Synthesis and biological activities of cis and trans 5‐amino‐3‐[(6‐chloro‐3‐pyridyl)methyl]amino‐1‐(5,5‐dimethyl‐2‐oxo‐4‐substitutedphenyl‐1,3,2‐dioxaphosphinan‐2‐yl)‐4‐cyano(ethoxycarbonyl)‐1H‐pyrazoles

A series of novel title compounds have been designed and synthesized by a multi‐step reaction, the stereochemistry of the reaction was investigated, the structures of all compounds prepared have been confirmed by ¹H NMR, IR, EI‐MS spectroscopy and elemental analysis. The crystal structures of cis 6b and trans 6b were determined by single crystal X‐ray diffraction. The results of preliminary bioassay indicate that some compounds possess a certain extent inhibition effect against aphides at the concentration of 250 ppm.     

Synthesis and antimicrobial activity of new benzofuranyl‐1,3‐benzoxazines and 1,3‐benzoxazin‐2‐ones

New benzofuranyl‐1,3‐benzoxazines and 1,3‐benzoxazin‐2‐ones are synthesized in which benzofuran is coupled with 1,3‐benzoxazines and 1,3‐benzoxazin‐2‐ones through ‐CONH‐ and ‐COCH₂‐ bridges, respectively. The antimicrobial activity of these compounds is reported.     

One‐pot synthesis of 2‐acylimino‐3‐aryl‐1,3‐thiazoline derivatives in aqueous media

The one‐pot two‐step synthesis for acyliminothiazolines by treatment of N,N'‐substituted thioureas with α‐bromocarbonyl compounds under aqueous media was described. Compared to classical reaction in organic solvents, this method consistently has the advantages of short reaction time and being environmentally friendly.     

Ready access to 7,8‐dihydro‐ and 1,2,3,4‐tetrahydro‐1,6‐naphthyridine‐5(6H)‐ones from simple pyridine precursors

Short pathways are described for the synthesis of a representative example of each of the 7,8‐dihydro‐and 1,2,3,4‐tetrahydro‐1,6‐naphthyridine‐5(6H)‐one ring systems from simple pyridine precursors. An attempted synthesis of the related 4,6‐dihydro‐1,6‐naphthyridin‐5(1H)‐one ring system from a common intermediate was unsuccessful.     

The reaction of aryl and heteroarylhydrazines with aryl‐trifluoromethyl β‐diketones

We report the results obtained when five aromatic or heteroaromatic hydrazines react with six β‐diketones bearing trifluoromethyl and aryl substituents. Forty‐two compounds have been isolated corresponding to two isomeric trifluoromethyl pyrazoles and the intermediate 5‐CF₃, 5‐OH pyrazolines. The results have provided useful information for establishing the mechanism of the synthesis of pyrazoles.     

Cyclization of 2‐benzoylamino‐N‐methyl‐thiobenzamides to 3‐methyl‐2‐phenylquinazolin‐4‐thiones

Acylation of 2‐amino‐N‐methyl‐thiobenzamide with substituted benzoyl chlorides has been used to synthesize the corresponding 2‐benzoylamino‐N‐methylthiobenzamides. Subsequent sodium methoxide‐catalyzed ring closure gives the corresponding 3‐methyl‐2‐phenylquinazoline‐4‐thiones. These compounds were characterized by means of their ¹H‐ and ¹²C‐NMR spectra. The kinetics of the cyclization reaction has been followed with UV‐VIS spectroscopy at 100 °C in methanolic solutions of sodium methoxide.     

Synthesis and characterization of 4‐aryl‐5‐(1‐aryl‐2‐methyl‐2‐nitropropyl)‐1,2,3‐selenadiazoles

The synthesis of a new set of selenadiazoles, 4‐aryl‐5‐(1‐aryl‐2‐methyl‐2‐nitropropyl)‐1,2,3‐selenadiazoles ( 4 ) derived from 2‐[4‐methyl‐4‐nitro‐1,3‐diarylpentylidene]‐1‐hydrazinecarboxamide ( 3 ) has been reported. THF has been found to be the solvent of choice for this reaction. Structural features of 3 and 4 have been analyzed by NMR and X‐ray techniques.     

Reactions of cephalosporin sulfones 3. Synthesis of 2‐phenylhydrazonocephem‐sulfones. A new potential entry to 2‐aminocephems

Reaction of cephem sulfones 1a‐e with aryldiazonium salts gives the 2‐azo compounds which immediately rearrange into the corresponding 2‐hydrazono derivatives 2a‐e .     

Behavior of 3‐benzylamino‐5‐aryl‐2(3H)‐furanones towards some nitrogen nucleophiles

Ring closure of 2‐N‐benzylamino‐3‐aroylpropionic acids ( 3 ) with acetic anhydride afforded 3‐N‐benzylamino‐5‐aryl‐2(3H)‐furanones ( 4 ). The reaction of the furanones ( 4 ) with benzylamine in benzene was found to be time dependent. Thus refluxing the reaction mixture for 1 h only afforded the open‐chain amides ( 5a‐c ). When the reaction was conducted for 3 h the 2(3H)‐pyrrolones ( 6 ) were obtained. Hydrazine hydrate affected ring opening of the furanones to give the hydrazides ( 5d‐f ). Also, semicarbazide converted ( 4 ) into the corresponding semicarbazide derivatives ( 5g‐i ). The hydrazides ( 5d‐f ) were reacted with benzoyl chloride to give the corresponding diaroylhydrazines ( 5j‐l ). The open‐chain derivatives ( 5 ) were converted into a variety of heterocycles: isothiazolones ( 7 ), dihydropyridazinones ( 8 ), 1,3,4‐oxadiazoles ( 9 ) and 1,2,4‐triazole derivatives ( 10 ) via cyclization reactions.     

Convenient synthesis of N‐substituted 1‐alkyl and 1‐aryl‐3‐aminoisoquinolines

Cyclocondensation of 2‐acylphenylacetonitriles 1 with amines affords 1‐substituted 3‐aminoisoquinolines 2 in good yields.     

Synthesis of some new 4‐substituted‐3, 5‐bis(2‐pyridyl)‐1h‐pyrazole

Several 4‐substituted‐3, 5‐bis(2‐pyridyl)‐1H‐pyrazoles, where the substituent is chloro, bromo, iodo, nitro, diazo, were synthesized under mild reaction conditions in high yields. The structures of the products were characterized by ¹H NMR, ¹³C NMR, ESI‐MS, IR and elemental analyses.     

Synthesis of 2‐phenylquinolin‐4‐amines substituted with diverse amino and aminoalkyl groups

Facile synthetic approaches to 2‐phenylquinolin‐4‐amines containing an aminoalkyl group at N⁴ of the quinolin‐4‐amine and amino or aminoalkyl groups at the phenyl moiety are presented.     

A novel one‐pot oxidative deformylation of N‐formyldihydroquinolines employing ferric chloride hexahydrate. Synthesis of 4‐chloro‐2‐phenylquinolines and 4‐chloro‐2‐(1,3‐diphenyl‐1H‐pyrazol‐4‐yl)quinolines

A novel versatile one‐pot oxidative deformylation approach has been developed to synthesize 4‐chloro‐2‐phenylquinolines and 4‐chloro‐2‐(1,3‐diphenyl‐1H‐pyrazol‐4‐yl)quinolines from the corresponding N‐formyldihydroquinolines.     

Reactions of 2‐amino‐4h‐1‐benzopyran‐4‐one with 4‐oxo‐4h‐1‐benzopyran‐3‐carbaldehydes

The title aldehyde 1 reacts smoothly with the enamine moiety of 2 ‐aminochromone 2 to produce hitherto unreported 3‐(2‐hydroxybenzoyl)‐5H‐1‐benzopyrano[2,3‐b]pyridin‐5‐one (azaxanthone) 5 . This reaction has been extended for the synthesis of bisazaxanthone 9.     

Regioselective synthesis of pentacyclic polyheterocycles: Sequential [3,3] sigmatropic rearrangement of 4‐(4′‐aryloxybut‐2′‐ynyloxy)‐1‐phenyl‐1,8‐naphthyridin‐2(1H)‐ones

A number of 4‐aryloxymethyl‐6‐phenyl‐2H‐pyrano[3,2‐c][1,8]naphthyridin‐5(6H)‐ones ( 4a‐f ) are regioselectively synthesized in 72‐78% yield by the Claisen rearrangement of 4‐(4′‐aryloxybut‐2′‐ynyloxy)‐1‐phenyl‐1,8‐naphthyridin‐2(1H)‐ones ( 3a‐f ) in refluxing chlorobenzene for 4‐6 h. These products are then subjected to a second Claisen rearrangement catalyzed by anhydrous AlCl₃ at room temperature for 2 h to give hitherto unreported pentacyclic heterocycles ( 5a‐f ) in 78‐85% yield.     

Facile preparation of 7,11‐di(4‐nitrobenzenesulfonyl)‐diaza‐1,4‐dioxa‐7,11‐spiro[4,7]dodecan‐9‐one

Compound 1 as a key intermediate for the synthesis of 3,3,7,7‐tetrakis‐(difluoroamino)octahydro‐1,5‐dinitro‐1,5‐diazocine (HNFX) and 3,3‐bis(difluoroamino)octahydro‐1,5,7,7‐tetranitro‐1,5‐diazocine (TNFX) is described. Cycloalkylation of 3 with 1,3‐dibromopropan‐2‐ol ( 4 ) afforded 1,5‐protected‐1,5‐diazocine 2 , followed by chromic acid oxidation to ketone 1 in good yield.     

Studies with 3‐functionally substituted 2‐arylhydrazononitriles: A new route to 3‐substituted‐2‐arylhydrazononitriles, 4‐amino‐pyrazole‐5‐carbonitriles,azadienes and cinnolines

3‐Amino‐3‐phenyl‐2‐phenylazoacrylonitrile 6 is obtained in good yield via reaction of 5 with phenyl magnesium bromide. The compound 6 is readily converted into 4a . The so formed alkanenitrile reacted with phenylmagnesium bromide to yield 8 . Compound 8 could be also obtained from reaction of 9 with phenylmagnesium bromide. The arylhydrazononitriles 8 and 4a reacted with chloroacetonitrile to yield the 4‐aminopyrazoles 12a,b . Compound 12a reacted with acetic anhydride to yield the 15a and with benzoyl chloride to yield the pyrazole 16 which was converted into 15b . Refluxing 10 in acetic acid gave a mixture of the azadiene 21 and the cinnoline 22 is obtained. The azadiene 21 is converted into 22 either thermally or photochemically.