Chlorotrimethylsilane → HCID 66756800, compound

HRID 1642602Notes

Reaction equation

HRID 1642602 reaction equation
BrCCBr.C[Si](Cl)(C)C.I[CH2:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.CC1C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.[CH2:40]([O:47][C:48]1[CH:53]=[C:52](I)[CH:51]=[CH:50][C:49]=1[N:55]1[S:59](=[O:61])(=[O:60])[N:58]([CH2:62][CH2:63][Si:64]([CH3:67])([CH3:66])[CH3:65])[C:57](=[O:68])[CH2:56]1)[C:41]1[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=1>CN(C=O)C.CCOC(C)=O.[Zn].C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH2:11]([C:52]1[CH:51]=[CH:50][C:49]([N:55]2[S:59](=[O:60])(=[O:61])[N:58]([CH2:62][CH2:63][Si:64]([CH3:66])([CH3:67])[CH3:65])[C:57](=[O:68])[CH2:56]2)=[C:48]([O:47][CH2:40][C:41]2[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=2)[CH:53]=1)[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1

Participants

10

Reactant 5

HCID 6397ChlorotrimethylsilaneHCID 78391,2-DibromoethaneHCID 12098Benzyl iodideHCID 80271Tri-o-tolylphosphineHCID 667569375-(2-Benzyloxy-4-iodophenyl)-1,1-dioxo-2-(2-trimethylsilanylethyl)-1,2,5-thiadiazolidin-3-one

Product 1

HCID 66756800HCID 66756800, compound

Reagents, catalysts & solvents 4

HCID 23994ZincCatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 6228DimethylformamideSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

Zinc dust (7.2 g) is placed in a 250 mL round bottom flask, placed under vacuum and heated with a heat gun for 5-8 min. The hot solid is allowed to cool slowly to ambient temperature. DMF (50 mL) is added, followed by 1,2-dibromoethane (0.8 mL). The mixture is placed under an atmosphere of N2 and heated again until effervescence occurs and the reaction maintains itself. The mixture is cooled to ambient temperature and TMSCl (0.8 mL) is added and stirred for 30 min. Iodomethylbenzene (6.2 g, 28 mmol) is added and the mixture stirred for 30 min. at ambient temperature. The reaction is monitored by TLC until the starting material is converted to the Znl, at which point Pd2 dba3 (0.8 g, 0.874 mmol) and P(o-tolyl)3 (1.0 g, 3.28 mmol) are added. A solution of 5-(2-benzyloxy-4-iodophenyl)-1,1-dioxo-2-(2-trimethylsilanylethyl)-1,2,5-thiadiazolidin-3-one (10.0 g, 18.3 mmol) in DMF is added slowly dropwise. The mixture is stirred at ambient temperature overnight. The reaction is diluted with EtOAc, filtered through Celite and washed with EtOAc. The organic mixture is washed with 100 mL of 1N HCl, 150 mL of saturated sodium chloride and dried over MgSO4. The solution is then filtered through a plug of silica gel and concentrated to afford an orange oil. The oil is triturated with 4:1 hexane/ether. The crude material is chromatographed eluting with 4:1 hexane/EtOAc. The pure fractions are concentrated to an orange oil and hexane is added. The solution is filtered and washed with hexane to afford 5-(4-benzyl-2-benzyloxyphenyl)-1,1-dioxo-2-(2-trimethylsilanylethyl)-1,2,5-thiadiazolidin-3-one.

Workup

  1. temperatureheated with a heat gun for 5-8 min
  2. temperatureheated again until effervescence
  3. temperatureThe mixture is cooled to ambient temperature
  4. stirringthe mixture stirred for 30 min. at ambient temperature
  5. additionare added
  6. stirringThe mixture is stirred at ambient temperature overnight
  7. filtrationfiltered through Celite
  8. washwashed with EtOAc
  9. washThe organic mixture is washed with 100 mL of 1N HCl, 150 mL of saturated sodium chloride
  10. dry with materialdried over MgSO4
  11. filtrationThe solution is then filtered through a plug of silica gel
  12. concentrationconcentrated
  13. customto afford an orange oil
  14. customThe oil is triturated with 4:1 hexane/ether
  15. customThe crude material is chromatographed
  16. washeluting with 4:1 hexane/EtOAc
  17. concentrationThe pure fractions are concentrated to an orange oil and hexane
  18. additionis added
  19. filtrationThe solution is filtered
  20. washwashed with hexane

Sources & evidence

ORD record
ord-29b0b2ee8baf4807b60c622e166999bc
Source dataset
uspto-grants-2012_02
Patent number
US08119666B2

Reaction notes

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