Functional polymers. XXVII: 2[2-hydroxy-4-acryloxy(methacryloxy)phenyl]2H-benzotriazole: Monomers,polymers, and copolymers

2(2,4-Dihydroxyphenyl)2H-benzotriazole has been prepared in about 50% yield by condensation ofo-nitrobenzenediazonium chloride with resorcinol followed by reductive cyclization of the initially obtained azo compound with zinc and sodium hydroxide. The condensation of the diazonium salt had to be carried out under carefully controlled conditions and in acidic medium, otherwise bis-condensation occurred which, after reductive cyclization, yielded 2(2,4-dihydroxyphenyl)1,3-2H-dibenzotriazole. 2(2,4-Dihydroxyphenyl)2H-benzotriazole was allowed to react with acryloyl or methacryloyl chloride. Monoacylation in the 4-position occurred by interfacial acylation technique and 2[2-hydroxy-4-acryloxy (or 4-methacryloxy)]2H-benzotriazole was obtained in over 60% yield. The two monomers were homopolymerized and copolymerized with styrene, methyl methacrylate, andn-butyl acrylate to polymers of high molecular weight. Incorporation of 2[2-hydroxy-4-acryloxy (or 4-methacryloxy)]2H-benzotriazole into the copolymer was from 1 to 10 mol% of the comonomer mixture. The ultraviolet spectra of monomers, homo- and copolymers were also determined.This paper is dedicated to Professor Dr.Karl Schlögl on the occasion of his 60th birthday with our warmest wishes.     

Functional polymers. XII: Synthesis and polymerization of 2(2-vinyl-4-hydroxyphenyl)2H-benzotriazole and 2(3-vinyl-4-hydroxyphenyl)2H-benzotriazole

Condensation of diazotizedo-nitroaniline with 3-ethylphenol or with 2-ethylphenol followed by reduction of the resulting azo compound with zinc dust in sodium hydroxide solution gave 2-(2-ethyl-4-hydroxyphenyl)2H-benzotriazole and 2(3-ethyl-4-hydroxyphenyl)2H-benzotriazole, respectively. The individual compounds were acetylated, brominated withN-bromosuccinimide to the corresponding 1-bromoethyl compounds which were then dehydrobrominated with triethyl amine in acetonitrile and hydrolyzed to 2(2-vinyl-4-hydroxyphenyl)2H-benzotriazole or 2(3-vinyl-4-hydroxyphenyl)2H-benzotriazole. The two monomers could be polymerized and copolymerized with styrene and methyl methacrylate. The ethyl as well as the vinyl compounds and the corresponding polymers, when tested, are ineffective as ultraviolet absorbers as they have structures of 4-hydroxyphenyl rather than 2-hydroxyphenyl compounds with respect to the benzotriazole ring. A careful NMR analysis for the correct structural assignment is also described.Part XI:S. Yoshida andO. Vogl, Makromol. Chem., in press.     

Functional polymers,XL. Syntheses of mono- and di(4-methoxy)benzotriazolesubstituted 2,4-dihydroxyaceto(or benzo)phenones

Eight benzotriazoles and (4-methoxy)benzotriazoles, mono- or di-substituted derivatives of 2,4-dihydroxyaceto(or benzo)phenone were synthesized by azo coupling of (4-methoxy)2-nitrobenzenediazonium chloride with 2,4-dihydroxyaceto(or benzo)phenone followed by reductive cyclization. Pure mono-substituted compounds were very difficult to prepare. Careful selection of thepH for the azo coupling and selection of the proper reagents for the reductive cyclization were essential. All compounds were characterized by their ultraviolet, infrared¹H and¹³C NMR spectra and their elemental analysis. These compounds have both the 2(2-hydroxyphenyl)2H-benzotriazole unit and a 2-hydroxyaceto(or benzo)phenone unit in the same molecule and are effective and useful ultraviolet absorbers.Dedicated to Prof. Dr.K. Komarek, Vienna, on the occasion of his 60^th birthday with best wishes.     

Reaction of 6-methoxybenzo[b]furan-3(2H)-one and benzo[b]thiophen-3(2H)-one with 2-aryl-1,1-dicyanoethylenes as a convenient synthetic route to substituted 2-amino-4-aryl-1,3-dicyano-7-methoxydibenzo[b,d]furans and 2-amino-4-aryl-3-cyano-4H-benzothieno[3,2-b]pyrans

The reactions of 6-methoxybenzo[b]furan-3(2H)-one with 2-aryl-1,1-dicyanoethylenes and malononitrile or with aromatic aldehyde and two moles of malononitrile afford 2-amino-4-aryl-1,3-dicyano-7-methoxydibenzo[b,d]furans. The reactions of benzo[b]thiophen-3(2H)-one with 2-aryl-1,1-dicyanoethylenes or with aromatic aldehyde and one mole of malononitrile produce 2-amino-4-aryl-3-cyano-4H-benzothieno[3,2-b]pyrans.     

Synthesis of partially saturated N-substituted 4H-3,1-benzothiazine-2(1H)-thiones

Summary Acid-catalyzed reaction of 2-arylidenecyclohexanones1 with N-substituted dithiocarbamic acids2 gave open-chain addition products3 and4. Dehydration of3 and4 afforded only one of the three possible isomeric N-substituted 4H-3,1-benzothiazine-2(1H)-thiones5 and6.

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Synthese von partiell gesättigten N-substituierten 4H-3,1-Benzothiazin-2-(1H)-thionen

Zusammenfassung Die säurekatalysierte Reaktion von 2-Arylidencyclohexanonen1 mit N-substituierten Dithiocarbaminsäure2 ergab die offenkettigen Additionsprodukte3 und4. Die Dehydratation von3 und4 führte ausschließlich zu einem der drei möglichen N-substituierten 4H-3,1-Benzothiazin-2(1H)-thion-Isomeren5 und6.

     

聚丙烯酸[2,5-双(对甲氧基苯甲酰氧基)苄酯]及聚甲基丙烯酸[2,5-双(对甲氧基苯甲酰氧基)苄酯]的合成

周其凤等曾报道聚丙烯酸［２,５－双（对甲氧基苯甲酰氧基）节酯］［１］和聚甲基丙烯酸［２,５－双（对甲氧基苯甲酰氧基）苄酯］［２］的合成．但后来的研究发现,在合成单体的条件下出现的一种未见报道的异常反应［３］使产物成分复杂化,因此当时报道的聚合物可能不是聚丙烯酸［２,５－双－（对甲氧基苯甲酰氧基）苄酯］或聚甲基丙烯酸［２,５－双（对甲氧基苯甲酰氧基）苄酯］,而可能是共聚物．针对这一问题,我们重新设计了合成路线以避免发生上述副反应,成功地合成了丙烯酸或ａ－甲基丙烯酸［２,５－双－（对甲氧基苯甲酰氧基…     

Synthesis ofO-methyloximes and nitrones of a series of substituted 4-[2-hydroxy-2-(1H-1,2,4-triazol-1-ylmethyl)cyclohexylidenemethyl]-benzaldehydes and their fungicidal activity

O-Methyloximes and nitrones of a series of substituted 4-[2-hydroxy-2-(1H-1,2,4-triazol-1-ylmethyl)cyclohexylidenemethyl]benzaldehydes have been synthesized, and their fungicidal activity has been assayed. All of them exhibit low fungicidal activity in thein vitro assays and high activity in thein vivo assays; theO-methyl oximes are more active than the corresponding nitrones.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2082–2087, December, 1993.     

Synthesis of amino-substituted 1,3-bis(tert-butyl-NNO-azoxy)benzenes 2.* 2-amino and 2,4-diamino derivatives

Oxidation of one of the amino groups of 2-bromo-4,6-dichloro-1,3-phenylenediamine to the nitroso group followed by its conversion into thetert-butyl-NNO-azoxy group afforded a derivative ofm-(tert-butyl-NNO-azoxy)aniline,viz., 2-bromo-3-(tert-butyl-NNO-azoxyl)-4,6-dichloroaniline. Analogously, the second amino group was converted into thetert-butyl-NNO-azoxy group to form a derivative of 1,3-bis(tert-butyl-NNO-azoxy)benzene,viz., 3-bromo-2,4-bis(tert-butyl-NNO-azoxyl)-1,5-dichlorobenzene The reaction of the latter with ammonia yielded 2-amino- and 2,4-diamino-substituted 1,3-bis-(tert-butyl-NNO-azoxyl)benzenes. For Part 1, see Ref. 1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2126–2130, November, 1999.     

Reactions of cyclic 1,3-dicarbonyl compounds with 1,2(1,4)-dihydro-1-methyl-2(4)-methylene-N-heterocycles. A new access to 6,12-methano-dibenz[d,g]-[1,3]oxazocinones

Summary The enamine-type methylene-N-heterocycles1–5 react with cyclic 2-ethoxymethylene-1,3-dicarbonyl compounds6 to give 2-[2-(hetarylidene)ethylidene]-1,3-dicarbonyl compounds7–14. The result of the reactions between 1,2-dihydro-1-methyl-2-methylene-quinoline (1a) and cyclic 1,3-dicarbonyl compounds depends on the nature of the dihydro intermediatesA/B. Dehydrogenation of keton intermediatesA results in 2-(1,2-dimethyl-4(1H)-quinolylidene)-1,3-dicarbonyl compounds17–21. Enol intermediatesB with 6-membered dicarbonyl ring form 6,12-methano-dibenz-[d,g][1,3]oxazocinones22–25.¹H NMR spectra and X-ray structure analysis prove the structure of23.

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Reaktionen cyclischer 1,3-Dicarbonylverbindungen mit 1,2(1,4)-Dihydro-1-methyl-2(4)-methylen-N-heterocyclen. Ein neuer Zugang zu 6,12-Methano- dibenz[d,g][1,3]oxazocinonen

Zusammenfassung Aufgrund ihres Enamincharakters reagieren die Methylen-N-heterocyclen1–5 mit cyclischen 2-Ethoxymethylen-1,3-dicarbonylverbindungen6 zu den 2-[2-(Hetaryliden)ethyliden]-1,3-dicarbonylverbindungen7–14. Das Ergebnis der Reaktionen zwischen 1,2-Dihydro-1-methyl-2-methylen-chinolin (1a) und cyclischen 1,3-Dicarbonylverbindungen hängt von der Natur der zwischenzeitlich entstehenden DihydroverbindungenA/B ab. Die Intermediat-KetoneA gehen durch Dehydrierung während der Reaktion in die 2-(1,2-Dimethyl-4(1H)chinolyliden)-1,3-dicarbonylverbindungen17–21 über. Die Intermediat-EnoleB mit sechsgliedrigem Dicarbonylring bilden in intramolekularer Reaktion die 6,12-Methano-dibenz[d,g][1,3]oxazocinone22–25, deren Struktur am Beispiel der Verbindung23 durch¹H-NMR sowie durch Röntgenkristallstrukturanalyse bewiesen wird.

     

Synthesis,characterization and thermal analysis of [Fe(N2H4)2(CH3COO)2]

[Fe(N₂H₄)₂(CH₃COO)₂] was synthesised and characterized for the first time by chemical analysis, magnetic measurements, electronic and IR spectral studies. Its thermal reactivity was ascertained by thermogravimetric (TG) and derivative thermogravimetric (DTG) techniques and it has been concluded that unlike some other metal carboxylate hydrazinates, it does not show any autocatalytic behaviour. The decomposition was also subjected to kinetic analysis using the equations of Coats-Redfern and Horowitz-Metzger by the method of weighted least-squares.     

Synthesis of 2-thio derivatives of 4-phenyl-9H-pyrimido[4,5-b]indole

The reaction of 3-benzylidene-2-ethoxyindolenine tetrafluoroborate with thiourea gives a mixture of 4-phenylpyrimido[4,5-b]indole-2(1H)-thione, its 3,4-dihydro derivative, and the corresponding disulfide, the product ratio depending on the reaction conditions. A number of transformations of the resulting compounds, in particular, those giving 2-alkylthio pyrimidoindole derivatives are described. Dedicated to the memory of Academician V. A. Koptyug on the occasion of the 75th anniversary of his birth. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1032–1037, June, 2006.     

Synthesis of 2-oxazolidinones from (1S,2S)-2-amino-1-(4-nitrophenyl)-1,3-propanediol

A series of isomeric 2-oxazolidinones has been synthesized from (1S, 2S)-2-amino-1-(4-nitrophenyl)-1,3-propanediol. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 579–584, April, 2006.     

Reactions with pyrrolidine-2,4-diones,II: New approaches to the synthesis of substituted 5,6-dihydropyrrolo[3,4-d][1,2,3]triazol-4(2H,4H)ones

Summary Approaches leading to 5,6-dihydro-5,6-diphenyl-2-substituted-pyrrolo[3,4-d][1,2,3]-triazol-4(2H,4H)-ones (10) are described. The first approach consists of cyclodehydrating 3(or 4)-hydroxyimino-1,5-diphenyl-4(or 3)-(4-substituted phenylhydrazono)pyrrolidin-2-ones (4,7) with boiling acetic anhydride. The second approach involves cyclization of 3(or 4)-acetoxyimino-1,5-diphenyl-4(or 3)-(4-substituted phenylhydrazono)pyrrolidin-2-ones (8,9) with elimination of acetic acid upon treatment with sodium hydroxide.Part of the work has been presented at the 8^th International Congress of Heterocyclic Chemistry (August 1981), Graz, Austria     

Synthesis and antimicrobial activity of some 2-alkyl-2H-1,4-benzothiazin-3(4H)-ones and 2-alkylbenzo[d]imidazolo[2,1-b]-thiazolidin-3-ones

Summary Sodium 2-aminothiophenoxide (1) reacts with ethyl 2-bromoalkanoates (2) under direct cyclization to form 2-alkyl-2H-1,4-benzothiazin-3(4H)-ones (3). Reaction of the sodium salt of 2-mercaptobenzimidazole (4) with2 or 2-bromoalkanoic acids (5) affords only S-alkylated products (6 or7, respectively). The cyclization products — 2-alkylbenzo[d]imidazolo[2,1-b]thiazolidin-3-ones (8) — can be obtained only from the corresponding 2-(2-benzimidazolylthio)alkanoic acids (7) by the action of acetic anhydride. Both compounds3 and8 exhibit only moderate antimicrobial activity against some gram-positive bacteria.

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Synthese und antimikrobielle Wirkung von einigen 2-Alkyl-2H-1,4-benzothiazin-3(4H)-onen und 2-Alkylbenzo[d]imidazolo[2,1-b]thiazolidin-3-onen

Zusammenfassung Bei der Reaktion von Natrium-2-aminothiophenolat mit 2-Bromoalkansäure-ethylestern (2) entstehen als Cyclisierungsprodukte 2-Alkyl-2H-1,4-benzothiazin-3(4H)-one (3). Die Umsetzung von Natriumbenzimidazol-2-thiolat mit2 oder mit 2-Bromoalkansäuren (5) liefert nur S-Alkylierungsprodukte (6 oder7). Die Cyclisierungsprodukte — 2-Alkylbenzo[d]imidazolo[2,1-b]thiazolidin-3-one (8) — sind nur durch Umsetzung von entsprechenden 2-(2-Benzimidazolylthio)-alkansäuren (7) mit Acetanhydrid erhältlich. Die Verbindungen3 und8 weisen nur mäßige antimikrobielle Wirkung gegen einige gram-positive Bakterien aus.

     

Tautomerism of 1,2,4-triazino[2,3-a]benzimidazol-5(4)H-3-ones

Studies by X-ray diffraction and quantum chemical methods demonstrated that 1,2,4-triazino[2,3-a]benzimidazol-5(4)H-3-ones exist in the condensed state primarily in the 5H-tautomeric form, whereas these compounds exist, most likely, predominantly as 4H tautomers in the gas phase. The low-barrier tautomerism of 1,2,4-triazino[2,3-a]benzimidazol-5(4)H-3-ones occurs through the intermediate formation of hydrogen-bonded cyclic dimers followed by the concerted two-proton transfer. N-Alkylation of both the electroneutral and N-anionic forms of 2-methyl-1,2,4-triazino[2,3-a]benzimidazol-5(4)H-3-one affords predominantly N(4)-alkyl derivatives. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 475–483, March, 2006.     

A novel heterocyclic system — dihydro-2H-1,5,2,4-dioxadiazine. 2,4-Dimethyldihydro-2H-1,5,2,4-dioxadiazine hydrochloride: synthesis and NMR study

The first representative of a novel heterocyclic system, namely, 2,4-dimethyldihydro-2H-1,5,2,4-dioxadiazine hydrochloride, was synthesized.     

1,3-bis(2,4,6-trinitrophenylaminooxy)propane and its 4-cyano-2,6-dinitrophenyl congener: Synthesis and properties

Starting from N-hydroxyphthalimide (5) and 1,3-dibromopropane (6) we obtained 1,3-bis(phthalimidooxy)propane (7) which led to 1,3-bis(aminooxy)propane dihydrochloride (8). From its reaction with picryl chloride or 4-cyano-2,6-dinitrochlorobenzene, the two title compounds (4b, 4a) were obtained. ¹H-NMR and ¹³C-NMR spectra are presented. For comparison with the analogous N-methoxy-2,6-dinitro-4-R-anilines 1a, 1b (R=CN or R=NO₂), wer report the hydrophobic characteristics (by RPTLC), electronic spectra for the neutral compounds and their anions, pK _a values, and the behavior towards oxidizers (DPPH, PbO₂, Pb(CH₃COO)₄, KMnO₄ and Ag₂O); DPPH converts compounds 1a, 1b and 4a, 4b into betainic structures 2a, 2b respectively.     

Efficient Synthesis of Novel 3-[5-(1H-Benzimidazol-2-Ylmethanesulfonyl)-4-Phenyl-4H-(1,2,4)Triazol-3-Yl]-1H-(1,8)Naphthyridin-4-One Derivatives

Abstract

of 1,4-dihydro-4-oxo-1,8-naphthyridine-3-carbohydrazide (4) with substituted phenyl isothiocyanates (5) in ethanol under reflux for 30 min gave thiosemicarbazide derivatives 6, which on cyclization in 2N NaOH under refluxing conditions for 1 h resulted in 3-(5-mercapto- 4-phenyl-4H-1,2,4-triazol-3-yl)-1,8-naphthyridin-4(1H)-one (7). Alternatively, 7 could also be prepared from following sequence of reactions, i.e., 4 → 8 → 7. In another sequence of reactions, condensation of 7 with chloroacetic acid in dimethylformamide (DMF) and K₂CO₃ as a mild base at 120 °C for 2 h resulted in 2-((5-(1,4-dihydro-4-oxo-1,8-naphthyridin-3-yl)-4-phenyl-4H-1,2,4-triazol-3-yl)sulfanyl)acetic acid (10). The latter, on reaction with substituted o-phenylenediamine (11) in 6N HCl for 4 h yielded 3-(5-((1H-benzo[d]imidazol-2-yl)methylthio)-4-phenyl-4H-1,2,4-triazol-3-yl)-1,8-naphthyridin-4(1H)-one (12). Alternatively, 12 could also be prepared by reacting 7 with 13 in DMF and K₂CO₃ as a mild base at 120 °C for 2 h, followed by oxidation with H₂O₂ resulting in the corresponding sulfonyl derivatives 14.     

Some chemical properties of 2,3-dihydro-4H-[1,3]thiazino[3,2-a]benzimidazol-4-one and 2-aryl-2,3-dihydro-4H-[1,3]thiazino[3,2-a]benzimidazol-4-ones

We have studied the reaction of 2,3-dihydro-4H-[1,3]thiazino[3,2-a]benzimidazol-4-one and 2-aryl-2,3-dihydro-4H-[1,3]thiazino[3,2-a]benzimidazol-4-ones with amines, alkylating reagents, and hydrogen peroxide. We have shown that the presence of an aryl substituent at the 2 position of [1,3-thiazino[3,2-a]benzimidazol-4-ones has a substantial effect on the direction of the reactions. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 445–452, March, 2006.     

1,1-Dichloro-2,2,2-trihaloethyl Isocyanates and N-(1-Chloro-2,2,2-trihaloethylidene)urethanes in the Synthesis of 4-Trihalomethyl-2H-1,3-benzoxazin-2-ones

4-Trihalomethyl-2H-1,3-benzoxazin-2-ones have been synthesized by the reaction of 1,1-dichloro-2,2,2-trihaloethyl isocyanates or N-(1-chloro-2,2,2-trihaloethylidene)urethanes with 3-dialkylamino(alkoxy)phenols. The character of the products from the addition of nucleophiles has been shown to depend on the nature of the nucleophile and the trihalomethyl group.