Sodium borohydride → 6-Bis(phenylmethyl)amino-4,5-diamino-pyridine-3-carboxylic acid ethyl ester

HRID 1268833Notes

Reaction equation

HRID 1268833 reaction equation
[BH4-].[Na+].[CH2:3]([O:5][C:6]([C:8]1[CH:9]=[N:10][C:11]([N:18]([CH2:26][C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)[CH2:19][C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)=[C:12]([N+:15]([O-])=O)[C:13]=1[NH2:14])=[O:7])[CH3:4]>CO.ClCCl.O.[Ni](Cl)Cl>[CH2:3]([O:5][C:6]([C:8]1[CH:9]=[N:10][C:11]([N:18]([CH2:26][C:27]2[CH:28]=[CH:29][CH:30]=[CH:31][CH:32]=2)[CH2:19][C:20]2[CH:21]=[CH:22][CH:23]=[CH:24][CH:25]=2)=[C:12]([NH2:15])[C:13]=1[NH2:14])=[O:7])[CH3:4]

Participants

6

Reactant 2

HCID 4311764Sodium borohydride2×HCID 690647034-Amino-6-bis(phenylmethyl)amino-5-nitro-pyridine-3-carboxylic acid ethyl ester

Product 1

HCID 690704746-Bis(phenylmethyl)amino-4,5-diamino-pyridine-3-carboxylic acid ethyl esterYield 24.1%

Reagents, catalysts & solvents 3

HCID 16212333Nickel chloride hydrateCatalystHCID 887MethanolSolventHCID 6344DichloromethaneSolvent

Procedure

Sodium borohydride (151 mg, 4.1 mmol) was added to a solution of nickel (II) chloride hydrate (261 mg, 1.1 mmol) in MeOH (26 mL). After 30 min. at room temperature, a solution of 4-amino-6-bis(phenylmethyl)amino-5-nitro-pyridine-3-carboxylic acid ethyl ester (0.9 g, 2.2 mmol) in dichloromethane (5 mL) was added followed by the addition of sodium borohydride (353 mg). The mixture was stirred over night then filtered through a layer of silica gel. The organic was diluted with dichloromethane, washed with brine and dried over sodium sulfate. The organics were filtered, concentrated and purified by column chromatography (dichloromethane:methanol, 20:1). 11 was obtained as a white solid (200 mg). 1H NMR (400 MHz, d6-DMSO) δ: 1.26 (t, J=7.1 Hz, 3H), 4.21 (s, 4H), 4.22 (q, J=7.1 Hz, 2H), 4.52 (s, 2H), 6.73 (s, 2H), 7.14–7.31 (m, 10H), 8.01 (s, 1H). ESIMS, M/Z, 377 (M+1)+.

Workup

  1. filtrationthen filtered through a layer of silica gel
  2. additionThe organic was diluted with dichloromethane
  3. washwashed with brine
  4. dry with materialdried over sodium sulfate
  5. filtrationThe organics were filtered
  6. concentrationconcentrated
  7. custompurified by column chromatography (dichloromethane:methanol, 20:1)

Sources & evidence

ORD record
ord-22383ad2578a4a9cbeb39c3c72ee2280
Source dataset
uspto-grants-2007_04
Patent number
US07199119B2

Reaction notes

Loading…