Hydrochloric Acid → HCID 13503440, compound

HRID 485257Notes

Reaction equation

HRID 485257 reaction equation
Cl.[Cl:2][C:3]1[CH:8]=[CH:7][C:6]([CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][C:14]([OH:16])=O)=[CH:5][CH:4]=1.S(Cl)(Cl)(=O)=O.[CH3:22][CH2:23][O:24][C:25]([C:27]1[CH:28]=[CH:29][C:30]([NH2:33])=[CH:31][CH:32]=1)=[O:26]>[Pd].[Zn].C(OCC)(=O)C.ClCCl.C1C=CC=CC=1.O>[Cl:2][C:3]1[CH:4]=[CH:5][C:6]([CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][C:14]([NH:33][C:30]2[CH:29]=[CH:28][C:27]([C:25]([O:24][CH2:23][CH3:22])=[O:26])=[CH:32][CH:31]=2)=[O:16])=[CH:7][CH:8]=1

Participants

11

Reactant 4

HCID 313Hydrochloric AcidHCID 2337BenzocaineHCID 24648Sulfuryl chlorideHCID 135034416-(4-Chlorophenyl)hexanoic acid

Product 1

HCID 13503440HCID 13503440, compound

Reagents, catalysts & solvents 6

HCID 23938PalladiumCatalystHCID 23994ZincCatalystHCID 241BenzeneSolventHCID 962WaterSolventHCID 6344DichloromethaneSolvent2×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
115 °C

Procedure

A mixture of 55 g. of mossy zinc, 5.4 g. of mercuric chloride, 90 ml. of water, and 3 ml. of concentrated hydrochloric acid is stirred for 5 minutes, and the solution is decanted. To the residue is suquentially added 35 ml. of water, 80 ml. of 37% hydrochloric acid, 45 ml. of toluene, and 30.0 g. of 5-p-chlorobenzoylvalerica cid. This mixture is refluxed at 115° C. for 28 hours, with the addition of 25 ml. of concentrated hydrochloric acid at 6 hour intervals. The solution is cooled, diluted with 100 ml. of water, and the organic layer is separated and saved. The aqueous layer is extracted with three 100 ml. portions of ether. The ether extracts and organic layer are combined, washed with 100 ml. of water, then 100 ml. of brine, dried over magnesium sulfate, and evaporated to an oil. This oil is distilled on a Kugelrohr apparatus collecting the fraction that boils at 160°-170° C. (60 mm.), giving 22.0 g. of 6-(p-chlorophenyl)hexanoic acid as an oil. To a solution of 19.0 g. of this oil in 200 ml. of benzene is added dropwise 33.1 g. of sulfonyl chloride. The mixture is refluxed 5 hours, cooled, and evaporated three times from 250 ml. of benzene, to yield 21.09 g. of brown liquid. This liquid is dissolved in 200 ml. of dichloromethane, and a solution of 28.4 g. of benzocaine in 200 ml. of dichloromethane is added, and the mixture is stirred overnight. The mixture is filtered, and the filtrate is extrcted with 100 ml. of 10% hydrochloric acid, 100 ml. of saturated sodium bicarbonate solution, and 100 ml. of brine; then it is dried over magnesium sulfate and evaporated to a solid. The solid is boiled in 400 ml. of toluene, treated with 1 g. of charcoal, filtered, and boiled down, giving 23.0 g. of crystalline solid. A 4.1 g. portion of this solid, 100 mg. of 10% palladium on carbon, and 50 ml. of ethyl acetate are hydrogenated in a Parr apparatus giving, after crystallization from toluene, 3.81 g. of the desired product as colorless crystals, m.p. 107°-108° C.

Workup

  1. additionA mixture of 55 g
  2. customthe solution is decanted
  3. temperatureThe solution is cooled
  4. additiondiluted with 100 ml
  5. customof water, and the organic layer is separated
  6. extractionThe aqueous layer is extracted with three 100 ml
  7. washwashed with 100 ml
  8. dry with materialof brine, dried over magnesium sulfate
  9. customevaporated to an oil
  10. distillationThis oil is distilled on a Kugelrohr apparatus
  11. customcollecting the fraction that boils at 160°-170° C. (60 mm.)
  12. customgiving 22.0 g
  13. temperatureThe mixture is refluxed 5 hours
  14. temperaturecooled
  15. customevaporated three times from 250 ml
  16. customof benzene, to yield 21.09 g
  17. dissolutionThis liquid is dissolved in 200 ml
  18. filtrationThe mixture is filtered
  19. dry with materialthen it is dried over magnesium sulfate
  20. customevaporated to a solid
  21. additionof toluene, treated with 1 g
  22. filtrationof charcoal, filtered
  23. customgiving 23.0 g
  24. customgiving
  25. customafter crystallization from toluene, 3.81 g

Sources & evidence

ORD record
ord-e12b7825f5ad4a96a54cfa12688bfb6f
Source dataset
uspto-grants-1985_08
Patent number
US04536346

Reaction notes

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