Methane, dichloromethoxy- → HCID 16738489、化合物

HRID 1844229ノート

反応式

HRID 1844229 の反応式
CCN(C(C)C)C(C)C.[Br:10][C:11]1[CH:16]=[C:15]([CH:17]2[O:21][CH2:20][CH2:19][O:18]2)[CH:14]=[CH:13][C:12]=1[OH:22].[CH3:23][O:24][CH:25](Cl)Cl>C(Cl)Cl>[Br:10][C:11]1[CH:16]=[C:15]([CH:17]2[O:18][CH2:19][CH2:20][O:21]2)[CH:14]=[CH:13][C:12]=1[O:22][CH2:23][O:24][CH3:25]

参加物

5

反応物 3

HCID 21004Methane, dichloromethoxy-HCID 81531DiisopropylethylamineHCID 19701587HCID 19701587、化合物

生成物 1

HCID 16738489HCID 16738489、化合物収率 94%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

実験手順

(iPr)2NEt (6.0 mL, 35.0 mmol) was added dropwise to a stirred and cooled (0° C.) solution of alcohol 3a (4.0 g, 16.3 mmol) in CH2Cl2 (50 mL). After 15 min methoxymethylene chloride (MOMCl) (1.6 mL, 28 mmol) was added dropwise over a period of 5 min, and stirring was continued for 1 h. The cold bath was removed, and stirring was continued for 12 h. The reaction mixture was diluted with water (10 mL) and extracted with CH2Cl2. The combined organic extracts were washed with brine, dried over Na2SO4, and evaporated. The residue was purified by flash chromatography using hexanes-ethyl acetate mixture (5:1) as eluent to give compound 4a (4.4 g, 94%) as a colorless liquid. Rf=0.48 (25% EtOAc-hexanes); IR (neat) 2956, 2889, 1606, 1497, 1246, 1100, 1043 cm−1; 1H NMR (300 MHz, CDCl3) δ 7.64 (d, J=1.8 Hz, 1H), 7.31 (dd, J=8.7, 2.1 Hz, 1H), 7.10 (d, J=8.1 Hz, 1H), 5.70 (s, 1H), 5.21 (s, 2H), 4.02 (m, 4H), 3.46 (s, 3H); 13C NMR (75 MHz, CDCl3) δ 154.2, 132.8, 131.4, 126.7, 115.5, 112.6, 102.5, 94.8, 65.1, 56.2; EIMS (m/z, rel intensity) 290 (M++2, 54), 288 (M+, 58), 259 (23), 257 (23), 209 (56), 73 (100).

後処理

  1. stirringstirring
  2. customThe cold bath was removed
  3. stirringstirring
  4. waitwas continued for 12 h
  5. additionThe reaction mixture was diluted with water (10 mL)
  6. extractionextracted with CH2Cl2
  7. washThe combined organic extracts were washed with brine
  8. dry with materialdried over Na2SO4
  9. customevaporated
  10. customThe residue was purified by flash chromatography

出典と根拠

ORDレコード
ord-4cdf1f0d97ba4d118ee5d657203f977a
出典データセット
uspto-grants-2015_02
特許番号
US08946287B2

反応ノート

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