3-Phenylprop-2-En-1-Ol → Methyl-2-((E)-3-phenyl-allyloxycarbonylamino)-benzoate

HRID 33996

Reaction equation

HRID 33996 reaction equation
[CH3:1][O:2][C:3](=[O:13])[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][C:5]=1[N:10]=[C:11]=[O:12].N1C=CC=CC=1.[CH2:20]([OH:29])[CH:21]=[CH:22][C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1>C(Cl)Cl>[CH3:1][O:2][C:3](=[O:13])[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][C:5]=1[NH:10][C:11]([O:29][CH2:20]/[CH:21]=[CH:22]/[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)=[O:12]

Participants

5

Reactant 3

HCID 3083-Phenylprop-2-En-1-OlHCID 1049PyridineHCID 519494Methyl 2-isocyanatobenzoate

Product 1

HCID 58757606Methyl-2-((E)-3-phenyl-allyloxycarbonylamino)-benzoateYield 85%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

A solution of methyl-2-isocyanatobenzoate (71)(1 g, 5.6 mmol) in CH2Cl2 (100 mL) was cooled to 0° C. and treated with pyridine (7 mL, 84 mmol). Cinnamyl alcohol (2.25 g, 1.68 mmol) in CH2Cl2 (150 mL) was added dropwise to the stirring solution over a period of 1 hour and the reaction mixture was allowed to stir for 12 hours, under nitrogen. The reaction mixture was washed in brine (100 mL). The aqueous phase was washed with CH2Cl2 (3×100 mL). The organic phases were combined and washed with 1N HCl (200 mL) and dried over MgSO4. Purification was achieved through flash column chromatography (80% Pet ether:EtOAc) to furnish the carbamate (72) as a colourless solid (85%). 1H NMR (250 MHz, CDCl3) δ 10.9 (br, s, 1H, NH), 8.45 (dd. 1H, J=1.0, 8.5 Hz, aromatic H), 8.01 (dd, 1H, J=1.66, 8.0 Hz, aromatic H), 7.54 (ddd, 1H, J=1.67, 7.3, 8.5 Hz, aromatic H), 7.5-7.2 (m, 5H, coc aromatic H), 7.03 (ddd, 1H, J=1.2, 8.0 Hz, aromatic H), 6.71 (d, 1H, J=16 Hz, 3′-H), 6.35 (dt, 1H, J=6.3, 16 Hz, 2′-H), 4.48 (dd, 2H, J=1.3, 6.3, 1′-H), 3.91 (s, 1H); 13C NMR (62.9 MHz, CDCl3) δ 169.0 (ester carbonyl), 153.5 (CO-carbamate), 141.9 (aromatic quat), 136.8 (aromatic quat), 135.0 (methine), 131.3 (methine), 129.0 (methine), 128.4 (methine), 127.1 (methine), 123.9 (alkenic methine), 122.0 (methine), 119.3 (methine). 114.8 (aromatic quat), 66.1 (methylene-Coc), 57.7 (OCH3). IR (neat) ν 3295, 3116, 3025, 2957, 2242, 1956, 1927, 1814, 1732, 1697, 1592, 1532, 1450, 1305, 1245, 1165, 1090, 1038, 976, 913, 856, 836, 819, 766, 743, 692 cm−1; MS m/z 311 (M+. +1), 268, 212, 188, 152, 117.

Workup

  1. washThe reaction mixture was washed in brine (100 mL)
  2. washThe aqueous phase was washed with CH2Cl2 (3×100 mL)
  3. washwashed with 1N HCl (200 mL)
  4. dry with materialdried over MgSO4
  5. customPurification

Sources & evidence

ORD record
ord-53252d4892a84e9d9998dbda4ffe40d2
Source dataset
uspto-grants-2008_09
Patent number
US07429658B2

Linked notes

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