Carbon Tetrachloride → HCID 59394014, compound

HRID 453229Notes

Reaction equation

HRID 453229 reaction equation
[CH2:1]([O:3][C:4]([CH:6]1[N:16]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[CH2:15][C:9]2[N:10]=[CH:11][NH:12][C:13](=O)[C:8]=2[CH2:7]1)=[O:5])[CH3:2].[CH2:24]([O:26][C:27]([CH:29]1[N:38]([C:39]([O:41][C:42]([CH3:45])([CH3:44])[CH3:43])=[O:40])[CH2:37][C:36]2C(=O)[NH:34][CH:33]=[N:32][C:31]=2[CH2:30]1)=[O:28])[CH3:25].[C:47]([Cl:51])(Cl)(Cl)[Cl:48].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>ClCCCl>[CH2:1]([O:3][C:4]([CH:6]1[N:16]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[CH2:15][C:9]2[N:10]=[CH:11][N:12]=[C:13]([Cl:48])[C:8]=2[CH2:7]1)=[O:5])[CH3:2].[CH2:24]([O:26][C:27]([CH:29]1[N:38]([C:39]([O:41][C:42]([CH3:43])([CH3:45])[CH3:44])=[O:40])[CH2:37][C:36]2[C:47]([Cl:51])=[N:34][CH:33]=[N:32][C:31]=2[CH2:30]1)=[O:28])[CH3:25]

Participants

7

Reactant 4

HCID 5943Carbon TetrachlorideHCID 11776TriphenylphosphineHCID 136158778HCID 136158778, compoundHCID 136158779HCID 136158779, compound

Product 2

HCID 59394014HCID 59394014, compoundHCID 59394776HCID 59394776, compound

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent

Procedure

To a solution of the mixture of 4-oxo-4,5,6,8-tetrahydro-3H-pyrido[3,4-d]pyrimidine-6,7-dicarboxylic acid 7-tert-butyl ester 6-ethyl ester and 4-Oxo-3,5,7,8-tetrahydro-4H-pyrido[4,3-d]pyrimidine-6,7-dicarboxylic acid 6-tert-butyl ester 7-ethyl ester (1.5 g, 4.64 mmol) in DCE (25 mL), carbon tetrachloride (1.34 mL, 13.9 mmol) and triphenylphosphine (2.43 g, 9.28 mmol) are added. The reaction is heated at reflux and after completion of reaction as judged by LCMS. The solvents are removed and the products are isolated using FCC eluting with heptane:EtOAc 80:20. At this point the two products are separated. 4-Chloro-5,8-dihydro-6H-pyrido[3,4-d]pyrimidine-6,7-dicarboxylic acid 7-tert-butyl ester 6-ethyl ester MS (ESI) m/z 342.1 (M+1) and 4-chloro-7,8-dihydro-5H-pyrido[4,3-d]pyrimidine-6,7-dicarboxylic acid 6-tert-butyl ester 7-ethyl ester MS (ESI) m/z 342.1 (M+1) are isolated as an almost 4:1 ratio.

Workup

  1. additionare added
  2. temperatureThe reaction is heated
  3. temperatureat reflux
  4. customafter completion of reaction
  5. customThe solvents are removed
  6. customthe products are isolated
  7. washeluting with heptane:EtOAc 80:20
  8. customAt this point the two products are separated

Sources & evidence

ORD record
ord-58e0615ce4df479f8772bf21182ff557
Source dataset
uspto-grants-2013_07
Patent number
US08492393B2

Reaction notes

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