Simple method for the synthesis of 2-trichloromethyl-4-quinazolones

Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 698–699, May, 1991.     

3-取代苯甲酰氨基-2-硫代-2,4-噻唑烷二酮类衍生物的新合成法

通过简便的路线合成了8个3-取代苯甲酰氨基-2-硫代-2,4-噻唑烷二酮衍生物,并对其反应机理进行了讨论.所有化合物的结构均经元素分析、₁HNMR、IR和MS谱确认.初步的生物活性测试结果表明,代表化合物表现出良好的抗菌活性和植物生长调节活性.     

2-硫代-4-噻唑啉酮衍生物的合成

2-硫代-4-噻唑啉酮(1)与醛反应, 再用甲醛和胺进行胺甲基化, 合成5-芳基亚甲基-3-确定胺甲基-2-硫代-4-噻唑啉酮.     

Synthesis and properties of 2-isopropyl-3-aryl-4-quinazolones

A number of N-isobutyrylanthranilic acid arylamides (I) were obtained. Under the influence of phosphorus trichloride, I are cyclized to 2-isopropyl-3-aryl-4-quinazolones. The UV and IR spectra and biological activity of the quinazolone compounds were studied.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 1000–1002, July, 1972.     

POCl3 chlorination of 4-quinazolones

The reaction of quinazolones with POCl(3) to form the corresponding chloroquinazolines occurs in two distinct stages, which can be separated through appropriate temperature control. An initial phosphorylation reaction occurs readily under basic conditions (R(3)N, aq pK(a) > 9) at t < 25 °C to give a variety of phosphorylated intermediates. Pseudodimer formation, arising from reaction between phosphorylated intermediates and unreacted quinazolone, is completely suppressed at these temperatures, provided the system remains basic throughout the POCl(3)addition. Clean turnover of phosphorylated quinazolones to the corresponding chloroquinazoline is then achieved by heating to 70-90 °C. (N)- and (O)-phosphorylated intermediates, involving multiple substitution at phosphorus, have been identified and their reactions monitored using a combination of (1)H, (31)P, and (19)F NMR. Kinetic analysis of the reaction profiles suggest that the various intermediates react with both Cl(-) and Cl(2)P(O)O(-), but product formation arises exclusively from reaction of (O)-phosphorylated intermediates with Cl(-). (O)- and (N)-phosphorylated intermediates equilibrate rapidly on the time scale of the reaction. A minimum of 1 molar equiv of POCl(3) is required for efficient conversion of the intermediates to product.     

1,3-二取代-2-硫代咪唑啉-4-酮的合成

1-苯甲酰基-3-芳基硫脲与氯乙酰氯反应合成了1-芳基-3-苯甲酰基-2-硫代咪唑啉-4-酮,与二氯乙酰氯反应合成了1-芳基-3-苯甲酰基-5-氯-2-硫代咪唑啉-4-酮,与三氯乙酰氯反应时仅得到了硫脲的分解重组产物苯甲酰基芳胺.产物结构经红外光谱、核磁共振谱和高分辨质谱表征.     

New method for the synthesis of cis-2-thiahydrindane derivatives

A new method was worked out for the stereospecific synthesis of derivatives of cis-1,3-disubstituted cis-2-thiahydrindanes; the method is based on the reaction of sulfur dichloride with cis-1,2-divinylcyclohexane and is distinguished by its simplicity and high yields. It was established that two stereoisomeric sulfoxides that differ only with respect to the orientation of the sulfoxide oxygen atom are formed in the oxidation of cis-1,3-dichloromethy1-2-thiahydrindane. The structures of cis-1,3-dichloromethy1-cis-2-thiahydrindane and its oxidation products were studied by ¹H NMR spectroscopy, ¹H NMR spectroscopy with the addition of a shift reagent [tris(1,1,1,2,2,3,3-heptafluoro-7,7-dimethyloctane-4,6-dionato)europium], and ¹³C NMR spectroscopy.Communication XIV from the series Study of the reaction of sulfur halides with unsaturated compounds. See [1] for communication XIII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 462–466, April, 1978.     

A new approach for the synthesis of pteridines: The synthesis of 3-substituted-2-thioxo-1,2-dihydro-4(3H)-pteridinones

3-Substituted-2-thioxo-1,2-dihydro-4(3H)-pteridinones can be conveniently prepared by the reaction of methyl 3-isothiocyanato-2-pyrazinecarboxylate 2 with N-nucleophiles. The scope and limitations of the method are presented. The tautomeric form of 2-thioxo-1,2-dihydro-4(3H)pteridinones was determined on the basis of a ¹³C-[¹H]-NOE experiment.     

New method of synthesis of 1,5-benzodiazepin-2-ones from 4-hydroxycoumarin

A new method of synthesis of 1,5-benzodiazepine-2-ones, from 4-hydroxycoumarin and substituted 1,2-phenylenediamines by heating in xylene or acetic acid-ethanol, is reported.     

Novel method for synthesis of 4-hydroxyhexahydropyrimidine-2-thiones

4-Hydroxyhexahydropyrimidine-2-thiones were obtained by reaction of N-(azidomethyl)- or N-(p-tlylsulfonylmethyl)thioureas with anions of 1,3-dicarbonyl compounds. The corresponding 1,2,3,6-tetrahydropyrimidine-2-thiones were synthesized by dehydration of the pyrimidines obtained.     

Design,synthesis and evaluation of PPAR gamma binding activity of 2-thioxo-4-thiazolidinone derivatives

We designed and synthesized a series of 2-thioxo-4-thiazolidinone derivatives and evaluated them on peroxisome proliferator activated receptor γ(PPARγ) binding activities.Through the biological assays,compounds 18 and 38 were highlighted with K_i values of 12.15 nmol/Land 14.46 nmol/L,respectively.Then structure-activity relationship(SAR) was analyzed to screen privileged structural modifications.Moreover,molecular fitting of these compounds onto the approved drug Rosightazone in the PPARγligand binding domain was performed to elucidate the SAR and explore potential receptor-ligand interactions.These results demonstrate that the 2-thioxo-4-thiazolidinones can be considered as new promising molecular probes with excellent binding activities to PPARγ.     

Pyridine-based,microwave-assisted one-pot synthetic protocol for the synthesis of ethyl 3-substituted-4-oxo-2-thioxo-1,2,3,4-tetrahydropyrimidine-5-carboxylates

Pyridine has been used for one-pot, two-component synthesis of ethyl 3-substituted-4-oxo-2-thioxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate derivatives in moderate to good yields by condensing N-substituted thioureas with diethyl ethoxymalonate under microwave irradiation.     

Synthesis of 2-thioxo-1,3-thiazolidin-4-one derivatives

A series of new 2-thioxo-1,3-thiazolidin-4-one derivatives containing arylidene, arylazo, and aminomethylene fragments in position 5 of the rhodanine cycle was synthesized. Dedicated to Academician V. A. Tartakovsky on the occasion of his 75th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1564–1569, August, 2007.     

The synthesis and properties of some derivatives of 2-oxo-4-thioxo- and 2, 4-dithioxo-1h, 3h-pteridines

Some new derivatives of 2-oxo-4-thioxo- (I) and 2,4-dithioxo-1H, 3H-pteridine (II) have been prepared by treatment of 2,4-dioxo- (III) and 2-thioxo-4-oxo-1H,3H-pteridines (IV) with P₂S₅ in dioxane solution. The corresponding 4-phenylhydrazones, and the products of reaction of the pteridinethiones with aliphatic and aromatic amines and amino acids, have been obtained.     

2-硫代-4-咪唑啉二酮的合成与表征

咪唑啉酮衍生物是一类线粒体呼吸抑制剂,对果树黑斑病及由卵菌引起的霜霉病、疫病等的活性很好。2-硫代-5-苯基亚甲基4-咪唑啉二酮衍生物不能用通法制取,其起始原料烯基氨基酸不稳定。本文用三组分串联aza-Wittig堍反应合成2-硫代-3-烷基-5-苯基亚甲基4-咪唑啉二酮类化合物。合成路线如下：     

New method for the synthesis of 2-phenylproline and its derivatives

A new method has been developed for the synthesis of 2-phenylproline and its derivatives by intramolecular cyclization of the corresponding derivatives of N-(3-chloro-or 1-oxo-3-chloropropyl)--phenylglycine under phase transfer catalysis conditions.A. L. Mndzhoyan Institute of Fine Organic Chemistry, National Academy of Sciences of the Republic of Armenia, 375014 Yerevan, Armenia; e-mail: rafael@msrc.am. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 488–492, April, 2000.