Dimethyl Sulfoxide → HCID 86733037, compound

HRID 1729973Notes

Reaction equation

HRID 1729973 reaction equation
[CH3:1][C:2]1([CH3:22])[C@H:6]([C:7]([O:9][Si](C)(C)C)=[O:8])[N:5]2[C:14](=[O:21])[C@@H:15]([NH:16][Si](C)(C)C)[C@H:4]2[S:3]1.C1OC1C.ClC(Cl)C([O:31][N:32]=[C:33]([C:37]1[S:38][CH:39]=[CH:40][CH:41]=1)[C:34](Cl)=[O:35])=O.CS(C)=O>ClCCl>[CH3:1][C:2]1([CH3:22])[C@H:6]([C:7]([OH:9])=[O:8])[N:5]2[C:14](=[O:21])[C@@H:15]([NH:16][C:34](=[O:35])[C:33]([C:37]3[S:38][CH:39]=[CH:40][CH:41]=3)=[N:32][OH:31])[C@H:4]2[S:3]1

Participants

6

Reactant 4

HCID 679Dimethyl Sulfoxide2×HCID 6378Propylene OxideHCID 12900328HCID 12900328, compoundHCID 54155233HCID 54155233, compound

Product 1

HCID 86733037HCID 86733037, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

A solution of trimethylsilyl 2,2-dimethyl-6β-trimethylsilylaminopenam-3α-carboxylate [prepared from the corresponding amino-acid (0.864 g.)] and propylene oxide (1 ml.) in dichloromethane (20 ml.) was cooled to 0° and treated dropwise with a solution of 2-dichloroacetoxyimino(thien-2-yl)acetyl chloride syn-isomer; [prepared from the corresponding acid (0.753 g.)] in dichloromethane (12 ml.). The resulting solution was maintained at 0° for 1 hour and was then evaporated to a small bulk and partitioned between ethylacetate and saturated sodium bicarbonate solution. The aqueous phase was washed with ethyl acetate, acidified with 2N-hydrochloric acid; and extracted with ethyl acetate. The dried organic solution was evaporated to a small bulk and added dropwise to stirred petroleum spirit (b.p. 40°-60°). The resulting precipitate was collected, washed, and dried to afford the title acid (0.337 g., 24% based on amine), [α]D + 224° (c 0.57, DMSO), λmax. (pH 6 buffer) 288 nm (ε 6,400), λ inf. 270 nm (ε 5,800), νmax. (Nujol), 2600 and 1730 (CO2H), 1776 (β-lactam), 1670 and 1526 cm.-1 (CONH), τ (d6 -DMSO) values include 0.44 (d, J 6 Hz; NH), 2.45 and 2.9 (multiplets, aromatic protons), 5.78 (s; C-3H), 8.46 and 8.55 (2 s; CH3 groups).

Workup

  1. temperaturewas cooled to 0°
  2. temperatureThe resulting solution was maintained at 0° for 1 hour
  3. customwas then evaporated to a small bulk
  4. custompartitioned between ethylacetate and saturated sodium bicarbonate solution
  5. washThe aqueous phase was washed with ethyl acetate
  6. extractionand extracted with ethyl acetate
  7. customThe dried organic solution was evaporated to a small bulk
  8. additionadded dropwise
  9. customThe resulting precipitate was collected
  10. washwashed
  11. customdried
  12. customto afford the title acid (0.337 g., 24% based on amine), [α]D + 224° (c 0.57, DMSO), λmax
  13. custom0.44 (d, J 6 Hz; NH), 2.45 and 2.9 (multiplets, aromatic protons), 5.78 (s; C-3H), 8.46 and 8.55 (2 s; CH3 groups)

Sources & evidence

ORD record
ord-d61fa078acf04d69aeeff0f87727ce3d
Source dataset
uspto-grants-1976_11
Patent number
US03991046

Reaction notes

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