(6R)-7-[[(2Z)-2-(2-amino-1,3-thiazol-4-yl)-2-methoxyiminoacetyl]amino]-3-(azidomethyl)-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid → (6R)-3-(aminomethyl)-7-[[(2Z)-2-(2-amino-1,3-thiazol-4-yl)-2-methoxyiminoacetyl]amino]-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid

HRID 329932Notes

Reaction equation

HRID 329932 reaction equation
[N:1]([CH2:4][C:5]1[CH2:6][S:7][C@@H:8]2[CH:15]([NH:16][C:17](=[O:28])/[C:18](/[C:22]3[N:23]=[C:24]([NH2:27])[S:25][CH:26]=3)=[N:19]\[O:20][CH3:21])[C:14](=[O:29])[N:9]2[C:10]=1[C:11]([OH:13])=[O:12])=[N+]=[N-]>[Ni].CO.CO.C(O)(C(F)(F)F)=O>[NH2:1][CH2:4][C:5]1[CH2:6][S:7][C@@H:8]2[CH:15]([NH:16][C:17](=[O:28])/[C:18](/[C:22]3[N:23]=[C:24]([NH2:27])[S:25][CH:26]=3)=[N:19]\[O:20][CH3:21])[C:14](=[O:29])[N:9]2[C:10]=1[C:11]([OH:13])=[O:12]

Participants

5

Reactant 1

HCID 141548216(6R)-7-[[(2Z)-2-(2-amino-1,3-thiazol-4-yl)-2-methoxyiminoacetyl]amino]-3-(azidomethyl)-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid

Product 1

HCID 88601874(6R)-3-(aminomethyl)-7-[[(2Z)-2-(2-amino-1,3-thiazol-4-yl)-2-methoxyiminoacetyl]amino]-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acidYield 45%

Reagents, catalysts & solvents 3

HCID 935NickelCatalystHCID 887MethanolSolvent2×HCID 86669916Methanol trifluoroacetic acidSolvent

Procedure

To a stirred suspension of Raney nickel (16 g.) in MeOH (13 ml.) at 0° was added a solution of 3-azidomethyl-7-[2-(2-aminothiazol-4-yl)-2-((Z)-methoxyimino)acetamido]ceph-3-em-4-carboxylic acid (2.96 g.) in MeOH/TFA (14 ml., 1.13 ml.). After effervescence ceased the mixture was diluted with MeOH and filtered through paper. The filtrate was evaporated, the residue purified by HPLC using water/HOAc/MeOH 79:1:20 v/v/v as eluant and the product dried over P2O5 to give 3-aminomethyl-7-[2-(2-aminothiazol-4-yl)-2-((Z)-methoxyimino)acetamido]ceph-3-em-4-carboxylic acid trifluorocetate (yield 45%) having the following n.m.r. in solvent A:--3.5-4.2 (m, 4 H); 3.9 (s, 3 H); 5.15 (d, 1 H); 5.85 (d, 1 H); 6.75 (s, 1 H). The corresponding zwitterionic form was produced by passing an aqueous solution through an ion exchange column.

Workup

  1. filtrationfiltered through paper
  2. customThe filtrate was evaporated
  3. customthe residue purified by HPLC
  4. dry with materialthe product dried over P2O5

Sources & evidence

ORD record
ord-cf87f4decf364e38bebcc013bfe202e3
Source dataset
uspto-grants-1990_01
Patent number
US04894371

Reaction notes

Loading…