Influence of temperature on metal-organic frameworks

Reaction temperature is one of the key parameters in the synthesis of metal-organic frameworks （MOFs）. Though there is no convergence with regard to the various experimental parameters, reaction temperature has been found to have remarkable influence on the formation and structure of MOFs, especially toward the control of topology and dimensionality of the MOF structures. Theoretically, the reaction temperature affects directly the reaction energy barrier in reaction thermodynamics and the reaction rate in the reaction kinetics. This review aims to show the influence of reaction temperature on crystal growth/assembly, structural modulation and transformation of MOFs, and to provide primary information and insights into the design and assernblv of desired MOFs.     

MOLYBDENUM-SULFUR AND TUNGSTEN-SULFUR CLUSTERS AS CATALYSTS IN THE REDUCTIVE REACTION OF AZOBENZENE

A series of Mo-S and W-S clusters has been synthesized and used as catalysts in thereductive reaction of azobenzene.The reaction conditions are mild and the yields are fairlyhigh.The reaction mechanism is discussed.     

2020 Roadmap on gas-involved photo-and electro-catalysis

In this roadmap, we address the development and perspectives of hydrogen evolution reaction, oxygen reduction reaction, oxygen evolution reaction, carbon dioxide reduction reaction and nitrogen reduction.     

Facile synthesis of phthalan derivatives via a Pd-catalyzed tandem hydroalkynylation,isomerization, Diels-Alder cycloaddition and aromatization reaction

A novel Pd-catalyzed tandem reaction involving hydroalkynylation,isomerization.Diels-Alder cycloaddition and aromatization reaction to produce phthalan derivatives in moderate yields is reported.The reaction is atom economical and occurs in a highly ordered fashion.The reaction mechanism is discussed.     

Theoretical study on the reaction of VS~ (~3∑~-,~1Γ)with CO

Two possible reaction mechanisms of VS~ (~3∑~-,~1Γ)with CO in the gas phase have been studied by using B3LYP/TZVP and CCSD(T)/6-311 G(3dr,3pd)methods:the O/S exchange reaction(VS~ CO→VO~ CS)and the S-transfer reaction (VS~ CO→V~ COS).The two reactions proceed via two-step and one-step mechanism,respectively.The barriers of the triplet and singlet PESs are 30.6 and 50.9 kcal/mol,respectively,for O/S exchange reaction and 7.3 and 50.2 kcal/mol,respectively, for the S-transfer reaction.The results indicate that the triplet ground state reaction is more favorable,and the S-transfer reaction is more favorable than the O/S exchange reaction,which is in good agreement with the experimental observation.     

Theoretical study on the reaction of VS^＋（^3∑^-, 1^Г） with CO

Two possible reaction mechanisms of VS^＋（^3∑^-, 1^Г） with CO in the gas phase have been studied by using B3LYP/TZVP and CCSD（T）/6-311＋G （3df, 3pd） methods： the O/S exchange reaction （VS^＋＋CO→VO^＋＋CS） and the S-transfer reaction （VS^＋ ＋ CO → V^＋ ＋ COS）. The two reactions proceed via two-step and one-step mechanism, respectively. The barriers of the triplet and singlet PESs are 30.6 and 50.9 kcal/mol, respectively, for O/S exchange reaction and 7.3 and 50.2 kcal/mol, respectively, for the S-transfer reaction. The results indicate that the triplet ground state reaction is more favorable, and the S-transfer reaction is more favorable than the O/S exchange reaction, which is in good agreement with the experimental observation.     

Pulse radiolysis study on the mechanisms of reactions of CCl_3OO radical with quercetin, rutin and epigallocatechin gallate

The mechanisms of reactions between CCI3OO radical and quercetin, rutin and epigal-locatechin gallate (EGCG) have been studied using pulse radiolytic technique. It is suggested that the electron transfer reaction is the main reaction between CCI3OO radical and rutin, EGCG, but there are two main pathways for the reaction of CCI3OO" radical with quercetin, one is the electron transfer reaction, the other is addition reaction. The reaction rate constants were determined. It is proved that quercetin and rutin are better CCI3OO radical scavengers than EGCG.     

Topological studies on IRC paths of the isomerization reaction of silicon methyl-nitrene

On the basis of kinetic study of isomerization reaction of H_3Si-N, ab initio (RHF, UHF/6-31G) calculations on some points of the singlet and triplet reaction paths were carried out. The breakage and formation of chemical bond in the reaction are discussed. The calculated results show that there is a transitional structure of three-membered ring on each of reaction paths. A 'structural transition region' and a 'structural transition state' in both of studied reaction are found. Our previous conclusion that the structure transition state (STS) always appears before the energy transition state (ETS) in endothermic reaction and after ETS in exothermic reaction is further confirmed. The relationship between the change of spin density distribution and the structural transition state are investigated.     

The effects of ultrasound frequency and power on the activation energy in Si-KOH reaction system

The activation energy is the minimum amount of energy required to initiate a reaction. It is one of the important indexes for appraising a reaction. The chemical reaction rate is closely related to the value of activation energy, and reducing activation energy is propitious to promoting a chemical reaction. In the present paper, the relationship between the activation energy in Si-KOH reaction system and the ultrasound frequency and power has been discussed for the first time. The range of ultrasound frequency and power is 40-100kHz （interval by 20kHz） and 10-50W （interval by 10W）, respectively. The experimental clata indicate that the activation energy decreases with the increasing ultrasound power. Comparing with the activation energy without ultrasound irradiation, the results in our paper indicate that ultrasound irradiation could reduce the activation energy in Si-KOH reaction system and increase the reaction rate.     

Exploration of structure and mechanism of insoluble gels formed in microwave-assisted Suzuki coupling for poly(9,9-dihexylfluorene)s

A series of poly(9,9-dihexylfluorene)s (PDHFs) have been synthesized via microwave-assisted Suzuki and Yamamoto coupling reactions. Compared with the conventional oil-bath heating (48 h, Mw 20100 g/mol by Suzuki reaction and Mw 24000 g/mol by Yamamoto reaction), microwave-assisted polymerization can yield PDHFs with higher molecular weights (Mw 37200 g/mol by Suzuki reaction and Mw 43400 g/mol by Yamamoto reaction) in shorter time (14 and 60 min). However, sometimes formation of insoluble gels was observed together with PDHF in Suzuki coupling reaction. PDHF and insoluble gels were analyzed by XPS, elemental analysis, FTIR, TGA and DSC. Experimental results demonstrated that H2O might take part in the Suzuki coupling reaction under microwave condition, which could make the cross-linking reaction occur and form gels.     

A One‐Pot Tandem Ugi Multicomponent Reaction (MCR)/Click Reaction as an Efficient Protecting‐Group‐Free Route to 1H‐1,2,3‐Triazole‐Modified α‐Amino Acid Derivatives and Peptidomimetics

By a one‐pot tandem Ugi multicomponent reaction (MCR)/click reaction sequence not requiring protecting groups, 1H‐1,2,3‐triazole‐modified Ugi‐reaction products 6a – 6n (Scheme 1 and Table 2), 7a – 7b (Table 4), and 8 (Scheme 2) were synthesized successfully. i.e., terminal, side‐chain, or both side‐chain and terminal triazole‐modified Ugi‐reaction products as potential amino acid units for peptide syntheses. Different catalyst systems for the click reaction were examined to find the optimal reaction conditions (Table 1, Scheme 1). Finally, an efficient Ugi MCR+Ugi MCR/click reaction strategy was elaborated in which two Ugi‐reaction products were coupled by a click reaction, thus incorporating the triazole fragment into the center of peptidomimetics (Scheme 3). Thus, the Ugi MCR/click reaction sequence is a convenient and simple approach to different 1H‐1,2,3‐triazole‐modified amino acid derivatives and peptidomimetics.     

A kinetic study of the high temperature rearrangement of 4‐ethyl‐3,5‐diphenyl‐4H‐1,2,4‐triazole

The kinetics of the thermal rearrangement 4‐ethyl‐3,5‐diphenyl‐4H‐1,2,4‐triazoles, 1 , to the corresponding 1‐ethyl‐3,5‐diphenyl‐1‐alkyl‐1H‐1,2,4‐triazoles, 2 , was studied in 15‐Crown‐5 and octadecane at 330 °C. The reaction was very slow in octadecane but proceed well in 15‐Crown‐5. The reaction order for the reaction was not constant but changed from an initial second order rate law towards a first order rate law as the reaction progressed. This was confirmed by the concentration dependent reaction order, n_c, which was larger than the time dependent rate law, n_t. The rationale for the observation was, that at high substrate concentrations the reaction order was second order while at lower concentrations a competing solvent assisted reaction plays an increasing important role. The data were in agreement with a mechanism in which the neutral 4‐alkyl‐triazoles in an intermolecular nucleophilic displacement reaction form a triazolium triazolate, which in a subsequent nucleophilic reaction gives the observed product.     

Synthesis of 5‐aryl and 5‐amidocamptothecins

A variety of 5‐aryl‐(20S)‐camptothecin derivatives were synthesized by the reaction of 5‐hydroxy‐(20S)‐camptothecin with aromatic hydrocarbons under Friedel‐Craft reaction conditions in moderate to good yield as diastereomeric pairs. The methodology was then extended for the synthesis of 5‐amido‐(20S)‐camptothecin derivatives by reacting 5‐hydroxy‐(20S)‐camptothecin with alkyl and aryl nitriles under Ritter type reaction conditions. The reaction is presumed to proceed through an iminium ion intermediate under Friedel Craft and Ritter type reaction condition, which is further trapped by nucleophile present in the reaction medium. J. Heterocyclic Chem., 00 , 00 (2011).     

Synthesis of 15‐Cyano‐12‐oxopentadecano‐15‐lactone and 15‐Cyano‐ 12‐oxopentadecano‐15‐lactam

15‐Cyano‐12‐oxopentadecano‐15‐lactone was synthesized in 59% total yield starting from 2‐nitrocyclododecanone by Michael addition to acrylaldehyde, followed by reaction with trimethylsilylcyanide, hydrolysis, ring‐expansion, and Nef reaction. A two‐step, one‐pot synthesis of intermediate 2‐hydroxy‐4‐(1‐nitro‐2‐oxycyclododecyl)butanenitrile from 3‐(1‐nitro‐2‐oxocyclododecyl)propanal was developed and the conditions for the Nef reaction were studied. 15‐Cyano‐12‐oxopentadecano‐15‐lactam was synthesized in 40% total yield starting from 2‐nitrocyclododecanone by Michael addition to acrylaldehyde, followed by Strecker reaction, ring‐expansion, and Nef reaction. The conditions for the Strecker and Nef reactions were studied. The structures of the target compounds, intermediates, and by‐product were characterized by IR, ¹H‐ and ¹³C‐NMR, and elemental analysis or MS.     

Quinolone analogues 6 [1‐5]. Synthesis of 3‐halogeno‐1‐methylpyridazino[3,4‐b]quinoxalin‐4(1H)‐ones

The reaction of the quinoxaline N‐oxides 7a,b with diethyl ethoxymethylenemalonate gave the 1‐methylpyridazino[3,4‐b]quinoxaline‐4,4‐dicarboxylates 8a,b , whose reaction with N‐bromosuccinimide or N‐chlorosuccinimide afforded the 3‐halogeno‐1‐methylpyridazino[3,4‐b]quinoxaline‐4,4‐dicarboxylates 9a‐d. The reaction of compounds 9a‐d with hydrazine hydrate resulted in hydrolysis and decarboxylation to provide the 3‐halogeno‐1‐methylpyridazino[3,4‐b]quinoxaline‐4‐carboxylates 10a‐d , whose reaction with nitrous acid effected oxidation to furnish the 3‐halogeno‐4‐hydroxy‐1‐methylpyridazino[3,4‐b]quinoxaline‐4‐carboxylates 11a‐d , respectively. The reaction of compounds 11a‐d with hydrazine hydrate afforded the 3‐halogeno‐1‐methylpyridazino[3,4‐b]quinoxalin‐4‐ols 12a‐d , whose oxidation provided the 3‐halogeno‐1‐methylpyridazino[3,4‐b]quinoxalin‐4(1H)‐ones 6a‐d , respectively. Compounds 6a‐d had antifungal activities in vitro.     

Theoretical Studies on the Diastereoselectivity in the Lewis Acid Catalyzed Carbonyl?Ene Reaction: A Fundamental Role of Electrostatic Interaction

Lewis acids affect reactivity, selectivity, and mechanism in the carbonyl‐ene reaction. The diastereoselectivity in the glyoxylate‐ene reaction depends on Lewis acids. While the SnCl₄‐promoted reaction can be achieved with a high level of anti‐selectivity, the use of Al reagents leads to a high syn‐selectivity. The origin of the Lewis acid dependency of the diastereoselectivity in the carbonyl? ene reaction of (E)‐but‐2‐ene with glyoxylate was theoretically studied (HF/6‐31G*) from the point of view of differences and similarities between the ene and the Diels–Alder reactions. Though it has been widely accepted that the endo‐preference would be less obvious in the ene reaction than in the Diels–Alder reaction, our ab initio molecular studies showed that the electrostatic interaction between carbonyl O‐atom lone pair and cationic allylic central C‐atom of ene component exists in the Lewis acid‐promoted carbonyl–ene reaction to affect the transition‐state conformation. It is illustrated that such an electrostatic interaction is essential to control the exo/endo‐selectivity, which provides the diastereoselectivity of the product in the transition state of the Lewis acid promoted carbonyl? ene reaction.     

Evaluation of the thermal degradation of PC/ABS/montmorillonite nanocomposites

Polycarbonate (PC)/acrylonitrile‐butadiene‐styrene (ABS) polymer alloy/montmorillonite (MMT) nanocomposites were prepared using a direct melt intercalation technique. The pyrolytic degradation and the thermo‐oxidative degradation of the polymer alloy and the nanocomposites were studied by thermogravimetric analysis (TGA). The kinetic evaluations were performed by the model‐free kinetic analysis and the multivariate non‐linear regression. Apparent kinetic parameters for the overall degradation were calculated. The results show that PC/ABS/MMT nanocomposites have high thermal stability and low flammability. Their pyrolytic degradation and the thermo‐oxidative degradation model are different. The pyrolytic degradation reaction of the polymer is a two‐step parallel reaction model: nth‐order reaction model, and ath‐degree autocatalytic reaction with an nth‐order reaction autocatalytic reaction, whereas the thermal oxidative degradation reaction of the polymer is a two‐step following reaction model: A → B → C of nth‐order reaction model, and autocatalytic reaction model. Copyright © 2005 John Wiley & Sons, Ltd.     

Chemoselective Synthesis of β‐Amino Ester or β‐Lactam via Sonochemical Reformatsky Reaction

A series of β‐amino esters were synthesized by the reaction of N‐tosyl aldimine or N‐hydroxy aldimine with bromoacetate by sonochemical Reformatsky reaction. The β‐N‐hydroxyamino ester was obtained and the formed sensitive hydroxylamino functionality was resistant under the reaction condition. The β‐lactam also was synthesized by the reaction of N‐p‐methoxy aldimine as reacting substrate under this sonochemical Reformatsky reaction condition.     

Synthesis of 1H,7H,12bH‐Pyrano[3′,4′: 5,6]pyrano[3,4‐c][1]benzopyran‐1‐one via Domino Knoevenagel/Hetero‐Diels?Alder Reaction with Theoretical Investigations

The CuI‐catalyzed intramolecular oxa‐Diels? Alder reaction of 2‐(prop‐2‐yn‐1‐yloxy)benzaldehydes as unactivated terminal alkynes with 4‐hydroxy‐6‐methyl‐2H‐pyran‐2‐one is described. The reaction proceeds with remarkable chemoselectivity to yield pyranones 3 (Scheme 1). A theoretical investigation of the reaction in terms of HOMO? LUMO interactions in the gas phase is also reported. The reaction could be regarded as an inverse‐electron‐demand Diels? Alder cycloaddition. The theoretical results are in high agreement with the experimental evidences.     

Multicomponent Approach to Hydantoins and Thiohydantoins Involving a Deep Eutectic Solvent

We report an efficient synthetic strategy to diverse hydantoins and thiohydantoins involving a three‐component reaction with the aid of deep eutectic solvent. Here, N,N′‐dimethyl urea and N,N′‐dimethyl thiourea play a dual role as reactant and reaction medium along with l ‐(+)‐tartaric acid. The three‐component reaction provides an easy access to 5‐amino‐1,3‐dialkyl‐substituted hydantoins and thiohydantoins in good yields.