4-Toluenesulfonyl chloride → HCID 86624835, compound

HRID 550721Notes

Reaction equation

HRID 550721 reaction equation
[CH2:1]([O:4][N:5]1[C:10](=[O:11])[C:9]2[S:12][CH:13]=[CH:14][C:8]=2[NH:7][C:6]1=[O:15])[CH:2]=[CH2:3].Br[CH2:17][CH2:18][OH:19].[S:20](Cl)([C:23]1[CH:29]=[CH:28][C:26]([CH3:27])=[CH:25][CH:24]=1)(=[O:22])=[O:21]>N1C=CC=CC=1>[CH2:1]([O:4][N:5]1[C:10](=[O:11])[C:9]2[S:12][CH:13]=[CH:14][C:8]=2[N:7]([CH2:17][CH2:18][O:19][S:20]([C:23]2[CH:29]=[CH:28][C:26]([CH3:27])=[CH:25][CH:24]=2)(=[O:22])=[O:21])[C:6]1=[O:15])[CH:2]=[CH2:3]

Participants

5

Reactant 3

HCID 73974-Toluenesulfonyl chlorideHCID 108982-BromoethanolHCID 67200450HCID 67200450, compound

Product 1

HCID 86624835HCID 86624835, compound

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Procedure

3-Allyloxy-1H-thieno[3,2-d]pyrimidine-2,4-dione (from previous example) was alkylated with 2-bromoethanol via general procedure B1. The intermediate alcohol was treated with tosyl chloride (3 eq) in pyridine (0.2 M). After 4 hours, the reaction mixture was partitioned between EtOAc and water. The organic layer was dried over MgSO4 and concentrated to give toluene-4-sulfonic acid 2-(3-allyloxy-2,4-dioxo-3,4-dihydro-2H-thieno[3,2-d]pyrimidin-1-yl)-ethyl ester. This material could be used crude or could be further purified by chromatography in 1:1 EtOAc/hexanes. The tosylate was treated with pyrrolidine (1.5 eq) and Et3N (1.5 eq) in CHCl3. The reaction was heated to 55° C. for 2 hours. Additional pyrrolidine (2 eq) was added and the reaction was stirred overnight at 55° C. The reaction was cooled, washed with water, and concentrated. The crude intermediate was deprotected via general procedure D2 to give the title compound which was purified by mass-triggered preparative HPLC. 1H NMR (DMSO-d6) δ 8.14 (d, 1H, J=5.4 Hz), 7.32 (d, 1H, J=5.4 Hz), 4.14 (t, 2H, J=6.9 Hz), 3.60-3.30 (m, 4H), 2.67 (t, 2H, J=6.9 Hz), 1.69-1.60 (m, 4H); Electrospray MS: 322 (M+H); retention time: 1.24 min.

Workup

  1. customthe reaction mixture was partitioned between EtOAc and water
  2. dry with materialThe organic layer was dried over MgSO4
  3. concentrationconcentrated

Sources & evidence

ORD record
ord-83436c2ec8574d9ca85da37d19f1a95a
Source dataset
uspto-grants-2011_05
Patent number
US07947691B2

Reaction notes

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