Allyl Alcohol → HCID 86588599, compound

HRID 396937Notes

Reaction equation

HRID 396937 reaction equation
[C:1]([C:4]1[C:15]([N+:16]([O-:18])=[O:17])=[CH:14][C:7]([O:8][CH2:9][CH2:10][C:11]([OH:13])=[O:12])=[C:6]([O:19][CH3:20])[CH:5]=1)([OH:3])=[O:2].O.[C:22]1(C)[CH:27]=CC(S(O)(=O)=O)=C[CH:23]=1.C(O)C=C>>[C:1]([C:4]1[C:15]([N+:16]([O-:18])=[O:17])=[CH:14][C:7]([O:8][CH2:9][CH2:10][C:11]([OH:13])=[O:12])=[C:6]([O:19][CH3:20])[CH:5]=1)([OH:3])=[O:2].[CH3:27][CH:22]=[CH2:23]

Participants

4

Reactant 3

HCID 7858Allyl AlcoholHCID 521998p-Toluenesulfonic acid monohydrateHCID 10684512HCID 10684512, compound

Product 1

HCID 86588599HCID 86588599, compoundYield 795.6%

Procedure

A mixture of 3-(4-carboxy-2-methoxy-5-nitrophenoxy)propanoic acid 1 (20 g, 74.3 mmol) and p-toluene sulphonic acid monohydrate (2.3 g, 7.4 mmol) in allyl alcohol (240 mL, 3.5 mol) was refluxed for 7 hours then allowed to cool. The allyl alcohol was then removed in vacuo, and the residue triturated with dilute HCl acid (3×75 ml) and collected by filtration. This solid was taken up in EtOAc, and the resulting solution washed with water (3×50 ml) and brine (3×50 ml) and dried over sodium sulphate. Evaporation in vacuo afforded 2 as a white solid (19.27 g, 84%): mp 128-130° C.; 1H-NMR (270 MHZ, CDCl3) δ2.92 (t, 2H, J=6.35 Hz); 3.94 (s, 3H); 4.38 (t, 2H, J=6.41 Hz); 4.65 (d, 2H, J=5.61 Hz); 5.27 (dd, 1H, J1=1.28 Hz, J2=19.42 Hz); 5.33 (dd, 1H, J1=1.28 Hz, J2=17.04 Hz); 5.92 (m, 1H); 7.15 (s, 1H); 7.45 (s, 1H); 13C NMR (67.8 MHZ, CDCl3): δ34.1, 56.5, 65.0, 65.4, 108.5, 111.3, 118.3, 122.9, 131.8, 141.1, 149.1, 152.6, 167.1, 170.0; IR (Nujol); ν 1730, 1630, 1550, 1430, 1390, 1290, 1230, 1190, 1170, 1070, 1030, 1010 cm−1; MS (EI) m/z (relative intensity): 325 (M+•, 19), 251 (3), 213 (2), 196 (3), 211 (3), 113 (19), 91 (4), 71 (9), 55 (6); HRMS: calcd. for C14H15NO8 325.0798, found 232.0773.

Workup

  1. temperaturewas refluxed for 7 hours
  2. temperatureto cool
  3. customThe allyl alcohol was then removed in vacuo
  4. customthe residue triturated with dilute HCl acid (3×75 ml)
  5. filtrationcollected by filtration
  6. washthe resulting solution washed with water (3×50 ml) and brine (3×50 ml)
  7. dry with materialdried over sodium sulphate
  8. customEvaporation in vacuo

Sources & evidence

ORD record
ord-65bf006e8e3f4420bb7e98ae515a154a
Source dataset
uspto-grants-2003_08
Patent number
US06608192B1

Reaction notes

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