Ammonium Chloride → HCID 58557331, compound

HRID 1969570Notes

Reaction equation

HRID 1969570 reaction equation
[F-].C[N+](C)(C)C.[CH3:7][C:8]([S@@:11](/[N:13]=[CH:14]/[C:15]1[N:16]=[C:17]2[CH:23]=[CH:22][N:21]([S:24]([C:27]3[CH:33]=[CH:32][C:30]([CH3:31])=[CH:29][CH:28]=3)(=[O:26])=[O:25])[C:18]2=[N:19][CH:20]=1)=[O:12])([CH3:10])[CH3:9].C[Si](C)(C)[C:36]([F:39])([F:38])[F:37].[NH4+].[Cl-]>C1COCC1.[Cl-].[Na+].O.CCOC(C)=O>[CH3:10][C:8]([S@@:11]([NH:13][CH:14]([C:15]1[N:16]=[C:17]2[CH:23]=[CH:22][N:21]([S:24]([C:27]3[CH:28]=[CH:29][C:30]([CH3:31])=[CH:32][CH:33]=3)(=[O:25])=[O:26])[C:18]2=[N:19][CH:20]=1)[C:36]([F:39])([F:38])[F:37])=[O:12])([CH3:7])[CH3:9]

Participants

8

Reactant 4

HCID 25517Ammonium ChlorideHCID 67803Tetramethylammonium fluorideHCID 552549(Trifluoromethyl)trimethylsilaneHCID 58557252HCID 58557252, compound

Product 1

HCID 58557331HCID 58557331, compoundYield 99.3%

Reagents, catalysts & solvents 3

HCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolventHCID 57417360Sodium chloride; waterSolvent

Conditions

Temperature
-78 °C

Procedure

To a dry flask charged with 4 Å molecular sieves (5 g) and tetramethyl-ammonium fluoride (0.553 g, 5.93 mmol) was added THF (20 mL). The reaction mixture was stirred for about 30 min after which it was cooled to about −78° C. and a solution of (S,E)-2-methyl-N-((5-tosyl-5H-pyrrolo[2,3-b]pyrazin-2-yl)methylene)propane-2-sulfinamide (1.20 g, 2.97 mmol) in THF (10 mL) was added. After about 15 min trimethyl(trifluoromethyl)silane (0.877 mL, 5.93 mmol) was added to the reaction mixture. The mixture was allowed to warm to −35 to −45° C. After about 3 h, the reaction mixture was cooled to −78° C. and aqueous NH4Cl was added. The reaction mixture was allowed to warm to rt. EtOAc (30 mL) and brine (30 mL) were added. The organic layer was separated, dried over anhydrous Na2SO4, filtered and concd in vacuo to provide crude (S)-2-methyl-N-(2,2,2-trifluoro-1-(5-tosyl-5H-pyrrolo[2,3-b]pyrazin-2-yl)ethyl)propane-2-sulfinamide (1.4 g, 99%) as a foamsulfonamide which was used without further purification. LC/MS (Table 1, Method a) Rt=2.49 min; MS m/z 475 (M+H)+.

Workup

  1. temperatureto warm to −35 to −45° C
  2. waitAfter about 3 h
  3. temperaturethe reaction mixture was cooled to −78° C.
  4. temperatureto warm to rt
  5. customThe organic layer was separated
  6. dry with materialdried over anhydrous Na2SO4
  7. filtrationfiltered

Sources & evidence

ORD record
ord-6ad9bf1a9cf24a04bbdd271f7d1847d1
Source dataset
uspto-grants-2013_04
Patent number
US08426411B2

Reaction notes

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