1,3-Dithiane → (3-Buten-1-yl)(1,3-dithian-2-yl)diphenylsilane

HRID 2306508

반응식

HRID 2306508 반응식
[S:1]1[CH2:6][CH2:5][CH2:4][S:3][CH2:2]1.C([Li])CCC.[CH2:12]([Si:16]([C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1)([C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1)F)[CH2:13][CH:14]=[CH2:15]>C1COCC1>[CH2:12]([Si:16]([CH:2]1[S:3][CH2:4][CH2:5][CH2:6][S:1]1)([C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1)[C:18]1[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=1)[CH2:13][CH:14]=[CH2:15]

참가 물질

5

반응물 3

HCID 104511,3-DithianeHCID 22015847(3-Buten-1-yl)diphenylfluorosilaneHCID 178418339Butyllithium

생성물 1

HCID 15349849(3-Buten-1-yl)(1,3-dithian-2-yl)diphenylsilane

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매2회

실험 절차

To a solution of 1,3-dithiane (6.77 g, 56.3 mmol) in THF (120 mL) at −78° C. was added dropwise over 10 min n-butyllithium (1.6 Min hexane, 50 mmol), and the solution was stirred for 2 h under argon. A solution of 31 (11.1 g, 43.3 mmol) in THF (100 mL) was added, the mixture was stirred for 3 h at −78° C., and overnight at rt. The reaction mixture was quenched with water (100 mL) and the organic layer isolated. The aqueous layer was extracted with two 100-mL portions of ethyl ether. The combined organic extracts were washed with saturated aqueous NaCl, dried over Na2SO4, and concentrated. Flash chromatography over silica gel (1/9 EtOAc:hexane) gave 32 contaminated with 1,3-dithiane. The latter was removed by sublimation (54° C., 8.0 mM Hg). Recrystallization from Et2O provided pure 32 as a colorless solid (14.8 g, 96%): Rf=0.40 (1/49 EtOAc:hexane); mp 474° C.; 1H NMR (300 MHz, CDCl3) δ 7.66 (d, J=7.8 Hz, 4H), 7.43 (m, 6H), 5.90 (m, 1H), 5.02 (dd, J=17.1, 1.7 Hz, 1H), 4.91 (dd, J=10.2, 1.7 Hz, 1H), 4.26 (s, 1H), 2.92 (t, J=11.8 Hz, 2H), 2.71 (m, 2H), 2.19 (m, 2H), 2.07 (m, 2H), 1.37 (m, 2H); 13C NMR (75 MHz, CDCl3) δ 141.1, 135.9, 132.4, 130.2, 128.0, 113.2,32.3, 31.5, 27.5,25.8, 10.5; IR (film) 3068 (m), 3047 (m), 2897 (s), 2840 (m), 1961 (w), 1890 (w), 1826 (w), 1639 (m), 1490 (w), 1429 (s), 1275 (m), 1112 (s), 1003 (m), 911 (s), 785 (m), 744 (s), 703 (s) cm−1; MS (FAB) m/e (rel. intensity) 357 (MH+, 11), 356 (11), 355 (25), 301 (18), 279 (13), 237 (36), 227 (11), 225 (18), 221 (14), 215 (14), 213 (18), 212 (12), 211 (100), 209 (9), 207 (15); HRMS (FAB) calcd for C20H23S2Si: 355.1010 (MH+−2), found: 355.1020. Anal. Calcd for C20H24S2Si: C, 67.36; H, 6.78. Found: C, 67.08; H, 6.78.

후처리

  1. stirringthe mixture was stirred for 3 h at −78° C.
  2. customovernight
  3. customat rt
  4. customThe reaction mixture was quenched with water (100 mL)
  5. customthe organic layer isolated
  6. extractionThe aqueous layer was extracted with two 100-mL portions of ethyl ether
  7. washThe combined organic extracts were washed with saturated aqueous NaCl
  8. dry with materialdried over Na2SO4
  9. concentrationconcentrated

출처 및 근거

ORD 기록
ord-327beb335425451ba2b21f63a74233c3
출처 데이터셋
uspto-grants-2002_08
특허 번호
US06441212B1

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