Mercaptopyrrolidone carbon penems derivatives
A methyl compound technology, applied in the field of new-type mercaptopyrrolidone carbapenem derivatives, can solve the problems of not meeting clinical needs, narrow antibacterial spectrum, unsatisfactory effect, etc.
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Embodiment 1
[0119] Example 1 Preparation of (3S)-2-oxo-3-mercapto-1-(N-tert-butoxycarbonylpyrrolidin-3-yl)pyrrolidine
[0120] In the dry reaction bottle, add (3S)-3-formylmercapto-2-oxopyrrolidine 14.5g (0.1mol) and 200ml tetrahydrofuran, stir to dissolve, add powdery potassium carbonate 14g, heat up to reflux. A tetrahydrofuran solution of 25 g (0.1 mol) / 100 ml of N-1-tert-butoxy-3-bromo-pyrrolidine was added dropwise. After the dropwise addition, keep stirring for 2 hours. The reaction solution was filtered, concentrated to dryness under reduced pressure, added 100ml of 3mol / L hydrochloric acid, stirred for 2h, and adjusted to a pH above 8 with a dilute alkali solution, and a yellow solid was precipitated, which was recrystallized from a methanol / acetone mixed solution to obtain 21g of a light yellow solid. Yield: 73.4%.
Embodiment 2
[0121] Example 2 Preparation of (3S)-2-oxo-3-mercapto-1-(N-tert-butoxycarbonylazetidin-3-yl)pyrrolidine
[0122] In the dry reaction bottle, add (3S)-3-formylmercapto-2-oxopyrrolidine 14.5g (0.1mol) and 300ml tetrahydrofuran, stir to dissolve, add powdery potassium carbonate 14g, heat up to reflux. Add 26 g (0.11 mol) of 3-bromo-N-tert-butoxycarbonyl azetidine in batches. After the addition, keep stirring and react for 4 hours, filter the reaction solution, concentrate to dryness under reduced pressure, add 100 ml of 3 mol / L hydrochloric acid, Stir for 2 hours, adjust to alkaline with dilute alkali solution, and precipitate a yellow solid, which is recrystallized from a methanol / acetone mixed solution to obtain 18.7 g of a light yellow solid, yield: 65.3%.
Embodiment 3
[0123] Example 3 (4R, 5S, 6S)-3-[(3S)-2-oxo-1-(N-tert-butoxycarbonylpyrrolidin-3-yl)pyrrolidin-3-yl]thio -6-[(1R)-1-Hydroxyethyl]-4-methyl-7-oxo-1-azabicyclo-[3,2,0]-2-ene-2-carboxylic acid p-nitrobenzyl Preparation of esters
[0124] In a dry reaction flask, add (4R, 5S, 6S)-3-diphenoxyphosphoryloxy-6-[(1R)-1-hydroxyethyl]-4-methyl-7-oxo-1- Azabicyclo-[3,2,0]-2-ene-2-carboxylic acid p-nitrobenzyl ester 17.8g (30mmol) in acetonitrile (180ml) solution cooled to below -10°C, add diisopropylethylamine 7ml and (3S)-2-oxo-3-mercapto-1-(N-tert-butoxycarbonylpyrrolidin-3-yl)pyrrolidine 10g (35mmol) in acetonitrile 100ml solution, stirred at 0°C for 15h. After the reaction was completed, 500 ml of ethyl acetate was added to dilute, washed with water and saturated brine successively, the organic layer was dried and concentrated to obtain 15.8 g of light yellow solid, yield: 82.7%.
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