Polyfluorinated hydrazones in organic synthesis

A preparative one-step method for the synthesis of 1,1,1,5,5,5-hexafluoro-4-trifluoromethylpentane-2,3-dione dihydrazone from perfluoro-4-methylpent-2-ene and hydrazine hydrate has been developed. Oxidation of this dihydrazone with bromine in water gives 3-diazo-1,1,1,5,5,5-hexafluoro-4-trifluoromethylpentane-2-one. The same product is obtained from 3-hydrazono-1,1,1,5,5,5-hexafluoro-4-trifluoromethylpentane-2-one under similar conditions.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2039–2041, November, 1994.This work was supported by the Russian Foundation for Basic Research (the project code 94-03-08548).     

Polyfluorinated hydrazones in organic synthesis

Oxidation ofN,N-unsubstituted 1,1,1,5,5,5-hexafluoro-4-trifIuoromethylpentane-2,3-dione bishydrazone with sulfuryl chloride or bromine in CCl₄ gives 1-amino-5-trifluoromethyl-4-(1,1,1,3,3,3-hexafluoroisopropyl)-1,2,3-triazole in high yield. Its structure has been confirmed by X-ray structural analysis.For Part 1 see Ref. 1.Deceased.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No.12, pp. 2465–2467, December, 1995.The work was supported by the Russian Foundation for Basic Research (Project Nos. 94-03-08548 and 94-03-08338) and the International Science Foundation (Grants NDL 000 and NDL 300).     

Preparation,Structure and Thermal Decomposition of Cu(II) Complexes with 2-Chloro- and 2,3-Dichlorobenzoic Acids and Imidazole

The reaction products of Cu(II) 2-chlorobenzoate and imidazole (1), and of Cu(II) 2,3-dichlorobenzoate and imidazole (2) formulated as CuL'₂·3imd and CuL"·3imd (L' = C₇H₄ClO₂, L" = C₇H₄Cl₂O₂ ^?, imd = imidazole), were prepared and characterized by means of structural and spectroscopic measurements and thermochemical properties. The blue (1) and green (2) compounds crystallize in the monoclinic system with space group C2/c, cell parameters a = 20.753(4), b = 8.414(2), c = 14.429(3) Å, β = 90.15(3)°, V = 2519.5(9) &Aringsup3;, Z = 4 for (1) and a = 21.335(4), b = 8.417(2), c = 15.030(3) Å, β = 94.11(3)°, V = 2692.1(10) &Aringsup3;, Z = 4 for (2). The complexes decompose at 483 K.     

Acetylenchemie, 33. Mitt.: Synthese von 2-substituierten Dihydrofuro[2,3-b]chinolinen

Summary The reaction of 3-iodo-4-methoxy-2(1H)-quinolinone (1) and 3-iodo-4,6,8-trimethoxy-2(1H)-quinolinone (2) with 2-methyl-3-butyn-2-ol under modified Heck-conditions gave the 2-substituted derivatives 2-(1-hydroxy-1-methylethyl)-4-methoxyfuro[2,3-b]-quinoline (3) and 2-(1-hydroxy-1-methylethyl-4,6,8-trimethoxyfuro[2,3-b]-quinoline (4). By a subsequent hydrogenation-reaction with a homogeneous catalyst (PtO₂/Rh₂O₃), the furoquinoline-derivatives yielded the dihydrofuro-[2,3-b]quinolines, identified as 2-(1-hydroxy-1-methylethyl-4-methoxy-2,3-dihydrofuro[2,3-b]quinoline (5) (racemic platydesmine) and 2-(1-hydroxy-1-methylethyl)-4,6,8-trimethoxy-2,3-dihydrofuro-[2,3-b]quinoline (6) (racemic precursor of O⁴-methylptelefolonium salt).

     

Synthesis and crystal structures of two new uranyl coordination compounds obtained in aqueous solutions of 1-butyl-2,3-dimethylimidazolium chloride

Abstract

Two new uranyl coordination compounds, [C₉H₁₇N₂]₃[(UO₂)₂(CrO₄)₂Cl₂(H₂O)₂]Cl·5H₂O (1) and (C₉H₁₇N₂)[(UO₂)(C₂O₄)Cl] (2), have been synthesized by adding potassium dichromate (K₂Cr₂O₇) or oxalic acid dihydrate (H₂C₂O₄·2H₂O) solution into an aqueous solution of uranyl nitrate and 1-butyl-2,3-dimethylimidazolium chloride [Bmmim]Cl. [Bmmim]Cl provides the charge balance and Cl ions that coordinate with uranyl ions. The fundamental building units of 1 and 2 are UO₆Cl pentagonal bipyramidal structures. Compound 1 exhibits a graphene-like structure with a system molar ratio of 1:1 for U:Cr and crystallizes in the orthorhombic space group Pbca, with a = 25.644(3) Å, b = 12.996(14) Å and c = 29.198(4) Å. 16-Membered rings are formed by CrO₄^2? and UO₂²⁺ in the crystal structure of 1. Compound 2 crystallizes in monoclinic space group P2₁/n, with a = 10.759(3) Å, b = 11.395(3) Å, c = 14.149(4) Å, β = 102.962(9)° and shows one-dimensional (1D) serrated chains. Within the crystal structures of 1 and 2, C–H_[Bmmim]Cl?O hydrogen bonds are identified. O–H_water?Cl hydrogen bonds are also detected in the crystal structure for 1.     

Zur Reaktion von 4-Alkylaminodihydro-2(1H)-pyridinthionen bzw. -onen mit Ethylmalonsäure-bis-trichlorphenylester

4-Alkylamino-2(1H)-pyridinethiones (1) react with bis-trichlorphenylethylmalonate (3) to give four isomeric products: 5-thioxo-1,6-naphthyridine-2(1H)-ones (4), 7,7-dimethyl-4H-thiopyrano[2,3-b]pyridine-4-ones (6), 2,2-dimethyl-2H-thiopyrano[2,3-b]pyridine-5,7-dioles (7) and 2,2-dimethyl-2H-thiopyrano[2,3-b]pyridine-5(3H)-ones (8). On treatment with alkali the thioxogroup of4 is hydrolyzed and 1,6-naphthyridinediones (5) are formed. Compound5 can also be synthesized by heating the alkylaminopyridones (2) together with3.6 can be hydrolyzed to 2-thioxo-3-pyridylpropylketones (12). On treatment with diluted alkali or conc. acid the aminogroup of7 and8 is hydrolyzed and10 is formed. By heating in 20% NaOH10 is transformed to the dihydroxymercapto-3-pyridylmethylketone (11).

Herrn Prof. Dr.Erich Ziegler mit den besten Wünschen zum 70. Geburtstag gewidmet.     

Facile Iodine(III)-Mediated Approach for the Regioselective Chlorination of 2-Aryl-2,3-dihydro-4(1H)-quinolones

Oxidation of 2-aryl-2,3-dihydro-4(1H)-quinolones (1) with 1.5 equivalents of (dichloroiodo)benzene in dichloromethane at room temperature leads to regioselective chlorination, thereby offering an efficient method for the synthesis of new 2-aryl-6-chloro-2,3-dihydro-4(1H)-quinolones (3).     

One-pot synthesis of chromeno[2,3-b]isoindolo[1,2-e]pyrrole-12,13-dione derivatives by sequential reaction of ninhydrin, 2-aminochromen-4-ones and arylamines

Stirring an equimolar mixture of ninhydrin 1 and 2-aminochromen-4-ones 2 in CH₃COOH at room temperature produced 6a,11a-dihydroxy-6H-chromeno[2,3-b]indeno[2,1-d]pyrrole-11,12(6aH,11aH)-diones 3, which on heating with aromatic amines 6 in acetic acid produced 11b-hydroxy-7-N-arylimino-6H-chromeno[2,3-b]isoindolo[1,2-e]pyrrole-12,13(11bH)-diones 7.     

Oxidative cross-coupling of some 2,6- and N,N-disubstituted aniline derivatives with 4-aminophenol mediated by cerium(IV) ions in aqueous perchloric acid

Summary The mechanism of the oxidation of mixtures of 2,6-dimethylaniline (1), N,N-dimethylaniline (2), 2,6-diethylaniline (3), N,N-diethylaniline (4), N-methylaniline (5), 2,6-difluoroaniline (6), and 2,3,5,6-tetrafluoroaniline (7) with 4-aminophenol (8) by cerium(IV) ions in aqueous perchloric acid has been investigated. The indoaniline salts [O=C₆H₄=N-C₆H₂(R ¹)₂NH(R ²)₂]⁺ClO ₄ ^– (R ¹=H,R ²=CH₃, C₂H₅ orvice versa) are formed as intermediates in the cross-coupling reaction; they undergo oxidation to imino-4-benzoquinone (9) and its corresponding derivatives by cerium(IV) ions in high yields. The mechanism of this process is discussed.

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Durch Cer(IV)-Ionen induzierte oxidative Kreuzkupplung einiger 2,6- und N,N-disubstituierter Anilinderivate mit 4-Aminophenol in wässriger Perchlorsäure

Zusammenfassung Die Oxidation von Mischungen von 2,6-Dimethylanilin (1), N,N-Dimethylanilin (2), 2,6-Diethylanilin (3), N,N-Diethylanilin (4), N-Methylanilin (5), 2,6-Difluoranolin (6) und 2,3,5,6-Tetrafluoranilin (7) mit 4-Aminophenol (8) durch Cer(IV)-Ionen in wässriger Perchlorsäure wurde untersucht. Als Zwischenprodukte der Kreuzkupplungsreaktion treten die Indoanilinsalze [O=C₆H₄=N-C₆H₂(R ¹)₂NH(R ²)₂]⁺ClO ₄ ^– (R ¹=H,R ²=CH₃, C₂H₅ oder umgekehrt) auf. Diese werden durch Cer(IV)-Ionen in hohen Ausbeuten zu Imino-4-benzochinon (9) und seinen entsprechenden Derivaten oxidiert. Der Mechanismus dieses Vorgangs wird diskutiert.

     

Preparation of new 2‐amino‐ and 2,3‐diamino‐pyridine trifluoroacetyl enamine derivatives and their application to the synthesis of trifluoromethyl‐containing 3H‐pyrido[2,3‐b][1,4] diazepinols

The synthesis of a novel series of the intermediates N²(N³)‐[1‐alkyl(aryl/heteroaryl)‐3‐oxo‐4,4,4‐trifluoroalk‐1‐en‐1‐yl]‐2‐aminopyridines [F₃CC(O)CH?CR¹(2? NH?C₅H₃N)] and 2,3‐diaminopyridines [F₃CC(O)CH?CR¹(2‐NH₂‐3‐NH? C₅H₃N)], where R¹ = H, Me, C₆H₅, 4‐FC₆H₄, 4‐CIC₆H₄, 4‐BrC₆H₄, 4‐CH₃C₆H₄, 4‐OCH₃C₆H₄, 4,4′‐biphenyl, 1‐naphthyl, 2‐thienyl, 2‐furyl, is reported. The corresponding series of 2‐aryl(heteroaryl)‐4‐trifluoromethyl‐3H‐pyrido[2,3‐b][1,4]diazepin‐4‐ols obtained from intramolecular cyclization reaction of the respective trifluoroacetyl enamines or from the direct cyclocondensation reaction of 4‐methoxy‐1,1,1‐trifluoroalk‐3‐en‐2‐ones with 2,3‐diaminopyridine, under mild conditions, is also reported.     

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.

     

新型四酰胺杯[4]氮杂冠醚的合成及对阴离子的光化学传感性质研究

合成了一类新型四酰胺杯[4]氮杂冠醚(5a, 5b), 用紫外和荧光光谱研究了主体与阴离子客体之间的识别性能. 主体分子5a或5b加入到对硝基酚氧阴离子的CHCl₃溶液中, 主客体间形成超分子复合物使得客体阴离子423 nm处吸光度降低且溶液从黄色变为无色. 受体5a, 5b与p-NO₂C₆H₄O^－, F^－, 相互作用, 荧光光谱发生变化, 并且对于p-NO₂C₆H₄O^－具有较好的选择性识别能力, 其荧光光谱强度改变强弱的顺序为p-NO₂C₆H₄O^－＞F^－＞H₂PO₄^－>>Cl^－, Br^－, I^－. 荧光光谱滴定的结果经非线性拟合, 结果表明主客体间形成1∶1络合物.     

The reaction of nitroso oxides with olefins: Concerted or nonconcerted addition?

The mechanism of the interaction of nitroso oxides (RNOO) with olefins was studied at MCQDPT2/6-311+G(3df, 2p)//CASSCF(10; 9)/6-311G(d) level of theory. The following reaction channels were considered: (1) (3 + 2)-cycloaddition and nonconcerted biradical addition of nitroso oxide (2) through the terminal oxygen atom and (3) through the nitrogen atom to the C=C multiple bond. It was shown for the cases of (A) cis/trans-HNOO + C₂H₄, (B) cis/trans-HNOO + C₂F₄, (C) cis/trans-PhNOO + C₂H₄, and (D) cis/trans-PhNOO + C₂H₃CH₃ model systems that the typical reaction of nitroso oxides with alkenes was cycloaddition. For olefins with a decreased electron density at the multiple bond, as in system B, a substantial contribution of the one-center mechanism with the formation of biradical intermediates is possible.     

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     

3-Methyl[1,3,4]thiadiazino[2,3-b]quinazolin-6-ones

4H,6H-[1,3,4]Thiadiazino[2,3-b]quinazolin-6-one with a methyl group in position 3 (6a) has been synthesised by the condensation of 3-amino-2-mercapto-3H-quinazolin-4-one (1) with allyl bromide (2) followed by treatment with bromine and subsequent dehydrohalogenation of the brominated product (4) with ethanolic sodium hydroxide. Its isomeric 3-methyl-2H,6H-[1,3,4]thiadiazino[2,3-b]quinazolin-6-one (6b) has also been obtained by condensation of1 and bromoacetone (7) followed by cyclisation of the intermediates (8 or9) with hydrobromic acid or with concentrated sulphuric acid. The structures have been established on the basis of IR and PMR data.

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3-Methyl[1,3,4]thiadiazino[2,3-b]chinazolin-6-one

Zusammenfassung Zur Synthese von 4H,6H-[1,3,4]thiadiazino[2,3-b]chinazolin-6-on (6a) wurde die Kondensation von 3-Amino-2-mercapto-3H-chinazolin-4-on (1) mit Allylbromid mit nachfolgender Behandlung mit Brom und Dehydrohalogenierung des bromierten Produktes4 mit ethanolischer Natronlauge herangezogen. Das zu6a isomere 2H,6H-Produkt6b wurde ebenfalls durch Kondensation von1 mit Bromaceton und nachfolgender Cyclisierung der Zwischenprodukte8 bzw.9 mit HBr oder H₂SO₄ erhalten. Die Strukturen wurden mittels IR und NMR abgesichert.

     

Untersuchungen von Reaktionsmechanismen durch Isotopenmarkierung,VII. Zum Mechanismus der Ringverengung von 2,2-Dichlor-6-methyl-4H-1-thiochroman-3,4-dion

It is shown by use of¹⁴C-labeling that the ring contraction reaction of 2,2-dichloro-6-methyl-4H-1-thiochroman-3,4-dione (1) leads to elimination of C-2 as CO₂. Formation of the 5-methyl-2,3-dihydrobenzo[b]thiophen-2,3-dione (2) is suggested to proceed via hydrolytic opening of the thiolactone-binding in1. recyclisation and subsequent oxidation by unreacted1.

Herrn emer. Univ. Prof. Dr.E. Ziegler zur Vollendung seines 70. Lebensjahres mit besten Wünschen gewidmet.     

Synthesis,crystal structure,and catalytic performance of two 3-D supramolecular compounds: (C7N2H7)3(C7N2H6) · PMo12O40 · 2H2O and (C7N2H7)3(C7N2H6)2 · AsMo12O40 · 3H2O

Two organic–inorganic compounds based on Keggin building blocks have been synthesized by hydrothermal methods, (C₇N₂H₇)₃(C₇N₂H₆)?·?PMo₁₂O_40?·?2H₂O (1) and (C₇N₂H₇)₃(C₇N₂H₆)_2?·?AsMo₁₂O_40?·?3H₂O (2) (C₇N₂H₆?=?benzimidazole). Single-crystal X-ray analysis revealed that 1 crystallized in the triclinic system, P-1 space group with a?=?9.8980(4)?Å, b?=?11.2893(4)?Å, c?=?25.8933(9)?Å, α?=?93.307(2)°, β?=?90.630(2)°, γ?=?108.330(2)°, V?=?2740.68(18)?ų, Z?=?2, R ₁(F)?=?0.0740, ωR ₂(F ²)?=?0.1511, and S?=?1.037; 2 crystallized in the triclinic system, P-1 space group with a?=?12.3353(4)?Å, b?=?13.2649(4)?Å, c?=?20.2878(6)?Å, α?=?95.6630(10)°, β?=?100.1720(10)°, γ?=?99.3940(10)°, V?=?3195.72(17)?ų, Z?=?2, R ₁(F)?= 0.0329, ωR₂ (F ²)?=?0.1236, and S?=?1.088. The two compounds show a layer framework constructed from Keggin-polyoxoanion clusters and benzimidazole via hydrogen bonds and π–π stacking interactions, resulting in a 3-D supramolecular network. Both have high catalytic activity for oxidation of methanol. When the initial concentration of the methanol is 5.37?g?m^?3 in air and the flow velocity is 4.51?mL?min^?1, methanol is completely eliminated at 150°C for 1 (160°C for 2).     

Neue Synthesen und Kristallstrukturen von Bis(fluorphenyl)quecksilber,Hg(Rf)2 (Rf = C6F5, 2, 3, 4, 6‐F4C6H, 2, 3, 5, 6‐F4C6H, 2, 4, 6‐F3C6H2, 2, 6‐F2C6H3)

New Syntheses and Crystal Structures of Bis(fluorophenyl) Mercury, Hg(R_f)₂ (R_f = C₆F₅, 2, 3, 4, 6‐F₄C₆H, 2, 3, 5, 6‐F₄C₆H, 2, 4, 6‐F₃C₆H₂, 2, 6‐F₂C₆H₃) Bis(fluorophenyl) mercury compounds, Hg(R_f)₂ (R_f = C₆F₅, C₆HF₄, C₆H₂F₃, C₆H₃F₂), are prepared in good yields by the reactions of HgF₂ with Me₃SiR_f. The crystal structures of Hg(2, 3, 4, 6‐F₄C₆H)₂ (monoclinic, P2₁/n), Hg(2, 3, 5, 6‐F₄C₆H)₂ (monoclinic, C2/m), Hg(2, 4, 6‐F₃C₆H₂)₂ (monoclinic, P2₁/c) and Hg(2, 6‐F₂C₆H₃)₂ (triclinic, P1) are described.     

Synthese et reactivite d'organomagnesiens perfluores. V.[1] Synthese et identification de nouveaux composes perfluoroalkyles du mercure a chaine longue.

The reaction of mercuric salts HgY₂ or organic mercuric compounds R_HHgX with long chain perfluorinated Grignard reagents R_FMgBr leads to a series of new perfluoroalkyl mercury derivatives with the general formula R_FHgZ (R_F=C₄F₉, C₆F₁₃, C₈F₁₇ ; Z=R_F,R_H,Y with Y = I,Br,Cl, NO₃,OCOCH₃,OCOCF₃).The synthesis of these organomercuric compounds is described, and their spectroscopic properties are reported.     

有机锡9-芴酮-4-甲酸酯的合成、结构及抗癌活性

合成了3个有机锡9-芴酮-4-甲酸酯:三苯基锡9-芴酮-4-甲酸酯[(C₆H₅)₃Sn(C₁₄H₇O₃)](1)、三环己基锡9-芴酮-4-甲酸酯[(C₆H₁₁)₃Sn(C₁₄H₇O₃)](2)和三(2-甲基-2-苯基丙基)锡9-芴酮-4-甲酸酯[(C₆H₅C(CH₃)₂CH₂)₃Sn(C₁₄H₇O₃)](3)。通过元素分析、红外光谱、核磁共振谱(¹H、¹³C和¹¹⁹Sn)、热重分析进行了表征;用单晶X射线衍射方法测定了化合物的晶体结构,并对其进行了量子化学计算和体外抗...