108-30-5Relevant articles and documents
Photoinduced hydrometalation and hydrogenation of activated olefins with molybdenum and tungsten dihydrides (Cp2MH2)
Ko,Bookman,Kochi
, p. 1833 - 1842 (1990)
The early-transition-metal hydrides Cp2MoH2, Cp2WH2, and Cp2ReH rapidly form a series of electron donor-acceptor (EDA) complexes with various activated olefins as shown by the spontaneous appearance of vivid colors, the absorption energies of which correlate with the electron affinity of the olefinic acceptor and the oxidation (ionization) potential of the hydridometal donor in accord with Mulliken theory. Deliberate excitation of the charge-transfer absorption band leads to the quantitative hydrometalation of fumaronitrile by Cp2MoH2 at 25°C, and the structure of the σ hydrido alkyl adduct Cp2Mo(CHCNCH2CN)H (I) has been established by X-ray crystallography, (space group P21, monoclinic, with a = 8.090 (3) A?, b = 10.282 (4) A?, c = 8.316 (3) A?, β = 116.92 (3)°, V = 617 A?3, Z = 2, R = 0.028, Rw = 0.028 for 1802 reflections with I > 3σ having 2θ ≤ 60°). Under the same photochemical conditions, the tungsten analogue Cp2WH2 effects quantitative hydrogenation and leads to succinonitrile together with the olefinic π-adducts to tungstenocene in high yields. (In both cases, the thermal (dark) processes are nonexistent) The charge-transfer mechanism for olefin hydrometalation and hydrogenation stemming from charge separation in the EDA complex (i.e. [Cp2MH2?+,>C--C ?ox of the hydridometal species and the subsequent facile proton transfer from the labile cation radical Cp2MH2?+ (M = Mo, W) to the acceptor moiety. The close similarity of the photoinduced process for olefin hydrometalation and hydrogenation of various activated olefins with those effected thermally at higher temperatures is discussed.
Nickel promoted functionalization of CO2 to anhydrides and ketoacids
Greenburg, Zoe R.,Jin, Dong,Williard, Paul G.,Bernskoetter, Wesley H.
, p. 15990 - 15996 (2014)
The reductive functionalization of carbon dioxide into high value organics was accomplished via the coupling with carbon monoxide and ethylene/propylene at a zerovalent nickel species bearing the 2-((di-t-butylphosphino)methyl)pyridine ligand (PN). An initial oxidative coupling between carbon dioxide, olefin, and (PN)Ni(1,5-cyclooctadiene) afforded five-membered nickelacycle lactone species, which were produced with regioselective 1,2-coupling in the case of propylene. The propylene derived nickelacycle lactone was isolated and characterized by X-ray diffraction. Addition of carbon monoxide, or a combination of carbon monoxide and diethyl zinc to the nickelacycle lactone complexes afforded cyclic anhydrides and 1,4-ketoacids, respectively, in moderate to high yields. The primary organometallic product of the transformation was zerovalent (PN)Ni(CO)2. This journal is
Selective hydrogenation of maleic anhydride over Pd/Al2O3 catalysts prepared via colloid deposition
Yuan, Hongjing,Zhang, Chunlei,Huo, Weitao,Ning, Chunli,Tang, Yong,Zhang, Yi,Cong, Dequan,Zhang, Wenxiang,Luo, Jiahuan,Li, Su,Wang, Zhenlu
, p. 141 - 145 (2014)
Pd/Al2O3 catalysts were prepared via colloid deposition and the performance of the catalysts was examined in the selective hydrogenation of maleic anhydride to succinic anhydride. When the reaction was carried on in a batch system with 1,4-dioxane as the solvent (353 K and 1.0 MPa), high conversion of maleic anhydride (>98%) and high selectivity (>99%) for succinic anhydride were observed after 5 h. The as-prepared Pd/Al2O3 catalyst also showed excellent performance in solvent-free system and fixed-bed systems. The maleic anhydride (MA) conversion was greater than 98%, and high selectivity (>99%) for succinic anhydride was obtained after 1600 h in a fixed bed reacter. The results showed that the activity of the Pd/Al2O3 catalysts was excellent due to its high active surface area. [Figure not available: see fulltext.]
Heterogeneous catalysts for the cyclization of dicarboxylic acids to cyclic anhydrides as monomers for bioplastic production
Rashed, Md. N.,Siddiki,Ali, Md. A.,Moromi, Sondomoyee K.,Touchy, Abeda S.,Kon, Kenichi,Toyao, Takashi,Shimizu, Ken-Ichi
, p. 3238 - 3242 (2017)
Cyclic anhydrides, key intermediates of carbon-neutral and biodegradable polyesters, are currently produced from biomass-derived dicarboxylic acids by a high-cost multistep process. We present a new high-yielding process for the direct intramolecular dehydration of dicarboxylic acids using a reusable heterogeneous Lewis acid catalyst, Nb2O5·nH2O. Various dicarboxylic acids, which can be produced by a biorefinery process, are transformed into the corresponding cyclic anhydrides as monomers for polyester production. This method is suitable for the production of renewable polyesters in a biorefinery process.
Clay catalysis: A convenient and rapid formation of anhydride from carboxylic acid and isopropenyl acetate under microwave irradiation
Villemin,Labiad,Loupy
, p. 419 - 424 (1993)
The Montmorillonite KSF catalyses the synthesis of anhydrides from carboxylic acids in the presence of isopropenyl acetate under microwave irradiations.
Vanadium(v) oxoanions in basic water solution: A simple oxidative system for the one pot selective conversion of l-proline to pyrroline-2-carboxylate
Biancalana, Lorenzo,Tuci, Giada,Piccinelli, Fabio,Marchetti, Fabio,Bortoluzzi, Marco,Pampaloni, Guido
, p. 15059 - 15069 (2017)
The unprecedented, direct chemical oxidation of l-proline to pyrroline-2-carboxylate was achieved in water (pH 9-10) by means of NH4VO3/NH3 or V2O5/MOH (K = Na, K), and the anion was fully characterized as ammonium or alkaline metal salts. Quantitative yield and higher atom economy performance were achieved with the latter system, the alkaline salts being more stable than the ammonium one. Different mixed valence V(iv)/V(v) compounds precipitated from the reaction mixtures depending on the nature of the employed base. A possible reaction mechanism is proposed according to DFT calculations. The analogous reaction of trans-4-hydroxy-l-proline with NH4VO3/NH3 afforded pyrrole-2-carboxylic acid in 81% yield, while sarcosine underwent prevalent decomposition under similar experimental conditions. Instead, no reaction was observed with primary (glycine, l-alanine, l-phenylalanine) and tertiary α-amino acids (N,N-dimethyl-l-phenylalanine, N,N-dimethylglycine).
Mechanism of synthesis of maleic and succinic anhydrides by carbonylation of acetylene in solutions of palladium complexes
Bruk,Oshanina,Kozlova,Temkin,Odintsov
, p. 1071 - 1083 (1998)
The mechanism of synthesis of maleic and succinic anhydrides from acetylene and CO in the PdBr2 - LiBr - organic solvent catalytic system was studied using the procedure of advancement and discrimination of hypotheses. The hypotheses were obtained using the data bank on elementary steps and the Comb1 combinatorial program. The discrimination of the hypotheses was based on the data of NMR and IR spectroscopy, studies of isotope exchange, the role of potential organic intermediates, the kinetic isotope effect, and one-factor kinetic experiments. The most probable mechanism of synthesis of maleic anhydride includes insertion of acetylene and CO into the Pd - Pd bond of the Pd1 complex, which is formed from Pd11 at the initial step of the process. Succinic anhydride results from the intramolecular transformation of the hydride complex of palladium and maleic anhydride. The palladium hydride complexes detected in the contact solution apparently play the crucial role in the conjugation of oxidation, reduction, and addition type reactions.
Efficient cyclodehydration of dicarboxylic acids with oxalyl chloride
Kantin, Grigory,Chupakhin, Evgeny,Dar'in, Dmitry,Krasavin, Mikhail
, p. 3160 - 3163 (2017)
Literature examples illustrating the use of oxalyl chloride to prepare dicarboxylic acid anhydrides are surprisingly limited. At the same time, we have discovered a method involving the use of this readily available reagent which allowed the preparation of novel cyclic anhydrides where other, more conventional, methods had failed. Herein, we demonstrate that the method is applicable to a wide diversity of substrates, delivers good to excellent yields of cyclic anhydrides without chromatographic purification and can be considered a synthetic tool of choice whenever dicarboxylic acid cyclodehydration is required.
Gas-phase hydrogenation of maleic anhydride to γ-butyrolactone at atmospheric pressure over Cu-CeO2-Al2O3 catalyst
Yu, Yang,Guo, Yanglong,Zhan, Wangcheng,Guo, Yun,Wang, Yanqin,Wang, Yunsong,Zhang, Zhigang,Lu, Guanzhong
, p. 77 - 81 (2011)
Cu-CeO2-Al2O3 catalyst, prepared by co-precipitation method, was investigated for the gas-phase hydrogenation of maleic anhydride (MA) to γ-butyrolactone (GBL) at atmospheric pressure and the catalyst deactivation was also studied. Effects of catalyst composition, reaction temperature, and liquid hourly space velocity (LHSV) of raw material on the catalytic performance of Cu-CeO2-Al2O3 catalyst were investigated. The catalyst (molar ratio of Cu:Ce:Al = 1:1:2) showed better catalytic performance, in which both the conversion of MA and the selectivity of GBL kept 100% within two hours under the reaction conditions of 6 mL catalyst, 0.1 MPa, 220-280 °C, 30 mL min-1 H2, 0.6 h-1 LHSV of 20 wt.% MA/GBL. As for Cu-CeO2-Al 2O3 catalyst, smaller crystallite size of Cu and higher Cu surface area are favorable to increase its catalytic performance. The deactivation of Cu-CeO2-Al2O3 catalyst is due to formation of the compact wax-like deposition on the catalyst surface, which is probably ascribed to the strong adsorption of succinic anhydride and then polymerization on the catalyst surface. The catalytic performance of the regenerated catalyst can be recovered completely by the regeneration method of N2-air-H2 stage treatment.
Ni/Al2O3 catalysts derived from spinel NiAl2O4 for low-temperature hydrogenation of maleic anhydride to succinic anhydride
Li, Jie,Ren, Yuanhang,Yue, Bin,He, Heyong
, p. 1166 - 1173 (2017)
Ni/Al2O3 catalysts were derived from spinel NiAl2O4 with different Ni content ((2.5, 5 and 7.5) wt%). The catalysts were obtained by H2 reduction and were investigated for the low-temperature hydrogenation of maleic anhydride (MA) to produce succinic anhydride (SA). The characterization results showed that Ni0 active sites were mainly derived during the H2 reduction from spinel NiAl2O4. Among the catalysts studied, employing the optimum preparation and reaction conditions with Ni(5%)/Al2O3 yielded the highest catalytic performance. A near-100% conversion of MA and ～90% selectivity to SA were achieved at 120 °C and 0.5 MPa of H2 with a weighted hourly space velocity (MA) of 2 h?1.
