Potassium Carbonate → Methyl 2-[N-(tert-Butoxycarbonyl)-N-[(2'-cyanobiphenyl-4-yl)methyl]amino]-3-nitrobenzoate

HRID 1831010Notes

Reaction equation

HRID 1831010 reaction equation
[C:1]([O:5][C:6]([NH:8][C:9]1[C:18]([N+:19]([O-:21])=[O:20])=[CH:17][CH:16]=[CH:15][C:10]=1[C:11]([O:13][CH3:14])=[O:12])=[O:7])([CH3:4])([CH3:3])[CH3:2].C(=O)([O-])[O-].[K+].[K+].[CH3:28][C:29]1[CH:34]=[CH:33][C:32]([C:35]2[CH:42]=[CH:41][CH:40]=[CH:39][C:36]=2[C:37]#[N:38])=[CH:31][CH:30]=1.BrCC1(CBr)C=CC(C2C=CC=CC=2C#N)=CC1>C(#N)C>[C:1]([O:5][C:6]([N:8]([C:9]1[C:18]([N+:19]([O-:21])=[O:20])=[CH:17][CH:16]=[CH:15][C:10]=1[C:11]([O:13][CH3:14])=[O:12])[CH2:28][C:29]1[CH:30]=[CH:31][C:32]([C:35]2[CH:42]=[CH:41][CH:40]=[CH:39][C:36]=2[C:37]#[N:38])=[CH:33][CH:34]=1)=[O:7])([CH3:4])([CH3:2])[CH3:3]

Participants

6

Reactant 4

HCID 11430Potassium CarbonateHCID 1455122-Cyano-4'-methylbiphenylHCID 9965968Methyl 2-((tert-butoxycarbonyl)amino)-3-nitrobenzoateHCID 865948322-(4,4-Dibromomethylphenyl)benzonitrile

Product 1

HCID 10874596Methyl 2-[N-(tert-Butoxycarbonyl)-N-[(2'-cyanobiphenyl-4-yl)methyl]amino]-3-nitrobenzoate

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent2×

Procedure

30.1 g of methyl 2-tert-butoxycarbonylamino-3-nitrobenzoate [BAN], 40.8 g of potassium carbonate and 160 ml of acetonitrile were added to the acetonitrile solution in which unreacted 2-(4-methylphenyl)benzonitrile [MPB] and 2-(4,4-dibromomethylphenyl)benzonitrile as an analogue of BMB were contaminated, and the reaction was allowed to proceed at about 82° C. for about 5 hours under stirring. After cooling to room temperature, the precipitated crystals were filtered off, and the filtrate was concentrated to give methyl 2-[N-t-butoxycarbonyl-N-[(2′-cyanobiphenyl-4-yl)methyl]amino]-3-nitrobenzoate [BBN]. The concentrated material was dissolved in 190 g of methanol, and 106 g of concentrated hydrochloric acid was added dropwise thereto. The resulting solution was heated to a reflux temperature over 2 hours, and stirred for 2 hours under reflux, whereby, the reaction was allowed to proceed. The reaction solution was cooled, and precipitated crystals were collected by filteration and dried to give 35.1 g of methyl 2-[N-(2′-cyanobiphenyl-4-yl)methylamino]-3-nitrobenzoate [MBN] (yield relative to 2-(4-methylphenyl)benzonitrile [MPB] was 76.1%)

Workup

  1. filtrationthe precipitated crystals were filtered off
  2. concentrationthe filtrate was concentrated

Sources & evidence

ORD record
ord-3fa5f3473cf04e46be41b3103d25c389
Source dataset
uspto-grants-2006_06
Patent number
US07067546B2

Reaction notes

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