194°C. IR (Nujol, 1630 cm-1. 1H NMR (300 MHz, DMSO-d6, δ, 8.33 (d, 1 H, J, 11.8 Hz, 6.84 (d, 1 H, J, 11.8 Hz, 3.40 (s, 3 H, 3.18 (s, 3 H, 2.23 (s, 6 H, 13C NMR (100 MHz, DMSO-d6, δ, 183.2, 162.6, 134.7, 104.1, 51.7, 44.3, 18.5, 18.1. MS (MALDI, dithranol, m/z, 200 [C9H14NS2, Compound 5c: yield 40, mp 224°C (dec, darkening from 175°C, IR Nujol, 1626 cm
    • 2].


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