Thermolysis of hexasubstituted-4,5-dihydro-3H-pyrazoles: Synthesis of 1-alkoxy- and 1-acetoxy-1,2,2,3,3-pentasubstituted-cyclopropanes

A series of 5-alkoxy- and 5-acetoxy-4,4-dimethyl-3,3,5-trisubstituted-4,5-dihydro-3H-pyrazoles 2a-f (hexasubstituted pyrazolines) was synthesized by oxidation of the corresponding 3,4-dihydro-2H-pyrazoles with lead tetraacetate in the appropriate solvents. The 5-acetoxy compounds were produced when the oxidations were carried out in methylene chloride. Oxidation with lead tetraacetate in dry alcoholic solvents resulted in the formation of the 5-alkoxy derivatives as the major products. Thermolysis of the hexasubstituted-4,5-dihydro-3H-pyrazoles 2a-f in cyclohexane or as the melt at high temperature yielded the 1-alkoxy- and 1-acetoxy-1,2,2,3,3-pentasubstituted cyclopropanes 3a-f in good yields. Trace amounts of alkene products were formed in several reactions. No products attributable to cycloreversion pathways were detected. The product distributions were consistent with extrusion of nitrogen gas from 2a-f to yield the singlet 1,3-diradical, closure of which resulted in cyclopropane formation with partial retention of stereochemistry.     

Bulk rigid-rod molecular composites of articulated rod copolymers with thermoplastic pendants

Bulk rigid-rod molecular composites were successfully obtained by powder consolidation of a copolymer containing both the reinforcing rigid-rod segments and the thermoplastic matrix. By chemically linking the reinforcing segments and the matrix molecule, the copolymer was designed to minimize phase separation in the molecular composite. The copolymer was an articulated rigid-rod poly(p-phenylenebenzobisthiazole), aPBT, with an aromatic poly(ether ketone), mPEK, thermoplastic pendant grafted at the points of articulation. The copolymer powder was pre-formed and compression molded at an elevated temperature, which resulted in bulk rigid-rod molecular composites with three-dimensionally isotropic properties. Compared to the neat mPEK homopolymer, significant increases in glass transition temperature T_g and tensile properties have been realized for the aPBT-g(mPEK) copolymers with low rod content. Taking into account the aspect ratio of the aPBT, the bulk rigid-rod molecular composite showed a tensile modulus as predicted by the Halpin-Tsai equation. In addition, x-ray scattering revealed minimal rod aggregation. However, for the copolymer of higher rod content, significant phase separation was observed in the copolymer powder, which resulted in a decrease in T_g as well as reinforcement efficiency of the bulk rigid-rod molecular composite as compared to those derived from the copolymers of low rod content. © 1992 John Wiley & Sons, Inc.     

Synthesis,processing, and third-order nonlinear optical properties of benzobisthiazole polymers containing thiophene moieties

Benzobisthiazole polymers containing mono-, bi-, and terthiophene moieties were synthesized through polycondensation in polyphosphoric acid of 2,5-diamino-1,4-benzenedithiol dihydrochloride with thiophene-2,5-dicarboxylic acid, 2,2′-bithiophene-5,5′-dicarboxylic acid, and 2,2′:5′,2″-terthlophene-5,5″-dicarboxylic acid, or their corresponding diacid chlorides, respectively. Intrinsic viscosities of up to 8.1 dL/g (methanesulfonic acid, 30°C) were recorded. Polymer structures were verified by elemental analysis and spectroscopic comparison of the polymers with appropriate model compounds. Onset of breakdown under thermogravimetric analysis in air occurred in the 460–590°C range with the benzobisthiazole polymers containing a monothiophene linkage being the most stable. Films suitable for third-order optical susceptibility measurements could be prepared by extrusion techniques from the benzobisthiazole polymer containing a monothiophene linkage. Degenerate four wave mixing measurements on this film yielded a third order optical susceptibility χ⁽³⁾ of approximately 4.5 × 10^?10 esu. © 1993 John Wiley & Sons, Inc.     

Unexpected formation of a xanthone in the synthesis of a bisbenzoxazole

Recently we reported the synthesis in polyphosphoric acid of a graft copolymer consisting of a rigid-rod poly[benzo(1,2-d;4,5-d′)bisthiazole-2,6-diyl]-1,4-phenylene backbone and flexible poly(oxy-1,3-phenylenecarbonyl-1,4-phenylene) side-chains [1]. However, upon extension of this synthetic approach to the analogous graft copolymer with a poly[benzo(1,2-d:5,4-d′)bisoxazole-2,6-diyl]-1,4-phenylene backbone, we encountered some unexpected results due to methyl group migration. In order to better understand these results, we carried out the synthesis of selected benzothiazole and benzoxazole structures under appropriate reaction conditions. The results are reported in this article.     

Effect of Methacrylated Hyperbranched Polymers on the Fracture Properties of Denture Base Materials

Hyperbranched polymers have the potential to reinforce crosslinked polymeric materials. In this study several concentrations of a methacrylated hyperbranched polyether are formulated with a denture base resin and cured. The denture base resin is a polymethyl methacrylate based resin. The fracture toughness of each of these concentrations was measured and compared to control. Only the 1% concentration had a significantly higher fracture toughness compared to the control. This is similar to other results that are found in the literature.     

Multidimensional benzobisoxazole rigid-rod polymers. II. Processing,characterization, and morphology

A high-torque rheometer was used to facilitate the polycondensation of 4-[5-amino-6-hydroxybenzoxazol-2-yl]benzoic acid (ABA) with trimesic acid and 1,3,5,7-tetrakis(4-carboxylatophenyl)adamantane to yield two- and three-dimensional benzobisoxazole polymers, respectively. Although the resultant polymer dopes exhibited improved homogeneity compared to polymer dopes previously prepared in glassware, improved polymer solution viscosities were not achieved. Fibers spun from the two- and three-dimensional polymers did not show a significant increase in compressive strength compared to fibers of the linear or one-dimensional benzobisoxazole polymer derived from the homopolymerization of ABA. Morphological studies of the polymer fibers and films by wide-angle X-ray scattering and scanning electron microscopy strongly indicated more lateral disorder and a more isotropic character for the three-dimensional structures compared to the one-dimensional structures. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 3457–3466, 1997     

Rigid-Rod benzobisthiazole polymers with reactive fluorene moieties: Synthesis and characterization

High purity 2,7-fluorenedicarboxylic acid chloride was synthesized in a multistep reaction scheme from 2,7-dibromofluorene. Subsequent polycondensation in polyphosphoric acid of 2,5-diamino-1,4-benzenedithiol dihydrochloride with terephthaloyl chloride and 2,7-fluorenedicarboxylic acid chloride led to rigid-rod benzobisthiazole polymers with reactive fluorene moieties. The proportion of fluorene in the resultant polymers was controlled through reaction stoichiometry. Soluble polymers with intrinsic viscosities as high as 33.7 dL/g (methanesulfonic acid, 30°C) were obtained if the polymerization temperature was not allowed to exceed 165°C. Insoluble, presumably crosslinked polymers were obtained at higher temperature (190–200°C). Thermal characterization of the polymers by differential thermal analysis and thermal gravimetric analysis/mass spectroscopy did not disclose any thermal transition to 450°C. Onset of weight loss in air did not occur until over 550°C.     

Synthesis of 4,4-dimethyl-3,4-dihydro-3,3,5-trisubstituted-2H-pyrazoles and N-benzoyl derivatives: Method for “Hydrolysis” of unreactive amides and carbamates

Addition of organolithium reagents to 4,4-dimethyl-3,5-disubstituted-4H-pyrazoles produced a series of 4,4-dimethyl-3,4-dihydro-3,3,5-trisubstituted-2H-pyrazoles, 2–6 , in good yield. The reaction was stereoselective: addition of organolithium compounds occurred only to carbon-3 of 4,4-dimethyl-3-alkyl-5-aryl-4H-pyrazoles. The 3,4-dihydro-2H-pyrazoles were found to be of high sensitivity to oxygen. For long term storage and ease of handling, N-benzoyl derivatives were synthesized. Removal of the protecting group could not be accomplished by use of many standard sets of conditions. Deprotection was accomplished in high yield by reaction of the N-benzoyl-4,4-dimethyl-3,4-dihydro-3,3,5-trisubstituted-2H-pyrazoles with anhydrous potassium t-butoxide in toluene [heated under reflux (ultra-pure argon)] in the presence of a phase transfer catalyst (18-Crown-6). Cleavage of a N-carbamate derivative was also achieved by this phase transfer approach. This methodology should be applicable to the hydrolysis of unreactive amides and carbamates in general.     

Multidimensional benzobisoxazole rigid-rod polymers. I. Preparation and characterization

Two- and three-dimensional rigid-rod polymers containing benzobisoxazole structures were prepared through the polycondensation in polyphosphoric acid of 4-[5-amino-6-hydroxybenzoxazol-2-yl]benzoic acid (ABA) with trimesic acid and 1,3,5,7-tetrakis(4-carboxylatophenyl)adamantane, respectively. Thermal properties of the polymers were determined by differential scanning calorimetry, thermogravimetric/mass spectral analysis, and isothermal aging studies. The multidimensional polymers exhibited lower solution viscosities and lower thermooxidative stabilities than the one-dimensional polymer generated by the homopolymerization of ABA under identical reaction conditions. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 3451–3456, 1997     

Characterization,processing, and properties of an aromatic poly (ether ketone)

Poly(oxy-1,3-phenylenecarbonyl-1,4-phenylene), mPEK, was synthesized in a methane sulfonic acid/phosphorus pentoxide medium through the polycondensation of 3-phenoxybenzoic acid. The polymer was soluble at room temperature in strong acids and common organic solvents. Differential scanning calorimetry on mPEK indicated a glass transition temperature of 132°C and no detectable crystal melting behavior. The polymer was thermo-oxidatively stable up to 420°C in air as determined by thermogravimetric analysis. Thermal degradation resulted in a crosslinked polymer. Compression molding was successfully applied to consolidate mPEK powder into bulk specimens without causing degradation. Tensilefractured surfaces of the consolidated specimens were examined by scanning electron microscopy which strongly indicated adequate fusion of mPEK powder but also disclosed microvoids of uniform size, shape, and distribution. X-ray scattering revealed that mPEK powder was amorphous and that the consolidated mPEK specimens were structurally isotropic as well as amorphous. The bulk specimen density was determined to be 1.29 ± 0.01 g/cm³ and the three-dimensionally isotropic bulk tensile properties were shown to be 4.10 ± 0.10 GPa (modulus), 0.07 ± 0.01 GPa (strength), and 0.021 ± 0.006 (elongation at break). Tensile properties of the amorphous mPEK specimens compared favourably with literature values of state-of-the-art semicrystalline thermoplastics. Crystaline phases could be realized for mPEK by melt-processing, or precipitating from a solvent.