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91.
Benzonorbornadiene and heterobenzonorbornadiene were reacted with dimedone/acetylacetone and Mn(OAc)3 in the presence and absence of Cu(OAc)2. The reaction of benzonorbornadiene with dimedone gave mainly the dihydrofuran addition product, whereas the reaction with acetylacetone produced a rearranged product in addition to the dihydrofuran derivative. On the other hand, oxanorbornadiene gave unusual products such as the cycloproponated compound and a product arising from the incorporation of 2 mol of dimedone. The reaction of azanorbornadiene with 1,3-dicarbonyl compounds and Mn(OAc)3 always produced rearranged products. The mechanism of formation of the products is discussed. We generally observe that the cyclization reaction takes place after the oxidation of the initially formed radical.  相似文献   
92.
The reactions of hexachlorocyclotriphosphazatriene, N3P3Cl6, with N/O donor-type N-alkyl-o-hydroxybenzyl- and o-hydroxynaphthylamines result in novel mono- (3a, 4a and 4b), di- (5a and 5b), and tri- (3b, 6a, and 6b) spirocyclic phosphazene derivatives. The tetrakis-pyrrolidinophosphazene, 3b, has been obtained from the reaction of partly substituted compound 3a with the excess pyrrolidine in tetrahydrofuran. The relationship between the endocyclic NPN (alpha) and exocyclic NPO (alpha') bond angles of the analogous spirocyclic phosphazenes with the deltaP shifts of NPO phosphorus atoms have been presented. It was observed that there is a linearity between alpha angles and deltaP shifts, while no linear relationship has been observed for alpha' angles. In addition, we have found the correlation between Delta(P-N) and deltaNPO shifts, which implies a linear relationship. Delta(P-N)=(a-b), where a and b are the average lengths of two adjacent P-N bonds. The structural investigations of all of the compounds have been made by elemental analyses; mass spectrometry; Fourier transform infrared spectroscopy; one-dimensional 1H, 13C, and 31P NMR; distortionless enhancement by polarization transfer; and two-dimensional correlation spectroscopy, heteronuclear shift correlation, and heteronuclear multiple-bond correlation homo- and heteronuclear correlation techniques. The solid-state structures of 3a, 4a, 4b, and 5a have been determined by X-ray crystallographic techniques. The asymmetric units of compounds 3a and 4a contain two independent molecules, and 3a has strong intermolecular N-H...N hydrogen bonds linking three phosphazene rings. The molecular structure of 6a looks like a propeller where the chemical environment of P1 is different from that of P2 and P3. On the other hand, compounds 5a and 5b are expected to exist as cis- or trans-geometric isomers and to be in cis (meso) or trans (racemic) configurations. The crystallographic and preliminary chiral solvating agents results show that both of them are trans (racemic). In addition, 6a and 6b are also expected to exist as cis-trans-trans- and cis-cis-cis-geometric isomers; both of them are found to be in cis-trans-trans geometries. According to the two-dimensional spectroscopic data, the possible conformations of 3a and 4a in CDCl3 are the same with the solid-state structures.  相似文献   
93.
Journal of Solid State Electrochemistry - In this study, a new amperometric biosensor for creatinine determination was developed. For this purpose, a polypyrrole-polyvinylsulfonate film was...  相似文献   
94.
2‐Hydroxyethyl acrylamide was successfully polymerized via single‐electron transfer initiation on the silicon surface and propagation through the reversible addition–fragmentation chain transfer (SET‐RAFT) polymerization at ambient temperature for different polymerization times. This work is the first time application of the surface‐initiated SET‐RAFT mechanism to afford the preparation of well‐defined poly(2‐hydroxyethyl acrylamide) [poly(HEAAm)] brushes at ambient temperature. The polymerization was well controlled and produced poly(HEAAm) brushes on the silicon surface with a well‐defined target molecular weight. The controlled nature of the polymerization was further demonstrated in the presence of sulfur atoms at the chain ends in X‐ray photoelectron spectroscopy experiments. The grafting density (σ, chains nm?2) and the average distance between grafting points (D, nm) were found to be 0.42 chains nm?2 and 1.74 nm, respectively, indicating moderate grafting density. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 1140–1146  相似文献   
95.
A novel type of hypervalent iodine(III) reagents, vinylbenziodoxolones (VBX), has been synthesized in a one-pot reaction from 2-iodobenzoic acid. VBX is bench stable, has been thoroughly characterized and the cyclic structure is supported by X-ray analysis. The reactivity of VBX was investigated in vinylation of nitrocyclohexane, and delivered vinylated products with opposite regioselectivity compared to acyclic vinyl(aryl)iodonium salts. The reagents could become a powerful tool in vinylation reactions under both metal-free and metal-catalyzed conditions.  相似文献   
96.
Effects of multiwall carbon nanotube (MWCNT) addition on the electrical conductivities, optical transparencies and fluorescence emissions of poly(vinyl acetate-co-butyl acrylate) (P(VAc-co-BuA))/MWCNT composite films were studied. Optical transmission, fluorescence emission and two point probe resistivity techniques were used to determine the variations of the optical, fluorescence and electrical properties of the composites, respectively. Transmitted photon intensity (I tr), fluorescence emission intensity (I fl) and surface resistivity (ρ s) of the composite films were monitored as a function of MWCNT mass fraction (M) at room temperature. All these measured quantities of the composites were decreased by increasing the content of MWCNT in the composite. The conductivity and the optical results were attributed to the classical and site percolation theories, respectively. The fluorescence results, however, possessed both the site and classical percolation theories at low and high MWCNT content regions, respectively.  相似文献   
97.
1,3,3a,7a-Tetrahydro-2-benzofuran was used as key compound for the synthesis of various bishomoinositol derivatives. The diene was subjected to an epoxidation reaction for further functionalization of the diene unit. The bisepoxide obtained was submitted to a ring-opening reaction with acid in the presence of water. Various bishomoinositols were synthesized. However, when the reaction was carried out in the presence of acetic anhydride, a substituted 3-oxabicyclo[3.3.1]nonane skeleton was formed. The mechanism of the formation of the products is discussed.  相似文献   
98.
A simple and efficient unusual coupling reaction of 9-(2-hydroxy-4,4-dimethyl-6-oxocyclohex-1-en-1-yl)-3,3-dimethyl-2,3,4,9-tetrahydro-1H-xanthen-1-one and its derivatives was accomplished in the presence of Mn2+, Cu2+, Cd2+, Hg2+, Fe3, or La3+. The structure elucidation was accomplished by IR, 1H NMR, 13C NMR, X-ray crystallography, UV-Visible and elemental analysis. A reaction mechanism is proposed.  相似文献   
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