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

HRID 2306508

反応式

HRID 2306508 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 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.

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 NaCl
  8. dry with materialdried over Na2SO4
  9. concentrationconcentrated

出典と根拠

ORDレコード
ord-327beb335425451ba2b21f63a74233c3
出典データセット
uspto-grants-2002_08
特許番号
US06441212B1

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