HCID 23295757, compound → HCID 23295760, compound

HRID 1954010Notes

Reaction equation

HRID 1954010 reaction equation
Br[CH2:2][C:3]1[CH:4]=[C:5]([CH2:11][CH:12]([P:23]([O:29][CH:30]([CH3:32])[CH3:31])(=[O:28])[O:24][CH:25]([CH3:27])[CH3:26])[P:13]([O:19][CH:20]([CH3:22])[CH3:21])(=[O:18])[O:14][CH:15]([CH3:17])[CH3:16])[CH:6]=[C:7]([CH2:9]Br)[CH:8]=1.[C:33]([O-:36])(=[S:35])[CH3:34].[K+]>CN(C=O)C>[C:33]([S:35][CH2:2][C:3]1[CH:4]=[C:5]([CH2:11][CH:12]([P:23]([O:29][CH:30]([CH3:32])[CH3:31])(=[O:28])[O:24][CH:25]([CH3:27])[CH3:26])[P:13]([O:19][CH:20]([CH3:22])[CH3:21])(=[O:18])[O:14][CH:15]([CH3:17])[CH3:16])[CH:6]=[C:7]([CH2:9][S:35][C:33](=[O:36])[CH3:34])[CH:8]=1)(=[O:36])[CH3:34]

Participants

4

Reactant 2

HCID 23295757HCID 23295757, compoundHCID 23670855Potassium ethanethioate

Product 1

HCID 23295760HCID 23295760, compoundYield 70.6%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Conditions

Temperature
0 °C

Procedure

To a solution of bisphosphonate 17 (2 g, 3.2 mmol) in 12 ml of anhydrous DMF under nitrogen is added at 0° C. via a cannula a solution of potassium thioacetate (1.1 g, 9.6 mmol) in 15 ml of anhydrous DMF. The mixture is stirred for 1.50 h at 0° C., quenched with water and extracted with EtOAc. The organic layer is dried over Na2SO4, filtered and evaporated. The residue is purified by flash chromatography (silica gel, MeOH:CH2Cl2 /0:100-2:98) to give bisthioacetate 18 (1.38 g, 70%) as a light yellow oil. IR (neat) 2980, 2932, 2230, 1692, 1600 cm-1 ; 1H NMR (CDCl3): δ 1.16 (6H, d, J=6.2 Hz), 1.18 (6H, d, J=6.2 Hz), 1.23 (12H, d, J=6.2 Hz), 2.26 (6H, s), 2.40 (1H, tt, J=24, 6.3 Hz), 3.07 (2H, td, J=16.5, 6.3 Hz), 4.00 (4H, s), 4.67 (4H, m), 6.95 (1H, s), 6.99 (2H, s); 13C NMR (CDCl3): δ 23.72, 23.75, 23.78, 23.84, 23.87, 23.90, 24.14, 30.25, 31.35 (t, J=4.8 Hz), 33.17, 40.59 (t, J=134 Hz), 70.98 (d, J=3 Hz), 71.01 (d, J=3 Hz), 71.15 (d, J=3 Hz), 71.28 (d, J=3 Hz), 127.24, 128.55, 137.62, 140.99 (t, J=7.6 Hz), 194.77; MS (APCI) m/z (relative intensity) 611 (MH+, 100), 569 (63), 527 (58), 485 (37), 453 (31)); MS (FAB) m/z (relative intensity) 611 (MH+, 100); HRMS calcd for C26H45O8P2S2 (MH+) 611.2031, found 611.2029.

Workup

  1. customquenched with water
  2. extractionextracted with EtOAc
  3. dry with materialThe organic layer is dried over Na2SO4
  4. filtrationfiltered
  5. customevaporated
  6. customThe residue is purified by flash chromatography (silica gel, MeOH:CH2Cl2 /0:100-2:98)

Sources & evidence

ORD record
ord-2c795aa0bf744e7abcd057be4452807b
Source dataset
uspto-grants-2000_09
Patent number
US06121253

Reaction notes

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