4-Chlorobenzenesulfonyl chloride → But-3-yn-1-yl 4-chlorobenzene-1-sulfonate

HRID 1177664Notes

Reaction equation

HRID 1177664 reaction equation
[CH2:1]([OH:5])[CH2:2][C:3]#[CH:4].C(N(CC)CC)C.[Cl:13][C:14]1[CH:19]=[CH:18][C:17]([S:20](Cl)(=[O:22])=[O:21])=[CH:16][CH:15]=1>C1(C)C=CC=CC=1>[CH2:1]([O:5][S:20]([C:17]1[CH:18]=[CH:19][C:14]([Cl:13])=[CH:15][CH:16]=1)(=[O:22])=[O:21])[CH2:2][C:3]#[CH:4]

Participants

5

Reactant 3

HCID 73984-Chlorobenzenesulfonyl chlorideHCID 8471TriethylamineHCID 135663-Butyn-1-OL

Product 1

HCID 26369912But-3-yn-1-yl 4-chlorobenzene-1-sulfonate

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent2×

Conditions

Temperature
2.5 °C

Procedure

A solution of 3-butyn-1-ol (365 g, 5.21 mol), triethylamine (526 g, 5.21 mol), and toluene (419 mL) was added to a cooled (0-5° C.) stirred solution of 4-chlorobenzenesulfonyl chloride (1.0 kg, 4.74 mol) and toluene (2.10 L). The reaction temperature was maintained below 20° C. during the addition. Precipitation of triethylamine hydrochloride salt occurred during the reaction. The reaction mixture was stirred at room temperature for 2-4 h. The triethylamine hydrochloride byproduct was separated by filtration and washed with toluene (2×350 mL). The combined filtrates were concentrated to remove toluene under reduced pressure above 45° C. to maintain the residue as a liquid. 2-Propanol (1.20 L) was added to the residue and the stirred solution was cooled to 20-25° C. Water (1.80 L) was added over 15 m. The slurry of product and solvent was cooled to 0-5° C. and stirred for 1 h. The white solid product was collected by filtration, washed with 33% aqueous 2-propanol (v/v), and vacuum dried to give 4-chloro-benzenesulfonic acid but-3-ynyl ester with 99% purity (as determined by HPLC.

Workup

  1. temperatureThe reaction temperature was maintained below 20° C. during the addition
  2. customPrecipitation of triethylamine hydrochloride salt
  3. customoccurred during the reaction
  4. customThe triethylamine hydrochloride byproduct was separated by filtration
  5. washwashed with toluene (2×350 mL)
  6. concentrationThe combined filtrates were concentrated
  7. customto remove toluene under reduced pressure above 45° C.
  8. temperatureto maintain the residue as a liquid
  9. addition2-Propanol (1.20 L) was added to the residue
  10. temperaturethe stirred solution was cooled to 20-25° C
  11. additionWater (1.80 L) was added over 15 m
  12. temperatureThe slurry of product and solvent was cooled to 0-5° C.
  13. stirringstirred for 1 h
  14. filtrationThe white solid product was collected by filtration
  15. washwashed with 33% aqueous 2-propanol (v/v), and vacuum
  16. customdried

Sources & evidence

ORD record
ord-9837a56820d64e168e768205156a77f5
Source dataset
uspto-grants-2010_11
Patent number
US07842837B2

Reaction notes

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