Ethanamine, 2,2,2-trifluoro- → 1-[3-Chloro-5-[2-(trifluoromethyl)cyclopropyl]-2-pyridyl]cyclopropanecarbonitrile

HRID 578867Notes

Reaction equation

HRID 578867 reaction equation
[Cl:1][C:2]1[C:3]([C:10]2([C:13]#[N:14])[CH2:12][CH2:11]2)=[N:4][CH:5]=[C:6]([CH:8]=[CH2:9])[CH:7]=1.[F:15][C:16]([F:20])([F:19])[CH2:17]N.N([O-])=O.[Na+].[Cl-].[NH4+]>C1(C)C=CC=CC=1.[Fe](Cl)(Cl)Cl.C1(C2C3NC(C(C4C=CC=CC=4)=C4N=C(C(C5C=CC=CC=5)=C5NC(=C(C6C=CC=CC=6)C6C=CC=2N=6)C=C5)C=C4)=CC=3)C=CC=CC=1.O>[Cl:1][C:2]1[C:3]([C:10]2([C:13]#[N:14])[CH2:11][CH2:12]2)=[N:4][CH:5]=[C:6]([CH:8]2[CH2:9][CH:17]2[C:16]([F:20])([F:19])[F:15])[CH:7]=1

Participants

8

Reactant 4

HCID 9773Ethanamine, 2,2,2-trifluoro-HCID 25517Ammonium ChlorideHCID 23668193Sodium NitriteHCID 895443761-(3-Chloro-5-vinyl-2-pyridyl)cyclopropanecarbonitrile

Product 1

HCID 895441591-[3-Chloro-5-[2-(trifluoromethyl)cyclopropyl]-2-pyridyl]cyclopropanecarbonitrileYield 61.2%

Reagents, catalysts & solvents 3

HCID 1363371375,10,15,20-tetraphenyl-21H,23H-porphine iron (III) chlorideCatalystHCID 962WaterSolventHCID 1140TolueneSolvent

Procedure

1.4 g 1-(3-chloro-5-vinyl-2-pyridyl)cyclopropanecarbonitrile (step 1) was dissolved in 2.0 ml toluene and 14 mg 5,10,15,20-tetraphenyl-21H,23H-porphine iron(III) chloride was added. Then 30 ml water was added, followed by 1.4 g 2,2,2-trifluoroethanamine and 1.1 g sodium nitrite. The reaction mixture was stirred for 3 hours at ambient temperature. Then saturated ammonium chloride solution was added and the mixture was extracted with dichloromethane. The organic phase was washed with water, dried over anhydrous sodium sulfate, filtered and concentrated. Crude material was obtained as a dark oil, which was purified by flash chromatography on silica gel with heptane/ethyl acetate as a solvent. Thus, 1.2 g of 1-[3-chloro-5-[2-(trifluoromethyl)cyclopropyl]-2-pyridyl]cyclopropanecarbonitrile was obtained as a brown oil. 1H-NMR (CDCl3): 8.25 ppm (s, 1H), 7.44 ppm (s, 1H), 2.35 ppm (m, 1H), 1.85 ppm (m, 1H), 1.75 ppm (m, 2H), 1.60 ppm (m, 2H), 1.50 ppm (m, 1H), 1.24 ppm (m, 2H).

Workup

  1. extractionthe mixture was extracted with dichloromethane
  2. washThe organic phase was washed with water
  3. dry with materialdried over anhydrous sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customCrude material was obtained as a dark oil, which
  7. customwas purified by flash chromatography on silica gel with heptane/ethyl acetate as a solvent

Sources & evidence

ORD record
ord-686eb7eeb4f8444a8859fffd3208465b
Source dataset
uspto-grants-2015_05
Patent number
US09040708B2

Reaction notes

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