Synthesis of acridinedione derivatives as laser dyes

Synthesis of 9-alkyl, 10-alkyl, 9,10-dialkyl, and 10-aryl-3,4,6,7,9,10-hexahydro-1,8(2H,5H)acridinedione (2a–r) are described as a new class of laser dyes. Reactions of diamines with methylene bis(cyclohexane-1,3-dione) yielded the respective bisacridinediones (3a–e). These dyes lase around 478–494 nm and are compared with the standard dye coumarin-102. © 1996 John Wiley & Sons, Inc.     

Heterogyclization of triketones of the 2-(3-oxopropyl)-cyclohexane-1,3-dione series

Triketones of the 2-(3-oxopropyl) cyclohexane-1,3-dione series have been shown for the first time to react with boron trifluoride etherate to give the novel 5-oxo-5,6,7,8-tetrahydrochromylium fluoroborates, which in turn react with ammonia to give 5-oxo-5,6,7,8-tetrahydroquinolines. These were also obtained directly from ammonium acetate and 2-(3-oxopropyl)cyclohexane-1,3-diones.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 915–918, July, 1985.     

Synthesis of 2-acyl-4-hydroxycyclohexane-1,3-diones — Kairomones and protective substances of some insects

The synthesis of some derivatives of β-triketones based on a new synthon — 4-hydroxycyclohexane-1,3-dione — is described. Using the proposed scheme, 4-hydroxy-2-(octadec-9Z,12Z-dienoyl)cyclohexane-1,3-dione, a kairomone of some species of Lepidoptera, has been obtained. Institute of Bioorganic Chemistry, Belorussian Academy of Sciences, Minsk. Belorussian State University, Minsk. Translated from Khimiya Prirodnikh Soeinenii, No. 2, pp. 197–203. March–April, 1994.     

Fluorinated 2-benzoylcyclohexane-1,3-diones and their vinylogous acyl chlorides in the reactions with primary and secondary amines

The reaction of 5,5-dimethyl-2-[(3-fluoro- and 4-fluoro)benzoyl]cyclohexane-1,3-diones with primary and secondary amines affords their exocyclic enamine derivatives. Under similar conditions 5,5-dimethyl-2-(2-fluorobenzoyl)]cyclohexane-1,3-dione undergoes dehydrofluorination and intramolecular cyclization to give 3,3-dimethyl-2,3,4,9-tetrahydro-1H-xanthene-1,9-dione. The reaction of vinylogous substitution of the enol derivatives of the fluorinated 5,5-dimethyl-2-benzoylcyclohexane-1,3-diones (vinylogous acyl chlorides) with amines results in the formation of the endocyclic enaminoderivatives.     

Tetrahydrochromenylium and -Thiochromenylium Salts from Triketones of the 2-(3-Oxopropyl)cyclohexane-1,3-dione Series

We have worked out the optimal conditions for synthesis of 2,4-diaryl-5-oxo-5,6,7,8-tetrahydrochromenylium and -thiochromenylium salts based on triketones of the 2-(1,3-diaryl-3-oxopropyl)cyclohexane-1,3-dione series. For the first time, along with 5-oxo-substituted salts, we have obtained 5-thioxo-5,6,7,8-tetrahydrothiochromenylium salts. A necessary condition for the formation of the latter on treatment with acids and S-nucleophiles is the presence of electron-donor groups on the aryl substituents of the indicated triketones.     

Synthesis of exo- and endocyclic enamino derivatives of 2-(3-arylprop-2-enoyl)cyclohexane-1,3-diones

Condensation of 2-acetylcyclohexane-1,3-diones with aromatic aldehydes in the presence of piperidine, pyrrolidine, hexamethyleneimine, or morpholine gave the corresponding 2-(3-arylprop-2-enoyl)cyclohexane-1,3-diones as the major products and 2-[3-aryl-1-cycloalkylaminoprop-2-en-1-ylidene]cyclohexane-1,3-diones as minor ones. Endocyclic enamino derivatives were synthesized in two steps through enol methyl ethers which reacted with amines. Endocyclic enamino derivatives of 2-(3-arylprop-2-enoyl)cyclohexane-1,3-diones containing an aryl group on the nitrogen atom readily underwent cyclization to 1,2,3,4,5,6,7,8-octahydroquinoline-4,5-dione derivatives.     

无溶剂条件下氨基磺酸锂催化合成氧杂蒽化合物

在无溶剂条件下, 芳香醛与 5,5-二甲基-1,3-环己二酮或1,3-环己二酮经氨基磺酸锂催化缩合反应合成了氧杂蒽. 结果表明, 当催化剂用量为3%(摩尔分数)时, 在120 ℃反应 40~70 min, 产率高达 90% 以上. 此外, 探讨了该反应的氨基磺酸锂催化机理. 该合成方法具有操作简单, 反应时间短、 产率高及对环境友好等优点, 是现有氧杂蒽化合物合成方法的一个重要补充.     

Synthesis of 5-(trifluoromethyl)cyclohexane-1,3-dione and 3-amino-5-(trifluoromethyl)cyclohex-2-en-1-one: new trifluoromethyl building block

A simple synthesis of 5-(trifluoromethyl)cyclohexane-1,3-dione and 3-amino-5-(trifluoromethyl)cyclohex-2-en-1-one from the sodium salt of methyl or ethyl-4-hydroxy-2-oxo-6-(trifluoromethyl)cyclohex-3-en-1-oate is demonstrated. The compounds represent highly functionalized reactive intermediates for the synthesis of organic and heterocyclic compounds containing a trifluoromethyl group.     

Envirocat EPZ-10: A Solid Acid Catalyst for the Synthesis of 1,8-Dioxo-octahydroxanthenes in Aqueous Medium

An efficient method for synthesis of 1,8-dioxo-octahydroxanthenes using EPZ-10 as a heterogeneous catalyst is developed. In this method, aldehydes and dimedone / cyclohexane-1,3-dione are heated at 70 °C in the presence of a catalytic amount of EPZ-10 in water as a universal solvent, affording the corresponding 1,8-dioxo-octahydroxanthenes in moderate to excellent yields. Also, domino Knoevenagel / hetero-Michael-addition reaction is described in water without any catalyst with excellent yields. The major advantages of this method are excellent yields, short reaction time, and ease of operation. This green protocol works well with dimedone as well as cyclohexane-1,3-dione.     

A green protocol for catalyst-free synthesis of 1-oxo-hexahydroxanthenes in aqueous medium

An efficient and eco-friendly synthesis of 1-oxo-hexahydroxanthenes has been expediently accomplished by a reaction of salicylaldehyde with cyclohexane-1,3-dione or dimedone in water as universal solvent at reflux condition without a catalyst. Excellent yields of the products, operational simplicity, simple work-up and catalyst-free synthesis are attractive features of this green protocol.     

Homologues of p-Menthane Derivatives in Roman Camomile

5-Isopropyl-2-propyl-2-cyclohexen-1-one ( 1 ) and 5-isopropyl-2-(2-methylpropyl)-2-cyclohexen-1-one ( 2 ), homologues of the p-methene ketone carvotanacetone, have been identified in the oil of Anthemis nobilis. Their synthesis involved allylation of a cyclohexane-1,3-dione, and the acid-catalyzed cyclization to dihydrofurans of the 2-allylcyclohexane-1,3-diones is described. The stereochemistry of metal hydride reduction of 3-ethoxy-5-isopropyl-2-propyl-2-cyclohexen-1-one ( 18 ) is mentioned in the course of the synthesis of the natural products. Some biogenetic considerations are discussed.     

Condensation of 1,3-diketones with 1,8-diaminonaphthalene: Synthesis ofbis(2,3-dihydroperimidine-2-spiro)cycloalkanes

Summary Cyclic 1,3-diketones like cyclopentane-1,3-dione, cyclohexane-1,3-dione, and 5,5-dimethylcyclohexane-1,3-dione react with 1,8-diaminonaphthalene to afford new condensed heterocyclic spiro systems.

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Kondensation von 1,3-Diketonen mit 1,8-Diaminonaphthalin: Synthese vonBis(2,3-dihydroperimidin-2-spiro)cycloalkanen

Zusammenfassung Cyclische 1,3-Diketone wie Cyclopentan-1,3-dion, Cyclohexan-1,3-dion und 5,5-Dimethylcyclohexan-1,3-dion reagieren mit 1,8-Diaminonaphthalin zu neuen kondensierten heterocyclischen Spiranen.

     

Synthesis and alkylation of 3-cyano-4-isobutyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-2-thiol

By reaction of isovaleric aldehyde with cyanothioacetamide and cyclohexane-1,3-dione, 3-cyano-4-isobutyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-1-thiol has been obtained, and subsequently used in synthesis of the corresponding substituted 2-alkylthiohexahydroquinolines.Lugansk T. G. Shevchenko State Pedagogical Institute, Lugansk 348011, Ukraine. N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117913, Russia. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 230–231, February, 1999.     

Regioselective annulation of propargyl alcohols with ambident-enols: A Ca(II)-catalyzed trisubstituted benzochromene synthesis

Highly regioselective, 6-endo cyclization between propargyl alcohols and ambident enols such as naphthols, 4-hydroxy coumarin, cyclohexane-1,3-dione, 5,5-dimethylcyclohexane-1,3-dione is described using Ca(OTf)₂ under solvent free conditions. The reaction proceeds through a cascade annulation which involves an etherification, Claisen type rearrangement, allene formation and endocyclization. Further, we extended this method to the synthesis of iodo-derivative and demonstrated the reactivity in cross-coupling reactions.     

Reactions of 2-benzylidene-3-methyl-4-nitro-2,5-dihydrothiophene 1,1-dioxide with CH acids

2-Benzylidene-3-methyl-4-nitro-2,5-dihydrothiophene 1,1-dioxide reacted with acyclic CH acids (acetylacetone, diethyl malonate, and its derivatives) according to the 1,4-addition pattern, whereas reactions of the title compound with cyclohexane-1,3-dione and 5,5-dimethylcyclohexane-1,3-dione (dimedone) were complicated by subsequent intramolecular heterocyclization leading to thieno[3,2-b]chromene derivatives.     

Efficient syntheses of novel indeno[1,2-b]chromenone derivatives via hetero-Diels-Alder reactions of 2-(arylmethylene)-1H-indene-1,3(2H)-diones with enaminones

Efficient syntheses of novel 10-aryl-5a-(arylamino)-9-hydroxy-5a,6,7,8-tetrahydroindeno[1,2-b]chromen-11(10H)-one derivatives has been reported by [4+2] cycloaddition reactions of electron-deficient 2-(arylmethylene)-1H-indene-1,3(2H)-dione heterodienes with electron-rich enaminones in [bmim]BF₄ at 80?°C and in acetic acid at 80?°C. Dimedone/cyclohexane-1,3-dione enaminones have been used as dienophiles in Inverse Electron Demand hetero-Diels-Alder reactions. The products were obtained in high yields by a simple work up.     

3-Aryl- and 2,3-Diaryl-4-oxo-4,5,6,7-tetrahydroindazoles. 1. Reactions of Phenyl- and Tosylhydrazones of Dimedone and Cyclohexane-1,3-dione with Substituted Benzaldehydes

Sixteen 3-aryl-4-oxo-2-phenyl-4,5,6,7-tetrahydroindazoles were obtained from the reaction of the phenylhydrazones of dimedone and cyclohexane-1,3-dione with 3-bromo-, 4-bromo-, 4-chloro-, 4-fluoro-, 2-hydroxy-, 4-hydroxy-, 4-methoxy-, 2-nitro-, 3-nitro-, 4-nitro-, and 4-dimethylamino-benzaldehydes. The interaction of the tosylhydrazones of dimedone and cyclohexane-1,3-dione with the substituted benzaldehydes gave thirteen 3-aryl-4-oxo-4,5,6,7-tetrahydroindazoles. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1662–1668, November 2005.     

Three-component one-pot synthesis of pyrazino[2,3-a]acridine derivatives under catalyst-free conditions

A new series of pyrazino[2,3-a]acridine derivatives were prepared, via three-component reaction of quinoxalin-6-amine, aromatic aldehydes and 5,5-dimethyl cyclohexane-1,3-dione or cyclohexane-1,3-dione in ethanol as a solvent at reflux. The advantages of this protocol include mild reaction conditions, easy purification, high yields, and catalyst-free approach.     

Quinazolines and 1,4-benzodiazepines LXXXII. Reaction of 2-hydrazino-benzodiazepines with 1,3-diearbonyl compounds

The 2-hydrazinobenzodiazepines 1 were reacted with acelylacelone to form the hydroxy-pyrazolines 2 which were converted to the triazolobenzodiazcpines 6 and the 2-pyrazolyl-benzodiazepine 4 . Ring cleavage of the hydrazone 8 obtained from cyclohexane-1,3-dione and 1a led similarly to the 1-(4-oxopentyl)triazolol)enzodiazepine 12 .