Pyridine → Phenyl (4-(trifluoromethyl)pyridin-2-yl)carbamate

HRID 73660Notes

Reaction equation

HRID 73660 reaction equation
[NH2:1][C:2]1[CH:7]=[C:6]([C:8]([F:11])([F:10])[F:9])[CH:5]=[CH:4][N:3]=1.[C:12]1([O:18][C:19](Cl)=[O:20])[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.N1C=CC=CC=1>C(Cl)Cl.CCOCC>[C:12]1([O:18][C:19](=[O:20])[NH:1][C:2]2[CH:7]=[C:6]([C:8]([F:9])([F:11])[F:10])[CH:5]=[CH:4][N:3]=2)[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1

Participants

6

Reactant 3

HCID 1049Pyridine2×HCID 15891Phenyl chloroformateHCID 27783152-Amino-4-(trifluoromethyl)pyridine

Product 1

HCID 57955188Phenyl (4-(trifluoromethyl)pyridin-2-yl)carbamateYield 92.2%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 6344DichloromethaneSolvent

Procedure

A solution of the commerically available 2-amino-4-trifluoromethylpyridine (20.86 g, 128.7 mmol) in 250 mL CH2Cl2 was treated with phenylchloroformate (17.81 mL, 141.5 mmol) and pyridine (22.85 mL, 283 mmol). During addition of the pyridine a yellow precipitate formed and a considerable exotherm was observed. After 0.5 h the homogeneous reaction was diluted with 1 L Et2O and washed with 1 N bisulfate buffer (pH 2) and sat. NaHCO3. The organic layer was dried with Na2SO4 and evaporated to yield a gray solid. Trituration with Et2O:hexanes (1:5) gave the title compound as white crystals (33.5 g, 92% Yield). 1H-NMR (DMSO-d6) δ 11.28 (s, 1H), 8.60 (d, J=5.1 Hz, 1H), 8.12 (bs, 1H), 7.40 to 7.48 (m, 3H), 7.22 to 7.31 (m, 3H); MS [M+H]+=283.1; LCMS RT=3.51.

Workup

  1. customformed
  2. customAfter 0.5 h the homogeneous reaction
  3. washwashed with 1 N bisulfate buffer (pH 2) and sat. NaHCO3
  4. dry with materialThe organic layer was dried with Na2SO4
  5. customevaporated
  6. customto yield a gray solid

Sources & evidence

ORD record
ord-f9bc35480ee241bb95885f8879e54f92
Source dataset
uspto-grants-2014_09
Patent number
US08829185B2

Reaction notes

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