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Lithium diisopropylamide → HCID 90372982, compound

HRID 930365
Notes
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Reaction equation

HRID 930365 reaction equation
C([N-]C(C)C)(C)C.[Li+].O1CCCC1.CCCCCCC.C(C1C=CC=CC=1)C.[CH3:29][N:30]([CH3:38])/[N:31]=[C:32](\[CH3:37])/[C:33]([F:36])([F:35])[F:34].[Br:39][C:40]1[CH:41]=[C:42](/[C:47](=[N:50]\[S@@:51]([C:53]([CH3:56])([CH3:55])[CH3:54])=[O:52])/[CH2:48][F:49])[C:43]([F:46])=[N:44][CH:45]=1>C1COCC1.C1(C)C=CC=CC=1>[Br:39][C:40]1[CH:41]=[C:42]([C@@:47]([NH:50][S@@:51]([C:53]([CH3:56])([CH3:55])[CH3:54])=[O:52])([CH2:37]/[C:32](=[N:31]/[N:30]([CH3:38])[CH3:29])/[C:33]([F:36])([F:35])[F:34])[CH2:48][F:49])[C:43]([F:46])=[N:44][CH:45]=1
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

7

Reactant 4

HCID 2724682Lithium diisopropylamideHCID 22742125Tetrahydrofuran heptane ethylbenzolHCID 58668234HCID 58668234, compoundHCID 90373167HCID 90373167, compound

Product 1

HCID 90372982HCID 90372982, compoundYield 68.8%

Reagents, catalysts & solvents 2

HCID 1140
Toluene
Solvent
HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

Lithium diisopropylamide, 2.0M solution in tetrahydrofuran/heptane/ethylbenzene (1.474 ml, 2.95 mmol) was added dropwise via syringe to a solution of (E)-1,1-dimethyl-2-(1,1,1-trifluoropropan-2-ylidene)hydrazine (0.454 g, 2.95 mmol) in THF 4.0 mL at −78° C. After stirring at −78° C. for 1 h, the solution was added dropwise via cannula to a solution of (R,E)-N-(1-(5-bromo-2-fluoropyridin-3-yl)-2-fluoroethylidene)-2-methylpropane-2-sulfinamide (0.500 g, 1.474 mmol) in toluene 4 mL cooled to −78° C. The reaction was stirred 3 h at −78° C. before being quenched with saturated aqueous ammonium chloride at −78° C. The mixture was warmed up to room temperature and diluted with water and EtOAc. The layers were separated and the aqueous layer was extracted with EtOAc three times. The combined organic layers were washed with brine, dried on sodium sulfate, filtered and concentrated. The crude material was purified by column chromatography using a gradient of 10-50% EtOAC/Hexane to give 0.50 g of (R)-N-((S,Z)-2-(5-bromo-2-fluoropyridin-3-yl)-4-(2,2-dimethylhydrazono)-1,5,5,5-tetrafluoropentan-2-yl)-2-methylpropane-2-sulfinamide (0.50 g, 1.014 mmol, 68.8% yield). MS m/z=494.9 [M+H]+. Calculated for C16H22BrF5N4OS: 493.3.

Workup

  1. temperaturecooled to −78° C
  2. stirringThe reaction was stirred 3 h at −78° C.
  3. custombefore being quenched with saturated aqueous ammonium chloride at −78° C
  4. temperatureThe mixture was warmed up to room temperature
  5. additiondiluted with water and EtOAc
  6. customThe layers were separated
  7. extractionthe aqueous layer was extracted with EtOAc three times
  8. washThe combined organic layers were washed with brine
  9. customdried on sodium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated
  12. customThe crude material was purified by column chromatography

Sources & evidence

ORD record
ord-f71f2973ff1f4abfacca6be30bdc61fa
Source dataset
uspto-grants-2016_03
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US09296734B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes