A promising cation of 4-aminofurazan-3-carboxylic acid amidrazone in desensitizing energetic materials

For the development of energetic materials, insensitive compounds have attracted considerable attention due to their improved safety and lower cost than those of sensitive energetic compounds during production, transportation, and application. In this study, insensitive 4-aminofurazan-3-carboxylic acid amidrazone was used as a cation to obtain four derivatives which were determined by X-ray single crystal diffraction. It is interesting to note that all four derivatives are insensitive to impact and friction, while the velocities of detonation for derivatives are superior to that of insensitive TATB (1,3,5-triamino-2,4,6-trinitrobenzene). Multi-factors analysis shows that the cation of 4-aminofurazan-3-carboxylic acid amidrazone is a promising furazan-based cation in desensitizing energetic compounds.

4-Aminofurazan-3-carboxylic acid amidrazone was used to obtain four derivatives confirmed by X-ray diffraction. The derivatives are insensitive to impact and friction, while the velocities of detonation are superior to that of 1,3,5-triamino-2,4,6-trinitrobenzene.     

Activator free diastereoselective 1,3-dipolar cycloaddition: a quick access to coumarin based spiro multi heterocyclic adducts

A formal diastereoselective 1,3-dipolar cycloaddition of azomethine ylide and coumarin derivatives to construct coumarin based spiro multi heterocyclics has been described. The in situ generation of azo-ylide was achieved for various heterocyclic carbonyls (indenoquinoxaline and isatin). This transformation is also suitable for maleimide dipolarophiles for the synthesis of hydro-maleimide derivatives. These decarboxylative annulations neither required any catalyst nor any activator. Further the pure products were isolated by filtration from the reaction mixture after the reaction under ambient conditions.

A formal diastereoselective decarboxylative 1,3-dipolar cycloaddition of azomethine ylide and coumarins is achieved for the synthesis of spiro multi heterocyclic adducts without engaging any catalyst or activator in good yields.     

A step-wise synthetic approach is necessary to access γ-conjugates of folate: folate-conjugated prodigiosenes

Despite the vast literature that describes reacting folic acid with a pharmacophore, this route is ineffective in providing the correct regioisomer of the resulting conjugate. We herein present a step-wise route to the preparation of nine folate conjugates of the tripyrrolic prodigiosene skeleton. The strict requirement for step-wise construction of the folate core is demonstrated, so as to achieve conjugation at only the desired γ-carboxylic acid and thus maintain the α-carboxylic site for folate receptor (FRα) recognition. Linkages via ethylenediamine, polyethylene glycol and glutathione are demonstrated.

Despite the vast literature that describes reacting folic acid with a pharmacophore, this route is ineffective in providing the correct regioisomer of the resulting conjugate.     

Cobalt(iii)-catalyzed site-selective C–H amidation of pyridones and isoquinolones

In this study, Cp*Co(iii)-catalyzed site-selective amidation of pyridones and isoquinolones using oxazolones as the amidation reagent is reported. This approach features mild conditions, high efficiency and good functional tolerance. Furthermore, gram-scale preparation and preliminary mechanism experiments were carried out. It provides a straightforward approach for the direct modification of pyridone derivatives.

In this study, Cp*Co(iii)-catalyzed site-selective amidation of pyridones and isoquinolones using oxazolones as the amidation reagent is reported.     

Application of decarboxylation reactions for improvement of dielectric properties of a methacrylic polymer

In this work, we present a method based on thermally induced decarboxylation to solve the incompatibility of dielectric properties and the developability in aqueous developer solution of dielectric materials for the application in photodefinable insulating materials. Herein, malonic acid 2-hydroxyethyl methacrylate monoester, a methacrylate monomer with β-keto acid is synthesized via phosphotungstic acid catalyzed esterification of 2-hydroxyethyl methacrylate and malonic acid. Further polymerisation is conducted with the obtained monomer to prepare poly(2-hydroxyethyl methacrylate-co-malonic acid 2-hydroxyethyl acrylate monoester). The thermally induced decarboxylation behaviors of the prepared polymer are confirmed with TGA, pyrolysis-GCMS analysis, and IR analysis. D_f/D_k tests and dissolution tests are carried out to investigate the influences of decarboxylation on the dielectric properties and dissolubility in aqueous solution, respectively. The results demonstrate that the significant changes in dielectric properties and dissolubility are due to the thermally induced decarboxylation.

Thermally induced decarboxylation solves the incompatibility between development in aqueous developer and dielectric performance.     

Preparation of spiro[indole-3,5′-isoxazoles] via Grignard conjugate addition/spirocyclization sequence

A highly efficient one-pot procedure combining conjugate addition of Grignard reagents to (2-nitroalkenyl)indoles and sub-sequent Brønsted acid-assisted spirocyclization allowed for preparation of 4′H-spiro[indole-3,5′-isoxazoles] in a diastereomerically selective fashion. Utilization of alkyl Grignard reagents provided an easy access to 4′-alkylsubstituted derivatives hardly available by other means.

One-pot procedure combining conjugate addition of Grignard reagents to (2-nitroalkenyl)indoles and subsequent acid-assisted spirocyclization allowed for diastereoselective preparation of 4′H-spiro[indole-3,5′-isoxazoles].     

Metal-free heterogeneous and mesoporous biogenic graphene-oxide nanoparticle-catalyzed synthesis of bioactive benzylpyrazolyl coumarin derivatives

We report the preparation of graphene oxide nanoparticles (GONPs), a metal-free, heterogeneous, non-toxic, reusable and mesoporous green-(acid)-catalyst obtained by sugar carbonization through a micro-wave chemical synthesis method for the synthesis of bio-active benzylpyrazolyl coumarin derivatives (BCDs) under thermal conditions (50 °C) in ethanol solvent. The obtained products were purified by re-crystallization from ethanol, assuring usability of GONPs in multicomponent reactions (MCRs) that could find wide application in the synthesis of a variety of biologically potent molecules of therapeutic significance.

Graphene oxide catalyst, obtained by table sugar carbonization, is envisaged for the synthesis of bio-active benzylpyrazolyl coumarin derivatives with considerable yield and remarkable re-usability.     

Exploring organic photosensitizers based on hemicyanine derivatives: a sustainable approach for preparation of amide linkages

Hemicyanine derivatives C1–C4 have been synthesized and show strong absorption in the visible region, good water solubility, efficient intersystem crossing, a high singlet oxygen quantum yield and high ability to transport electrons from the donor to acceptor. These hemicyanine derivatives were utilized as photocatalysts in additive/base free oxidative amidation of aromatic aldehydes in mixed aqueous media under visible light irradiation at low catalytic loading. The hemicyanine derivative C4 exhibited recyclability upto four cycles and reusability upto five cycles in oxidative amidation of aromatic aldehydes. Among all the hemicyanine derivatives, C4 shows a high photocatalytic efficiency due to a high singlet oxygen quantum yield. All the mechanism investigations showed involvement of reactive oxygen species generated by the organic triplet photosensitizer based on hemicyanine derivative for carrying out oxidative amidation of aldehyde. Our results will encourage the design of new “metal free” organic photosensitizers and their application in photocatalysis.

Hemicyanine derivatives C1–C4 have been synthesized and utilized as photocatalysts in additive/base free oxidative amidation of aromatic aldehydes in mixed aqueous media under visible light irradiation at low catalytic loading.     

7-Alkoxy-appended coumarin derivatives: synthesis,photo-physical properties,aggregation behaviours and current–voltage (I–V) characteristic studies on thin films

In this study, we designed and synthesised a series of coumarin derivatives appended with a long alkoxy chain on the seventh position of the coumarin-3-carboxylate/carboxylic acid core to make thin film materials. Synthesised compounds were characterized by their UV and fluorescence spectra in solutions as well as their films prepared by both LB and spin-coated methods. The surface morphology and electrical behaviour of thin films were judged by AFM, SEM and I–V characteristic mapping respectively. Isotherm, UV-Vis absorption and fluorescence spectroscopic investigations revealed the formation of aggregates on thin films. The result of SEM and AFM images provides the information about the length and height of aggregates on the thin films of coumarin derivatives. From I–V characteristics, it was found that at room temperature, the spin-coated films of coumarin derivatives containing an ester functional group exhibited a threshold switching behaviour, whereas derivatives containing the carboxylic acid functional group showed both threshold and bipolar switching behaviours. We also noticed that the I–V characteristic features of synthesized materials depended on the length of the alkyl chain of individual series.

In this article, we demonstrate the design, synthesis and physico-chemical characteristics, including electrical switching behaviours of long alkoxy-appended coumarin carboxylate/carboxylic acid in thin films.     

Strategies for the direct oxidative esterification of thiols with alcohols

This review paper provides an overview of the main strategies for the oxidative esterification of thiols with alcohols. The review is divided into two major parts according to final products. The first includes the methods for the synthesis of sulfinic esters, while the second contains the procedures for the fabrication of sulfonic ester derivatives.

This review paper provides an overview of the main strategies for the oxidative esterification of thiols with alcohols.     

Hercynite silica sulfuric acid: a novel inorganic sulfurous solid acid catalyst for one-pot cascade organic transformations

Herein, we delignated the synthesis of a novel inorganic sulfurous magnetic solid acid catalyst by the immobilization of an extremely high content of sulfuric acid functionalities on the amorphous silica-modified hercynite nanomagnetic core–shell via a simple method. Silica sulfuric acid (SSA) modified hercynite nanocomposite (hercynite@SSA) combines excellent recoverability and stability characteristics of hercynite (which can be regarded as a ferro spinel with Fd3m space group and cubic crystal structure) with the strong Brønsted acid properties of –SO₃H groups. This nanomagnetic solid acid was found to be an efficient and facile strong solid acid catalyst for the synthesis of bis(pyrazolyl)methanes via two different one-pot multicomponent methodologies under green conditions. The hercynite@SSA catalyst shows excellent catalytic activity and reusability in the ethanolic medium among different solid acid materials. A plausible reaction mechanism is proposed for this synthesis.

A novel inorganic sulfurous nanomagnetic solid acid composite was synthesized and its catalytic activity was evaluated in the synthesis of bis(pyrazolyl)methane derivatives. The catalyst displayed excellent activity and recoverability under green conditions.     

Design,in silico studies,and synthesis of new 1,8-naphthyridine-3-carboxylic acid analogues and evaluation of their H1R antagonism effects

New 1,8-naphthyridine-3-carboxylic acid derivatives were designed, synthesized and evaluated for their in vivo antihistaminic activity on guinea pig trachea by using chlorpheniramine as the standard drug. It was found that compound 5a1 displayed a promising bronchorelaxant effect in conscious guinea pigs using the in vivo model. A molecular docking study was performed to understand the molecular interaction and binding mode of the compounds in the active site of the H1 receptor. Furthermore, in silico computational studies were also performed to predict the binding modes and pharmacokinetic parameters of these derivatives. Prior to the start of experimental lab work, PASS software was used to predict the biological activities of these compounds. An in silico PASS, Swiss ADME assisted docking approach was found to be suitable to derive and synthesize effective antihistaminic agents for the present study.

New 1,8-naphthyridine-3-carboxylic acid derivatives were designed, synthesized and evaluated for their in vivo antihistaminic activity on guinea pig trachea by using chlorpheniramine maleate as the standard drug.     

Total synthesis of diazaquinomycins H and J using double Knorr cyclization in the presence of triisopropylsilane

The first total synthesis of diazaquinomycins H (1) and J (2), which are promising anti-tuberculosis natural product leads, has been achieved via selective amidation of diamine 6 with Meldrum''s acid derivatives, subsequent EDC coupling with 3-oxobutanoic acid, followed by double Knorr cyclization in the presence of triisopropylsilane (TIPS). We found that the addition of TIPS was crucial to obtain pure diazaquinomycins H and J, while preventing isomerization of the terminal iso-branched tail in sulfuric acid. Our developed synthesis provided diazaquinomycins H (1) and J (2) in 8 steps from commercially available starting materials in 25% and 21% overall yields, respectively. The spectroscopic data of synthetic diazaquinomycins H (1) and J (2) agreed very favorably with those of reported natural products.

The first total syntheses of antitubercular diazaquinomycins H (1) and J (2) were achieved in 25% and 21% overall yields, respectively.     

Vitamin B1-catalyzed aerobic oxidative esterification of aromatic aldehydes with alcohols

A straightforward aerobic oxidative esterification of aryl aldehydes with alcohols has been developed for the synthesis of substituted esters by employing vitamin B1 as a cost-effective, metal-free, and eco-friendly NHC catalyst. Air is used as a green terminal oxidant. The reaction is a useful addition to the existing NHC-catalytic oxidative esterification.

An aerobic oxidative esterification of aryl aldehydes with alcohols has been developed by employing vitamin B1 as a cost-effective, metal-free, and eco-friendly NHC catalyst.     

Green synthesis of coumarin derivatives using Brønsted acidic pyridinium based ionic liquid [MBSPy][HSO4] to control an opportunistic human and a devastating plant pathogenic fungus Macrophomina phaseolina

An eco-friendly simple protocol has been devised for the preparation of coumarin derivatives using doubly Brønsted acidic task specific ionic liquid (TSIL) as a catalyst. Solvent-free conditions were employed for the reaction of different substituted phenols with β-ketoester in TSIL to produce corresponding substituted coumarin derivatives in good to excellent yields at ambient conditions; at room temperature and with reduced reaction times. The ionic liquid catalyst can be recycled and reused up to five times. All the synthesized coumarins were evaluated for their antifungal activities against Macrophomina phaseolina, a plant as well as an opportunistic human pathogenic fungus affecting more than 500 plant species worldwide and with no registered commercial fungicide available against it, to date. Amongst all the coumarins tested, compounds 3f and 3i showed excellent antifungal activity comparable to reference fungicide mancozeb. The current methodology provides an easy and expedient way to access the coumarin core in search of potential fungicides for sustainable agriculture.

An eco-friendly simple protocol has been devised for the preparation of coumarin derivatives using doubly Brønsted acidic task specific ionic liquid (TSIL) as a catalyst.     

Diamines as switchable-hydrophilicity solvents with improved phase behaviour

Removing solvents by distillation is not a sustainable process because it requires the use of volatile solvents and a high energy input. An alternative is to use a switchable-hydrophilicity solvent (SHS), which can be removed from products and recycled without any distillation step. SHSs are solvents that reversibly switch between hydrophilic and hydrophobic forms with the addition and removal of a trigger such as CO₂. Monoamine SHSs can be separated from dissolved products by extraction into carbonated water, but the solvent removal is limited by the distribution coefficient of the SHS between the carbonated water phase and the product phase. In this article, the use of diamines as SHSs with improved distribution coefficients is explored. Several diamine SHSs are identified and their properties compared to those of monoamine SHSs. Comparisons include the pK_aH (the pK_a of the conjugate acid of a base) and log K_ow (log of the octanol–water partition coefficient) requirements for amines to act as SHSs, distribution coefficients, removal from hydrophobic liquids, switching speeds, and risks to the environment and human health and safety.

Diamine switchable-hydrophilicity solvents can be removed from products, by carbonated water, with much greater efficiency than past switchable solvents.     

Synthesis of chiral 1,4-oxazepane-5-carboxylic acids from polymer-supported homoserine

The preparation of novel 1,4-oxazepane-5-carboxylic acids bearing two stereocenters is reported in this article. Fmoc-HSe(TBDMS)-OH immobilized on Wang resin was reacted with different nitrobenzenesulfonyl chlorides and alkylated with 2-bromoacetophenones to yield N-phenacyl nitrobenzenesulfonamides. Their cleavage from the polymer support using trifluoroacetic acid (TFA) led to the removal of the silyl protective group followed by spontaneous lactonization. In contrast, TFA/triethylsilane (Et₃SiH)-mediated cleavage yielded 1,4-oxazepane derivatives as a mixture of inseparable diastereomers. The regioselectivity/stereoselectivity depended on the substitution of the starting 2-bromoacetophenones and was studied in detail. Catalytic hydrogenation of the nitro group improved the separability of the resulting diastereomeric anilines, which allowed us to isolate and fully characterize the major isomers.

The preparation of novel 1,4-oxazepane-5-carboxylic acids bearing two stereocenters is reported in this article.     

Folic acid functionalization for targeting self-assembled paclitaxel-based nanoparticles

Hetero-nanoparticles self-assembled from a conjugate bearing folic acid as the targeting agent, and another bearing paclitaxel as the active agent are reported. Hetero-nanoparticles containing varying percentages of folic acid conjugates are characterised, and their biological activity is determined.

Self-assembled hetero-nanoparticles are obtained by mixing paclitaxel and folic acid conjugates.     

Copper(ii)-catalyzed synthesis of multisubstituted indoles through sequential Chan–Lam and cross-dehydrogenative coupling reactions

Starting from arylboronic acids and ester (Z)-3-aminoacrylates, one-pot syntheses of diverse indole-3-carboxylic esters have been described through copper(ii)-catalyzed sequential Chan–Lam N-arylation and cross-dehydrogenative coupling (CDC) reactions. The initial Chan–Lam arylation can proceed in DMF at 100 °C for 24 h to give ester (Z)-3-(arylamino)acrylate intermediates in the presence of Cu(OAc)₂/tri-tert-butylphosphine tetrafluoroborate, a catalytic amount of myristic acid as the additive, KMnO₄ and KHCO₃. Sequentially, these in situ arylated intermediates can undergo an intramolecular oxidative cross-dehydrogenative coupling process in mixed solvents (DMF/DMSO = 2 : 1) at 130 °C to give C3-functionalized multi-substituted indole derivatives.

One-pot syntheses of diverse indole-3-carboxylic esters have been described through copper(ii)-catalyzed sequential oxidative Chan–Lam N-arylation and cross-dehydrogenative coupling (CDC) reaction.     

Solvent-free synthesis of phytosterol linoleic acid esters at low temperature

Phytosterol unsaturated fatty acid esters show much higher oil solubility than free phytosterol. Thus, development of a green and low-cost method for the preparation of phytosterol fatty acid esters is highly desirable in the food industry. Herein, we have developed a simple chemical method toward efficient preparation of phytosterol linoleic acid esters at very mild temperature (60 °C) using 4-dodecylbenzenesulfonic acid (DBSA) as the catalyst. In this work, low-temperature esterification of phytosterols (soybean sterol) with linoleic acid could produce the corresponding phytosterol esters above 95% conversion under solvent-free conditions. In addition, this simple method could be applied to produce phytosterol esters through esterification of phytosterol with an unsaturated fatty acid mixture resulting from the hydrolysis of various vegetable oils. Importantly, no extra organic solvents and no extra water-removal operations or equipment were required in this chemical esterification method. The mechanism investigation suggested that the DBSA-catalyzed low-temperature esterification would form micro-emulsions of water-in-oil (W/O), which could achieve automatic separation of water from the hydrophobic system to avoid reverse reaction hydrolysis and rapidly promote the equilibrium reaction towards phytosterol esters.

Herein, we have developed a simple chemical method toward efficient preparation of phytosterol linoleic acid esters through esterification at very mild temperature (60 °C) using 4-dodecylbenzenesulfonic acid (DBSA) as the catalyst.