Menozzi G, Mosti L, Schenone P, Donnoli D, Schiariti F, Marmo E
Istituto di Scienze Farmaceutiche dell'Università, Genova, Italy.
Farmaco. 1990 Feb;45(2):167-86.
Reaction of ethyl or methyl 2-dimethylaminomethylene-3-oxoalkanoates 2 with phenylhydrazine gave the corresponding esters of 5-substituted 1-phenyl-1H-pyrazole-4-carboxylic acids 3 in high yields. Esters 3 were hydrolyzed to the relative carboxylic acids 4, which were converted by heating to 5-substituted 1-phenyl-1H-pyrazoles 5 in excellent yields. Reaction of methyl 5,5-dimethyl-3-dimethylaminomethylene-2,4-dioxohexanoate with phenylhydrazine afforded methyl 1-phenyl-4-pivaloyl-1H-pyrazole-5-carboxylate 8 b, which was converted as above to the corresponding carboxylic acid 10 b and this to 1-phenyl-4-pivaloyl-1H-pyrazole 11 b. Starting from 5-methoxymethyl-1-phenyl-1H-pyrazole, 1-phenyl-1H-pyrazole-5-acetic acid 18 and its alpha-methyl derivative 19 were also synthesized. Compounds 18, 19, 10 b and 11 b showed a strong antiinflammatory activity in rats; the same compounds in general as well as 8 b, showed appreciable analgesic and antipyretic activities in mice and rats, respectively.
2-二甲基氨基亚甲基-3-氧代链烷酸乙酯或甲酯2与苯肼反应,以高产率得到5-取代的1-苯基-1H-吡唑-4-羧酸3的相应酯。酯3水解为相应的羧酸4,通过加热将其转化为5-取代的1-苯基-1H-吡唑5,产率极高。5,5-二甲基-3-二甲基氨基亚甲基-2,4-二氧代己酸甲酯与苯肼反应得到1-苯基-4-新戊酰基-1H-吡唑-5-羧酸甲酯8b,将其按上述方法转化为相应的羧酸10b,再将其转化为1-苯基-4-新戊酰基-1H-吡唑11b。从5-甲氧基甲基-1-苯基-1H-吡唑出发,还合成了1-苯基-1H-吡唑-5-乙酸18及其α-甲基衍生物19。化合物18、19、10b和11b在大鼠中表现出强烈的抗炎活性;一般来说,相同的化合物以及8b在小鼠和大鼠中分别表现出明显的镇痛和解热活性。