Sodium Carbonate → ethyl 3-(benzyloxy)-4-oxo-9-phenyl-6,7-dihydro-4H-pyrido[1,2-a]pyrimidine-2-carboxylate

HRID 346488Notes

Reaction equation

HRID 346488 reaction equation
[CH2:1]([O:8][C:9]1[C:14](=[O:15])[N:13]2[CH2:16][CH2:17][CH:18]=[C:19](Br)[C:12]2=[N:11][C:10]=1[C:21]([O:23][CH2:24][CH3:25])=[O:22])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:26]1(B(O)O)[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1.C(=O)([O-])[O-].[Na+].[Na+]>C(#N)C.O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH2:1]([O:8][C:9]1[C:14](=[O:15])[N:13]2[CH2:16][CH2:17][CH:18]=[C:19]([C:26]3[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=3)[C:12]2=[N:11][C:10]=1[C:21]([O:23][CH2:24][CH3:25])=[O:22])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

7

Reactant 3

HCID 10340Sodium CarbonateHCID 66827Phenylboronic AcidHCID 21080172ethyl 3-(benzyloxy)-9-bromo-4-oxo-6,7-dihydro-4H-pyrido[1,2-a]pyrimidine-2-carboxylate

Product 1

HCID 21080170ethyl 3-(benzyloxy)-4-oxo-9-phenyl-6,7-dihydro-4H-pyrido[1,2-a]pyrimidine-2-carboxylateYield 68.4%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 6342AcetonitrileSolvent

Conditions

Temperature
90 °C

Procedure

A mixture of intermediate 15, ethyl 3-(benzyloxy)-9-bromo-4-oxo-6,7-dihydro-4H-pyrido[1,2-a]pyrimidine-2-carboxylate, (0.477 g, 1.18 mmol) in acetonitrile (15 ml) and water (15 ml) was treated with phenylboronic acid (0.190 g, 1.53 mmol), sodium carbonate (0.275 g, 2.6 mmol) and tetrakis(triphenylphosphine)palladium(0) (0.200 g). The reaction mixture was degassed, flushed with argon and heated at 90° C. for 30 min. The reaction mixture was then concentrated in vacuo, diluted with ethyl acetate, washed with water and brine, dried over anhydrous magnesium sulfate and concentrated. Chromatography of the residue on silica gel (elution gradient of ethyl acetate in hexane) gave 0.325 g (68% yield) of the title material as a clear oil. 1HNMR 400 MHz (CDCl3) δ (PPM): 1.26 (3H, t, J=7.1 Hz, CH3), 2.68 (2H, m, CH2), 4.27 (2H, q, J=7.1 Hz, OCH2), 4.32 (2H, t, J=7.6 Hz, CH2), 5.34 (2H, s, OCH2), 6.73 (1H, t, J=4.8 Hz, CH), 7.3–7.55 (10H, m, aromatics). HRMS (ESI+) calculated for C24H23N2O4 [M+H+]: 403.1658; found: 403.1659.

Workup

  1. customThe reaction mixture was degassed
  2. customflushed with argon
  3. concentrationThe reaction mixture was then concentrated in vacuo
  4. additiondiluted with ethyl acetate
  5. washwashed with water and brine
  6. dry with materialdried over anhydrous magnesium sulfate
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-20b9093bcb694353b608341893a14c6c
Source dataset
uspto-grants-2007_02
Patent number
US07173022B2

Reaction notes

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