Boron tribromide → ethyl(E)-3-{2-[3-(1-adamantyl)-4-hydroxyphenyl]-5-pyrazinyl}-2-propenoate

HRID 508663ノート

反応式

HRID 508663 の反応式
[C:1]12([C:11]3[CH:12]=[C:13]([C:25]4[CH:30]=[N:29][C:28](/[CH:31]=[CH:32]/[C:33]([O:35][CH2:36][CH3:37])=[O:34])=[CH:27][N:26]=4)[CH:14]=[CH:15][C:16]=3[O:17]CC3C=CC=CC=3)[CH2:10][CH:5]3[CH2:6][CH:7]([CH2:9][CH:3]([CH2:4]3)[CH2:2]1)[CH2:8]2.B(Br)(Br)Br>C(Cl)Cl>[C:1]12([C:11]3[CH:12]=[C:13]([C:25]4[CH:30]=[N:29][C:28](/[CH:31]=[CH:32]/[C:33]([O:35][CH2:36][CH3:37])=[O:34])=[CH:27][N:26]=4)[CH:14]=[CH:15][C:16]=3[OH:17])[CH2:2][CH:3]3[CH2:4][CH:5]([CH2:6][CH:7]([CH2:9]3)[CH2:8]1)[CH2:10]2

参加物

4

反応物 2

HCID 25134Boron tribromideHCID 53259588ethyl(E)-3-{2-[3-(1-adamantyl)-4-benzyloxyphenyl]-5-pyrazinyl}-2-propenoate

生成物 1

HCID 136121078ethyl(E)-3-{2-[3-(1-adamantyl)-4-hydroxyphenyl]-5-pyrazinyl}-2-propenoate収率 94.5%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒2 回

実験手順

A solution of ethyl(E)-3-{2-[3-(1-adamantyl)-4-benzyloxyphenyl]-5-pyrazinyl}-2-propenoate (477 mg, 0.96 mmol), 1.0 M boron tribromide (3.86 mmol) in CH2Cl2 (3.86 mL), and CH2Cl2 (13 mL) was stirred at −78° C. under argon for 2 h, quenched with water (50 mL), and extracted with EtOAc (100 mL, 50 mL, and 30 mL). The extracts were washed (brine) and dried. After solvent removal at reduced pressure, the residue was purified on silica gel (20% to 33% EtOAc/hexane) to give 367 mg (94%) of ethyl(E)-3-{2-[3-(1-adamantyl)-4-hydroxyphenyl]-5-pyrazinyl}-2-propenoate as a yellow solid, mp 212-215° C. IR 3352, 2843, 1686 cm−1; 1H NMR (CDCl3) δ 1.35 (t, J=7.3 Hz, 3H, OCH2CH3), 1.79 (bs, 6H, AdCH2), 2.10 (bs, 3H, AdCH), 2.18 (bs, 6H, AdCH2), 4.29 (q, J=7.3 Hz, 2H, OCH2CH3), 5.32 (s, 1H, OH), 6.77 (d, J=8.5 Hz, 1H, 5-ArH), 6.97 (d, J=15.9 Hz, 1H, CH═CHCO), 7.71 (d, J=15.9 Hz, 1H, CH═CHCO), 7.75 (dd, J=8.5 Hz, 2.4 Hz, 1H, 6-ArH), 7.98 (d, J=2.4 Hz, 1H, 2-ArH), 8.62 (d, J=1.2 Hz, 1H, 3-PyrH), 8.97 ppm (d, J=1.2 Hz, 1H, 6-PyrH). HRMS calcd C25H28N2O3 [M+H]+ 405.2173. found 405.2181.

後処理

  1. customquenched with water (50 mL)
  2. extractionextracted with EtOAc (100 mL, 50 mL, and 30 mL)
  3. washThe extracts were washed (brine)
  4. customdried
  5. customAfter solvent removal at reduced pressure
  6. customthe residue was purified on silica gel (20% to 33% EtOAc/hexane)

出典と根拠

ORDレコード
ord-184f96858abb41008bcb1345532630c3
出典データセット
uspto-grants-2015_08
特許番号
US09096544B2

反応ノート

読み込み中…