Tributylborane → HCID 9913119, compound

HRID 1838270Notes

Reaction equation

HRID 1838270 reaction equation
C([Li])(C)(C)C.[C:6]([C:8]1[CH:13]=[CH:12][C:11]([N:14]2[C@H:19]([CH3:20])[CH2:18][N:17]([C:21]([NH:23][C:24]3[CH:25]=[N:26][C:27]([S:30](C)(=[O:32])=[O:31])=[CH:28][CH:29]=3)=[O:22])[C@@H:16]([CH3:34])[CH2:15]2)=[CH:10][C:9]=1[C:35]([F:38])([F:37])[F:36])#[N:7].C(B(CCCC)CCCC)CCC.C([O-])(=O)C.[Na+].[NH2:57]OS(O)(=O)=O>O.O1CCCC1.CCCCC>[NH2:57][S:30]([C:27]1[N:26]=[CH:25][C:24]([NH:23][C:21]([N:17]2[CH2:18][C@@H:19]([CH3:20])[N:14]([C:11]3[CH:12]=[CH:13][C:8]([C:6]#[N:7])=[C:9]([C:35]([F:38])([F:37])[F:36])[CH:10]=3)[CH2:15][C@@H:16]2[CH3:34])=[O:22])=[CH:29][CH:28]=1)(=[O:32])=[O:31]

Participants

9

Reactant 5

HCID 31216TributylboraneHCID 76284hydroxylamine-O-sulfonic acidHCID 517045Sodium AcetateHCID 69108002HCID 69108002, compoundHCID 178418306HCID 178418306, compound

Product 1

HCID 9913119HCID 9913119, compoundYield 19.8%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8003PentaneSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-30 °C

Procedure

A 7.3 ml portion of 1.54 M pentane solution of tert-butyl lithium was added dropwise to 100 ml of THF solution containing 2.48 g of trans-4-(4-cyano-3-trifluoromethylphenyl)-N-(6-methanesulfonyl-3-pyridyl)-2,5-dimethylpiperazine-1-carboxamide at −78° C., and then the mixture was stirred at −30° C. for 15 minutes. After cooling again to −78° C., this was mixed with 15.5 ml of 1.0 M tetrahydrofuran solution of tri-n-butyl borane, warmed up to room temperature spending 1 hour and then heated under refulx for 18 hours. Under ice-cooling, this was mixed with 5.91 g of sodium acetate, 50 ml of water and 491 mg of hydroxylamine-O-sulfonic acid and stirred overnight at room temperature. The reaction mixture was extracted with ethyl acetate, the organic layer was washed with saturated sodium bicarbonate solution and saturated brine in that order and dried over magnesium sulfate, and then the solvent was evaporated. The thus obtained mixture was subjected to a silica gel column chromatography and eluted with chloroform-methanol (9:1, v/v) to obtain 414 mg of the title compound. Thereafter, this was crystallized twice from ethanol to obtain 271 mg of the title compound as crystals.

Workup

  1. temperatureAfter cooling again to −78° C.
  2. temperaturewarmed up to room temperature
  3. waitspending 1 hour
  4. temperatureheated under refulx for 18 hours
  5. temperatureUnder ice-cooling
  6. stirringstirred overnight at room temperature
  7. extractionThe reaction mixture was extracted with ethyl acetate
  8. washthe organic layer was washed with saturated sodium bicarbonate solution and saturated brine in that order
  9. dry with materialdried over magnesium sulfate
  10. customthe solvent was evaporated
  11. washeluted with chloroform-methanol (9:1

Sources & evidence

ORD record
ord-6c87b80de02a4c01a22bcda28b6a22d1
Source dataset
uspto-grants-2004_01
Patent number
US06673799B1

Reaction notes

Loading…