Hetero Diels–Alder Reactions with a Dicationic Urea Azine Derived Azo Dienophile and Their Use for the Synthesis of an Electron-Rich Pentacene

Herein, the first hetero Diels–Alder (DA) reactions with a stable, dicationic urea azine derived azo dienophile, synthesized by two-electron oxidation of a neutral urea azine are reported. Several charged DA products were synthesized in good yield and fully characterized. The DA adduct of anthracene is in thermal equilibrium with the reactants at room temperature, and the reaction enthalpy and entropy were determined from the temperature-dependent equilibrium constant. Furthermore, base addition to solutions of the pentacene DA product led to deprotonation, cleavage of the N−N bond, and formation of an electron-rich 6,13-bisguanidinyl-substituted pentacene. The redox and optical properties of this new pentacene derivative were studied. Furthermore, the dication resulting from its two-electron oxidation was synthesized and fully characterized. The results disclose a new elegant route to electron-rich pentacene derivatives.     

Modified soybean oil as a reactive diluent: Synthesis and characterization

Soybean oil was modified in two steps: (1) conjugation of soybean oil and (2) Diels‐Alder addition with 3‐(trimethoxysilyl)propyl methacrylate, 2,2,2‐trifluoroethyl methacrylate and triallyl ether acrylate. The structures were characterized using ¹H NMR, ¹³C NMR, ¹³C‐¹H gradient heteronuclear single quantum coherence (gHSQC) NMR spectroscopy, and MALDI‐TOF mass spectrometry. The ¹³C‐¹H gHSQC NMR spectra helped confirm the formation of a cyclohexene ring in all reactions, indicating a Diels‐Alder addition. The diluent efficiency of modified soybean oil was evaluated in long oil alkyd formulation. Triallyl ether functionalized soybean oil resulted in the highest reduction in the viscosity of the alkyd formulations. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3045–3059     

Asymmetric Diels—Alder Reaction Catalyzed by Novel Chiral Dibenzo[a,c] cycloheptadiene Bis（oxazoline） Metal Complexes

A series of novel chiral C2-symmetric bis (oxazoline) ligands have been synthesized.The copper and magnesium complexes,prepared in situ from copper(Ⅱ)-triflate of magnesium triflate with the new enantiopure oxazoline ligands,were evaluated as chiral catalysts in the enantioselective Diels-Alder reaction of cyclopentadiene with N-crotenoyl-oxazolidin-2-one.Primary results showed that diastereoselectivity up to 94% and enantioselectivity up to 68% ee for endo products were observed respectively with these ligands.     

Diels–Alder modification of poly(ethylene terephthalate‐co‐anthracene‐2,6‐carboxylate) with N‐substituted maleimides

Dimethyl 2,6‐anthracene dicarboxylate is used as a comonomer in the synthesis of functional copolymers that are subject to modification with Diels–Alder reactions. The formation of poly(ethylene terephthalate‐co‐2,6‐anthracenate), containing less than 20 mol % of the anthracene‐2,6‐dicarboxylate structural units, provides materials that are tractable and soluble. The anthracene units of the copolymers undergo Diels–Alder reactions with N‐substituted maleimides. The grafting of N‐alkylmaleimides affords soluble, hydrophobic polymers, whereas grafting with maleimide‐terminated poly(ethylene glycol) affords hydrophilic polymers. Because this reaction proceeds below the melting point of the copolymers, the procedure can be applied to thin films, whereby the surface properties are modified. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3256–3263, 2002     

Dehydrocoupling and Diels–Alder reactions on siloxane polymers

Dehydrocoupling reactions between linear poly(methylhydrosiloxane) {Me₃SiO–[MeSi(H)O]_n–SiMe₃} and alcohols such as cholesterol, anthracene‐9‐carbinol, (12‐crown‐4)‐2‐carbinol, pyrene‐1‐carbinol, 4‐methyl‐5‐thiazoleethanol, and 4‐pyridilpropanol were introduced under catalytically mild conditions. The degrees of conversion of Si? H bonds in polysiloxane were monitored with ¹H NMR spectra. The reaction of the 9‐methoxyanthracene adduct on siloxane polymers and maleimide derivatives (maleimide, N‐ethylmaleimide, and maleic acid anhydride) produced [2+4]‐cycloadducts in very high yields. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4013–4019, 2002