Synthesis of Some New Thiazoles and Pyrazolo[1,5-a]pyrimidines Containing an Antipyrine Moiety

Ethyl 2-{2-[4-(2,3-dimethyl-5-oxo-1-phenyl-3-(pyrazolin-4-yl)]-2-cyano-1-(phenylamino)vinylthio}-acetate, 2-[4-(2,3-dimethyl-5-oxo-1-phenyl-(3-pyrazolin-4-yl))(1,3-thiazol-2-yl)]2-(4-oxo-3-phenyl-(1,3-thiazoilidin-2-ylidene))ethanenitrile, 2-[4-(2,3-dimethyl-5-oxo-1-phenyl(3-pyrazolin-4-yl))(1,3-thiazol-2-yl)]-2-(4-methyl-3-phenyl(1,3-thiazolin-2-ylidene))ethanenitrile, 2-(5-acetyl-4-methyl-3-phenyl(1,3-thiazolin-2-ylidene))-2-[4-(2,3-dimethyl-5-oxo-1-phenyl(3-pyrazolin-4-yl))(1,3-thiazol-2-yl)]ethanenitrile, and ethyl 2-(cyano(4-(2,3-dihydro-1,5-dimethyl-3-oxo-2-phenyl-1H-pyrazol-4-yl)thiazol-2-yl)methylene)-2,3-dihydro-4-methyl-3-phenylthiazole-5-carboxylate were synthesized by treatment of 2-(4-(2,3-dihydro-1,5-dimethyl-3-oxo-2-phenyl-1H-pyrazol-4-yl)thiazol-2-yl)-3-mercapto-3-(phenylamino)-acrylonitrile with appropriate halo ketones or halo esters. Also, 4-{2-[5,7-dimethyl-2-(phenylamino)(7a-hydropyrazolo[1,5-a]pyrimidin-3-yl](1,-thiazol-4-yl)}-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one derivatives were synthesized via reaction of 4-{2-[5-amino-3-(phenylamino)pyrazolin-4-yl](1,3-thiazol-2-yl)}-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one with β-diketone or β-keto ester. All synthesized compound were established by elemental analysis, spectral data, and alternative synthesis whenever possible.     

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。     

Investigation of reactions of the organozinc reagents prepared from zinc and dialkyl dibromomalonates with the derivatives of 2-arylmethyleneindan-1,3-dione and 5-arylmethylene-2,2-dimethyl-1,3-dioxane-4,6-dione

Organozinc compounds prepared from dialkyl dibromomalonates and zinc react with 2-arylmethyl-eneindan-4,6-diones, 5-arylmethylene-2,2-dimethyl-1,3-dioxane-4,6-diones, as well as with 2-[4-(1,3-dioxoindan-2-ylidenemethyl)phenyl]methyleneindan-1,3-dione and 5-[4-(2,2-dimethyl-4,6-dioxo-1,3-dioxane-2-ylidenemethyl)phenyl]methylene-2,2-dimethyl-1,3-dioxane-4,6-diones to form dialkyl 3-aryl-1′3′-dioxaspiro(cyclopropane-2,2′-indan)-1,1-dicarboxylates, dimethyl 3-aryl-6,6-dimethyl-5,7-dioxa-4,8-dioxaspiro[2,5]octan-2,2-dicarboxylates, dialkyl 2-{4-[3,3-bis (alkoxycarbonyl)-1′,3′-dioxaspiro(cyclopropane-2,2′-indan)-1-yl]phenyl}-1′,3′-dioxaspiro[cyclopropane-2,2′-indan]-1,1-dicarboxylates, and dialkyl 2-{4-[2,2-bis(alkoxycarbonyl)-6,6′-dimethyl-4,8-dioxo-5,7-dioxaspiro[2,5]oct-1-yl]phenyl}-6,6-dimethyl-4,8-dioxo-5,7-dioxaspiro[2,5]octan-1,1-dicarboxylate respectively.     

Lactam and amide acetals. 52. Reaction of dimethylformamide diethylacetal with 2,2-dimethyl-4,6-dioxo-1,3-dioxane (Meldrum's acid)

Depending on the conditions of carrying out the reaction of dimethylformamide diethylacetal with the Meldrum's acid, either 2,2-dimethyl-4,6-dioxo-5-(N,N-dimethyl-aminomethylene)-1,3-dioxane or N,N,N¹N¹-tetramethylformamidinium salt of 2,2-dimethyl-4,6-dioxo-5-(2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-yl)methylene-1,3-di-oxane are formed. The two compounds can react with primary amines to form N-substituted 2,2-dimethyl-4.,6-dioxo-5-aminomethylene-1,3-dioxanes.For Communication 51, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 184–187, February, 1988.     

Stereochimie d'heterocycles du groupe IVB—II : Syntheses stereoselectives d'hydrogeno-1 et d'alkyl-1 sila-1 cyclobutanes

The reaction between n-butyllithium and 1,2 (or 1,3)-dimethyl-1-t-butoxy-1-silacyclobutanes proceeds with retention of configuration at silicon, and yields 10/90 (or 80/20) Z/E mixture of 1,2 (or 1,3)-dimethyl-1-n-butyl-1-silacyclobutanes. Methylation of 2 (or 3)-methyl-1-t-butoxy-1-silacyclobutanes (Z/E = 15/85 or 65/35) by methylmagnesium iodide gives 15/85 (or 65/35) Z/E mixture of 1,2 (or 1,3)-dimethyl-1-silacyclobutanes. The proposed configurations for substituted silacyclobutanes are supported by spectroscopic data (RMN) and chemical results (correlation of configuration and stereomutation of hydrogenosilacyclobutanes).     

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.     

水溶剂中芳醛与5，5－二甲基－1，3－环己二酮的反应

芳醛1与5，5－二甲基－1，3－环己二酮（2）在氯化三乙基苄基铵（TEBA）催 化下在水中生成2，2'－芳业甲基双（3－羟基－5，5－二甲基－2－环己烯－1－酮 ）（3），若在体系中有对甲苯磺酸存在时则生成3，3，6，6－四甲基－9－芳基－ 1，8－二氧代八氢化氧杂蒽（4）或3，3－二甲基－9－（3－羟基－5，5－二甲基 －2－环己烯－1－酮－2－基）－1－氧代四氢代氧杂蒽（6）而不是生成3，产率接 近定量。     

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.     

KF-Al_2O_3催化下达米酮与查尔酮的麦克尔加成反应

5，5-二甲基-1，3-环己二酮（达米酮）、1，3-二芳基-2-丙烯-1-酮（查尔酮 ）在KF-Al_2O_3催化下，在DMF中进行麦克尔加成反应，生成产物为1，3-二芳基- 3-（5，5-二甲基-3-羟基-2-环己烯-1-酮-2-基）-1-丙酮，产率良好。     

THE PHOTOREACTIONS AND FREE RADICAL INDUCED REACTIONS OF 1,3-DIMETHYLURACIL IN METHANOL AND OTHER ALCOHOLS

Abstract— Photoexcited 1,3-dimethyluracil (DMU) reacts with methanol to give 1,3-dimethyl-6-hydroxymethyl-5-hydrouracil ( 1 a) in addition to cyclobutane type dimers and 1,3-dimethyl-6-methoxy-5-hydrouracil ( 2 a). Free radical induced reaction, initiated by photodecomposition of di- t -butyl peroxide with light of wavelength greater than 290nm, leads to 1 a, 5,6-dihydroxymethyl-5,6-dihydro-1,3-dimethyl-uracil ( 1 d) and 6-hydroxymethyl-1,3-dimethyluracil as the products.     

Smiles rearrangement—XV: The S→N type rearrangement in uracil derivatives

The reaction of 1,3-dimethyl-6-(2-acetamidophenylthio)uracil 6 with caustic alkali followed by methylation gave 1,3-dimethyl-6-(2-methylthioanilino)uracil 7 accompanied with 1,3-dimethyl-5-acetyl-6-(2-methythioanilino)uracil 8. Pyrimido[1,5]benzothiazepine 10 was obtained in high yield by the Smiles rearrangement of 6, trapping of the resulting thiolate ion with formalin and subsequent acid-catalysed cyclization. Treatment of 1,3-dimethyl-6-(2-aminophenylthio)uracil 5 with hot acetic acid gave 1,3-bis[(2-benzothiazolyl)acetyl]-1,3-dimethylurea 12. Upon heating 5 or N-acetyl derivative 6 in dimethylsulfoxide, 5-thiaisoalloxazine 3 was obtained in moderate yield. Mechanisms of the observed reactions were discussed.     

Reactions with Hydrazonoyl Halides 611: Synthesis of 2,3-Dihydro-1,3,4-Thiadiazoles

2-[1,2-Diaza-3-(2,3-dimethyl-5-oxo-1-phenyl(3-pyrazolin-4-yl))prop-2-enylidene]-3-phenyl-5-substituted 1,3,4-thiadiazolines and 2-{[4-(2,3-dimethyl-5-oxo-1-phenyl(3-pyrazolin-4-yl))(1,3-thiazol-2-yl)]cyanomethylene}-3-phenyl-5-substitu- ted 1,3,4-thiadiazolines were synthesized from hydrazonoyl halides and 4-{-2-aza-2-[(methylthiothioxomethyl)amino]vinyl}-2,3-dimethyl-1-phenyl-3-pyrazoin-5-one and 2-[4-(2,3-dimethyl-5-oxo-1-phenyl-3-pyrazolin-4-yl)-1,3-thiazol-2-yl]ethane-nitrile, respectively. All synthesize compounds were elucidated by elemental analysis, spectra, and alternative synthesis routes, whenever possible.     

Tetracyanoethylene pi-complex chemistry. Indirect spectrophotometric determination of Diels-Alder-active 1,3-dienes

An indirect spectrophotometric method, based on the rapid Diels-Alder reaction between cisoid 1,3-dienes and tetracyanoethylene (TCNE) and the destruction of an aromatic-TCNE pi-complex, was developed to determine eleven 1,3-dienes in the 0.05-1.00 x 10(-3)M range. These dienes were: cyclopentadiene; 1,3-cyclohexadiene; trans-1,3-pentadiene; 2,4-dimethyl-1,3-pentadiene; trans-2-methyl-1,3-pentadiene; 2-methyl-1,3-butadiene; 9-methylanthracene; 9,10-dimethylanthracene; 1,6-diphenyl-1,3,5-hexatriene; 2,3-dimethyl-1,3-butadiene; and 1,4-diphenyl-1,3-butadiene. Three 1,3-dienes were determined in the 0.05-1 x 10(-4)M range: cyclopentadiene, trans-2-methyl-1,3-pentadiene, and anthracene. The limit of detection for cyclopentadiene in carbon tetrachloride solutions is 0.11 microg/ml. Fourteen 1,3-dienes were found to form stable pi-complexes and could not be determined by the proposed method. For these 1,3-dienes, the spectra of some of the complexes are reported; in addition, relative equilibrium constants for the pi-complexes of 2,5-dimethyl-2,4-hexadiene, cis-1,3-pentadiene, 4-methyl-1,3-pentadiene, and 1,3-cyclo-octadiene were estimated. An explanation of the transient colour in the 1,3-diene-TCNE Diels-Alder reaction is suggested.     

Unexpected course of rearrangement of substituted S-(1(3H)-isobenzofuranone-3-yl)isothiuronium bromides

Three series of S-(1(3H)-isobenzofuranone-3-yl)isothiuronium bromides differing in substitution at the isothiuronium moiety (none, one or two methyl groups) and at the benzene ring were prepared and characterized. These salts were then treated with various bases (acetate, triethylamine, Na₂CO₃) to give either 1-hydroxy-3-oxo-1,3-dihydro-2H-isoindol-2-carbothioamides or the product of S to N isobenzofuranone-3-yl migration, i.e., 1,3-dimethyl-1-(3-oxo-1,3-dihydro-2-benzofuran-1-yl)thioureas. If ammonia was used in reaction with N,N′-dimethyl isothiuronium salts then 3-hydroxy-2,3-dihydro-1H-isoindol-1-ones were formed together with 1,3-dimethyl-1-(3-oxo-1,3-dihydro-2-benzofuran-1-yl)thioureas in parallel reaction with the yields increasing with ammonia concentration. The formation of isoindolones takes place in two steps with an aldehyde intermediate, which can be trapped with N,N-dimethylhydrazine.     

含取代噁唑结构的新型吡唑肟衍生物的合成与生物活性

为了发现具有良好生物活性的吡唑肟化合物,以唑螨酯为先导化合物,在吡唑肟中引入取代噁唑结构,设计并制备了20个未见文献报道的新型吡唑肟衍生物,利用1H NMR,13C NMR和元素分析确证了目标产物的结构.生物活性测试结果显示,部分目标化合物在500和100μg/mL浓度下对粘虫或蚜虫表现出优良的杀虫活性,其中5-(3-氟苯氧基)-1,3-二甲基-1H-吡唑-4-甲酰基-O-{[5-(4-氯苯基)噁唑-2-基]甲基}肟(9j)、5-(4-氟苯氧基)-1,3-二甲基-1H-吡唑-4-甲酰基-O-{[5-(4-氯苯基)噁唑-2-基]甲基}肟(9k)、5-(4-叔丁基苯氧基)-1,3-二甲基-1H-吡唑-4-甲酰基-O-{[5-(4-氯苯基)噁唑-2-基]甲基}肟(9r)和5-(4-甲氧基苯氧基)-1,3-二甲基-1H-吡唑-4-甲酰基-O-{[5-(4-氯苯基)噁唑-2-基]甲基}肟(9s)在浓度为100μg/mL时对粘虫的防治效果均达100%,5-(4-溴苯氧基)-1,3-二甲基-1H-吡唑-4-甲酰基-O-{[5-(4-氟苯基)噁唑-2-基]甲基}肟(9g)和9s在浓度为100μg/mL时对蚜虫的杀灭活性均为100%.此外,化合物9s在500μg/mL时对朱砂叶螨的防治效果为70%.     

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.     

Isomerization of perfluoro-3,3-diethylindan-1-one into perfluoro-1,3-dimethyl-4-ethyl-1 H-isochromen under the action of antimony pentafluoride

The heating of perfluoro-3,3-diethylindan-1-one with SbF₅ at 180°C after treatment of the reaction mixture with anhydrous HF afforded perfluoro-1,3-dimethyl-4-ethylisochromen, and after hydrolysis, perfluoro-1,3-dimethyl-4-ethyl-1H-isochromen-1-ol. The latter under the action of NaHCO₃ converted into 5,6,7,8-tetrafluoro-1,3-bis(trifluoromethyl)-1H-isochromen-1-ol. Both isochromenols reacted with SOCl₂ gave the corresponding polyfluoro-1-chloro-1H-isochromens. On dissolving isochromenols in CF₃SO₃H and isochromens in SbF₅ perfluoro-1,3-dimethyl-4-ethylisochromenyl and 5,6,7,8-tetrafluoro-1,3-bis(trifluoromethyl)isochromenyl cations were generated which by hydrolysis were converted into the corresponding isochromenols.     

Reaction of 4,4-Dimethyl-1,3-dioxane with Dinitriles

The reaction of 4,4-dimethyl-1,3-dioxane with bis(2-cyano)diethyl ether or 1,2-di(beta-cyanoethoxy)ethane yields the corresponding bis[2-(4,4-dimethyl-5,6-dihydro-2-oxazinyl)]diethyl ether and 1,2-di{beta-[2-(4,4-dimethyl-5,6-dihydro-2-oxazinyl)]ethoxy}ethane which are readily hydrolyzed under the action of aqueous alkali to give 3-methyl-3-amino-1-butanol.     

[f]-Fused purine-2,6-diones: Synthesis of new [1,3,5]- and [1,3,6]-thiadiazepino-[3,2-f]-purine ring systems

Summary 6-Phenyl-1,3-dimethyl-2,4-dioxo-1,2,3,4,8,9-hexahydro-[1,3,5]-thiadiazepino-[3,2-f]-purine (5) was obtained by a three-step synthesis from 8-mercapto-1,3-dimethyl-3,7-dihydro-1H-purine-2,6-dione (1) and 2-(benzoylamino)-ethyl chloride (2)via 8-(benzoylaminoethylthio)-1,3-dimethyl-3,7-dihydro-1H-purine-2,6-dione (3) and its chloromido derivative4. The analogous 9-phenyl-1,3-dimethyl-2,4-dioxo-1,2,3,4,6,7-hexahydro-[1,3,6]-thiadiazepino-[3,2-f]-purine (7) was synthesized either from compound1 and N-(2-chloroethyl)-benzimido chloridevia N-(chloroethyl)-S-(1,3-dimethyl-2,4-dioxo-1,2,3,4-tetrahydro-7H-purin-8-yl)-benzothioimide (6), or alternatively from 7-(2-benzoylaminoethyl)-8-bromo-1,3-dimethyl-3,7-dihydro-1H-purine-2,6-dione (9), its 8-mercapto derivative10 and the corresponding chloroimido compound11 being the intermediates.Part of this paper was presented as a preliminary report at the Congress of Czech and Slovak Chemical Societies, Olomouc, Czech Republic, September 13–16, 1993     

Synthesis of some substituted 1,3-thiazolines and 1,3-thiazolidines

Sodium salts of 2, 2-dimethyl-4-mercapto-5-oxo-1,3-thiazoline and 2-oxo-3-mercapto-1-thia-4-azaspiro[4.5]dec-3-ene, obtained from a solvate of sodium cyanodithioformate with three molecules of dimethylformamide, acetone, or cyclohexanone in the presence of morpholine, react with chlorothioformic dimethylamide with the formation of 2,2-dimethyl-5-oxo-4-(dimethylaminothiocarbonylthio)-1,3-thiazoline and 2-oxo-3-(dimethylaminothiocarbonylthio)-1-thia-4-azaspiro[4.5]dec-3-ene, respectively, and during acidolysis by hydrochloric acid they are converted to 2,2-dimethyl-5-oxo-4-thiono-1,3-thiazolidine and 2-oxo-3-thiono-1-thia-4-azaspiro[4.5]decane. The latter compounds are facilely phosphorylated by dialkyl chlorophosphonates at the nitrogen atom. The reaction of the solvate of sodium cyanodithioformate with three molecules of dimethylformamide with chloroacetone in the presence of morpho-line occurs anomalously with the formation of cyanothioformic morpholide.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2590–2593, November, 1990.