Acetic acid, 2-(triphenylphosphoranylidene)-, ethyl ester → HCID 66833546, compound

HRID 579531Notes

Reaction equation

HRID 579531 reaction equation
[CH:1]([CH:3]1[CH2:12][C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[CH2:5][N:4]1[C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])=O.[CH2:20]([O:22][C:23]([CH:25]=P(C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)=[O:24])[CH3:21]>C1COCC1>[CH2:20]([O:22][C:23](=[O:24])/[CH:25]=[CH:1]/[CH:3]1[CH2:12][C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[CH2:5][N:4]1[C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])[CH3:21]

Participants

4

Reactant 2

HCID 70670Acetic acid, 2-(triphenylphosphoranylidene)-, ethyl esterHCID 12190329tert-Butyl 3-formyl-3,4-dihydroisoquinoline-2(1H)-carboxylate

Product 1

HCID 66833546HCID 66833546, compoundYield 82%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A solution of tert-butyl 3-formyl-3,4-dihydroisoquinoline-2(1H)-carboxylate (8.4 g, 32.2 mmol) in dry THF (200 mL, 0.16 M) was treated with (ethoxycarbonylmethylene)triphenylphosphorane (12.8 g, 37.0 mmol) in one portion. After stirring at room temperature overnight, the solvent was evaporated, and the resulting residue was dissolved in ether. Heptane was added and the precipitated triphenylphosphine oxide was filtered off. The filtrate was concentrated and purified by flash chromatography (5-20% ethyl acetate in hexane) affording (E)-tert-butyl 3-(3-ethoxy-3-oxoprop-1-enyl)-3,4-dihydroisoquinoline-2(1H)-carboxylate as yellow oil (8.7 g, 82%). 1H NMR (CDCl3, 500 MHz) δ 7.21-7.14 (m, 2H), 7.14-7.07 (m, 2H), 6.74 (dd, J1=15.8 Hz, J2=4.8 Hz, 1H), 5.79 (dd, J1=15.8 Hz, J2=1.3 Hz, 1H), 4.72 (d, J=16.5 Hz, 1H), 4.35 (d, J=16.5 Hz, 1H), 4.11 (qw, J=14.4 Hz, 2H), 3.18 (dd, J1=15.8 Hz, J2=6.2 Hz 1H), 2.84 (d, J=15.8 Hz, 1H), 1.49 (s, 9H), 1.23 (t, J=14.4 Hz, 3H). ESI MS found for C19H25NO4 m/z [354.4 (M+23)].

Workup

  1. customthe solvent was evaporated
  2. dissolutionthe resulting residue was dissolved in ether
  3. additionHeptane was added
  4. filtrationthe precipitated triphenylphosphine oxide was filtered off
  5. concentrationThe filtrate was concentrated
  6. custompurified by flash chromatography (5-20% ethyl acetate in hexane)

Sources & evidence

ORD record
ord-4346235c84644daab1a15c28fd651f78
Source dataset
uspto-grants-2015_05
Patent number
US09040703B2

Reaction notes

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