PHOTOINDUCED ADDITION REACTIONS OF CHLORANIL WITH FURAN DERIVATIVES

Photoinduoed reaction of chloranil (TCBQ) with 2-methylfuran la and 2,5-dimethylfuran 1b in benzene gave addition products 2a and 2b respecvely together with tetrachlorohydroquinone 3. A mechanism of sequential electron and proton transfer from la or 1b to ~3TCBQ followed by coupling of the furfuryl and semiquinone radical pairs was proposed and is evidenced by the photo-CIDNP studies of the TCBQ-1a and TCBQ-1b systems.

Furan Derivatives and Polyketides from the Fungus Irpex lacteus

Eight new furan derivatives,irpexins A‒H(1‒8),two new polyketides,irpexins I and J(9 and 10),together with nine known compounds were isolated from the fermentation of Irpex lacteus.The structures and absolute configurations were elucidated on the basis of extensive spectroscopic methods and Mosher ester reaction.All compounds shows no cytotoxicity to human MCF-7 and Hela cancer cell lines at the concentration of 10μM.

How Baking Process Conditions Influence on Occurrence of Furan and Its Derivatives in Typical Polish Breads

Bread is still the most important food in Polish households. Staropolski and Pytlowy are two typical Polish breads, prepared with wheat and rye flour. The aim of this study was to examine the occurrence of volatile contaminants such as furan and its derivatives, and present a volatile profile of the most common furan derivatives in the described products. To measure concentration of chemical compounds such as furan and furan derivatives, fast and effective solid-phase micro-extraction/gas chromatography/mass spectrometry （SPME/GC/MS） methods were adapted. This study showed the differences in furan occurrence between Pytlowy and Staropolski, however, the greater differences were observed between different times and temperatures of baking rather than between the bread types. Clearly, the higher concentrations were found in products prepared during the longest baking time period of 50 min, and temperatures of 230 ℃ and 240 ℃. The highest furan level was detected in Staropolski 28.89 ± 1.16/μg/kg, baked for 50 min at 230 ℃ in bread crust. The volatile fraction of bread crust was composed of 5-9 furan derivatives while crumb layer contained only furan-2-pentyl. It was concluded that furan is present in almost each type of bread and percentage of furan derivatives in all volatile fractions ranged from 0.5 % to 60.6% in crust of examined bars.

High-fructose corn syrup production and its new applications for 5-hydroxymethylfurfural and value-added furan derivatives:Promises and challenges

High fructose corn syrup has been industrially produced by converting glucose to fructose by glucose isomerases,tetrameric metalloenzymes widely used in industrial biocatalysis.Advances in enzyme engineering and commercial production of glucose isomerase have paved the way to explore more efficient variants of these enzymes.The 5-hydroxymethylfurfural can be produced from high fructose corn syrup catalytic dehydration,and it can be further converted into various furanic compounds chemically or biologically for various industrial applications as a promising platform chemical.Although the chemical conversion of 5-hydroxymethylfurfural into furanic compounds has been extensively investigated in recent years,bioconversion has shown promise for its mild conditions due to the harsh chemical reaction conditions.This review discusses pro-tein engineering potential for improving glucose isomerase production and recent advancements in bioconversion of 5-hydroxymethylfurfural into value-added furanic derivatives.It suggests bi-ological strategies for the industrial transformation of 5-hydroxymethylfurfural.

Extrapolation of the gold-catalyzed cycloisomerization to the palladium-catalyzed cross-coupling/cycloisomerization of acetylenic alcohols for the synthesis of polysubstituted furans:Scope and application to tandem processes

This paper describes the development of an integrated approach for the preparation of diverse furan derivatives from acetylenic alcohols by gold and palladium catalyzed π-activation chemistry.Notably,this new method was found to be amenable to cyclooctyl-containing substrates,which represents a significant extension to this methodology compared with our previous reports.Furthermore,this newly developed method allowed for the direct construction of cyclooctyl furans from their synthetic precursors under Sonogashira conditions.Experimental results revealed that palladium played two major functions in these reactions,including（1） an essential catalyst in the cross-coupling reaction of the substrates;and（2）facilitating the cyclization of the acetylenic alcohol intermediates through a typical π-activation process.The scope of this chemistry was highlighted by the one-pot synthesis of 3-iodofuran,which provided an opportunity for further functionalization（via coupling methods）.Finally,the AuBr3 protocol was also elaborated to domino cyclization/C-H activation reactions,as well as the cyclization of acyclic precursors.Taken together,the results of this study demonstrate that gold and palladium catalysts can be used to complement each other in cyclization reactions.

Furans-Maleimides Diels-Alder Reactions in Protic Ionic Liquid

The authors have studied the Diels-Alder reactions between furan derivatives and maleimide derivatives in an ionic liquid and have found that higher reactivity can be obtained in a protic ionic liquid [Mim]Tf2N than in the conventional organic solvent. Furthermore, in the Diels-Alder reactions of 2- and 2,5-alkylfurans with N-alkylma- leimide, the reactivity increases by extending the alkyl chain length of N-alkylmaleimide. In addition, it was demon- strated that endo-selectivity increases when 2,5-disubstituted furans are used. These results will be explained by comparing the stability of the Diels-Alder adduct with that of the products obtained from the reactions of 2-substituted furans and 2,5-disubstituted furans.

Synthesis and biological activity of novel N-(3-furan-2-yl-1-phenyl-1H-pyrazol-5-yl) amides derivatives

A series of novel N-（3-furan-2-yl-l-phenyl-lH-pyrazol-5-yl） amides derivatives were designed and synthesized. Their structures were confirmed by 1H NMR, 13C NMR and HRMS. All title compounds were evaluated for their herbicidal and antifungal activities. Preliminary bioassay results indicated that the title compounds showed good to moderate herbicidal activity at 1000 mg/L. Compound 6q presented the best activity against Digitaria sanguinalis （L） Scop., Amaranthus retroflexus L. and Arabidopsis thaliana with an inhibition degree of five. Compound 6d also showed an inhibition degree of five against D. sanguinalis. In addition, at 50 mg/L, most compounds exhibited good in vitro antifungal activity against Sclerotinia sclerotiorum, with compound 6c showing over 90% antifungal activity against S. sclerotiorum and Pellicularia sasakii.

Comparison of 2-acetylfuran,2-ethylfuran,and 2-methylfuran spherically expanding flame intrinsic instabilities

The intrinsic instability of three furan derivatives, namely, 2-acetylfuran(AF), 2-ethylfuran(EF), and 2-methylfuran(MF), is experimentally and theoretically investigated and compared. A deep-learning-based end-to-end system is used to segment the cells and measure the crack length on the cellular flame front of the spherically expanding flame to quantitively investigate the flame morphology. Moreover, the flame front radius profile is quantitively investigated to shed light on the correlation between disturbance amplitude and flame radius. With the use of the linear stability model, the theoretical critical flame radius and Peclet number are obtained and compared to their corresponding experimental results to characterize the outset of cellularization and evaluate the flame instability propensity. Our analysis shows that compared with AF and EF, MF is prone to cellularization at a smaller flame radius and has a faster cell proliferation rate and crack length growth rate before reaching the hydrodynamic saturation limit. Meanwhile, the average area of saturated cells tends to be similar for the three furan derivatives. Furthermore,AF premixed flame does not exhibit cellularization before the flame radius is less than 45 mm in low initial pressure.

A new method for the synthesis of 3-hydroxymethylbenzofuran

A new one-step synthesis of 3-hydroxymethylbenzofuran, based on intramolecular cyclization of 2- （methoxymethyl）-2-（2＇-methoxymethyl-4＇-methylphenyl）-butanone I under diluted hydrochloric acid in THF, was developed. The mechanism for this process was investigated via chemical equilibrium shift of tautomer in acidic conditions. The applicability of this new method was studied further in this paper.

Self-extinguishing and transparent epoxy resin modified by a phosphine oxide-containing bio-based derivative

A phosphine oxide-containing bio-based curing agent was synthesized by addition reaction between furan derivatives and diphenylphosphine oxide.The molecular structure of the as-prepared bio-based curing agent was confirmed by Fourier transform infrared spectroscopy and nuclear magnetic resonance spectroscopy.Dynamic mechanical analysis results indicated that with the increase of bio-based curing agent content,the glass transition temperature of epoxy/bio-based curing agent composites decreased,which was related to the steric effect of diphenylphosphine oxide species that possibly hinder the curing reaction as well as the reduction in the cross-linking density by mono-functional N-H.By the addition of 7.5 wt-%bio-based curing agent,the resulting epoxy composite achieved UL-94 V-0 rating,in addition to limiting oxygen index of 32.0 vol-%.With the increase of content for the bio-based curing agent,the peak of heat release rate and total heat release of the composites gradually decreased.The bio-based curing agent promoted the carbonization of the epoxy matrix,leading to higher char yield with good thermal resistance.The high-quality char layer served as an effective barrier to retard the diffusion of decomposition volatiles and oxygen between molten polymers and the flame.This study provides a renewable strategy for fabricating flame retardant and transparent epoxy thermoset.