Thiophenol → 4-{[(3,5-Dimethyl-pyridin-2-ylmethyl)-amino]-methyl}-3-hydroxymethyl-benzonitrile

HRID 1592667Notes

Reaction equation

HRID 1592667 reaction equation
[C:1]([C:3]1[CH:31]=[CH:30][C:6]([CH2:7][N:8]([CH2:21][C:22]2[C:27]([CH3:28])=[CH:26][C:25]([CH3:29])=[CH:24][N:23]=2)S(C2C=CC=CC=2[N+]([O-])=O)(=O)=O)=[C:5]([CH2:32][OH:33])[CH:4]=1)#[N:2].C([O-])([O-])=O.[K+].[K+].C1(S)C=CC=CC=1>CN(C=O)C>[CH3:28][C:27]1[C:22]([CH2:21][NH:8][CH2:7][C:6]2[CH:30]=[CH:31][C:3]([C:1]#[N:2])=[CH:4][C:5]=2[CH2:32][OH:33])=[N:23][CH:24]=[C:25]([CH3:29])[CH:26]=1

Participants

5

Reactant 3

HCID 7969ThiophenolHCID 11430Potassium CarbonateHCID 67271378N-(4-cyano-2-hydroxymethyl-benzyl)-N-(3,5-dimethyl-pyridin-2-ylmethyl)-2-nitro-benzene-sulfonamide

Product 1

HCID 672721574-{[(3,5-Dimethyl-pyridin-2-ylmethyl)-amino]-methyl}-3-hydroxymethyl-benzonitrileYield 35.5%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a solution of N-(4-cyano-2-hydroxymethyl-benzyl)-N-(3,5-dimethyl-pyridin-2-ylmethyl)-2-nitro-benzene-sulfonamide (0.82 g, 1.76 mmol) dissolved in DMF (35 mL) was added K2CO3 (1.21 g, 8.75 mmol) and thiophenol (0.54 mL, 5.28 mmol). The mixture was stirred at room temperature for 3 hours then concentrated in vacuo and redissolved in CH2Cl2 (50 mL). The mixture was filtered through a celite plug and the filtrate was concentrated in vacuo to afford a yellow solid. Purification by column chromatography on silica gel (hexane:EtOAc, 4:1, v/v →EtOAc) afforded 4-{[(3,5-dimethyl-pyridin-2-ylmethyl)-amino]-methyl}-3-hydroxymethyl-benzonitrile (0.176 g, 35%) as a yellow solid. 1H NMR (CDCl3) δ 2.20 (s, 3H), 2.28 (s, 3H), 3.82 (s, 2H), 3.99 (s, 2H), 4.65 (s, 2H), 7.26 (s, 1H), 7.36 (d, 1H, J=6.0 Hz), 7.55 (d, 1H, J=6.0 Hz), 7.64 (s, 1H), 8.20 (s, 1H).

Workup

  1. concentrationthen concentrated in vacuo
  2. dissolutionredissolved in CH2Cl2 (50 mL)
  3. filtrationThe mixture was filtered through a celite plug
  4. concentrationthe filtrate was concentrated in vacuo
  5. customto afford a yellow solid
  6. customPurification by column chromatography on silica gel (hexane:EtOAc, 4:1, v/v →EtOAc)

Sources & evidence

ORD record
ord-a173b55702fd4a70ad6a54b291753a26
Source dataset
uspto-grants-2007_11
Patent number
US07291631B2

Reaction notes

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