Synthesis of annelated [a]aza-anthracenones and thieno[3,2-g]aza-naphthalenones through ring transformation of 2H-pyran-2-one followed by photocyclization

A concise synthesis of some new classes of heterocycles (4-aryl-11-oxo-1,2,3,11-tetrahydro-1,3a-diaza-cyclopenta[a]anthracen-6-carbonitriles and 5-aryl-12-oxo-1,3,4,12-tetrahydro-2H-1,4a-diazabenzo[a]anthracene-7-carbonitriles) has been developed by the ring transformation of suitably functionalized 2H-pyran-2-one with α-oxoketene cyclic aminals to intermediates (8-aroyl-5-aryl-2,3-dihydro-1H-imidazo[1,2-a]pyridine-7-ylidene)-acetonitriles and (9-aroyl-6-aryl-1,2,3,4-tetrahydropyrido[1,2-a]pyrimidin-8-ylidene)-acetonitriles) followed by their photocyclization either in CHCl₃ or acetonitrile. This reaction was further explored for the synthesis of methyl 4-aryl-11-oxo-1,2,3,11-tetrahydro-1,3a,9-triaza-cyclopenta[a]anthracene-6-carboxylate, 4-aryl-11-oxo-1,2,3,11-tetrahydro-1,3a,9-triaza-cyclopenta[a]anthracene-6-carbonitriles, 5-aryl-12-oxo-1,3,4,12-tetrahydro-2H-1,4a,10-triazabenzo[a]anthracene-7-carbonitriles, 4-aryl-10-oxo-1,2,3,10-tetrahydro-9-thia-1,3a-diazadicyclopenta[a,g]naphthalene-6-carbonitriles and 5-aryl-11-oxo-1,3,4,11-tetrahydro-2H-10-thia-1,4a-diazacyclopenta[b]phenanthrene-7-carbonitriles from the similar reactions.     

2-Quinazolinones and their cyclic homologs (review)

Methods for the synthesis of 2-quinazolinones, 1,2-dihydro-3H-1,4-benzodiazepin-2-ones, 1,2,3,4-tetrahydro-1,5-benzodiazocin-2-ones, and 1,2,3,4-tetrahydro-5H-1,6-benzodiazonin-2-ones are examined along with the peculiarities of their structure, their tautomerism, their chemical properties, and their biological activity.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 723–738, June, 1979.     

Cycloaddition of 1-Aryl-3-trimethylsiloxy-1,3-butadienes in the Synthesis of Natural Quinone Analogs

7-Hydroxy-5-(2-methoxyphenyl)-2-methyl-6-R-1,4-naphthoquinones, 8-hydroxy-1-(2-methoxyphenyl)-3-oxo-1,2,3,4-tetrahydro-9,10-anthraquinone, and 2-ethoxycarbonyl-8-hydroxy-1-(2-methoxyphenyl)-3-trimethylsiloxy-1,1a,4,4a-tetrahydro-9,10-anthraquinone were synthesized by reactions of 1-(2-methoxyphenyl)-2-R-3-trimethylsiloxy-1,3-butadienes with 2-bromo-5-methyl-1,4-benzoquinone and juglone. 1-Aryl-2-ethoxycarbonyl-3-trimethylsiloxy-1,3-butadienes reacted with 1,4-naphthoquinone to afford 1-aryl-2-ethoxycarbonyl-3-hydroxy-9,10-anthraquinones and their 4,4a-dihydro derivatives.     

Synthesis of 2-aryl-5H-[1,3,4]-thiadiazolo[2,3-b]quinazolin-5-ones

3-Amino-2-thioxo-1,2,3,4-tetrahydroquinazolin-4-ones were converted into 2-aryl-5H-[1,3,4]thiadiazolo[2,3-b]quinazolin-5-ones on treatment with carboxylic acids and POCl₃. 3-Arylmethylidenamino-2-thioxo-1,2,3,4-tetrahydroquinazolin-4-ones also cyclized to 2-aryl-5H-[1,3,4]thiadiazolo[2,3-b]quinazolin-5-ones when oxidized with potassium chlorate in acetic acid, but on heating they were deaminated to give 2-thioxo-1,2,3,4-tetrahydroquinazolin-4-one and aryl nitriles. __________ Translated from Khimiya Geteotsiklicheskikh Soedinenii, No. 5, 787–791, May, 2006.     

Cyclization of fluoroalkyl-containing 1,3-dicarbonyl compounds with ethylenediamine hydroperchlorate to 1,4-diazepines

2,3-Dihydro-1H-1,4-diazepines and 1,2,3,4-tetrahydro-1,4-diazepin-5-ones were obtained by direct condensation of fluorine-containing 1,3-diketones and 1,3-keto ethers, respectively, with ethylenediamine monohydroperchlorate. The structure of the compounds was confirmed by¹H NMR, mass spectrometry and molecular weight determination.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 890–896, April, 1991.     

Synthesis and Properties of 1,3-Diaryl-5,6-dihydro-8H-imidazo[2,1-c]-1,4-oxazinium Bromides

It has been established that the condensation of 3-(4-methoxyphenylamino)-5,6-dihydro-2H-1,4-oxazine with substituted phenacyl bromides occurs at the exocyclic nitrogen atom with formation of 3-aryl-3-hydroxy-1-(4-methoxyphenyl)-2,5,6,8-tetrahydro-3H-imidazo[2,1-c]-1,4-oxazinium bromides. By treatment of the latter with acetic anhydride 3-aryl-1-(4-methoxyphenyl)-5,6-dihydro-8H-imidazo[2,1-c]-1,4-oxazinium bromides are formed. The structures of the compounds synthesized were determined via ¹H NMR spectroscopy and X-ray diffraction.     

A New Route to 2-Aryl-4-quonolones via Thallium(III) p-Tolylsulphonate Mediated Oxidation of 2-Aryl-1,2,3,4-tetrahydro-4-quinolones

Oxidation of 2-aryl-1,2,3,4-tetrahydro-4-quinolones (1a-f) to 2-aryl-4-quinolones (2a-f) using thallium(III) p-tolylsulphonate in refluxing dimethoxyethane has been described. A mechanistic scheme for this new transformation has been proposed.     

Synthesis and structure of 3-arylidene and 3-hetarylidene-1,2-dihydro-3H-1,4-benzodiazepin-2-ones and their affinity toward CNS benzodiazepine receptors

The condensation of 5-aryl-7-bromo-1,2-dihydro-3H-1,4-benzodiazepin-2-ones with aromatic aldehydes gives 5-aryl-3-arylidene-and 5-aryl-7-bromo-3-hetarylidene-1,2-dihydro-3H-1,4-benzodiazepin-2-ones. X-ray diffraction structural analysis yielded the molecular and crystal structures of 7-bromo-3-(4′-methoxybenzylidene)-5-phenyl-1,2-dihydro-3H-1,4-diazepin-2-one and showed that this compound has cis configuration. Radioligand analysis was used to study the affinity of these products toward central nervous system and peripheral benzodiazepine receptors. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1213–1225, August, 2007.     

A New Synthetic Approach Towards the Synthesis of 2-(3-Aryl-2H-1,4-benzthiazin-2-yl)-3-aryl-2H-1,4-benzothiazines

Synthesis of 2-(3-Aryl-2H-1,4-benzthiazin-2-yl)-3-aryl-2H-1,4-benzothiazines (3 a-e) from 3-aryl-5(4H)-isoxazolones (1 a-e) and 2-aminothiophenol (2).     

Interaction of Cyclic Schiff's Bases with 2-Methylthiopyrimidine-4,6-dione Enol Acetate. Synthesis of 5-(2-Acetyl-6,7-dimethoxy-1,2,3,4-tetrahydro-1-isoquinolyl)-6-hydroxy-2-methylthio-1,4-dihydro-4-pyrimidinones

5-(2-Acetyl-1,2,3,4-tetrahydro-1-isoquinolyl)-6-hydroxy-2-methylthio-1,4-dihydro-4-pyrimidinones have been obtained by the interaction of 3,4-dihydroisoquinolines with 2-methylthio-4-oxo-1,4-dihydro-6-pyrimidinyl acetate. It was shown that N,O-methyl derivatives are formed in interaction of the obtained products with diazomethane.     

含1,2,3-三氮唑结构的1,5-苯并硫氮杂[艹卓]的合成及其抑真菌活性

设计合成了三类含1,2,3-三氮唑结构的1,5-苯并硫氮杂[艹卓]化合物3-(1H-1,2,3-三氮唑)-4-芳基-2,5-二氢-1,5-苯并硫氮杂[艹卓](5a^5f)、3-(2H-1,2,3-三氮唑)-4-芳基-2,3-二氢-1,5-苯并硫氮杂[艹卓](6a^6f)和3-(1H-1,2,3-三氮唑)-4-芳基-2,3,4,5-四氢-1,5-苯并硫氮杂[艹卓](7a^7f).研究了中间体及目标产物的合成条件,分离出其中两个副产物并进行了结构确定.目标产物的抑真菌活性测试表明,化合物5a^5f对真菌具有良好的抑制作用,对新生隐球菌的抑制效果尤为突出.初步抑真菌构效关系研究表明, 1H-1,2,3-三氮唑环和C=C双键是化合物5a^5f抑真菌活性的关键官能团.     

Hypervalent Iodine Oxidation of 2-Aryl-1,2,3,4-tetrahydro-4-quinolones: An Easy Access to 2-Aryl-4-quinolones

Oxidation of 2-aryl-1,2,3,4-tetrahydro-4-quinolones (1a-e) using iodobenzene diacetate in methanolic potassium hydroxide leads to dehydrogenation of 1 thereby providing an easy access to 2-aryl-4-quinolones (2a-e).     

Synthesis of 2-Aryl-2,3-dihydro-4H-[1,3]thiazino[3,2-a]benzimidazol-4-ones and 7-Aryl-2,3,6,7-tetrahydro-5H-imidazo[2,1-b]-1,3-thiazin-5-ones

The reaction of 2-mercaptobenzimidazole, 5-ethoxy-2-mercaptobenzimidazole, and 2-mercaptoimidazoline with cinnamoyl chloride, its derivatives, and heteroanalogs was studied. Convenient methods were found for the synthesis of 2-aryl-2,3-dihydro-4H-[1,3]thiazino[3,2-a]benzimidazol-4-ones and 7-aryl-2,3,6,7-tetrahydro-5H-imidazo[2,1-b]-1,3-thiazin-5-ones.     

Versatile synthesis of chiral 2-substituted-5-oxo-1,2,3,4-tetrahydro-5H-1,4-benzodiazepines as novel scaffolds for peptidomimetic building

The stereocontrolled synthesis of phenylalanine and tryptophan derived 5-oxo-1,2,3,4-tetrahydro-5H-1,4-benzodiazepine derivatives is described. This new methodology involves a modified Strecker reaction of N-Boc protected amino aldehydes and methyl anthranilate, reduction of the resulting α-amino nitriles, and lactamization. The resulting 2-substituted-5-oxo-1,2,3,4-tetrahydro-5H-1,4-benzodiazepines were further functionalized at position 4 by alkylation or acylation reactions. One of these new tryptophan-derived 1,4-benzodiazepines showed significant selective binding affinity at cholecystokinin CCK₁ receptors (IC₅₀=156.5±33.2 nM).     

1,2,3,5-Tetrahydro-4H-1,5-benzodiazepin-4-ones and 1,2,3,4-tetrahydro-5H-1,4-benzodiazepin-5-ones from the reaction of hydrazoic acid on 1,2,3,4-tetrahydroquinolin-4-ones

The Schmidt reaction on 1,2,3,4-telrahydroquinolin-4-ones (1) gave 1,2,3,5-telrahydro-l,5-benzodiazepin-4-ones (II) and 1,2,3,4-tetrahydro-1,4-benzodiazepin-5)-ones(III). The ratio of II and III is dependent upon substituents present on the nitrogen ring atom of the quinolinones.     

A study of 1,2,3,4-tetrahydro-4-azafluorene-3,9-diones

Intramolecular cyclization of the diamides and N,N-dimethylamides of -[indan-1,3-dion-2-yl]benzylmalonic acids (I) has given 1-aryl-2-carbamoyl-1,2,3,4-tetrahydro-4-azafluorene-3, 9-diones and 1-aryl-4-methyl-2-methylcarbamoyl-1,2,3,4-tetrahydro-4-azafluorene-3,9-diones (II). The structure of compounds II was shown by chemical methods: bromination, xanthylation, and hydrolysis in alkaline and acid media, and also by a study of IR and UV spectra.     

Design and synthesis of novel tricycles based on 4H-benzo[1,4]thiazin-3-one and 1,1-dioxo-1,4-dihydro-2H-1lambda6-benzo[1,4]thiazin-3-one

This paper reports our recent efforts to develop novel tricycles based on 4H-benzo[1,4]thiazin-3-one ( 2) and 1,1-dioxo-1,4-dihydro-2H-1lambda(6)-benzo[1,4]thiazin-3-one (3) using 1,5-difluoro-2,4-dinitrobenzene (1). All of these tricycles integrate two privileged structures into one skeleton, including 3,8-dihydro-5-thia-1,3,8-triaza-cyclopenta[b]naphthalene-7-one (4, 10, 12), 5,5-dioxo-3,5,6,8-tetrahydro-5lambda(6)-thia-1,3,8-triaza-cyclopenta[b]naphthalene-7-one (5, 11), 3,8-dihydro-5-thia-1,2,3,8-tetraaza-cyclopenta[b]naphthalene-7-one (6), 5,5-dioxo-3,5,6,8-tetrahydro-5lambda(6)-thia-1,2,3,8-tetraaza-cyclopenta[b]naphthalene-7-one (7), 3,8-dihydro-1H-5-thia-1,3,8-triaza-cyclopenta[b]naphthalene-2,7-dione (8), and 5,5-dioxo-3,5,6,8-tetrahydro-1H-5lambda(6)-thia-1,3,8-triaza-cyclopenta[b]naphthalene-2,7-dione (9). A typical library of scaffold 5 was synthesized in a parallel solution-phase manner and analyzed by HPLC-UV-MS or HPLC-UV-ELSD method.     

无外加催化剂条件下2-氨基-3-腈基-4-芳基-7,7-二甲基-5-氧 代-4H-5,6,7,8- 四氢苯并-[b]-吡喃-3-羧酸乙酯的合成

亚苄基氰基乙酸乙酯(1)与5,5-二甲基-1,3-环已二酮在乙二醇中不加任何催化剂于80℃反应2～3h得2-氨基-4-芳基-7,7-二甲基-5-氧化-4H-5,6,7,8-四氢苯并-[b]-吡喃-3-羧酸乙酯(3),产率75%～93%。     

A revised structure for plumbazeylanone

The structure of plumbazeylanone has been revised, by X-ray crystallography, to 1,2,3,4-tetrahydro-5-hydroxy-1,4-diketo-2-methyl-2,3-di(5′-hydroxy-2'-methyl-1,4-naphthoquinon-3′-yl)naphthalene.     

Cycloacylation of N-phenyl-N′-R-thioureas with 3-aryl-2-propenoyl chlorides

Cycloalkylation of N-phenyl-N′-R-thiourea with 3-aryl-2-propenoyl chlorides in acetone gives as products 6-aryl-3-phenyl-2-(R-imino)-2,3,5,6-tetrahydro-4H-1,3-thiazin-4-one and their hydrochlorides. The same reaction carried out in acetone in the presence of K₂CO₃ leads to the formation of 6-aryl-3-phenyl-2-(R-imino)-2,3,5,6-tetrahydro-4H-1,3-thiazin-4-ones, N-(3-aryl-2-propenoyl)-N-phenylthioureas, 3-aryl-2-propenoylanilides, and phenyl isothiocyanate.