3-甲基-5-氰基-6-氨基-1-苯基-4-(3,4-二甲氧基苯基)-1,4-二氢吡喃[2,3-c]吡唑的合成和晶体结构

标题化合物C22H20N4O3 3是由2-氰基-3-(3,4-二甲氧基苯基)丙烯腈1和3-甲基-1-苯基-2-吡唑-5-酮2在KF-Al2O3催化下在N,N-二甲基甲酰胺(DMF)溶剂中反应而得。结构通过单晶X-射线衍射分析确定,其晶体属于三斜晶系,空间群Pī,a = 9.450(3),b = 10.876(2), c = 11.435(2) ,a = 115.51(1), b = 102.82(1),g = 98.47(2), Mr = 388.42, V = 994.1(3) 3,Dc = 1.298 g/cm3, Z = 2, m (MoKa) = 0.089 mm-1, F(000) = 408。晶体结构用直接法解出,使用全矩阵最小二乘法对原子参数进行修正,最后的偏离因子R = 0.0420,wR = 0.1070。单晶X-射线衍射分析表明平面Ⅰ与平面Ⅱ、平面Ⅲ、平面Ⅳ的夹角分别为102.31、29.24和1.43。平面Ⅱ与平面Ⅲ和平面Ⅳ的夹角分别为73.50和100.91,平面Ⅲ和平面Ⅳ的夹角为27.81, 另外晶体中还存在分子间氢键。     

水中3-甲基-6-氨基-5-氰基-4-芳基-1-苯基-1，4-二氢吡喃[2，3-c]吡唑的洁净合成

在水溶剂中并有三乙基苄基氯化铵（TEBA）存在下，取代芳亚甲基丙二腈与3- 甲基-1-苯基-2-吡唑啉-5-酮缩合成为3-甲基-6-氨基-5-氰基-4-芳基-1-苯基-1， 4-二氢吡喃[2,3-c]吡唑，此法为相应化合物的合成提供了一种快速、方便、高效 和洁净的方法。     

Greener approach towards the facile synthesis of 1,4-dihydropyrano[2,3-c]pyrazol-5-yl cyanide derivatives at room temperature

This report describes triethylammonium acetate (TEAA) ionic liquid catalyzed one pot synthesis of 6-amino-4-aryl-5-cyano-3-methyl-1-phenyl-1,4-dihydropyrano[2,3-c]pyrazoles by the reaction of aromatic aldehyde, malononitrile and 3-methyl-1-phenyl-2-pyrazolin-5-one at room temperature. TEAA plays dual role as reaction media and catalyst. It can also be easily recovered and reused in several runs. TEAA provides greener reaction protocol to present methodology which obviates the need of organic solvents, expensive and toxic catalyst.     

Convenient synthesis of spiro[indoline-3,4'-pyrano[2,3-c]pyrazole] and spiro[acenaphthyl-3,4'-pyrano[2,3-c]pyrazoles] via fourcomponent reaction

The base promoted four-component reaction of hydrated hydrazine, dimethyl acetylenedicarboxylate, isatines and malononitrile (ethyl cycanoacetate) in ethanol afforded polysubstituted spiro[indoline-3,4‘-pyrano[2,3-c]pyrazoles] and spiro[acenaphthyl-3,4-pyrano[2,3-c]pyrazoles]     

金属氯化物对硼氢化钠还原α-氯代苯乙酮的影响

以芳醛、麦氏酸和3-甲基-1-苯基-5-氨基吡唑为原料, 经微波辐射一步得到4-芳基-3-甲基-6-氧代-1-苯基-4,5,6,7-四氢吡啶并[2,3-c]吡唑衍生物, 反应2～6 min完成, 产率高. 产物结构通过红外、核磁共振、元素分析及单晶X射线分析确证.     

微波促进下6-氨基-4-芳基-5-氰基-3-甲基-1-苯基吡啶[2,3-c]并吡唑的合成

5-氨基-3-甲基-1-苯基吡唑与芳亚甲基丙二腈在少量乙二醇中, 经微波辐射得到6-氨基-4-芳基-5-氰基-3-甲基-1-苯基吡啶[2,3-c]并吡唑衍生物, 反应4～8 min完成, 产率为71%～90%, 产物结构通过红外、核磁共振、元素分析及单晶X射线分析表征.     

Synthesis of (1H)-3,4-Dihydropyrrolo[2,1-c][1,4]oxazin-1-one Derivatives

It has been found that some acyl derivatives of 1,2,3,4-tetrahydro-1-indolizin-1-one 1and (1H)-3,4-dihydropyrrolo[1,2-a]pyrazin-1-one 2 show remarkable anti-inflammatory and analgesic activities1,2. The interest in extending the study of structure-activity relationships and search of new potent anti-inflammatory and analgesic agents led us to design and synthesize (1H)-3,4-dihydropyrrolo[2,1-c][1,4]oxazin-1-one 3 derivatives. NO 1 NNHO2 87654321ONO3 A few examples of the p…     

Studies in the Vilsmeier-Haack reaction,part VII: Synthesis and reaction of 3-methyl-1-phenyl-4-acetyl hydrazono 2-pyrazoline-5-one(-5-thione)

Summary The keto (thio) tautomers1–4 of the hydrazono pyrazolone, thiopyrazolone derivatives underwent simultaneous diformylation, chlorination (desulphurization) and ring closure under Vilsmeier reaction conditions giving the pyrazolo[3,4-c]pyrazole aminoacroleins (5,6). Treatment of5 and/or6 with proper reagents afforded the corresponding pyrazolo[3,4-c]pyrazoles with different heterocyclic systems at the 3-position.The structures of these compounds were confirmed by elemental analysis, IR and¹H-NMR spectroscopy. All synthesized compounds have been screened in vitro for their antibacterial activities against a number of Gram-positive and Gram-negative bacteria.

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Untersuchungen zur Vilsmeier-Haack Reaktion, 7. Mitt.: Synthese und Reaktionen von 3-Methyl-1-phenyl-4-acetylhydrazono-2-pyrazolin-5-on(-5-thion)

Zusammenfassung Die Keto-(Thio)-Tautomeren1–4 der Hydrazonopyrazolon-/Thiopyrazolon-Derivate gingen unter Vilsmeier-Bedingungen zugleich Diformylierung, Chlorierung (Entschwefelung) und Ringschluß zu Pyrazolo[3,4-c]pyrazol-aminoacroleinen5 und6 ein. Aus5 und/oder6 konnten die entsprechenden Pyrazolo[3,4-c]pyrazole mit verschiedenen heterocyclischen Systemen in 3-Position erhalten werden. Die Strukturen der Verbindungen wurden mittels Elementaranalyse, IR und¹H-NMR überprüft. Alle synthetisierten Verbindungen wurden in vitro bezüglich ihrer antibakteriellen Aktivität gegenüber einer Anzahl Gram-positiver und Gram-negativer Bakterien untersucht.

     

Polyethylene glycol-promoted synthesis of pyrimido[1,2-a]benzimidazole and pyrano[2,3-c]pyrazole derivatives in water

Synthesis of pyrimido[1,2-a]benzimidazole and pyrano[2,3-c]pyrazole derivatives were achieved using polyethylene glycol (PEG-400) as promoting reaction medium in water under catalyst-free conditions at reflux and room temperature, respectively. The structure of pyrimido[1,2-a]benzimidazole was confirmed using ¹H NMR, ¹³C NMR, DEPT, and HMBC experiments. The promising points for the present methodology are efficiency, generality, high yield, short reaction time, cleaner reaction profile, ease of product isolation, simplicity, potential of recycling reaction medium, and finally agreement with green chemistry protocols.     

Reactions of 6-Amino-5-Cyano-3-Methyl-1,4-Diphenyl-1H 4H-Pyrano[2,3-C]Pyrazole and its Methanimidate

Reaction of 6-amino-5-cyano-3-methyl-1,4-diphenyl- 1H,4H-pyrano[2,3-c]pyrazole 1 with triethyl orthoformate in acetic anhydride gave its methanimidate 2, which reacts with primary aliphatic and aromatic amines to give 4,6-dihydro-3-methyl-1,4-diphenyl-6- (alkyl)pyrazolo[4′,3′:5,6]pyrano[2,3-d]pyrimidine-5(lH)- imine 3 and the starting compound 1 , respectively. Treatment of 1 with o-aminophenol gave 5-(2-benzoxalyl)- 1,4-dihydro-3-methyl-1,4-diphenylpyrano[2,3-c]pyrazol- 6-amine 9.     

Synthesis of 5-Hydroxymethyl-8-methyl-3-(3-aryl-[1,2,4]oxadiazol-5-yl)-2H-pyrano[2,3-c]pyridin-2-ones and Their Esters

New 5-hydroxymethyl-8-methyl-3-(3-aryl-[1,2,4]oxadiazol-5-yl)-2H-pyrano-[2,3-c]pyridin-2-ones and their esters were synthesized. The structure of obtained compounds was determined through a complete ¹H NMR analysis.     

新型受体呋喃并[3’,4’:5,6]吡啶并[2,3-c]吡唑的合成及对阴离子的识别研究

设计并合成了5种呋喃并[3’,4’:5,6]吡啶并[2,3-c]吡唑受体分子, 利用紫外-可见吸收光谱考察了其与F－, Cl－, Br－, AcO－, 等阴离子的作用. 结果表明该类受体分子与阴离子形成氢键配合物, 导致呋喃并吡啶并吡唑受体的光谱发生变化. 测定了配合物的结合比和稳定常数, 发现受体化合物对F－, AcO－离子具有良好的选择性, 对其它多种阴离子无影响. Job曲线表明受体分子与阴离子间形成1∶1型的配合物.     

Electrochemically induced one pot synthesis of 1,4-dihydropyrano[2,3-c]-pyrazole-5-carbonitrile derivatives via a four component-tandem strategy

An efficient one pot, multicomponent-tandem synthesis of highly functionalized 1,4-dihydropyrano[2,3-c]-pyrazole-5-carbonitrile is reported by electrochemically induced condensation of ethyl acetoacetate, hydrazine hydrate, malononitrile and various aromatic aldehydes. The reaction is carried out in an undivided cell, at a constant current in the presence of NaBr as a supporting electrolyte and ethanol as solvent.     

磷酸氢二钾催化多组分一锅法反应合成1,4-二氢吡喃并[2,3-c]吡唑衍生物

绿色、简便、高效的催化四组分反应合成吡喃并[2,3-c]吡唑类杂环化合物是当今有机化学领域的研究热点。 本文发展了在水与聚乙二醇(PEG-200)的混合液中,廉价易得的磷酸氢二钾(K₂HPO₄·3H₂O)催化乙酰乙酸乙酯、水合肼、芳香醛和丙二腈的多组分“一锅法”反应,合成一系列1,4-二氢吡喃并[2,3-c]吡唑-5-腈衍生物,产率为88%~98%。 该方法避免了使用复杂昂贵的催化剂和繁琐的纯化过程。     

An environmentally friendly synthesis of 1,4-dihydropyrano[2,3-c]pyrazole derivatives catalyzed by tungstate sulfuric acid

An efficient three-component synthesis of 6-amino-4-aryl-5-cyano-3-metriyl-1-phenyl-1,4-dihydropyrano[2,3-c]pyrazoles via a reaction between 3-methyl-1-phenyl-2-pyrazolin-5-one,aromatic aldehydes and malononitrile using tungstate sulfuric acid as a catalyst was described.Mild conditions,good to excellent yields,easily available catalyst and easy work-up are the key features of this method.     

Theophylline as a new and green catalyst for the one-pot synthesis of spiro[benzo[a]pyrano[2,3-c]phenazine] and benzo[a]pyrano[2,3-c]phenazine derivatives under solvent-free conditions

A green, convenient, high yielding and one-pot procedure for the synthesis of novel spiro[benzo[a]pyrano[2,3-c]phenazine] derivatives by domino multi-component condensation reaction between 2-hydroxynaphthalene-1,4-dione, benzene-1,2-diamines, ninhydrine, and malononitrile in the presence of a catalytic amount of 1,3-dimethyl-7H-purine-2,6-dione (theophylline) as an expedient, eco-friendly and reusable solid base catalyst under thermal, microwave irradiation and solvent-free conditions. This procedure has also been applied successfully for the synthesis of benzo[a]pyrano[2,3-c]phenazines.     

活性炭负载硫化锡纳米颗粒作为高效可重复使用Lewis酸催化剂催化三组分一锅法合成4H-吡喃[2,3-c]吡唑衍生物(英文)

Tin sulfide nanoparticles(SnS -NPs) were prepared in aqueous solution at room temperature on the surface of activated carbon(AC) and were investigated using field-emission scanning electron mi-croscopy(FE-SEM), transmission electron microscopy(TEM), X-ray diffraction, reflective ultravio-let-visible spectrophotometry, and spectrofluorimetry. Calculations based on the SEM and TEM images showed that the sizes of the SnS -NPs immobilized on the AC were 30–70 nm. The prepared nanocomposite was used as a heterogeneous Lewis acid catalyst for the three-components one-pot synthesis of 4H-pyrano[2,3-c]pyrazole derivatives in ethanol at 80 ℃. The reactions were efficiently performed in the presence of the prepared catalyst in short reaction times, and gave the desired products in high yields. This catalyst can be easily recovered by simple filtration and recycled up to eight consecutive times without significant loss of its efficiency.     

An Efficient Four-Component Synthesis of Multisubstituted Pyrano[2,3-c]pyrazole

A series of substituted pyrano[2,3-c]pyrazole derivatives were synthesized by a one-pot reaction of methyl 4-methyl-3-oxovalerate, phenylhydrazine, aromatic aldehyde, and malononitrile in ethanol with catalysis by triethylamine. The title compounds were obtained in good to excellent yields. A possible mechanism for this reaction was proposed.     

四组分一锅法合成多取代吡喃[2,3-c]吡唑-5-腈

在三乙胺催化下,以乙酰乙酸甲酯、苯肼、芳醛和丙二腈等4组分为原料,经一锅法合成了一系列多取代的吡喃并[2,3-c]吡唑衍生物(5a～5j),反应在10～15 min内即可完成.所有产物由IR、1HNMR和MS确证.该方法具有产率高、操作简单等优点.     

Tin sulfide nanoparticles supported on activated carbon as an efficient and reusable Lewis acid catalyst for three-component one-pot synthesis of 4H-pyrano[2,3-c]pyrazole derivatives

Tin sulfide nanoparticles (SnS‐NPs) were prepared in aqueous solution at room temperature on the surface of activated carbon (AC) and were investigated using field‐emission scanning electron mi‐croscop...