LC polyimides. XXVII. Cholesteric poly(ester-imide)s derived from chiral i-pentyloxyterephthalic acids

(S)-Pentyloxyterephthalic acid was prepared by alkylation of dimethyl trimethylsiloxyterephthalate with (S)-2-methylbutan-1-ol tosylate. (S,S)-2,5-bis-i-pentyloxyterephthalic acid was prepared analogously by alkylation of diethyl-2,5-bis(trimethylsiloxy)terephthalate. A series of cholesteric poly(ester-imide)s was synthesized from (S)-pentyloxyterephthalic acid and N-(4'-hydroxyphenyl)-4-hydroxyphthalimide. 2-(4'-Chlorophenoxy)terephthalic acid was used as comonomer. The 1 : 1 copolyester of both terephthalic acids forms a Grandjean texture in the shearing of the cholesteric melt. A second series of cholesteric poly(ester-imide)s was prepared from (S,S)-2,5-bispentyloxyterephthalic acid and the aforementioned imide diphenol. In this case 2,5-bis(dodecyloxy)terephthalic acid was used as comonomer to lower the melting point. The cholesteric phases of the resulting copoly(ester-imide)s did not form a Grandjean texture. © 1996 John Wiley & Sons, Inc.     

Macromolecular helicity inversion of poly(phenylacetylene) derivatives induced by various external stimuli

Unique macromolecular helicity inversion of stereoregular, optically active poly(phenylacetylene) derivatives induced by external achiral and chiral stimuli is briefly reviewed. Stereoregular, cis-transoidal poly(phenylacetylene)s bearing an optically active substituent, such as (1R,2S)-norephedrine (poly- 1 ) and β-cyclodextrin residues (poly- 2 ), show an induced circular dichroism (ICD) in the UV-visible region of the polymer backbone in solution due to a predominantly one-handed helical conformation of the polymers. However, poly- 1 undergoes a helix-helix transition upon complexation with chiral acids having an R configuration, and the complexes exhibit a dramatic change in the ICD of poly- 1 . Poly- 2 also shows the inversion of macromolecular helicity responding to molecular and chiral recognition events that occurred at the remote cyclodextrin residues from the polymer backbone; the helicity inversion is accompanied by a visible color change. A similar helix-helix transition of poly((R)- or (S)-(4-((1-(1-naphthyl)ethyl)carbamoyl)phenyl)acetylene) is also briefly described.     

LC-POLYIMIDES. 37. POLY(ESTER-IMIDE)S DERIVED FROM N,N′-BIS(4-CARBOXY-PHENYL)BIPHENYL-3,3′-4,4′-TETRA-CARBOXYLIC IMIDE AND VARIOUS α,ω-DIHYDROXYALKANES

A new imide monomer was prepared from ethyl-4-amino-benzoate and biphenyl-3,3′-4,4′-tetracarboxylic anhydride (BTCA). This new momoner was polycondensed with various α,ω-dihydroxyalkanes. The resulting poly(ester-imide)s, PEIs, were characterized by elemental analyses, inherent viscosities DSC-measurements optical microscopy, and X-ray measurements using synchrotron radiation. All PEIs formed a crystalline smectic H-phase in the solid state. Depending on the length of the spacer individual members of this series formed either an enantiotropic smectic-A phase, a monotropic smectic-A phase or no liquid crystalline phase at all. Long spacers and odd numbers of CH₂-groups favored the formation of liquid-crystalline (LC-) phases.     

Asymmetric anionic polymerization of optically active N-1-cyclohexylethylmaleimide

Chiral (S)-(−)-N-1-cyclohexylethylmaleimide [(S)-CEMI] and (R)-(+)-N-1-cyclohexylethylmaleimide [(R)-CEMI] were synthesized successfully and then polymerized with chiral complexes of (−)-sparteine or (S,S)-(1-ethylpropylidene)bis(4-benzyl-2-oxazoline) [(S,S)-Bnbox] and organometal as initiators in toluene or tetrahydrofuran to obtain optically active polymers. The effects of the polymerization conditions on the optical activity and structure of poly(N-1-cyclohexylethylmaleimide)s were investigated with gel permeation chromatography, circular dichroism, specific rotation, and ¹³C NMR measurements. Poly[(R)-CEMI] obtained with dimethylzinc (Me₂Zn)/(S,S)-Bnbox had the highest specific rotation ([α]₄₃₅ = +323.7°). Complexes of Bnbox and diethylzinc or Me₂Zn were used very effectively as chiral initiators for the asymmetric anionic polymerization of (S)-CEMI and (R)-CEMI. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4682–4692, 2004     

Synthesis and chiroptical properties of L‐valine‐containing poly(phenylacetylene)s with (a)chiral pendant terminal groups

Poly(phenylacetylene)s containing L ‐valine residues (P 1 ) with (a)chiral pendant terminal groups R^(*) [?(HC?C{C₆H₄CONHCH[CH(CH₃)₂]COO? R^(*)})_n?]; R^(*) = 1‐octyl (P 1 o), (1S,2R,5S)‐(+)‐menthyl [P 1 (+)], (1R,2S,5R)‐(?)‐menthyl [P 1 (?)] are designed and synthesized. The polymers are prepared by organorhodium catalysts in high yields (yield up to 88%) with high molecular weights (M_w up to ?6.4 × 10⁵). Their structures and properties are characterized by NMR, IR, TGA, UV, and circular dichroism analyses. All the polymers are thermally fairly stable (T_d ≥ 320 °C). The chiral moieties induce the poly(phenylacetylene) chains to helically rotate in a preferred direction. The chirality of the pendant terminal groups affects little the helicity of the polymers but their bulkiness stabilizes the helical conformation against solvent perturbation. The backbone conjugation and chain helicity of the polymers can be modulated continuously and reversibly by acid. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2117–2129, 2006     

Electrochemical Synthesis and Optical Properties of a Chiral Poly[1,4‐bis(3′,4′‐ethylenedioxythienyl)‐phenylene] Derivative

Summary: Optically active poly[(R)‐ or (S)‐1,4‐bis(2‐(3′,4′‐ethylenedioxy)thienyl)‐2‐benzoic acid 1‐methylheptyl ester] was prepared by an electrochemical technique and characterized by circular dichroism measurements. It was found that the optical activity and optical rotation of the film could be controlled by adjusting the electronic state of the electrochemical process. Polymer films prepared in the oxidized state exhibit a weak Cotton effect, while the reduced polymer film exhibits the expected mirror‐image bisignate Cotton effect in the region of the π–π* transition of the polymer main chain. These results indicate that the main chain itself is chiral in the film state. This procedure has great potential for the preparation of functional electrochromic devices and the improved preparation of durable electrochromic devices based on the good film‐forming properties of the chiral polymer.

Cyclic voltammogram and CD spectra of the chiral polymer thin film produced here.     

Effect of spacer length on mesomorphic behaviours of chiral liquid crystal compounds containing (-)-menthyl

ABSTRACT

A homologous series of new chiral liquid crystal compounds, MnBEB (n = 4–10), was prepared by covalently linking a chiral (–)-menthyl with biphenyl-benzoate via a dicarboxylic spacer of varying length and parity. A combination of analysis methods, such as FT-IR, ¹H NMR spectra, differential scanning calorimetry (DSC), polarised optical microscopy (POM) and X-ray diffraction was carried out to systematically investigate their phase structures and phase transition behaviours. The length and parity of the flexible spacers has a profound influence on the T_m and T_c and a modest odd-even effect is observed for the chiral liquid crystal compounds MnBEB. Only compound M4BEB developed an N* phase with selectively reflection on heating and a blue phase on cooling process. In addition, increasing the length of the flexible spacers tends to narrow the temperature range of the N* phase and widen the smectic phase, moreover, the pitch becomes longer with the spacer increases.     

Asymmetric synthesis of (S,R)- and (R,R)-methiin stereoisomers

Abstract

An asymmetric synthesis of (+)- and (–)-methiine (S-methyl-(R)-cysteine sulfoxide) diastereomers has been developed. These natural sulfur compounds were isolated from a variety of Brassica vegetables. As the starting compound, (R)-cysteine was used, which was methylated to form (R)-S-methylcysteine. Then the oxidation of S-methylcysteine with tert-butyl hydroperoxide catalyzed by the chiral tetra(isopropylate)titanium/(S)- or (R)-Binol complex led to the formation of (1?R,2S)-(+)- or (1?R,2R)-(–)-methiin stereomers.     

Optically Biaxial,Re‐entrant and Frustrated Mesophases in Chiral,Non‐symmetric Liquid Crystal Dimers and Binary Mixtures

Sixteen optically active, non‐symmetric dimers, in which cyanobiphenyl and salicylaldimine mesogens are interlinked by a flexible spacer, were synthesized and characterized. While the terminal chiral tail, in the form of either (R)‐2‐octyloxy or (S)‐2‐octyloxy chain attached to salicylaldimine core, was held constant, the number of methylene units in the spacer was varied from 3 to 10 affording eight pairs of (R & S) enantiomers. They were probed for their thermal properties with the aid of orthoscopy, conoscopy, differential scanning calorimetry and X‐ray powder diffraction. In addition, the binary mixture study was carried out using chiral and achiral dimers with the intensions of stabilizing optically biaxial phase/s, re‐entrant phases and important phase sequences. Notably, one of the chiral dimers as well as some mixtures exhibited a biaxial smectic A (SmA_b) phase appearing between a uniaxial SmA and a re‐entrant uniaxial SmA phases. The mesophases such as chiral nematic (N*) and frustrated phases viz., blue phases (BPs) and twist grain boundary (TGB) phases, were also found to occur in most of the dimers and mixtures. X‐ray diffraction studies revealed that the dimers possessing oxybutoxy and oxypentoxy spacers show interdigitated (SmA_d) phase where smectic periodicity is over 1.4 times the molecular length; whereas in the intercalated SmA (SmA_c) phase formed by a dimer having oxydecoxy spacer the periodicity was found to be approximately half the molecular length. The handedness of the helical structure of the N* phases formed by two enantiomers was examined with the aid of CD measurements; as expected, these enantiomers showed optical activities of equal magnitudes but with opposite signs. Overall, it appears that the chiral dimers and mixtures presented herein may serve as model systems in design and developing novel materials exhibiting the apolar SmA_b phase possessing D_2h symmetry and nematic‐type biaxiality.     

Stable frustrated phases in chiral liquid crystals derived from optically active (R)- and (S)-3-ethylmercapto-2-methylpropionic acids

Highly optically pure (R)- and (S)-3-ethylmercapto-2-methylpropionic acids were synthesized by using optically active (D)- and (L)-2,10-camphorsultams as chiral auxiliaries, respectively. Their derivatives, (R)- and (S)-EMMPNmB (m=6-12), were prepared for investigation. Microscopic texture observations demonstrated that the materials possess three stable frustrated phases: BP, TGB_A* and TGB_C* phases. Interestingly, it was found that the N* phase behaves as an intermediary phase between BP and TGB_A* phases in a rather narrow temperature range (calc. 0.5-1.4°C). A study of the racemic mixture, (±)-EMMPNmB (m=10), indicated that the chirality of the molecule could suppress the formation of smectic phases in the heating process. An increase of alkyl chain length favoured the formation of the TGB phases particularly, in accompaniment with a change of TGB phases from monotropic to enantiotropic. Moderate maximum P _S values (calc. 14-19 nC cm^-2) and apparent tilt angle (calc. 20°) were obtained for the TGB_C* phase in a surface stabilized ferroelectric liquid crystal geometry.     

C–HPt(II) interaction-controlled self-assembly and photophysics of chiral bis(pyrrol-2-ylmethyleneamino)cyclohexane platinum(II) complexes

Reaction of (R,R)-(−)- and (S,S)-(+)-1,2-bis(pyrrol-2-ylmethyleneamino)cyclohexane with K₂PtCl₄ afforded chiral, neutral platinum(II) Schiff base complexes of (R,R)-PtL and (S,S)-PtL with high yields. The rare C–HPt(II) intermolecular interaction was found to show considerable strength and directionality for controlling M and P helical supramolecular architectures of (R,R)-PtL and (S,S)-PtL, respectively, in crystal lattices. More importantly, the open square-planar geometry of platinum(II) complexes allows axial C–HPt(II) interaction, resulting in the ³(ππ^*) excited state with some mixing of the Pt(II) metal character observed both in concentrated solutions and in the solid state at room temperature.     

Reagent control of stereochemistry in allylic additions to chiral aldehydes with CpMo(NO)(X)(2-methallyl) complexes of high enantiomeric purity

Reactions of (R)- and (S)-CpMo(NO)(η³-methallyl)X(X=camphorsulfonate, Cl, Br, I) with chiral α-substituted aldehydes yield homoallylic alcohols with high diastereoselectivity. Reactions of (R)- and (S)-CpMo(NO)(η³- methallyl)L ^S[L^S = (IS)-(+)-10-camphorsulfonate] with D -glyceraldehyde acetonide yield the corresponding homoallylic alcohols in >98% diastereomeric excess. Reactions with racemic 2-phenyl-propionaldehyde and nonracemic 3-benzyloxy-2-methylpropanol are also considered and show that there is very high reagent control of stereo-chemistry in additions to the carbonyl group.     

LC polyimides. XXI. Thermotropic poly(amide-imide)s based on trimellitimides

Polycondensation of α, ω-bis(-4-aminophenoxy) alkanes with trimellitic anhydride chloride (TMA-Cl) in m-cresol yielded a new class of poly(amideimide)s. Starting from the same diamine spacers poly(amideimides) with a more regular sequence of amide and imide groups were prepared by another synthetic method. All these poly(amide-imide)s are semi-crystalline and melt in the range of 250–300°C. They form a smectic-A phase over a narrow temperature range and suffer thermal degradation at the isotropization temperature (330–350°C). The smectic-A phase was characterized by optical microscopy (“batonnet texture”) and by synchrotron radiation measurements conducted at a heating rate of 20°C. Furthermore, it is demonstrated that slight variation of the chemical structure, such as methyl substituents or meta positions in the spacer prevent the formation of a LC phase. © 1995 John Wiley & Sons, Inc.     

Optically-active comb-branch liquid crystalline polymers having the chiral center in the flexible spacer unit. III. Copolymers of (S)-2-(4′-cyano-4-biphenylyloxy)-1-methylethoxy ethyl methacrylate and di[6-(4-methoxy-4′-oxybiphenyl) hexyl]-2-methylene butane-1,4-dioate

A new series of copolymers with optically-active liquid crystalline side chain units has been synthesized from the comonomers (S)-2-[2-(4′-cyano-4-biphenylyloxy-1-methylethoxy]ethyl methacrylate ( 1 ) and di[6-(4-methoxy-4′-oxybiphenyl)hexyl]-2-methylene butane-1,4-dioate ( 4 ). Chiral nematic phases were exhibited by two members of the series, rich in monomer 1 , while a smectic phase was exhibited in copolymers rich in 4 . While it was thought possible that ordered chiral liquid crystalline phases may be induced by copolymerizing chiral mesogenic monomers with mesogenic derivatives of itaconic acid where the high side chain density encourages greater ordering in the system, no evidence of smectic C^* phases could be found in the present systems. © 1993 John Wiley & Sons, Inc.     

Liquid-crystalline polyimides, 16. Chiral thermotropic copoly(ester-imide)s based on isosorbide and N-(4-carboxyphenyl)trimellitimide

A series of chiral copoly(ester-imide)s was prepared by polycondensation of N-(4-carboxy-phenyl)trimellitimide with mixtures of isosorbide and phenylhydroquinone. All copolyesters are non-crystalline. They form a cholesteric melt, when containing more than 50 mol-% of phenyl-hydroquinone. Containing 5 or 10 mol-% of isosorbide a “Grand-Jean” texture is detected above 300°C and 350°C, respectively.     

Molecular engineering of liquid crystalline polymers by “living” polymerization. XXXII. Synthesis and “living” cationic polymerization of 3-fluoro-4′-(ω-vinyloxyalkoxy)-4-biphenylyl (2r,3s)-2-fluoro-3-methylpentanoate with undecanyl and octyl alkyl groups

The synthesis and “living” cationic polymerization of 3-fluoro-4′-(11-vinyloxyundecany-loxy)-4-biphenylyl (2R,3S)-2-fluoro-3-methylpentanoate ( 12-11 ) and 3-fluoro-4′-(8-vi-nyloxyoctyloxy)-4-biphenylyl (2R,3S)-2-fluoro-3-methylpentanoate ( 12-8 ) are presented. Poly ( 12-11 )s and poly ( 12-8 )s with degrees of polymerization from 4.0 to 16.5 and poly-dispersities ≤ 1.13 have been synthesized and characterized by differential scanning cal-orimetry (DSC) and thermal optical polarized microscopy. Over the entire range of molecular weights poly ( 12-11 )s and poly ( 12-8 )s exhibit an enantiotropic S_A and an unidentified S_X phase. In addition, regardless of its molecular weight, poly ( 12-8 ) exhibits a S^*_c phase in between the S_A and S_x phases. Poly ( 12-11 ) and poly ( 12-8 ) show lower transition tem-peratures and broader temperature ranges of all their mesophases as compared to the corresponding polymers without a fluorine atom on the biphenyl group. The role of the connecting group between the biphenyl and chiral group of the mesogenic unit on the phase behavior of these polymers is also discussed. Copolymers of 12-8 with (2R,3S)-2-fluoro-3-methylpentyl 4′-(11-vinyloxyundecanyloxy)biphenyl-4-carboxylate ( 13-11 ) {i.e., poly-[( 12-8 )-co-( 13-11 )] (X/Y), where X/Y represents the molar ratio of monomer 12-8 to monomer 13-11 } with DP of ca. 11 and polydispersities lower than 1.23 were also syn-thesized and characterized. Their S_A and S^*_c mesophases exhibit continuous dependences of composition and this support the assignment of the mesophases exhibited by poly ( 12-8 ). © 1995 John Wiley & Sons, Inc.     

α‐Propargyl amino acid‐derived optically active novel substituted polyacetylenes: Synthesis,secondary structures,and responsiveness to ions

Novel optically active substituted acetylenes HC? CCH₂CR¹(CO₂CH₃)NHR² [(S)‐/(R)‐ 1 : R¹ = H, R² = Boc, (S)‐ 2 : R¹ = CH₃, R² = Boc, (S)‐ 3 : R¹ = H, R² = Fmoc, (S)‐ 4 : R¹ = CH₃, R² = Fmoc (Boc = tert‐butoxycarbonyl, Fmoc = 9‐fluorenylmethoxycarbonyl)] were synthesized from α‐propargylglycine and α‐propargylalanine, and polymerized with a rhodium catalyst to provide the polymers with number‐average molecular weights of 2400–38,900 in good yields. Polarimetric, circular dichroism (CD), and UV–vis spectroscopic analyses indicated that poly[(S)‐ 1 ], poly[(R)‐ 1 ], and poly[(S)‐ 4 ] formed predominantly one‐handed helical structures both in polar and nonpolar solvents. Poly[(S)‐ 1a ] carrying unprotected carboxy groups was obtained by alkaline hydrolysis of poly[(S)‐ 1 ], and poly[(S)‐ 4b ] carrying unprotected amino groups was obtained by removal of Fmoc groups of poly[(S)‐ 4 ] using piperidine. Poly[(S)‐ 1a ] and poly[(S)‐ 4b ] also exhibited clear CD signals, which were different from those of the precursors, poly[(S)‐ 1 ] and poly[(S)‐ 4 ]. The solution‐state IR measurement revealed the presence of intramolecular hydrogen bonding between the carbamate groups of poly[(S)‐ 1 ] and poly[(S)‐ 1a ]. The plus CD signal of poly[(S)‐ 1a ] turned into minus one on addition of alkali hydroxides and tetrabutylammonium fluoride, accompanying the red‐shift of λ_max. The degree of λ_max shift became large as the size of cation of the additive. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis and Characterization of Thermotropic Liquid Crystalline Poly(ester-imide)s

A series of thermotropic liquid crystalline poly(ester-imide)s was synthesized by melt polymerization of diacetoxynaphthalene acid and n-(ω-carboxyalkylene) trimellitic imides. All polymers with 2,6 substituent positions (n-2,6 PEIM) on the napthalene ring exhibit liquid crystalline phases, whereas polymers with 2,7 substituent positions (n-2,7 PEIM) do not. This result suggests that the kink structure of n-2,7 PEIMS would hinder the formation of liquid crystalline polymer. The copoly(ester-imide)s with an irregular sequence of aliphatic units and aromatic mesogens showed the liquid crystallinity with the lower transition temperatures and a lesser tendency to crystallize than homopoly(ester-imide)s. The semicrystalline polymers with more regular monomeric sequence in the main chain showed the hysteresis of viscoelastic property in the temperature cycle. A nematic glassy copolymer gave the higher molecular orientation to the fiber than a semicrystalline polymer. © 1997 John Wiley & Sons, Ltd.     

手性硼酸酯介入的不对称合成3† (R)-或(S)-1,1'-联-2-萘酚硼酸-(S)-脯氨酸酐促进的前手性亚胺的不对称硼烷还原

手性螺硼酸酯(R)-或(S)-1,1'-联-2-萘酚硼酸-(S)-脯氨酸酐[(R,S)-1或(S,S)-1]对前手性亚胺硼烷还原的不对称催化活性被观察到. 在(R,S)-1或 (S,S)-1存在下, 由前手性二烷基酮或烷基苯酮与苯胺缩合生成的前手性亚胺在THF中被硼烷还原, 高产率地给出手性仲胺, 其对映体纯度高达74% ee. 其中, 三种手性仲胺[N-(2-戊基)苯胺, N-(3-甲基-2-丁基)苯胺和N-(4-甲基-2-戊基)苯胺]系首次合成.     

A Homochiral Poly(2-oxazoline)-based Membrane for Efficient Enantioselective Separation

Chiral separation membranes have shown great potential for the efficient separation of racemic mixtures into enantiopure components for many applications, such as in the food and pharmaceutical industries; however, scalable fabrication of membranes with both high enantioselectivity and flux remains a challenge. Herein, enantiopure S-poly(2,4-dimethyl-2-oxazoline) (S-PdMeOx) macromonomers were synthesized and used to prepare a new type of enantioselective membrane consisting of a chiral S-PdMeOx network scaffolded by graphene oxide (GO) nanosheets. The S-PdMeOx-based membrane showed a near-quantitative enantiomeric excess (ee) (98.3±1.7 %) of S-(−)-limonene over R-(+)-limonene and a flux of 0.32 mmol m⁻² h⁻¹. This work demonstrates the potential of homochiral poly(2,4-disubstituted-2-oxazoline)s in chiral discrimination and provides a new route to the development of highly efficient enantioselective membranes using synthetic homochiral polymer networks.