Dissolution of latex films after γ‐ray treatment

Latex films were prepared by annealing pyrene (Py)‐labeled poly(methyl methacrylate) particles at glass‐transition temperature (100°C). These films were then irradiated by γ‐rays from ⁶⁰Co in a gamma cell at room temperature at the same dose rate (rad/h) for 30 min. Before dissolution films were annealed at elevated temperatures for a 30‐min time interval to complete the film formation process. Steady‐state fluorescence (SSF) technique were used to monitor the dissolution of these irradiated latex films. The dissolution of films in chloroform–heptane (80–20%) mixture was monitored in real time by the Py fluorescence intensity change. Relaxation constants k₀ and desorption coefficients D_d of polymer chains were measured. It was observed that both D_d and k₀ values first increased and then decreased by increasing the annealing temperature. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 129–137, 2002     

Poly(glycerol–sebacate) bioelastomers—kinetics of step‐growth reactions using Fourier Transform (FT)‐Raman spectroscopy

Kinetic studies of the esterification of glycerol (G) and sebacic acid (SA) at three molar ratios (0.6, 0.8, 1.0) and at three temperatures (120, 130, 140°C) to form poly(glycerol–sebacate) were performed and assessed using FT‐Raman spectroscopy. The quantitative changes in the concentrations of carboxylic acid and ester groups within the forming bioelastomer were measured and the chemical rate constants (k) determined from the kinetic scheme were first‐order, with respect to sebacic acid concentration. Increasing the reaction temperature by 20°C is noted to increase the chemical rate constant (k) by a factor of up to 4.5 and the total extent of conversion at early times for the molar ratios investigated. The activation energy (E_a) and the pre‐exponential factor (A₀) for these three stoichiometric ratios were calculated, which varied in accordance with the average functionality of the system. Under isothermal conditions, the chemical rate constant remained unchanged with an increase in the extent of the reaction (α) until a spontaneous transition resulted in the shift in the mechanism from kinetics to diffusion controlled. The Young's moduli of the PGS polymers were found to depend primarily on the average functionality of the system and the curing period. This investigation confirms the reaction mechanism for PGS polymer synthesis and shows the flexibility afforded to PGS properties and reaction times through varying the stoichiometric ratios of glycerol to sebacic acid. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Influence of technological parameters on the epoxidation of 1‐butene‐3‐ol over titanium silicalite TS‐2 catalyst

BACKGROUND: The influence of technological parameters on the epoxidation of 1‐butene‐3‐ol (1B3O) over titanium silicalite TS‐2 catalyst has been investigated. Epoxidations were carried out using 30%(w/w) hydrogen peroxide at atmospheric pressure. The major product from the epoxidation of B3O was 1,2‐epoxybutane‐3‐ol, with many potential applications. RESULTS: The influence of temperature (20–60 °C), 1B3O/H₂O₂ molar ratio (1:1–5:1), methanol concentration (5–90%(w/w)), TS‐2 catalyst concentration (0.1–6.0%(w/w)) and reaction time (0.5–5.0 h) have been studied. CONCLUSION: The epoxidation process is most effective if conducted at a temperature of 20 °C, 1B3O/H₂O₂ molar ratio 1:1, methanol concentration (used as the solvent) 80%(w/w), catalyst concentration 5%(w/w) and reaction time 5 h. Copyright © 2009 Society of Chemical Industry     

Oxidation kinetics in olive oil triacylglycerols under accelerated shelf‐life testing (25–75 °C)

A kinetic study of the autoxidation reaction in olive oil triacylglycerols stored in darkness at different temperatures (25, 40, 50, 60 and 75 °C), in absence of pro‐ and antioxidant compounds to avoid confounding effects, is described. After the induction period (IP) the decrease in the oxidizing substrate and the formation of primary oxidation products followed a pseudo‐zero‐order kinetic, and the calculated E_a from the Arrhenius equation for the formation of hydroperoxides was 32.1 kJ·mol^?1. The formation of secondary oxidation products followed a pseudo‐first‐order kinetic whose rate reaction constant also increased exponentially with temperature. The first oxidation index to exceed the upper limit in the EU regulations was PV, followed by K₂₃₂ and K₂₇₀. The time required reaching these limits and the rancidity threshold showed a potential dependence on temperature, and therefore with accelerated storage at 75 °C, POO shelf‐life in ambient conditions (25 °C) can be predicted. Finally, there was a good linear relationship between the time required to reach the rancidity threshold and the IP of the formation of the 2,4‐decadienal, and hence this instrumental determination could be useful to measure sensory recognition of the rancid defect in POO.     

Fischer‐Tropsch Synthesis Over Co‐Ru/γ‐Al2O3 Catalyst in Supercritical Media

The Fischer‐Tropsch synthesis (FTS) in gaseous and supercritical phases was examined in a continuous, high‐pressure fixed‐bed reactor by employing a cobalt catalyst (Co‐Ru/γ‐Al₂O₃). The kinetic modeling of the FTS was investigated in the reactor over a 60–80 mesh cobalt catalyst. The Langmuir‐Hinshelwood kinetic equation was used for both the Fisher‐Tropsch (FT) and water gas shift (WGS) reactions. The kinetic model was applied for simulation of the reactor with 16–20 mesh cobalt catalyst. The simulation results showed a good agreement with the experimental data. The experimental data showed that higher CO conversion and lower CH₄ and CO₂ selectivities were achieved in supercritical media compared to the gaseous phase. The BET surface area and pore volume enhancement results provided evidence of the higher in situ extraction and greater solubility of heavy hydrocarbons in supercritical media than in gaseous phases. Furthermore, the effects of supercritical solvent such as n‐pentane, n‐hexane, n‐heptane and their mixtures were studied. Moreover, the influence of reaction temperature, H₂/CO ratio, W/F_(CO+H2) and pressure tuning in the supercritical media FT synthesis were investigated, as well as the effect of the supercritical fluid on the heat transfer within the reactor. The product carbon distribution had a similar shape for all types of solvents and shifted to lighter molar mass compounds with increasing temperature, H₂/CO ratio, and W/F_(CO+H2). Finally, the product distribution shifted to higher molar mass hydrocarbons with increasing pressure. As a result, one may conclude that a mixture of hydrocarbon products of the FTS can be used as a solvent for supercritical media in Fischer‐Tropsch synthesis.     

Temperature effect on the swelling of PAAm‐κ‐carrageenan composites

The steady‐state fluorescence (SSF) technique was used for studying swelling of disc‐shaped polyacrylamide (PAAm)‐κ‐carrageenan (κC) composites which were prepared by free‐radical crosslinking copolymerization at 80°C. Pyranine was introduced as a fluorescence probe during polymerization. Swelling experiments were performed in water at various temperatures by real‐time monitoring of the pyranine (Py) fluorescence intensity, I which decreased as swelling proceeded. Stern–Volmer equation is modified for low quenching efficiencies to interpret the behavior of Py intensity during the swelling of PAAm‐κC composites. The Li‐Tanaka equation was used to determine the swelling time constants, τ₁, and cooperative diffusion coefficients, D₀, from fluorescence intensity, weight, and volume variations of the composites at various temperatures. It was observed that τ₁ first decreased up to 40°C and then increased; naturally, D₀ increased up to 40°C and then decrease for all κC content gels. Swelling activation energies, ΔE, were measured for the swelling composites, which are found to be exothermic and endothermic in between 30–40 and 40–60°C, respectively. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Thermal decomposition behavior of γ‐irradiated poly(vinyl acetate)/poly(methyl methacrylate) miscible blends

Miscible polymer blends based on various ratios of poly(vinyl acetate) (PVAc) and poly(methyl methacrylate) (PMMA) were prepared in film form by the solution casting technique using benzene as a common solvent. The thermal decomposition behavior of these blends and their individual homopolymers before and after γ‐irradiation at various doses (50–250 kGy) was investigated. The thermogravimetric analysis technique was utilized to determine the temperatures at which the maximum value of the rate of reaction (T_max) occurs and the kinetic parameters of the thermal decomposition. The rate of reaction curves of the individual homopolymers or their blends before or after γ‐ irradiation displayed similar trends in which the T_max corresponding to all polymers was found to exist in the same position but with different values. These findings and the visual observations of the blend solutions and the transparency of the films gave support to the complete miscibility of these blends. Three transitions were observed along the reaction rate versus temperature curves; the first was around 100–200°C with no defined T_max, which may arise from the evaporation of the solvent. The second T_max was in the 340–380°C range, which depended on the polymer blend and the γ‐irradiation condition. A third transition was seen in the rate of reaction curves only for pure PVAc and its blends with PMMA with ratios up to 50%, regardless of γ‐ irradiation. We concluded that γ‐irradiation improved the thermal stability of PVAc/PMMA blends, even though the PMMA polymer was degradable by γ irradiation. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1773–1780, 2006     

Synthesis of α‐Carbolines Starting from 2,3‐Dichloropyridines and Substituted Anilines

9H‐α‐Carbolines have been prepared via consecutive intermolecular Buchwald–Hartwig reaction and Pd‐catalyzed intramolecular direct arylation from commercially available 2,3‐dichloropyridines and substituted anilines. The combination of a high reaction temperature (180 °C) and the use of DBU were found to be crucial for the intramolecular direct arylation reactions of the 3‐chloro‐N‐phenylpyridin‐2‐amines as no reaction was observed at 120 °C and 180 °C using different inorganic and other organic bases. On the other hand, nitrogen‐methylated pyridine analogues of these substrates {N‐[3‐chloro‐1‐methylpyridin‐2(1H)‐ylidene]anilines} do undergo ring closure at 120 °C, with K₃PO₄ as base, affording the respective 1‐methyl‐1H‐α‐carbolines in good yields.     

Carbon dioxide sorption and diffusion in poly(3‐hydroxybutyrate) and poly(3‐hydroxybutyrate‐CO‐3‐hydroxyvalerate)

CO₂ sorption and diffusion in poly(3‐hydroxybutyrate) and three poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) copolymers were investigated gravimetrically at temperatures from 25° to 50°C and pressures up to 1 atm. The sorption behavior proved to be linear for all the copolymers studied. An additional set of measurements performed in a pressure decay apparatus at 35°C showed that the linearity could be extrapolated to pressures up to 25 atm. The sorption results obtained from both techniques were in good agreement. The poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) sorption kinetics were increasingly non‐Fickian at the higher temperatures, thus preventing the calculation of diffusion coefficients above 35°C. Interestingly, this was not the case for poly(3‐hydroxybutyrate), and diffusion coefficients and permeabilities could be calculated at all of the investigated temperatures. The 35°C permeabilities were fairly low, which is attributed to the high degree of crystallinity of this polyester family. Finally, the poly(3‐hydroxybutyrate) barrier properties against CO₂ are successfully compared with those of some selected common thermoplastics. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2391–2399, 1999     

Pd‐Ag/α‐Al2O3 Catalyst Deactivation in Acetylene Selective Hydrogenation Process

The selective hydrogenation of acetylene to ethylene over Pd‐Ag/α‐Al₂O₃ catalysts prepared by different impregnation/reduction methods was studied. The best catalytic performance was achieved with the sample prepared by sequential impregnation. A kinetic model based on first order in acetylene and 0.5th order in hydrogen for the main reaction and second‐order independent decay law for catalyst deactivation was used to fit the conversion time data and to obtain quantitative assessment of catalyst performances. Fair fits were observed from which the reaction and deactivation rate constants were evaluated. Coke deposition amounts showed a good correlation with catalyst deactivation rate constants, indicating that coke formation should be the main cause of catalyst deactivation.     

Thermogravimetric analysis of poly(3‐hydroxybutyrate) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)

The thermal degradation of poly(3‐hydroxybutyrate) (PHB) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) [P(HB‐HV)] was studied using thermogravimetry (TG). In the thermal degradation of PHB, the temperature at the onset of weight loss (T_o) was derived by T_o = 0.97B + 259, where B represents the heating rate (°C/min). The temperature at which the weight loss rate was maximum (T_p) was T_p = 1.07B + 273, and the final temperature (T_f) at which degradation was completed was T_f = 1.10B + 280. The percentage of the weight loss at temperature T_p (C_p) was 69 ± 1% whereas the percentage of the weight loss at temperature T_f (C_f) was 96 ± 1%. In the thermal degradation of P(HB‐HV) (7:3), T_o = 0.98B + 262, T_p = 1.00B + 278, and T_f = 1.12B + 285. The values of C_p and C_f were 62 ± 7 and 93 ± 1%, respectively. The derivative thermogravimetric (DTG) curves of PHB confirmed only one weight loss step change because the polymer mainly consisted of the HB monomer only. The DTG curves of P(HB‐HV), however, suggested multiple weight loss step changes; this was probably due to the different evaporation rates of the two monomers. The incorporation of 10 and 30 mol % of the HV component into the polyester increased the various thermal temperatures (T_o, T_p, andT_f) by 7–12°C (measured at B = 20°C/min). © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2237–2244, 2001     

Improved photochromic and fatigue performance of (E)‐dicyclopropylmethylene‐(2,5‐dimethyl‐3‐furylethylidene)‐succinicanhydride doped in polyurethane thin film

Improved photochromic properties and fatigue performance of (E)‐dicyclopropylmethylene‐(2,5‐dimethyl‐3‐furylethylidene)‐succinicanhydride doped in polyurethane thin film were discussed in this study. Fulgide 1‐E doped in polyurethane polymer films was heated at various annealing temperatures. Upon irradiation with UV light (366 nm), fulgide 1‐E undergoes a conrotatory ring closure to the pink‐colored closed form 1‐C . The latter color was switched back to the original color when the films were irradiated with white light. The kinetics of photocoloration and photobleaching processes was followed spectrophotometrically by monitoring the absorbance of the ring‐closed product 1‐C at its λ_max of 525 nm. The first‐order plots of photocoloration reaction show distinct linear line and the slope of which corresponding to the first‐order rate constants k. It was found that for photocoloration reaction, the rate constant of the photocoloration reaction is slower than the photobleaching reaction, and both reactions decrease with increasing the annealing temperatures. It was found that there was almost complete loss of photochemical fatigue resistance of fulgide 1 doped in polyurethane polymer film irrespective of the annealing temperature. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

Synthesis and characterization of degradable copoly(trans‐4‐hydroxy‐L‐proline/ϵ‐caprolactone)

The melt polycondensation reaction of N‐protected trans‐4‐hydroxy‐L ‐proline (N‐Z‐Hpr) and ?‐caprolactone (?‐CL) over a wide range of molar fractions in the feed produced new and degradable poly(N‐Z‐Hpr‐co‐?‐CL)s with stannous octoate as a catalyst. The optimal reaction conditions for the synthesis of the copolymers were obtained with 1.5 wt % stannous octoate at 140°C for 24 h. The synthesized copolymers were characterized by IR spectrophotometry, ¹H NMR, differential scanning calorimetry, and Ubbelohde viscometry. The values of the inherent viscosity (η_inh) and glass‐transition temperature (T_g) of the copolymers depended on the molar fractions of N‐Z‐Hpr. With an increase in the trans‐4‐hydroxy‐N‐benzyloxycarbonyl‐L ‐proline (N‐CBz‐Hpr) feed from 10 to 90 mol %, a decrease in η_inh from 2.47 to 1.05 dL/g, and an increase in T_g from ?48 to 49°C were observed. The in vitro degradation of these poly(N‐CBz‐Hpr‐co‐?‐CL)s was evaluated from weight‐loss measurements. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 3176–3182, 2003     

Thermal degradation of poly(3‐hydroxybutyrate) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) as studied by TG,TG–FTIR,and Py–GC/MS

The thermal degradation kinetics of poly(3‐hydroxybutyrate) (PHB) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) [poly(HB–HV)] under nitrogen was studied by thermogravimetry (TG). The results show that the thermal degradation temperatures (T_o, T_p, and T_f) increased with an increasing heating rate (B). Poly(HB–HV) was thermally more stable than PHB because its thermal degradation temperatures, T_o(0), T_p(0), and T_f(0)—determined by extrapolation to B = 0°C/min—increased by 13°C–15°C over those of PHB. The thermal degradation mechanism of PHB and poly(HB–HV) under nitrogen were investigated with TG–FTIR and Py–GC/MS. The results show that the degradation products of PHB are mainly propene, 2‐butenoic acid, propenyl‐2‐butenoate and butyric‐2‐butenoate; whereas, those of poly(HB–HV) are mainly propene, 2‐butenoic acid, 2‐pentenoic acid, propenyl‐2‐butenoate, propenyl‐2‐pentenoate, butyric‐2‐butenoate, pentanoic‐2‐pentenoate, and CO₂. The degradation is probably initiated from the chain scission of the ester linkage. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1530–1536, 2003     

Thermal Behavior and Specific Heat Capacity of 1‐t‐Butyl‐3,3‐dinitroazetidinium Perchlorate

1‐t‐Butyl‐3,3‐dinitroazetidinium perchlorate (TDNAZ ⋅ HClO₄) was synthesized, DSC and TG/DTG methods were used to study the thermal behavior of TDNAZ⋅HClO₄ under a non–isothermal condition. The intense exothermic decomposition process of DSC curves were analyzed to obtain its kinetic parameters. Continuous specific heat capacity (C _p) mode of micro–calorimeter was used to determine its C _p, its specific molar heat capacity (C _{p ,m}) was 365.70 J mol⁻¹ K⁻¹ at 298.15 K. The self‐accelerating decomposition temperature (T _SADT), thermal ignition temperature (T _TIT), and critical temperature of thermal explosion (T _b) were obtained to evaluate its thermal stability and safety. The above results of TDNAZ ⋅ HClO₄ were compared with those of 3,3‐dinitroazetidinium perchlorate (DNAZ ⋅ HClO₄), and the effect of tert‐butyl group on them was discussed.     

Hydrogenation of cis‐1,4‐polyisoprene catalyzed by Ru(CHCH(Ph))Cl(CO)(PCy3)2

Hydrogenation is a useful method which has been used to improve oxidative and thermal degradation resistance of diene‐based polymers. The quantitative hydrogenation of cis‐1,4‐polyisoprene which leads to an alternating ethylene–propylene copolymer was studied in the present investigation. To examine the influence of key factors on the reaction, such as catalyst concentration, polymer concentration, hydrogen pressure, and temperature, a detailed study of the hydrogenation of cis‐1,4‐polyisoprene catalyzed by the Ru complex, Ru(CH?CH(Ph))Cl(CO)(PCy₃)₂ was carried out by monitoring the amount of hydrogen consumed. Infrared and ¹H‐NMR spectroscopic measurements confirmed the final degree of hydrogenation. The hydrogenation of cis‐1,4‐polyisoprene followed pseudo‐first‐order kinetics in double‐bond concentration up to high conversions of double bond, under all sets of conditions studied. The kinetic results suggested a first‐order behavior with respect to total catalyst concentration as well as with respect to hydrogen pressure. The apparent activation energy for the hydrogenation process, obtained from an Arrhenius plot, was 51.1 kJ mol^?1 over the temperature range of 130 to 180°C. Mechanistic aspects of the catalytic process are discussed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3259–3273, 2004     

Plasticization of cellulose diacetate by graft copolymerization of ε‐caprolactone and lactic acid

Graft copolymerization of ε‐caprolactone (CL) and lactic acid (LA) onto cellulose diacetate (CDA) at the residual hydroxyl positions was conducted to obtain thermoplastic CDA. The effects of the reaction temperature and time and the CL/LA molar ratio in the feed on the progress of the graft copolymerization were investigated. The molecular weight of CDA was increased by this graft copolymerization. The oxycaproyl and lactyl molar substitutions (MS_CL and MS_LA, respectively) in grafted CDA (g‐CDA) were determined through ¹H‐NMR spectral analysis. These MS values were controllable by changing the reaction conditions adequately. The flow temperature and melt viscosity of g‐CDA decreased with an increase in the total substitution of MS_CL and MS_LA, and transparent polymer sheets could be obtained from the resulting g‐CDA by hot pressing at around 200°C without adding any plasticizer. The mechanical properties of the molded g‐CDA samples varied widely, depending on the different combinations of the MS_CL and MS_LA values; the g‐CDA sheets became elastic when the MS_CL was larger than the MS_LA, and their tensile strengths were enhanced as the MS_LA was increased. It was thus found that CDA was successfully plasticized by this graft copolymerization. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2621–2628, 2002     

Kinetics of hydrogenation of 4‐chloro‐2‐nitrophenol catalyzed by Pt/carbon catalyst

Hydrogenation of 4‐chloro‐2‐nitrophenol (CNP) was carried out at moderate hydrogen pressures, 7–28 atm, and temperatures in the range 298–313 K using Pt/carbon and Pd/γ‐Al₂O₃ as catalysts in a stirred pressure reactor. Hydrogenation of CNP under the above conditions gave 4‐chloro‐2‐aminophenol (CAP). Dechlorination to form 2‐aminophenol and 2‐nitrophenol is observed when hydrogenation of CNP is carried out above 338 K, particularly with Pd/γ‐Al₂O₃ catalyst. Among the catalysts tested, 1%Pt/C was found to be an effective catalyst for the hydrogenation of CNP to form CAP, exclusively. To confirm the absence of gas–liquid mass transfer effects on the reaction, the effect of stirring speed (200–1000 rpm) and catalyst loading (0.02–0.16 g) on the initial reaction rate at maximum temperature 310 K and substrate concentration (0.25 mole) were thoroughly studied. The kinetics of hydrogenation of CNP carried out using 1%Pt/C indicated that the initial rates of hydrogenation had first order dependence with respect to substrate, catalyst and hydrogen pressure in the range of concentrations varied. From the Arrhenius plot of ln rate vs 1000/T, an apparent activation energy of 22 kJ mol^?1 was estimated. © 2001 Society of Chemical Industry     

Adsorption of Cr(VI) ions onto poly(ethylene glycol dimethacrylate‐1‐vinyl‐1,2,4‐triazole)

Poly(ethylene glycol dimethacrylate‐1‐vinyl‐1,2,4‐triazole) [poly(EGDMA‐VTAZ)] beads (average diameter = 150–200 μm) were prepared by copolymerizing ethylene glycol dimethacrylate (EGDMA) with 1‐vinyl‐1,2,4‐triazole (VTAZ). Poly(EGDMA‐VTAZ) beads were characterized by swelling studies and scanning electron microscope (SEM). The adsorption of Cr(VI) from solutions was carried at different contact times, Cr(VI) concentrations, pH, and temperatures. High adsorption rates were achieved in about 240 min. The amount of Cr(VI) adsorbed increased with increasing concentration and decreasing pH and temperature. The intraparticle diffusion rate constants at various temperatures were calculated. Adsorption isotherms of Cr(VI) onto poly(EGDMA‐VTAZ) have been determined and correlated with common isotherm equations such as Langmuir and Freundlich isotherm models. The Langmuir isotherm model appeared to fit the isotherm data better than the Freundlich isotherm model. The pseudo first‐order kinetic model was used to describe the kinetic data. The study of temperature effect was quantified by calculating various thermodynamic parameters such as Gibbs free energy, enthalpy, and entropy changes. The dimensionless separation factor (R_L) showed that the adsorption of metal ions onto poly(EGDMA‐VTAZ) was favorable. It was seen that values of distribution coefficient (K_D) decreasing with Cr(VI) concentration in solution at equilibrium (C_e) indicated that the occupation of activate surface sites of adsorbent increased with Cr(VI). © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Copper‐Catalyzed Cyclization and Azidation of γ,δ‐Unsaturated Ketone O‐Benzoyl Oximes

An intramolecular imination/azidation sequence has been realized through the tetrakis(acetonitrile)copper(I) hexafluorophophate [Cu(CH₃CN)₄PF₆]‐catalyzed reaction of γ,δ‐unsaturated ketone O‐benzoyl oximes with trimethylsilyl azide (TMSN₃). The reaction proceeds via the copper‐mediated N O cleavage and subsequent C N forming 5‐exo cyclization. The thus formed intermediate is then azidated to afford the corresponding dihydropyrrole product. Preliminary mechanistic investigations suggest that the cyclization step does not involve a radical intermediate.