Thiourea → 2,2,2-Trichloroethyl 2-methyl-7-[2-methoxyimino-2-(2-aminothiazol-4-yl)acetamido]-3-cephem-4-carboxylate

HRID 28295Notes

Reaction equation

HRID 28295 reaction equation
[CH3:1][CH:2]1[CH:7]=[C:6]([C:8]([O:10][CH2:11][C:12]([Cl:15])([Cl:14])[Cl:13])=[O:9])[N:5]2[C:16](=[O:29])[CH:17]([NH:18][C:19](=[O:28])[C:20](=[N:25][O:26][CH3:27])[C:21](=O)[CH2:22]Br)[C@H:4]2[S:3]1.[NH2:30][C:31]([NH2:33])=[S:32]>C(O)C>[CH3:1][CH:2]1[CH:7]=[C:6]([C:8]([O:10][CH2:11][C:12]([Cl:15])([Cl:14])[Cl:13])=[O:9])[N:5]2[C:16](=[O:29])[CH:17]([NH:18][C:19](=[O:28])[C:20](=[N:25][O:26][CH3:27])[C:21]3[N:30]=[C:31]([NH2:33])[S:32][CH:22]=3)[C@H:4]2[S:3]1

Participants

4

Reactant 2

HCID 2723790ThioureaHCID 1317114922,2,2-Trichloroethyl 2-methyl-7-(2-methoxyimino-3-oxo-4-bromobutyramido)-3-cephem-4-carboxylate

Product 1

HCID 1317114992,2,2-Trichloroethyl 2-methyl-7-[2-methoxyimino-2-(2-aminothiazol-4-yl)acetamido]-3-cephem-4-carboxylate

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

To a mixture of 2,2,2-trichloroethyl 2-methyl-7-(2-methoxyimino-3-oxo-4-bromobutyramido)-3-cephem-4-carboxylate (a mixture of syn and anti isomers) (0.94 g.) and ethanol (10 ml.) was added thiourea (0.12 g.), and the mixture was stirred for 40 minutes at room temperature. The reaction mixture was concentrated under reduced pressure, and the residue was shaken with ethyl acetate and water. The ethyl acetate layer was separated, and the remaining aqueous layer was neutralized with sodium bicarbonate and then extracted with ethyl acetate. Thus obtained ethyl acetate layers were combined together, washed with water, dried over magnesium sulfate, treated with activated charcoal and then concentrated under reduced pressure. The residue was pulverized in diethyl ether, collected by filtration and then dried to give 2,2,2-trichloroethyl 2-methyl-7-[2-methoxyimino-2-(2-aminothiazol-4-yl)acetamido]-3-cephem-4-carboxylate (syn isomer), which can be represented as 2,2,2-trichloroethyl 2-methyl-7-[2-methoxyimino-2-(2-imino-2,3-dihydrothiazol-4-yl)acetamido]-3-cephem-4-carboxylate (syn isomer), (0.6 g.). This compound was subjected to column chromatography on silica gel using a mixed solvent of benzene, ethyl acetate and acetic acid (10:10:1) as a developer, and the eluates containing the object compound were collected, washed with water, dried over magnesium sulfate and then concentrated under reduced pressure. The residue was pulverized in diethyl ether, collected by filtration and then dried to give pale brown powder of the purified object compound (syn isomer) (0.16 g.), mp 128° to 149° C. (dec.).

Workup

  1. concentrationThe reaction mixture was concentrated under reduced pressure
  2. stirringthe residue was shaken with ethyl acetate and water
  3. customThe ethyl acetate layer was separated
  4. extractionextracted with ethyl acetate
  5. washwashed with water
  6. dry with materialdried over magnesium sulfate
  7. additiontreated with activated charcoal
  8. concentrationconcentrated under reduced pressure
  9. filtrationcollected by filtration
  10. customdried

Sources & evidence

ORD record
ord-fc633e99b789495dbf381eadf1ca612d
Source dataset
uspto-grants-1980_09
Patent number
US04225707

Reaction notes

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