Sodium Hydroxide → Acetic acid, 2-(triphenylphosphoranylidene)-, methyl ester

HRID 2175310

Reaction equation

HRID 2175310 reaction equation
[Br-].[CH3:2][O:3][C:4](=[O:25])[CH2:5][P+:6]([C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)([C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1)[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1.[OH-].[Na+]>C(Cl)Cl.O>[C:13]1([P:6]([C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)([C:7]2[CH:8]=[CH:9][CH:10]=[CH:11][CH:12]=2)=[CH:5][C:4]([O:3][CH3:2])=[O:25])[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=1

Participants

5

Reactant 2

HCID 14798Sodium HydroxideHCID 2733211Phosphonium, (2-methoxy-2-oxoethyl)triphenyl-, bromide (1:1)

Product 1

HCID 17453Acetic acid, 2-(triphenylphosphoranylidene)-, methyl esterYield 93.2%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

A mixture of (2-methoxy-2-oxoethyl)triphenylphosphonium bromide (10.0 g, 24.08 mmol) in 100 mL DCM, 50 mL water and NaOH (10 N) (4.82 ml, 48.2 mmol) was vigorously shaken in a separatory funnel. The organic layer was separated and the aqueous phase was extracted with DCM. The combined organic layers were dried (MgSO4) and concentrated to give methyl 2-(triphenylphosphoranylidene)acetate (7.5 g, 93% yield) as a white solid. A solution of 3-chloro-2-methylbenzaldehyde (0.7 g, 4.53 mmol) and 2-(triphenylphosphoranylidene)acetate (1.817 g, 5.43 mmol) in MeOH (22.6 ml) was stirred at room temperature for 2 h. The mixture was concentrated and purified by flash chromatography (0-30% ethyl acetate:hexanes) to afford the title compound (0.23 g, 24% yield) as a clear colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.99 (d, J=15.9 Hz, 1H), 7.47-7.40 (m, 2H), 7.17-7.15 (m, 1H), 6.33 (d, J=15.9 Hz, 1H), 3.83 (s, 3H), 2.48 (s, 3H).

Workup

  1. customThe organic layer was separated
  2. extractionthe aqueous phase was extracted with DCM
  3. dry with materialThe combined organic layers were dried (MgSO4)
  4. concentrationconcentrated

Sources & evidence

ORD record
ord-a8c22b83402c484391b446e94507f69f
Source dataset
uspto-grants-2015_06
Patent number
US09062028B2

Linked notes

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