Acetic Acid → Methyl 3-Hydroxy-2-methylene-3-phenylpropionate

HRID 259688

Reaction equation

[CH:1](=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:9]([O:13][CH3:14])(=[O:12])[CH:10]=[CH2:11].N12CCN(CC1)CC2.C(O)(=O)C>C(OCC)C>[CH:1](=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[OH:8][CH:1]([C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1)[C:10](=[CH2:11])[C:9]([O:13][CH3:14])=[O:12]

Participants

Conditions

Temperature: 35 °C

Procedure

A mixture of benzaldehyde (82.1 mL, 0.81 mol), methyl acrylate (109.1 mL, 1.211 mol), 1,4-diazabicyclo (2,2,2) octane (13.6 g, 0.12 mol), and acetic acid (1.4 mL, 0.024 mol) was allowed to stir at 35° C. for 60 h, at which point the reaction was determined to have proceeded to 70% completion by 1H NMR. Methyl acrylate (20.9 mL, 0.23 mol) was then added and the solution was allowed to react at 35° C. for an additional 48 h. The mixture was diluted with diethyl ether (1.0 L) and was washed with 2×200 mL portions of a pH 7 phosphate buffer. After concentration in vacuo, the remaining mixture was distilled at reduced pressure (12 mm) to afford 6.5 g of unreacted benzaldehyde and 130.0 g (90%) of the desired product as a colorless oil: b.p. 130° C. (12 mm); IR (film) 1718, 1440 cm-1 ; 1H NMR (CDCl3) δ3.67 (s, 3H), 5.52 (br s, 1H), 5.83-5.85 (m, 1H), 6.29-6.31 (m, 1H), 7.23-7.39 (m, 5H); 13C NMR (75 MHz, CDCl3) δ51.8, 72.9, 125.8, 126.5, 127.7, 128.3, 141.2, 141.9, 166.6.

Workup

customto react at 35° C. for an additional 48 h
washwas washed with 2×200 mL portions of a pH 7 phosphate buffer
concentrationAfter concentration in vacuo
distillationthe remaining mixture was distilled at reduced pressure (12 mm)

Sources & evidence

ORD record: ord-9d25ff0266064d7d9465023a7276261c
Source dataset: uspto-grants-1996_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05523289

Linked notes

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