Lithium Hydroxide → 2-((E)-3-phenyl-allyloxycarbonylamino)-benzoic acid

HRID 33997Notes

Reaction equation

HRID 33997 reaction equation
C[O:2][C:3](=[O:23])[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][C:5]=1[NH:10][C:11]([O:13][CH2:14]/[CH:15]=[CH:16]/[C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)=[O:12].[Li+].[OH-].CCOC(C)=O>CO.C1COCC1>[C:17]1(/[CH:16]=[CH:15]/[CH2:14][O:13][C:11]([NH:10][C:5]2[CH:6]=[CH:7][CH:8]=[CH:9][C:4]=2[C:3]([OH:23])=[O:2])=[O:12])[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1

Participants

6

Reactant 3

HCID 3939Lithium HydroxideHCID 8857Ethyl AcetateHCID 58757606Methyl-2-((E)-3-phenyl-allyloxycarbonylamino)-benzoate

Product 1

HCID 587576422-((E)-3-phenyl-allyloxycarbonylamino)-benzoic acid

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranCatalystHCID 887MethanolSolvent

Procedure

Compound 72 (7.989 g, 26 mmol) was dissolved in aqueous methanol (3:1, 1200 mL) with THF (2-3 drops) to aid solubility. A solution of LiOH (3.12 g, 130 mmol) was added as a solid to the stirring reaction mixture at 0° C. and stirred for 40 minutes. The reaction was allowed to return to room temperature and stirred for 16 hours, at which time TLC (70% Pet ether:EtOAc) revealed complete reaction. Excess methanol and THF were evaporated in vacuo and the remaining solution acidified to pH 2 with conc. HCl, to furnish a colourless precipitate (73), which was collected by filtration and dried (92%). 1H NMR (250 MHz, CDCl3) δ 10.85 (s, 1H, acid OH), 10.80 (s, 1H, carbamate NH), 8.34-8.32 (d, 1H, aromatic H), 8.00 (dd, 1H, J=1.5, 7.9 Hz, aromatic H), 7.70-7.55 (m, 1H, aromatic H), 7.53-7.10 (m, 5H, aromatic coc), 6.75 (d, 1H, J=16 Hz, 3′-H), 6.46 (dt, 1H, J=6.2, 16 Hz, 2′-H), 4.82 (d, 2H, J=6.3 Hz, 1′-H); 13C NMR (62.9 MHz, CDCl3) δ 170.6 (ester carbonyl), 153.2 (CO carbamate), 142.0 (aromatic quat), 137.1 (aromatic quat), 135.1 (methine), 134.5 (alkenic methine), 132.5 (methine), 131.0 (methine), 127.7 (methine), 125.0 (alkenic methine), 122.6 (methine), 119.0 (methine), 116.5 (aromatic quat), 66.5 (methylene Coc). MS m/z 297 (M+. +1), 265, 252, 236, 224, 205, 189, 176, 149, 138, 117.

Workup

  1. customto return to room temperature
  2. customreaction
  3. customExcess methanol and THF were evaporated in vacuo

Sources & evidence

ORD record
ord-1e730a632304465c84925a140bdea95b
Source dataset
uspto-grants-2008_09
Patent number
US07429658B2

Reaction notes

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