Synthesis of 5-nitro-3,4-dihydropyrimidin-2(1<Emphasis Type="Italic">H</Emphasis>)-ones catalyzed by metal salts. Retro-Henry reaction with formation of <Emphasis Type="Italic">N,N′</Emphasis>-disubstituted ureas

Three-component condensation of α-nitroacetophenone with aromatic aldehydes and urea in the presence of iron(III), cobalt(II), nickel(II), and copper(II) salts as catalyst led to the formation of 4,6-diaryl-5-nitro-3,4-dihydropyrimidin-2(1H)-ones and N-benzoyl-N′-(1-aryl-2-nitroethyl)ureas. The latter were formed as a result of retro-nitroaldol (retro-Henry) reaction of intermediate 4,6-diaryl-6-hydroxy-5-nitro-3,4,5,6-tetra-hydropyrimidin-2(1H)-ones.     

Studies on the synthesis of 2-(2-arylvinyl)thieno[2,3-d]pyrimidines and 5-(2-arylvinyl)triazolothieno[3,2-e]pyrimidines

Synthesis of 2-(2-arylvinyl)thienopyrimidines, by the acid catalyzed condensation of nitriles with thiophene o-aminocarbonyl compounds, the condensation of aldehydes with thiophene o-aminoamides, the base catalyzed condensation of aldehydes with 2-methylthienopyrimidines and by the Wittig condensation of 2-thieno-pyrimidinylmethylphosphonium salts with aldehydes is described. Isomeric 5-methyltriazolothienopyrimidines were found to react, under basic condition, with aldehydes yielding 5-(2-arylvinyl)triazolo[2,3-c]thieno-pyrimidines. While 5-styryltriazolo[4,3-c] isomers resisted acid catalysed isomerization, they were found to isomerize to triazolo[2,3-c]pyrimidines under base catalysis.     

1,2,3,6,7,11b-Hexahydro-4H-pyrimido[2,1-a]isoquinoline-2-ones

The reaction of 1-methyl-3,4-dihydroisoquinolinium salts with acrylamide forms 2-(2-carbamoylethyl)-1-methyl-3,4-dihydroisoquinolinium salts, which are cyclized by the action of bases to form 11b-methyl-1,2,3,6,7,11b-hexahydro-4H-pyrimido[2,1-a]isoquinolin-2-one. Treatment of this compound with iodomethane yields 5, 11b-dimethyl-2-oxo-1,2,3,6,7,11b-hexahydro-4H-pyrimido[2,1-a]isoquinolinium iodide. The 11b-methylpyrimido[2,1-a]isoquinolin-2-one enters into condensation with aromatic aldehydes, forming the corresponding styryl compounds.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 499–502, April, 1993.     

4-Thionazolidones,derivatives and analogs

A hitherto unknown isomer of rhodanine, 4-thiothiazolid-2-one (isorhodanine), is prepared by boiling thiazolidine-2, 4-dione with P₂S₅ in anhydrous dioxane for 3 hr. Isorhodanine I is characterized by great reactivity of the methylene and thione groups. The 4-phenylhydrazone and 4-phenylimino derivatives of I are prepared, as well as condensation products obtained by condensing I with aromatic aldehydes and diazonium salts. 5-Methylisorhodanine is also prepared. A derivative of I containing a quinoline ring is further obtained by reacting I with anthranilaldehyde.For Part II see [2].     

The reaction of diethyl oxalate with some azolidones

The condensation of thiazolidine-2, 4-dione, rhodanine, isorhodanine, 2-thiohydantoin, and pseudothiohydantoin with diethyl oxalate has given products which are azolidone-5-glyoxalic acids or their esters. In these compounds, the glyoxalic acid residue is readily replaced under the action of diazonium salts, aromatic nitroso compounds, and aromatic aldehydes with the formation of 5-arylazo-, 5-arylimino-, and 5-arylideneazolidones. 5-Arylidenerhodanines are also formed from 5-isopropylidene-and 5-(β-acetyl-α-methylethylidene)rhodanines by their reaction with aromatic aldehydes and ketones.     

2-Styryl-4H-1,3-benzoxazin-4-onium salts

A method was developed for the synthesis of 2-styryl-4H-1,3-benzoxazin-4-onium salts by condensation of 2-alkylbenzoxazinonium salts with aromatic aldehydes. It is shown that these same compounds are formed by acid condensation of salicylamides, salicylnitrile, or salicylaldoxime with aromatic aldehydes in acetic anhydride. The hydrolysis and alcoholysis of the synthesized salts were studied.     

Synthesis of higher epoxides by the joint catalytic oxidation of aldehydes and olefins

Conclusions The selective catalytic epoxidation of 1-alkenes by molecular oxygen was accomplished in the presence of C₂-C₅ alipahtic aldehydes and catalysts, viz., the salts of Cu(II), Ni(II), Fe(III), or Zr(IV).Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2269–2272, October, 1985.     

Chemistry of indole

The condensation of salts of 1-methyl-2-aminoindole with aldehydes in excess alkali gives Schiff bases, while salts of 1-methyl-3-arylidene-2-iminoindolines are obtained in the absence of alkali. The latter may give 12-aryl-5,7-dimethylindolo[2,3-b]--carbolines (I) on reaction with excess 1-methyl-2-aminoindole. Dihydro compounds (II) are formed as intermediates.See [1] for communication XXXI.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1368–1373, October, 1972.     

Reactions of substituted furan-2-carboxaldehydes and furo[b]pyrrole type aldehydes with benzothiazolium salts

A series of new push-pull compounds were synthesised by reaction of 5-aryl- furan-2-carboxaldehydes and furo[b]pyrrole type aldehydes with benzothiazolium salts. These new condensation products represent highly conjugated systems that have potential biological activity. The reaction of furo[b]pyrrole type aldehydes with benzothiazolium salts give potential precursors of cyanine dyes.     

2-Methyl-s-triazolo[1,5-b]isoquinolin-5(10H)-one

Acetamidrazone hydrochloride reacts with homophthalic anhydride to give 3-o-carboxybenzyl-5-methyl-1,2,4-triazole 1, which can be cyclised to 2-methyl-s-triazolo[1,5-b] isoquinolin-5(10H)-one 2. Reduction with lithium aluminium hydride gives 5,10-dihydro-2-methyl-s-triazolo [1,5-b] isoquinoline, while condensation with aromatic aldehydes gives 10-arylmethylene derivatives. Coupling with arenediazonium salts gives the 10-arylhydrazones of 5,10-dihydro-2-methyl-s-triazolo [1,5-b] isoquinoline-5,10-diones, while condensation with p-nitrosodimethylaniline gives the 10-imino derivative. Alkylation of 2 produces the corresponding 10,10-dialkyl derivatives.     

Ein neuer zugang zu indeno[1,2-b]pyridinen

A new synthesis of 5H-indeno[1,2-6]pyridines [IV] starting from 4-cyanobutyrophenones [I] or their cyclization products, the 6-phenyl-3,4-dihydropyridin-2-ones [II], is reported. The condensation of I or II in polyphosphoric acid with aromatic or heteroaromatic aldehydes [III] yields 1,2,3,4-tetrahydro-5H-indeno[1,2-b]pyridin-2-ones [IV]. 2,3,4,4a,5,9b-Hexahydro-1H-indeno[1,2-b]pyridines [X, XI] which were previously difficult to obtain can now be easily synthesized from compounds IV.     

The reaction of diethyl oxalate with some azolidones

The condensation of thiazolidine-2, 4-dione, rhodanine, isorhodanine, 2-thiohydantoin, and pseudothiohydantoin with diethyl oxalate has given products which are azolidone-5-glyoxalic acids or their esters. In these compounds, the glyoxalic acid residue is readily replaced under the action of diazonium salts, aromatic nitroso compounds, and aromatic aldehydes with the formation of 5-arylazo-, 5-arylimino-, and 5-arylideneazolidones. 5-Arylidenerhodanines are also formed from 5-isopropylidene-and 5-(-acetyl--methylethylidene)rhodanines by their reaction with aromatic aldehydes and ketones.     

FeCl3-Catalyzed Condensation of 2-Naphthol and Aldehydes under Solvent-Free Reaction Conditions: An Efficient and Green Alternative for the Synthesis of 14-Aryl(Alkyl)-14-H-dibenzo[a, j]xanthenes

An iron‐catalyzed condensation of 2‐naphthol with aldehydes has been described. In the presence of a catalytic amount of iron(III) chloride (5 mol%), the condensation reaction of 2‐naphthol and aldehydes underwent smoothly to generate the corresponding products in good to excellent yields under base‐, acid‐, ligand‐, additive‐, and solvent‐free reaction conditions.     

Thermal properties of complexes of lanthanides(III) and some of d-block elements with 5-chloro-2-methoxybenzoic acid

The thermal properties of 5-chloro-2-methoxybenzoates of lanthanides(III) and Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) were studied in air and nitrogen atmospheres. The complexes were obtained as mono-, di-, tetra- and pentahydrates with a metal to ligand ratio of 1:3 (in the case of lanthanides(III)) and 1:2 (in the case of d-block elements). They have colours typical for Ln³⁺ and M²⁺ ions. All complexes are polycrystalline compounds. When heated they dehydrate to form anhydrous salts which next in air are decomposed to the oxides of the respective metals while in nitrogen to the mixtures of metal oxides, oxychlorides and carbon. This revised version was published online in July 2006 with corrections to the Cover Date.     

A New Route to Mercury-Containing Triphenylphosphonium Salts with Electron-Withdrawing Groups at the P Atom and Some Transformations of These Compounds

(Aroylmethyl)triphenylphosphonium salts react with mercury(II) trifluoroacetate with replacement of the labile methylene hydrogen atom by the HgOCOCF₃ group to give mercury-containing triphenylphosphonium salts in quantitative yields. Treatment of the mercurated salts with potassium carbonate yields mercury-containing triphenylphosphonium ylides of symmetrical and unsymmetrical structures, which enter Wittig reaction with aromatic aldehydes to form the corresponding mercurated olefins (Z isomers) and triphenylphosphine oxide.     

Reaction of 4-R-2-phenyltetrahydrobenzo[b]pyrylium and 9-R-sym-octahydroxanthylium salts with furfural and related compounds

The condensation of furfural, 5-methylfurfural, and 2-thiophenecarbaldehyde with 4-R-2-phenyltetrahydrobenzo[b]pyrylium and 9-R-sym-octahydroxanthylium salts was studied. Condensation conditions under which acidophobic aldehydes of the furan series do not undergo resinification were found. 8-Furfurylidene and 8-thenylidene derivatives of 4-R-2-phenyltetrahydrobenzo[b]pyrylium and bisfurfurylidene and bisthenylidene derivatives of 9-R-sym-octahydroxanthylium salts were obtained for the first time. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1160–1165, August, 2008.     

新型Schiff碱单核配合物的合成及光谱特征

首次报道了新型Schiff碱配合物-双[N,N’-亚乙基-2,2’-(苯亚甲基)二(3,4-二甲基吡咯-5-醛缩亚胺)]合单金属配合物MH_2L[M=Mn(Ⅱ)、Fe(Ⅲ)Cl、Cr(Ⅲ)Cl、Cu(Ⅱ)、Co(Ⅱ)、Ni(Ⅱ)、Zn(Ⅱ)]的合成方法及光谱特征。     

Directions of reactions of 6-amino-, -acetylamino-, and -benzoylaminodeoxyvasicinones with aldehydes

6-Acetylamino- and -benzoylamino-9-arylidenedeoxyvasicinones were synthesized by reaction of 6-amino(3), -acetylamino- (4), and -benzoylamino- (5) -deoxyvasicinones (DOV) with aromatic aldehydes and furfurol in glacial acetic acid. It was shown that the amino group of 6-aminodeoxyvasicinone underwent acylation upon reaction with aldehydes to form 6-acetylamino-DOV, which reacted with aldehydes to form 9-arylidene derivatives. Carrying out this condensation in toluene, o-xylene, and ethanol produced a mixture of condensation products at the 6-amino-and a-CH₂-groups. It was found that condensati on of 3 with 4-nitrobenzaldehyde in pyridine formed exclusively the Schiff bases. Methods for preparing 6-nitrodeoxyvasicinone and for its reduction were improved.     

Fused s-triazino heterocycles. VIII. 1,3,4,6,9b-pentaazaphenalenes. Reactions of a methyl and bromomethyl side chain

Enhanced reactivity of the methyl group of 2-t-butyl-5-methyl-1,3,4,6,9b-pentaazaphenalene allowed acetic anhydride-catalyzed condensation reactions with several aromatic aldehydes, and base-catalyzed alkylation reactions with several alkyl halides to take place, albeit in low yields. Of the many nucleophiles tried, only salts of carboxylic acids, in the presence of 18-crown-6, were able to displace bromine from 2-(bromomethyl)-5-methyl-1,3,4,6,9b-pentaazaphenalene.     

Chemical examination of embelia ribes—VI Synthesis of some new methylene-bisbenzoquinones

By the condensation of 2,5-dihydroxybenzoquinone (I) with various aldehydes (bis-desundecyl)vilangins and anhydrovilangins (II and III), have been synthesized and their properties recorded.