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

HRID 33990ノート

反応式

HRID 33990 の反応式
[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]

参加物

4

反応物 2

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 21584188Chloroform methanol溶媒

実験手順

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.

後処理

  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)

出典と根拠

ORDレコード
ord-50a5fff8d56d40ed94a0f74d165c22cd
出典データセット
uspto-grants-2008_09
特許番号
US07429658B2

反応ノート

読み込み中…