Water → 5-(4-(2-(1-ethylcyclopentyloxy)-2-oxoethoxy)-3,5-dimethylphenyl)-5H-dibenzo[b,d]thiophenium 4-((4R)-4-((8R,9S,10S,13R,14S,17R)-10,13-dimethyl-3,7,12-trioxohexadecahydro-1H-cyclopenta[a]phenanthren-17-yl)pentanoyloxy)-1,1,2,2-tetrafluorobutane-1-sulfonate

HRID 1841859Notes

Reaction equation

HRID 1841859 reaction equation
[Br-].[CH2:2]([C:4]1([O:9][C:10](=[O:34])[CH2:11][O:12][C:13]2[C:18]([CH3:19])=[CH:17][C:16]([S+:20]3[C:24]4[CH:25]=[CH:26][CH:27]=[CH:28][C:23]=4[C:22]4[CH:29]=[CH:30][CH:31]=[CH:32][C:21]3=4)=[CH:15][C:14]=2[CH3:33])[CH2:8][CH2:7][CH2:6][CH2:5]1)[CH3:3].[CH3:35][C@:36]12[CH2:52][CH2:51][C:50](=[O:53])[CH2:49][CH:48]1[CH2:47][C:46](=[O:54])[C@@H:45]1[C@@H:37]2[CH2:38][C:39](=[O:75])[C@@:40]2([CH3:74])[C@H:44]1[CH2:43][CH2:42][C@@H:41]2[C@H:55]([CH3:73])[CH2:56][CH2:57][C:58]([O:60][CH2:61][CH2:62][C:63]([F:72])([F:71])[C:64]([F:70])([F:69])[S:65]([O-:68])(=[O:67])=[O:66])=[O:59].[Na+].O>ClCCl>[CH3:35][C@:36]12[CH2:52][CH2:51][C:50](=[O:53])[CH2:49][CH:48]1[CH2:47][C:46](=[O:54])[C@@H:45]1[C@@H:37]2[CH2:38][C:39](=[O:75])[C@@:40]2([CH3:74])[C@H:44]1[CH2:43][CH2:42][C@@H:41]2[C@H:55]([CH3:73])[CH2:56][CH2:57][C:58]([O:60][CH2:61][CH2:62][C:63]([F:72])([F:71])[C:64]([F:69])([F:70])[S:65]([O-:68])(=[O:66])=[O:67])=[O:59].[CH2:2]([C:4]1([O:9][C:10](=[O:34])[CH2:11][O:12][C:13]2[C:14]([CH3:33])=[CH:15][C:16]([S+:20]3[C:21]4[CH:32]=[CH:31][CH:30]=[CH:29][C:22]=4[C:23]4[CH:28]=[CH:27][CH:26]=[CH:25][C:24]3=4)=[CH:17][C:18]=2[CH3:19])[CH2:8][CH2:7][CH2:6][CH2:5]1)[CH3:3]

Participants

5

Reactant 3

HCID 962WaterHCID 58463086sodium 4-((4R)-4-((8R,9S,10S,13R,14S,17R)-10,13-dimethyl-3,7,12-trioxohexadecahydro-1H-cyclopenta[a]phenanthren-17-yl)pentanoyloxy)-1,1,2,2-tetrafluorobutane-1-sulfonateHCID 867124585-(4-(2-(1-ethylcyclopentyloxy)-2-oxoethoxy)-3,5-dimethylphenyl)-5H-dibenzo[b,d]thiophenium bromide

Product 1

HCID 867124645-(4-(2-(1-ethylcyclopentyloxy)-2-oxoethoxy)-3,5-dimethylphenyl)-5H-dibenzo[b,d]thiophenium 4-((4R)-4-((8R,9S,10S,13R,14S,17R)-10,13-dimethyl-3,7,12-trioxohexadecahydro-1H-cyclopenta[a]phenanthren-17-yl)pentanoyloxy)-1,1,2,2-tetrafluorobutane-1-sulfonateYield 80.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

5-(4-(2-(1-ethylcyclopentyloxy)-2-oxoethoxy)-3,5-dimethylphenyl)-5H-dibenzo[b,d]thiophenium bromide (4.20 g, 7.79 mmol) and sodium 4-((4R)-4-((8R,9S,10S,13R,14S,17R)-10,13-dimethyl-3,7,12-trioxohexadecahydro-1H-cyclopenta[a]phenanthren-17-yl)pentanoyloxy)-1,1,2,2-tetrafluorobutane-1-sulfonate (4.78 g, 7.56 mmol) were dissolved in dichloromethane (225 mL) and water (225 mL) and stirred at room temperature overnight. The dichloromethane layer was separated and the aqueous phase washed with dichloromethane (3×250 mL). The combined organic layers were washed with water (4×250 mL), concentrated in vacuo and residual water removed via azeotrope with acetonitrile (2×250 mL) to afford the title compound (6.48 g, 80%) as a white solid. 1H NMR (500 MHz, (CD3)2CO) δ: 8.53 (d, J=8 Hz, 2H), 8.37 (d, J=8 Hz, 2H), 8.04 (t, J=7.5 Hz, 2H), 7.85 (t, J=7.5 Hz, 2H), 7.52 (s, 2H), 4.57 (s, 2H), 4.32 (t, J=7 Hz, 2H), 3.06-3.17 (m, 3H), 2.95 (t, J=12.5 Hz, 1H), 2.66-2.83 (m, 3H), 2.2-2.54 (m, 8H), 1.57-2.14 (m, 13H), 1.48 (s, 3H), 1.25-1.41 (m, 7H), 1.90-1.12 (m, 6H), 0.82-0.89 (m, 9H).

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 (4×250 mL)
  4. concentrationconcentrated in vacuo and residual water
  5. customremoved via azeotrope with acetonitrile (2×250 mL)

Sources & evidence

ORD record
ord-90a0cbf4979747328309e27b78a286ee
Source dataset
uspto-grants-2015_02
Patent number
US08945814B2

Reaction notes

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