The Reactions of 6-(tert-Butyl)-3-hydrazino-1,2,4-triazin-5(2H)-one with Carbonyl Compounds

The reaction of 6-(tert-butyl)-3-hydrazino-1,2,4-triazin-5(2H)-one with acetone and benzaldehyde yields the corresponding hydrazones. In the presence of thionyl chloride the benzaldehyde hydrazone is converted to 3-(tert-butyl)-6-phenyl-1,2,4-triazolo[4,3-b]-1,2,4-triazin-2(1H)-one and this can also be formed via the acylation of the starting hydrazinotriazinone using benzoyl chloride.     

Easy formation of SNH products in reactions of indoles and pyrroles with 3-aryl-1,2,4-triazin-5(2H)-ones in the presence of tosyl chloride

The reactions of 3-aryl-1,2,4-triazin-5(2H)-ones with indoles and pyrroles in the presence of p-toluenesulfonyl chloride afforded 3-aryl-6-hetaryl-1,2,4-triazin-5(2H)-ones in high yields. The latter are products of the nucleophilic substitution of hydrogen.     

A study of the Claisen rearrangement of 7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one derivatives

Summary The Claisen rearrangement of 7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one (2 a) gave 7-hydroxy-8-(1-phenyl-2-propenyl)-3-phenyl-(4H)-1-benzopyran-4-one (3 a) and 2,3-dihydro-2,6-diphenyl-3-methyl-(7H)furo[2,3-h]-1-benzopyran-7-one (7 a). 2-Methyl-7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one (2 b) afforded4 b and7 b. 8-Methyl-7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one (12) gave only the alkali soluble product 7-hydroxy-8-methyl-6-(1-phenyl-2-propenyl)-3-phenyl-(4H)-1-benzopyran-4-one (13).3 a,4 b, and13 were further cyclized in acidic medium to9 a,10 b, and14 followed by dehydrogenation.This paper is dedicated to Dr. F. M. Dean, Department of Organic Chemistry, Robert Robinson Laboratories, University of Liverpool, Liverpool, U. K., on his retirement     

微波作用下1-苯基-5-[5-(芳胺羰基甲硫基)-4-苯基-1,2,4-三唑-3-甲硫基]四唑的合成及生物活性

采用微波和相转移催化法通过1-苯基-5-(4-苯基-1,2,4-三唑-5-巯基-3-甲硫基)四唑(2)与2-氯乙酰芳胺(3)反应高效、快速地合成了10种尚未见文献报道的1-苯基-5-[5-(芳胺羰基甲硫基)-4-苯基-1,2,4-三唑-3-甲硫基]四唑. 其结构经 IR, ¹H NMR, ¹³C NMR 和元素分析表征. 生物活性实验结果表明, 该类化合物在较低浓度下部分化合物对小麦芽有很好的促进作用.     

The formation of 1,2,4-triazolylimidazolidine-2,4-diones in reactions of 3-aryl-1,2,4-triazin-5(2H)-ones with alkylureas

Recyclization of the addition products of alkylureas to 3-aryl-1,2,4-triazin-5(2H)-ones affording 1,2,4-triazole derivatives was found to occur in Ac₂O.     

Direct introduction of heterocyclic units into porphyrin derivatives

In the reaction with quinazoline and 5-phenyl-1,2,4-triazin-5(2H)-one, 5,10,15,20-tetra(4-methoxyphenyl)porphyrin exhibits nucleophilic properties. In quinazoline excess, C—C coupling occurs at the C=N bond of azines and position 3 of the aryl ring to form 5,10,15,20-tetrakis(3-heteryl-4-methoxyphenyl)porphyrins. Monoheteryl-substituted porphyrin was obtained by the reaction of equimolar amounts of 5,10,15,20-tetra(4-methoxyphenyl)porphyrin and 5-phenyl-1,2,4-triazin-5(2H)-one.     

Synthesis of 4-Amino-6-R-4,5-dihydro-3-phenacylthio-1,2,4-triazin-5-ones and 8H-3-R-7-Aryl-1,2,4-triazino[3,4-b][1,3,4]thiadiazin-4-ones

A study was carried out on the reaction of 4-amino-6-R-2,3,4,5-tetrahydro-3-thioxo-1,2,4-triazin-5-ones with halo ketones in alkaline media to yield 4-amino-6-R-4,5-dihydro-3-phenacylthio-1,2,4-triazin-5-ones, which then convert to 8H-3-R-7-aryl-1,2,4-triazino[3,4-b][1,3,4]thiadiazin-4-ones.     

Conversion of 6-phenylimino-2H-thiopyran-4-amines to 1-phenyl-2,3-dihydro-4(1H)-pyridinones

Summary 6-Phenylimino-3,6-dihydro-2H-thiopyran-4-amines (1) were converted to 1-phenyl-5,6-dihydropyridine-2(1H)-thiones (3). Those were akylated and hydrolyzed, thus yielding 6-methylthio-1-phenyl-2,3-dihydro-4(1H)-pyridinones (5). Finally, the methylthio group was removed withRaney nickel giving the title compounds6. The relative configurations of the formed diastereoisomeric dihydropyridinones have been investigated by NOE measurements.

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Umwandlung von 6-Phenylimino-2H-thiopyran-4-aminen zu 1-Phenyl-2,3-dihydro-4(1H)-pyridinonen

Zusammenfassung 6-Phenylimino-3,6-dihydro-2H-thiopyran-4-amine (1) wurden in 1-Phenyl-5,6-dihydropyridin-2(1H)-thione (3) umgewandelt. Diese wurden alkyliert und zu 6-Methylthio-1-phenyl-2,3-dihydro-4(1H)-pyridinonen (5) hydrolysiert. Zuletzt gelangte man durch selektives Entfernen der Methylthiogruppe mitRaney-Nickel zu den Titelverbindungen6. Die relativen Konfigurationen der gebildeten diastereomeren Dihydropyridinone wurden durch NOE-Messungen aufgeklärt.

     

Study of the Products of Iodocyclization of 4-Allyl-5-phenyl-1,2,4-triazole-3-thione

The interaction of 4-allyl-5-phenyl-1,2,4-triazole-3-thione with iodine proceeds with the formation of a mixture of 6-iodomethyl-3-phenyl-5,6-dihydrothiazolo[2,3-c]-1,2,4-triazole and 6-iodo-3-phenyl-6,7-dihydro-5H-1,2,4-triazolo[3,4-b]-1,3-thiazine. The structures of the cyclization products obtained were established on the basis of the ¹H NMR spectra of their dehydroiodinated derivatives. 6-Methyl-3-phenylthiazolo[2,3-c]-1,2,4-triazole, 3-phenyl-5H-1,2,4-triazolo[3,4-b]-1,3-thiazine, and 3-phenyl-7H-1,2,4-triazolo[3,4-b]-1,3-thiazine are formed on eliminating HI from the cyclization products.     

新型3-取代-6-(4-氯苯基)-7-(1H-1,2,4-三唑-1-基)-1',2',4'-三唑[3,4-b]-1",3",4"-噻二嗪衍生物的合成及抗菌活性

通过3-取代-4-氨基-5-巯基-1,2,4-三唑(3a～3m)和2-溴-2-(1H–1,2,4-三唑-1-基)-4′-氯代苯乙酮(2)的缩合反应, 合成了13个新型3-取代-6-(4-氯苯基)-7-(1H-1,2,4-三唑-1-基)-1',2',4'-三唑[3,4-b]-1",3",4"-噻二嗪衍生物4a～4m. 化合物结构经元素分析, ¹H NMR, IR和MS进行了表征. 抗菌试验表明所合成的化合物对细菌表现出中等程度的抑制活性.     

4,5-dihydro-5,5-dimethyl-3-oxo-3H-1,2,4-triazole-1-oxide. The unpredicted azoxy-regioisomer

Summary 4,5-Dihydro-5,5-dimethyl-3-oxo-3H-1,2,4-triazole (1) is converted to the title azoxy compound4 by peroxytrifluoroacetic acid. The structure assignment of4 is based on an X-ray analysis.Ab initio calculations were employed to rationalize the reaction path leading to the triazole-1-oxide4 and not to the expected regioisomer triazole-2-oxide3.

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4,5-Dihydro-5,5-dimethyl-3-oxo-3H-1,2,4-triazol-1-oxid. Das unerwartete Regioisomere

Zusammenfassung 4,5-Dihydro-5,5-dimethyl-3-oxo-3H-1,2,4-triazol (1) wird mit Trifluorperessigsäure in die Titel-Azoxy-Verbindung4 umgewandelt. Die Strukturzuordnung von4 basiert auf einer Röntgenstrukturanalyse. Mittelsab initio-Rechnungen wird versucht zu erklären, weshalb die Reaktion zum Triazol-1-oxid4 und nicht zum erwarteten regioisomeren Triazol-2-oxid3 führt.

     

Heterocyclic Synthesis Using Nitrilimines,Part 12: Synthesis and Bioactivity of 5-Carboxymethylthio-1,2,4-triazoles

The reaction of 4-amino-5-phenyl-3,5-thiaaza-4-pentenoic acid 3 with various nitrilimines 2 led to the formation of substituted carboxymethylthio derivatives of 1,2,4-triazoles (4a–l) rather than the amino derivatives 5 or imidazole derivatives 6. The spectral data of the synthesized compounds are in full agreement with its molecular structure.     

Reactions of trimethinecyanines of the 1,3-dioxenium series with nucleophiles. The structures of the parent carbocation and of a product of its reaction with methanol

The chemistry and the regioselectivity of alcoholysis, aminolysis, and hydrolysis of symmetrical trimethinecyanine carbenium ions in 4-[3-(2,2-diorganyl-6-phenyl-4H-1,3-dioxen-4-ylidene) prop-1-enyl]-2,2-diorganyl-6-phenyl-1,3-dioxenium perchlorates (4a,b) were investigated. The structures of trimethinecyanine 4,5:4′,5′-bisannelated at the methine chain (3) and of a product of the reaction of nonannelated trimethinecyanine with the methoxide anion were established by X-ray diffraction analysis,¹H NMR spectroscopy, and quantum-chemical calculations (PM3). The nucleophile attacks the mesomeric π-conjugated system of the trimethinecyanine cation selectivily at the C(6) atom of one of the dioxenium fragrments, the second dioxenium ring being deactivated. Alcoholysis affords products of addition of the methoxy group to trimethinecyamines. In the course of aminolysis and hydrolysis, the dioxenium ring that is subjected to the attack eliminates acetone to form 1,3-dioxenylidenepropenylic derivatives of 1,3-enaminoketones and 1,3-ketoenols, respectively. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 521–529, March. 1999.     

4-Phosphoranylidene-5(4H)-oxazolones — A novel synthesis and properties

Summary 4-Phosphoranylidene-5(4H)-oxazolones (2), a hardly known class of phosphorus ylides, were readily prepared from 4-unsubstituted-5-(4H)-oxazolones (1) by treatment with Ph₃P-Br₂, Bu₃P-Br₂, Ph₃P-CCl₄, or Ph₃P-CBr₄ adducts in the presence of triethylamine in CH₂Cl₂ at room temperature in a novel, efficient one-pot procedure. The spectroscopic properties of the ylides are reported and discussed.

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4-Phosphoranyliden-5(4H)-oxazolone — Eine neue Synthese und Eigenschaften

Zusammenfassung 4-Phosphoranyliden-5(4H)-oxazolone, eine sehr wenig bekannte Gruppe der Phosphor-ylide, wurden auf einfache Weise nach einem neuen Eintopfverfahren mit guten Ausbeuten hergestellt. Als Ausgangsverbindungen wurden 4-unsubtituierte-5-(4H)-Oxazolone (1) eingesetzt, die unter der Einwirkung von Addukten wie Ph₃P-Br₂, Bu₃P-Br₂, Ph₃P-CCl₄ oder Ph₃P-CBr₄ in Anwesenheit von Triethylamin in CH₂Cl₂ bei Zimmertemperatur die Titelverbindungen liefern. Die spektroskopischen Eigenschaften der Ylide werden berichtet und diskutiert.

     

Reactions of aroylpyruvic acids withS-methylisothiosemicarbazide hydroiodide and studies of the crystal structures of the reaction products

The reactions ofp-chlorobenzoyl- and benzoylpyruvic acids withS-methylisothiosemicarbazide hydroiodide gave 3-methylthio-6-(p-chlorophenacyl)-2,5-dihydro-1,2,4-triazin-5-one and 6-phenacyl-2,3,4,5-tetrahydro-1,2,4-triazine-3,5,-dione, respectively. The molecular and crystal structures of the compounds synthesized were studied by X-ray diffraction analysis. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 704–708, April, 1998.     

Acetylenchemie, 14. Mitt.: PTC-Umsetzung von 9(10H)-Acridinon mit 3-Chlor-3-phenyl-1-propin und 3-Brom-1-phenyl-1-propin

Summary Reaction of 9(10H)-acridinone (2) with 3-chloro-3-phenyl-1-propyne under PTC conditions affords 1-methyl-2-phenyl-6H-pyrrolo[3,2,1-de]acridin-6-one (1 b), 10-(2-chloro-1-methyl-2-phenyl-ethenyl)-9(10H)-acridinone (4), 10-(3-phenyl-1-propynyl)-9(10H)-acridinone (7), and 10-(4-methylene-2,3-diphenyl-2-cyclobuteneylidenemethyl)-9(10H)-acridinone (5). The structure of the last compound which crystallizes in the triclinic system with the space group , was confirmed by X-ray diffraction. Under the same conditions 10-(3-phenyl-2-propynyl)-9(10H)-acridinone (3) and 10-(3-phenyl-1-propynyl)-9(10H)-acridinone (6) were obtained from 9(10H)-acridinone (2) and 3-bromo-1-phenyl-1-propyne.

     

The (E)/(Z)-ratio in the reaction of 5-(2-aryl-2-oxoethyl)-2-thioxo-4-oxo-1,3-thiazolidines with bromine

Summary 3-Aryl-, 3-benzyl-, and 3H-5-(2-aryl-2-oxoethyl)-2-thioxo-4-oxo-1,3-thiazolidines3a–h react with bromine in acetic acid solution to give mixtures of the respective 5-aroylmethylene (E) and (Z) diastereomeric derivatives5 and6. They contain more than 85% of the (E)-diastereomers along with some pure isomers. The intermediacy of the 5-bromo derivatives4 is proven and a plausible route of the reaction is presented. Structures of compounds3–6 are evidenced by analytical and spectral data.

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Das Verhältnis von (E)- und (Z)-Isomeren bei der Reaktion von 5-(2-Aryl-2-oxomethyl)-2-thioxo-4-oxo-1,3-thiazolidinen mit Brom

Zusammenfassung 3-Aryl-, 3-Benzyl- und 3H-5-(2-Aryl-2-oxoethyl)-2-thioxo-4-oxo-1,3-thiazolidine3a–h reagieren mit Brom in essigsaurer Lösung zu Gemischen der entsprechenden diastereomeren 5-Arylmethylen-Derivate ((E) und (Z))5 und6. Sie enthalten mehr als 85% des (E)-Diastereomeren. Die intermediäre Natur der 5-Brom-Derivate4 wird bewiesen; ein Reaktionsweg wird vorgeschlagen. Die Strukturen der Verbindungen3–6 werden durch analytische und spektroskopische Daten abgesichert.

     

NMR studies of 4(3H)-quinazolinones and 4(3H)-quinazolinethiones

Summary Unambiguous¹H and¹³C NMR assignments for 4(3H)-quinazolinones1–6 and their corresponding 4-thiones7–12 have been made. This resulted in the revision of the previous assignments for the two benzenoid carbons (C-5 and C-8) of quinazolinones1,2,4, and5. Thionation of the nucleophilic amides1–6 has been found to cause a distinct change in the¹³C chemical shift of particularly C-4, but also of those of C-4a, C-5, and C-8a. One-bond and several long range heteronuclear coupling constants for the compounds have also been measured.

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Kernresonanzspektroskopie von 4(3H)-Chinazolinonen und 4(3H)-Chinazolinthionen

Zusammenfassung Die¹H- und¹³C-NMR-Spektren der 4(3H)-Chinazolinone1–6 und ihrer entsprechenden 4-Thione7–12 wurden zugeordnet. Dabei zeigte sich, daß eine frühere Zuordnung der beiden benzoiden Kohlenstoffe (C-5 und C-8) der Chinazolinone1,2,4 und5 falsch war. Ersatz des Sauerstoffs durch Schwefel in den nukleophilen Amiden1–6 führt insbesondere für C-4, aber auch für C-4a, C-5 und C-8a zu einer deutlichen Änderung der chemischen Verschiebung. Heteronukleare Kopplungskonstanten über eine und über mehrere Bindungen wurden bestimmt.

     

The synthesis of 5H-thiazolo[2,3-c][1,2,4]triazine derivatives and substituted 3-(2-acylvinylthio)-1,2,4-triazin-5-ones from 6-methyl-3-thioxo-1,2,4-triazin-5-one, 1-acyl-2-bromoacetylenes,and α-acetylenic ketones. X-ray study of 3-benzoyl-6-methyl-5H-thiazolo[2,3-c][1,2,4]triazin-5-one

3-Acyl-6-methyl-5H-thiazolo[2,3-c][1,2,4]triazines were synthesized by reaction of 1-acyl-2-bromoacetylenes with 6-methyl-3-thioxo-1,2,4-triazin-5-one in methanol in the presence of triethylamine at 20 °C. The structure of 3-benzoyl-6-methyl-5H-thiazolo[2,3-c][1,2,4]triazine was established by X-ray structural analysis. Substituted 3-(2-acetylvinylthio)1,2,4-triazin-5-ones were obtained by the reaction of -acetylenic ketones with 6-methyl-3-thioxo-1,2,4-triazin-5-one under the same conditions. The structures of the new compounds were confirmed by IR,¹H, and¹³C NMR spectroscopy.Deceased.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2971–2975, December, 1996.     

New 1,2,4-triazine-containing podands: synthesis and properties

A method of one-step C-C coupling of 1,5-bis(2,6-dimethylphenoxy)-3-oxapentane (1a) and 1,8-bis(2,6-dimethylphenoxy)-3,6-dioxaoctane (1b) with 3-methylthio- (2) and 3-amino-1,2,4-triazine (3) and 3-aryl-1,2,4-triazin-5-one (6-8) has been described. The reaction of compounds 1a,b with compounds 2 and 3 in the presence of trifluoroacetic acid results in the addition of the dimethylphenoxy group to the unsubstituted C(5) carbon atom of the triazine ring. The reactions of triazinones 6-8 with compounds 1a,b in a mixture of trifluoroacetic acid and organic anhydrides are accompanied by the acylation of the nitrogen atom adjacent to the reaction center and affords bis[(3-R-1-acyl-5-oxo-1,4,5,6-tetrahydro-1,2,4-triazin-6-yl)-2,6-dimethylphenoxy]-3-oxapentane or -3,6-dioxaoctane. The obtained adducts can smoothly be oxidized under mild conditions to form more stable products of nucleophilic hydrogen substitution in the triazine ring. The extraction and transport of Ca²⁺ and Mg²⁺ cations through an organic membrane by the compounds synthesized are discussed.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2210–2215, October, 2004.