Triphenylphosphine → Methyl 3-{3-[5-(3-dimethylaminopropoxy)pyrimidin-2-yl]-benzyl}-2-oxo-2,3-dihydrobenzoxazole-5-carboxylate

HRID 655333Notes

Reaction equation

HRID 655333 reaction equation
[O:1]=[C:2]1[NH:6][C:5]2[CH:7]=[C:8]([C:11]([O:13][CH3:14])=[O:12])[CH:9]=[CH:10][C:4]=2[O:3]1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH3:34][N:35]([CH3:54])[CH2:36][CH2:37][CH2:38][O:39][C:40]1[CH:41]=[N:42][C:43]([C:46]2[CH:47]=[C:48]([CH2:52]O)[CH:49]=[CH:50][CH:51]=2)=[N:44][CH:45]=1.C(OC(N=NC(OC(C)(C)C)=O)=O)(C)(C)C>C1COCC1>[CH3:54][N:35]([CH3:34])[CH2:36][CH2:37][CH2:38][O:39][C:40]1[CH:45]=[N:44][C:43]([C:46]2[CH:47]=[C:48]([CH:49]=[CH:50][CH:51]=2)[CH2:52][N:6]2[C:5]3[CH:7]=[C:8]([C:11]([O:13][CH3:14])=[O:12])[CH:9]=[CH:10][C:4]=3[O:3][C:2]2=[O:1])=[N:42][CH:41]=1

Participants

6

Reactant 4

HCID 11776Triphenylphosphine2×HCID 97268Di-tert-butyl azodicarboxylate2×HCID 12395109Methyl 2-oxo-2,3-dihydro-1,3-benzoxazole-5-carboxylateHCID 59484942{3-[5-(3-Dimethylaminopropoxy)pyrimidin-2-yl]phenyl}methanol

Product 1

HCID 58486066Methyl 3-{3-[5-(3-dimethylaminopropoxy)pyrimidin-2-yl]-benzyl}-2-oxo-2,3-dihydrobenzoxazole-5-carboxylate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

1.84 g (9.5 mmol) of methyl 2-oxo-2,3-dihydrobenzoxazole-5-carboxylate and 4.75 g (14.25 mmol) of polymer-bound triphenylphosphine (3 mmol/g) are added to a solution of 3.03 g (10.45 mmol) of {3-[5-(3-dimethylaminopropoxy)pyrimidin-2-yl]phenyl}methanol in 40 ml of THF. The suspension is shaken at room temperature for 30 min. The suspension is cooled in an ice bath, and 3.35 g (14.25 mmol) of di-tert-butyl-azodicarboxylate are added in portions. After the mixture has been stirred at room temperature for 24 h, a further 4.75 g (14.25 mmol) of polymer-bound triphenylphosphine (3 mmol/g) and 3.35 g (14.25 mmol) of di-tert-butyl azodicarboxylate are added, and the mixture is shaken at room temperature for a further 24 h. The reaction mixture is filtered, the filtrate is evaporated to dryness, and the residue is purified by column chromatography on silica gel, giving 947 mg of “A64”; m.p. 125° C., ESI: 463 (M+H); Rt=3.07 min (method C);

Workup

  1. temperatureThe suspension is cooled in an ice bath
  2. stirringAfter the mixture has been stirred at room temperature for 24 h
  3. stirringthe mixture is shaken at room temperature for a further 24 h
  4. filtrationThe reaction mixture is filtered
  5. customthe filtrate is evaporated to dryness
  6. customthe residue is purified by column chromatography on silica gel
  7. customgiving 947 mg of “A64”

Sources & evidence

ORD record
ord-d9437d7c069a4e3a8363d8f9eb9b0656
Source dataset
uspto-grants-2011_12
Patent number
US08071593B2

Reaction notes

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