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

HRID 508663노트

반응식

HRID 508663 반응식
[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

참가 물질

4

반응물 2

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

생성물 1

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

시약·촉매·용매 1

HCID 6344Dichloromethane용매2회

실험 절차

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.

후처리

  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)

출처 및 근거

ORD 기록
ord-184f96858abb41008bcb1345532630c3
출처 데이터셋
uspto-grants-2015_08
특허 번호
US09096544B2

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