4-Toluenesulfonyl chloride → HCID 9794668, compound

HRID 1250259Notes

Reaction equation

HRID 1250259 reaction equation
C1(C)C=CC(S(Cl)(=O)=O)=CC=1.[CH3:12][C:13]1[CH:18]=[CH:17][C:16](/[CH:19]=[CH:20]/[CH2:21][CH:22](O)[CH3:23])=[CH:15][C:14]=1[N+:25]([O-:27])=[O:26].[CH2:28]([N:30](CC)CC)C>ClCCl>[CH3:28][NH:30][CH:22]([CH2:21]/[CH:20]=[CH:19]/[C:16]1[CH:17]=[CH:18][C:13]([CH3:12])=[C:14]([N+:25]([O-:27])=[O:26])[CH:15]=1)[CH3:23]

Participants

5

Reactant 3

HCID 73974-Toluenesulfonyl chlorideHCID 8471TriethylamineHCID 18327740HCID 18327740, compound

Product 1

HCID 9794668HCID 9794668, compoundYield 25.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
25 °C

Procedure

p-Toluenesulfonyl chloride (1.91 g, 10.0 mmol) was added, in one portion, to a stirred solution of (4E)-5-(4-methyl-3-nitropheny)-4-penten-2-ol (1.70 g, 7.69 mmol) in triethylamine (5 mL) and dichloromethane (10 mL) at 10° C. under nitrogen. The cooling bath was removed, and the mixture was stirred at 25° C. for 16 h. Saturated aqueous NaHCO3 (10 mL) was then added and the biphasic mixture was vigorously stirred for 2 h. The layers were separated and the aqueous layer was extracted once with dichloromethane (10 mL). The combined organic layers were dried (Na2SO4) and evaporated, and the residue was combined with DMF (7 mL) and 40% aqueous methylamine (20 mL). This mixture, also biphasic, was vigorously stirred at 25° C. for 18 h, poured into a mixture of 30% aqueous NaOH (2 mL) and saturated aqueous NaCl (50 mL), and extracted with ether (3×30 mL). The ether extracts were dried (Na2SO4) and evaporated, and the residue was column chromatographed on 100 g of Merck silica gel 60 (70-230 mesh) with 5% (v/v) methanol, 5% triethylamine (v/v) in benzene. This gave 453 mg (25.2% yield) of yellow oil.

Workup

  1. customThe cooling bath was removed
  2. additionSaturated aqueous NaHCO3 (10 mL) was then added
  3. stirringthe biphasic mixture was vigorously stirred for 2 h
  4. customThe layers were separated
  5. extractionthe aqueous layer was extracted once with dichloromethane (10 mL)
  6. dry with materialThe combined organic layers were dried (Na2SO4)
  7. customevaporated
  8. stirringThis mixture, also biphasic, was vigorously stirred at 25° C. for 18 h
  9. additionpoured into a mixture of 30% aqueous NaOH (2 mL) and saturated aqueous NaCl (50 mL)
  10. extractionextracted with ether (3×30 mL)
  11. dry with materialThe ether extracts were dried (Na2SO4)
  12. customevaporated
  13. customchromatographed on 100 g of Merck silica gel 60 (70-230 mesh) with 5% (v/v) methanol, 5% triethylamine (v/v) in benzene

Sources & evidence

ORD record
ord-7638107cf55e4c08bad513319c13b845
Source dataset
uspto-grants-2002_01
Patent number
US06337351B1

Reaction notes

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