Potassium Carbonate → 5-Cyano-2-{[(3,5-dimethyl-pyridin-2-ylmethyl)-(2-nitro-benzenesulfonyl)-amino]-methyl}-benzoic acid methyl ester

HRID 251258Notes

Reaction equation

HRID 251258 reaction equation
[CH3:1][C:2]1[C:3]([CH2:9][NH:10][S:11]([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][C:15]=2[N+:20]([O-:22])=[O:21])(=[O:13])=[O:12])=[N:4][CH:5]=[C:6]([CH3:8])[CH:7]=1.[CH3:23][O:24][C:25](=[O:36])[C:26]1[CH:31]=[C:30]([C:32]#[N:33])[CH:29]=[CH:28][C:27]=1[CH2:34]Br.C([O-])([O-])=O.[K+].[K+]>CC#N>[CH3:23][O:24][C:25](=[O:36])[C:26]1[CH:31]=[C:30]([C:32]#[N:33])[CH:29]=[CH:28][C:27]=1[CH2:34][N:10]([CH2:9][C:3]1[C:2]([CH3:1])=[CH:7][C:6]([CH3:8])=[CH:5][N:4]=1)[S:11]([C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][C:15]=1[N+:20]([O-:22])=[O:21])(=[O:12])=[O:13]

Participants

5

Reactant 3

HCID 11430Potassium CarbonateHCID 17965928Methyl 2-(bromomethyl)-5-cyanobenzoateHCID 67272193N-(3,5-dimethyl-pyridin-2-ylmethyl)-2-nitro-benzenesulfonamide

Product 1

HCID 672721615-Cyano-2-{[(3,5-dimethyl-pyridin-2-ylmethyl)-(2-nitro-benzenesulfonyl)-amino]-methyl}-benzoic acid methyl esterYield 97.3%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Conditions

Temperature
80 °C

Procedure

To a solution of N-(3,5-dimethyl-pyridin-2-ylmethyl)-2-nitro-benzenesulfonamide (0.60 g, 1.87 mmol) dissolved in CH3CN (10 mL) was added 2-bromomethyl-5-cyano-benzoic acid methyl ester (0.50 g, 1.96 mmol) and K2CO3 (0.72 g, 5.61 mmol). The mixture was stirred at 80° C. for 3 hours, then concentrated in vacuo and redissolved in CH2Cl2 (50 mL). Saturated aqueous NaHCO3 (50 mL) was added and the mixture was extracted with CH2Cl2 (3×50 mL). The combined organic extracts were dried (Na2SO4), filtered, and concentrated in vacuo to give a brown oil. Purification via column chromatography on silica gel (CH2Cl2:MeOH, 99:1, v/v) afforded 5-cyano-2-{[(3,5-dimethyl-pyridin-2-ylmethyl)-(2-nitro-benzenesulfonyl)-amino]-methyl}-benzoic acid methyl ester as a yellow solid (0.90 g, 97%). 1H NMR (CDCl3) δ 2.15 (s, 3H), 2.22 (s, 3H), 3.88 (s, 2H), 5.15 (s, 2H), 7.05 (s, 1H), 7.61-7.72 (m, 5H), 7.83 (s, 1H), 7.95 (d, 1H, J=7.5 Hz), 8.06 (s, 1H).

Workup

  1. concentrationconcentrated in vacuo
  2. dissolutionredissolved in CH2Cl2 (50 mL)
  3. additionSaturated aqueous NaHCO3 (50 mL) was added
  4. extractionthe mixture was extracted with CH2Cl2 (3×50 mL)
  5. dry with materialThe combined organic extracts were dried (Na2SO4)
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customto give a brown oil
  9. customPurification via column chromatography on silica gel (CH2Cl2

Sources & evidence

ORD record
ord-b428273e139743c894f0ceee7d6bf676
Source dataset
uspto-grants-2011_01
Patent number
US07863293B2

Reaction notes

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