HRID453229

反应详情

EQUATION

反应方程式

REACTANTS

反应物

HCID5943

Carbon tetrachloride

CCl4

HCID11776

Triphenylphosphine

C18H15P

结构：CCOC(=O)C1Cc2nc[nH]c(=O)c2CN1C(=O)OC(C)(C)C

HCID136158778

未命名化合物

结构：CCOC(=O)C1Cc2c(nc[nH]c2=O)CN1C(=O)OC(C)(C)C

HCID136158779

未命名化合物

PRODUCTS

生成物

结构：CCOC(=O)C1Cc2c(Cl)ncnc2CN1C(=O)OC(C)(C)C

HCID59394014

未命名化合物

结构：CCOC(=O)C1Cc2ncnc(Cl)c2CN1C(=O)OC(C)(C)C

HCID59394776

未命名化合物

AUXILIARIES

试剂、催化剂与溶剂

溶剂HCID11

1,2-Dichloroethane

C2H4Cl2

PROCEDURE

实验过程

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

后处理

additionare added
temperatureThe reaction is heated
temperatureat reflux
customafter completion of reaction
customThe solvents are removed
customthe products are isolated
washeluting with heptane:EtOAc 80:20
customAt this point the two products are separated

来源与证据

来源类型: Open Reaction Database
ORD 记录: ord-58e0615ce4df479f8772bf21182ff557
来源数据集: uspto-grants-2013_07
DOI: 10.6084/m9.figshare.5104873.v1
专利: US08492393B2
来源说明: uspto-grants-2013_07

反应 SMILES

[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]