Water → 4-Nitrobenzyl 7-[2-(2-formamido-4-thiazolyl)-2-methoxyiminoacetamido]-3-cephem-4-carboxylate

HRID 2296177Notes

Reaction equation

HRID 2296177 reaction equation
C[Si](CC(N)=O)(C)C.[NH2:9][CH:10]1[C:30](=[O:31])[N:12]2[C:13]([C:17]([O:19][CH2:20][C:21]3[CH:26]=[CH:25][C:24]([N+:27]([O-:29])=[O:28])=[CH:23][CH:22]=3)=[O:18])=[CH:14][CH2:15][S:16][C@H:11]12.[CH:32]([NH:34][C:35]1[S:36][CH:37]=[C:38]([C:40](=[N:44][O:45][CH3:46])[C:41](Cl)=[O:42])[N:39]=1)=[O:33].O>C(Cl)Cl>[CH:32]([NH:34][C:35]1[S:36][CH:37]=[C:38]([C:40](=[N:44][O:45][CH3:46])[C:41]([NH:9][CH:10]2[C:30](=[O:31])[N:12]3[C:13]([C:17]([O:19][CH2:20][C:21]4[CH:22]=[CH:23][C:24]([N+:27]([O-:29])=[O:28])=[CH:25][CH:26]=4)=[O:18])=[CH:14][CH2:15][S:16][C@H:11]23)=[O:42])[N:39]=1)=[O:33]

Participants

6

Reactant 4

HCID 962WaterHCID 357676Acetamide, 2-(trimethylsilyl)-HCID 12775080p-Nitrobenzyl 7-amino-3-cephem-4-carboxylateHCID 537143512-(2-Formamidothiazol-4-yl)-2-methoxyiminoacetyl chloride

Product 1

HCID 1317124414-Nitrobenzyl 7-[2-(2-formamido-4-thiazolyl)-2-methoxyiminoacetamido]-3-cephem-4-carboxylateYield 93.9%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
40 °C

Procedure

N,N-Dimethylformamide (3 drops) was added to a suspension of 2-(2-formamidothiazol-4-yl)-2-methoxyiminoacetic acid (syn isomer, 23 g.) in thionyl chloride (230 ml) and stirred at 60° C. for 5 minutes. After concentrating the solution in vacuo, benzene was added to the residue. The precipitates were collected by filtration, washed with benzene (30 ml.) three times and diethyl ether in turn to give 2-(2-formamidothiazol-4-yl)-2-methoxyiminoacetyl chloride (anti isomer, 18 g.). On the other hand, trimethylsilylacetamide (46 g.) was added to a suspension of 4-nitrobenzyl 7-amino-3-cephem-4-carboxylate (16.8 g.) in methylene chloride (168 ml.), and stirred at 40° C. for an hour. To the suspension was gradually added 2-(2-formamidothiazol-4-yl)-2-methoxyiminoacetyl chloride (anti isomer, 13.6 g.) at -5° to 0° C., and stirred at the same temperature for an hour. Water (150 ml.) was added to the resultant solution and stirred for 15 minutes. The recipitates were collected by filtration, washed with water and dried over phosphorus pentoxide under reduced pressure to give 4-nitrobenzyl 7-[2-(2-formamidothiazol-4-yl)-2-methoxyiminoacetamido]-3-cephem-4-carboxylate (anti isomer, 25.7 g.).

Workup

  1. customat -5° to 0° C.
  2. stirringstirred at the same temperature for an hour
  3. stirringstirred for 15 minutes
  4. filtrationThe recipitates were collected by filtration
  5. washwashed with water
  6. dry with materialdried over phosphorus pentoxide under reduced pressure

Sources & evidence

ORD record
ord-fdb945df378042bfbe479131a9695ca8
Source dataset
uspto-grants-1984_01
Patent number
US04427674

Reaction notes

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