Data on synthesis and thermo-mechanical properties of stimuli-responsive rubber materials bearing pendant anthracene groups
Jakob ManhartSanthosh Ayalur‐KarunakaranSimone RadlAndreas OesterreicherA. MoserChristian GanserChristian TeichertGerald PinterWolfgang KernThomas GrießerSandra Schlögl
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The photo-reversible [4πs+4πs] cycloaddition reaction of pendant anthracene moieties represents a convenient strategy to impart wavelength dependent properties into hydrogenated carboxylated nitrile butadiene rubber (HXNBR) networks. The present article provides the 1H NMR data on the reaction kinetics of the side chain functionalization of HXNBR. 2-(Anthracene-9-yl)oxirane with reactive epoxy groups is covalently attached to the polymer side chain of HXNBR via ring opening reaction between the epoxy and the carboxylic groups. Along with the identification, 1H NMR data on the quantification of the attached functional groups are shown in dependence on reaction time and concentration of 2-(anthracene-9-yl)oxirane. Changes in the modification yield are reflected in the mechanical properties and DMA data of photo-responsive elastomers are illustrated in dependence on the number of attached anthracene groups. DMA curves over repeated cycles of UV induced crosslinking (λ>300 nm) and UV induced cleavage (λ=254 nm) are further depicted, demonstrating the photo-reversibility of the thermo-mechanical properties. Interpretation and discussion of the data are provided in "Design and application of photo-reversible elastomer networks by using the [4πs+4πs] cycloaddition reaction of pendant anthracene groups" (Manhart et al., 2016) [1].Keywords:
Side chain
Proton NMR
In the [3 + 2] cycloaddition of a range of nitrile oxides with homochiral vinyl ethers the diastereoselectivity observed is dependent on the chiral auxiliary used. A brief comparison is made with the diastereoselectivity of the corresponding [4 + 2] nitrosoalkene cycloaddition, and also to the nitrile oxide cycloaddition to chiral acrylic acid esters bearing the most successful auxiliaries from the vinyl ether study.
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The 1,3-dipolar cycloaddition reaction of nitrile oxides with carbon dipolarophiles is a versatile and powerful synthetic method to prepare isoxazolines. In particular nitrile oxide cycloaddition reactions with exocyclic methylene or alkylidene compounds generally proceed regioselectively leading to spiro heterocyclic compounds. This review deals with progress in the field of nitrile oxide cycloaddition chemistry for the synthesis of spiro isoxazolines. Keywords: Nitrile oxide, dipolar cycloaddition, heterocycle, spiro, exocyclic methylene, isoxazoline
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The enantioselective N-heterocyclic carbene-catalysed formal 2+2- and 2+2+2- cycloadditions of ketenes with isothiocyanates can be investigated. At room temperature, the reaction of N-arylthiocyanates favours the 2+2-cycloaddition. However, at −40°C, N-benzoylisothiocyanates undergo the 2+2+2-cycloaddition. This chapter discusses cycloaddition-type addition reactions. Specifically, it covers three types of cycloadditions: 2+2-cycloaddition, 2+3-cycloaddition and 2+4-cycloaddition. Miscellaneous cycloaddition reactions are separately described at the end of the chapter.
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Abstract Fluorescence changing of anthracene crystals in air, O2, N2, recorded at room temperature is reported. Two different products formed under irradiation of anthracene were isolated and recognized as anthracene dimer and anthraquinone. A correlation between the above fluorescence change and the photochemical behaviour of anthracene was found.
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1,3-Dipolar cycloaddition has been employed as a powerful synthetic procedure by which five-membered heterocyclic frameworks are constructed together with forming two bonds in a single manipulation. Among the various functionalized nitrile oxides reported, the ethoxycarbonyl derivative 1 is commonly used in organic synthesis. In this chapter, another generation method for 6 from easily available nitroisoxazolone 10 is introduced, which proceeds under mild conditions without using any special reagents. 2-Methyl-4-nitroisoxazol-5(2H)-one 10 having multifunctionalities reveals versatile reactivity to serve as a precursor for polyfunctionalized systems. The carbamoyl group of the nitrile oxide plays an important role not only as an electron-withdrawing group but also as an accelerator in the cycloaddition by forming a hydrogen bond with a dipolarophilic nitrile. The electron-withdrawing carbamoyl group realizes the cycloaddition with electron-rich dipolarophiles, which is inverse electron-demand 1,3-dipolar cycloaddition.
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The factor group splitting of B 1u bands of anthracene crystals is studied using the mixed crystal technique. Mixed crystals of anthracene and anthracene-D10 have been analysed, in order to find experimental evidence for the doublet structure of the bands at 737–727 cm-1 and 475–465 cm-1.
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Abstract The synthesis of 1‐azabenz[a]anthracene and 9‐azabenz[a]anthracene are presented.
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The involvement of 1,3-dipolar cycloaddition (1,3-DP), double bond migration, metathesis, and nitrile oxide (including in situ-generated nitrile oxide) as dipoles, together with the C=C bond containing dipolarophiles, in the syntheses of 2-isoxazolines is presented. Methods for synthesizing isoxazolines (other than 1,3-DP cycloaddition) were also presented briefly. Various methods of nitrile oxide preparation, especially in situ-generated procedures, are presented. Special attention was paid to the application of various combinations of 1,3-DP cycloaddition with double bond migration (DBM) and with alkene metathesis (AM) in the syntheses of trisubstituted isoxazolines. Allyl compounds of the type QCH2CH=CH2 (Q = ArO, ArS, Ar, and others) play the role of dipolarophile precursors in the combinations of DPC mentioned, DBM and AM. Mechanistic aspects of cycloadditions, i.e., concerted or stepwise reaction mechanism and their regio- and stereoselectivity are also discussed from experimental and theoretical points of view. Side reactions accompanying cycloaddition, especially nitrile oxide dimerization, are considered. 2-Isoxazoline applications in organic synthesis and their biological activity, broad utility in medicine, agriculture, and other fields were also raised. Some remaining challenges in the field of 1,3-DP cycloaddition in the syntheses of isoxazolines are finally discussed.
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