HCID 21311858, compound → HCID 21311879, compound

HRID 971841Notes

Reaction equation

HRID 971841 reaction equation
[CH:1]([N:3]1[C:6](=[O:7])[CH:5]([NH:8][C:9](=[O:18])[CH2:10][O:11][C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[CH:4]1[S:19][C:20](OC(=O)C)([CH3:22])[CH3:21])=[O:2]>C1C=CC=CC=1>[CH:1]([N:3]1[C:6](=[O:7])[CH:5]([NH:8][C:9](=[O:18])[CH2:10][O:11][C:12]2[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=2)[CH:4]1[S:19][C:20]([CH3:22])=[CH2:21])=[O:2]

Participants

3

Reactant 1

HCID 21311858HCID 21311858, compound

Product 1

HCID 21311879HCID 21311879, compound

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

A solution of 0.051 g of 1-formyl-2-(2-acetyloxy-2-propyl-mercapto)-3-(N-phenyloxyacetyl-amino)-azetidin-4-one in 3 ml of anydrous benzene is treated with 0.13 g of tristriphenyl-phosphine-rhodium chloride and boiled for 3 hours under reflux. The initially red solution turns brown, with a small quantity of a precipitate forming. After cooling, the precipitate is filtered off and the filtrate is evaporated under reduced pressure. The residue is chromatographed on 5 g of acid-washed silica gel, with fractions of 5 ml each being collected. The elution is carried out with 10 ml of benzene, 30 ml of a 9:1-, 25 ml of a 4:1- and 10 ml of a 1:1-mixture of benzene and ethyl acetate and then with 25 ml of ethyl acetate. Fractions 2-6 yield a rhodium complex having a strong CO-absorption at 5.18μ in the infra-red absorption spectrum. A small quantity of 1-formyl-2-isopropenylmercapto-3-(N-phenyloxyacetyl-amino)-azetidin-4-one can be isolated from fractions 10- 12, while fractions 15- 17 yield the 2-isopropenylmercapto-3-(N-phenyloxyacetyl-amino)-azetidin-4-one of the formula ##STR23## in an amorphous form. The product is obtained in crystalline form when the solution of the eluate is filtered through 0.5 g of acid-washed silica gel and the product is eluted with a 1:1-mixture of benzene and ethyl acetate, m.p. 156°-158°; [α]D20 = -70° ± 2° (c = 0.665 in chloroform); infra-red absorption spectrum (in methylene chloride): characteristic bands at 3.07μ, 5.65μ, 5.96μ, 6.29μ, 6.59μ, 6.74μ, 8.19μ, 9.25μ and 9.92μ.

Workup

  1. temperatureunder reflux
  2. customforming
  3. temperatureAfter cooling
  4. filtrationthe precipitate is filtered off
  5. customthe filtrate is evaporated under reduced pressure
  6. customThe residue is chromatographed on 5 g of acid-washed silica gel, with fractions of 5 ml each
  7. custombeing collected
  8. washThe elution
  9. customFractions 2-6 yield a rhodium complex
  10. customa strong CO-absorption at 5.18μ in the infra-red absorption spectrum

Sources & evidence

ORD record
ord-a3804456b0db45f79ea2bba20ce31679
Source dataset
uspto-grants-1979_07
Patent number
US04161476

Reaction notes

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