Potassium fluoride-promoted reaction of (2-chloro-2-nitroethenyl)benzenes with 1,3-dicarbonyl compounds. A general synthesis of 6,6-dimethyl-2-nitro-3-phenyl-3,5,6,7-tetrahydro-4(2H)benzofuranones and some analogs

A convenient procedure to prepare in good yields 6,6-dimethyl-2-nitro-3-phenyl-3,5,6,7-tetrahydro-4(2H)-benzofuranones starting from (2-chloro-2-nitroethenyl)benzenes and 5,5-dimethyl-1,3-cyclohexanedione in the presence of potassium fluoride is reported. This method also proved efficient with other 1,3-dicarbonyl compounds, and has been successfully extended to 1,3-cyclohexanedione, 2,5-pentanedione, dibenzoylmethane and ethyl acetoacetate.     

Allylsilane and diallylsilane reactions with functionalized ethylene ketals or benzodioxoles

The bis-allylation of ethylene ketal and catechol ketal derivatives of 2,5-hexanedione occurred with a great stereoselectivity. The tetraallylation of bis-catechol ketal derivatives of 2,5-hexanedione and 2-methyl-1,3-cyclohexanedione or the diallylation of 4-phenylbutan-2-one derivatives arise in good yields and these compounds were suitable substrates for ring-closing metathesis leading to 4,4-dialkylcyclopentenes. Condensation of 1,8-bistrimethylsilyl-2,6-octadiene (Bistro) with 4-phenylbutan-2-one catechol ketal derivatives or 2-methylcyclohexan-1,3-dione mono catechol ketal afforded in good yields cyclic and tricyclic products 12 or 23, respectively.     

Electrochemical oxidation of 1,3-diketones in the presence of hydrohalic acid salts

In the presence of a mediator (sodium iodide) acetylacetone dimerizes with the formation of 3,4-diacetylhexane-2,5-dione, with a yield up to 90%. Salts of 2-halosubstituted 1,3-diketones form more highly enolized cyclic 1,3-diketones — 1,3-cyclohexanedione and dimedone under analogous conditions, with a yield up to 90%.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 154–158, January, 1992.     

Multicomponent Synthesis of 2,5-Dioxo- and 4-Aryl-5-oxo-2-thioxo-1,2,3,4,5,6,7,8-octahydroquinazolines

Ten 2,5-dioxo- and 4-aryl-5-oxo-2-thioxo-1,2,3,4,5,6,7,8-octahydroquinazolines have been synthesized in three-component interactions of 1,3-cyclohexanedione or dimedone, urea or thiourea, and substituted benzaldehydes (3-bromo-, 4-bromo-, 4-fluoro-, 4-methoxy-, 3,4-methylenedioxy-, and 3-nitro-). 9-Aryl-4,5-dioxo-1,2,3,4,5,6,7,8-octahydro-9H-xanthenes were also formed in these reactions.     

在离子液体中4-芳基-5-氧代-1,4,5,6,7,8-六氢喹啉-3-羧酸酯的合成

以芳醛、氨基巴豆酸酯和5,5-二甲基-1,3-环己二酮或1,3-环己二酮为原料在离子液体[bmimBF₄]中合成了一系列4-芳基-5-氧代-1,4,5,6,7,8-六氢化喹啉-3-羧酸酯, 该方法具有产率高、环境友好等特点. 产物的结构通过红外光谱和核磁共振氢谱进行表征, 并通过X单晶衍射分析进一步证实产物的结构.     

Synthesis and calming activity of 9-(4-<Emphasis Type="Italic">β</Emphasis>-D-allopyranosyloxyphenyl)-decahydroacridine-1,8-dione derivatives

Seven helicid derivatives containing decahydroacridine-1,8-dione were prepared via the reactions between 1,3-cyclohexanedione or 5,5-dimethyl-1,3-cyclohexanedione and the corresponding Schiff base. The structures of the helicid derivatives were characterized by IR, ¹H NMR, and HR-MS spectrum. The target compounds were evaluated by their hypnotic-sedative activity in vivo. The preliminary bioassay tests showed that some of the compounds had more potent activity than that of helicid.     

A convenient one-pot synthesis of substituted 2-pyrone derivatives

2-Pyrone derivatives were prepared in a one step procedure from readily available (chlorocarbonyl)phenyl ketene and 1,3-diketones such as 2,4-pentanedione, 1,3-diphenyl-1,3-propanedione, 1-phenyl-1,3-butanedione, 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione, 1,3-dimethyl-pyrimidine-2,4,6-trione and ethyl 2,4-dioxopentanoate. A mechanism is presented to account for the formation of the products. This method provides an easy route to prepare 3,4,5,6-tetrasubstituted 2-pyrones in good to excellent yields and in a short experimental time.     

Solid-state radical reactions of 1,3-cyclohexanediones with in situ generated imines mediated by manganese(III) acetate under mechanical milling conditions

Under solid-state conditions, manganese(iii) acetate-mediated radical reactions of 1,3-cyclohexanedione and 5,5-dimethyl-1,3-cyclohexanedione with in situ generated imines proceeded efficiently by mechanical milling at room temperature and good to excellent yields were achieved.     

Phendione and anisylhydroresorcinol in the synthesis of 1,7-phenanthroline derivatives

Condensation of 5-phenyl-1,3-cyclohexanedione and 5-(p-methoxyphenyl)-1,3-cyclohexanedione with 5-quinolylamine and aldehydes of aromatic, heteroaromatic, and cyclohexene series provided new 7-aryl(heteryl, cyclohexenyl)-10-phenyl- or (p-methoxyphenyl)-7,10,11,12-tetrahydro-9H-benzo[b][1,7]phenanthrolin-8-ones containing two asymmetrical atoms C⁷ and C¹⁰. ¹H NMR spectroscopy revealed the presence of diastereomers in the target reaction products.     

氢化喹啉及其芳(杂)环稠合衍生物的合成

通过环己二酮与β-二腈基苯乙烯的Michael加成得到2-氨基-3-氰基-4-芳基-5-氧代-1,4,5,6,7,8-六氢喹啉(1); 4-苯基六氢喹啉(1a)与环己二酮发生胺的加成缩合反应生成2-N-(3-氧代-1-环己烯基)氨基-3-氰基-4-苯基-5-氧代-1,4,5,6,7,8-六氢喹啉(2), 在碱性和氯化亚铜催化下进一步环合成4-苯基-5-氨基-二-(2-氧代环己烷)并[b,g]-1,3-二氢萘啶(3). 芳醛、α-萘胺和环己二酮在乙醇中共回流, 则一锅法完成9-芳基-5,6,7,8,9,10-六氢苯并[c]吖啶酮(4)的合成. 对合成中所涉及的化学反应机理进行了尝试性的讨论. 新化合物1a～4c均经IR, ¹H NMR 及元素分析证明其结构.     

Photochemical Synthesis of 2-Alkylidene-1,3-cyclocalkanediones. Preliminary Communication

Photolysis (λ = 254 nm) of 4-(tert-butyl)-4,6,7,8-tetrahydro-7,7-dimethy-2H-1-benzopyran-2,5(3H)-dione ( 3a ) in t-BuOH affords 2-(2,2-dimethylpropylidene)-5,5-dimethyl-1,3-cyclohexanedione ( 1a ) in 80% yield via homolysis of the lactone O? CO bond and subsequent ketene elimination.     

Reactions of Bisazomethines of the Naphtalene Series with 1,3-Diketones

Bisazomethines prepared from aromatic dialdehydes and 2-naphthylamine were for the first time reacted with the following diketones: 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione, 5-phenyl-1,3-cyclohexanedione, indandione, and 2,2-dimethyl-1,3-dioxane-4,6-dione was studied. The reactions with 1,3-diketones of the cyclohexane series yield benzophenanthridine derivatives. The reactions with indandione, depending on conditions, give either bisarylideneindandiones or bisdihydrobenzo[f]indenoquinoline. As evidenced by the ^13C NMR and IR spectra, in the case of biphenyl-4,4'-dicarbaldehyde bis[N-(2-naphthyl)imine] and 2,2-dimethyl-1,3-dioxane-4,6-dione, 4,4'-bis(3-oxo-1,2,3,4-tetrahydrobenzo[f]quinolin-1-yl)biphenyl is formed.     

Green synthesis of naphtho[2,3-f]quinolin-13-one and naphtho[2,3-a]acridin-1(2H)-one derivatives catalyzed by heteropoly acid supported montmorillonite K-10 clay

Herein, synthesis of a series of naphtho[2,3-f]quinolin-13-one and naphtho[2,3-a]acridin-1(2H)-one derivatives directly by one-pot multi-component reaction of 1,3-dicarbonyl compounds (1,3-indanedione/1,3-cyclohexanedione), 2-aminoantharacene/2-naphthylamine and various substituted aldehydes under solvent-free conditions using heteropoly-11-molybdo-1-vanadophosphoric acid supported on montmorillonite K-10 clay catalyst (10% PVMoK-10) is reported. The successful formation of naphtho[2,3-f]quinolin-13-one and naphtho[2,3-a]acridin-1(2H)-one derivatives was confirmed by various spectroscopic techniques. This study offers a green approach for the synthesis of novel quinolinone derivatives.     

超声辐射下一步法合成2-氨基-3-氰基-4-芳基-7，7-二甲基-5-氧代-5，6，7，8-四氢-4H-苯并[b]吡喃

芳醛、丙二腈和5，5-二甲基-1，3-环己二酮在乙二醇中不加任何催化剂经超 声辐射5-7min得2-氨基-3-氰基-4-芳基-7，7-二甲基-5-氧代-4H-5，6，7，8-四氢 苯并[b]吡喃，产率88％—96％．     

Synthesis of alkyl 4-aryl-2-methyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylates

Reactions of alkyl acetoacetates, aromatic aldehydes, ammonium acetate, and 1,3-cyclohexanedione afford alkyl 4-aryl-2-methyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylates. The structure of compounds obtained was established with the help of IR, ¹H NMR, and mass spectra and by X-ray diffraction analysis.     

Synthesis of N-substituted acridinediones and polyhydroquinoline derivatives in refluxing water

Acridinediones were synthesized by the one-pot Hantzsch condensation of an aromatic aldehyde, 5,5-dimethyl-1,3-cyclohexanedione, and aniline/4-methylaniline in re?uxing water. This method has then been extended to the four-component reaction of an aromatic aldehyde, 5,5-dimethyl-1,3-cyclohexanedione, ethyl acetoacetate and ammonium acetate for the synthesis of polyhydroquinoline derivatives. This is an environmentally friendly and efficient procedure providing good to excellent yields.     

顺（反）-2，4，7-三芳基5-氧代4H-5，6，7，8-四氢苯并吡喃衍生物的合成

在酸或碱怀条件下，5，5-二甲基-1，3-环已二酮和5-芳基-1，3-环已二酮与 查尔酮首先进行Michael加成反应，进而环合为7，7-二甲基-2，4-二芳基-5-氧代- 4H-5，6，7，8-四氢苯并吡喃衍生物和含有两个手性原子的顺和反-2，4，7-三芳 基-5-氧代-4H-5，6，7，8-四氢苯并吡喃衍生物。讨论了反应机理并且通过~1H NMR光谱和NOE差谱确定其产物构型。所合成新的多氢苯并吡喃衍生物的分子结构 均经红外光谱、核磁共振光谱和元素分析予以证实。     

新型树形化合物1,3,5-三-[7-(7-甲基-2,2-二-(2,2-二羟甲基-3-羟基丙氧基羰基)-6,8-二氧杂螺[3.5]-壬基)]苯的合成

以丙酮和甲酸乙酯为原料, 在醇钠的作用下合成了1,3,5-三乙酰基苯(1). 1与二溴新戊二醇在酸的作用下发生缩酮化反应, 制成1,3,5-三-(1-甲基-2,6-二氧杂-4,4-二溴甲基环己基)苯(2). 2与5,5-二甲基-4,6-二氧杂-1,3-环己二酮在乙醇钠的作用下合成了1,3,5-三-[7-(7-甲基-2,2-二-乙氧羰基-6,8-二氧杂螺[3.5]-壬基)]苯(3). 将3在氯仿中与季戊四醇进行酯交换反应得到产物1,3,5-三-[7-(7-甲基-2,2-二-(2,2-二羟甲基-3-羟基丙氧基羰基)-6,8-二氧杂螺[3.5]-壬基)]苯(4). 收率为47.7%. 标题化合物及中间产物使用IR, ¹H NMR和MS或元素分析进行了表征.     

水介质中5-氧代-4-芳基-1,4,5,6,7,8-六氢喹啉-3-羧酸甲酯的合成

在水介质中有三乙基苄基氯化铵(TEBA)存在下, 以芳醛、β-氨基巴豆酸甲酯、5,5-二甲基-1,3-环己二酮(或1,3-环己二酮)三组分混合反应, 一步合成了5-氧代-4-芳基-1,4,5,6,7,8-六氢喹啉-3-羧酸甲酯. 该反应具有操作简单、产率高、环境友好的优点.     

Iodine-catalyzed three-component one-pot synthesis of novel 1,8-dioxo-decahydroacridines derivatives bearing benzene sulfonamide moiety

An efficient synthetic method for 1,8-dioxo-decahydroacridines derivatives bearing the biologically active sulfonamide moiety is described. Aromatic aldehyde reacted with 5,5-dimethyl-1,3-cyclohexanedione and sulfanilamide, with molecular iodine as catalyst, to give 1,8-dioxo-decahydroacridines derivatives in high to excellent yield. The structures of these compounds were established on the basis of elemental (C, H and N) and spectral analysis (¹H NMR, ¹³C NMR, MS and FTIR). All the compounds were tested for their cytotoxic activity in vitro against three human tumor cell lines: human mammary cancer cells (MCF-7), human cervical carcinoma cells (Hela), and human lung cancer cells (A549) by the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay. Most of them showed moderate to potent cytotoxic activity against the tested cell lines. Among them, the most active compound 4e exhibited more efficient activity (10.92 μM) against MCF-7 cells than cisplatin (11.06 μM).