Ammonium fluoride → HCID 11997511, compound

HRID 1985721Notes

Reaction equation

HRID 1985721 reaction equation
C(OC([N:8]1[CH2:20][C@@H:19]([CH3:21])[N:18]2[C@H:10]([CH2:11][C:12]3[C:17]2=[N:16][C:15]([CH:22](C(C)(C)C(C)C)[O:23][SiH](C)C)=[C:14]([CH:33]=[CH:34]O[Si](C(C)(C)C)(C)C)[CH:13]=3)[CH2:9]1)=O)(C)(C)C.[F-].[NH4+]>>[NH3:8].[CH3:21][C@@H:19]1[CH2:20][NH:8][CH2:9][C@@H:10]2[N:18]1[C:17]1[N:16]=[C:15]3[CH2:22][O:23][CH2:34][CH2:33][C:14]3=[CH:13][C:12]=1[CH2:11]2

Participants

4

Reactant 2

HCID 25516Ammonium fluorideHCID 131727480HCID 131727480, compound

Product 2

HCID 222AmmoniaHCID 11997511HCID 11997511, compoundYield 15.4%

Conditions

Temperature
0 °C

Procedure

A solution of 0.154 g (4R,9aR)-7-[2-(tert-Butyl-dimethyl-silanyloxy)-vinyl]-6-[dimethyl-(1,1,2-trimethyl-propyl)-silanyloxymethyl]-4-methyl-3,4,9,9a-tetrahydro-1H-2,4a,5-triaza-fluorene-2-carboxylic acid tert-butyl ester in and 0.154 g ammonium fluoride in 3.00 ml was heated to reflux for 4 h. The reaction mixture was partitioned between water and ethyl acetate. The phases were separated and the organic phase was washed with brine dried over sodium sulfate and evaporated. To as solution of the residue in 3.00 ml dichloromethane was added at 0° C. 0.14 ml triethylsilane and 0.14 ml trifluoroacetic acid and the mixture was stirred at 0° C. for 2 h. To the resulting solution was added 0.7 ml trifluoroacetic acid and the mixture was allowed to thaw to room temperature over 17 h. The solvent was evaporated and the residue was partitioned between water and ethyl acetate. The phases were separated and the pH of the aqueous phase was adjusted to 12.00 by addition of 2N aqueous sodium hydroxide and the product was extracted with methylenechloride and purified by chromatography on silica gel with dichloromethane:methanol:ammonia=90:10:1 to yield 0.0047 g of the title compound as slightly yellow oil. (MS: 246.3 (M+H+))

Workup

  1. temperatureto reflux for 4 h
  2. customThe reaction mixture was partitioned between water and ethyl acetate
  3. customThe phases were separated
  4. washthe organic phase was washed with brine
  5. dry with materialdried over sodium sulfate
  6. customevaporated
  7. additionTo as solution of the residue in 3.00 ml dichloromethane was added at 0° C
  8. additionTo the resulting solution was added 0.7 ml trifluoroacetic acid
  9. customthaw to room temperature
  10. customover 17 h
  11. customThe solvent was evaporated
  12. customthe residue was partitioned between water and ethyl acetate
  13. customThe phases were separated
  14. additionthe pH of the aqueous phase was adjusted to 12.00 by addition of 2N aqueous sodium hydroxide
  15. extractionthe product was extracted with methylenechloride
  16. custompurified by chromatography on silica gel with dichloromethane

Sources & evidence

ORD record
ord-39d57cbd49cc40b892ce7a9789961a1a
Source dataset
uspto-grants-2009_06
Patent number
US07547699B2

Reaction notes

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