4-Toluenesulfonyl chloride → HCID 54137828, compound

HRID 275777Notes

Reaction equation

HRID 275777 reaction equation
[C:1]1([CH3:11])[CH:6]=[CH:5][C:4]([S:7](Cl)(=[O:9])=[O:8])=[CH:3][CH:2]=1.[OH:12][CH2:13][C@@H:14]1[O:31][C:18]2=[C:19]3[C:23](=[CH:24][CH:25]=[C:17]2[O:16][CH2:15]1)[NH:22][C:21]([C:26]([O:28][CH2:29][CH3:30])=[O:27])=[CH:20]3>ClCCl.CN(C)C1C=CN=CC=1>[C:1]1([CH3:11])[CH:6]=[CH:5][C:4]([S:7]([O:12][CH2:13][C@H:14]2[O:31][C:18]3=[C:19]4[C:23](=[CH:24][CH:25]=[C:17]3[O:16][CH2:15]2)[NH:22][C:21]([C:26]([O:28][CH2:29][CH3:30])=[O:27])=[CH:20]4)(=[O:9])=[O:8])=[CH:3][CH:2]=1

Participants

5

Reactant 2

HCID 73974-Toluenesulfonyl chlorideHCID 11076723HCID 11076723, compound

Product 1

HCID 54137828HCID 54137828, compoundYield 90%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent

Procedure

4-Toluenesulphonyl chloride (2.23 g) was added in one portion to a stirred solution of ethyl (S)-2,3-dihydro-2-(hydroxymethyl)-7H-1,4-dioxino[2,3-e]indole-8-carboxylate (2.65 g) in dry dichloromethane (120 ml) at 0° C. 4-Dimethylaminopyridine (1.52 g) was then added and the cooling bath removed. The resulting solution was stirred at ambient temperature for 72 hours, then diluted with dichloromethane (150 ml) and washed successively with water (80 ml), saturated aqueous copper sulphate solution (2×100 ml), and then dried over sodium sulphate. Evaporation of the solvent under reduced pressure gave a purple foam which was purified by flash column chromatography on silica eluting with a 1:1 mixture of petroleum ether (b.p. 40-60° C.) and ethyl acetate, to give ethyl (S)-2,3-dihydro-2-[(4-toluenesulphonyloxy)methyl]-7H-1,4-dioxino[2,3-e]indole-8-carboxylate (3.71 g) as a colourless oil which solidified on standing.

Workup

  1. customthe cooling bath removed
  2. additiondiluted with dichloromethane (150 ml)
  3. washwashed successively with water (80 ml), saturated aqueous copper sulphate solution (2×100 ml)
  4. dry with materialdried over sodium sulphate
  5. customEvaporation of the solvent under reduced pressure
  6. customgave a purple foam which
  7. customwas purified by flash column chromatography on silica eluting with a 1:1 mixture of petroleum ether (b.p. 40-60° C.) and ethyl acetate

Sources & evidence

ORD record
ord-bef2c32288d64b56aeba962567d41e53
Source dataset
uspto-grants-2002_03
Patent number
US06353002B2

Reaction notes

Loading…