Allyl Alcohol → 4-(4-Hydroxymethyl-2-methoxy-5-nitrophenoxy)butyric acid allyl ester

HRID 33990노트

반응식

HRID 33990 반응식
[OH:1][CH2:2][C:3]1[C:15]([N+:16]([O-:18])=[O:17])=[CH:14][C:6]([O:7][CH2:8][CH2:9][CH2:10][C:11]([OH:13])=[O:12])=[C:5]([O:19][CH3:20])[CH:4]=1.[CH2:21](O)[CH:22]=[CH2:23]>CO.C(Cl)(Cl)Cl>[CH2:23]([O:12][C:11](=[O:13])[CH2:10][CH2:9][CH2:8][O:7][C:6]1[CH:14]=[C:15]([N+:16]([O-:18])=[O:17])[C:3]([CH2:2][OH:1])=[CH:4][C:5]=1[O:19][CH3:20])[CH:22]=[CH2:21]

참가 물질

4

반응물 2

HCID 7858Allyl AlcoholHCID 42753554-[4-(Hydroxymethyl)-2-methoxy-5-nitrophenoxy]butanoic acid

생성물 1

HCID 587576444-(4-Hydroxymethyl-2-methoxy-5-nitrophenoxy)butyric acid allyl ester수율 72%

시약·촉매·용매 1

HCID 21584188Chloroform methanol용매

실험 절차

A mixture of compound 51 (7.00 g 24.50 mmol), allyl alcohol (80 mL) and p-tosic acid (742 mg, 3.90 mmol) was heated at reflux under a N2 atmosphere for 4 hOURS, at which time TLC (2% MeOH/CHCl3) indicated that reaction had gone to completion. Excess allyl alcohol was evaporated in vacuo to afford the crude compound (52), which was partitioned between NaHCO3 (50 mL) and EtOAc (50 mL). The organic layer was washed with water (3×50 mL), brine (3×50 mL) and then dried (MgSO4), and concentrated in vacuo. Purification by flash chromatography (CHCl3) yielded the product as an orange-brown solid (5.78 g, 72%). MP=73-75° C. 1H NMR (250 MHz, CDCl3) δ 7.70 (s, 1H), 7.16 (s, 1H), 6.00-5.84 (m, 1H), 5.36-5.21 (m, 2H), 4.94 (d, J=6.3 Hz), 4.62-4.59 (m, 2H), 4.13 (t, J=6.2 Hz, 2H), 3.97 (s, 3H), 2.67-2.56 (m, 3H), 2.20 (pent, J=6.7 Hz, 2H). 13C NMR 5173.1 (C12), 154.7 (Cquat.), 147.3 (Cquat.), 139.6 (Cquat.), 133.2 (Cquat.), 132.4 (C14), 118.7 (C15), 111.1 (C6), 109.9 (C3), 68.6 (C9), 65.6 (C13), 62.7 (C1), 56.7 (C8), 30.9 (C11), 24.6 (C10). IR (cm−1) 3329.4, 3100.0, 2972.1, 1734.5, 1647.9, 1577.4, 1508.1, 1281.5, 932.8, 884.0, 815.8, 758.2, 662.2. MS (M+ —OH) 308. Anal. Calcd for C16H19NO7: C, 55.38; H, 5.89; N, 4.31. Found: C, 52.41; H, 5.86; N, 4.67.

후처리

  1. temperaturewas heated
  2. customindicated that reaction
  3. customExcess allyl alcohol was evaporated in vacuo
  4. customto afford the crude compound (52), which
  5. customwas partitioned between NaHCO3 (50 mL) and EtOAc (50 mL)
  6. washThe organic layer was washed with water (3×50 mL), brine (3×50 mL)
  7. dry with materialdried (MgSO4)
  8. concentrationconcentrated in vacuo
  9. customPurification by flash chromatography (CHCl3)

출처 및 근거

ORD 기록
ord-50a5fff8d56d40ed94a0f74d165c22cd
출처 데이터셋
uspto-grants-2008_09
특허 번호
US07429658B2

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