Water → Ethyl 4-(benzyloxy)-7-bromo-2-naphthoate

HRID 1107635ノート

反応式

HRID 1107635 の反応式
[Br:1][C:2]1[CH:11]=[C:10]2[C:5]([C:6]([OH:17])=[CH:7][C:8]([C:12]([O:14][CH2:15][CH3:16])=[O:13])=[CH:9]2)=[CH:4][CH:3]=1.C([O-])([O-])=O.[K+].[K+].[CH2:24](Br)[C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1.O>CN(C=O)C>[CH2:24]([O:17][C:6]1[C:5]2[C:10](=[CH:11][C:2]([Br:1])=[CH:3][CH:4]=2)[CH:9]=[C:8]([C:12]([O:14][CH2:15][CH3:16])=[O:13])[CH:7]=1)[C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1

参加物

6

反応物 4

HCID 962WaterHCID 7498Benzyl BromideHCID 11430Potassium CarbonateHCID 10613762HCID 10613762、化合物

生成物 1

HCID 10667770Ethyl 4-(benzyloxy)-7-bromo-2-naphthoate収率 986.4%

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

反応条件

温度
25 °C

実験手順

A solution of 6 (8.04 g, 2.2 mmol) in anhydrous DMF (150 mL) under Ar was treated with K2CO3 (5.65 g, 40.9 mmol), benzyl bromide (5.59 g, 32.7 mmol, 1.2 equiv) and BU4NI (402 mg, 1.1 mmol, 0.04 equiv). After stirring for 11 h at 25° C., the reaction mixture was poured into H2O (200 mL) and extracted with EtOAc (3×200 mL). The combined organic layers were washed with saturated aqueous NaCl, dried (MgSO4) and concentrated. The resulting solid was recrystallized from 5% EtOAc-hexane to afford 12 (8.36 g, 10.49 g theoretical, 80%) as white needles. An additional 2.13 g (20%) of 12 was obtained by chromatography (SiO2, 4×20 cm, 10% EtOAc-hexane) of the crystallization mother liquors: mp 105° C. (needles, hexane); 1H NMR (CDCl3, 250 MHz) δ8.19 (d, 1H, J=8.8 Hz), 8.10 (s, 1H), 8.05 (d, 1H, J=1.8 Hz), 7.61 (dd, 1H, J=1.9, 8.9 Hz), 7.50 (m, 6H), 5.28 (s, 2H), 4.45 (q, 2H, J=7.1 Hz), 1.46 (t, 3H, J=7.1 Hz); 13C NMR (CDCl3, 100 MHz) δ166.5, 154.7, 136.4, 134.7, 130.8, 130.7, 129.1, 128.7, 128.3, 127.6, 126.3, 124.2, 122.5, 121.5, 104.6, 70.4, 61.4, 14.4; IR (KBr) vmax 2986, 1716, 1589, 1578, 1406, 1369, 1331, 1279, 1238, 1098, 1025, 962, 892, 816, 767, 725, 691 cm-1 ; FABHRS (NBA) m/z 384.0370 (M+, C20H17BrO3 requires 384.0361).

後処理

  1. extractionextracted with EtOAc (3×200 mL)
  2. washThe combined organic layers were washed with saturated aqueous NaCl
  3. dry with materialdried (MgSO4)
  4. concentrationconcentrated
  5. customThe resulting solid was recrystallized from 5% EtOAc-hexane

出典と根拠

ORDレコード
ord-89ba1954475e4030ae7f545938ac54fe
出典データセット
uspto-grants-2000_05
特許番号
US06060608

反応ノート

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