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

HRID 33990Notes

Reaction equation

HRID 33990 reaction equation
[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]

Participants

4

Reactant 2

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

Product 1

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

Reagents, catalysts & solvents 1

HCID 21584188Chloroform methanolSolvent

Procedure

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.

Workup

  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)

Sources & evidence

ORD record
ord-50a5fff8d56d40ed94a0f74d165c22cd
Source dataset
uspto-grants-2008_09
Patent number
US07429658B2

Reaction notes

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