Imidazole → diisopropyl (E)-3-acetoxymethyl-4-t-butyldiphenylsilyloxybut-1-enylphosphonate

HRID 1708086ノート

反応式

HRID 1708086 の反応式
[C:1]([O:4][CH2:5][CH:6]([CH2:19][OH:20])/[CH:7]=[CH:8]/[P:9](=[O:18])([O:14][CH:15]([CH3:17])[CH3:16])[O:10][CH:11]([CH3:13])[CH3:12])(=[O:3])[CH3:2].N1C=CN=C1.[Si:26](Cl)([C:39]([CH3:42])([CH3:41])[CH3:40])([C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1)[C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1>C1COCC1>[C:1]([O:4][CH2:5][CH:6]([CH2:19][O:20][Si:26]([C:39]([CH3:42])([CH3:41])[CH3:40])([C:33]1[CH:34]=[CH:35][CH:36]=[CH:37][CH:38]=1)[C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1)/[CH:7]=[CH:8]/[P:9](=[O:18])([O:14][CH:15]([CH3:16])[CH3:17])[O:10][CH:11]([CH3:13])[CH3:12])(=[O:3])[CH3:2]

参加物

5

反応物 3

HCID 795ImidazoleHCID 94078tert-ButyldiphenylchlorosilaneHCID 10357901diisopropyl (E)-3-acetoxymethyl-4-hydroxybut-1-enylphosphonate

生成物 1

HCID 21765581diisopropyl (E)-3-acetoxymethyl-4-t-butyldiphenylsilyloxybut-1-enylphosphonate収率 94.3%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

実験手順

To a solution of diisopropyl (E)-3-acetoxymethyl-4-hydroxybut-1-enylphosphonate (3 g, 9.7 mmol ) and imidazole (1.7 g, 25 mmol) in anhydrous THF (60 ml) at 0° C. was added t-butyldiphenylsilylchloride (3.2 ml, 12.7 mmol). After stirring at room temperature for 3 h, the solvent was removed and the residue was partitioned between chloroform (100 ml) and brine (30 ml). The organic phase was dried (MgSo4), evaporated in vacuo and chromatographed on silica gel, eluting with chloroform of increasing polarity to chloroform-methanol (100:1) to give diisopropyl (E)-3-acetoxymethyl-4-t-butyldiphenylsilyloxybut-1-enylphosphonate as an oil (5 g, 94%); υmax (film) 3071, 3050, 2977, 2931, 2858, 1743, 1630, 1582, 1472,and 1425 cm-1 ; δH (CDCl3) 1.05 [9H, s, C(CH3)3 ], 1.26 (3H, d, J 6 Hz, CH3CH), 1.27 (3H, d, J 6 Hz, CH3CH), 1.32 [6H, d, J 6.3 Hz, (CH3)2CH], 1.98 (3H, s, CH3CO), 2.74 (1H, m, CH), 3.72 (2H, m, CH2), 4.22 (2H, m, CH2), 4.65 (2H, m, 2×CH(CH3)2 ], 5.76 (1H, ddd, J 1, 17 and 18 Hz, PCH=CH), 6.99 (1H, ddd, J 7, 17 and 22 Hz, PCH=CH), 7.3-7.7 (10H, m, 2×C6H5) (Found: C, 63.42; H, 8.22%. C29H43O6PSi requires C, 63.71; H, 7.93%.).

後処理

  1. customthe solvent was removed
  2. customthe residue was partitioned between chloroform (100 ml) and brine (30 ml)
  3. customThe organic phase was dried (MgSo4)
  4. customevaporated in vacuo
  5. customchromatographed on silica gel
  6. washeluting with chloroform
  7. temperatureof increasing polarity to chloroform-methanol (100:1)

出典と根拠

ORDレコード
ord-5d137eb318c046bcb6dae21e376348e4
出典データセット
uspto-grants-1994_10
特許番号
US05356886

反応ノート

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