2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane → 2-{5-[6-(3-Ethyl-oxetan-3-ylmethoxy)-hexyl]-thiophen-2-yl}-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane

HRID 2242775ノート

反応式

HRID 2242775 の反応式
[CH2:1]([C:3]1([CH2:7][O:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][C:15]2[S:16][CH:17]=[CH:18][CH:19]=2)[CH2:6][O:5][CH2:4]1)[CH3:2].C([Li])CCC.C(O[B:29]1[O:33][C:32]([CH3:35])([CH3:34])[C:31]([CH3:37])([CH3:36])[O:30]1)(C)C>C1COCC1>[CH2:1]([C:3]1([CH2:7][O:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][C:15]2[S:16][C:17]([B:29]3[O:33][C:32]([CH3:35])([CH3:34])[C:31]([CH3:37])([CH3:36])[O:30]3)=[CH:18][CH:19]=2)[CH2:4][O:5][CH2:6]1)[CH3:2]

参加物

5

反応物 3

HCID 50177412-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 592072913-Ethyl-3-(6-thiophen-2-yl-hexyloxymethyl)oxetaneHCID 178418339Butyllithium

生成物 1

HCID 592073002-{5-[6-(3-Ethyl-oxetan-3-ylmethoxy)-hexyl]-thiophen-2-yl}-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane収率 72.3%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

実験手順

To a stirred solution of 3-ethyl-3-(6-thiophen-2-yl-hexyloxymethyl)-oxetane (6.0 g, 21.28 mmol) in dry THF (70 ml) is added n-butyllithium (2.5 M in hexanes, 8.10 ml, 21.28 mmol) dropwise at −78° C. under nitrogen. After complete addition, the mixture is allowed to warm to room temperature, with stirring, over 2 h, followed by the addition of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3.96 g, 21.28 mmol). The resultant mixture is stirred overnight at room temperature. The reaction is quenched with water, and the reaction mixture is extracted with ethyl acetate (3×70 ml). The combined organic extracts are washed with water, brine, and dried over sodium sulphate. The solvent is removed under reduced pressure and the residue is purified by column chromatography on silica, eluting with petroleum ether/ethyl acetate (9:1), to give a yellow oil (6.28 g, 72%). 1H NMR (300 MHz, CDCl3): δ (ppm) 7.45 (d, J=3.4 Hz, 1H, Ar—H), 6.85 (d, J=3.4 Hz, 1H, Ar—H), 4.44 (d, J=5.8 Hz, 2H, OCH2), 4.36 (d, J=5.8 Hz, 2H, OCH2), 3.51 (s, 2H, OCH2), 3.45 (t, J=6.4 Hz, 2H, OCH2), 2.83 (t, J=7.6 Hz 2H, ArCH2), 1.32-1.77 (m, 22H, CH2 and CH3), 0.88 (t, J=7.4 Hz, 3H, CH3); δ (ppm) 153.5 (quat.), 145.6 (quat.), 137.3 (CH), 125.9 (CH), 83.9 (quat.), 78.6 (OCH2), 73.4 (OCH2), 71.5 (OCH2), 43.4 (quat.), 31.6 (CH2), 30.1 (CH2), 29.4 (CH2), 28.8 (CH2), 26.8 (CH2), 25.9 (CH2), 24.8 (CH3), 8.2 (CH3); MS (m/e): 408 (M+, 0.5%), 223 (27), 165 (30), 141 (35), 123 (100), 97 (52).

後処理

  1. additionAfter complete addition
  2. customThe reaction is quenched with water
  3. extractionthe reaction mixture is extracted with ethyl acetate (3×70 ml)
  4. washThe combined organic extracts are washed with water, brine
  5. dry with materialdried over sodium sulphate
  6. customThe solvent is removed under reduced pressure
  7. customthe residue is purified by column chromatography on silica
  8. washeluting with petroleum ether/ethyl acetate (9:1)

出典と根拠

ORDレコード
ord-d79e6c91643d4e7c84e7a880d5f40cca
出典データセット
uspto-grants-2010_03
特許番号
US07674397B2

反応ノート

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