2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane → 2-{4-[6-((3-Ethyloxetan-3-yl)methoxy)hexyl]phenyl}-4,4,5,5-tetramethyl-[1,3,2]-dioxaborolane

HRID 2242781ノート

反応式

HRID 2242781 の反応式
Br[C:2]1[CH:7]=[CH:6][C:5]([CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][O:14][CH2:15][C:16]2([CH2:20][CH3:21])[CH2:19][O:18][CH2:17]2)=[CH:4][CH:3]=1.C([Li])CCC.C(O[B:31]1[O:35][C:34]([CH3:37])([CH3:36])[C:33]([CH3:39])([CH3:38])[O:32]1)(C)C>C1COCC1>[CH2:20]([C:16]1([CH2:15][O:14][CH2:13][CH2:12][CH2:11][CH2:10][CH2:9][CH2:8][C:5]2[CH:6]=[CH:7][C:2]([B:31]3[O:35][C:34]([CH3:37])([CH3:36])[C:33]([CH3:39])([CH3:38])[O:32]3)=[CH:3][CH:4]=2)[CH2:19][O:18][CH2:17]1)[CH3:21]

参加物

5

反応物 3

HCID 50177412-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 592073013-((6-(4-Bromophenyl)hexyloxy)methyl)-3-ethyloxetaneHCID 178418339Butyllithium

生成物 1

HCID 592072862-{4-[6-((3-Ethyloxetan-3-yl)methoxy)hexyl]phenyl}-4,4,5,5-tetramethyl-[1,3,2]-dioxaborolane収率 71%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

実験手順

To a stirred solution of 3-[6-(4-bromophenyl)hexyloxymethyl]-3-ethyl-oxetane (2.0 g, 5.63 mmol) in dry THF (20 ml) is added n-butyllithium (2.5 M in hexanes, 2.25 ml, 5.63 mmol) dropwise at −78° C. under nitrogen, with stirring. After complete addition, the mixture is stirred for another 20 min, followed by the addition of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.05 g, 5.64 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 (3×50 ml). The combined organic extracts are washed with water, brine, and dried (Na2SO4). 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 7:3), to give a brown oil (1.60 g, 71%). 1H NMR (300 MHz, CDCl3): δ(ppm) 7.72 (d, J=8.1 Hz, 2H, Ar—H), 7.17 (d, J=8.1 Hz, 2H, Ar—H), 4.43 (d, J=5.8 Hz, 2H, OCH2), 4.35 (d, J=5.8 Hz, 2H, OCH2), 3.48 (s, 2H, OCH2), 3.41 (t, J=6.4 Hz, 2H, OCH2), 2.60 (t, J=7.9 Hz, 2H, ArCH2), 1.72 (q, J=7.5 Hz, 2H, CH2), 1.56 (m, 4H, CH2), 1.32 (m, 14H, CH2 and CH3); 0.86 (t, J=7.5 Hz 3H, CH3); 13C NMR (75 MHz, CDCl3): δ (ppm) 146.1 (quat.), 134.8 (CH), 127.8 (CH), 83.5 (quat.), 78.5 (OCH2), 73.3 (OCH2), 71.5 (OCH2), 43.4 (quat.), 36.1 (CH2), 31.3 (CH2), 29.5 (CH2), 29.0 (CH2), 26.7 (CH2), 26.0 (CH2), 24.8 (CH3), 8.2 (CH3).

後処理

  1. additionAfter complete addition
  2. stirringthe mixture is stirred for another 20 min
  3. customThe reaction is quenched with water
  4. extractionthe reaction mixture is extracted with ethyl acetate (3×50 ml)
  5. washThe combined organic extracts are washed with water, brine
  6. dry with materialdried (Na2SO4)
  7. customThe solvent is removed under reduced pressure
  8. customthe residue is purified by column chromatography on silica
  9. washeluting with petroleum ether/ethyl acetate (9:1 to 7:3)

出典と根拠

ORDレコード
ord-ed5788b8deba45afb161fa31932009bb
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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