1-Methylpiperazine → 2-[5-(4-Methyl-piperazin-1-ylmethyl)-2-nitro-phenylamino]-4-phenyl-thiazole-5-carboxylic acid ethyl ester

HRID 1667679Notes

Reaction equation

HRID 1667679 reaction equation
[CH2:1]([O:3][C:4]([C:6]1[S:10][C:9]([NH:11][C:12]2[CH:17]=[C:16]([CH:18]=O)[CH:15]=[CH:14][C:13]=2[N+:20]([O-:22])=[O:21])=[N:8][C:7]=1[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)=[O:5])[CH3:2].[CH3:29][N:30]1[CH2:35][CH2:34][NH:33][CH2:32][CH2:31]1.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+]>ClCCl>[CH2:1]([O:3][C:4]([C:6]1[S:10][C:9]([NH:11][C:12]2[CH:17]=[C:16]([CH2:18][N:33]3[CH2:34][CH2:35][N:30]([CH3:29])[CH2:31][CH2:32]3)[CH:15]=[CH:14][C:13]=2[N+:20]([O-:22])=[O:21])=[N:8][C:7]=1[C:23]1[CH:24]=[CH:25][CH:26]=[CH:27][CH:28]=1)=[O:5])[CH3:2]

Participants

5

Reactant 3

HCID 531671-MethylpiperazineHCID 5049666Sodium triacetoxyborohydrideHCID 866428052-(5-Formyl-2-nitro-phenylamino)-4-phenyl-thiazole-5-carboxylic acid ethyl ester

Product 1

HCID 866428062-[5-(4-Methyl-piperazin-1-ylmethyl)-2-nitro-phenylamino]-4-phenyl-thiazole-5-carboxylic acid ethyl esterYield 68.5%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

A mixture of 0.080 g (0.2 mmole) of 2-(5-formyl-2-nitro-phenylamino)-4-phenyl-thiazole-5-carboxylic acid ethyl ester (VI.1b), 2 mL of dichloromethane and 0.027 mL (0.24 mmole) of 1-methyl-piperizine was stirred at ambient temperature for 10 minutes, then 0.064 g (0.3 mmole) of sodium triacetoxyborohydride was added. The mixture was stirred at ambient temperature for 2 hours and was then diluted with 10 mL of dichloromethane. The mixture was washed with 3 mL of saturated sodium bicarbonate. The aqueous layer was extracted twice with 5 mL of dichloromethane. The combined organic layers were washed with brine, dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. The residue was purified by silica gel chromatography, eluting with methanol-dichloromethane (gradient 0:100-5:95) to give 0.066 g of 2-[5-(4-methyl-piperazin-1-ylmethyl)-2-nitro-phenylamino]-4-phenyl-thiazole-5-carboxylic acid ethyl ester (VI.1c) as an orange solid.

Workup

  1. stirringThe mixture was stirred at ambient temperature for 2 hours
  2. washThe mixture was washed with 3 mL of saturated sodium bicarbonate
  3. extractionThe aqueous layer was extracted twice with 5 mL of dichloromethane
  4. washThe combined organic layers were washed with brine
  5. dry with materialdried over anhydrous magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. customThe residue was purified by silica gel chromatography
  9. washeluting with methanol-dichloromethane (gradient 0:100-5:95)

Sources & evidence

ORD record
ord-78bbc88d7e6e4d47bf008a03242d9aca
Source dataset
uspto-grants-2011_10
Patent number
US08044213B2

Reaction notes

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