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

HRID 251260Notes

Reaction equation

HRID 251260 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-dc3cf14ceec4461991565587cc23b376
Source dataset
uspto-grants-2011_01
Patent number
US07863293B2

Reaction notes

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