Allyl bromide → 4-(Allyloxymethyl)benzophenone

HRID 40452노트

반응식

HRID 40452 반응식
[Br:1][CH2:2][C:3]1[CH:16]=[CH:15][C:6]([C:7]([C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)=[O:8])=[CH:5][CH:4]=1.[OH:17][CH2:18][C:19]1[CH:32]=[CH:31][C:22]([C:23]([C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)=[O:24])=[CH:21][CH:20]=1.[H-].[Na+].[CH2:35](Br)[CH:36]=[CH2:37]>C1COCC1>[Br:1][CH2:2][C:3]1[CH:16]=[CH:15][C:6]([C:7]([C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)=[O:8])=[CH:5][CH:4]=1.[CH2:37]([O:17][CH2:18][C:19]1[CH:32]=[CH:31][C:22]([C:23]([C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)=[O:24])=[CH:21][CH:20]=1)[CH:36]=[CH2:35]

참가 물질

7

반응물 4

HCID 7841Allyl bromideHCID 24758Sodium hydrideHCID 1229514-(Bromomethyl)benzophenoneHCID 13149642(4-(Hydroxymethyl)phenyl)(phenyl)methanone2회

생성물 2

HCID 1229514-(Bromomethyl)benzophenoneHCID 212535414-(Allyloxymethyl)benzophenone수율 92%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매

실험 절차

4-Bromomethyl benzophenone (2) was prepared as described in Reference Example 1. 4-Bromomethyl benzophenone (2) was converted into 4-Hydroxylmethyl benzophenone (3) as described in Reference Example 2. To a solution of 3 (0.5 g, 3.4 mmol) in dry THF (10 ml) was added sodium hydride (0.3 g, 60% dispersion in mineral oil, 6.7 mmol). The mixture was stirred for 5 min, then allyl bromide (0.8 g, 6.7 mmol) was added. The mixture as stirred for 18 h. the quenched with water and concentrated in vacuo. The residue was portioned between DCM and water, the organic layer collected, dried over MgSO4 and concentrated. A mineral oil impurity was removed using a silica plug eluting with petrol then ethyl acetate to yield 9 (0.6 g, 92%) as a yellow oil; δH (CDCl3) 4.08 (dt, 2H, J=1.4, 5.5 Hz, OCH2CH═CH2), 4.60 (s, 2H, ArCH2O), 5.24 (ddt 1H, J=1.4, 3.2, 10.3 Hz, OCH2CH═CHH), 5.34 (ddt 1H, J=1.4, 3.2, 17.3 Hz, OCH2CH═CHH), 5.88-6.08 (m, 1H, OCH2CH═CHH), 7.42-7.50 (m, 4H, 3-, 3′-, 5-, 5′-H), 7.54-7.62 (m, 1H, 4′-H), 7.78-7.82 (m, 4H, 2-, 2′-, 6-, 6′-H) ppm; δC (CDCl3) 61.4, 71.3 (ArCH2O, OCH2CH═CH2), 117.3 (OCH2CH═CH2), 127.0, 128.1 (3-, 3′-, 5-, 5′-C), 129.8, 130.1 (2-, 2′-, 6-, 6′-C), 132.2 (4′-C), 134.3 (OCH2CH═CH2), 136.6, 137.5 (1-, 1′-C), 143.1 (4-C), 196.2 (C═O) ppm; νmax (thin film) 3061, 2855, 1658, 1609, 1447, 1412, 1278, 1089, 924 cm−1; m/z (Er) 252 ([M+], 85%), 222 (100%); found 252.1158, C17H16O2 requires 252.1150.

후처리

  1. stirringThe mixture as stirred for 18 h. the
  2. customquenched with water
  3. concentrationconcentrated in vacuo
  4. customthe organic layer collected
  5. dry with materialdried over MgSO4
  6. concentrationconcentrated
  7. customA mineral oil impurity was removed
  8. washeluting with petrol

출처 및 근거

ORD 기록
ord-bb9fd4a1bd8342cab351638db965c603
출처 데이터셋
uspto-grants-2013_09
특허 번호
US08530212B2

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