2,4,6-Trimethylpyridine → Ethyl 14-chloro-2-(1-methylethyl)-5,9,13-trimethyl-2,4,8,12-tetradecatetraenoate

HRID 892637Notes

Reaction equation

HRID 892637 reaction equation
[CH2:1]([O:3][C:4](=[O:25])[C:5]([CH:22]([CH3:24])[CH3:23])=[CH:6][CH:7]=[C:8]([CH3:21])[CH2:9][CH2:10][CH:11]=[C:12]([CH3:20])[CH2:13][CH2:14][CH:15]=[C:16]([CH3:19])[CH2:17]O)[CH3:2].CC1C=C(C)N=C(C)C=1.[Cl-].[Li+].CS([Cl:41])(=O)=O>C(OCC)C.O.CN(C)C=O>[CH2:1]([O:3][C:4](=[O:25])[C:5]([CH:22]([CH3:24])[CH3:23])=[CH:6][CH:7]=[C:8]([CH3:21])[CH2:9][CH2:10][CH:11]=[C:12]([CH3:20])[CH2:13][CH2:14][CH:15]=[C:16]([CH3:19])[CH2:17][Cl:41])[CH3:2]

Participants

8

Reactant 4

HCID 79532,4,6-TrimethylpyridineHCID 31297Methanesulfonyl chlorideHCID 433294Lithium ChlorideHCID 54363154Ethyl 14-hydroxy-2-(1-methylethyl)-5,9,13-trimethyl-2,4,8,12-tetradecatetraenoate

Product 1

HCID 54546229Ethyl 14-chloro-2-(1-methylethyl)-5,9,13-trimethyl-2,4,8,12-tetradecatetraenoateYield 88%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 6228DimethylformamideSolvent

Procedure

To a mixture of the hydroxyester compound which is 14-hydroxy-2-(1-methylethyl)-5,9,13-trimethyl-2,4,8,12-tetradecatetraenoic acid ethyl ester (71.0 mg, 0.20 mmol), S-collidine (26.7 mg, 0.22 mmol), lithium chloride (8.5 mg, 0.20 mmol) and dimethylformamide (1 ml) is added methanesulfonyl chloride (25.2 mg, 0.22 mmol) under nitrogen atmosphere while stirring on an ice-bath. The stirring is continued at the same temperature for 5 hours. After confirming disappearance of the starting compound, to the reaction mixture are added water and ethyl ether and the organic layer is separated. The organic layer is washed with water, dried (MgSO4) and concentrated. The resulting residue is chromatographed (n-hexane/ethyl acetate =10:1) on silica gel column to give the desired 14-chloro-2-(1-methylethyl)-5,9,13-trimethyl-2,4,8,12-tetradecatetraenoic acid ethyl ester (64.6 mg, 86%) from the desired fraction.

Workup

  1. customthe organic layer is separated
  2. washThe organic layer is washed with water
  3. dry with materialdried (MgSO4)
  4. concentrationconcentrated
  5. customThe resulting residue is chromatographed (n-hexane/ethyl acetate =10:1) on silica gel column

Sources & evidence

ORD record
ord-2ae31746d8a5474cb6a1675c71217cd2
Source dataset
uspto-grants-1992_06
Patent number
US05118827

Reaction notes

Loading…