Sodium methanethiolate → (2-Amino-6-methylsulfanyl-3-nitro-pyridin-4-yl)-benzyl-carbamic acid ethyl ester

HRID 639666Notes

Reaction equation

HRID 639666 reaction equation
[CH3:1][S-:2].[Na+].[CH2:4]([O:6][C:7](=[O:27])[N:8]([C:16]1[CH:21]=[C:20](Cl)[N:19]=[C:18]([NH2:23])[C:17]=1[N+:24]([O-:26])=[O:25])[CH2:9][C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)[CH3:5]>CO.C1COCC1.CO>[CH2:4]([O:6][C:7](=[O:27])[N:8]([C:16]1[CH:21]=[C:20]([S:2][CH3:1])[N:19]=[C:18]([NH2:23])[C:17]=1[N+:24]([O-:26])=[O:25])[CH2:9][C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)[CH3:5]

Participants

5

Reactant 2

HCID 4378561Sodium methanethiolateHCID 57856589(2-Amino-6-chloro-3-nitro-pyridin-4-yl)-benzyl-carbamic acid ethyl ester

Product 1

HCID 67455771(2-Amino-6-methylsulfanyl-3-nitro-pyridin-4-yl)-benzyl-carbamic acid ethyl esterYield 95.8%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 21899815MeOH tetrahydrofuranSolvent

Procedure

Sodium methanethiolate (180 mg) was added portion-wise to a stirred suspension of (2-amino-6-chloro-3-nitro-pyridin-4-yl)-benzyl-carbamic acid ethyl ester (300 mg) in methanol:THF (3:1, 4 ml). The mixture was sealed in a ReactiVial then left to stir at room temperature for 2 hours. The reaction mixture was diluted with methanol then pre-absorbed directly onto silica gel. The crude was columned on Isco Companion on a silica column (12 g, Redisep), eluting with EtOAc:heptane, increasing the gradient linearly from 30:70 to 50:50 over 6 column volumes. The desired fractions were combined and evaporated to provide the title compound (297 mg) as a yellow gum.

Workup

  1. customThe mixture was sealed in a ReactiVial
  2. waitthen left
  3. customthen pre-absorbed directly onto silica gel
  4. washeluting with EtOAc
  5. temperatureheptane, increasing the gradient linearly from 30:70 to 50:50 over 6 column volumes
  6. customevaporated

Sources & evidence

ORD record
ord-fd0ec1c99d2b41608eadd7332b78afef
Source dataset
uspto-grants-2010_04
Patent number
US07691877B2

Reaction notes

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