Hexane → HCID 121390087, compound

HRID 926377Notes

Reaction equation

HRID 926377 reaction equation
Br[C:2]1[C:3]([C:12]([F:15])([F:14])[F:13])=[CH:4][C:5]([C:8]([F:11])([F:10])[F:9])=[N:6][CH:7]=1.C([Li])CCC.CCCCCC.[CH:27](=[N:30][S@:31]([C:33]([CH3:36])([CH3:35])[CH3:34])=[O:32])[CH2:28][CH3:29].[CH:37](=[N:40][S:41]([C:43]([CH3:46])([CH3:45])[CH3:44])=[O:42])[CH2:38][CH3:39].[Cl-].[NH4+]>C(OCC)C.C1(C)C=CC=CC=1>[F:13][C:12]([F:15])([F:14])[C:3]1[CH:4]=[C:5]([C:8]([F:11])([F:10])[F:9])[N:6]=[CH:7][C:2]=1[C@@H:27]([NH:30][S@:31]([C:33]([CH3:36])([CH3:35])[CH3:34])=[O:32])[CH2:28][CH3:29].[F:13][C:12]([F:15])([F:14])[C:3]1[CH:4]=[C:5]([C:8]([F:11])([F:10])[F:9])[N:6]=[CH:7][C:2]=1[C@H:37]([NH:40][S@:41]([C:43]([CH3:46])([CH3:45])[CH3:44])=[O:42])[CH2:38][CH3:39]

Participants

10

Reactant 6

HCID 8058HexaneHCID 25517Ammonium ChlorideHCID 37859531HCID 37859531, compoundHCID 76223432HCID 76223432, compoundHCID 89726942HCID 89726942, compoundHCID 178418339Butyllithium

Product 2

HCID 89733984HCID 89733984, compoundYield 14%HCID 121390087HCID 121390087, compoundYield 15%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 3283Diethyl EtherSolvent

Conditions

Temperature
-78 °C

Procedure

To a solution of 5-bromo-2,4-bis-trifluoromethyl-pyridine (200 mg, 0.685 mmol) in dry diethyl ether (1.5 ml) at −78° C. was added a 2.5 M solution of n-butyllithium in hexane (0.25 ml, 0.685 mmol) and the mixture was stirred at −78° C. for 15 min. A solution of (S)-2-methyl-propane-2-sulfinic acid propylideneamide (Comp. No. 13b) (85 mg, 0.527 mmol) in dry toluene (1 ml) was added at −78° C., the mixture was stirred for 5 min at −78° C. and then poured into a saturated aqueous ammonium chloride solution. The mixture was extracted 3 times with dichloromethane, dried over sodium sulfate, and after evaporation of all solvents the crude product was purified by flash chromatography (silica gel, elution with heptane/ethyl acetate) to give 27 mg (14%) of (S)-2-methyl-propane-2-sulfinic acid [(S)-1-(4,6-bis-trifluoromethyl-pyridin-3-yl)-propyl]-amide (LC/MS (method 2; MS ionization method ES−): Rt=1.3 min; m/z=375.1 (M+1−)) and 29 mg (15%) of (S)-2-methyl-propane-2-sulfinic acid [(R)-1-(4,6-bis-trifluoromethyl-pyridin-3-yl)-propyl]-amide (LC/MS (method 2; MS ionization method ES−): Rt=1.3 min; m/z=375.12 (M+1−)).

Workup

  1. stirringthe mixture was stirred for 5 min at −78° C.
  2. extractionThe mixture was extracted 3 times with dichloromethane
  3. dry with materialdried over sodium sulfate
  4. customafter evaporation of all solvents the crude product
  5. customwas purified by flash chromatography (silica gel, elution with heptane/ethyl acetate)

Sources & evidence

ORD record
ord-f0b42da24e1d4d10806b645093a425a7
Source dataset
uspto-grants-2016_03
Patent number
US09284333B2

Reaction notes

Loading…