Triethylamine → benzyl N-(6-chloropyridin-3-yl)carbamate

HRID 965127Notes

Reaction equation

HRID 965127 reaction equation
[NH2:1][C:2]1[CH:3]=[CH:4][C:5]([Cl:8])=[N:6][CH:7]=1.C(N(CC)CC)C.Cl[C:17]([O:19][CH2:20][C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)=[O:18]>C(Cl)(Cl)Cl>[CH2:20]([O:19][C:17]([NH:1][C:2]1[CH:3]=[CH:4][C:5]([Cl:8])=[N:6][CH:7]=1)=[O:18])[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1

Participants

5

Reactant 3

HCID 8471TriethylamineHCID 10387Benzyl chloroformateHCID 793055-Amino-2-chloropyridine

Product 1

HCID 19075567benzyl N-(6-chloropyridin-3-yl)carbamateYield 53.3%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent2×

Procedure

5-Amino-2-chloropyridine(643 mg)in 3 mL of chloroform containing 505 mg of triethylamine was stirred with 853 mg of benzyl chloroformate for 4 hours at 60 degrees C. The mixture was then diluted with 20 mL of chloroform and washed with water, saturated sodium bicarbonate and brine, dried over anhydrous magnesium sulfate and evaporated to give 700 mg of 5-benzyloxycarbonylamino-2-chloropyridine. 5-Benzyloxy carbonylamino-2-chloropyridine (272 mg) and 163 mg of 2,4-dichlorophenol were stirred overnight at room temperature in 1 mL of dimethylformamide containing 138 mg of potassium carbonate. The reaction mixture was evaporated to dryness under high vacuum and partitioned between ethyl acetate and water. The ethyl acetate layer was washed with water, saturated sodium bicarbonate and brine, dried over anhydrous magnesium sulfate and evaporated. Hydrogenolysis in methanol over palladium on carbon gave 5-amino-2-(2,4-dichlorophenoxy) pyridine. The 5-amino-2-(2,4-dichlorophenoxy)pyridine was treated with 4-(trifluoromethylmercapto)phenylisocyanate under conditions similar to those in Example 1 to give N-[2-(2,4-dichlorophenoxy)pyrid-5-yl]-N'-[4-trifluoromethyl mercapto)phenyl]urea.

Workup

  1. washwashed with water, saturated sodium bicarbonate and brine
  2. dry with materialdried over anhydrous magnesium sulfate
  3. customevaporated

Sources & evidence

ORD record
ord-ad3068781b224b86a89b26aeeac936e9
Source dataset
uspto-grants-1998_06
Patent number
US05773459

Reaction notes

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