Solid state reactions of nitrogenous heterocyclic compounds(Ⅰ)——Solid state reactions of 3-methyl-l-phenyl-5-pyrazolone with carbonyl compounds

The solid state reaction of 3-methyl-1-phenyl-5-pyrazolone (MPP) with aromatic aldehydes and ke-tones benzil derivatives and imides,and the solid state Michael addition reaction of MPP with 4-arylidene-3-methyl-1-phenyl-5-pyrnzolone 2 were investigated.Some new solid state reactions between the reactants were found,from which a series of new compounds were obtained The structures of the products were identified by IR,1H NMR,MS,elemental analyses and also by X-ray crystal analysis,and the reaction mechanism of MPP with aromatic aldehydes and ketones was proposed     

Ca(NO3)2•4H2O-catalysed Biginelli Reaction: One-pot Synthesis of 1,2,3,4-Tetrahydropyrimidin-2-ones/pyrimidine-2-thiones under Solvent-free Conditions

The synthesis of 1,2,3,4-dihydropyrimidinone/thione derivatives was achieved in good to excellent yields using calcium(II) nitrate as catalyst to promote the Biginelli three-component condensation reaction from a diversity of aromatic aldehydes, β-keto compounds and urea or thiourea. The reaction was carried out under solvent-free conditions.     

The efficient synthesis of 14-alkyl or aryl 14H-dibenzo[a,j]xanthenes catalyzed by bismuth(Ⅲ)chloride under solvent-free conditions

An efficient method for the synthesis of 14-alkyl or aryl 14H-dibenzo[a,j]xanthene derivatives by the reaction of β-naphthol,and aldehydes in the presence of a catalytic amount of bismuth（Ⅲ） chloride（BiCl₃） under solvent-free conditions at 110℃is described.Aliphatic and aromatic aldehydes were used in the reaction and in all cases the desired products were synthesized successfully.This reaction was studied under different temperatures;the maximum yield was obtained in a short reaction period at 110℃.The method offers the advantages of high yields,short reaction times,simplicity and easy workup compared to the conventional method of syntheses.     

Propylphosphonic anhydride(T3P~) catalyzed one-pot synthesis of α-aminonitriles

The Strecker reaction was performed via a one-pot three component condensation of hetero aromatic/aromatic aldehydes, secondary amines and trimetylsilyl cyanide in the presence of propylphosphonic anhydride(T3P~) to accomplish the corresponding a-aminonitriles. The main advantages of this method are very short reaction time and excellent yields.     

An Efficient One-pot Synthesis of β-Amino/β-Acetamido Carbonyl Compounds via ZrCl4-catalyzed Mannich-type Reaction

Zirconium(IV) chloride catalyzed efficient one-pot synthesis of β-amino/β-acetamido carbonyl compounds at room temperature is described. In the presence of ZrCl4, the three-component Mannich-type reaction via a variety of in situ generated aldimines, with various ketones, aromatic aldehydes and aromatic amines in ethanol, led to the formation of β-amino carbonyl compounds and the four-component Mannich-type reaction of aromatic aldehydes with various ketones, acetonitrile and acetyl chloride resulted in the corresponding β-acetamido carbonyl compounds in high to excellent yields. This methodology has also been applied towards the synthesis of dimeric β-amino/β-acetamido carbonyl compounds.     

Sulfonated poly(4-vinylpyridine) heteropolyacid salts:A reusable green solid catalyst for Mannich reaction

Sulfonated poly（4-vinylpyridine） heteropolyacid salts acted as a heterogeneous catalyst to effectively catalyze the one-pot synthesis of β-amino carbonyl compounds via the Mannich reaction between aromatic aldehydes, aromatic ketone, and aromatic amines. In addition, the catalyst could be easily recovered by the filtration and reused six times without significant loss of catalytic activity.     

采用燃烧技术制备CuO纳米粒子:一种高效且环境友好的用于芳族醛合成芳族腈催化剂(英文)

CuO nanoparticles were synthesized using an energy-efficient and rapid solution combustion technique with malic acid employed as a fuel. The combustion-derived CuO nanoparticles were used as catalysts in a one-pot synthesis of aromatic nitriles from aromatic aldehydes and hydroxylamine hydrochloride. The catalyst was characterized by X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray analysis, transmission electron microscopy, and Brunauer-Emmett-Teller surface area analysis. The catalytic activity of the CuO nanoparticles in the synthesis of aromatic nitriles from aromatic aldehydes was evaluated. The present protocol offers the advantages of a clean reaction, simple methodology, short reaction duration (1-2 min), and high yield (85%-98%). The catalytic activity of the CuO nanoparticles was found to be higher than that of bulk CuO powder under the same conditions. The catalyst can also be recovered and reused up to four times with no significant loss of catalytic activity. The present approach is inexpensive and is a convenient technique suitable for industrial production of CuO nanoparticles and nitriles.     

Solid state reactions of nitrogenous heterocyclic compounds (Ⅱ)——Solid state reactions of indole with carbonyl compounds

Solid state Michael addition reaction of indole with α,β-unsaturaled carbonyl compounds was carried out,by which a series of compounds containing three different heterocyclic groups binding to one carbon atom were obtained.In the presence of Lewis acid,indole could undergo the solid state condensation reaction with aromatic ketones and aldehydes or quinones.The solid state reaction showed higher selectivity and yield than solution reaction The structures of products were identified by IR,1H NMR,MS,elemental analysis and X-ray crystal analysis.The reaction mechanism was also proposed.     

无溶剂条件下用于合成3,4-二氢嘧啶-2(1H)-酮的高效、可磁性回收Fe_3O_4纳米粒子催化剂(英文)

The catalytic activity of Fe3O4 nanoparticles (NPs) in a one-pot three component condensation reaction consisting of an aromatic aldehyde, urea or thiourea, and a β-dicarbonyl under solvent-free conditions was investigated. This reaction affords the corresponding dihydropyrimidinones (thiones) in high to excellent yields. Compared with the classical Biginelli reactions this method consistently gives a high yield, easy magnetic separation, a short reaction time, and catalyst reusability.     

Mukaiyama Aldol Reaction of 1,2-Bis(trimethylsiloxy)Cyclobutene Catalyzed by Magnesium( Ⅱ）Iodide

Efficient Mukaiyama-type aldol reaction of 1,2-bis(trimethylsiloxy)cyclobutene with aromatic aldehydes catalyzed by MgI2 is reported.The resulting succinoylation product of aldehyde was converted into the synthetic useful γ-lactone and butenolide derivatives.     

Ga(OTf)3-catalyzed Three-component Mannich Reaction in Water Promoted by Ultrasound Irradiation

Ga(OTf)₃‐catalyzed three‐component Mannich reaction of aromatic aldehydes, aromatic amines and cycloketones in water promoted by ultrasound gave the corresponding β‐amino cycloketones in good to excellent yields and good anti selectivities.     

Synthesis of 4‐((2‐hydroxynaphthalen‐1‐yl)(aryl)methyl)‐5‐methyl‐2‐phenyl‐1H‐pyrazol‐3(2H)‐ones using nano‐Zn‐[2‐boromophenyl‐salicylaldimine‐methylpyranopyrazole]Cl2 nanoparticles

Nano‐Zn‐[2‐boromophenyl‐salicylaldimine‐methylpyranopyrazole]Cl₂ (nano‐[Zn‐2BSMP]Cl₂) as a nanoparticle Schiff base complex and a catalyst was introduced for the solvent‐free synthesis of 4‐((2‐hydroxynaphthalen‐1‐yl)(aryl)methyl)‐5‐methyl‐2‐phenyl‐1H‐pyrazol‐3(2H)‐ones by the multicomponent condensation reaction of various aromatic aldehydes, β‐naphthol, ethyl acetoacetate, and phenyl hydrazine at room temperature.     

Chemoselectivity in the Reaction of 2‐Diazo‐3‐oxo‐3‐phenylpropanal with Aldehydes and Ketones

The chemoselectivity in the reaction of 2‐diazo‐3‐oxo‐3‐phenylpropanal ( 1 ) with aldehydes and ketones in the presence of Et₃N was investigated. The results indicate that 1 reacts with aromatic aldehydes with weak electron‐donating substituents and cyclic ketones under formation of 6‐phenyl‐4H‐1,3‐dioxin‐4‐one derivatives. However, it reacts with aromatic aldehydes with electron‐withdrawing substituents to yield 1,3‐diaryl‐3‐hydroxypropan‐1‐ones, accompanied by chalcone derivatives in some cases. It did not react with linear ketones, aliphatic aldehydes, and aromatic aldehydes with strong electron‐donating substituents. A mechanism for the formation of 1,3‐diaryl‐3‐hydroxypropan‐1‐ones and chalcone derivatives is proposed. We also tried to react 1 with other unsaturated compounds, including various olefins and nitriles, and cumulated unsaturated compounds, such as N,N′‐dialkylcarbodiimines, phenyl isocyanate, isothiocyanate, and CS₂. Only with N,N′‐dialkylcarbodiimines, the expected cycloaddition took place.     

Rapid Synthesis of 1,2,3,4-Tetrahydropyrimidin-2-ones Using Zn（NH2SO3）2 as a Catalyst under Microwave Irradiation

Rapid synthesis of 1,2,3,4-tetrahydropyrimidin-2-ones （THPO） from aromatic aldehydes, β-ketoester and urea （or thiourea） using zinc sulfamate as the catalyst under microwave irradiation was described here. Compared with the classical Biginelli reaction, this new method consistently has the advantages of good yields （76%-96%）, short reaction time （3-15 min）, no corrosion to equipments, ease of manipulation, and low cost catalyst.     

Synthesis,characterization and application of 3‐methyl‐1‐sulfonic acid imidazolium tetrachloroferrate as nanostructured catalyst for the tandem reaction of β‐naphthol with aromatic aldehydes and amide derivatives

3‐methyl‐1‐sulfonic acid imidazolium tetrachloroferrate {[Msim]FeCl₄} was prepared and fully characterized by fourier transform infrared spectroscopy (FT‐IR), X‐ray diffraction (XRD), thermal gravimetric analysis (TGA), differential thermal gravimetric (DTG), field emission scanning electron microscopy (FESEM), energy dispersive X‐ray analysis (EDX) and vibrating sample magnetometer (VSM) and used, as an efficient catalyst, for the tandem reaction of β‐naphthol with aromatic aldehydes and benzamide at 110 °C under solvent‐free conditions to give 1‐amidoalkyl‐2‐naphthols in high yields and very short reaction times.     

Yb(OTf)3催化苯乙酮、芳香醛和芳香胺的Mannich反应: 三组分“一锅法”合成β-氨基酮衍生物

报道了稀土化合物Yb(OTf)₃催化的苯乙酮、芳香醛和芳香胺Mannich反应, 三组分“一锅法”合成了一系列的β-氨基酮衍生物. 该方法操作简单、条件温和、产率较高、催化剂可重复使用, 且对环境友好.     

Sulphamic Acid （H2NSO3H）-Catalyzed Multicomponent Reaction of β-Naphthol： An Expeditious Synthesis of Amidoalkyl Naphthols

Sulphamic acid （H2NSO3H） was found to be an efficient catalyst for the multicomponent condensation reaction of β-naphthol, aromatic aldehydes and urea or amides to afford the corresponding α-amidoalkyl-β-naphthols in good yields. The remarkable features of this new procedure are high conversions, short reaction time, clean reaction profiles and simple experimental and work-up procedures.     

Synthesis,kinetics and mechanism of the reaction of a quasi‐aromatic copper(II) complex, [Cu(PnAO)‐6H]0, with aromatic aldehydes

The quasi‐aromatic metal complex (1,1,2,8,9,9‐hexamethyl‐4,6‐dioxa‐5‐hydro‐3,7,10,14‐tetraazacyclotetradecane‐2,7,10,12‐tetraene)copper(II), [Cu(PnAO)‐6H]⁰ (AH), was synthesized. Reactions of AH were studied spectrophotometrically in acidic media (pH = 1 ∼ 2, EtOH:H₂O = 1:4 v/v) with para‐substituted benzaldehydes (ald). The Cu,2N,3C quasi‐aromatic heterocyclic ring in AH is highly reactive at the central‐aromatic‐carbon atom, C12, to most aldehydes. A novel parallel, competitive and consecutive second‐order reaction mechanism is proposed. To obtain the rate constants following this mechanism, the Gauss‐Newton‐Marquardt and Runge‐Kutta methods were employed. Consistent results were obtained. Effects of acidity, solvent, temperature and substituent R (RH, CH₃, OCH₃, Cl) of the aromatic aldehydes on the reaction rate constants were studied. The results support the proposed SN2 mechanism. A linear free energy relationship between the rate constant k₁ and the Hammett parameters for the substituted benzaldehydes as well the activation parameters are presented. © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 33: 1–8, 2001     

Outer‐sphere reduction of hexacyanoferrate(III) by enolizable and nonenolizable aldehydes in alkaline medium

Outer‐sphere reduction of hexacyanoferrate(III) by some enolizable/nonenolizable aldehydes (viz., aliphatic, heterocyclic, and aromatic aldehydes) in alkaline medium has been studied spectrophotometrically at λ_max = 420 nm. The reactions are first order each in [aldehyde] and [Fe(CN)₆^3?]. The rate increases with an increase in [OH^?] in the oxidation of aliphatic and heterocyclic aldehydes, whereas it is independent of [OH^?] in the reaction with aromatic aldehydes. The intervention of free radicals in the reaction mixture was carried out using both acrylonitrile and acrylamide scavenger in two different experiments. The kinetic results indicate that the oxidation of benzaldehyde in aqueous medium proceeds at a slower rate than the aliphatic aldehydes (other than formaldehyde) and furfural. The values of third‐order rate constant (k₃) at 308 K in the oxidations of some aliphatic aldehydes and furfural follow the order (CH₃)₂CH? > CH₃CH₂? > CH₃? > C₄H₃O? > H? . The rate constants correlate with Taft's σ* value, the reaction constant being negative (–9.8). The pseudo–first‐order rate constants in the oxidations of benzaldehyde and substituted benzaldehydes follow the order ? NO₂ > ? H > ? Cl > ? OCH₃. The Hammett plot is also linear with a ρ value (0.6488) for meta‐ and para‐substituted benzaldehydes. The kinetic isotope effect for benzaldehyde (k_H/k_D = 1.93 at 303 K) was obtained. The rate‐determining step is the outer‐sphere formation of Fe(CN)₆^4? and free radicals, which is followed by the rapid oxidation of free radicals by Fe(CN)₆^3? to give products. The kinetic data and hence thermodynamic parameters have been used to distinguish enolizable and nonenolizable aldehydes. An attempt has also been made to correlate kinetic data with hydration equilibrium constants of some aliphatic aldehydes. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 44: 494–505, 2012