tert-Butyl bromoacetate → Diphenylmethyl 7-[2-(2-tritylamino-4-thiazolyl)-2-(tert.-butoxycarbonylmethyloxyimino)-acetamido]-3-acetoxymethyl-ceph-3-eme-4-carboxylate

HRID 851830Notes

Reaction equation

HRID 851830 reaction equation
[C:1]([NH:20][C:21]1[S:22][CH:23]=[C:24]([C:26](=[N:60][OH:61])[C:27]([NH:29][CH:30]2[C:58](=[O:59])[N:32]3[C:33]([C:42]([O:44][CH:45]([C:52]4[CH:57]=[CH:56][CH:55]=[CH:54][CH:53]=4)[C:46]4[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=4)=[O:43])=[C:34]([CH2:37][O:38][C:39](=[O:41])[CH3:40])[CH2:35][S:36][C@H:31]23)=[O:28])[N:25]=1)([C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.Br[CH2:63][C:64]([O:66][C:67]([CH3:70])([CH3:69])[CH3:68])=[O:65]>[Ag]=O.CN(C)C=O>[C:1]([NH:20][C:21]1[S:22][CH:23]=[C:24]([C:26](=[N:60][O:61][CH2:63][C:64]([O:66][C:67]([CH3:70])([CH3:69])[CH3:68])=[O:65])[C:27]([NH:29][CH:30]2[C:58](=[O:59])[N:32]3[C:33]([C:42]([O:44][CH:45]([C:52]4[CH:53]=[CH:54][CH:55]=[CH:56][CH:57]=4)[C:46]4[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=4)=[O:43])=[C:34]([CH2:37][O:38][C:39](=[O:41])[CH3:40])[CH2:35][S:36][C@H:31]23)=[O:28])[N:25]=1)([C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1)([C:14]1[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=1)[C:8]1[CH:9]=[CH:10][CH:11]=[CH:12][CH:13]=1

Participants

5

Reactant 2

HCID 79177tert-Butyl bromoacetateHCID 131712161Diphenylmethyl 3-acetoxymethyl-7-[2-(2-tritylamino-4-thiazolyl)-2-hydroxyimino-acetamido]-ceph-3-eme-4-carboxylate

Product 1

HCID 131712393Diphenylmethyl 7-[2-(2-tritylamino-4-thiazolyl)-2-(tert.-butoxycarbonylmethyloxyimino)-acetamido]-3-acetoxymethyl-ceph-3-eme-4-carboxylate

Reagents, catalysts & solvents 2

HCID 92152Silver(II) oxideCatalystHCID 6228DimethylformamideSolvent

Procedure

A mixture of 0.85 g of the product of Step D, 0.8 ml of tert.-butyl bromoacetate and 4 ml of dimethylformamide stood in an ice bath for 5 minutes and then 1.7 g of silver oxide were added thereto. The mixture was stirred for one hour after removal of the bath and the mixture was vacuum filtered. The filter was rinsed with ethyl acetate and 80 ml of water were added to the filtrate which was decanted. The aqueous phase was extracted twice with 20 ml of ethyl acetate and the combined organic phases were washed twice with 50 ml of aqueous sodium chloride solution, dried, treated with 80 mg of activated carbon and vacuum filtered. The filter was rinsed with ethyl acetate and the filtrate was evaporated to dryness under reduced pressure. The residue was taken up in isopropyl ether and after efflorescence, the mixture was vacuum filtered. The product was rinsed with isopropyl ether and dried to obtain 0.724 g of the syn isomer of diphenylmethyl 7-[2-(2-tritylamino-4-thiazolyl)-2-(tert.-butoxycarbonylmethyloxyimino)-acetamido]-3-acetoxymethyl-ceph-3-eme-4-carboxylate with Rf=0.34 (methylene chloride containing 5% of ether).

Workup

  1. customafter removal of the bath
  2. filtrationfiltered
  3. washThe filter was rinsed with ethyl acetate and 80 ml of water
  4. additionwere added to the filtrate which
  5. customwas decanted
  6. extractionThe aqueous phase was extracted twice with 20 ml of ethyl acetate
  7. washthe combined organic phases were washed twice with 50 ml of aqueous sodium chloride solution
  8. customdried
  9. additiontreated with 80 mg of activated carbon and vacuum
  10. filtrationfiltered
  11. washThe filter was rinsed with ethyl acetate
  12. customthe filtrate was evaporated to dryness under reduced pressure
  13. filtrationfiltered
  14. washThe product was rinsed with isopropyl ether
  15. customdried

Sources & evidence

ORD record
ord-204ca85a82524f9181f17191601c3ed3
Source dataset
uspto-grants-1983_05
Patent number
US04386210

Reaction notes

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