Pyrazolidine derivatives

Pyrazolidine Derivatives. The reduction of some aminopyrazole quaternary salts (301) with sodium borohydride or lithium aluminium hydride leads to pyrazolidinone derivatives, e.g. (302), and ring-opened products.  

The scope and limitations of the reaction of hydrazine hydrate with unsaturated diesters or /8-anilino-diesters to give ethyl-3-oxopyrazolidine-4-carboxylates (303) have been investigated. Cleavage of the diesters to 

On irradiation in acetone solution, the pyrazolidinone (304) gives the spiro-epoxide (305), whereas its isomer (306) undergoes oxidative dimerization to (307).2  

Elguero, R. Jacquier, and S. Mignonac-Mondon, Bull. Soc. chim. France, 1972, 2807. 

---

Prostaglandins 195—197, 242 — 244, 273, 274,376, 411,413, 430, 438 Protocol form example 133 Prunasin 179,181 Psychopharmaceuticals 364 Purines 44, 266, 438, 439 Pyrazolidine derivatives 426 Pyrethroid insecticides 359 Pyridine alkaloids 66 4-Pyridinecarboxylic acid hydrazide reagent 318... 

Purpuric acid lb 174 Pyrazolidine derivatives la 426 3,5-Pyrazolidindione derivatives lb 20 Pyrazolinone derivatives lb 277 Pyrazolin-5-one derivatives lb 327,329 Pyrazone lb 332 Pyrene lb 379 PyrethrinI lb 18 Pyrethrin II lb 18 Pyrethroids lb 86,87 Pyrethroid insecticides la 359 Pyridine alkaloids la 66 lb 279 Pyridine derivatives lb 119,244 Pyridinium carbinols lb 65 Pyridinium glycols lb 65 Pyridoxal la 157,158,253 Pyridoxamine la 253 Pyridoxine la 253... 

Reaction of secoestrone aldehyde 306 with half an equivalent of hydrazine hydrate led to aldazine 307, which undergoes a criss-cross reaction in the presence of BF3-OEt2 to furnish a decacyclic pyrazolidine derivative 308 in 74% yield (Scheme 44) <2002T6843>. 

As another important mechanistic type, fragmentation into at least three products that are formed more or less simultaneously has to be mentioned. Such [5 - 2 + 2 + 1] reactions were encountered in 2-pyrrolidinones (65, 67), certain pyrazolidine derivatives (68, 72, 73), l,2,4-triazolidine-3-ones (69) and l,2,4-triazolidine-3,5-diones (70), 2//-pyrrol-2-ones (71), 1,3-dithiolane 1-oxides (78), 1,2,3,4-thiatriazoles (74), 1,2,4-oxadiazolines (75), and in several rings containing sulfur in an oxidized state (76-79,82). Most of these molecules have an exocyclic double bond. 

Pyrazolidine derivatives 16 were obtained from the intermolecular [3+2] cydo dd- between hydrazones 14 and olefins 15 <03TL3351>. A convenient method for the symhel s of 7//-pyrazole-4-carboxylic acid esters 18 from 3-ketaminoesters 17 has been reported using... 

Pavelka K, Vojtisek O, Bremova A, Kaukova D, Handlova D. A new pyrazolidine derivative— Benetazone Spofa—in short-and medium-term treatment of rheumatoid arthritis. (Doubleblind comparative study with phenylbutazone). Int J Clin Pharmacol Biopharm 1976 14(l) 20-8. 

Diimines 1 react with sulfur dichloride or disulfur dichloride to give the 1,2,6-thiadiazines 2aj.23 When compounds 1 are treated with thionyl chloride, the 1,2,6-thiadiazine S-oxides 3a-l are formed.23,24 On heating in toluene to 90°C, compounds 2a-j are converted into the pyrazoles 4 by extrusion of sulfur. The pyrazoles 4 can also be obtained by heating the diimines 1 in pyridine for 8 hours with sulfur dichloride, disulfur dichloride, or thionyl chloride. In contrast, the tetrahydro-l,2,6-thiadiazines23 obtained from 1,3-diamines and sulfur dichloride cannot be converted to pyrazolidine derivatives by extrusion of sulfur. When compounds 2 a j or 3a-l are heated at 60 °C in tetrahydrofuran containing 6M potassium hydroxide, the starting materials 1 are recovered. 

The azo-compound (248) rearranges thermally to the pyrazole (249). The 1-pyrazoline (250) is formed from the thioketen 5-oxide Bu Pr C=C=SO and 2-diazopropane.The allyl chloride H2C=C(COPh)CH2Cl reacts with 1,1-dimethylhydrazine to yield the pyrazolidine derivative (251). Numerous betaines (252 R, R, R = H or Me) have been prepared by the action of aromatic aldehydes on the appropriate pyrazolidinones. Treatment of diethyl acetylmalonate with 1,1-dimethylhydrazine affords the amine-imide (253). ... 

Sulfinpyrazone, a pyrazolidine derivative, is a potent uricosuric agent which also has antithrombotic and platelet inhibitory effects (see Figure 92). It lacks antiinflammatory and analgesic properties. Sulhnpyrazone inhibits renal tubular reabsorption of uric acid. It reduces renal tubular secretion of other organic anions, e.g., paraaminohippuric acid and salicylic acid, and displaces other organic anions bound extensively to plasma proteins (e.g., sulfonamides, salicylates). It is not intended for the relief of an acute attack of gout. 

Bicyclic pyrazolidine derivatives (213) and (215) can be converted into diazo compounds (214) and (216), respectively, on treatment with tosyl azide in the presence of triethylamine in dichloro-methane or acetonitrile <87JCS(P1)885>. This diazo transfer reaction is initiated by an electrophilic attack of tosyl azide on the carbanion generated from the respective bicyclic compounds (Scheme 33). 

Besides ampicillin there are numerous other drugs which cause maculopapular eruptions. The drugs most frequently mentioned are other penicillins, streptomycin, rifampicin, sulfonamides, pyrazolidine derivatives (phenylbutazone), pyrazolones, barbiturates, tricyclic antidepressants, hydantoin derivatives, indomethacin, quinine, and meprobamate (Kauppinen 1972 Korting 1972 Louis and Schulz 1973 Schuppli 1972 Thiers et al. 1964). 

Ozeki S, Tejima K (1974) Drug interaction. II. Binding of some pyrazolone and pyrazolidine derivates to bovine serum albumin. Chem Pharm Bull (Tokyo) 22 1297 Perelmutter L, Khera K (1969) Rat mast cells in human reagin detection. Lancet 1 1269 Rocklin RE, MacDermott RP, Chess L, Schlossman SF, David JP (1974) Studies on mediators production by highly purified human T and B lymphocytes. J Exp Med 140 1303 Rockoff ID, Brash R, Kuhn C (1970) Contrast media as histamine liberators. Invest Radiol 5 503... 

Asymmetric inverse-electron-demand 1,3-dipolar cycloaddition of C,A-cyclic azomethine imines with c-rich dipolarophiles was accomplished with a high stereo-selectivity by using an axially chiral dicarboxylic catalyst (40)." The metal-free silicon Lewis-acid-catalysed 3-1-2-cycloadditions of A-acylhydrazones with cyclopentadiene provides a mild access to pyrazolidine derivatives in excellent... 

The [3 + 2] cycloaddition between hydrazones and olefins was accelerated in the presence of a catalytic amount of Hf(OTf)4 under mild conditions. The corresponding pyrazolidine derivatives were obtained in moderate to high yields using this novel Lewis acid catalysis for [3+2] cycloaddition reactions (eq 16). ... 

Giampietro and Wolfe once again illustrated the first Pd-catalyzed carboamination reaction for the synthesis of substituted pyrazolidines with good yields and excellent diastereoselectivity (Scheme 40.10). In this strategy, N-substituted butenyl hydrazine was reacted with an external aryl halide in the presence of the Pd catalyst to afford disubstituted pyrazolidine derivatives. " ... 

Feprazone, a new pyrazolidine derivative with an anti-inflammatory action similar to that of phenylbutazone, potentiates the activity of oral anticoagulants, although not as much as phenylbutazone (34 ). 

---