1-(2-Quinoxalyl)-, 1-[3,5-Di(trifluoromethyl)phenyl]-, 1-(2-Carboxyphenyl)-, and 1-Ethoxycarbonyl-4-oxo-4,5,6,7-tetrahydroindazoles

The corresponding 1-(2-quinoxalyl)-, 1-[3,5-di(trifluoromethyl)phenyl]-, and 1-ethoxycarbonyl-3-methyl-4-oxo-4,5,6,7-tetrahydroindazoles have been obtained from reactions of 2-acetyl-1,3-cyclohexanedione, its 5,5-dimethyl and 5-(2-furyl) derivatives, with 2-hydrazinoquinoxaline, 3,5-di(trifluoromethyl)phenylhydrazine, and ethoxycarbonylhydrazine. On interaction with ethoxycarbonylhydrazine the intermediate 2-[1-(-ethoxycarbonyl)hydrazino]ethylidene-1,3-cyclohexanediones were also isolated. From the potassium salt of 2-formyldimedone and 2-carboxyphenylhydrazine hydrochloride, 2-(2-carboxyphenyl)hydrazinomethylene-5,5-dimethyl-1,3-cyclohexanedione was obtained, the cyclization of which in ethanol in the presence of HCl led to 1-(2-carboxyphenyl)- and 1-(2-ethoxycarbonylphenyl)-6,6-dimethyl-4-oxo-4,5,6,7-tetrahydroindazole.     

Synthesis of 4- and 6-methyl derivatives of 5,7-dioxo(4h,6h)-1,3-dithiolo[4,5-d]pyrimidine based on methylbarbituric acids,spectroscopic characteristics and acidity constants

We have obtained previously unknown 1-methyl- and 1,3-dimethyl-5-diethylaminothiocarbonylthiobarbituric acids by reaction of sodium diethyldithiocarbamate with 5-phenyliodonium betaines of 1-methyl- and 1,3-dimethylbarbituric acids. Cyclization of these compounds upon heating in conc. H₂SO₄ gives methyl-substituted 5,7-dioxo(4H,6H)-1,3-dithiolo[4,5-d]pyrimidine-2-diethylimmonium hydrosulfates; the derivative of 1-methylbarbituric acid forms a mixture of 4-methyl- and 6-methyl-substituted compounds (21). We isolated perchlorates of 4-methyl- and 4,6-dimethyl-substituted derivatives in pure form. By treatment of the immonium salt with sodium sulfide or selenide, we obtained 4-methyl- and 4,6-dimethyl-5,7-dioxo(4H,6H)-1,3-dithiolo[4,5-d]pyrimidine-2-thiones and 4-methyl-, 6-methyl-, and 4,6-dimethyl-2-selenones. We characterized the isomeric 4- and 6-methyl-substituted selenones by electronic absorption spectra and ionization constants (7.65 and 4.0). The differences in the pK values and in the electronic absorption spectra makes it possible to distinguish the substitution site in N-mono-substituted derivatives of 5,7-dioxo(4H,6H)-1,3-dithiolo[4,5-d]pyrimidine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1526–1533, November, 1993.     

1-(1-Phthalazinyl)- and 1-(4methoxyphenyl)-6,6dimethyl-4oxo-4,5,6,7-tetrahydroindazole

2-(1-Phthalazinylhydrazino)methylene-(IIIa) or 2-(1-phthalazinylhydrazino)ethylidene-5,5-dimethyl-1,3-cyclohexanediones (IIIb) were prepared from 1-hydrazinophthalazine and 2 formyl- or 2-acetyldimedone. Cyclization of IIIb in the presence ofp- TsOH gave 1-(1-phthalazinyl)3, 6, 6-trimethyl-4-oxo-4, 5, 6, 7-tetrahydroindazole. Reaction of 4-methoxyphenylhydrazine with 2 formyl- and 2-acetyidimedone gave the corresponding 1-(4methoxyphenyl)-4-oxo-4, 5, 6, 7-tetrahydroindazole. In the case of 2 -formyldimedone the intermediate 2-(4methoxyphenylhydrazinomethylene)-5, 5-dimethyl-1,3-cyclohexanedione was isolated.Riga Technological University, Riga LV-1658. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 708–710, May, 1996. Original article submitted December 31, 1995.     

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.     

2-[2-(2,3-Dihydrobenzimidazolylidene)]- and 2-[2-(2,3-Dihydropyrido[2,3-d]imidazolylidene)]-5,5-dimethyl-1,3-cyclohexanediones

The reaction of 2-aminocarbonyl-5,5-dimethyl-1,3-cyclohexanedione with 2,3-diaminopyridine, 1,2-phenylenediamine (and its 4-methyl, 4-nitro, 4-carboxy, and 4-benzoyl derivatives), and 3,3-diaminobenzidine gave the corresponding 2-[2-(2,3-dihydrobenzimidazolylidene)]- and 2-[2-(2,3-dihydropyrido[2,3-d]imidazolylidene)]-5,5-dimethyl-1,3-cyclohexanediones. Their structure was confirmed by ¹H NMR spectroscopic data and X-ray analysis.     

3-acyl-1,5-benzodiazepines in the reactions of 5,5-dimethyl-2-formylcyclohexane-1,3-dione with certain 1,2-diaminobenzenes

Reaction of 5,5-dimethyl-2-formylcyclohexane-1,3-dione with 4-methyl-, 4-benzoyl-, and 4-nitro-1,2-diaminobenzenes gave the corresponding 2-(2-amino-4-methylphenylaminomethylene)-, 2-(2-amino-5-benzoylphenylaminomethylene)-, and 2-(2-amino-5-nitrophenylaminomethylene)-5,5-dimethylcyclohexane-1,3-diones. When treated with hydrochloric acid, they cyclize to 7-methyl-, 8-benzoyl-, and 8-nitro-3,3-dimethyl-2,3,4,5-tetrahydro-1H-dibenzo[b,e][1,4]diazepinon hydrochlorides. Under hydrolytic conditions the salts of 3,3,7-trimethyl-2,3,4,5-tetrahydro-1H-dibenzo[b,e][1,4]diazepinone and 3,3-dimethyl-2,3,4,5-tetrahydro-1H-dibenzo[b,e][1,4]diazepinone undergo the C₁₁−N₁₀ bond cleavage to give N-(2-aminophenyl)- and N-(2-amino-5-methylphenyl)-substituted 3-amino-2-formyl-5,5-dimethylcyclohex-2-enones. Ring opening of the hydrochlorides of 8-benzoyl-, and 3,3-dimethyl-8-nitro-2,3,4,5-tetrahydro-1H-dibenzo[b,e][1,4]diazepinones occurs at the C−N₅ bond and gives the starting enamines. Riga Technical University, Riga LV-1658, Latvia; Translated from Khimiya Geterotsiklicheskikh Soedinenii, N. 5, pp. 696–700, May, 1999.     

Synthesis and properties of N,N′-bis(1,3-indanedion-2-yl)imidazolium betaine

A method for the synthesis of a new type of onium derivative of 1,3-indanedione — N,N-bis(1,3-indanedion-2-yl)imidazolium betaine — by anhydride condensation of N-(1,3-indanedion-2-yl)-N-carboxymethylimidazolium betaine with phthalic anhydride was developed. The new substance is an acid and forms stable salts.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 771–774, June, 1991.     

Reaction of 5,5-dimethyl-4-cyanomethylene-1,3-oxathiolan-2-one with amines and ammonia

A simple method for the synthesis of 5,5-dimethyl-4-cyanomethylene-2-cyanomethyl-2-[1-methyl-1-(carbamoyloxy)ethyl]-1,3-dithiolanes was developed on the basis of the reaction of 5,5-dimethyl-4-cyanomethylene-1,3-oxathiolan-2-one with amines (primary and secondary) and ammonia.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 335–338, March, 1992.     

Reusable silica-bonded S-sulfonic acid catalyst for three-component synthesis of 2-amino-5-oxo-5,6,7,8-tetrahydro-4H-chromenes and 2-amino-4H-pyrans in aqueous ethanol

Silica-bonded S-sulfonic acid (SBSSA)-catalyzed, facile, one-pot, three-component coupling of 5,5-dimethyl-1,3-cyclohexanedione (dimedone) or 5,5-dimethyl-1,3-cyclohexanedione, aromatic aldehydes, and malononitrile at reflux temperature is described for preparation of 2-amino-5-oxo-5,6,7,8-tetrahydro-4H-chromene derivatives. 2-Amino-3-cyano-6-methyl-4-phenyl-4H-pyran-5-ethylcarboxylate derivatives can also be prepared in good yield under the same experimental conditions by use of ethyl acetoacetate, aldehydes, and malononitrile. The catalyst, silica-bonded S-sulfonic acid, was reused and recycled without any loss of activity or product yield.     

On the oxidation of N-methylpyrimidinium salts

Oxidation of 1,2-dihydro-1,3-dimethyl-2-oxopyrimidinium bisulfate ( 1 ⁺·HSO) with hydrogen peroxide in acetic acid in the presence of potassium iodide gave 1,3-dimethyl-5-iodouracil (65-70%), 1,3-dimethyluracil (10-15%) and 3-methyl-2,4-oxazolidinedione (10-15%). Similar results were obtained on oxidation of the iodide ( 1⁺·I^? ). Oxidation of 1-methyl-4-phenylpyrimidinium iodide or oxidation of 1-methyl-4-phenylpyrimidinium methylsulfate in the presence of potassium iodide gave 1,6-dihydro-5-iodo-1-methyl-6-oxo-4-phenylpyrimidine.     

无外加催化剂条件下芳香醛与活性亚甲基化合物的缩合反应和迈克尔加成反应

在DMF溶剂中，不外加催化剂使芳香醛(1)与2,2-二甲基-1,3-二氧六环-4,6-二酮(2)发生缩合反应生成2,2-二甲基-5-芳亚甲基-1,3-二氧六环-4,6-二酮(3a～f)。在同样条件下，芳香醛与5,5-二甲基-1,3-环己二酮(4)则发生缩合和迈克尔加成反应生成2,2'-芳亚甲基双(3-羟基5,5-二甲基-2-环己烯-1-酮)(5a～h)。用单晶X-射线分析法确定了产物5b的晶体结构。     

Mechanistic studies in the attempted synthesis of 5,5-dimethyl-2-isopropylidene-1,3-cyclohexanedione

In contrast to the corresponding cyclopentanedione derivative, 5,5-dimethyl-2-isopropyl-2-phenylsulfinyl-1,3-cyclohexanedione (3) does not undergo the expected cis-elimination of phenylsulfenic acid on warming in CH₂Cl₂ to afford the title compound 1, but instead gives an equimolar mixture of 5,5-dimethyl-2-(1 ′-isopropyl-4′,4′-dimethyl-2′,6′-dioxocyclohexyl)-2-isopropyl-1, 3-cyclohexanedione (9) and S-phenyl benzenethiosulfonate (10). These products result from dimerization of the 4,4-dimethyl-1-isopropyl-2,6-dioxocyclohexylradical (7) andthephenylsulfinyl radical (8), respectively. Diploma Thesis, University of Hamburg, 1990.     

2-Substituted 5-oxo-5,6,7,8-tetrahydroquinazolines

Twenty novel 2-substituted 5-oxo-5,6,7,8-tetrahydroquinazolines in reactions of 2-formyl-1,3-cyclohexanedione and its 5,5-dimethyl- and 5-phenyl derivatives with 4-chloro- and 4-carbonylaminobenzamidines, 3- and 4-carbamidinopyridines, 2-carbamidinopyrazine, 2-carbamidino-5-trifluoromethylpyridine, 1-carbamidinopyrrolidine, 4-carbamidinomorpholine, and 1-carbamidino-3,5-dimethylpyrazole have been obtained.Riga Technical University, Riga LV-1658, Latvia; e-mail: marina@osi.lv. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 212–26, February, 2000.     

6,6-Dimethyl-4,8-dioxospiro[2.5]octane-1,1,2,2-tetracarbonitrile in the synthesis of heterocyclic compounds of the 2,3-dihydrofuran and 5,6,7,8-tetrahydro-4h-chromene series

6,6-Dimethyl-4,8-dioxospiro[2.5]octane-1,1,2,2-tetracarbonitrile (III), synthesized by the interaction of tetracyanoethylene with 2-bromo-5,5-dimethyl-1,3-cyclohexanedione, reacts with alcohols and ketoximes to form 2-alkoxy-2-(3-alkoxycarbonyl-2,2-dimethylpropyl)-5-amino-3-dicyanomethylene-4-cyano-2,3-dihydrofurans and 2-alkylidenaminoxy-2-(3-alkylidenaminoxycarbonyl-2,2-dimethylpropyl)-5-amino-3-dicyanomethylene-4-cyano-2,3-dihydrofurans. Compound III with triarylphosphines forms 2-(triarylphosphoranilidenamino)-7,7-dimethyl-5-oxo-5,6,7,8-tetrahydro-4H-chromene-3,4,4-tricarbonitriles. Chuvash State University, Cheboksary 428015, Russia. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 170–181, February, 1998.     

A Convenient Synthesis of 3-Aryl-3-(5,5-dimethyl-3-hydroxy-2-cyclohexene-1-one-2-yl) Propanic Esters Catalyzed by KF-Alumina

A series of 3-aryl-3-(5,5-dimethyl-3-hydroxy-2-cyclohexene-1-one-2-yl) propanic esters were synthesized by reaction of aromatic aldehydes, 5,5-dimethyl-1,3-cyclohexanedione and isopropylidene malonate in alcohols catalyzed by KF-Al₂O₃. The structure of 4a was determined by X-ray analysis.     

A facile ZrO<Subscript>2</Subscript> nanoparticles catalyzed synthesis of 2-amino-5-arylpyrimido[4,5-<Emphasis Type="Italic">b</Emphasis>]quinolinediones

In this investigation, an efficient and ecofriendly multicomponent reaction is described for the green synthesis of 2-amino-5-arylpyrimido[4,5-b]quinolinedione derivatives using ZrO₂ (NPs). In this protocol, the reaction of 2,6-diaminopyrimidin-4(1H)-one, arylaldehyde and 1,3-cyclohexanedione or 5,5-dimethyl-1,3-cyclohexanedione in the presence of ZrO₂ (NPs) in ethylene glycol at 120 °C produced the desired products in excellent yields (90–98 %) and short reaction times (8–60 min.). Use of recyclable catalyst, green solvent, easy workup and excellent yields are the notable features of this method.     

Iodocyclization of 2-[allyl(methallyl)sulfanyl]-6-(trifluoromethyl)pyrimidin-4(3<Emphasis Type="Italic">H</Emphasis>)-ones

Iodination of 2-[allyl(methallyl)sulfanyl]-6-(trifluoromethyl)pyrimidin-4(3H)-ones was accompanied by cyclization to 2,3-dihydro[1,3]thiazolo[3,2-a]pyrimidin-4-ium triiodides. 3-(Iodomethyl)-3-methyl- 7-oxo-5-(trifluoromethyl)-2,3-dihydro[1,3]thiazolo[3,2-a]pyrimidin-4-ium triiodide was reduced with sodium iodide to 3,3-dimethyl-7-oxo-5-(trifluoromethyl)-2,3-dihydro[1,3]thiazolo[3,2-a]pyrimidin-4-ium iodide.     

离子液体1-乙基-3-丁基磺酸咪唑对甲苯磺酸盐催化合成氧杂蒽

以1-乙基咪唑为原料,合成了布朗斯特酸性离子液体--1-乙基-3-丁基磺酸咪唑对甲苯磺酸盐(IL1),并将其用于催化芳香醛与5,5-二甲基-1,3-环己二酮或1,3-环己二酮在无溶剂条件下合成了系列氧杂蒽类化合物,其结构经¹H NMR, ¹³C NMR和ESI-MS表征。研究结果表明：当IL1用量为5 mol%,于80 ℃反应40 min,收率78%~95%; IL1循环使用3次,收率86%~89%,催化活性无明显变化。     

Synthesis and properties of 5-(5-nitro-2-furyl)thiazolines

The reactions of 2-amino-4-methyl-5-(5-nitro-2-furyl)thiazole with excess methyl iodide leads to 3,4-dimethyl-2-methylamino-5-(5-nitro-2-furyl)thiazolium iodide, which is converted to 2-imino-3,4-dimethyl-5-(5-nitro-2-furyl)thiazoline under the influence of bases. The iminothiazoline structure was proved by comparison of the spectral characteristics of its acetyl derivative and the isomeric 2-(N-acetyl-N-methyl) amino-4-methyl-5-(5-nitro-2-furyl)thiazole. The pKa values of 2-amino-4-methyl-5-(5-nitro-2-furyl)thiazole and 3,4-dimethyl-2-imino-5-(5-nitro-2-furyl)-thiazoline were determined, and the constant of the aminothiazole-iminothiazoline tautomeric equilibrium was calculated.Translated from Khimiya Geterosiklicheskikh Soedinenii, No. 10, pp. 1337–1340, October, 1985.     

KF-Al2O3催化下3-芳基-3-(5，5-二甲基-3-羟基-2-环己烯-1-酮-2-基)丙酰胺衍生物的合成

芳醛、5，5—二甲基—1，3—环己二酮、丙二酸亚异丙酯、芳胺在KF-Al2O3催 化下，在DMF中反应生成3—芳基—3—(5，5—二甲基—3—羟基—2—环己烯—1— 酮—2—基)丙酰胺衍生物，产率良好。