Thermal Ring Opening Research Articles

Origin of a Kinetically Selective Route for Thermoreversible Valence Tautomerism-Based Photoswitching in O-Heterocycles Containing Conjugated Dienes.

The thermal electrocyclic ring opening of fused cis-cyclobutene to cis,cis-diene is prohibited according to the Woodward-Hoffmann (WH) rules; nonetheless, experiments provide firm evidence for their formation. However, the mechanism, electronic structure, and behavior during the reaction are ambiguous. Herein, we attempt to gain insights into the mechanism of thermal ring opening in four O-heterocycles containing a conjugated diene as the core skeleton. The results emphasize that the reaction initiates with a conrotatory ring opening to produce a cis,trans-diene as a strained transient intermediate following the WH rules but ultimately leads to a forbidden product. The conversion of cis,trans-diene to cis,cis-diene is kinetically preferred through double-bond rotation, involving the formation of a singlet biradicaloid. The expected H-shift is unfavorable because the requirement of suprafacial H transfer incorporates additional strain, while the transfer of other available H is symmetry-forbidden. The increased electrophilicity at O promotes C-O dissociation in the 8-membered cyclic cis,trans-dienes with fused benzene. This enables thermoreversible photoswitching via a two-step mechanism and kinetically refutes the direct disrotatory pathway. These systems can outperform energy storage, and critical insight into their mechanism with the aid of comprehensive electronic structure analysis would assist in their rational design in the future.

Card-bisphenol based bio-silica reinforced poly(urethane-co-benzoxazine) foam for an electrical insulation

Agricultural waste by-products such as cashew nut shell liquid and rice husk ash were utilized for the syntheses of card-bisphenol (C) and precipitated bio-silica (S), respectively. A hydroxyl terminated card-bisphenol based benzoxazine resin (CHB) was synthesized and then converted it into soft-foam namely benzoxazine-co-urethane pre-polymer (CHB-UF) by polymerizing with hexamethylene diisocyanate (HMDI) in the absence of any catalysts or foaming agents. Subsequent thermal ring opening polymerization of CHB-UF at 200 °C provides poly(benzoxazine-co-urethane) hard-foam (PCHB-UF) with little shrinkage. Similarly, different weight ratios of precipitated bio-silica (0–15 wt%) reinforced bio-based PCHB-UF hard-foam composites (PCHB-UFS) were prepared to utilize them for high-k dielectrics and hydrophobic applications. The foam microstructure was ascertained through the field emission scanning electron microscopy (FE-SEM). The reinforcement of bio-silica into the CHB-UF foam increases the value of dielectric constant according to the increase in weight percentage concentration, which might be due to the reduction in volume of voids. The neat PCHB-UF possesses the value of dielectric constant of 7.04 with lower value of dielectric loss of 0.01. Similarly, the values of dielectric constant and dielectric loss of 15 wt% bio-silica reinforced composites (PCHB-UFS15) are 10.1 and 0.08 respectively. The PCHB-UFS15 has shown hydrophobic nature with the value of water contact angle of 135°. Data obtained from different studies suggest that the bio-foam composites obtained from sustainable sources can be considered as an efficient dielectric materials used for electronics insulation.

A chiral photoswitch based on enantiospecific interconversion between binaphthyl and helicenoid skeletons.

A novel chiral photoswitch composed of a binaphthyl unit and a hexafluorocyclopentene ring has been synthesized. This chiral photoswitch exhibited thermally reversible photochromism between the binaphthyl and helicenoid forms based on 6π-electrocyclization. The helicity of the binaphthyl moiety was reversed upon stereospecific photocyclization and reverted back during the thermal ring opening.

Transformation of 5-acylated N-fluoroalkyl-1,2,3-triazoles to trifluoromethylated ring-fused isoquinolines, 1,3-oxazines, and 1,3-oxazin-6-ones via ketenimines.

A one-pot multistep methodology leading to trifluoromethylated cyclopenta[c]isoquinolines, indeno[1,2-c]isoquinolines, 6,6-difluoro-1,3-oxazines, or 1,3-oxazin-6-ones, based on the reaction of 5-acylated N-pentafluoroethyl-substituted 1,2,3-triazoles is presented. A thermal ring opening of the starting triazoles, followed by a 1,2-acyl shift formed reactive ketenimines which cyclized after a rearrangement in a substrate-specific manner to provide new trifluoromethylated heterocyclic products.

Bicyclic N-dihalocyclopropylamide derivatives as precursors of nitrogen-containing fused polycyclic systems.

Examples of carbon-carbon bond-forming cyclisation reactions, involving allyl cations generated by the thermal ring-opening of halocyclopropanes, have been scarcely reported. In this contribution, we are describing the results of a study conducted with N-dihalocyclopropylamide substrates, designed as precursors of cyclic iminium intermediates that were aimed at participating in intramolecular reactions with electron-rich aromatic groups. Competitive side-reactions were identified, and access to the desired polycyclic products was carefully evaluated. The results were found to be strongly dependent on the substitution pattern of the nucleophilic aromatic moieties, as well as on the sizes of the rings of the target products. In spite of the rather moderate yields generally obtained, this approach represents a particularly short and inexpensive route to various interesting nitrogen-containing polycyclic systems, namely benzoindolizidine, benzoquinolizidine, piperidinobenzoazepane and azepanoisoquinoline compounds.

Thermal and (Thermo-Reversible) Photochemical Cycloisomerization of 1H-2-Benzo[c]oxocins: From Synthetic Applications to the Development of a New T-Type Molecular Photoswitch.

A novel T-type molecular photoswitch based on the reversible cyclization of 1H-2-benzo[c]oxocins to dihydro-4H-cyclobuta[c]isochromenes has been developed. The switching mechanism involves a light-triggered ring-contraction of 8-membered 1H-2-benzo[c]oxocins to 4,6-fused O-heterocyclic dihydro-4H-cyclobuta[c]isochromene ring systems, with reversion back to the 1H-2-benzo[c]oxocin state accessible through heating. Both processes are unidirectional and proceed with good efficiency, with switching properties─including reversibility and half-life time─easily adjusted via structural functionalization. Our new molecular-switching platform exhibits independence from solvent polarity, originating from its neutral-charge switching mechanism, a property highly sought-after for biological applications. The photoinduced ring-contraction involves a [2+2] conjugated-diene cyclization that obeys the Woodward-Hoffmann rules. In contrast, the reverse process initiates via a thermal ring-opening (T > 60 °C) to produce the original 8-membered 1H-2-benzo[c]oxocins, which is thermally forbidden according to the Woodward-Hoffmann rules. The thermal ring-opening is likely to proceed via an ortho-quinodimethane (o-QDM) intermediate, and the corresponding switching mechanisms are supported by experimental observations and density functional theory calculations. Other transformations of 1H-2-benzo[c]oxocins were found upon altering reaction conditions: prolonged heating of the 1H-2-benzo[c]oxocins at a significantly elevated temperature (72 h at 120 °C), with the resulting dihydronaphthalenes formed via the o-QDM intermediate. These reactions also proceed with good chemoselectivities, providing new synthetic protocols for motifs found in several bioactive molecules, but are otherwise difficult to access.

Mono-, di-, tri- and tetra-silacyclobutenes: Strain energy, hyperconjugation and ring-opening reaction

The ring strain, π-σ hyperconjugation and ring-opening reaction of silicon-substituted cyclobutenes (monosilacyclobutenes, disilacyclobutadienes, trisilacyclobutenes and tetrasilacyclobutene) are systemically studied at the level of B3LYP/6–311 + G(d,p). The strengths of the ring strains are characterized by the bond angle deviation from the normal angle of hybrid orbitals of the silicon and carbon atoms. A reasonable correlation is found between the strain energy and the departure of the bond path length from a linear geometrical bond. The positions of strongly-bent σ bonds are regarded as an important factor that causes different strains in silacyclobutenes. The π-σ hyperconjugation is directly estimated using the second order perturbation energy from the NBO analysis and we found that hyperconjugation is responsible for relaxing the ring strain in silacyclobutenes. The thermal ring opening reactions of silacyclobutenes are predicted to possess a symmetry-allowed conrotatory mechanism. The contribution of the bond energy is the main factor that dictates the ring-opening process to be either endothermic or exothermic.

Structurally Designed Imine Skeletal Pyrenyl Pendant Pyridine Core Polybenzoxazine nSiO2/PBZ Hybrid Polymer Nanocomposites

Novel polybenzoxazine-silica (nSiO2/PBZ) hybrid nanocomposites were designed and synthesized using carbazole terminal pyrenyl pyridine core imine skeletal benzoxazine monomer (PYCBZ) and nanosilica (nSiO2) through in situ sol-gel method. The FT-IR and Raman spectral studies ascertained the formation of nanosilica reinforced polybenzoxazine hybrid nanocomposites. The nSiO2/PBZ hybrid nanocomposites exhibited excellent thermal stability and higher char yield than that of neat PBZ. The elevation in glass transition temperature of the nanocomposites was evidenced by the limited motion of the polymeric network with the introduction of nanosilica particles in the PBZ matrices. The hydrophobic nature of a less polar nSiO2 in the composites zipped the water uptake behaviour of (nSiO2/PBZ) hybrid nanocomposites to low percentage. The shift in the absorption peak reveals that the nanosilica particles were successfully incorporated through thermal ring opening polymerization of benzoxazine. The homogeneous reinforcement of nSiO2 particles retains the fluorescent properties of polybenzoxazine. The uniform molecular level dispersion of nano SiO2 onto polybenzoxazine networks were confirmed from transmission electron microscope and scanning electron microscope images.

Modifying Woodward–Hoffmann Stereoselectivity Under Vibrational Strong Coupling

AbstractVibrational strong coupling (VSC) has recently been shown to change the rate and chemoselectivity of ground‐state chemical reactions via the formation of light–matter hybrid polaritonic states. However, the observation that vibrational‐mode symmetry has a large influence on charge‐transfer reactions under VSC suggests that symmetry considerations could be used to control other types of chemical selectivity through VSC. Here, we show that VSC influences the stereoselectivity of the thermal electrocyclic ring opening of a cyclobutene derivative, a reaction which follows the Woodward–Hoffmann rules. The direction of the change in stereoselectivity depends on the vibrational mode that is coupled, as do changes in rate and reaction thermodynamics. These results on pericyclic reactions confirm that symmetry plays a key role in chemistry under VSC.

Modifying Woodward-Hoffmann Stereoselectivity Under Vibrational Strong Coupling.

Vibrational strong coupling (VSC) has recently been shown to change the rate and chemoselectivity of ground‐state chemical reactions via the formation of light–matter hybrid polaritonic states. However, the observation that vibrational‐mode symmetry has a large influence on charge‐transfer reactions under VSC suggests that symmetry considerations could be used to control other types of chemical selectivity through VSC. Here, we show that VSC influences the stereoselectivity of the thermal electrocyclic ring opening of a cyclobutene derivative, a reaction which follows the Woodward–Hoffmann rules. The direction of the change in stereoselectivity depends on the vibrational mode that is coupled, as do changes in rate and reaction thermodynamics. These results on pericyclic reactions confirm that symmetry plays a key role in chemistry under VSC.

Stereoselective synthesis of PEGylated azoles via 1,3-dipolar cycloaddition

Abstract Diastereoselective synthesis of PEGylated imidazolidines, oxazolidines, thiazolidines, pyrrolo[3,4-c]pyrroles and fulleropyrrolidines in high yields is reported. The 1,3-dipolar cycloaddition of azomethine ylides generated via thermal ring-opening of PEGylated aziridines to ketenimines, ketenes, thioketones, maleimides, DMAD and fullerene C60 was found to proceed under different conditions. The use of C O, C N and C S dipolarophiles requires more harsh reaction conditions, compared with C C and C C dipolarophiles, to suppress the side reaction of aziridine “dimerization”. The stereocontrol of the product configuration is achieved through stereospecificity of two consecutive concerted reactions: electrocyclic aziridine ring opening followed by 1,3-dipolar cycloaddition of the resulting azomethine ylide: only trans-adducts are formed from cis-aziridines, whereas trans-aziridines give exclusively cis-adducts. The structure and molecular-mass distribution of the resulting PEGylated heterocycles are exhaustively characterized by 1H, 13C NMR, IR and HRMS.

A tetraphenylethylene-functionalized benzoxazine and copper(II) acetylacetonate form a high-performance polybenzoxazine

In this study, we synthesized TPE-BZ, a new tetraphenylethylene (TPE)-functionalized benzoxazine (BZ) monomer (1,1,2,2-tetrakis(3-phenyl-3,4-dihydro-2H-benzo[e] [1,3]oxazin-6-yl)ethane), through reduction of the Schiff base formed from TPE-4OH–CHO (1,1,2,2-tetra(3-formyl-4-hydroxyphenyl)ethylene) and aniline and subsequent reaction with paraformaldehyde. Fourier transform infrared (FTIR) spectroscopy, nuclear magnetic resonance spectroscopy, and mass spectrometry confirmed the structure of the TPE-BZ monomer. We used differential scanning calorimetry (DSC), FTIR spectroscopy, and thermogravimetric analysis (TGA) to investigate the thermal ring opening polymerization (ROP) and thermal stability of the TPE-BZ monomer after thermal treatment at various temperatures (from room temperature to 250 °C). The TGA profiles revealed that thermal treatment at 250 °C under a N2 atmosphere gave a poly(TPE-BZ) that possessed excellent thermal stability and a high char yield (435 °C, 64.3 wt%). Furthermore, water contact angle measurements of the poly(TPE-BZ) obtained at 210 °C for 2 h indicated a relatively low surface free energy (18.6 mJ m−2), presumably because of strong intramolecular hydrogen bonding between the phenolic OH groups and the N-Mannich bridge in the polybenzoxazine matrix. We also employed DSC, FTIR spectroscopy, and TGA to examine the specific interactions in TPE-BZ/Cu(acac)2 complexes. DSC analysis revealed that blending the TPE-BZ monomer with various weight ratios of Cu(acac)2 lowered the thermal curing temperature of TPE-BZ from 250 to 239 °C, accompanied by a lower curing temperature at 189 °C. Using the Kissinger method, the activation energy of the TPE-BZ/Cu(acac)2 complex (127 kJ mol−1) was lower than that of the TPE-BZ monomer (141 kJ mol−1), suggesting that Cu(acac)2 functioned as a catalyst that initiated ROP of the oxazine units, while providing a product that retained high thermal stability.

Concise Access to the Skeleton of Protoilludane Sesquiterpenes through a Photochemical Reaction Cascade: Total Synthesis of Atlanticone C.

In a single photochemical operation (λ≥350 nm) an easily accessible indanone derivative was converted into a structurally complex precursor of the protoilludane sesquiterpenes. The product (60 % yield) contains all 15 carbon atoms of the skeleton in the required connectivity and was transformed into the natural product atlanticone C (9 steps, 6 % overall yield). In addition, it was shown that other protoilludanes, such as Δ6‐protoilludene and paesslerin A, can be prepared in a concise fashion via the photochemical key intermediate. The photochemical reaction cascade comprises an ortho photocycloaddition, a thermal disrotatory ring opening and a regioselective disrotatory [4π] photocyclization.

Concise Access to the Skeleton of Protoilludane Sesquiterpenes through a Photochemical Reaction Cascade: Total Synthesis of Atlanticone C

AbstractIn a single photochemical operation (λ≥350 nm) an easily accessible indanone derivative was converted into a structurally complex precursor of the protoilludane sesquiterpenes. The product (60 % yield) contains all 15 carbon atoms of the skeleton in the required connectivity and was transformed into the natural product atlanticone C (9 steps, 6 % overall yield). In addition, it was shown that other protoilludanes, such as Δ6‐protoilludene and paesslerin A, can be prepared in a concise fashion via the photochemical key intermediate. The photochemical reaction cascade comprises an ortho photocycloaddition, a thermal disrotatory ring opening and a regioselective disrotatory [4π] photocyclization.

Modulation of photochromic properties of spirooxazine bearing sulfobutyl substituent by metal ions

A novel spirooxazine bearing sulfobutyl substituent on the indoline part of the molecule has been synthesized and its photochromic properties and complex formation with metal ions have been studied. Under UV light irradiation of colorless acetonitrile solution of spirooxazine the open merocyanine form having an absorption band in visible region of the spectrum with λmax = 625 nm is generated. Thermal back reaction of merocyanine form to spirooxazine with the rate constant 1.10 s−1 at 298 K has been observed. Interaction of spirooxazine with Mg2+, Ca2+, Cd2+, Zn2+ or Pb2+ ions in the dark leads to the formation of complexes of merocyanine form demonstrating a visible absorption band shifted from 20 to 8 nm relative to the uncomplexed merocyanine form. The activation energy of metal-induced coloration process in the dark is in the range of 84–88 kJ mol−1 and does not depend on the nature of the metal ions. This suggests that the process of thermal ring opening of the spiro form is the rate limiting step of complex formation. The degree of conversion of spirooxazine to complexed merocyanine form strongly depends on metal ions nature and irradiation wavelength.

A vector‐based representation of the chemical bond for predicting competitive and noncompetitive torquoselectivity of thermal ring‐opening reactions

AbstractWe present a new vector‐based representation of the chemical bond referred to as the bond‐path frame‐work set B = {p, q, r}, where p, q, and r represent three paths with corresponding eigenvector‐following paths with lengths H*, H, and the bond‐path length from the quantum theory of atoms in molecules (QTAIM). We find that longer path lengths H of the ring‐opening bonds predict the preference for the transition state inward (TSIC) or transition state outward (TSOC) of thermal ring opening reactions in agreement with experiment for all five reactions R1‐R5. Competitiveness and noncompetitiveness have traditionally been considered using activation energies within transition state theory that is known to fail for thermal ring‐opening reactions. Consequently, we find that the activation energy for R3 does not satisfactorily determine competitiveness or provide consistent agreement with experimental yields. We choose a selection of five competitive and noncompetitive reactions; methyl‐cyclobutene (R1), ethyl‐methyl‐cyclobutene (R2), iso‐propyl‐methyl‐cyclobutene (R3), ter‐butyl‐methyl‐cyclobutene (R4), and phenyl‐methyl‐cyclobutene (R5). Therefore, in this investigation we provide a new criterion, within the QTAIM framework, to determine whether the reactions R1‐R5 are competitive or noncompetitive. We that find R2, R3, and R5 are competitive and R1 and R4 are noncompetitive reactions in contrast to the results from the activation energies, calling into question the reliability of activation energies.

A combined experimental and theoretical study of the thermal [3+2] cycloaddition of carbonyl ylides with activated alkenes

4-Benzoyl-3,5-diaryltetrahydrofuran-2,2-dicarbonitriles were first synthesized from 2,2-dicyano-3-aryloxiranes and chalcones at toluene reflux; the 4,5-cis products proved to be predominantly formed and were isolated. Whereas shortened reaction times were observed by using microwave irradiation or catalytic cuprous chloride, no significant stereoselectivity change was in general noticed. Reacting 2,2-dicyano-3-aryloxiranes with 2-cyclopentenone next afforded 3-aryl-4-oxohexahydro-1H-cyclopenta[c]furan-1,1-dicarbonitriles, and the endo stereoisomers were isolated. That no stereoselectivity change was noticed in the presence of cuprous chloride rather suggests an impact of the salt on the epoxide ring opening. Finally, treatment of 2,2-dicyano-3-aryloxiranes by 2-morpholinoacrylonitrile yielded 3-cyano-3-morpholino-5-phenyltetrahydrofuran-2,2-dicarbonitriles from which the preponderant trans isomers were isolated. Importantly, the molecular mechanism of the domino reaction between 2,2-dicyano-3-phenyloxirane and 2-cyclopentenone was studied. The rate-determining thermal ring opening of the oxirane is followed by a non-concerted pseudoradical-type reaction of the carbonyl ylide with 2-cyclopentenone. Using the bond evolution theory also allowed the regioselectivity of this non-polar reaction to be explained.

One-Pot Substitution Approach for the Syntheses of Nonfunctional and Functional Poly[(amino acid ester)phosphazene] Biomaterials

Biodegradable polyphosphazenes are important class of biomaterials. Their preparation typically requires specialized setup, inert conditions, and cumbersome and multiple processes. This work focuses on the synthesis of both nonfunctional and novel functional poly[(amino acid ester)phosphazene]s using a simplified thermal ring opening polymerization in air, followed by one-pot (1P) room temperature substitution, also in air. While some hydrolysis was inevitable under such conditions, purified materials with lower polydispersity indices than previously reported and acceptable yields were successfully and reproducibly obtained. The poly[(amino acid ester)phosphazene]s developed in this work are based on l-alanine, l-phenylalanine, and l-methionine with l-glutamic acid to render them functionality. Characterization of these synthesized materials demonstrated that the 1P substitution was successful in developing mono- and co-substituted poly[(amino acid ester)phosphazene]s. Cytotoxicity studies on 2D films showed the materials to be compatible with NIH-3T3 fibroblasts while confocal imaging of cells showed a well-spread morphology with abundant F-actin within the cytoskeleton. The l-phenylalanine-based poly[(amino acid ester)phosphazene]s also showed significantly enhanced cell viability over tissue culture polystyrene at days 1 and 3 of cultivation (p < 0.01). Overall, this study has shown that poly[(amino acid ester)phosphazene]s can be obtained with acceptable yields and straightforward reaction conditions, leading to materials suitable for broader biomedical applications.

THEORETICAL MODELING OF ELECTROCYCLIC 2 Н -PYRAN AND 2 Н -1,4-OXAZINE RING OPENING REACTIONS IN PHOTO- AND THERMOCHROMIC SPIROPYRANS AND SPIROOXAZINES

The detailed mechanism of thermal ring opening reactions of 2 H -pyran and 2 Н -1,4-oxazine systems in a broad range of spiropyran and spiro-1,4-oxazine derivatives was studied by density functional method calculations (PBE0/6-311+G(d,p)). The study revealed mechanistic features and the dependence of activation parameters of this electrocyclic reaction on the steric and electronic properties of spirofused rings in the studied compounds. Authors: Igor V. Dorogan*, Vladimir I. Minkin

Altered torquoselectivity of fluorine in the iron-tricarbonyl-mediated thermal ring opening of 3-fluorocyclobutene: a density-functional exploration

There are eight possible pathways for the iron-tricarbonyl-assisted thermal electrocyclic ring opening of fluorocyclobutene due to variations in the orientation of the binding of Fe(CO)3 relative to the fluorine substituent (R1 or R2), stereoselectivity (conrotatory or disrotatory, i.e., C or D), and the torquoselectivity of fluorine (inward-facing or outward-facing, i.e., in or out). A density functional study revealed that the energetically favored pathway is R1 Din. Not only is the D mode favored energetically, but the in configuration was observed to be the lowest-lying mode of R1, despite the general tendency of fluorine substituents to prefer an out configuration. Data on the activation hardness and aromaticity indices such as BAC and HOMA lead to the same conclusion. However, the R2 mode surprisingly shows no particular preference for either the Cout or the Dout pathway (i.e., the R2 mode shows less stereoselectivity than R1). This behavior occurs due to the influences of both the fluorine substituent and metal coordination. Also, the geminal bond orbitals σ(C-F) and σ*(C-F) appear to participate in ring opening, given the excellent correlation of ∆BE with the activation barrier of the transition state.