Potassium Carbonate → HCID 125501437, compound

HRID 1778128Notes

Reaction equation

HRID 1778128 reaction equation
[CH3:1][C:2]([CH3:24])([Si:4]([CH3:23])([CH3:22])[O:5][CH2:6][CH2:7][CH2:8][S:9](=[O:21])[CH2:10][CH2:11][CH2:12][O:13][Si:14]([CH3:20])([CH3:19])[C:15]([CH3:18])([CH3:17])[CH3:16])[CH3:3].FC(F)(F)C([NH2:29])=O.[O-2].[Mg+2].C(OI(C1C=CC=CC=1)OC(=O)C)(=O)C.C(=O)([O-])[O-].[K+].[K+]>ClCCl.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.[Rh+2].[Rh+2]>[NH:29]=[S:9](=[O:21])([CH2:10][CH2:11][CH2:12][O:13][Si:14]([CH3:20])([CH3:19])[C:15]([CH3:16])([CH3:17])[CH3:18])[CH2:8][CH2:7][CH2:6][O:5][Si:4]([CH3:23])([CH3:22])[C:2]([CH3:24])([CH3:1])[CH3:3]

Participants

8

Reactant 5

HCID 11430Potassium CarbonateHCID 67717Trifluoroacetamide2×HCID 76724Iodobenzene diacetate2×HCID 6850729Magnesium monoxideHCID 123389700HCID 123389700, compound

Product 1

HCID 125501437HCID 125501437, compoundYield 72%

Reagents, catalysts & solvents 2

HCID 152122Dirhodium tetraacetateCatalyst2×HCID 6344DichloromethaneSolvent2×

Procedure

To a solution of 2,2,3,3,13,13,14,14-octamethyl-4,12-dioxa-8-thia-3,13-disilapentadecane 8-oxide in anhydrous dichloromethane (150 mL) was added trifluoroacetamide (7.60 g, 2 eq), magnesium oxide (5.256 g. 4 eq), rhodium acetate dimer (432 mg, 0.03 eq), and (diacetoxyiodo)benzene (15.75 g, 1.5 eq) under nitrogen atmosphere at room temperature. The greenish reaction mixture was stirred at room temperature for 18 hours. Then additional amount of trifluoroacetamide (3.0 g), rhodium acetate dimer (300 mg), (diacetoxyiodo)benzene (5.0 g), and anhydrous DCM (100 mL) was added. The mixture was stirred at room temperature for another 3 hours and then filtered through a pad of celite and silica gel. The pad was washed first with DCM followed by MeOH-DCM (1:5). The filtrate was concentrated and the brown oil was taken up into methanol (200 mL). Potassium carbonate (22.53 g, 5 eq) was added to the newly formed solution. After the mixture was stirred at room temp for 2 hours, it was filtered through a pad of celite and silica gel. The pad was washed first with DCM-EtOAC (1:1) followed by a later 10% (v/v) addition of MeOH with stirring of the sediment on top of the pad. The filtrate was concentrated and the residue mixture was treated with DCM-EtOAc (2:3) with stirring at room temp for 30 minutes. The mixture was filtered again through a pad of celite and silica gel. This filtration and concentration circle may be repeated a couple of times such that most of the solid by-product was removed and a reddish oil was obtained. Purification by a gradient column chromatography (EtOAc-HEX 1:20 to 1:1) provided the title compound as a redish oil (9.538 g) with a total yield of 72% for 4 steps.

Workup

  1. customThe greenish reaction mixture
  2. stirringThe mixture was stirred at room temperature for another 3 hours
  3. filtrationfiltered through a pad of celite and silica gel
  4. washThe pad was washed first with DCM
  5. concentrationThe filtrate was concentrated
  6. stirringAfter the mixture was stirred at room temp for 2 hours
  7. filtrationit was filtered through a pad of celite and silica gel
  8. washThe pad was washed first with DCM-EtOAC (1:1)
  9. additionfollowed by a later 10% (v/v) addition of MeOH
  10. stirringwith stirring of the sediment on top of the pad
  11. concentrationThe filtrate was concentrated
  12. additionthe residue mixture was treated with DCM-EtOAc (2:3)
  13. stirringwith stirring at room temp for 30 minutes
  14. filtrationThe mixture was filtered again through a pad of celite and silica gel
  15. filtrationThis filtration and concentration circle
  16. customwas removed
  17. customa reddish oil was obtained
  18. customPurification by a gradient column chromatography (EtOAc-HEX 1:20 to 1:1)

Sources & evidence

ORD record
ord-9255ffd7ab57447981b817ff6e27fe91
Source dataset
uspto-grants-2016_02
Patent number
US09266869B2

Reaction notes

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