4,5-Dihydroxyimidazolidin-2-ones in an α-ureidoalkylation reaction of N-(carboxyalkyl)-, N-(hydroxyalkyl)-, and N-(aminoalkyl)ureas 3. α-Ureidoalkylation of N-[2-(dimethylamino)ethyl]urea

α-Ureidoalkylation of N-[2-(dimethylamino)ethyl]urea with 1,3-unsubstituted, 1,3-dialkyl-, and 1,3-dimethyl-4,5-diphenyl-4,5-dihydroxyimidazolidin-2-ones(thiones) was systematically studied. Hitherto unknown N-[2-(dimethylamino)ethyl]glycolurils and their hydrochlorides were synthesized. The yields of the target glycoluril hydrochlorides decreased on going from 1,3-H₂- to 1,3-dialkyl-4,5-dihydroxyimidazolidin-2-ones and increased with the introduction of phenyl groups at the positions 4 and 5 of the starting 4,5-dihydroxyimidazolidin-2-one. X-ray diffraction study showed that 2-[2-(dimethylamino)ethyl]glycoluril crystallizes in the form of a conglomerate.     

Synthesis and reactions of 1-(4-chloro-, 3-chloro-, 2-chloro-, 2,4-dichloro-, and 2,4-difluorophenyl)-6,6-dimethyl-4-oxo-4,5,6,7-tetrahydroindazoles

Reaction of the potassium salt of 2-formyldimedone with hydrochlorides of 4-chloro-, 3-chloro-, 2-chloro-, 2,4-dichloro-, and 2,4-difluorophenylhydrazines gave the corresponding 2-arylhydrazinomethylene-dimedones which cyclized in acid media to 1-substituted 6,6-dimethyl-4-oxo-4,5,6,7-tetrahydroindazoles. Oxidation of the latter with selenious acid gave the corresponding 4,5-dioxo-4,5,6,7-tetrahydroindazoles which were further converted into 3-aryl-5,5-dimethyl-4,5-dihydro-3H-pyrazolo[4,3-a]phenazines and 2,6-diaryl-4,4-dimethyl-4,5-dihydro-1H(3H)-indazolo[4,5-g]imidazoles.Riga Technical University, Riga LV-1658, Latvia; e-mail: marina@osi.lv. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, 533–539, April, 2000.     

The reaction of acetic acid 2‐selenoxo‐2H‐pyridin‐1‐yl esters with benzynes: A convenient route to Benzo[b]seleno[2,3‐b]pyridines

Benzyne and its 3,4,5,6‐tetraphenyl, 3‐ and 4‐methyl, 3‐methoxy and 4,5‐difluoro derivatives react with acetic acid 2‐selenoxo‐2H‐pyridin‐1‐yl esters 4a‐e to give benzo[b]seleno[2,3‐b]pyridines 10–15 in modest yields. The benzynes were generated by one or more of the following methods: diazotization of anthranilic acids 5a‐g with isoamyl nitrate; mild thermal decomposition of 2‐diazoniobenzenecarboxylate hydrochlorides 6a‐d treatment of (phenyl)[o‐(trimethylsilyl)phenyl]iodonium triflate (7) with tetrabutylammonium fluoride; and treatment of 2‐trimethylsilylphenyl triflates 8a‐c with cesium fluoride. In all the reactions, the corresponding 2‐(methylselenenyl)pyridines 16a‐d were also obtained suggesting that these reactions may involve selenium addition to benzyne via a SET (single electron transfer).     

Reactions of β-methoxyvinyl trifluoromethyl ketones with 2-pyridinecarboxamidrazone: A convenient route to trifluoromethylated 4,5-dihydro-1H-1-picolinoylpyrazole hydrochlorides

A new series of six 3-aryl-5-hydroxy-5-trifluoromethyl-4,5-dihydro-1H-1-picolinoylpyrazole hydrochlorides were synthesised in one-step in high yields by the reaction of β-methoxyvinyl trifluoromethyl ketones with 2-pyridinecarboxamidrazone in the presence of hydrochloric acid. The hydrochloride salts were easily converted to the respective new series of free trifluoromethylated 4,5-dihydro-1H-1-picolinoylpyrazoles using triethylamine in anhydrous diethyl ether. X-ray structure and NMR data from the pyrazole hydrochlorides are reported.     

Macroheterocycles. 34. Synthesis and enantiomeric selectivity of chiral azacrown

Chiral azacrown ethers were obtained by the condensation of (4S,5S)-4,5-ditosyl-oxymethyl-2,2-dimethyl-1,3-dioxolane with 6-benzyl-3,9-dioxa-6-azaundecane-1,11-diol. Their debenzylation and deacetalization were realized. The enantiomeric selectivity in the complex formation between the obtained crown ethers and the hydrochlorides of L- and D-valine methyl esters was determined by a potentiometric method. The chiral azacrown ethers exhibit higher enantioselectivity than their oxygen analogs.See [1] for Communication 33.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 687–691, May, 1988.     

Cyclic isothioureido compounds. II. Reaction of trans-3a,4,5,9b-tetrahydronaphth[1,2-d]-imidazoline-2-thiones with α-bromoketones

The reaction of trans-3a,4,5,9b-tetrahydronaphth[1,2-d]imidazoline-2-thiones ( 8 ) with α-bromoketones gave, depending upon the structure of the α-bromoketones, reaction solvent and reaction temperature, the hydrobromides of tetrahydronaphth[1,2-d]imidazolin-2-ylthiomethyl ketone ( 10 ), hexahydro-8-hydroxynaphth[1′,2′:4,5]imidazo[2,1-b]thiazoles ( 5, 11, 19 and 20 ) or tetrahydronaphth[1′,2′:4,5]imidazo[2,1-b]-thiazoles ( 12 and 16 ). Structural determinations based on ir and nmr spectroscopies are discussed.     

A Novel and Expedient Synthesis of 7‐Pyrimidinylpyrimido[4,5‐d]pyrimidinones

A novel and efficient procedure for the synthesis of new 7‐pyrimidinylpyrimido[4,5‐d]pyrimidinone derivatives was elaborated via the base‐promoted cyclodimerization reaction of 5‐[(dimethylamino)methylidene]‐6‐iminopyrimidine‐2,4(1H,3H)‐dione hydrochlorides. In an analogous manner, a 2‐thioxo analog was prepared starting with the corresponding 2‐thioxopyrimidin‐4‐one.     

Neue Tetrathiocyanato-Diamin-Chromiate mit Naphthylaminen

New Tetrathiocyanato Diamin Chromiates with Naphthylamines Substitution reactions of anhydrous K₃[Cr(NCS)₆] with α- and β-naphthyl- amine without applying of solvents were carried out. The formulae of the new positionisomer complex anions were established with a series of double decomposition reactions with the hydrochlorides of some heterocyclic N-bases and cobalt(III) amines. From spectroscopical investigations -UV and UR) some structural problems are resolved.     

Synthesis of β-Aminoketones of the Adamantane Series

4-(1-Adamantyl)-1-aminobutan-3-one hydrochlorides were synthesized by the Mannich reaction of (1-adamantyl)acetone with paraformaldehyde and secondary amine hydrochlorides (diethylamine, dibenzylamine, piperidine). Analogous reactions of 1-adamantyl(methyl)amine with acetone, p-hydroxyacetophenone, and methyl 2-thienyl ketone gave 1-[(1-adamantyl)methylamino]propan-3-one hydrochlorides.     

6,8-Dimethylpyrimido[4,5-c]pyridazine-5,7(6H,8H)-dione: new heterocyclizations based on SN-methodology. Unexpected formation of the first iso-π-electronic analogue of the still unknown dibenzo[a,o]pycene

N₍₂₎-Oxide and 3-amino derivatives of 6,8-dimethylpyrimido[4,5-c]pyridazine-5,7(6H,8H)-dione have been shown to react with primary alkylamines in the presence of an oxidant to produce condensed imidazolines or imidazoles. Both conversions based on S_N^H-strategy represent a new approach to imidazoline-(imidazole-)ring annulation. Heterocyclic analogues of the still unknown dibenzo[a,o]pycene were obtained as a by-products of the above transformations upon using of cyclohexylamine.     

Synthesis and Enantiomeric Selectivity of Chiral Crown Ethers

Condensation of (4S,5S)-4,5-dihydroxymethyl-2-substituted dioxolanes with polyethylene glycols ditosylates yielded new chiral crown ethers. By potentiometry the enantioselectivity of complexing between the compounds obtained and L- and D-valine methyl ester hydrochlorides was evaluated.     

Synthesis and Biological Activity of β-Aminoketones,Secondary Aminopropanols and Oximes of 2-Aminothiophene Series

Russian Journal of General Chemistry - The reactions of substituted 3-dietliylaminopropan-1-ones hydrochlorides with 2-amino-6-(H, alkyl)-4,5,6,7-tetrahydrobenzo[b]thiophene-3-carbonitriles and...     

Preparation and Reactions of Pyridinium Ylids via Decarboxylation of Pyridinium Betaines

Ylids are charged organic compounds with characters differ from regular organic compounds1. Nitrogen ylids, due to their instabilities, are not studied as vastly as phosphorus or sulfur ylids2. Nitrogen ylids are generally obtained by removing proton of the quaternary nitrogen salts with base3,4. In this work, we tried to study the generation of pyridinium ylids 4 via decarboxylation process in neutral condition and study the related reactions with electrophiles. The precursor of pyridiniu…     

Three-component condensation of 4-aminoisothiazole derivatives with aldehydes and Meldrum’s acid. Synthesis of 6,7-dihydro-4H-isothiazolo[4,5-b]pyridin-5-ones

A convenient method was developed for the synthesis of previously unknown substituted 6,7-dihydro-4H-isothiazolo[4,5-b]pyridin-5-ones based on the three-component condensation of 4-aminoisothiazole hydrochlorides, Meldrum’s acid, and aromatic aldehydes.     

Convenient Synthesis of Some Novel Pyridazinone‐Bearing Triazole Moieties

The chemoselective reactions of 2‐(5‐mercapto‐4‐phenyl‐4H‐[1,2,4]triazol‐3‐ylmethyl)‐6‐p‐tolyl‐4,5‐dihydro‐2H‐pyridazin‐3‐one ( 3 ) with different electrophiles were evaluated. Triazole 3 reacted with alkyl halides in the presence of triethylamine in alcohol to give the corresponding S‐substituted derivatives. On the basis of S‐chemoselective reactions of triazole 3 , a series of amino acid 10a – d and dipeptide derivatives 12a – d were prepared via azide coupling of the corresponding hydrazides 9 and 15 with amino acid ester hydrochlorides, respectively. N‐Substituted triazoles 6a – c or 7a – d attached to pyridazin‐3‐one moiety were successfully formed by the reaction of 3 with activated acrylic acid derivatives or with amines. Antibacterial activities of the synthesized derivatives were investigated through correlation with Escherichia coli FabH inhibitory activities using molecular modeling docking software. The antimicrobial activity of synthesized compounds was evaluated, showing best inhibition zone for N‐substituted carboxylic acid 5a and N‐substituted nitrile 5c parallel to the molecular modeling studies.     

Synthesis of N6-phosphorylated sydnone imines and their functionalization via 4-Li derivatives. Novel bicyclic sydnone imines

The highly efficient gram-scale method for preparation of up to date hardly available N₆-phosphorylated sydnone imines based on the reaction of sydnone imine hydrochlorides with substituted phosphinate or phosphonate acids chlorides in the presence of a base was elaborated. A possibility of straight deprotonation of sydnone imines with n-BuLi followed by the reaction 4-Li-derivatives thus obtained with electrophiles was demonstrated. Novel representatives of bicyclic sydnone imines fused via 4,5-edge of the oxadiazolium ring were obtained. Also sydnone imines containing both phosphorus and sulfur functionalities were obtained with high yields.     

2-Ethoxy-3,4-dihydroquinoline in the synthesis of 4,5-dihydroimidazo[1,2-a]quinolines

The amination of 2-ethoxy-3,4-dihydroquinoline by phenacylammonium salts has been studied. The products of this reaction are 2-phenacylamino-3,4-dihydroquinoline hydrochlorides and these are converted to 1-aryl-4,5-dihydroimidazo[1,2-a]quinolines by refluxing in aqueous solution with a catalytic amount of HCl.T. G. Shevchenko Teaching Institute, Chernigov 250038. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 946–949, July, 1997.     

Reactions of alkylthiochloroacetylenes with O,N-and S,N-containing bifunctional nucleophiles

Conclusions Reaction of alkylthiochloroacetylenes with N-alkyl-N-(2-hydroxyethyl)amines proceeds with formation of N-alkyl-N-(2-hydroxyethyl) amides of alkylthioacetic acids, and reaction with 2-hydroxyethyl- and 2-mercaptoethylamine results in 2-(alkylthiomethyl)-4,5-dihydro-1,3-oxazoles and the hydrochlorides of alkylthioethynyl(2-aminoethyl) sulfides respectively.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 616–619, March, 1988.     

Synthesis of some sym-triazole derivatives

3,5-Di(hydroxyalkyl) derivatives of 4-amino-1,2,4-triazole and the corresponding derivatives of 1,2,4-triazole obtained by diazotizing them are converted by reaction with SOCl₂ into the hydrochlorides of 4-amino-3,5-di(chloroalkyl)-1,2,4-triazoles and 3,5-di(chloroalkyl)-1, 2,4-triazoles. The dinitrate of 3,5-di(hydroxymethyl)-1,2,4-triazole has been prepared. When the cyanohydrazide of glycolic acid is heated with hydrazine hydrate, 4,5-diamino-3-hydroxymethyl-1, 2,4-triazole is formed.     

Synthesis and transformations of 2-(2-furyl)- and 2-[β-(2-furyl)vinyl]imidazo[4,5-f]quinolines

The corresponding 2-(2-furyl)- and 2-[-(2-furyl)vinyl]imida zo[4,5-f]quinolines were obtained by condensation of 5,6-diaminoquinoline and 5-amino-6-rnethylaminoquinoline with furfural, furylacrolein, and their 5-bromo and 5-nitro derivatives and also with the hydrochlorides of imino esters of furancarboxylic and furylacrylic acids. Alkylation, acetylation, nitration, and substitution of the halogen in the furan ring by a nitro group were studied.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 440–442, April, 1973.