Acetic Anhydride → HCID 13104431, compound

HRID 1758693Notes

Reaction equation

HRID 1758693 reaction equation
[C:1]([CH2:9][CH:10]([CH3:14])[C:11]([OH:13])=O)(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C([O:18][C:19](=[O:21])[CH3:20])(=O)C.CC1C=C(C2C=CC=CC=2)OC1=O.CC1C(=O)OC(C2C=CC=CC=2)C=1.[CH2:48]1[S:52][CH2:51][NH:50]C1C(O)=O.C(N(CC)CC)C.C(CC(C)C(N1C(C(O)=O)CSC1)=O)(=O)C1C=CC=CC=1.C(C(Br)C(C)C(N1C(C(O)=O)CSC1)=O)(=O)C1C=CC=CC=1.[C:106]([O-:109])(=[S:108])[CH3:107].[K+]>C(#N)C.ClCCl.O1CCOCC1>[C:106]([S:108][CH:9]([C:1](=[O:8])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1)[CH:10]([CH3:14])[C:11]([N:50]1[CH:20]([C:19]([OH:18])=[O:21])[CH2:48][S:52][CH2:51]1)=[O:13])(=[O:109])[CH3:107]

Participants

12

Reactant 9

HCID 7918Acetic AnhydrideHCID 8471TriethylamineHCID 9934TimonacicHCID 744922-Methyl-4-oxo-4-phenylbutanoic acidHCID 113557793-methyl-5-phenyl-2(5H)-furanoneHCID 131044283-Methyl-5-phenylfuran-2(3H)-oneHCID 13104429HCID 13104429, compoundHCID 23670855Potassium ethanethioateHCID 53672350HCID 53672350, compound2×

Product 1

HCID 13104431HCID 13104431, compound

Reagents, catalysts & solvents 2

HCID 312751,4-DioxaneSolventHCID 21877088Acetonitrile methylene chlorideSolvent

Procedure

A mixture of 25 g. (0.13 mole) of 3-benzoyl-2-methylpropionic acid and 15.5 ml. of acetic anhydride is refluxed for 4 hours. The solvent is removed in vacuo and the residue is stripped several times with toluene to give a mixture of 3-methyl-5-phenyl-2(3H)-furanone and 3-methyl-5-phenyl-2(5H)-furanone. The preceding mixture is dissolved is 200 ml. of dioxane and 17.3 g. (0.13 mole) of L-thiazolidine-4-carboxylic acid, and 13.2 g. (0.13 mole) of triethylamine is added. The mixture is refluxed for 38 hours and filtered while hot. The filtrate is concentrated in vacuo to provide a gum. The gum is partitioned between ethyl acetate and dilute aqueous hydrochloric acid. The organic layer is dried over sodium sulfate and the solvent is removed in vacuo. The residue is slurried in ether, filtered and the solid washed with n-hexane to give 6.0 g. of white crystals. Recrystallization from acetone-hexane with the aid of activated carbon gives 4.0 g. of [ 4R-(4R*,2'R*)]-3-(3-benzoyl-2-methylpropionyl)-4-thiazolidinecarboxylic acid. Bromination of the preceding compound gives a mixture of [4R-(4R*,2'S*,3'R*)]-3-(3-benzoyl-3-bromo-2-methylpropionyl)-4-thiazolidinecarboxylic acid and [4R-(4R*,2'S*,3'S*)]-3-(3-benzoyl-3-bromo-2-methylpropionyl)-4-thiazolidinecarboxylic acid. The mixture of diastereomers is reacted with potassium thioacetate in acetonitrile-dichloromethane and the product is chromatographed on silica gel as for Example 1 to give the product of the Example as a white powder.

Workup

  1. additionA mixture of 25 g
  2. customThe solvent is removed in vacuo
  3. customto give
  4. dissolutionThe preceding mixture is dissolved
  5. temperatureThe mixture is refluxed for 38 hours
  6. filtrationfiltered while hot
  7. concentrationThe filtrate is concentrated in vacuo
  8. customto provide a gum
  9. customThe gum is partitioned between ethyl acetate and dilute aqueous hydrochloric acid
  10. dry with materialThe organic layer is dried over sodium sulfate
  11. customthe solvent is removed in vacuo
  12. filtrationfiltered
  13. washthe solid washed with n-hexane
  14. customto give 6.0 g
  15. customRecrystallization from acetone-hexane with the aid of activated carbon
  16. customgives 4.0 g
  17. customBromination of the preceding compound gives
  18. additionThe mixture of diastereomers
  19. customthe product is chromatographed on silica gel as for Example 1
  20. customto give the product of the Example as a white powder

Sources & evidence

ORD record
ord-8f0843c2ac1a4576869498b6b8656c3b
Source dataset
uspto-grants-1983_02
Patent number
US04374249

Reaction notes

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