Dimethylformamide → 4-(4-methylphenoxy)benzenesulfonyl Chloride

HRID 1594530Notes

Reaction equation

HRID 1594530 reaction equation
[CH3:1][C:2]1[CH:7]=[CH:6][C:5]([O:8][C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)=[CH:4][CH:3]=1.[Cl:15][S:16](O)(=[O:18])=[O:17].C(Cl)(=O)C(Cl)=O.CN(C=O)C>ClCCl>[CH3:1][C:2]1[CH:7]=[CH:6][C:5]([O:8][C:9]2[CH:10]=[CH:11][C:12]([S:16]([Cl:15])(=[O:18])=[O:17])=[CH:13][CH:14]=2)=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 6228DimethylformamideHCID 24638Chlorosulfonic acidHCID 65578Oxalyl chlorideHCID 74351p-Phenoxytoluene

Product 1

HCID 37584684-(4-methylphenoxy)benzenesulfonyl ChlorideYield 57%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
40 °C

Procedure

To a solution of 1.84 g (10.0 mmol) of 4-methyldiphenyl ether (J. Chem. Soc., Perkin Trans. 1; 1992, 407-408, which article is entirely incorporated herein by reference) with 2 mL of dichloromethane in an ice-bath was added a solution of chlorosulfonic acid (0.73 mL, 11.0 mmol) in 2 mL of dichloromethane dropwise. The resulting mixture was stirred at 0° C. to room temperature for 2 hr, and then oxalyl chloride (11.14 mL, 13.0 mmol) was added dropwise, followed by 0.15 mL of DMF. The resulting mixture was heated to 40° C. for 1 hr and then allowed to cool to room temperature over a 2 hr period. The reaction mixture was poured into ice-pH 7 phosphate buffer (50 mL), then extracted with ethyl acetate:Hexane (4:3) (3×150 mL). The combined organic layers were washed with brine (75 mL). The aqueous layer was extracted with ethyl acetate/Hexane(4:3) (150 mL). The organic layer was dried over Na2SO4, then evaporated by vacuum to give crude product as white solid. This solid was triturated with hexane and collected by filtration, then dried under high vacuum to give 1.555 g (57%) of 4-(4-methylphenoxy)benzenesulfonyl chloride as white solid: mp 295-300° C. 1H-NMR (dMSO-d6) δ 2.34 (s, 3H), 6.91-6.99 (dd, J=7.7,8.4 Hz, 4H), 7.24-7.27 (d, J=8.4 Hz, 2H), 7.61-7.63 (d, J=8.1 Hz, 2H).

Workup

  1. temperatureto cool to room temperature over a 2 hr period
  2. extractionextracted with ethyl acetate:Hexane (4:3) (3×150 mL)
  3. washThe combined organic layers were washed with brine (75 mL)
  4. extractionThe aqueous layer was extracted with ethyl acetate/Hexane(4:3) (150 mL)
  5. dry with materialThe organic layer was dried over Na2SO4
  6. customevaporated by vacuum
  7. customto give crude product as white solid
  8. customThis solid was triturated with hexane
  9. filtrationcollected by filtration
  10. customdried under high vacuum

Sources & evidence

ORD record
ord-c8e2860b2df04819873422ebaced4a14
Source dataset
uspto-grants-2001_09
Patent number
USH0001992H1

Reaction notes

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