Methyl chloroformate → 3,3a,4,5-tetrahydro-3a-methoxycarbonyl-N-[4'-(trifluoromethyl)phenyl]-2H-benz[g]indazole-2-carboxamide

HRID 2396077

Reaction equation

C(NC(C)C)(C)C.C([Li])CCC.[F:13][C:14]([F:38])([F:37])[C:15]1[CH:20]=[CH:19][C:18]([NH:21][C:22]([N:24]2[CH2:32][CH:31]3[C:26]([C:27]4[CH:36]=[CH:35][CH:34]=[CH:33][C:28]=4[CH2:29][CH2:30]3)=[N:25]2)=[O:23])=[CH:17][CH:16]=1.Cl[C:40]([O:42][CH3:43])=[O:41]>C1COCC1.CCCCCC>[CH3:43][O:42][C:40]([C:31]12[CH2:30][CH2:29][C:28]3[CH:33]=[CH:34][CH:35]=[CH:36][C:27]=3[C:26]1=[N:25][N:24]([C:22]([NH:21][C:18]1[CH:17]=[CH:16][C:15]([C:14]([F:13])([F:37])[F:38])=[CH:20][CH:19]=1)=[O:23])[CH2:32]2)=[O:41]

Participants

Conditions

Temperature: 0 °C

Procedure

To a solution of 0.9 ml of diisopropylamine in 10 ml of THF, at -78°C., was added 2.3 ml of 2.5 M n-butyl lithium in hexane and the mixture wasstirred for 5 mins. To this solution was added a solution of 1.0 g of the title compound of Step A in 5 ml of THF. The reaction was warmed to 0° C., recooled to -78° C. and then 0.75 ml of methyl chloroformate was added. The reaction mixture was then stirred for 24 h, with gradual warming to room temperature, quenched with 0.5 ml of glacial acetic acid, and poured into a 5% solution of aqueous NaHCO3. The mixture was extracted with chloroform, dried over magnesium sulfate and concentrated. Chromatography on silica gel with 30% ethyl acetate hexane afforded 0.25 g of the title compound, m.p. 177° to 180° C.

Workup

customrecooled to -78° C.
temperaturewith gradual warming to room temperature
customquenched with 0.5 ml of glacial acetic acid
additionpoured into a 5% solution of aqueous NaHCO3
extractionThe mixture was extracted with chloroform
dry with materialdried over magnesium sulfate
concentrationconcentrated

Sources & evidence

ORD record: ord-88dc0f73e0bb490381b6c96a8d352748
Source dataset: uspto-grants-1996_02
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05491162

Linked notes

Loading…