Ethyl Acetate → di-tert-butyl [({2-[1-methyl-5-(tritylamino)-1H-pyrazol-4-yl]-2-oxoacetyl}imino)bis(2,1-ethanediyl)]biscarbamate

HRID 459659Notes

Reaction equation

HRID 459659 reaction equation
[C:1](N1C=CN=C1)(=[O:9])[C:2](N1C=CN=C1)=[O:3].[CH3:15][N:16]1[C:20]([NH:21][C:22]([C:35]2[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=2)([C:29]2[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=2)[C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)=[C:19](N)[CH:18]=[N:17]1.[NH:42]([CH2:53][CH2:54][NH:55][C:56](=[O:62])[O:57][C:58]([CH3:61])([CH3:60])[CH3:59])[CH2:43][CH2:44][NH:45][C:46](=[O:52])[O:47][C:48]([CH3:51])([CH3:50])[CH3:49].C(OCC)(=O)C>CN(C)C=O.C(Cl)Cl>[CH3:15][N:16]1[C:20]([NH:21][C:22]([C:35]2[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=2)([C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)[C:29]2[CH:30]=[CH:31][CH:32]=[CH:33][CH:34]=2)=[C:19]([C:1](=[O:9])[C:2]([N:42]([CH2:43][CH2:44][NH:45][C:46](=[O:52])[O:47][C:48]([CH3:49])([CH3:50])[CH3:51])[CH2:53][CH2:54][NH:55][C:56](=[O:62])[O:57][C:58]([CH3:61])([CH3:60])[CH3:59])=[O:3])[CH:18]=[N:17]1

Participants

7

Reactant 4

HCID 8857Ethyl AcetateHCID 1004391,1'-OxalyldiimidazoleHCID 15157893tert-butyl N-{2-[(2-{[(tert-butoxy)carbonyl]amino}ethyl)amino]ethyl}carbamateHCID 685167251-methyl-N5-trityl-1H-pyrazole-4,5-diamine

Product 1

HCID 86760460di-tert-butyl [({2-[1-methyl-5-(tritylamino)-1H-pyrazol-4-yl]-2-oxoacetyl}imino)bis(2,1-ethanediyl)]biscarbamateYield 64.1%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolvent2×HCID 6344DichloromethaneSolvent

Procedure

To a solusion of 1,1′-oxalyldiimidazole (1.52 g) in N,N-dimethylformamide (16 ml) was added 1-methyl-N5-trityl-1H-pyrazole-4,5-diamine (1.42 g) under ice-cooling, and the mixture was stirred at room temperature for 1 hour. To the reaction mixture was added a solution of di-tert-butyl [iminobis(2,1-ethanediyl)]biscarbamate (4.55 g) in N,N-dimethylformamide (4 ml) under ice-cooling, and the mixture was stirred at room temperature for 1 day and then allowed to stand at room temperature for 9 days. To the reaction mixture were added ethyl acetate (50 ml) and methylene chloride (20 ml). The resulting precipitate was collected by filtration and dried in vacuo to give di-tert-butyl [({2-[1-methyl-5-(tritylamino)-1H-pyrazol-4-yl]-2-oxoacetyl}imino)bis(2,1-ethanediyl)]biscarbamate (1.79 g) as a solid. The mother liquor was washed successively with water, 5% aqueous citric acid solution and brine. The organic layer was dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. The crystalline residue was washed with a mixed solvent of methylene chloride and diethyl ether, dried in vacuo and combined with the former solid to give di-tert-butyl [({2-[1-methyl-5-(tritylamino)-1H-pyrazol-4-yl]-2-oxoacetyl}imino)bis(2,1-ethanediyl)]biscarbamate (2.44 g).

Workup

  1. temperaturecooling
  2. temperaturecooling
  3. stirringthe mixture was stirred at room temperature for 1 day
  4. waitto stand at room temperature for 9 days
  5. filtrationThe resulting precipitate was collected by filtration
  6. customdried in vacuo

Sources & evidence

ORD record
ord-b2f1ba606dbb4ce7b2de841cd49538a8
Source dataset
uspto-grants-2007_03
Patent number
US07192943B2

Reaction notes

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