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Synlett
Volumn , Issue 15, 2007, Pages 2390-2394
Efficient synthesis of trimethylsilyl-substituted dithieno[2,3-b:3′, 2′-d]thiophene, tetra[2,3-thienylene] and hexa[2,3-thienylene] from substituted [3,3′]bithiophenyl
Author keywords

Bithiophenyl; Cyclization; Fused ring system; Heterocycles; Macrocylces
Indexed keywords

HEXA(2,3 THIEENYLENE); MACROCYCLIC COMPOUND; OLIGOTHIOPHENE; TETRA(2,3 THIENYLENE); TRIMETHYLSILYL DERIVATIVE; UNCLASSIFIED DRUG;
EID: 34948814514     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-2007-985582     Document Type: Article
Times cited : (49)
References (36)
  • 11
    • 0034671517 scopus 로고    scopus 로고
    • From Dr. Rajca's work: (a) Rajca, A.; Wang, H.; Pink, M.; Rajca, S. Angew. Chem. Int. Ed. 2000, 39, 4481;
    • From Dr. Rajca's work: (a) Rajca, A.; Wang, H.; Pink, M.; Rajca, S. Angew. Chem. Int. Ed. 2000, 39, 4481;
  • 12
    • 34948849462 scopus 로고    scopus 로고
    • Angew. Chem. 2000, 112, 4655.
    • (2000) Chem , vol.112 , pp. 4655
    • Angew1
  • 24
    • 34948839131 scopus 로고    scopus 로고
    • Compounds 6 and 7 were prepared according to the method from ref. 12.
    • Compounds 6 and 7 were prepared according to the method from ref. 12.
  • 25
    • 34948816889 scopus 로고    scopus 로고
    • Preparation of 8: n-BuLi (2.5 M in hexane, 15.0 mL, 37.5 mmol, 2.2 equiv) was added dropwise to diisopropylamine (5.5 mL, 38.9 mmol, 2.3 equiv) in Et2O (30 mL) at 0°C After keeping at 0°C for 0.5 h, the prepared LDA solution was transferred by syringe into a solution of 7 (5.44 g, 16.8 mmol) with anhyd Et2O. After keeping at 0°C for 2 h, the reaction mixture was cooled to -78°C, then trimethyl-chlorosilane (10.8 mL, 85.1 mmol, 5.1 equiv) was added dropwise. The reaction mixture was kept at -78°C for 1 h and then warmed slowly to r.t. overnight. After quenching with H2O (50 mL, the crude product was extracted with Et2O (3 x 40 mL) and washed with H2O (50 mL, and then dried over MgSO4. After removing the solvent in vacuo, the residue was purified by column chromatography on silica gel with PE (60-90°C) as eluent to yield 8 7.00 g, 89.1, as a white solid. From two other react
    • -1.
  • 26
    • 34948829316 scopus 로고    scopus 로고
    • Preparation of 9: To a solution of 8 (1.00 g, 2.13 mmol) in anhyd Et2O (80 mL, t-BuLi (2.5 M, 3.9 mL, 4.6 equiv) was added dropwise at -78°C After keeping at -78°C for 2 h, anhyd (PhSO 2)2S (0.67 g, 2.13 mmol, 1.0 equiv) was added, then the reaction mixture was kept at -78°C for 2 h and warmed slowly to r.t. overnight. The reaction mixture was quenched with H2O (50 mL, extracted with Et2O (2 x 40 mL) and then washed with H2O (2 x 50 mL, After drying over MgSO4, the solvent was removed in vacuo. The residue was purified by column chromatography on silica gel with PE (60-90°C) as eluent to yield 9 (0.47 g, 64.8, as a white solid. From two other reactions on a 1.00-g and 3.00-g scale of 8, using n-BuLi (2.3 equiv, 0.38 g (52.4, and 1.10 g (51.0, of 9 were obtained, respectively; mp 49-50°C 1H NMR 400 MHz, CDCl 3
    • -1.
  • 27
    • 34948826659 scopus 로고    scopus 로고
    • Preparation of 1: To a solution of 9 (2.11 g, 6.19 mmol) in CHCl3 (30 mL, TFA (2.0 mL) was added dropwise at r.t. The reaction progress was monitored by TLC analysis. After stirring at r.t. for 1 h, the reaction mixture was quenched with H2O (10 mL, extracted with CHCl3 (3 x 50 mL, and then washed with sat. NaHCO3 (40 mL) and H2O (2 x 40 mL, After drying over MgSO4, the solvent was removed in vacuo. A white powder of 1 (1.20 g, 98.7, was obtained. From another reaction on a 2.09-g scale of 9, 1.17 g (97.2, of 1 was obtained; mp 84-85°C (lit.10b 86-87°C, 1H NMR (400 MHz, CDCl3, δ, 7.40 (d, J, 5.2 Hz, 2 H, 7.38 (d, J, 5.2 Hz, 2 H, 13C NMR (100 MHz, CDCl3, δ, 139.0, 138.3, 127.5, 118.8. MS (EI, 70 eV, m/z, 196 (100, M, IR (KBr, 2955, 2894 (CH) cm -1
    • -1.
  • 28
    • 34948839653 scopus 로고    scopus 로고
    • Preparation of 10 and 11: To a solution of 8 (2.00 g, 4.27 mmol) in anhyd Et2O (60 mL, n-BuLi (2.5 M, 4.0 mL, 10.0 mmol, 2.3 equiv) was added dropwise at -78°C After keeping at -78°C for 2 h, anhyd CuCl2 (1.7 g, 12.6 mmol, 3.0 equiv) was added. The reaction mixture was kept at -78°C for 2 h, and then slowly warmed to r.t. overnight. The reaction mixture was quenched with H2O (50 mL, extracted with Et2O (3 x 40 mL, washed with H2O (50 mL, and then finally dried over MgSO4. After removing the solvent in vacuo, the residue was purified by column chromatography on silica gel with PE (60-90°C) as eluent to yield 10 (0.55 g, 41.5, as a pale white crystal and 11 (0.40 g, 36.5, as a white powder. For 10: mp 302°C(sublimation, 1H NMR (400 MHz, CDCl3, δ, 7.06 (s, 4 H, 0.32 (s, 36 H, 13C NMR 100 MHz, CDCl3
    • -1.
  • 29
    • 34948848845 scopus 로고    scopus 로고
    • Compounds 2 and 3 were prepared from 10 and 11, respectively according to the method used for the preparation of 1 from 9. Compound 2: mp 252-253°C (lit.13 253-256°C, 1H NMR (400 MHz, CDCl3, δ, 7.40 (d, J, 5.4 Hz, 4 H, 6.96 (d, J, 5.4 Hz, 4 H, MS (EI, m/z, 328 (100, M, HRMS (ESI, m/z [M, H, calcd for C16H9S4: 328.9587; found: 328.9588. IR: 3101.2, 2926.0 (CH) cm-1. Compound 3: mp 281-283°C (sublimation, 1H NMR (400 MHz, CDCl3, δ, 7.33 (d, J, 5.2 Hz, 2 H, 7.08 (d, J, 5.2 Hz, 2 H, 6.97 (d, J, 5.2 Hz, 2 H, 6.92 (d, J, 5.1 Hz, 2 H, 6.79 (d, J, 5.2 Hz, 2 H, 6.44 (d, J, 5.1 Hz, 2 H, 13C NMR 100 MHz, CDCl3, δ, 135.4, 133.4, 133.3, 132.1, 131.9, 131.5, 131.0, 130.4
    • -1.
  • 30
    • 34948910902 scopus 로고    scopus 로고
    • Crystal Data for 10: M, 701.36, C34H 52S4Si4, triclinic, space group P1, a, 12.6217(9) Å, b, 13.2892(9) Å, c, 13.3125(9) Å, α, 110.0070(10)°, β, 1114940(10)°, γ, 96.1850(10)°, V, 1881.6(2) Å3, Z, 2, Dcalcd= 1.238 g/cm3. A colorless crystal of dimensions 0.30 x 0.23 x 0.11 mm was used for measurement at 293 (2) K with the ω scan mode on a Bruker Smart APEX diffractometer with CCD detector using Mo-Kα radiation λ, 0.71073 Å, The data were corrected for Lorentz and polarization effects and absorption corrections were performed using SADABS 21b program. The crystal structures were solved using the SH ELXTL21c program and refined using full matrix least squares. The positions of hydrogen atoms were calculated theoretically and included in the final cycles of refineme
    • 21c program and refined using full matrix least squares. The positions of hydrogen atoms were calculated theoretically and included in the final cycles of refinement in a riding model along with attached carbons. The final cycle of full-matrix least-squares refinement was based on 7240 independent reflections [I > 2σ(I)] and 357 variable parameters with R1 = 0.0667, wR2 = 0.1979. The supplementary crystallographic data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.uk/data_request/cif. Please quote the reference number CCDC: 652683.
  • 31
    • 0004283942 scopus 로고    scopus 로고
    • University of Göttingen: Germany
    • (b) Sheldrick, G. M. SADABS; University of Göttingen: Germany, 1996.
    • (1996) SADABS
    • Sheldrick, G.M.1
  • 32
    • 34948895242 scopus 로고    scopus 로고
    • Sheldrick, G. M. SHELXTL Version 5.1; Bruker Analytical X-ray Systems, Inc, Madisonv, WI, 1997
    • (c) Sheldrick, G. M. SHELXTL Version 5.1; Bruker Analytical X-ray Systems, Inc.: Madisonv / WI, 1997.
  • 33
    • 34948826140 scopus 로고    scopus 로고
    • Crystal Data for 11: M, 1045.17, C43H 61Cl3S6Si6, triclinic, space group P1, a, 11.8377(12) Å, b, 14.0164(15) Å, c, 17.9101(18) Å, α, 94.620(2)°, β, 103.881(2)°, γ, 94.390(2)°, V, 2861.4(5) Å3, Z, 2, Dcalcd =1.213 g/cm3. A colorless crystal of dimensions 0.30 x 0.11 x 0.11 mm was used for measurement at 293 (2) K. The structure was solved by the same methods as used for 10. The final cycle of full-matrix least-squares refinement was based on 11009 observed reflections [I > 2σI, and 541 variable parameters with R1, 0.0731, wR2, 0.1255. The supplementary crystallographic data can be obtained free of charge from the Cambridge Crystallographic Data Centre via
    • 3. A colorless crystal of dimensions 0.30 x 0.11 x 0.11 mm was used for measurement at 293 (2) K. The structure was solved by the same methods as used for 10. The final cycle of full-matrix least-squares refinement was based on 11009 observed reflections [I > 2σ(I)] and 541 variable parameters with R1 = 0.0731, wR2 = 0.1255. The supplementary crystallographic data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.uk/data_request/cif. Please quote the reference number CCDC: 652684.

* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.