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

HRID 8538

反応式

HRID 8538 の反応式
[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]

参加物

5

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

実験手順

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 M in 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 NaCI, dried over Na2SO4, and concentrated. Flash chromatography over silica gel (1/9EtOAc: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 47–49° 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 (109), 209 (9), 207 (15); HRMS (FAB) calcd for C20H13S2Si: 355.1010 (MH+-2), found: 355.1020. Anal. Calcd for C20H24S2Si: C, 67.36; H, 6.78. Found: C, 67.08; H, 6.78.

後処理

  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 NaCI
  8. dry with materialdried over Na2SO4
  9. concentrationconcentrated

出典と根拠

ORDレコード
ord-4da5c44b296f486dad78480c8775c10a
出典データセット
uspto-grants-2006_08
特許番号
US07087776B2

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