Mechanistic study of acetylene carbonylation to anhydrides of dicarboxylic acids in solutions of palladium complexes

Брук, Л. Г.; Oshanina, I. V.; Kozlova, A. P.; Воронцов, Е. В.; Темкин, О. Н.

doi:10.1016/1381-1169(96)00108-2

Cited by 37 publications

(22 citation statements)

References 4 publications

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“…2), the character of influence of added oxidants (CuBr2, Fe2(SO4)3, p-benzoquinone, chloranil), and the data of IR spectroscopy provide grounds for believing that compounds of Pd I are responsible for the catalytic activity. 8 The period of formation of the catalyst is matched in time by the decrease in the potential of the platinum electrode from -240 to 60--80 mV and also by a decrease in the intensity of the absorption band at 2120 cm -I (the terminal CO group) and an increase in the intensity of the bands at 1948 and 1935 cm -I (bridging CO groups) in the I R spcctrum of the sample. These facts are in good agreement with the assumption that during the period of catalyst formation, Pd II is reduced to Pd I.…”

Section: Samentioning

confidence: 99%

Mechanisms of synthesis of maleic and succinic anhydrides by carbonylation of acetylene in solutions of palladium complexes

et al. 1998

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The mechanism of synthesis of maleic and succinic anhydrides from acetylene and CO in the PdBr2--LiBr--organie 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 Combl 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 Pd I complex, which is formed from Pd II at the initial step of the process. Succinic anhydride results from the intramolecufar transformation of the hydride complex of palladium and maleic anhydride. The palladium hydride complexes detected in the contact solution apparently play the crucial rote in the conjugation of oxidation, reduction, and addition type reactions.Key words: reaction mechanisms, advancement and discrimination of hypotheses; alkynes, carbonylation, kinetics, isotope effect; suecinic anhydride, maleic anhydride, synthesis from acetylene and CO. Carbonylation of alkynes makes it possible to synthesize numerous oxygen-containing organic compounds (saturated and unsaturated acids, esters, amides, tactones, ketones, anhydrides) under mild conditions and presents both practical and theoretical interest, i-4 Recently, 5 the most promising method for the synthesis of methyl methacrylate has been developed; the method is based on the carbonylation of methylacetylene in solutions of palladium complexes.Palladium derivatives are the most active catalysts for the reactions of alkynes with carbon monoxide involving other reactants. 6 The catalytic methods for the synthesis of polyesters, succinic anhydride and products based on it, esters of alkynylcarboxylic acids, and citraconic anhydride developed in recent years are of practical interest. 6Cobalt-and palladium-based catalysts often promote simultaneous occurrence of oxidative, reductive, and "additive" (not redox) carbonylation of alkynes. 4,6 A number of studies have been devoted to the mechanism of conjugation of reactions of various redox types. 6,7 This study deals with the mechanism of the recently discovered synthesis of succinic anhydride 7 and also with the relationship between the mechanisms of formation of succinic and maleic anhydrides.* Dedicated to the memory of Academician M. E. Vol'pin timed to his 75th birthday. ExperimentalExperiments were carried out in a gas-flow-type reactor maintained at a constant temperature (40 ~ with intense stirring of the gas and liquid phases under atmospheric pressure. The initial solution (PdBr2--LiBr--organic solvent) was prepared directly in the reactor. A gas mixture (CO and C2H~) of the required composition was prepared beforehand in a gas meter and supplied to the reactor through columns with a drying agent at a velocity of ~2.2 L (L rain...

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Section: Samentioning

confidence: 99%

Mechanisms of synthesis of maleic and succinic anhydrides by carbonylation of acetylene in solutions of palladium complexes

et al. 1998

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“…The results of papers [18][19][20][21][22], and also the results stated in this work allow us to speak about one more important factor-a possibility to control the selectivity and reactions rates by corresponding steady state choice or by conditions creation for the transition into oscillatory modes. As it mentioned above, selectivity of MA synthesis carrying out at the conditions of significant nonlinearity, rises in 2 times.…”

Section: Synthesis Of Sa and Mamentioning

confidence: 92%

“…In other catalytic systems (PdBr 2 -LiBr) we found the chaotic oscillations by using of PhA, and new oscillatory reaction of PhA and MAc oxidative carbonylation to phenylmaleic (3-phenyl-2,5-furandione) and citraconic (3-methyl-2,5-furandione) anhydrides, accordingly, in the system PdBr 2 -LiBr-CH 3 COCH 3 -H 2 O, O 2 being used as an oxidant [18]. The bistability phenomenon has been established earlier in the similar reaction of acetylene in CH 3 CN-H 2 O system.…”

Section: Introductionmentioning

confidence: 95%

“…The bistability phenomenon has been established earlier in the similar reaction of acetylene in CH 3 CN-H 2 O system. The little change of the oxygen pressure in the initial gas mixture has changed sharply the synthesis selectivity of the succinic anhydride (dihydro-2,5-furandione) (SA) (additive carbonylation (3)) and maleic anhydride (dihydro-2,5-dioxofuran) (MA) (oxidative carbonylation (4)) [18,19]. The selectivity on the MA varies from 33% up to 93% [19].…”

Section: Introductionmentioning

confidence: 99%

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Alkynes Carbonylation Reactions in Solutions of Palladium Complexes as a New Class of Oscillatory Processes

et al. 2009

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“…The reaction of the alkynes 252 with CO/O 2 in dioxane catalysed by a new triple catalytic system, PdCl 2 /chlorohydroquinone(HQCI)/NPMoV produced the maleic anhydrides 253 (Scheme 98). 126 The authors 126 consider that the reaction proceeds via a similar mechanism to that shown by Heck 127 130 A study of the in situ formation of the organic intermediates, the kinetic isotope effect, the isotope exchange, and the oxygen effect on the process direction, revealed that maleic anhydride 254 is most likely a key intermediate in the succinic anhydride 255 formation. Maleic anhydride undergoes transformations through the mediation of a palladium hydride complex A (Scheme 99).…”

Section: Cyclic Anhydride and Imide Synthesismentioning

confidence: 92%

Synthesis of heterocycles by carbonylation of acetylenic compounds

et al. 2004

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Mechanistic study of acetylene carbonylation to anhydrides of dicarboxylic acids in solutions of palladium complexes

Cited by 37 publications

References 4 publications

Mechanisms of synthesis of maleic and succinic anhydrides by carbonylation of acetylene in solutions of palladium complexes

Mechanisms of synthesis of maleic and succinic anhydrides by carbonylation of acetylene in solutions of palladium complexes

Alkynes Carbonylation Reactions in Solutions of Palladium Complexes as a New Class of Oscillatory Processes

Synthesis of heterocycles by carbonylation of acetylenic compounds

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