85-44-9Relevant articles and documents
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Shreve,Welborn
, p. 279,282 (1943)
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Oxidation of o-xylene to phthalic anhydride over V2O5/TiO2 catalysts: III. Study of organic residue formed on the catalyst surface
Dias, Cristina R.,Portela, M. Farinha,Bond, Geoffrey C.
, p. 284 - 294 (1996)
An organic residue is formed on V2O5/TiO2 (anatase) catalysts during the oxidation of o-xylene and o-tolualdehyde. V2O5 catalysts supported on TiO2 (0.6, 1, and 5% V2O5/TiO2), prepared by wet impregnation, were exposed to o-xylene/air and o-tolualdehyde/air mixtures under different operating conditions, and, after different times of exposure to reaction conditions, the catalysts were characterized by FTIR spectroscopy and temperature programmed oxidation. The compounds formed were also extracted and analyzed by mass spectrometry. Organic molecules containing no more than two aromatic rings, formed by dimerization of adsorbed molecules, were detected and their characteristics were found to vary with features of the catalytic surface and with operating conditions. Larger contents of residue were obtained at lower temperatures and lower contact times and, for some experimental conditions, a constant amount of such compounds was observed after l h of exposure under reaction conditions. The analysis of samples used with different reactant mixtures showed that adsorbed o-xylene can lead to the formation of a "residue" on the surface.
Orthoamides and iminium salts, LXXXIX. Reactions of N,N,N',N',N'',N'',N''',N'''-octamethylacetylene-bis(carboxamidinium) tetrafluoroborate with nucleophilic reagents - New methods for the preparation of amidinium salts and ketene aminals
Drandarov, Konstantin,Tiritiris, Ioannis,Kantlehner, Willi
, p. 225 - 241 (2015)
The acetylene-bis(carboxamidinium) salt 4 dehydrates carboxylic acids to the corresponding anhydrides, as the byproduct 2-oxo-but-2-en-amidinium salt 6b was isolated. Aromatic hydroxy compounds and 2-furyl-methylmercaptan add to the triple bond of the salt 4 to give 2-aryloxy- and 2-alkylmercapto-but-2-enebis( amidinium) salts 7-9. According to this reaction principle, 2-organoamino-buten-2-ene-bis(amidinium) salts 10 and 11 were prepared from 4 and primary and secondary amines, whereas 4-chlorobenzhydrazide reacted with 4 to give the imidazole-3-carboxamidinium salt 13. The reaction of CH2-acidic compounds as malononitrile or ethyl cyanoacetate with the bis(amidinium) salt 4 affords 2-cyanomethylene-but-3-enamidinium salts 15. With the CH-acidic diethyl 2-bromomalonate, compound 4 undergoes a Michael-initiated ring closure cyclopropenation reaction with further ring opening by the released Br- to the corresponding 2-diethoxycarbonylmethylene- 3-bromo-but-3-enamidinium salt 18. Unlike cyclopentadiene and furane, the reaction of N-methylpyrrole and bis(amidinium) salt 4 does not lead to Diels-Alder [4 + 2] cycloadduct but to the Michaeltype 1:1 adduct 20. Pyrrole- and thiophene-2-carboxamidinium salts 23-25 can be prepared from compound 4 and esters of glycine, N-methylglycine (sarcosine), and mercaptoacetic acid, respectively. The derivatives of quinoxaline-2-carboxamidinium salts 29 are accessible from aromatic 1,2-diamines and compound 4. The reaction of the CH2/NH-acidic cyanoacetamide with the bis(amidinium) salt 4 produced the 3-pyrroline-2-on derivatives 33.
The Decisive Cooperation of Metal and Oxygen Ions of Nickel Oxide During the Oxidation of o-Xylene
Hauffe, K.,Buss, D. H.,Glemser, O.
, p. 109 - 112 (1995)
As can be concluded from the experimental results at 450 deg C in the reaction mixtures consisting of N2-O2-o-Xylene, both nickel oxide pure and doped with Li2O or In2O3 is unsuited as catalyst for the oxidation of o-xylene to phthalic anhydride.In contrast to NiO which ionosorbs both oxygen and o-xylene, NiO-Li2O, a strong ionosorbent for o-xylene, prevents the ionosorption of oxygen because of the large concentration of holes.Since gaseous oxygen does not react with ionosorbed o-xylene but a reduction of nickel oxide to metallic nickel has been observed in spite of t he fact of enough oxygen in the gas phase it can be assumed that o-xylene is forced to remove oxygen ions from the NiO lattice under generation of oxygen-ion vacanxies and nickel atoms.The predominant portions of the reaction products are H2O and CO2.With undoped nickel oxide and NiO-In2O3 which were not reduced under the same experimental conditions, the reaction products had roughly the same composition. The reduction of NiO-LiO2 however will be prevented in a gas mixture with a high oxygen pressure which oxidizes the formed nickel atoms on the surface of NiO-Li2O to nickel oxide making possible the entrance of oxygen from the gas phase and, therefore, the oxidation of o-xylene. A turbulent motion of a 2-component catalyst powder from NiO-1molepercent Li2O covered with ionosorbed 0-xylene and ZnO-1molpercent In2O3 covered with ionosorbed oxygen in the same gas mixture resulted in the same reaction products as in the presence of sole NiO-Li2O under simultaneous reduction of nickel oxide.From that we can conclude that the oxidation of o-xylene by oxygen ions of NiO occurs more easily than the reaction with ionosorbed oxygen on ZnO-In2O3 which obviously seems to be bounded too strongly.This result is also confirmed by the prevention of the oxidation of gaseous o-xylene in the presence of only ZnO-In2O3. Finally, the operation of the carrier catalyst V2O5/TiO2 which is employed for the oxidation of o-xylene to phthalic anhydride will be prevented to a large extent in simultaneous presence of nickel oxide either pure or doped with Li2O and In2O3 in roughly the same amount.This result can be mentioned as a proof for the interaction of a 2-component catalyst the mechanism of which is at present not satisfactorily understood.
Photoinduced FeCl3-Catalyzed Alkyl Aromatics Oxidation toward Degradation of Polystyrene at Room Temperature?
Zhang, Guoxiang,Zhang, Zongnan,Zeng, Rong
supporting information, p. 3225 - 3230 (2021/09/28)
While polystyrene is widely used in daily life as a synthetic plastic, the subsequently selective degradation is still very challenging and highly required. Herein, we disclose a highly practical and selective reaction for the catalytically efficient oxidation of alkyl aromatics (including 1°, 2°, and 3° alkyl aromatics) to carboxylic acids. While dioxygen was used as the sole terminal oxidant, this protocol was catalyzed by the inexpensive and readily available ferric compound (FeCl3) with irradiation of visible light (blue LEDs) under only 1 atmosphere of O2 at room temperature. This system could further facilitate the selective degradation of polystyrene to benzoic acid, providing an important and practical tool to generate high-value chemical from abundant polystyrene wastes.
Thermal Decomposition of [Cu(H2O)2(C8H4O4)], [CuNi(H2O)4(C8H4O4)2], and [Ni(H2O)2(C8H4O4)2](H2O)2 with the Formation of Metal and Bimetal Nanoparticles
Ishchenko, A. V.,Rudina, N. A.,Yudanova, L. I.
, p. 1663 - 1670 (2021/08/24)
Abstract: A comparison is made of the thermoanalytical characteristics and the composition and structure of solid products of the thermal decomposition of ortho-phthalates [Cu(H2O)2(C8H4O4)], [CuNi(H2O)4(C8H4O4)2], and [Ni(H2O)2(C8H4O4)](H2O)2. It is found that the thermal decomposition of these compounds upon heating to 500°C in a He atmosphere can be conditionally divided into two stages: dehydration and decarboxylation. Polymer conglomerates containing uncoated Cu nanoparticles as large as 75 nm are embedded into the polymer matrix of the composite obtained via the thermal decomposition of [Cu(H2O)2(C8H4O4)]. Three types of nanoparticles with sizes of 40–85, 15–25, and 10–15 nm are embedded in the polymer matrices of composites. The particles are Cux/Ni1?x solid solutions of different compositions, obtained via the thermolysis of [CuNi(H2O)4(C8H4O4)2]. It is found that the onset temperature of [CuNi(H2O)4(C8H4O4)2] decarboxylation at the third part of the second stage with the formation of a three-phase region correlates with the temperature of decomposition of Cux/Ni1?–?x solid solutions in the binary metal system, due apparently to the quantum size effect.