tert-Butyl hydroperoxide → 2-(2,2dimethylpropionyloxymethyl)-3,4,7,8-tetrahydro-6H-cyclopenta[g]quinazolin-4,6-dione

HRID 1038947Notes

Reaction equation

HRID 1038947 reaction equation
[C:1]([O:5]O)(C)([CH3:3])[CH3:2].[CH3:7][C:8]([CH3:28])([CH3:27])[C:9]([O:11][CH2:12][C:13]1[NH:22][C:21](=[O:23])[C:20]2[C:15](=[CH:16][C:17]3CCC[C:18]=3[CH:19]=2)[N:14]=1)=[O:10]>C(Cl)Cl>[CH3:7][C:8]([CH3:28])([CH3:27])[C:9]([O:11][CH2:12][C:13]1[NH:22][C:21](=[O:23])[C:20]2[C:15](=[CH:16][C:17]3[CH2:18][CH2:3][C:1](=[O:5])[C:2]=3[CH:19]=2)[N:14]=1)=[O:10]

Participants

4

Reactant 2

HCID 6410tert-Butyl hydroperoxideHCID 1360653082-(2,2-dimethylpropionyloxymethyl)-3,4,7,8-tetrahydro-6H-cyclopenta[g]quinazolin-4-one

Product 1

HCID 1360652992-(2,2dimethylpropionyloxymethyl)-3,4,7,8-tetrahydro-6H-cyclopenta[g]quinazolin-4,6-dioneYield 45.3%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a stirred solution of (Ph3SiO)2CrO2 (L. M. Baker and W. L. Carrick, J. Org. Chem. 1970, 35, 774) (10.6 mg, 0.017 mmol) in CH2Cl2 (5 ml) was added sequentially aqueous 70% tert-butyl hydroperoxide (0.18 ml, 1.3 mmol) and 2-(2,2-dimethylpropionyloxymethyl)-3,4,7,8-tetrahydro-6H-cyclopenta[g]quinazolin-4-one (0.1 g, 0.33 mmol). The mixture was stirred at room temperature with protection from the light for 24 h. The solvents were removed in vacuo and the residue purified by column chromatography (20 g of silica gel) eluting with a gradient of 10-30% EtOAc in CHCl3 to yield 2-(2,2-dimethylpropionyloxymethyl)-3,4,7,8-tetrahydro-6H-cyclopenta[g]quinazolin-4,6-dione as a white solid (47 mg, 45%); m.p. 185-190° C.; 1H-NMR (DMSO-d6) δ 1.23 (s, 9H, CMe3), 2.72 (m, 2H, 7-H), 3.25 (m, 2H, 8-H), 5.00 (s, 2H, 2-CH2), 7.70 (s, 1H, 9-H), 8.29 (s, 1H, 5-H), 12.20 (br, 1H, NH); MS (FAB, m/z): Found 315 [(M+H)+, 100%], 337 [(M+Na)+, 75%]; HRMS: measured 315.1360; calculated for C17H19N2O4 (M+H)+: 315.1345. Found C, 64.18; H, 5.72; N, 8.81. C17H18N2O4.0.2H2O requires C, 64.23; H, 5.79; N, 8.82%.

Workup

  1. customThe solvents were removed in vacuo
  2. customthe residue purified by column chromatography (20 g of silica gel)
  3. washeluting with a gradient of 10-30% EtOAc in CHCl3

Sources & evidence

ORD record
ord-02218a60303741a18806eb226767730f
Source dataset
uspto-grants-2013_10
Patent number
US08552016B2

Reaction notes

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