Synthesis Of Bis-pyrazoline Derivative Modified By Amino Acid

Heterocyclic compounds were widely distributed in nature, and were widely used indrugs and optical fields. Five-membered heterocyclic compounds were used in many fieldsbecause of its common to see and excellent biological activity. As a kind of five-memberedheterocyclic compounds, more and more attentions have been paid to pyrazoline derivativesbecause of its drugs and optically activities. Pyrazoline derivatives can treat many diseasessuch as inflammations and swellings. They can be made for pesticides, herbicides, acaricides,etc. And they also can be made for fluorescent whitening agent, electroluminescent andfluorescent probes fields. Therefore, pyrazoline derivatives have great research value anddevelopment prospects.Amino acid derivatives were widely used in drugs and industry fields in recent years. In order toimprove applicability and physiological activities of pyrazoline derivatives, by means ofcombining pyrazoline with amino acids, many new amino-modified pyrazoline were obtained.In this study, the glycine and L-phenylalanine were synthesized into toluenesulfonyl aminoacid hydrazide through a series of reactions. On the other side, chalcone analogues weresynthesized through aldol condensation. Lastly, chalcone analogues were reacted withtoluenesulfonyl amino acid hydrazide and the amino acid modified pyrazoline derivativeswere obtained. The resulting compounds have not been reported, and structures wereconfirmed by elemental analysis,1H NMR, IR and MS.The work is composed of the follows:1. Hydrazine hydrate were used as the starting materials under microwave irradiation. Aseries of pyrazole aldehydes were obtained using Vilsmeier-Haak reaction in facile conditions.And then pyrazole aldehydes reacted with hypnone derivatives,16kinds of chalconeanalogues were synthesized. And determine the optimal conditions by orthogonal experiments.The molar ratio of pyrazole aldehydes and hypnone derivatives were1:1, microwaveirradiation power140W, microwave irradiation time30min, catalyst’s dosage0.5g. And theaverage yields of chalcone analogues were more than85%determined by experiments.2. Glycine and phenylalanine were used as the starting materials. Then glycine andphenylalanine reacted with methanol solution of thionyl chloride, and heat up andcircumfluence in methanol solution of thionyl chloride. Glycine methyl ester hydrochlorideand phenylalanine methyl ester hydrochloride were synthesized. Then glycine methyl esterhydrochloride and phenylalanine methyl ester hydrochloride reacted with p-toluenesulfonylchloride, and glycine methyl ester of p-toluenesulfonyl and phenylalanine methyl ester ofp-toluenesulfonyl were synthesized. Lastly, glycine methyl ester of p-toluenesulfonyl andphenylalanine methyl ester of p-toluenesulfonyl reacted with hydrazine, and heat up and circumfluence in ethanol. P-toluenesulfonyl glycine hydrazide and P-toluenesulfonylphenylalanine hydrazide were synthesized. And make sure the optimal reaction conditionsthough comparative experiment. The molar ratio of amino acids and hydrazine were1:2,reaction time2h. And the average yields of p-toluenesulfonyl amino acids hydrazide were80%in these conditions.3. Reactions were under microwave irradiation, and in high boiling point solvent.P-toluenesulfonyl glycine hydrazide and p-toluenesulfonyl phenylalanine hydrazide reactedwith chalcone analogues,32kinds of pyrazoline derivatives modified by amino acid wereobtained. And the optimal reaction conditions were determined. The molar ratio of chalconeanalogues and p-toluenesulfonyl amino acid hydrazide were1:1.15, microwave irradiationpower140W, microwave irradiation time30min. And the average yields of pyrazolinederivatives were more than75%determined by experiments.