Thiophenol → Ethyl 4-[2-(2,6-bis-hydroxymethyl-pyridin-4-yloxy)-ethylamino]-butanoate

HRID 2173750Notes

Reaction equation

HRID 2173750 reaction equation
[OH:1][CH2:2][C:3]1[CH:8]=[C:7]([O:9][CH2:10][CH2:11][N:12](S(C2C=CC=CC=2[N+]([O-])=O)(=O)=O)[CH2:13][CH2:14][CH2:15][C:16]([O:18][CH2:19][CH3:20])=[O:17])[CH:6]=[C:5]([CH2:33][OH:34])[N:4]=1.C(=O)([O-])[O-].[Cs+].[Cs+].C1(S)C=CC=CC=1>C(#N)C>[OH:34][CH2:33][C:5]1[CH:6]=[C:7]([O:9][CH2:10][CH2:11][NH:12][CH2:13][CH2:14][CH2:15][C:16]([O:18][CH2:19][CH3:20])=[O:17])[CH:8]=[C:3]([CH2:2][OH:1])[N:4]=1

Participants

5

Reactant 3

HCID 7969ThiophenolHCID 10796Cesium carbonateHCID 66714046Ethyl 4-[[2-(2,6-bis-hydroxymethyl-pyridin-4-yloxy)-ethyl]-(2-nitro-benzenesulfonyl)-amino]-butanoate

Product 1

HCID 66714275Ethyl 4-[2-(2,6-bis-hydroxymethyl-pyridin-4-yloxy)-ethylamino]-butanoateYield 74.7%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

To a solution of 390 mg of ethyl 4-[[2-(2,6-bis-hydroxymethyl-pyridin-4-yloxy)ethyl]-(2-nitro-benzenesulfonyl)-amino]-butanoate in 10 ml of acetonitrile, under argon, was added 766 mg of caesium carbonate and 160 μl of thiophenol. The mixture was stirred for 17 hours at room temperature and then filtered through a sinter of porosity 4. The cake was washed with EtOAc and the filtrate was concentrated under reduced pressure and purified on a Mega BE-SCX, 2GM 12ML cartridge (Varian), using washing with MeOH and detachment of the expected product with a 2N solution of ammonia in MeOH. The fractions containing the desired product were combined and concentrated under reduced pressure. 183 mg of ethyl 4-[2-(2,6-bis-hydroxymethyl-pyridin-4-yloxy)-ethylamino]-butanoate were obtained. LC/MS (B): tr=0.68 min; [M+H]+: m/z 313.

Workup

  1. filtrationfiltered through a sinter of porosity 4
  2. washThe cake was washed with EtOAc
  3. concentrationthe filtrate was concentrated under reduced pressure
  4. custompurified on a Mega BE-SCX, 2GM 12ML cartridge (Varian)
  5. washusing washing with MeOH and detachment of the expected product with a 2N solution of ammonia in MeOH
  6. additionThe fractions containing the desired product
  7. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-2aababd0d3d24a02b23d731b64ecbd36
Source dataset
uspto-grants-2015_06
Patent number
US09056914B2

Reaction notes

Loading…