4-Toluenesulfonyl chloride → HCID 20148930, compound

HRID 569303Notes

Reaction equation

HRID 569303 reaction equation
[Cl:1][C:2]1[C:14]([Cl:15])=[C:13]([O:16][CH2:17][C:18]([OH:20])=[O:19])[CH:12]=[C:11]2[C:3]=1[C:4]1[C:9]([CH2:21][CH2:22]O)([CH2:10]2)[CH2:8][CH2:7][C:6](=[O:24])[CH:5]=1.C1(C(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C[Li].C1(C)C=CC(S([Cl:55])(=O)=O)=CC=1.[Cl-].[Li+]>CN(C)P(N(C)C)(N(C)C)=O.CCOCC.O>[Cl:55][CH2:22][CH2:21][C:9]12[CH2:8][CH2:7][C:6](=[O:24])[CH:5]=[C:4]1[C:3]1[C:11](=[CH:12][C:13]([O:16][CH2:17][C:18]([OH:20])=[O:19])=[C:14]([Cl:15])[C:2]=1[Cl:1])[CH2:10]2

Participants

9

Reactant 5

HCID 73974-Toluenesulfonyl chlorideHCID 10614TriphenylmethaneHCID 433294Lithium ChlorideHCID 14098158HCID 14098158, compoundHCID 178418348HCID 178418348, compound

Product 1

HCID 20148930HCID 20148930, compound

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 3283Diethyl EtherSolvent4×HCID 12679HexamethylphosphoramideSolvent

Procedure

In an atmosphere of dry nitrogen a solution of {[5,6-dichloro-9a-(2-hydroxyethyl)-3-oxo-2,3,9,9a-tetrahydro-1H-fluoren-7-yl]oxy}acetic acid (3.71 g, 10 mMole) in hexamethylphosphoramide (25 ml), anhydrous ether (50 ml) and triphenylmethane (10 mg) is stirred at 0° C. Methyllithium (12.6 ml of 1.6M) solution in ether=20 mMole) is added, dropwise with stirring, over a period of 30 minutes. A solution of p-toluenesulfonyl chloride (2 g, 10.5 mMole) in ether (15 ml) is added over a period of 30 minutes. Finally, dry lithium chloride (420 mg; 10 mMole) is added. The mixture is stirred and allowed to warm to room temperature over 20 hours. Ether (25 ml) and water (50 ml) is added and the layers separated. The organic layer is acidified with hydrochloric acid, washed four times with water (50 ml portions) and finally with a brine solution. After drying the organic phase with magnesium sulfate, the solvent is removed by evaporation at reduced pressure and the residue recrystallized from acetonitrile to give the desired product.

Workup

  1. stirringThe mixture is stirred
  2. customthe layers separated
  3. washwashed four times with water (50 ml portions)
  4. dry with materialAfter drying the organic phase with magnesium sulfate
  5. customthe solvent is removed by evaporation at reduced pressure
  6. customthe residue recrystallized from acetonitrile

Sources & evidence

ORD record
ord-82aa5d3cc6ce4b54b0bf59d26e19d50c
Source dataset
uspto-grants-1988_03
Patent number
US04731471

Reaction notes

Loading…