Poly(1,4‐cyclohexylenedimethylene‐1, 4‐cyclohexanedicarboxylate): analysis of parameters affecting polymerization and cis–trans isomerization

Weatherable semicrystalline polyesters based on 1,4‐cyclohexanedimethanol, 1,4‐cyclohexanedicarboxylic acid (CHDA) or dimethyl 1,4‐cyclohexane dicarboxylate (DMCD) can be prepared under normal melt‐phase conditions, using titanium tetrabutoxide as catalyst. The effect of monomer ratio, reaction temperature and catalyst loading on the final polymer properties was studied. Under the proper polymerization conditions, poly(1,4‐cyclohexylenedimethylene‐1,4‐cyclohexanedicarboxylate) polymers with high molecular weight can be obtained. During polymerization, isomerization can occur towards the thermodynamically stable cis‐trans ratio of 34–66 mol%. Carboxylic acid end groups can catalyze the isomerization and therefore the polymerization is more critical starting from CHDA rather than DMCD. Moreover, temperature control becomes a key factor to avoid or to limit isomerization. The study of the isomerization of the different monomers permitted a better understanding of the isomerization and therefore of the polymerization process. Copyright © 2011 Society of Chemical Industry     

Highly Enantioselective Cyclopropanation with Co(II)‐Salen Complexes: Control of cis‐ and trans‐Selectivity by Rational Ligand‐Design

Cyclopropanation of styrene derivatives with alkyl α‐diazoacetate in the presence of the second‐generation (salen)cobalt(II) complex 6 proceeded with excellent cis‐ and enantioselectivity. On the other hand, the cyclopropanation in the presence of complex 14 which was designed on the basis of the mechanism of asymmetric induction by complex 6 showed good trans‐ and excellent enantioselectivity.     

Trifluoromethanesulfonic Acid‐Catalyzed Tandem Semi‐Pinacol Rearrangement/Alkyne‐Aldehyde Metathesis Reaction of Arylpropagylsulfonamide‐Tethered 2,3‐Epoxycyclohexan‐1‐ols to Spiropiperidines

A simple and efficient trifluoromethanesulfonic acid‐catalyzed cycloisomerization of arylpropagylsulfonamide‐tethered 2,3‐epoxycyclohexan‐1‐ols is described. The cyclization proceeds via tandem semi‐pinacol rearrangement/alkyne‐aldehyde metathesis to afford spiropiperidines under mild reaction conditions.     

Preparation and characterization of core‐shell polystyrene/polyaniline/Pd composites and their catalytic properties for the reduction of 4‐nitrophenol

Herein, polystyrene/polyaniline/Pd (PS/PANI/Pd) core‐shell composite catalysts were prepared by a facile swelling‐diffusion‐interfacial polymerization method. PS microparticles were firstly prepared by dispersion polymerization and were swollen by aniline monomer without any surface modification. H₂PdCl₄ acid was used as palladium precursor. The was adsorbed on the surface of aniline‐swollen PS microparticles because of the electrostatic attraction between and anilinium positive ions protonated by H⁺, which was diffused from the aniline‐swollen PS microparticles. Then HCl solution was added to control the diffusion rate of anilinium positive ions and ammonium persulfate (APS) was used to polymerize the anilinium ions to get PANI shell. Due to the redox activity between PANI and Pd ions, Pd nanoparticles can be in situ formed on the surfaces of PS. Therefore, the core‐shell PS/PANI/Pd composite catalysts were obtained. The morphology and structure of the obtained composites was characterized by TEM, FT‐IR and EDX. Results showed that the products presented excellent catalytic properties for the reduction of 4‐nitrophenol (4‐NP) to 4‐aminophenol (4‐AP) in the presence of NaBH₄ by virtue of the interaction between Pd nanoparticles and conducive PANI shell. The catalytic reaction obeyed the pseudo‐first‐order reaction equations and the reaction rate constants were also calculated in this article. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44812.     

A Desymmetrization Approach to the Enantiopure syn/anti‐1,5‐Diols via Hydrolytic Kinetic Resolution (HKR) of Functionalized meso‐Bis‐Epoxides: Further Elaboration to syn/syn‐1,3,5‐Triols and Application to the Formal Synthesis of Cryptocarya Diacetate

A new approach has been developed for the synthesis of enantiopure syn/anti‐1,5‐diols by desymmetrization of functionalized meso‐bis‐epoxides using hydrolytic kinetic resolution (HKR). The usage of this protocol was demonstrated by converting syn‐1,5‐diols into syn/syn‐1,3,5‐triols and its subseqent application to the formal synthesis of cryptocarya diacetate.     

Efficient Syntheses of (Thio)phosphonylated Isobenzofurans by Tandem Nucleophilic Addition and Regioselective 5‐exo‐dig Addition to Carbon‐Carbon Triple Bond: Cooperative Effect to 1,8‐Diazabicyclo[5.4.0]undec‐7‐ene (DBU)

The tandem nucleophilic addition‐cyclization reaction of o‐alkynylbenzaldehydes or o‐alkynylacetophenones 2 with dialkyl phosphites or dialkyl phosphonothioates 1 took place very smoothly in the presence of 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) in THF at room temperature. In all cases, the reaction proceeded in a regioselective manner leading to the 5‐exo‐dig products 3 in excellent yields. The phenomenon of a 1,5‐sigmatropic hydrogen shift or a 1,5‐sigmatropic methyl shift was observed in this reaction depending on the different substituent groups such as R³ in the o‐alkynylbenzaldehyde or o‐alkynylacetophenone 2 substrates.     

Synthesis of high molecular weight copolymer of styrene and butadiene bearing high 1,4‐cis butadiene unit from copolymerization with CpTiCl3/methylaluminoxane catalyst

Copolymerization of styrene (St) and butadiene (Bd) with CpTiCl₃/methylaluminoxane (MAO) catalyst in the presence or absence of chloranil (CA) was investigated. The CpTiCl₃/MAO catalyst showed a high activity for the copolymerization of St with Bd. The 1,4‐cis contents in the Bd units for the copolymerization of St and Bd with the CpTiCl₃/MAO catalyst was observed, and the 1,4‐cis content was optimum at a MAO/Ti mole ratio of around 225. The effect of the polymerization temperature on the copolymerization was noted, as was the effect of the 1,4‐cis microstructure in the Bd units for the copolymerization of St and Bd. The addition of CA to the CpTiCl₃/MAO catalyst was found to influence the molecular weight of the copolymer. The high weight‐average molecular weight copolymer (M_w = ca. 50 × 10⁴) consisting of mainly a 1,4‐cis microstructure of Bd units (1,4‐cis = 80.0%) was obtained from the copolymerization with the CpTiCl₃/MAO catalyst in the presence of CA (CA/Ti mole ratio = 1) at 0°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2942–2946, 2003     

Rhodium‐Catalyzed Tandem Isomerization/Hydroformylation of the Bio‐Sourced 10‐Undecenenitrile: Selective and Productive Catalysts for Production of Polyamide‐12 Precursor

The hydroformylation of 10‐undecenenitrile ( 1 ) – a substrate readily prepared from renewable castor oil – in the presence of rhodium‐phosphane catalysts systems is reported. The corresponding linear aldehyde ( 2 ) can be prepared in high yields and regioselectivities with a (dicarbonyl)rhodium acetoacetonate‐biphephos [Rh(acac)(CO)₂‐biphephos] catalyst. The hydroformylation process is accompanied by isomerization of 1 into internal isomers of undecenenitrile ( 1‐int ); yet, it is shown that the Rh‐biphephos catalyst effectively isomerizes back 1‐int into 1 , eventually allowing high conversions of 1 / 1‐int into 2 . Recycling of the catalyst by vacuum distillation under a controlled atmosphere was demonstrated over 4–5 runs, leading to high productivities up to 230,000 mol ( 2 )⋅mol (Rh)⁻¹ and 5,750 mol ( 2 )⋅mol (biphephos)⁻¹. Attempted recycling of the catalyst using a thermomorphic multicomponent solvent (TMS) phase‐separation procedure proved ineffective because the final product 2 and the Rh‐biphephos catalyst were always found in the same polar phase. Auto‐oxidation of the linear aldehyde 2 into the fatty 10‐cyano‐2‐methyldecanoic acid ( 5 ) proceeds readily upon exposure to air at room temperature, opening a new effective entry toward polyamide‐12.

     

1,3‐Dioxolane‐Based Ligands as Rigid Analogues of Naftopidil: Structure–Affinity/Activity Relationships at α1 and 5‐HT1A Receptors

Conformational restriction of naftopidil led to the discovery of a new class of ligands with a 1,3‐dioxolane (1,3‐oxathiolane, 1,3‐dithiolane) structure that bind to α₁ adrenoceptor subtypes and 5‐HT_1A receptors. Adequate structural modifications address the selectivity toward one or the other receptor system.

     

Physical and thermal properties of l‐lactide/ϵ‐caprolactone copolymers: the role of microstructural design

Understanding the underlying role of microstructural design in polymers allows for the manipulation and control of properties for a wide range of specific applications. As such, this work focuses on the study of microstructure–property relationships in l‐ lactide/?‐caprolactone (LL/CL) copolymers. One‐step and two‐step bulk ring‐opening polymerization (ROP) procedures were employed to synthesize LL/CL copolymers of various compositions and chain microstructures. In the one‐step procedure, LL and CL were simultaneously copolymerized to yield P(LL‐stat‐CL) statistical copolymers. In the two‐step procedure, poly(l‐ lactide) (PLL) and poly(?‐caprolactone) (PCL) prepolymers were synthesized in the first step before CL and LL respectively were added in the second step to yield P[LL‐b‐(CL‐stat‐LL)‐b‐LL] and P[CL‐b‐(LL‐stat‐CL)‐b‐CL] block copolymers as the final products. The findings reveal that, in addition to the copolymerization procedure employed, the length and type of the prepolymer play important roles in determining the chain microstructure and thereby the overall properties of the final copolymer. Moreover, control over the degree of crystallinity and the type of crystalline domains, which is controlled during the polymer chemistry process, heavily influences the physical and mechanical properties of the final polymer. In summary, this work describes an interesting approach to the microstructural design of biodegradable copolymers of LL and CL for potential use in biomedical applications. © 2019 Society of Chemical Industry     

Functionalization of Acetalic C(sp3)‐H Bonds by Scandium(III) Triflate‐Catalyzed Intramolecular Redox Reactions: Tandem 1,4‐Hydride Transfer/1,5‐Cyclization Processes Leading to Protected 1‐Indanones

A new C C bond forming reaction leading to adjacent quaternary carbons is reported. It is a one‐pot hydride shift/cyclization process facilitated by the hydricity of the acetalic C H bonds, with benzylidenemalonate fragments as electrophilic hydride acceptors, and the catalysis of scandium(III) triflate. The reaction products are 1,2‐dihydroindane derivatives. Alkoxy and alkanethiolate groups can be also intramolecularly transferred from the acetalic carbon to the electrophilic benzylidenemalonate CC bond.     

Hydrophobic mesoporous acidic resin for hydroxyalkylation/alkylation of 2‐methylfuran and ketone to high‐density biofuel

Hydroxyalkylation/alkylation of biomass‐derived 2‐methylfuran with cyclic ketones (cyclopentanone and cyclohexanone) has great potential in synthesizing high‐density biofuel. But the conversion and selectivity are still unsatisfactory because the in‐situ formed water decreases the acidity of catalyst and induces side reaction. Herein, hydrophobic mesoporous resins with sulfonic acid group (PS) and fluoride sulfonic acid group (PCS) were synthesized by a simple solvothermal reaction and ion exchange treatment, which have good mesoporous structure with surface area of 300–700 m²/g. Notably, PS and PCS have better hydrophobicity and oleophilicity as compared to widely used sulfonic acid functional amberlyst‐15 and fluoride sulfonic acid functional nafion‐212. In the hydroxyalkylation/alkylation reaction, PS shows higher activity and selectivity than amberlyst‐15 while PCS surpasses nafion‐212. Furthermore, both PS and PCS have good recycling stability in consecutive 5 runs. After hydrodeoxygenation, two high‐density biofuels with density of 0.819 and 0.825 g/mL were obtained. © 2016 American Institute of Chemical Engineers AIChE J, 63: 680–688, 2017     

A new post‐metallocene catalyst for alkene polymerization: copolymerization of ethylene and 1‐hexene with titanium complexes bearing N,N‐dialkylcarbamato ligands

A new type of post‐metallocene polymerization catalyst based on titanium complexes with N,N‐dialkylcarbamato ligands was used to copolymerize ethylene and 1‐hexene. These easy‐to‐synthesize and stable complexes in combination with different organoaluminium co‐catalysts produce random ethylene/1‐hexene copolymers characterized by a broad molecular weight distribution and high 1‐hexene incorporation, as confirmed by SEC, DSC and ¹³C NMR analysis. The influence of the main reaction parameters on the polymerization reactions was studied including the type of catalyst components, solvent, temperature, the ethylene partial pressure and the [Al]/[Ti] ratio in the catalyst. A higher activity and a higher 1‐hexene incorporation were achieved with AlMe₃‐depleted methylalumoxane as co‐catalyst and chlorobenzene as solvent. © 2013 Society of Chemical Industry     

An Enantioselective Three‐Component Sulfa‐Michael/Aldol Cascade Reaction and its Application to the Synthesis of Thioaryl Substituted (−)‐Bestatin Derivatives

An efficient catalytic asymmetric three‐component sulfa‐Michael/aldol cascade reaction has been developed using a chiral multi‐functional catalyst. This reaction provided facile access to γ‐sulfur‐β‐nitro‐α‐hydroxy esters bearing three consecutive linear stereocenters in high yields (up to 97%) with excellent diastereo‐ (up to >97:3 dr) and enantioselectivities (>99% ee). These compounds were readily converted into 2‐nitroallylic alcohols and potentially bioactive γ‐sulfur‐β‐amino‐α‐hydroxy esters, which could be further used for the synthesis of Bestatin derivatives.