scholarly journals Efficient Production of Poly(Cyclohexene Carbonate) via ROCOP of Cyclohexene Oxide and CO2 Mediated by NNO-Scorpionate Zinc Complexes

Polymers ◽  
2020 ◽  
Vol 12 (9) ◽  
pp. 2148
Author(s):  
Sonia Sobrino ◽  
Marta Navarro ◽  
Juan Fernández-Baeza ◽  
Luis F. Sánchez-Barba ◽  
Agustín Lara-Sánchez ◽  
...  
Keyword(s):  
Ring Opening ◽  
Zinc Complexes ◽  
Efficient Production ◽  
Cyclohexene Oxide ◽  
X Ray Diffraction ◽  
Co Catalyst ◽  
X Ray ◽  
Mild Conditions ◽  
High Yields ◽  
Very High

New mono- and dinuclear chiral alkoxide/thioalkoxide NNO-scorpinate zinc complexes were easily synthesized in very high yields, and characterized by spectroscopic methods. X-ray diffraction analysis unambiguously confirmed the different nuclearity of the new complexes as well as the variety of coordination modes of the scorpionate ligands. Scorpionate zinc complexes 2, 4 and 6 were assessed as catalysts for polycarbonate production from epoxide and carbon dioxide with no need for a co-catalyst or activator under mild conditions. Interestingly, at 70 °C, 10 bar of CO2 pressure and 1 mol % of loading, the dinuclear thioaryloxide [Zn(bpzaepe)2{Zn(SAr)2}] (4) behaves as an efficient and selective one-component initiator for the synthesis of poly(cyclohexene carbonate) via ring-opening copolymerization of cyclohexene oxide (CHO) and CO2, affording polycarbonate materials with narrow dispersity values.

scholarly journals Syntheses, Solid-state Structures and Catalytic Activity of Zinc Carboxylate Complexes in Lactide Polymerization

2014 ◽  
Vol 69 (11-12) ◽  
pp. 1365-1374 ◽  
Author(s):  
Christoph Scheiper ◽  
Christoph Wölper ◽  
Dieter Bläser ◽  
Joachim Roll ◽  
Stephan Schulz
Keyword(s):  
Ring Opening ◽  
Zinc Complex ◽  
X Ray Diffraction ◽  
Polymerization Catalysts ◽  
Co Catalyst ◽  
Carboxylate Complexes ◽  
X Ray ◽  
Carboxylate Groups ◽  
Solid State Structures ◽  
Lactide Polymerization

Abstract Three dinuclear zinc carboxylate complexes [L1-3Zn(μ,η2-O2CPh)]2 (1, 2, 4) containing either the bidentate N,N′-chelating β-diketiminate ligand RNC(Me)C(H)C(Me)NR (R = 2,6-iPr2-C6H3, L1, complex 1), the tridentate O,N,N-chelating ligand OC(Me)C(H)C(Me)NCH2CH2NMe2 (L2, complex 2) or the bis-N,N′-chelating bis-β-diketiminate ligand RNC(Me)C(H)C(Me)NNC(Me)- C(H)C(Me)NR (R = 2,6-iPr2-C6H3, L3, complex 4) were synthesized and characterized including single-crystal X-ray diffraction. Reaction of the neutral bis-β-diketimine (L3(H)2) with two equivalents of ZnMe2 leads to the expected heteroleptic dinuclear zinc complex L3(ZnMe)2 3 in 93% yield. Further reaction with benzoic acid PhCO2H leads to complex 4. Complex 2 forms a rather strong carboxylate-bridged dimer, whereas the carboxylate groups in complexes 1 and 4 act as asymmetrical bridges between both Zn atoms, pointing to the formation of a weakly bonded dimer. The zinc atoms in 1 and 4 are tetrahedrally coordinated, whereas in 2 the coordination number is increased to five due to the coordination of the pendant donor arm. The ring opening polymerization (ROP) of rac-lactide was investigated with the zinc complexes 1-4 and diazabicycloundec-7-ene (DBU) as a co-catalyst. Complexes 2 and 3 are active polymerization catalysts, which in the presence of DBU converted 200 equiv. of rac-lactide into polylactide within 10 min at ambient temperature. The analysis of the crude polymer showed that the lactide polymerization with catalyst 2 occurs via a slightly modified activated-monomer mechanism.

Thiophene ring-opening reactions IV. Facile generation of novel ethyl 4-hydroxy-6-thioxonicotinate─1,3,4- thiadiazoline hybrids

2021 ◽  
Vol 18 ◽  
Author(s):  
Mohammed M. Abadleh ◽  
Ahmad H. Abdullah ◽  
Jalal A. Zahra ◽  
Salim S. Sabri ◽  
Firas F. Awwadi ◽  
...  
Keyword(s):  
Single Crystal ◽  
Spectral Data ◽  
1H Nmr ◽  
13C Nmr ◽  
Ring Opening ◽  
Thiophene Ring ◽  
X Ray Diffraction ◽  
X Ray ◽  
Mild Conditions ◽  
Ring Opening Reactions

: A set of triethylammonium 4-oxo-6-pyridinethiolate–1,3,4-thiadiazoline hybrids (3a-e) were prepared via the reaction of ethyl 2-chloro-6-cyclopropyl-3- nitro-4-oxothieno[2,3-b]pyridine- 5-carboxylate (2) with the appropriate thiobenzoyl- hydrazide (1a-e) in acetonitrile and triethylamine. These hybrids were readily converted, under neutral mild conditions, into the corresponding 4-hydroxy-6-thioxopyridine –thiadiazoline hybrids (5a-e). The structures of the latter set are supported by HRMS, 1H NMR and 13C NMR spectral data and further confirmed by single-crystal X-ray diffraction studies. Alkylation of these hybrids in the presence of triethylamine occurred exclusively at the 6-thioxosulfur, yielding the respective 6-sulfanyl derivatives (6a-c).

Synthesis of unsymmetrical organic carbonates catalyzed by a sulfonic acid-functionalized zirconium phosphonate

2011 ◽  
Vol 84 (3) ◽  
pp. 675-684 ◽  
Author(s):  
Jinliang Song ◽  
Binbin Zhang ◽  
Suxiang Wu ◽  
Qian Wang ◽  
Honglei Fan ◽  
...  
Keyword(s):  
Sulfonic Acid ◽  
Sulfamic Acid ◽  
X Ray Diffraction ◽  
X Ray ◽  
Organic Carbonates ◽  
Zirconium Phosphonate ◽  
Ft Ir ◽  
Xrd Techniques ◽  
High Yields ◽  
Very High

Synthesis of unsymmetrical organic carbonates by transesterification of various alcohols with diethyl carbonate (DEC) is an interesting topic in green chemistry. In this work, we synthesized a kind of zirconium phosphonate functionalized with pendent N-SO3H group by the reaction of ZrOCl2·8H2O with N,N-bis(phosphonomethyl)-sulfamic acid, which was formed from sulfamic acid through a Mannich-type reaction. The functionalized zirconium phosphonate was characterized by Fourier transform/infrared (FT/IR), N2 adsorption and desorption, scanning electron microscopy (SEM), and powder X-ray diffraction (XRD) techniques, and was used as the heterogeneous catalyst for the synthesis of unsymmetrical organic carbonates by transesterification of various alcohols with DEC. It was demonstrated that the catalyst is very active and selective for the reactions, and very high yields of the desired products could be obtained. In addition, the catalyst could be easily recovered and the decrease in catalytic activity and selectivity was minor after three-fold usage. The mechanism for the transesterification reactions is discussed.

Defect-Mediated Conductivity Enhancements in Na3-xPn1-xWxS4 (Pn = P, Sb) using Aliovalent Substitutions

2019 ◽  
Author(s):  
Till Fuchs ◽  
Sean Culver ◽  
Paul Till ◽  
Wolfgang Zeier
Keyword(s):  
Ionic Conductivity ◽  
Vacancy Concentration ◽  
Sodium Ion ◽  
High Ionic Conductivity ◽  
Ionic Conductors ◽  
X Ray Diffraction ◽  
X Ray ◽  
Solid State Batteries ◽  
Ion Conducting ◽  
Very High

<p>The sodium-ion conducting family of Na<sub>3</sub><i>Pn</i>S<sub>4</sub>, with <i>Pn</i> = P, Sb, have gained interest for the use in solid-state batteries due to their high ionic conductivity. However, significant improvements to the conductivity have been hampered by the lack of aliovalent dopants that can introduce vacancies into the structure. Inspired by the need for vacancy introduction into Na<sub>3</sub><i>Pn</i>S<sub>4</sub>, the solid solutions with WS<sub>4</sub><sup>2-</sup> introduction are explored. The influence of the substitution with WS<sub>4</sub><sup>2-</sup> for PS<sub>4</sub><sup>3-</sup> and SbS<sub>4</sub><sup>3-</sup>, respectively, is monitored using a combination of X-ray diffraction, Raman and impedance spectroscopy. With increasing vacancy concentration improvements resulting in a very high ionic conductivity of 13 ± 3 mS·cm<sup>-1</sup> for Na<sub>2.9</sub>P<sub>0.9</sub>W<sub>0.1</sub>S<sub>4</sub> and 41 ± 8 mS·cm<sup>-1</sup> for Na<sub>2.9</sub>Sb<sub>0.9</sub>W<sub>0.1</sub>S<sub>4</sub> can be observed. This work acts as a stepping-stone towards further engineering of ionic conductors using vacancy-injection via aliovalent substituents.</p>

Defect-Mediated Conductivity Enhancements in Na3-xPn1-xWxS4 (Pn = P, Sb) using Aliovalent Substitutions

2019 ◽  
Author(s):  
Till Fuchs ◽  
Sean Culver ◽  
Paul Till ◽  
Wolfgang Zeier
Keyword(s):  
Ionic Conductivity ◽  
Vacancy Concentration ◽  
Sodium Ion ◽  
High Ionic Conductivity ◽  
Ionic Conductors ◽  
X Ray Diffraction ◽  
X Ray ◽  
Solid State Batteries ◽  
Ion Conducting ◽  
Very High

<p>The sodium-ion conducting family of Na<sub>3</sub><i>Pn</i>S<sub>4</sub>, with <i>Pn</i> = P, Sb, have gained interest for the use in solid-state batteries due to their high ionic conductivity. However, significant improvements to the conductivity have been hampered by the lack of aliovalent dopants that can introduce vacancies into the structure. Inspired by the need for vacancy introduction into Na<sub>3</sub><i>Pn</i>S<sub>4</sub>, the solid solutions with WS<sub>4</sub><sup>2-</sup> introduction are explored. The influence of the substitution with WS<sub>4</sub><sup>2-</sup> for PS<sub>4</sub><sup>3-</sup> and SbS<sub>4</sub><sup>3-</sup>, respectively, is monitored using a combination of X-ray diffraction, Raman and impedance spectroscopy. With increasing vacancy concentration improvements resulting in a very high ionic conductivity of 13 ± 3 mS·cm<sup>-1</sup> for Na<sub>2.9</sub>P<sub>0.9</sub>W<sub>0.1</sub>S<sub>4</sub> and 41 ± 8 mS·cm<sup>-1</sup> for Na<sub>2.9</sub>Sb<sub>0.9</sub>W<sub>0.1</sub>S<sub>4</sub> can be observed. This work acts as a stepping-stone towards further engineering of ionic conductors using vacancy-injection via aliovalent substituents.</p>

An unusual reaction of a bridged triterpenoid α-diketone with acetic anhydride

1991 ◽  
Vol 56 (12) ◽  
pp. 2917-2935 ◽  
Author(s):  
Eva Klinotová ◽  
Václav Křeček ◽  
Jiří Klinot ◽  
Miloš Buděšínský ◽  
Jaroslav Podlaha ◽  
...  
Keyword(s):  
Acetic Acid ◽  
Nmr Spectroscopy ◽  
Acetic Anhydride ◽  
Spectral Methods ◽  
X Ray Diffraction ◽  
X Ray ◽  
Mild Conditions ◽  
Condensation Products ◽  
Unsaturated Lactones ◽  
C Nmr

3β-Acetoxy-21,22-dioxo-18α,19βH-ursan-28,20β-olide (IIIa) reacts with acetic anhydride in pyridine under very mild conditions affording β-lactone IVa and γ-lactones Va and VIIa as condensation products. On reaction with pyridine, lactones Va and VIIa undergo elimination of acetic acid to give unsaturated lactones VIIIa and IXa, respectively. Similarly, the condensation of 20β,28-epoxy-21,22-dioxo-18α,19βH-ursan-3β-yl acetate (IIIb) with acetic anhydride leads to β-lactone IVb and γ-lactone Vb; the latter on heating with pyridine affords unsaturated lactone VIIIb and 21-methylene-22-ketone Xb. The structure of the obtained compounds was derived using spectral methods, particularly 1H and 13C NMR spectroscopy; structure of lactone IVa was confirmed by X-ray diffraction.

scholarly journals Rapid four-component synthesis of dihydropyrano[2,3-c]pyrazoles using nano-eggshell/Ti(IV) as a highly compatible natural based catalyst

BMC Chemistry ◽  
2021 ◽  
Vol 15 (1) ◽  
Author(s):  
Arefeh Dehghani Tafti ◽  
Bi Bi Fatemeh Mirjalili ◽  
Abdolhamid Bamoniri ◽  
Naeimeh Salehi
Keyword(s):  
Thermo Gravimetric Analysis ◽  
Reaction Times ◽  
Diffraction Field ◽  
Gravimetric Analysis ◽  
X Ray Diffraction ◽  
X Ray ◽  
Solvent Free Conditions ◽  
High Yields ◽  
Work Up

AbstractNano-eggshell/Ti(IV) as a novel naturally based catalyst was prepared, characterized and applied for the synthesis of dihydropyrano[2,3-c]pyrazole derivatives. The characterization of nano-eggshell/Ti(IV) was performed using Fourier Transform Infrared spectroscopy, X-ray Diffraction, Field Emission Scanning Electron Microscopy, Energy-Dispersive X-ray Spectroscopy, and Thermo Gravimetric Analysis. Dihydropyrano[2,3-c]pyrazoles were synthesized in the presence of nano-eggshell/Ti(IV) via a four component reaction of aldehydes, ethyl acetoacetate, malononitrile and hydrazine hydrate at room temperature under solvent free conditions. The principal affairs of this procedure are mild condition, short reaction times, easy work-up, high yields, reusability of the catalyst and the absence of toxic organic solvents.

scholarly journals Ring-Opening Copolymerization of Cyclohexene Oxide and Cyclic Anhydrides Catalyzed by Bimetallic Scorpionate Zinc Catalysts

Polymers ◽  
2021 ◽  
Vol 13 (10) ◽  
pp. 1651
Author(s):  
Felipe de la Cruz-Martínez ◽  
Marc Martínez de Sarasa Buchaca ◽  
Almudena del Campo-Balguerías ◽  
Juan Fernández-Baeza ◽  
Luis F. Sánchez-Barba ◽  
...  
Keyword(s):  
Catalytic Activity ◽  
Reaction Mechanism ◽  
Catalytic System ◽  
Phthalic Anhydride ◽  
Ring Opening ◽  
High Selectivity ◽  
Zinc Complexes ◽  
Cyclohexene Oxide ◽  
Reaction Conditions ◽  
Cyclic Anhydrides

The catalytic activity and high selectivity reported by bimetallic heteroscorpionate acetate zinc complexes in ring-opening copolymerization (ROCOP) reactions involving CO2 as substrate encouraged us to expand their use as catalysts for ROCOP of cyclohexene oxide (CHO) and cyclic anhydrides. Among the catalysts tested for the ROCOP of CHO and phthalic anhydride at different reaction conditions, the most active catalytic system was the combination of complex 3 with bis(triphenylphosphine)iminium as cocatalyst in toluene at 80 °C. Once the optimal catalytic system was determined, the scope in terms of other cyclic anhydrides was broadened. The catalytic system was capable of copolymerizing selectively and efficiently CHO with phthalic, maleic, succinic and naphthalic anhydrides to afford the corresponding polyester materials. The polyesters obtained were characterized by spectroscopic, spectrometric, and calorimetric techniques. Finally, the reaction mechanism of the catalytic system was proposed based on stoichiometric reactions.

The synthesis and polymerization behaviour of silicon-bridged [1]- and [2]ferrocenophanes with sterically demanding trimethylsilyl substituents attached to the cyclopentadienyl rings

1995 ◽  
Vol 73 (11) ◽  
pp. 2069-2078 ◽  
Author(s):  
Timothy J. Peckham ◽  
Daniel A. Foucher ◽  
Alan J. Lough ◽  
Ian Manners
Keyword(s):  
Molecular Weight ◽  
Ring Opening ◽  
Ring Opening Polymerization ◽  
Monoclinic Space Group ◽  
Organometallic Polymers ◽  
X Ray Diffraction ◽  
X Ray ◽  
Cyclopentadienyl Ligands ◽  
Sterically Demanding ◽  
High Molecular Weight Poly

The silicon-bridged [1]ferrocenophane Fe(η-C5H3SiMe3)2(SiMe2) (5) was synthesized via the reaction of Li2[Fe(η-C5H3SiMe3)2]•tmeda (tmeda = tetramethylethylenediamine) with Me2SiCl2 in hexanes. The disilane-bridged [2]ferrocenophane Fe(η-C5H3SiMe3)2(Si2Me4) (7) was prepared using a similar route from the disilane ClMe2SiSiMe2Cl. Despite the presence of sterically demanding SiMe3 substituents on the cyclopentadienyl rings, compound 5 was found to undergo thermal ring-opening polymerization at 170 °C to produce very soluble, high molecular weight poly(ferrocenylsilane) 6 with Mw = 1.4 × 105, Mn = 8.4 × 104. However, the [2]ferrocenophane 7 was found to be resistant to thermal ring-opening polymerization even at 350 °C and decomposed above 380 °C. A single-crystal X-ray diffraction study of 7 revealed that the steric interactions between the bulky SiMe3 groups are relieved by a significant twisting of the disilane bridge with respect to the plane defined by the centroids of the cyclopentadienyl ligands and the metal atom. The angle between the planes of the cyclopentadienyl rings in 7 was found to be 5.4(6)°, slightly greater than that in the non-silylated analogue Fe(η-C5H4)2(Si2Me4) (4a) (4.19(2)°), and dramatically less than the corresponding tilt angle of the strained, polymerizable, silicon-bridged [1]ferrocenophane Fe(η-C5H4)2(SiMe2) (1) (20.8(5)°). The length of the Si—Si bond in 7 (2.342(3) Å) was found to be close to the sum of the covalent radii (2.34 Å). Crystals of 7 are monoclinic, space group C2/c, with a = 23.689(3) Å, b = 11.174(1) Å, c = 31.027(3) Å, β = 109.16(1)°, V = 7758(2) Å3, and Z = 12. Keywords: ring-opening polymerization, ferrocenophane, organometallic polymers.

Synthesis, Characterization and Optical Properties of PLA / P3HT Blends Thin Films

2021 ◽  
Vol 19 (5) ◽  
pp. 132-138
Author(s):  
Maan Abd-Alameer Salih ◽  
Q.S. Kareem ◽  
Mohammed Hadi Shinen
Keyword(s):  
Thin Films ◽  
Optical Properties ◽  
Spin Coating ◽  
Ring Opening ◽  
Energy Gap ◽  
Ring Opening Polymerization ◽  
X Ray Diffraction ◽  
X Ray ◽  
Conductivity Increase ◽  
Ft Ir

In this exploration Poly lactic corrosive (PLA) was orchestrated the ring-opening polymerization Poly lactic corrosive (PLA) blended with poly(3-hexylthiophene) (P3HT) which prepared by solution. Blends thin films Synthesis by spin coating technique and using Tetrahydrofuran (THF) as solvent. PLA powder was 'characterized by' 'X-ray' 'diffraction', '(FT-IR)'. pure Optical properties (PLA), (PLA)/P3HT blends thin films with different percentage of P3HT (0, 1, 2, and 3) wt% were investigated using UV-VS spectroscopy The results showed that the absorption, absorption coefficient, extinction coefficient and conductivity increase with increasing the rate of deformation P3HT, The energy gap decreases with increasing deformation.

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