Methanesulfonic Acid → 7-Amino-2-benzhydryloxycarbonyl-3-(2-dimethylaminomethyleneamino-thiazol-5-yl)-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene

HRID 2413428Notes

Reaction equation

HRID 2413428 reaction equation
[CH:1]([O:14][C:15]([C:17]1[N:18]2[CH:21]([S:22][CH2:23][C:24]=1[C:25]1[S:29][C:28]([N:30]=[CH:31][N:32]([CH3:34])[CH3:33])=[N:27][CH:26]=1)[CH:20]([NH:35]C(OC(C)(C)C)=O)[C:19]2=[O:43])=[O:16])([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.CS(O)(=O)=O.C(OCC)(=O)C>C(#N)C>[NH2:35][CH:20]1[C:19](=[O:43])[N:18]2[CH:21]1[S:22][CH2:23][C:24]([C:25]1[S:29][C:28]([N:30]=[CH:31][N:32]([CH3:34])[CH3:33])=[N:27][CH:26]=1)=[C:17]2[C:15]([O:14][CH:1]([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1)=[O:16]

Participants

5

Reactant 3

HCID 6395Methanesulfonic AcidHCID 8857Ethyl AcetateHCID 539806132-Benzhydryloxycarbonyl-7-t-butoxycarbonylamino-3-(2-dimethylaminomethyleneamino-thiazol-5-yl)-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene

Product 1

HCID 544020907-Amino-2-benzhydryloxycarbonyl-3-(2-dimethylaminomethyleneamino-thiazol-5-yl)-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-eneYield 100.7%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

Following the working method described in Example 15, 2-benzhydryloxycarbonyl-7-t-butoxycarbonylamino-3-(2-dimethylaminomethyleneamino-thiazol-5-yl)-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene (E-form) (0.77 g) is treated with methanesulphonic acid (0.8 cc) in acetonitrile (8 cc). 7-Amino-2-benzhydryloxycarbonyl-3-(2-dimethylaminomethyleneamino-thiazol-5-yl)-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene (E-form) (0.65 g) is obtained in the form of a crude brown froth (Rf=0.1, silica gel chromatographic plate; eluant: ethyl acetate), and this is redissolved in tetrahydrofuran (15 cc) and acylated, in accordance with the working method described in Example 1, with (thien-2-yl)acetyl chloride (0.15 cc) in the presence of triethylamine (0.17 cc). Chromatography is effected on a column (height: 28 cm; diameter: 2 cm) of silica gel (0.04-0.06 mm), elution being carried out under a pressure of 0.8 bar (80 kPa) by means of ethyl acetate, and 30 cc fractions being collected. Fractions 11 to 19, containing the pure product, are combined and concentrated to dryness under reduced pressure (30 mm Hg; 4 kPa) at 30° C. 2-Benzhydryloxycarbonyl-3-(2-dimethylaminomethyleneamino-thiazol-5-yl)-8-oxo-7-(thien-2-yl-acetamido)-5-thia-1-azabicyclo[4.2.0-oct-2-ene (E-form) (0.13 g) is obtained in the form of a yellow powder.

Sources & evidence

ORD record
ord-09e40e7c07264496b9bbf3cce796a241
Source dataset
uspto-grants-1985_01
Patent number
US04496560

Reaction notes

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