Water → HCID 22751995, compound

HRID 1679307Notes

Reaction equation

HRID 1679307 reaction equation
O[C:2]1([CH3:9])[C:6](=[O:7])[CH:5]=[C:4]([CH3:8])[O:3]1.[C:10]1([CH3:20])[CH:15]=[CH:14][C:13]([S:16](Cl)(=[O:18])=[O:17])=[CH:12][CH:11]=1.[OH2:21]>N1C=CC=CC=1.ClCCl>[C:10]1([CH3:20])[CH:15]=[CH:14][C:13]([S:16]([O:21][C:5]2[C:6](=[O:7])[CH:2]([CH3:9])[O:3][C:4]=2[CH3:8])(=[O:18])=[O:17])=[CH:12][CH:11]=1

Participants

6

Reactant 3

HCID 962WaterHCID 73974-Toluenesulfonyl chlorideHCID 13001393HCID 13001393, compound

Product 1

HCID 22751995HCID 22751995, compoundYield 75.5%

Reagents, catalysts & solvents 2

HCID 1049PyridineSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
-10 °C

Procedure

12.8 grams (0.1 m) of 4 hydroxy-2,5-dimethyl-2,3-dihydrofuran-3-one were dissolved in 70 ml of dry pyridine. The solution was stirred and cooled to -10° C in an ice-salt bath. With stirring a cold solution of 22.9 grams (0.12 m) of p-toluene sulfonylchloride in 50 ml of dry dichloromethane was added dropwise (temp. below -5° C). After completion of the addition (1 hour), stirring at 0° C was continued for 3 hours, and water (10 ml) was added in portions at intervals of 5 min., with stirring and cooling, so that the temperature did not rise above 5° C. The solution was then poured into 250 ml of ice-water. The mixture was extracted four times with dichloromethane, the combined extracts were successively washed with portions of ice-cold dilute sulphuric acid, water, sodium hydrogen carbonate solution and water. The dichloromethane solution is then dried with anhydrous sodium sulphate and evaporated to dryness. Crystallization from ethanol yielded 21.3 grams = 75.5% of the pure 4-p-toluene-sulfonyloxy-2,5-dimethyl-2,3-dihydrofuran-3-one with m.p. 70°-72° C. 3.5 grams (12.4 mmol) of the tosylate thus obtained were dissolved in a mixture of 15 ml of ethanol and 5 ml of water at 40° C. To this solution was added a solution of 1.68 grams (30 mmol) of sodium hydrogensulphide in 20 ml of ethanol, while a gentle stream of hydrogen sulphide was passed through the reaction mixture. After completion of the addition, which took one hour, stirring and passing of H2S into the solution were continued for 6 hours at 40° C and the reaction mixture was diluted with 200 ml of water, acidified with aqueous dilute hydrochloric acid (pH 5.5) and continuously extracted with ether for 18 hours. The extract was dried over anhydrous sodium sulphate and evaporated to dryness. From the residue the title compound was isolated in a quantity of 3 grams by preparative gaschromatography, using a column of 600 × 0.4 cm, a support of Diatoport S (a silanated silicagel) ex Hewlett Packard, loaded with 1% Carbowax 20 M (a polyethylene glycol ether with a molecular weight above 20,000) ex Hewlett Packard and 10% Apiezon (a mixture of stable alkanes) ex Shell Comp. Nitrogen was used as a carrier gas at a velocity of 40 ml per minute.

Workup

  1. additionwas added dropwise (temp. below -5° C)
  2. additionAfter completion of the addition (1 hour)
  3. stirringstirring at 0° C
  4. stirringwith stirring
  5. temperaturecooling, so that the temperature
  6. customdid not rise above 5° C
  7. extractionThe mixture was extracted four times with dichloromethane
  8. washthe combined extracts were successively washed with portions of ice-cold dilute sulphuric acid, water, sodium hydrogen carbonate solution and water
  9. dry with materialThe dichloromethane solution is then dried with anhydrous sodium sulphate
  10. customevaporated to dryness
  11. customCrystallization from ethanol

Sources & evidence

ORD record
ord-884aceb6b87949be912650b82539dabe
Source dataset
uspto-grants-1978_03
Patent number
US04080367

Reaction notes

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