Acetic Acid → HCID 131711761, compound

HRID 1395558Notes

Reaction equation

HRID 1395558 reaction equation
[OH:1][C:2]1[CH:7]=[CH:6][C:5]([CH:8]([C:45]([O:47][CH:48]([C:55]2[CH:60]=[CH:59][CH:58]=[CH:57][CH:56]=2)[C:49]2[CH:54]=[CH:53][CH:52]=[CH:51][CH:50]=2)=[O:46])[C:9]([NH:11][C@@H:12]2[C:43](=[O:44])[N:14]3[C:15]([C:27]([O:29][CH:30]([C:37]4[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=4)[C:31]4[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=4)=[O:28])=[C:16]([CH2:19][S:20][C:21]4[N:25]([CH3:26])[N:24]=[N:23][N:22]=4)[CH2:17][S:18][C@H:13]23)=[O:10])=[CH:4][CH:3]=1.C[O-].[Li+].[Cl:64]OC(C)(C)C.C(O)(=O)C>O1CCCC1.CO.C(OCC)(=O)C>[Cl:64][C:8]([C:5]1[CH:4]=[CH:3][C:2]([OH:1])=[CH:7][CH:6]=1)([C:45]([O:47][CH:48]([C:55]1[CH:56]=[CH:57][CH:58]=[CH:59][CH:60]=1)[C:49]1[CH:50]=[CH:51][CH:52]=[CH:53][CH:54]=1)=[O:46])[C:9]([NH:11][C@@H:12]1[C:43](=[O:44])[N:14]2[C:15]([C:27]([O:29][CH:30]([C:31]3[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=3)[C:37]3[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=3)=[O:28])=[C:16]([CH2:19][S:20][C:21]3[N:25]([CH3:26])[N:24]=[N:23][N:22]=3)[CH2:17][S:18][C@H:13]12)=[O:10]

Participants

8

Reactant 4

HCID 176Acetic AcidHCID 521297Tert-Butyl hypochloriteHCID 4177230Lithium methanolateHCID 131711762HCID 131711762, compound

Product 1

HCID 131711761HCID 131711761, compound

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-78 °C

Procedure

To a solution of diphenylmethyl 7β-(α-p-hydroxyphenyl-α-diphenylmethoxycarbonylacetamido)-3-(1-methyl-1H-tetrazol-5-yl)thiomethyl-3-cephem-4-carboxylate (310 mg) in tetrahydrofuran (15 ml) are added 2 M lithium methoxide in methanol (0.63 ml) and after 1 minute t-butyl hypochlorite (42.6 μl) at -78° C., and the mixture is stirred at -78° C. for 15 minutes. The reaction mixture is mixed with acetic acid (0.3 ml), warmed to room temperature, diluted with ethyl acetate, washed with water, dried over sodium sulfate, and evaporated to dryness under reduced pressure. The residue is chromatographed on silica gel (30 g) containing 10% water and eluted with a mixture of benzene and ethyl acetate (9:1) to give diphenylmethyl 7β-(α-chloro-α-p-hydroxyphenyl-α-diphenylmethoxycarbonylacetamido)-3-(1-methyl-1H-tetrazol-5-yl)thiomethyl-3-cephem-4-carboxylate (206 mg) NMR: δCDCl3 5.74dd(4.5;9 Hz)1H, together with the following 7α-methoxy compound.

Workup

  1. temperaturewarmed to room temperature
  2. washwashed with water
  3. dry with materialdried over sodium sulfate
  4. customevaporated to dryness under reduced pressure
  5. customThe residue is chromatographed on silica gel (30 g)
  6. additioncontaining 10% water
  7. washeluted with a mixture of benzene and ethyl acetate (9:1)

Sources & evidence

ORD record
ord-2686b716aaf644d490e3de4860ce0b33
Source dataset
uspto-grants-1980_05
Patent number
US04203982

Reaction notes

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