Reactions of monothiooxamides with N-nucleophiles. Synthesis of 4,5-dihydroimidazole-2-carboxanilides

A convenient procedure was developed for the preparation of 4,5-dihydroimidazole-2-carboxanilides by the reaction of monothiooxamides with ethylenediamine. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 753–757, April, 1999.     

Synthesis and nematicidal activities of 1,2,3-benzotriazin-4-one containing 4,5-dihydrothiazole-2-thiol derivatives against Meloidogyne incognita

Abstract

A series of novel 1,2,3-benzotriazin-4-one derivatives containing 4,5-dihydrothiazole-2-thiol were synthesized and characterized by ¹H NMR, ¹³C NMR, ¹⁹F NMR and HRMS. The bioassay results showed that compounds 3-(3-((4,5-dihydrothiazol-2-yl)thio)propyl)-7-methoxybenzo[d][1–3]triazin-4(3H)-one, 3-(3-((4,5-dihydrothiazol-2-yl)thio)propyl)-6-nitrobenzo[d][1–3]triazin-4(3H)-one, 7-chloro-3-(3-((4,5-dihydrothiazol-2-yl)thio)propyl)benzo[d][1–3]triazin-4(3H)-one exhibited good control efficacy against the cucumber root-knot nematode disease caused by Meloidogyne incognita at the concentration of 10.0?mg L^?1 in vivo. Compound 7-chloro-3-(3-((4,5-dihydrothiazol-2-yl)thio)propyl)benzo[d][1–3]triazin-4(3H)-one showed excellent nematicidal activity with inhibition 68.3% at a concentration of 1.0?mg L^?1. It suggested that the structure of 1,2,3-benzotriazin-4-one containing 4,5-dihydro-thiazole-2-thiol could be optimized further.     

2-乙氧羰基-3-甲基-4,5-四亚甲基吡咯的合成

以乙酰乙酸乙酯(1)为原料,在醋酸中与亚硝酸钠通过肟化反应制得N-羟基亚胺乙酰乙酸乙酯(2);2在醋酸缓冲溶液中经锌粉还原后与环己酮加成环化合成了2-乙氧羰基-3-甲基-4,5-四亚甲基吡咯(3),其结构经1H NMR,IR和元素分析表征。较适宜的反应条件为:1100 mmol,n(Zn)∶n(1)=2.9∶1.0,在醋酸中回流反应,总收率39%;以多步反应的最佳反应条件进行一锅煮合成3,收率50%。     

Novel reactivities of 2,2-dichloroimidazolidine-4,5-diones: synthesis of copper(I) diamidocarbene complex, 2-thioxo/selenoxoimidazolidine-4,5-dione,and 2,2-difluoroimidazolidine-4,5-dione

A new method for the in situ generation of five-membered diamidocarbenes (DACs 2) from 2,2-dichloroimidazolidine-4,5-diones is established by Cl/I exchange and elimination of iodine. The trapping of 2 with CuI, S, and Se provides a good route for the preparation of a dimeric (2a)CuI complex and 2-thioxo/selenoxoimidazolidine-4,5-diones, respectively. In contrast, Cl/F exchange is explored to yield exclusively 2,2-difluoroimidazolidine-4,5-diones.     

Photooxidation of Transition Metal Complexes of 1,3-Dithiole-2-thione-4,5-dithiolate (dmit) and 1,2-Dithiole-3-thione-4,5-dithiolate (dmt)

Metall(II) bis-chelates of 1,3-dithiole-2-thione-4,5-dithiolate (dmit) and 1,2-dithiole-3-thione-4,5-dithiolate (dmt) undergo in CHCl₃/CH₃CN (ratio 1:24) photooxidation to the metal(III) bis-chelates when irradiated at 313 nm. No side reactions were observed. There is no correlation between the quantum yields of photooxidation and the electrochemical halve-wave potentials. This holds also in comparison to maleonitriledithiolato chelates.     

2-甲基-4,5-二硝基三唑-1-氧化物的合成及其结构表征

以乙二醛、甲基肼和盐酸羟胺为起始原料,经缩合、肟化得到中间体肟基甲腙;该中间体不经分离直接加入到硫酸铜-吡啶-水体系中,经缩合环化得到2-甲基三唑-1-氧化物(MTO);随后用混酸(硝酸+硫酸)硝化得到目标产物2-甲基-4,5-二硝基三唑-1-氧化物(DNMTO);初步探讨了环化反应的机理,研究了反应温度与时间等因素对硝化反应的影响,确定了最佳硝化反应条件.与此同时,利用红外光谱、核磁共振、质谱及元素分析等分析了中间产物和DNMTO的组成和结构.结果表明,目标产物的总收率为16%,纯度为99%;最佳硝化反应温度为100℃,最佳硝化反应时间为0.5h.     

Synthesis of 2-thio derivatives of 4-phenyl-9H-pyrimido[4,5-b]indole

The reaction of 3-benzylidene-2-ethoxyindolenine tetrafluoroborate with thiourea gives a mixture of 4-phenylpyrimido[4,5-b]indole-2(1H)-thione, its 3,4-dihydro derivative, and the corresponding disulfide, the product ratio depending on the reaction conditions. A number of transformations of the resulting compounds, in particular, those giving 2-alkylthio pyrimidoindole derivatives are described. Dedicated to the memory of Academician V. A. Koptyug on the occasion of the 75th anniversary of his birth. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1032–1037, June, 2006.     

苯偶姻单酯无溶剂微波加热合成2-取代-4,5-二芳基咪唑衍生物

以醛为原料,在维生素B1作用下,经安息香缩合反应制得相应的苯偶姻衍生物,进而以此为原料与不同的酰化试剂酯化生成苯偶姻单酯.苯偶姻单酯与醋酸铵附着在固载体酸性氧化铝上,在无溶剂条件下微波加热合成了17种2-取代-4,5-二芳基咪唑,其中7种未见文献报道.该方法具有反应条件温和、反应时间短,且无需有机溶剂,是一种节能环保、易操作的合成方法.另外,所合成化合物的结构通过IR、高分辨质谱和核磁共振谱进行了确认.     

Two-step α-ureidoalkylation of ureas with 4,5-dihydroxyimidazolidin-2-ones

Two-step α-ureidoalkylation of ureas with various 4,5-dihydroxyimidazolidin-2-ones gave novel 1,3-dialkyl-4,5-bis(3-alkylureido)-, 1,3-dialkyl-4,5-bis[3-(2-pyrimidyl)ureido]-, or 1,3-dialkyl-4,5-bis(3,3-dialkylureido)imidazolidin-2-ones and ensembles of three imidazolidine rings. The structure of 4,5-bis(2-oxoimidazolidin-1-yl)imidazolidin-2-one was confirmed by X-ray diffraction data. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 140–145, January, 2007.     

Synthesis and chemical characteristics of 2-substituted thiazoline-4,5-diones. (Review)

Methods for the production of 2-substituted thiazoline-4,5-diones and their thermolysis in the presence of nucleophiles and dienophiles are examined. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1283–1301, September, 2006.     

Regio- and Stereoselective Synthesis of Thioglycosides from 4,5-Diphenyl- and 3,4,5-Triphenylimidazole-2-thione

Six new thioglycosides incorporating the 4,5-diphenyl- and 3,4,5-triphenylimidazole moiety have been successfully synthesized under both conventional and microwave conditions by reaction of the corresponding thiones with aceto-bromosugars in presence of triethylamine as base. Attempted preparation of the bis(glycosyl) derivatives from 4,5-diphenylimidazole-2-thione in the presence of different bases was unsuccessful. Evaluation of the glycosylthioimidazoles as disarmed donors has been investigated using different promoters; NBS/TMSOTf has been found to be an effective promoter for the activation of the anomeric center towards glycosylation reaction.     

Synthesis and Antioxidant,Anti-Inflammatory,and Analgesic Activity of Novel Polycyclic Pyrimido[4,5-b]quinolines

The behavior of the 2-methylthio-pyrimido[4,5-b]quinolin-4-one towards differently substituted amines is reported. Also, the reactivity of 3-aminothiazolo[3′,2′ :1,2]-pyrimido[4,5-b]quinoline-2-carbonitrile towards formic acid, urea, thiourea, formamide, and carbon disulfide is discussed. Some of the synthesized derivatives possess biological activities as anti-inflammatory and analgesic agents. Some of these selective biologically active compounds were screened for antioxidant properties.     

Synthesis and antituberculotic activity of some new imidazo[4,5-b]pyridine derivatives

The reactions of 2-acetylimidazo[4,5-b]pyridine hydrazone with some alkyl-and arylisothiocyanates and some orthoesters were carried out. Various new derivatives of the titled compound such as thiosemicarbazones, ethoxymethylenehydrazones, and derivatives of the new pyrido-[3′,2′:4,5]imidazo[1,2-d][1,2,4]triazine ring system were obtained. Biological data for selected compounds are presented. Published in Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1571–1579, October, 2006.     

Synthesis of 4,5-dihydroxyphthalonitrile

4,5-Dihydroxyphthalonitrile was synthesized from pyrocatechol in a simple way. The compound obtained is a convenient starting reagent for the preparation of 4,5-dialkoxyphthalonitriles.     

Synthesis and some properties of 2-acetylamido-4,5-benzo-1,3,2-dioxaphospholane

The reaction of pyrocatechol chlorophosphite with N-trimethylsilylacetamide gave 2-acetamido-4,5-benzo-1,3,2-dioxaphospholane. The reaction of this product with hexamethyldisilazane leads to 2-trimethylsiloxy-4,5-benzo-1,3,2-dioxaphospholane, while its reactions with diethylamine, trimethylsilyldiethylamine, and bis(dimethylamino)methane give 2-dialkylamino-4,5-benzo-1,3,2-dioxaphospholanes.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Branch, Russian Academy of Sciences, 420008 Kazan. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 220–222, January, 1992.     

Synthesis and reaction of N-butyl-N-isobutenyl-aminotrimethylsilane with 4,5-benzo-2-chloro-1,3,2-dioxaphospholane

The reaction of N-butylisobutyraldimine with trimethyliodosilane obtained in situ proceeds to give N-butyl-N-isobutenylaminotrimethylsilane, which reacts with 4,5-benzo-2-chloro-1,3,2-dioxaphospholane to yield 2-(N-butyl-N-isobutenylamino)-4,5-benzo-1,3,2-dioxaphospholane.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Science Center, Russian Academy of Sciences, 420083 Kazan. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1923–1924, August, 1992.     

4,5-二氢咪唑并[1,2-b]-1',2',4'-三唑-4-酮衍生物的合成与杀菌活性

应用芳基异氰酸酯与烯基膦亚胺1的氮杂Wittig反应, 得到的碳二亚胺2, 再与水合肼作用得到氨基咪唑啉酮衍生物4. 而后用4与芳基异氰酸酯(或酰氯)、三苯基膦、六氯乙烷和三乙胺“一锅”反应, 得到4,5-二氢咪唑并[1,2-b]-1',2',4'-三唑-4-酮衍生物6或7. 探讨了所合成新型稠杂环化合物的生物活性, 结果表明部分化合物表现出良好的杀菌活性. 如7c在50 mg/L浓度时, 对棉花枯萎菌、稻瘟菌、黄瓜灰霉菌和油菜菌核菌的抑制率均达100%.     

Synthesis of Some New Imidazo[4,5-B]Pyridine Derivatives Using 2-Cyanomethyl-1-Methyl-1H-Imidazo[4,5-B]Pyridine

Abstract

The reactions of 2-cyanomethyl-1-methyl-1H-imidazo[4,5-b]pyridine with isothiocyanates, nitroso compounds, acid chlorides, and thioglycolic acid were investigated. New imidazo[4,5-b]pyridine derivatives with various substituents in 2-position and derivatives of the new pyrrolo[2′,1′:2,3]imidazo[4,5-b]pyridine ring system were synthesized. The compounds obtained were tested in vitro for their tuberculostatic activity.