Pyridine → (+/-)-3-Pyridylmethyl-2-(2-naphthylmethoxy)-3,3,3-trifluoro-2-methylpropionate

HRID 973326Notes

Reaction equation

HRID 973326 reaction equation
[CH:1]1[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[CH:4]=[CH:3][C:2]=1[CH2:11][O:12][C:13]([CH3:21])([C:17]([F:20])([F:19])[F:18])[C:14](Cl)=[O:15].[N:22]1[CH:27]=[CH:26][CH:25]=[C:24]([CH2:28][OH:29])[CH:23]=1.N1C=CC=CC=1>C1C=CC=CC=1.C(OCC)(=O)C.C(O)C.C(N(CC)CC)C>[N:22]1[CH:27]=[CH:26][CH:25]=[C:24]([CH2:28][O:29][C:14](=[O:15])[C:13]([O:12][CH2:11][C:2]2[CH:3]=[CH:4][C:5]3[C:10](=[CH:9][CH:8]=[CH:7][CH:6]=3)[CH:1]=2)([CH3:21])[C:17]([F:19])([F:20])[F:18])[CH:23]=1

Participants

8

Reactant 3

HCID 1049PyridineHCID 75103-PyridinemethanolHCID 20314457(+/-)-2-(2-Naphthylmethoxy)-3,3,3-trifluoro-2-methylpropionyl chloride

Product 1

HCID 20314475(+/-)-3-Pyridylmethyl-2-(2-naphthylmethoxy)-3,3,3-trifluoro-2-methylpropionateYield 91.1%

Reagents, catalysts & solvents 4

HCID 241BenzeneSolvent2×HCID 702EthanolSolventHCID 8471TriethylamineSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
5 °C

Procedure

A solution of (±)-2-(2-naphthylmethoxy)-3,3,3-trifluoro-2-methylpropionyl chloride (4.3 g.) in benzene (20 ml.) is added, dropwise below 10° C., to a stirred solution of 3-pyridylmethanol (1.20 g.) and pyridine (1.10 g.) in benzene (20 ml.) and light petroleum (5 ml. b.p. 40°-60° C.). The mixture is stirred at 5° C. for 1 hour, and at ambient temperature for 18 hours. The mixture is filtered. The filtrate is diluted with ether, washed with water, aqueous sodium carbonate and water, dried with sodium sulphate, and evaporated to give an oil (4.1 g.). The oil is dissolved in a mixture of ethyl acetate, ethanol, and triethylamine (200:1:1) and is chromatographed on a column of silica gel (210 g.) made up in the same solvent. The column is eluted portionwise with the solvent. The first 350 ml. elutes an impurity (0.1 g.). The following 420 ml. of eluant is evaporated to give (±)-3-pyridylmethyl-2-(2-naphthylmethoxy)-3,3,3-trifluoro-2-methylpropionate (3.9 g.) as a syrup.

Workup

  1. waitat ambient temperature for 18 hours
  2. filtrationThe mixture is filtered
  3. additionThe filtrate is diluted with ether
  4. washwashed with water, aqueous sodium carbonate and water
  5. dry with materialdried with sodium sulphate
  6. customevaporated
  7. customto give an oil (4.1 g.)
  8. customis chromatographed on a column of silica gel (210 g.)
  9. washThe column is eluted portionwise with the solvent
  10. customof eluant is evaporated

Sources & evidence

ORD record
ord-06e64649f0cb47df9508b3918e320b9a
Source dataset
uspto-grants-1977_10
Patent number
US04055595

Reaction notes

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