Synthesis and chiroptical properties of optically active poly(ethynylcarbazole) derivatives: Substituent effect on the helix formation

Novel chiral acetylene monomers containing carbazole, 2‐ethynyl‐9‐[(S)‐2‐methylbutoxycarbonyl]carbazole ( 1 ), 3‐ethynyl‐9‐[(S)‐2‐methylbutoxycarbonyl]carbazole ( 2 ), 2‐ethynyl‐9‐[(S)‐2‐methylbutyl]carbazole ( 3 ), and 2‐ethynyl‐9‐[(S)‐4‐methylhexyl]carbazole ( 4 ) were synthesized and polymerized with [(nbd)RhCl]₂? Et₃N. The corresponding polyacetylenes with number‐average molecular weights ranging from 68,700 to 310,000 were obtained in good yields. Poly( 1 ) exhibited a large specific rotation and an intense Cotton effect in toluene, indicating that it formed a helix with predominantly one‐handed screw sense, while the other three polymers showed no evidence for taking a helical structure. Poly( 1 ) largely decreased the CD intensity upon heating from ?10 to 60 °C. Poly( 1 ) showed a Cotton effect in film state in a manner similar to solution state. No chiral amplification was observed in the copolymerization of 1 with achiral 2‐ethynyl‐9‐tert‐butoxycarbonylcarbazole ( 5 ). © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4450–4458, 2007     

Synthesis and properties of poly(phenylacetylenes) having two polar groups or one cyclic polar group on the phenyl ring

Phenylacetylene (PA) derivatives having two polar groups (ester, 2a – d ; amide, 4) or one cyclic polar group (imide, 5a – c ) were polymerized using (nbd)Rh⁺[(η⁶‐C₆H₅)B^?(C₆H₅)₃] catalyst to afford high molecular weight polymers (～1 × 10⁶ – 4 × 10⁶). The hydrolysis of ester‐containing poly(PA), poly( 2a) , provided poly(3,4‐dicarboxyPA) [poly ( 3 )], which could not be obtained directly by the polymerization of the corresponding monomer. The solubility properties of the present polymers were different from those of poly(PA) having no polar group; that is, poly( 2a )–poly( 2d ) dissolved in ethyl acetate and poly( 4 ) dissolved in N,N‐dimethylformamide, while poly(PA) was insoluble in such solvents. Ester‐group‐containing polymers [poly( 2a )–poly( 2d )] afforded free‐standing membranes by casting from THF solutions. The membrane of poly( 2a ) showed high carbon dioxide permselectivity against nitrogen (PCO₂/PN₂ = 62). © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5943–5953, 2006     

Rapid ruthenium-catalyzed synthesis of pyranopyrandiones by reconstructive carbonylation of cyclopropenones involving C[bond]C bond cleavage

Pyranopyrandiones were prepared by a novel ruthenium-catalyzed carbonylative dimerization of cyclopropenones via C-C bond cleavage. For example, treatment of dipropylcyclopropenone with a catalytic amount of Ru3(CO)12 and NEt3 in THF under 15 atm of carbon monoxide at 140 degrees C for 20 h gave a novel functional monomer, 3,4,7,8-tetrapropylpyrano[6,5-e]pyran-2,6-dione, in an isolated yield of 81%. Unsymmetrically substituted pyranopyrandiones were also obtained by ruthenium-catalyzed carbonylative coupling of cyclopropenones with alkynes under similar reaction conditions.     

Mössbauer study of the fraction of non-bridging oxygens in potassium borate glasses

A Mössbauer study was performed to find the fraction of non-bridging oxygens in potassium borate glasses containing a small amount of iron. The borate glasses with alkali contents of 15, 20, 25, 30 and 40 mol% were irradiated with ⁶⁰Co-γ rays at room temperature in a nitrogen atmosphere. The Mössbauer absorption area for the irradiation-induced Fe²⁺ increased with the total γ-ray dose in the range of 1 × 10⁶ ?2 × 10⁸ R, and became constant after irradiation ranging from 2 × 10⁸ R ? 1 × 10⁹ R. The absorption area for the Fe²⁺ at the saturated region was correlated with the difference in the glass structure, i.e., the fraction of the non-bridging oxygens was estimated from the increased absorption area for the Fe²⁺ as a function of the alkali content of the glasses. The fraction of the non-bridging oxygen increased with the alkali content of the glasses in the alkali region above 20 mol%, and about 14% of the fraction was obtained for an alkali content of 40 mol%.     

Synthesis and properties of amino acid esters of hydroxypropyl cellulose

The amino acid esters of hydroxypropyl cellulose (HPC) [R′ = H ( 2a ), CH₃ ( 2b ), CH₂CH(CH₃)₂ ( 2c ), CH₂CONH₂ ( 2d ), CH₂CH₂CONH₂ ( 2e ), CH₂CH₂CH₂CH₂ NHOCOC(CH₃)₃ ( 2f )] were synthesized in good yield by the reaction of t‐butoxycarbonyl (t‐Boc)‐protected amino acids with hydroxy groups of HPC ( 1 ; molar substitution (MS), 4.61). The amino acid functionalities displaying varied chemical nature, shape, and bulk were utilized and the bulk of the substituent on the α‐carbon of amino acids was elucidated to be of vital significance for the observed degree of incorporation (DS_Est). The ¹H NMR spectra and elemental analysis were employed to determine the degree of incorporation of amino acid moiety (DS_Est) and almost complete substitution of the hydroxy protons was revealed for 2a , 2b , and 2f . The presence of the peaks characteristic of the carbonyl group in the FTIR spectra furnished further evidence for the successful esterification of HPC. The starting as well as the resulting polymers ( 1 and 2a – f ) were soluble in polar organic solvents; however, the esterification of 1 with bulky organic moieties resulted in an increased hydrophobicity as all of the amino acid‐functionalized polymers ( 2a – f ) were insoluble in water. The onset temperatures of weight loss of 2a – f were 175–230 °C, indicating fair thermal stability. The amino acid functionalization led to the enhanced polymer chain stiffness, and the glass transition temperatures of the derivatized polymers were 30–40 °C higher than that of 1 (T_g 3.9 °C; cf. T_g of 2a – f , 35.1–43.3 °C). © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2326–2334, 2008     

Synthesis of end‐functionalized poly(phenylacetylene)s with well‐characterized palladium catalysts

End‐functionalized poly(phenylacetylene)s were synthesized by the polymerization of phenylacetylene (PA) using the well‐defined palladium catalysts represented as [(dppf)PdBr(R)] {dppf = 1,1′‐bis(diphenylphosphino)ferrocene}. The Pd catalysts having a series of R groups such as o‐tolyl, mesityl, C(Ph)?CPh₂, C₆H₄‐o‐CH₂OH, C₆H₄‐p‐CN, and C₆H₄‐p‐NO₂ in conjunction with silver triflate polymerized PA to give end‐functionalized poly(PA)s bearing the corresponding R groups in high yields. The results of IR and NMR spectroscopies and MALDI‐TOF mass analyses proved the introduction of these R groups at one end of each polymer chain. The poly(PA) bearing a hydroxy end group was applied as a macroinitiator to the synthesis of a block copolymer composed of poly(PA) and poly(β‐propiolactone) moieties. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Synthesis and properties of carbamate‐ and amine‐containing poly(phenylacetylenes)

The 3‐ and 4‐aminophenylacetylenes protected by t‐butoxycarbonyl (t‐Boc) and 9‐fluorenylmethoxycarbonyl (Fmoc) groups ( 3a – 6a ) were synthesized and polymerized using [(nbd)RhCl]₂ ( 1 ) and [(nbd)Rh⁺‐η⁶‐PhB^?Ph₃] ( 2 ) catalysts. The t‐Boc‐containing polymers [poly( 3a ) and poly( 4a )] were obtained in high yield (82–91%). Among the Fmoc‐protected monomers, the para‐derivative polymerized well [poly( 6a ); yield = 85–94%], whereas its meta‐substituted analogue did not afford high molecular weight polymer in good yield [poly( 5a ); yield = 10–15%]. The use of KN(SiMe₃)₂ as a cocatalyst in conjunction with 1 led to a dramatic increase in the molecular weight of the polymers. The acid‐ and base‐catalyzed removal of the t‐Boc and the Fmoc groups, respectively, generated primary amine‐containing polymers [poly( 3b )–poly( 6b )] which cannot be obtained directly by the polymerization of the corresponding monomers. The solubility characteristics of the polymers bearing protected amino groups were quite different from those of the unprotected ones, the former being soluble in polar solvents, whereas the latter displayed poor solubility even in polar protic or highly polar aprotic solvents. The attempts to accomplish the free‐standing membrane fabrication by solution casting were successful only for poly( 3a ), and an augmentation in the gas permeability and CO₂/N₂ permselectivity was discerned in comparison with the unsubstituted poly(phenylacetylene) and poly(m‐t‐butyldimethylsiloxyphenylacetylene). © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1853–1863, 2009     

Synthesis,properties, and gas permeability of novel poly(diarylacetylene) derivatives

Poly(diphenylacetylene)s having various silyl groups are soluble in common solvents, from whose membranes poly(diphenylacetylene) membranes can be obtained by desilylation. The oxygen permeability coefficients of the desilylated polymers are quite different from one another (120–3300 barrers) irrespective of the same polymer structure. When bulkier silyl groups are removed, the oxygen permeability increases to larger extents. Poly[1-aryl-2-p-(trimethylsilyl)phenylacetylene]s are soluble in common solvents, and afford free-standing membranes. These Si-containing polymer membranes are desilylated to give the membranes of poly[1-aryl-2-phenylacetylene]s. Both of the starting and desilylated polymers show very high thermal stability and high gas permeability. 1-Phenyl-2-p-(t-butyldimethylsiloxy)phenylacetylene polymerizes into a high-molecular-weight polymer. This polymer is soluble in common organic solvents to provide a free-standing membrane. Desilylation of this membrane yields a poly(diphenylacetylene) having free hydroxyl groups, which is the first example of a highly polar group-carrying poly(diphenylacetylene). The P/P and P/P permselectivity ratios of poly(1-phenyl-2-p-hydroxylphenylacetylene) membrane are as large as 47.8 and 45.8, respectively, while keeping relatively high P of 110 barrers. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5028–5038, 2006