几种具有电子级—受体结构的两亲性化合物的合成及鉴定

设计并合成了３种含有巴比妥酸基团的具有电子给－受体结构的两亲性有机分子，经元素分析、红外光谱，核磁共振谱确定了其结构，研究了醛与巴妥酸缩合的及醛的反应活性与其ＩＲ、ＮＭＲ谱的关系。     

超声辐射下水介质中三组分一锅合成吡喃并[2,3-d]嘧啶衍生物

报道了在超声波辐射下, 水相中无催化剂下通过芳香醛与丙二腈、巴比妥酸的一锅反应, 合成了一系列吡喃并[2,3-d]嘧啶衍生物. 在超声波辐射下, 不仅饱和芳香醛与丙二腈、巴比妥酸的一锅反应在室温下能高收率地进行, 而对于α,β-不饱和醛以及二元醛与丙二腈、巴比妥酸的一锅反应也能在室温下顺利进行, 获得较高的收率. 产物的结构通过IR, 1H NMR和元素分析表征. 该方法具有操作简单和环境友好等优点.     

微波辐射下吡啶[2,3-d]嘧啶衍生物的高效合成

本文以等摩尔的芳醛,巴比妥酸（或1,3-二甲基巴比妥酸）,5-氨基-2-甲基苯[d]噻唑为原料,以醋酸和乙二醇为溶剂,微波辐射下多组分一锅法合成了一系列新的吡啶[2,3-d]嘧啶衍生物。这种方法具有产率高,操作简便,反应时间短等优点。     

藏红花酸二醛的合成研究（英文）

本文提供了一种简单方便的合成2,6,11,15-四甲基-2,4,6,8,10,12,14-十六碳七烯二醛(藏红花酸二醛)的方法,即通过2,7-二甲基-2,4,6-辛三烯二醛与3-(5,5-二甲基-1,3-二恶烷-2-基)丁-2-烯基膦酸二乙酯或(3-甲基-4-氧代-2-丁烯-1-基)膦酸二乙酯进行霍纳尔-沃兹沃思-埃蒙斯(HWE)反应,以四氢呋喃为溶剂,氢化钠或叔丁醇钾为碱来合成藏红花酸二醛。所得到的化合物经过红外,核磁共振氢谱,碳谱以及质谱确认。     

三组分一锅法合成3-(2-喹啉基)薁甲酸甲酯衍生物

在质子酸作用下, 以1-甲酰基薁-3-甲酸甲酯、芳香胺和脂肪醛为原料, 三组分一锅法合成了一系列3-(2-喹啉基)薁甲酸甲酯衍生物. 该反应收率良好、操作简单、条件温和. 产物的结构通过红外光谱、核磁共振谱和元素分析证实, 同时给出了该反应可能的反应机理.     

5-（吲哚基-3-次甲基）（硫代）巴比妥酸的合成

以冰乙酸为催化剂,吲哚-3-甲醛与巴比妥酸或硫代巴比妥酸在无水乙醇中进行Knoevenagel缩合,合成了5-(吲哚基-3-次甲基)巴比妥酸或5-(吲哚基-3-次甲基)(硫代)巴比妥酸,其结构经1H NMR和IR表征.     

2,5- 二取代 2,3- 二氢-1,2,4- 均三唑并 [3,4 b] 1,3,4 噻二唑的合成及生物活性

３对硝基苯基／ 间硝基苯基４氨基５巯基１ ,２ ,４三唑与醛在酸催化作用下,合成了１７ 种新的稠杂环化合物． 研究了合成反应的条件及不同催化剂对反应产物的影响． 通过元素分析、红外光谱、核磁共振氢谱和质谱确证了结构,测定了生物活性． 结果表明,部分化合物抗菌作用较强．     

5-(取代吡唑基-4-次甲基)(硫代)巴比妥酸的合成

以冰乙酸为催化剂,将取代吡唑甲醛和巴比妥酸或硫代巴比妥酸在无水乙醇中进行Knoevenagel缩合反应,合成了6个5-（取代吡唑基-4-次甲基）（硫代）巴比妥酸。标题化合物经IR、1^HNMR、元素分析确证结构。     

5-(色酮基-3-次甲基)(硫代)巴比妥酸的合成

将巴比妥酸或硫代巴比妥酸、3-甲酰基色酮在乙酸-乙酸酐溶液(含乙酸酐10%)中进行缩合反应,制备了5-(色酮基-3-次甲基)(硫代)巴比妥酸.并经元素分析,IR,1H NMR及13C NMR确证了产物的结构.     

3-取代-5-芳基噁唑-4-酮类化合物的合成与生物活性

以香草醛和取代扁桃酸为原料, 经多步反应合成了N-取代苯乙基扁桃酰胺, 在对甲苯磺酸催化下, 和醛脱水关环, 得到一系列新颖的3-取代苯乙基-5-芳基噁唑-4-酮类化合物和N-扁桃酰四氢异喹啉类化合物. 所有化合物通过红外光谱、核磁共振氢谱、元素分析和高分辨质谱对其结构进行表征, 并对其构效关系进行了讨论.     

A study on the physical properties of low melting mixtures and their use as catalysts/solvent in the synthesis of barbiturates

In recent years, deep eutectic solvents have become attractive due to their interesting characteristics such as, physicochemical properties, low cost of components, easiness to prepare, low toxicity, bio-renewability, and biodegradability. In order to make the deep eutectic mixture more cost-effective and renewable, carbohydrate derivatives were linked with deep eutectic mixtures, since, carbohydrates are the most important and widespread renewable compounds on the earth. In this work, we have used low melting mixtures comprised of carbohydrates to create the reaction media for organic transformations. The physical properties such as density, viscosity, acidity, refractive index, surface tension, solubility, glass transition temperature, thermal stability, solvent polarity, and toxicity of the mixture were studied. Low melting mixtures were used as reaction media and catalysts for the effective synthesis of Barbiturates. The reaction between aldehydes and barbituric acid/thiobarbituric acid, and the reaction between aldehydes, barbituric acid/thiobarbituric acid, and malononitrile/dimedone were performed effectively with good to excellent yields. The recyclability of the catalyst/solvent was also established.     

Preparation of 5,5′‐pyrilidene and 5,5′‐quinolidene bis‐barbituric acid derivatives

NMR reaction following experiments were used to find optimal conditions for the barbituric acid double addition to aromatic and heteroaromatic carboxaldehydes. It was established that aromatic aldehydes with electron‐donating substituents such as hydroxy, methoxy, and dimethylamino produce only the single addition barbituric acid adduct (barbituric acid benzylidenes). If these electron‐donating substituents are transformed into electron‐withdrawing substituents by virtue of protonation (NMe₂ to NHMe₂⁺) then the double barbituric acid adduct becomes the sole product of the reaction. This is also true regardless of the reaction media if strong electron‐withdrawing substituents (such as a nitro group) are present. Considering that the reactive species for nitrogen containing aromatic heterocycles are actually the conjugated acids (electron deficient molecule) only the double barbituric acid adducts are isolated. All synthetic procedures presented are applicable to multi‐gram scale preparations of double barbituric acid adducts.     

The Reaction Activity of Aromatic Carbonyl Compounds with Diphenylphosphine Oxide Studied by 31P NMR

Abstract

A series of α-hydroxyphosphine oxides were prepared by the reactions of diphenylphosphine oxide and aromatic carbonyl compounds and characterized by ¹H NMR, ¹³C NMR, ³¹P NMR, FT-IR, ESI-MS, and HR-MS spectra. The reaction rates and experimental conditions of aromatic aldehydes and aromatic ketones were obviously different due to the activity of their carbonyls. The different substituents of the aromatic aldehydes affected the reaction rate too, and the quantitative reactivity of their substituent conformed to the Hammett equation. The results were confirmed by ³¹P NMR spectroscopy.     

室温离子液体促进的5-亚芳基巴比妥酸衍生物的合成

在室温离子液体1-丁基-3-甲基咪唑四氟硼酸盐([bmim]BF₄)存在下, 采用室温研磨和微波辐射的方法, 由芳香醛和巴比妥酸或硫代巴比妥酸经Knoevenagel缩合反应, 制备了相应的5-亚芳基巴比妥酸或5-亚芳烃基硫代巴比妥酸衍生物. 在室温研磨条件下反应2 h, 产率为78%～96%, 在微波辐射功率为160 W时反应20 s, 产率为82%～98%, 产物结构经¹H NMR确证.     

3,6-二取代-5,6-二氢-1,2,4-三唑并[3,4-b]-1,3,4-噻二唑的合成及生物活性

以３－芳基－４－氨基－５－巯基－１,２,４－三唑为原料,在酸催化下与醛类发生分子内的Ｍａｎｎｉｃｈ反应,合成了１４个标题化合物,其结构经元素分析、ＩＲ、＾１ＨＮＭＲ和ＭＳ确证。研究了反应条件。生物活性测定结果表明,部分化合物具有较强的生物活性。     

One-pot three-component synthesis of chromeno [2,3-d] pyrimidine derivatives: Novel,simple, and efficient electrochemical approach

An atom economical, selective, and convenient one-pot protocol for the synthesis of the medicinally privileged novel chromeno [2,3-d] pyrimidine scaffold, viz, multicomponent reaction of barbituric acid derivatives, 1,3 cyclic diketone, and various aldehydes in the presence of tetra n-butyl ammonium iodide (TBAI) as an electrolyte in water media under room temperature, is reported. This ecologically sound novel concept offers environmentally benign synthetic route, short reaction times, and easy workup procedure with excellent yield (88% to 90%) and is also beneficial for diversity-oriented large-scale processes. The synthesized products were characterized by IR, MS, NMR, and CHN analysis.     

Etude de la réactivité de la fonction carbonyle avec le cétène en présence d'un alcoxyde de titane. 1ère communication. Nouvelle méthode de synthèse de β-hydroxyesters

A new synthesis of β-hydroxyesters involving a reaction between a carbonyl compound, ketene and an alkyl-orthotitanate is described. The following carbonyl compounds have been studied: aldehydes, ketones, α-diketones, α- or γ-ketoesters. A reaction mechanism is proposed.     

A Novel Route for the Diastereoselective Synthesis of Dispiro[tetrahydroquinoline‐bis(2,2‐dimethyl[1,3]dioxane‐4,6‐dione)] Derivatives via a One‐Pot Domino Multicomponent Reaction of Arylamines,Aromatic Aldehydes,and Meldrum's Acid

A protocol has been developed for the diastereoselective synthesis of dispiro[tetrahydroquinoline‐bis(2,2‐dimethyl[1,3] dioxane‐4,6‐dione)] derivatives via a one‐pot domino multicomponent reaction of arylamines, aromatic aldehydes, and Meldrum's acid for the first time. The products, with remarkable diastereoselectivity, were successfully synthesized in acetic acid media in ambient temperature along with the suggested mechanism through combination of domino Knoevenagel, Michael, and Diels–Alder reactions. The products have been characterized by IR, mass, ¹H NMR, ¹³C NMR spectroscopy, and elemental analyses. The stereoselectivity of compounds was established with crystallography and NMR spectroscopy.     

水介质中微波促进一锅法合成吡喃并[2,3-d]嘧啶衍生物

水相中将芳香醛、丙二腈和巴比妥酸以等摩尔比混合,微波辐射5~15 min,合成了9种7-氨基-6-氰基-5-芳基吡喃并[2,3-d]嘧啶二酮,产率为80%~92%,避免了传统合成法反应时间长和中间体分离的繁琐操作,减少了环境污染。 产物结构通过IR、¹H NMR和元素分析测试技术进行了表征。