Tert-Butanesulfinamide → 2-Methyl-propane-2-sulfinic acid 1-[1-(3-chloro-5-trifluoromethyl-pyridin-2-yl)-cyclopropyl]-methylideneamide

HRID 578855Notes

Reaction equation

HRID 578855 reaction equation
[Cl:1][C:2]1[C:3]([C:12]2([CH:15]=O)[CH2:14][CH2:13]2)=[N:4][CH:5]=[C:6]([C:8]([F:11])([F:10])[F:9])[CH:7]=1.[CH3:17][C:18]([S:21]([NH2:23])=[O:22])([CH3:20])[CH3:19]>O1CCCC1.[Cl-].[Na+].O.[O-]CC.[Ti+4].[O-]CC.[O-]CC.[O-]CC>[Cl:1][C:2]1[C:3]([C:12]2([CH:15]=[N:23][S:21]([C:18]([CH3:20])([CH3:19])[CH3:17])=[O:22])[CH2:14][CH2:13]2)=[N:4][CH:5]=[C:6]([C:8]([F:11])([F:10])[F:9])[CH:7]=1

Participants

6

Reactant 2

HCID 3382465Tert-ButanesulfinamideHCID 715592821-(3-Chloro-5-trifluoromethyl-pyridin-2-yl)-cyclopropanecarbaldehyde

Product 1

HCID 781117472-Methyl-propane-2-sulfinic acid 1-[1-(3-chloro-5-trifluoromethyl-pyridin-2-yl)-cyclopropyl]-methylideneamideYield 71.7%

Reagents, catalysts & solvents 3

HCID 76524Titanium tetraethoxideCatalystHCID 8028TetrahydrofuranSolventHCID 57417360Sodium chloride; waterSolvent

Procedure

0.72 g of 1-(3-chloro-5-trifluoromethyl-pyridin-2-yl)-cyclopropanecarbaldehyde (step 2) was dissolved in 13 ml of tetrahydrofuran, then 1.32 g of titanium(IV)ethoxide and 355 mg of 2-methyl-propane-2-sulfinic acid amide were added to the solution. The reaction mixture was stirred at ambient temperature for 24 hours, then poured into brine. The resulting suspension was filtered, the filtrate extracted with ethyl acetate, the organic phase dried over sodium sulfate, filtered and concentrated. The residue was purified by chromatography on silica gel with cyclohexane/ethyl acetate (95:5) as eluent. Thus, 0.73 g of 2-methyl-propane-2-sulfinic acid 1-[1-(3-chloro-5-trifluoromethyl-pyridin-2-yl)-cyclopropyl]-methylideneamide was obtained as a pale yellow solid. 1H-NMR (CDCl3): 8.73 ppm (s, 1H), 7.95 ppm (s, 1H), 7.65 ppm (s, 1H), 1.70 ppm (m, 4H), 1.12 ppm (s, 9H).

Workup

  1. filtrationThe resulting suspension was filtered
  2. extractionthe filtrate extracted with ethyl acetate
  3. dry with materialthe organic phase dried over sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customThe residue was purified by chromatography on silica gel with cyclohexane/ethyl acetate (95:5) as eluent

Sources & evidence

ORD record
ord-44b64083462b432cb8e44718c7dc5f8f
Source dataset
uspto-grants-2015_05
Patent number
US09040708B2

Reaction notes

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