Hydrochloric Acid → 4-Oxobicyclo[3.2.1]oct-2-en-2-yl 2-methyl-3-methylthio-4-(pentafluoroethyl)benzoate

HRID 1910385Notes

Reaction equation

HRID 1910385 reaction equation
[CH3:1][C:2]1[C:10]([S:11][CH3:12])=[C:9]([C:13]([F:19])([F:18])[C:14]([F:17])([F:16])[F:15])[CH:8]=[CH:7][C:3]=1[C:4]([OH:6])=[O:5].C(Cl)(=O)C(Cl)=O.[CH:26]12[CH2:33][CH:30]([CH2:31][CH2:32]1)[C:29](=[O:34])[CH2:28][C:27]2=O.C(N(CC)CC)C.Cl>CN(C)C=O.CN(C1C=CN=CC=1)C.ClCCl>[CH3:1][C:2]1[C:10]([S:11][CH3:12])=[C:9]([C:13]([F:19])([F:18])[C:14]([F:16])([F:15])[F:17])[CH:8]=[CH:7][C:3]=1[C:4]([O:6][C:27]1[CH:26]2[CH2:33][CH:30]([C:29](=[O:34])[CH:28]=1)[CH2:31][CH2:32]2)=[O:5]

Participants

9

Reactant 5

HCID 313Hydrochloric AcidHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 144686Bicyclo(3.2.1)octane-2,4-dioneHCID 866614322-Methyl-3-(methylthio)-4-(pentafluoroethyl)benzoic acid

Product 1

HCID 866614334-Oxobicyclo[3.2.1]oct-2-en-2-yl 2-methyl-3-methylthio-4-(pentafluoroethyl)benzoate

Reagents, catalysts & solvents 3

HCID 6228DimethylformamideCatalystHCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent

Procedure

235 mg (0.783 mmol) of 2-methyl-3-(methylthio)-4-(pentafluoroethyl)benzoic acid were introduced into 20 ml of dry dichloromethane and admixed in succession with 129 mg (1.02 mmol) of oxalyl chloride and also with two drops of N,N-dimethyl-formamide. After the end of evolution of gas, the mixture was heated under reflux for another 10 minutes. Then, the contents were cooled and concentrated on a rotary evaporator. The residue was taken up in 20 ml of dry dichloromethane and admixed with 119 mg (0.861 mmol) of bicyclo[3.2.1]octane-2,4-dione and a catalytic amount of DMAP. Then 158 mg (1.57 mmol) of triethylamine were added dropwise. The mixture was stirred at RT for 16 hours. For working up, 3 ml of 1N hydrochloric acid were added. Following phase separation, the organic phase was freed from the solvent and the residue, finally, was purified by chromatography. This gave 280 mg of product with a purity of 90% by weight.

Workup

  1. temperatureAfter the end of evolution of gas, the mixture was heated
  2. temperatureunder reflux for another 10 minutes
  3. temperatureThen, the contents were cooled
  4. concentrationconcentrated on a rotary evaporator
  5. customFollowing phase separation
  6. customthe residue, finally, was purified by chromatography

Sources & evidence

ORD record
ord-650a0bfd436949819e41d8bea8219227
Source dataset
uspto-grants-2013_12
Patent number
US08603947B2

Reaction notes

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