Ammonia → HCID 131712336, compound

HRID 1758424Notes

Reaction equation

HRID 1758424 reaction equation
[CH:1]([NH:3][C:4]1[S:5][CH:6]=[C:7]([C:9](=[N:35][O:36][CH2:37][C:38](O)=[O:39])[C:10]([NH:12][CH:13]2[C:33](=[O:34])[N:15]3[C:16]([C:20]([O:22][CH2:23][C:24]4[CH:29]=[CH:28][C:27]([N+:30]([O-:32])=[O:31])=[CH:26][CH:25]=4)=[O:21])=[CH:17][CH2:18][S:19][C@H:14]23)=[O:11])[N:8]=1)=[O:2].C[N+:42](C)=CCl.[Cl-].P(Cl)(Cl)(Cl)=O.N.Cl>O1CCCC1.O.CN(C)C=O>[CH:1]([NH:3][C:4]1[S:5][CH:6]=[C:7]([C:9](=[N:35][O:36][CH2:37][C:38](=[O:39])[NH2:42])[C:10]([NH:12][CH:13]2[C:33](=[O:34])[N:15]3[C:16]([C:20]([O:22][CH2:23][C:24]4[CH:29]=[CH:28][C:27]([N+:30]([O-:32])=[O:31])=[CH:26][CH:25]=4)=[O:21])=[CH:17][CH2:18][S:19][C@H:14]23)=[O:11])[N:8]=1)=[O:2]

Participants

9

Reactant 5

HCID 222AmmoniaHCID 313Hydrochloric AcidHCID 24813Phosphorus oxychlorideHCID 77311Chloro-N,N-dimethylformiminium chlorideHCID 131712318HCID 131712318, compound

Product 1

HCID 131712336HCID 131712336, compound

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8028TetrahydrofuranSolvent4×

Procedure

Tetrahydrofuran (24 ml.) and 4-nitrobenzyl 7-[2-(2-formamidothiazol-4-yl)-2-carboxymethoxyiminoacetamido]-3-cephem-4-carboxylate (syn isomer, 3.07 g.) were added to Vilsmeier reagent prepared from N,N-dimethylformamide (0.756 g.) and phosphoryl chloride (1.59 g.) in tetrahydrofuran (6 ml.) at -10° to -5° C. and then stirred at the same temperature for 30 minutes. The solution was added dropwise to a mixture of tetrahydrofuran (50 ml.) and water (25 ml.) at -5° to 0° C. while keeping at pH 9 to 9.5 with aqueous ammonia, and stirred for 20 minutes at pH 7.5. After adjusting the resultant solution to pH 2.0 with 10% hydrochloric acid, tetrahydrofuran was removed in vacuo. Water was added to the residue and extracted with ethyl acetate. The extract was washed with a saturated aqueous solution of sodium chloride twice, an aqueous solution of sodium bicarbonate five times and a saturated aqueous solution of sodium chloride twice in turn, dried over magnesium sulfate and then concentrated in vacuo. The residue was pulverized with diethyl ether, collected by filtration and dried to give 4-nitrobenzyl 7-[2-(2-formamidothiazol-4-yl)-2-carbamoylmethoxyiminoacetamido]-3-cephem-4-carboxylate (syn isomer, 1.8 g.).

Workup

  1. stirringstirred for 20 minutes at pH 7.5
  2. customwas removed in vacuo
  3. additionWater was added to the residue
  4. extractionextracted with ethyl acetate
  5. washThe extract was washed with a saturated aqueous solution of sodium chloride twice
  6. dry with materialan aqueous solution of sodium bicarbonate five times and a saturated aqueous solution of sodium chloride twice in turn, dried over magnesium sulfate
  7. concentrationconcentrated in vacuo
  8. filtrationcollected by filtration
  9. customdried

Sources & evidence

ORD record
ord-69fd7f93d7434c45a1a6c283b5e83576
Source dataset
uspto-grants-1983_02
Patent number
US04372952

Reaction notes

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