Water → 5-(5-((2-(1-ethylcyclopentyloxy)-2-oxoethoxy)carbonyl)-2-methoxyphenyl)-5H-dibenzo[b,d]thiophenium 1,1-difluoro-2-(methacryloyloxy)ethanesulfonate

HRID 1841862Notes

Reaction equation

HRID 1841862 reaction equation
[I-].[CH2:2]([C:4]1([O:9][C:10](=[O:36])[CH2:11][O:12][C:13]([C:15]2[CH:16]=[CH:17][C:18]([O:34][CH3:35])=[C:19]([S+:21]3[C:25]4[CH:26]=[CH:27][CH:28]=[CH:29][C:24]=4[C:23]4[CH:30]=[CH:31][CH:32]=[CH:33][C:22]3=4)[CH:20]=2)=[O:14])[CH2:8][CH2:7][CH2:6][CH2:5]1)[CH3:3].[F:37][C:38]([F:50])([S:46]([O-:49])(=[O:48])=[O:47])[CH2:39][O:40][C:41](=[O:45])[C:42]([CH3:44])=[CH2:43].C([NH+](CC)CC)C.O>ClCCl>[F:50][C:38]([F:37])([S:46]([O-:49])(=[O:48])=[O:47])[CH2:39][O:40][C:41](=[O:45])[C:42]([CH3:44])=[CH2:43].[CH2:2]([C:4]1([O:9][C:10](=[O:36])[CH2:11][O:12][C:13]([C:15]2[CH:16]=[CH:17][C:18]([O:34][CH3:35])=[C:19]([S+:21]3[C:22]4[CH:33]=[CH:32][CH:31]=[CH:30][C:23]=4[C:24]4[CH:29]=[CH:28][CH:27]=[CH:26][C:25]3=4)[CH:20]=2)=[O:14])[CH2:5][CH2:6][CH2:7][CH2:8]1)[CH3:3]

Participants

5

Reactant 3

HCID 962WaterHCID 86660800Triethylammonium 1,1-difluoro-2-(methacryloyloxy)ethanesulfonateHCID 867124705-(5-((2-(1-ethylcyclopentyloxy)-2-oxoethoxy)carbonyl)-2-methoxyphenyl)-5H-dibenzo[b,d]thiophenium iodide

Product 1

HCID 867124685-(5-((2-(1-ethylcyclopentyloxy)-2-oxoethoxy)carbonyl)-2-methoxyphenyl)-5H-dibenzo[b,d]thiophenium 1,1-difluoro-2-(methacryloyloxy)ethanesulfonateYield 86.7%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

5-(5-((2-(1-ethylcyclopentyloxy)-2-oxoethoxy)carbonyl)-2-methoxyphenyl)-5H-dibenzo[b,d]thiophenium iodide (10.0 g, 16.2 mmol) and triethylammonium 1,1-difluoro-2-(methacryloyloxy)ethanesulfonate (5.64 g, 17.0 mmol, 1.05 eq) were dissolved in dichloromethane (200 mL) and water (200 mL) and stirred at r.t. overnight. The dichloromethane layer was separated and the aqueous phase washed with dichloromethane (3×250 mL). The combined organic layers were washed with water (3×250 mL), concentrated in vacuo and azeotroped with acetonitrile (2×100 mL) to afford the title compound (10.1 g, 86%) as a white hydroscopic solid. 1H NMR (300 MHz, (d-DMSO) δ: 8.52 (d, J=7.8 Hz, 2H), 8.35 (d, J=7.8 Hz, 2H), 8.27 (dd, J=8.1, 2.1 Hz, 1H), 7.98 (t, J=7.8 Hz, 2H), 7.78 (t, J=7.8 Hz, 2H), 7.55 (d, J=2.1 Hz, 1H), 7.54 (d, J=7.8 Hz, 1H), 6.09-6.13 (m, 1H), 5.76-5.79 (m, 1H), 4.74 (s, 2H), 4.62 (dd, J=15.6, 15.6 Hz, 2H), 4.05 (s, 3H), 1.83-1.98 (m, 7H), 1.45-1.65 (m, 6H), 0.79 (t, J=6.6 Hz, 3H).

Workup

  1. customThe dichloromethane layer was separated
  2. washthe aqueous phase washed with dichloromethane (3×250 mL)
  3. washThe combined organic layers were washed with water (3×250 mL)
  4. concentrationconcentrated in vacuo
  5. customazeotroped with acetonitrile (2×100 mL)

Sources & evidence

ORD record
ord-962c0c0181b04624ab65d666f65abb2e
Source dataset
uspto-grants-2015_02
Patent number
US08945814B2

Reaction notes

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