Derivatives Of ditraizinylamine and tritriazinylamine

2-Arylamino-4,6-dichloro-s-triazine reacts with cyanuric chloride in the presence of alkali to yield N,N-bis(4,6-dichloro-s-triazin-2-yl)-arylamine. In like manner, 2-substituted o-chloro-, p-chloro-, o-nitro- and p-carbomethoxyphenylamino-4,6-dimethoxy-s-triazines react with cyanuric chloride to yield the corresponding 4,6-dichloro-s-triazin-2-yl-4′,6′-dimethoxy-s-triazin-2′-ylaryl-amine, while anilino-, p-toluidino, o- and p-methoxyphenylamino and o-carbomethoxyphenylamino derivatives did not. The reaction of cyanuric chloride with 2,4-dichloro-6-ethylamino-s-triazine in the presence of alkali yields the condensation product of the ditriazinylamine type and the reaction of cyanuric chloride with ammonia yields N,N-bis(4,6-dichloro-s-triazin-2-yl)- or tris(4,6-dichloro-s-triazin-2-yl)amine.     

Reaction of some coumarin and 4,6-diaryl-2H-pyran derivatives with secondary amines

The reaction of piperidine, morpholine, piperazine or dimethylamine with several coumarins, 3-bromocoumarin, 4,6-diaryl-2H-pyran-2-ones and 3-bromo-4,6-diaryl-2H-thiopyran-2-ones gave o-hydroxycinnamic acid amides, benzofurans, open-chain δ-oxoamides and thiophene derivatives, respectively.     

Synthesis and reactions of 4,6-dimethoxyindole,an unusual indole system

A synthesis of 4,6-dimethoxyindole is described. Formylation or oxalylation reactions gave substitution at position 7 rather than the usual 3-substitution characteristic of other indoles. A synthesis of N,N-dimethyl-4,6-dimethoxytryptamine is presented along with NMR data for 3 and 7-substituted compounds in this series.     

Amination of 4,6- and 2,4-dichloropyrimidines with polyamines

Amination of a double excess of 4,6-dichloropyrimidine with various diamines in the presence of cesium carbonate in boiling dioxane quantitatively afforded the corresponding N,N′-bis(6-chloropyrimidin-4-yl) derivatives, while its reactions with tri- and tetraamines gave N,N′,N″-tris- and N,N′,N″,N‴-tetrakis(6-chloropyrimidin-4-yl) derivatives. Equimolar amounts of 2,4-dichloro- or 4,6-dichloropyrimidine and diamines reacted in the presence of Pd(0) complexes to form macrocyclic compounds containing pyrimidine fragments. Catalytic reactions of 4 equiv of diamines with 4,6-dichloropyrimidine can lead to the formation of 4,6-bis-(diamino)pyrimidines. Relations between the yield and the nature of diamine and catalytic system were found.     

Synthesis and thermal rearrangement of 2-(2-chloroethoxy)-4,6-disubstituted <Emphasis Type="Italic">sym</Emphasis>-triazines

On thermolysis of 4-methoxy- and 4-alkylamino-2-(2-chloroethoxy)-6-morpholino(piperidino)-sym-triazines, the corresponding oxazolo- or imidazo-sym-triazinones are formed by elimination of methyl chloride or hydrogen chloride, and 4,6-disubstituted 3-(2-chloroethyl)-sym-triazin-2-ones are formed from 4,6-dimorpholino(dipiperidino) derivatives.     

2-amino-4,6-lutidineN-oxide complexes formed from various copper(II) salts

Summary Copper(II) complexes of 2-amino-4,6-lutidineN-oxide (4,6DMAH) have been isolated as tetrafluoroborate, nitrate, chloride and bromide salts, and characterized by spectral methods (i.e., i.r., u.v.-vis. and e.s.r.). Variation of the ligand-to-copper(II) ratio yielded solids having the following empirical formulae: [Cu(4,6DMAH)₄]X₂ (X=BF₄), [Cu(4,6DMAH)₂X₂] (X=NO₃, Cl) and [Cu(4,6DMAH)X₂] (X=Br). In addition, a deprotonated ligand complex, Cu(4,6DMA)₂, was prepared using copper(II) acetate. The Sigand usually binds to the copper(II) centresvia theN-oxide oxygen and only the deprotonated ligand coordinatesvia the exocyclic nitrogen as well as the TV-oxide oxygen. The complexes involving coordinated anions and at least two ligands are monomeric while Cu(4,6DMAH)Br₂ is polymeric. The ring substituents affect either the stoichiometry or the stereochemistry of these solids when compared to less sterically demanding 2-aminopyridineN-oxides.     

Synthesis of 5,7-dichloro-2H-1-benzopyran-2-ol

The reaction of 4,6-dichloro-2-(methylthiomethoxy)cinnamaldehyde ( 3 ) or 4,6-dichloro-2-hydroxycinnamaldehyde ( 5 ) with mercuric chloride in hot aqueous acetonitrile gave 5,7-dichloro-2H-1-benzyopyran-2-ol ( 4 ) in good yield.     

Synthesis of Azo-Sulfa Drugs Based on 2-Pyridinone and 2-Pyridinethione

Some new azo sulfa drugs 3-cyano-4,6-diphenyl-1-[4-(N-substituted)sulfamyl]phenylazo-2-pyridinone dyes (1-6) and 3-cyano-4,6-diphenyl-1-[4-(N-substituted)sulfamyl]phenylazo-2-pyridinethione dyes (1′-6′) were synthesized by coupling of 4-(N-substituted)sulfamylbenzene diazonium salts with 3-cyano-4,6-diphenyl-2-pyridinone and/or with 3-cyano-4,6-diphenyl-2-pyridin-ethione. The corresponding iron (1a-6a, 1′a-6′a), copper (1b-6b, 1′b-6′b) and mercury (1c-6c, 1′c-6′c) chelates wvere also prepared. All synthesized compounds were screened in vitro for antibacterial and antifungal activities.     

Synthesis and Properties of 4,6-Dimethyl-5-pentyl-2-thioxo-1,2-dihydropyridine-3-carbonitrile and 3-Amino-4,6-dimethyl-5-pentylthieno[2,3-b]pyridines

The reaction of 3-pentylpentane-2,4-dione with cyanothioacetamide afforded 4,6-dimethyl-5-pentyl-2-thioxo-1,2-dihydropyridine-3-carbonitrile. Alkylation of the latter led to the formation of 2-alkylsulfanyl-4,6-dimethyl-5-pentylpyridine-3-carbonitriles or 3-amino-4,6-dimethyl-5-pentylthieno[2,3-b]pyridines, depending on the alkylating agent and reaction conditions. The structures of the key compounds were proved by 2D NMR spectroscopy and X-ray analysis. Biological activity of the synthesized compounds was evaluated in silico. Some compounds were experimentally found to stimulate growth of sunflower seedlings.

     

Synthesis of 3-substituted 1-aryl-4,6-dinitro-1H-indazoles based on picrylacetaldehyde and their behavior in nucleophilic substitution reactions

A method for the synthesis of 1-aryl-3-formyl-4,6-dinitro-1H-indazoles by the reaction of picrylacetaldehyde with aryldiazonium salts followed by intramolecular cyclization of the resulting picrylglyoxal monoarylhydrazones was developed. Various 4,6-dinitro-1-phenyl-1H-indazoles substituted in position 3 were prepared via transformations involving the formyl group of 3-formyl-4,6-dinitro-1-phenyl-1H-indazole. 3-R-4,6-Dinitro-1-phenyl-1H-indazoles (R = CHO, CN, 1,3-dioxolan-2-yl) react regiospecifically with anionic O-, S-, and N-nucleophiles, in particular, with replacement of only the 4-NO₂ group. Thus previously unknown 3-R-4-Nu-6-nitro-1-phenyl-1H-indazoles were synthesized (Nu is a nucleophile residue).     

α-Thioureidoalkylation of functionally substituted ureas: I. Tandem cyclization and esterification in reactions of <Emphasis Type="Italic">N</Emphasis>-(carboxyalkyl)ureas with 1,3-dialkyl-4,5-dihydroxy-4,5-diphenylimidazolidine-2-thiones in alcohols

Acid-catalyzed reactions of N-(carboxyalkyl)ureas with 1,3-dialkyl-4,5-dihydroxy-4,5-diphenylimidazolidine-2-thiones in methanol or propan-2-ol led to the formation of previously unknown ω-(4,6-dialkyl-2-oxo-3a,6a-diphenyl-5-thioxooctahydroimidazo[4,5-d]imidazol-1-yl)alkanoic acids and their methyl and isopropyl esters. The structure of some esters was proved by X-ray analysis. Methyl (4,6-diethyl-2-oxo-3a,6adiphenyl-5-thioxooctahydroimidazo[4,5-d]imidazol-1-yl)acetate showed anxiolytic effect.     

Synthesis and properties of some aryl-s-triazines

The synthesis and reactions of several substituted s-triazines were studied in attempts to prepare 4,6-bis(4-chlorophenyl)-s-lriazine-2-carboxylie acid ( 2 ) and 2-aldehyde ( 8 ). The 4,6-bis-(4-chlorophenyl)-s-triazine derivatives were surprisingly inert to a variety of reagents. 4,6-Bis-(4-chlorophenyl)-2-methyl-s-triazine ( 1 ) could not be oxidized with any of a variety of oxidants. On bromination 1 gave 4,6-bis(4-chlorophenyl)-2-dibromomethyl-s-triazine ( 4 ) which was resistant to hydrolysis but on oxidation with selenium dioxide gave 2 . Compound 2 was also prepared by the oxidation of 4,6-bis(4-chlorophenyl)-2-hydroxymethyl-s-triazme ( 7 ) with potassium permanganate. Other reagents did not oxidize 7 to 8 . 4,6-Bis(4-chloroanilino)-2-mcthyl-s-triazine ( 3 ) was also resistant to oxidizing agents. 2-Diazomethy1-4,6-dichloro-s-triazine ( 11 ) on reaction with 4-chloroaniline gave 4,6-bis(4-chloroanilino)-2-chloromethyl-s-triazine ( 12 ). All efforts to prepare 8 were unsuccessful.     

New,convenient synthesis of 2-alkyl- and 2-vinylpyrazolo[3,4-d]-pyrimidine derivatives

Treatment of 1,3-dimethyl-6-hydrazinouracil with the appropriate dimethylformamide dialkylacetal afforded the, corresponding 2-alkyl-5,7-dimethylpyrazolo[3,4-d]pyrimidine-4,6-(5H,7H)diones. The reaction of 1,3-dimethyl-6-(α-methylbenzylidenehydrazino)uracils with dimethylformamide dimethylacetal or triethyl orthoformate gave the corresponding 5,7-dimethyl-2-vinylpyrazolo[3,4-d]pyrimidine-4,6(5H,7H)diones, respectively. Similarly, treatment of 1,3-dimethyl-6-(α-methylbenzylidenehydrazino)uraeils with triethyl orthopropionate yielded the corresponding 5,7-dimethyl-3-ethyl-2-vinylpyrazolo[3,4-d]pyrimidine-4,6(5H,7H)diones.     

Syntheses of a new type of chiral phosphines from glucose

Methyl 3-deoxy-3-(diphenylphosphino)-4,6-O-benzylidene-α-D-altropyranoside (1) and methyl 2-deoxy-2-(diphenylphosphino)-4,6-O-benzylidene-α-D-altropyranoside (2) were prepared from methyl 2,3-anhydro-4,6-O-benzylidene-O-D-mannopyranoside and methyl 2,3-anhydro-4,6-O-benzyl-idene-α-D-allopyranoside,respectively,via regioselective and stcreospecific ring-opening reactions in high yields.Compounds 1 and 2 were oxidized to give the corresponding phosphine oxides (3 and 4).     

Reaction of N,N'-Di(methoxycarbonyl)-p-benzoquinonediimine with Meldrum's Acid and its Analogs

Reactions of 2,2-dimethyl-4,6-dioxo-1,3-dioxane (Meldrum's acid), 2,2-tetramethylene-4,6-dioxo-1,3-dioxane and 2,2-pentamethylene-4,6-dioxo-1,3-dioxane in the presence of MeONa gave rise instead of expectable products of Michael 1,4-addition the corresponding N,N'-di(methoxycarbonyl)-p-benzoquinonediimines substituted in the ring.     

INTERACTION OF 2,4,6-TRINITROTOLUENE AND ITS ANALOGUES WITH ALDEHYDES. SYNTHESIS OF BENZOANNELATED HETEROCYCLES FROM THE PRODUCTS OF CONDENSATION

ABSTRACT

2,4,6-Trinitrotoluene (TNT) and its sulfonyl analogue 2-isobutylsulphonyl-4,6-dinitrotoluene undergo smooth condensation with chloral and fluoral to give 2-R-4,6-dinitrophenyl-1-(trihalomethyl)ethanols which easily cyclize to give 4-R-6-nitro-2-trihalomethyl-2,3-dihydrobenzo[b]furans (R=NO₂, i-Bu; halogen = F or Cl) in the presence of K₂CO₃. 2-R′-sulphonyl-4,6-dinitrotoluenes, prepared from TNT, condense with aromatic aldehydes to form 1-(2-R′-sulphonyl-4,6-dinitro)-2-arylethenes in which the ortho-nitro group, upon interaction with NaN₃ was selectively substituted by the azido group. Thermolysis of the obtained azides gave 2-aryl-4-R′-sulphonyl-6-nitroindoles (R′ = Ph, i-Bu, PhCH₂). Such N-methylated indole (R′ = i-Bu) was regioselectively aminated.     

Intramolecular cyclization of O-(3,5-dinitrophenyl) and O-(3-amino-5-nitrophenyl) ketoximes, products of transformations of 1,3,5-trinitrobenzene. The synthesis of nitrobenzo[b]furans and 4-hydroxynitroindoles

O-(3,5-Dinitrophenyl) ketoximes obtained in the reactions of ketoximes with 1,3,5-trinitrobenzene undergo acid-catalyzed cyclization into 2-substituted or 2,3-disubstituted 4,6-dinitrobenzo[b]furans. In analogous cyclization, products of selective reduction of a nitro group in O-(3,5-dinitrophenyl) ketoximes unexpectedly yield, along with 6-amino-4-nitrobenzofurans, 4-hydroxy-6-nitroindoles. The 4-NO₂ group is displaced from 4,6-dinitrobenzo[b]furans in reactions with thiols in the presence of K₂CO₃. Conditions for nitration and sulfochlorination of 4,6-dinitrobenzo[b]furans in position 3 were found. Condensation of a 2-methyl derivative with dimethylformamide acetal was accomplished. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 984–991, May, 2007.     

Ring closure reactions of azidouracils to oxazolo- and isoxazolopyrimidines

Thermolysis of 6-azidouracils 1 in the presence of polyphosphoric acid leads either to oxazolo[5,4-d]pyrimidine-5,7-diones 5 (by reaction with benzoic acid 2a ) or to isoxazolo[3,4-d]pyrimidine-4,6-diones 7 (by reaction with aliphatic carboxylic acids 2b,c ). 5-Benzoylpyrimidinetriones 12 could be shown to cyclize to isoxazolo[5,4-d]pyrimidine-4,6-diones 15 by chlorination with phosphorus pentachloride and subsequent reaction with sodium azide.     

Ring transformations of 4H-pyrans. Pyridines from 2-amino-4H-pyrans

Ring transformations of 4H-pyrans into pyridines are reported. Treatment of 2-amino-4,6-diaryl-3,5-dicyano-4H-pyrans (I) with nitrosylsulfuric acid brings about their transformation into 3,5-dicyano-4,6-diaryl-2-pyridones (VI) which can also be obtained from α-benzoylcinnamonitriles (IX) and cyanoacetamide. Similarly, 2-amino-4,6-diaryl-5-carbethoxy-3-cyano-4H-pyrans (II) lead to 4,6-diaryl-5-carbethoxy-3-cyano-2-pyridones (VII). Treatment of both series of pyrans with sulfuric acid results in the formation of the corresponding 3,4-dihydro-2-pyridones (IV and V). Reaction of pyrans II with ammonium acetate in acetic acid yields 2-amino-4,6-diaryl-5-carbethoxy-3-cyanopyridines (XII). Pyrans I undergo an entirely different type of reaction upon treatment with this reagent leading to 2,4,6-triaryl-3,5-dicyano-1,4-dihydropyridines (XV).     

Photochemical reactions of 1-methyl-4,6-diaryl-2(1H)-pyrimidinones in the presence of thiols

Photochemical reactions of 1-methyl-4,6-diaryl-2(1H)pyrimidinones 1a-b in the presence of thiols 2 are described. Irradiation of 1-methyl-4,6-diaryl-2(1H)-pyrimidinones 1a-b in benzene in the presence of thiols 2 gave the unexpected 2:1-adducts, 3-methyl-4,6-diaryl-5-aralkylthio-6-(1′-methyl-4′,6′-diaryldihydro-pyrimidin-2-on)yl-1,3-diazabicyclo[2.2.0]hexan-2-ones 3-6, of 1 and 2, whereas irradiation of 1a-b alone in benzene resulted in recovery of the unchanged 1a-b.