Reaction #1929041

ord-90a0cbf4979747328309e27b78a286ee

Reaction equation

CCC1(OC(=O)COc2c(C)cc(-[s+]3c4ccccc4c4ccccc43)cc2C)CCCC1.[Br-]
5-(4-(2-(1-ethylcyclopentyloxy)-2-oxoethoxy)-3,5-dimethylphenyl)-5H-dibenzo[b,d]thiophenium bromide
C[C@H](CCC(=O)OCCC(F)(F)C(F)(F)S(=O)(=O)[O-])[C@H]1CC[C@H]2[C@@H]3C(=O)CC4CC(=O)CC[C@]4(C)[C@H]3CC(=O)[C@]12C.[Na+]
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
O
water
→
CCC1(OC(=O)COc2c(C)cc(-[s+]3c4ccccc4c4ccccc43)cc2C)CCCC1.C[C@H](CCC(=O)OCCC(F)(F)C(F)(F)S(=O)(=O)[O-])[C@H]1CC[C@H]2[C@@H]3C(=O)CC4CC(=O)CC[C@]4(C)[C@H]3CC(=O)[C@]12C
title compound
Yield 80.2%
CCC1(OC(=O)COc2c(C)cc(-[s+]3c4ccccc4c4ccccc43)cc2C)CCCC1.C[C@H](CCC(=O)OCCC(F)(F)C(F)(F)S(=O)(=O)[O-])[C@H]1CC[C@H]2[C@@H]3C(=O)CC4CC(=O)CC[C@]4(C)[C@H]3CC(=O)[C@]12C
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
Yield 80.2%

Reactants

CCC1(OC(=O)COc2c(C)cc(-[s+]3c4ccccc4c4ccccc43)cc2C)CCCC1.[Br-]
5-(4-(2-(1-ethylcyclopentyloxy)-2-oxoethoxy)-3,5-dimethylphenyl)-5H-dibenzo[b,d]thiophenium bromide
C[C@H](CCC(=O)OCCC(F)(F)C(F)(F)S(=O)(=O)[O-])[C@H]1CC[C@H]2[C@@H]3C(=O)CC4CC(=O)CC[C@]4(C)[C@H]3CC(=O)[C@]12C.[Na+]
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
O
water

Reagents

None

Solvents

ClCCl
dichloromethane

Conditions

Detailed conditions
See reaction.notes.procedure_details.

Workup

  1. 1
    OtherThe dichloromethane layer was separated
  2. 2
    Washthe aqueous phase washed with dichloromethane (3×250 mL)
  3. 3
    WashThe combined organic layers were washed with water (4×250 mL)
  4. 4
    Concentrationconcentrated in vacuo and residual water
  5. 5
    Otherremoved via azeotrope with acetonitrile (2×250 mL)

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).

Source

DOI: 10.6084/m9.figshare.5104873.v1Patent: US08945814B2uspto-grants-2015_02