HCID 19370400, compound → 100561-24-8

HRID 1608793Notes

Reaction equation

HRID 1608793 reaction equation
[CH2:1]([N:4]([CH2:20][CH2:21][CH3:22])[CH:5]1[CH2:19][CH:9]2[CH2:10][NH:11][C:12]3[CH:13]=[CH:14][C:15]([C:16]([NH2:18])=[O:17])=[C:7]([C:8]=32)[CH2:6]1)[CH2:2][CH3:3]>C(O)(=O)C.[Pd].CO.[O-2].[O-2].[Mn+4]>[CH2:20]([N:4]([CH2:1][CH2:2][CH3:3])[CH:5]1[CH2:19][C:9]2=[CH:10][NH:11][C:12]3[CH:13]=[CH:14][C:15]([C:16]([NH2:18])=[O:17])=[C:7]([C:8]=32)[CH2:6]1)[CH2:21][CH3:22]

Participants

6

Reactant 1

HCID 19370400HCID 19370400, compound

Product 1

HCID 60845100561-24-8

Reagents, catalysts & solvents 4

HCID 23938PalladiumCatalystHCID 178418406HCID 178418406, compoundCatalystHCID 176Acetic AcidSolventHCID 887MethanolSolvent

Procedure

The following enantiomer of the compound of Formula I ##STR9## can be prepared from the compound of Formula VII by reaction with an approximately equimolar mixture of carbon monoxide and ammonia in the presence of a catalyst, preferably a palladium catalyst such as bis(triphenylphosphine)palladium chloride or bis(triphenylphosphine)palladium bromide. The catalyst is preferably present in a ratio of about 0.05 mole per mole of reaction substrate. The preferred solvent is toluene, and the concentration of the reactant is about 0.5 to about 2.0 grams per 100 milliliters of solvent. The reaction vessel is sealed and the reaction mixture stirred at approximately 100° C. for approximately 6 hours. The use of such catalysts for the reaction of arylhalides with carbon monoxide is disclosed by Schoenberg and Heck, Journal of Organic Chemistry, 39, p. 3325 (1974) and Schoenberg, Bartoletti and Heck, Journal of Organic Chemistry, 39, p. 3318, (1974). The benzoyl group can then be removed by any of a number of methods known to the art, but preferably by reaction with approximately 4 equivalents of n-butyl lithium in freshly distilled tetrahydrofuran. The deprotection reaction is conducted at about -78°. The reaction is quenched by the addition of 1:1 (volume:volume) water and tetrahydrofuran, and the resulting 4-(di-n-propyl)amino-6-aminocarbonyl-1,2,2a,3,4,5-hexahydrobenz[cd]indole is isolated by evaporation of the tetrahydrofuran, extraction from the aqueous phase into a solvent such as methylene chloride, and evaporation of the solvent. Oxidation of the hexahydrobenz-[cd]indole by reaction with manganese dioxide in acetic acid by the method disclosed by Flaugh in U.S. Pat. No. 4,576,959 or palladium on carbon in methanol affords the desired 4-(di-n-propyl)amino-6-aminocarbonyl-1,3,4,5-tetrahydrobenz[cd]indole.

Sources & evidence

ORD record
ord-ddd3d8378f5b4cd99b4d01a316eca98b
Source dataset
uspto-grants-1995_03
Patent number
US05397799

Reaction notes

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