Imidazo pyrido imidazole-3-substituted benzyl acetates, and synthesis, antineoplastic activities and application thereof
A technology of azolopyridimidazole and benzyl acetate, which is applied to imidazopyrimidazole-3-substituted benzyl acetate, its synthesis, antitumor activity and application fields, can solve the problem of low toxicity and side effects and poor curative effect of antitumor drugs. ideal, high toxicity
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Embodiment 1
[0020] Example 1 Preparation of (6S)-4,5,6,7-tetrahydro-3H-imidazo[4,5-c]pyridine-6-carboxylic acid (1)
[0021]Add 6 mL of concentrated sulfuric acid dropwise to 30.00 g (0.193 mol) of L-histidine and 120 mL of distilled water under an ice bath, and stir evenly to dissolve completely. Then add 60 mL of formaldehyde solution (40%), and react in an oil bath at 60° C. for 8 hours. The reactant was cooled to room temperature, adjusted to pH 6 with concentrated ammonia water in an ice bath, and filtered. The obtained colorless precipitate was washed with water and then with acetone. Obtained 28.04 g (87%) of the title compound as a colorless solid. ESI-MS(m / z)167[M+H] + .
Embodiment 2
[0022] Example 2 Preparation of (6S)-N 3 , N 5 -di-Boc-4,5,6,7-tetrahydro-3H-imidazo[4,5-c]pyridine-6-carboxylic acid (2)
[0023] Disperse 10.52g (0.063mol) of (6S)-4,5,6,7-tetrahydro-3H-imidazo[4,5-c]pyridine-6-carboxylic acid (1) in 100mL of distilled water, ice bath 12.6 mL of aqueous NaOH (6N) was added dropwise. Add 31.59g (Boc) to the reaction solution 2 ° and 113mL of dioxane solution, adjust the pH to 9 with NaOH aqueous solution (6N). The reaction mixture was stirred at room temperature for 24 hours, TLC (chloroform:methanol:glacial acetic acid=15:1:0.06) showed that compound 1 disappeared. The reaction solution was adjusted to neutrality with saturated potassium hydrogensulfate aqueous solution under ice cooling. Concentrate under reduced pressure to remove dioxane, add 50 mL of distilled water to the residue, add saturated potassium bisulfate aqueous solution dropwise under ice bath to adjust the pH to 2, and extract with ethyl acetate (100 mL×1, 50 mL×2). Th...
Embodiment 3
[0024] Example 3 Preparation of (6S)-N 3 , N 5 -di-Boc-4,5,6,7-tetrahydro-3H-imidazo[4,5-c]pyridine-6-formylglycine benzyl ester (3a)
[0025] To 14.94g(40.7mmol)(6S)-N 3 , N 5 -di-Boc-4,5,6,7-tetrahydro-3H-imidazo[4,5-c]pyridine-6-carboxylic acid (2) and 200mL of anhydrous tetrahydrofuran (THF) solution, add 5.49g (40.7mmol) HOBt, after dissolving, add 9.15g (44.4mmol) DCC under stirring in an ice bath, and activate for 30min. Suspend 12.47g (37mmol) Tos Gly-OBzl in 200mL of anhydrous THF, adjust the pH to neutral with NMM, then add the suspension to the above activated reaction solution, and finally adjust the pH of the reaction solution to 8, reacted at room temperature for 16 hours, TLC showed that 2 basically disappeared, and filtered to remove dicyclohexyl urea (DCU). Concentrate the filtrate to dryness under reduced pressure and dissolve it with ethyl acetate, then filter again to remove DCU, and the filtrate is successively washed with saturated NaHCO 3 Aqueous s...
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