Acetic acid, 2-(triphenylphosphoranylidene)-, ethyl ester → Ethyl 3-(4-ethylamino-2-phenylamino pyrimidin-5-yl)acrylate

HRID 2300055Notes

Reaction equation

HRID 2300055 reaction equation
[CH2:1]([NH:3][C:4]1[C:9]([CH:10]=O)=[CH:8][N:7]=[C:6]([NH:12][C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[N:5]=1)[CH3:2].[C:19]([CH:24]=P(C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)([O:21][CH2:22][CH3:23])=[O:20]>O1CCCC1>[CH2:1]([NH:3][C:4]1[C:9]([CH:10]=[CH:24][C:19]([O:21][CH2:22][CH3:23])=[O:20])=[CH:8][N:7]=[C:6]([NH:12][C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[N:5]=1)[CH3:2]

Participants

4

Reactant 2

HCID 70670Acetic acid, 2-(triphenylphosphoranylidene)-, ethyl ester2×HCID 108240804-Ethylamino-2-phenylamino-pyrimidine-5-carbaldehyde

Product 1

HCID 54014983Ethyl 3-(4-ethylamino-2-phenylamino pyrimidin-5-yl)acrylateYield 86.6%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a room temperature solution of 4-ethylamino-2-phenylamino-pyrimidine-5-carboxaldehyde (320 mg, 1.32 mmol) in 12 mL of tetrahydrofuran was added (carbethoxymethylene)triphenylphosphorane (720 mg, 2.07 mmol). The reaction mixture was heated at reflux for 7 hours then stirred at room temperature overnight. An additional amount of (carbethoxymethylene)triphenylphosphorane (300 mg, 0.86 mmol) was added, and the reaction mixture was heated at reflux for an additional 8 hours then stirred at room temperature for 3 days. The reaction mixture was concentrated in vacuo, and the residue was purified by flash chromatography, eluting with 1:2 ethyl acetate:hexane, to provide 357 mg (86%) of ethyl 3-(4-ethylamino-2-phenylamino-pyrimidin-5-yl)acrylate, mp 125-126° C.

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureat reflux for 7 hours
  3. temperaturethe reaction mixture was heated
  4. temperatureat reflux for an additional 8 hours
  5. stirringthen stirred at room temperature for 3 days
  6. concentrationThe reaction mixture was concentrated in vacuo
  7. customthe residue was purified by flash chromatography
  8. washeluting with 1:2 ethyl acetate

Sources & evidence

ORD record
ord-ff32116a3bb7413ea007e51b51db3087
Source dataset
uspto-grants-2002_12
Patent number
US06498163B1

Reaction notes

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