Methylenealkane-Based Low-Viscosity Ester Oils: Synthesis and Outlook

Nifant’ev, Ilya E.; Bagrov, Vladimir V.; Vinogradov, Alexander A.; Vinogradov, A.; Ilyin, Sergey O.; Sevostyanova, N. T.; Баташев, С. А.; Ivchenko, Pavel V.

doi:10.3390/lubricants8050050

Cited by 11 publications

(4 citation statements)

References 41 publications

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“…The closely related methoxycarbonylation of methylenealkanes (Scheme 12b) was accompanied by the isomerization of the starting hydrocarbons; the rational design of the Pd/diphosphine catalyst had made it possible to reach average yields of the branched methyl esters [176]. The esters obtained were used in the synthesis of Group 5 oil base stocks with promising viscosity characteristics [177].…”

Section: Catalytic Transformations Of Methylenealkanesmentioning

confidence: 99%

Fair Look at Coordination Oligomerization of Higher α-Olefins

Nifant’ev

Ivchenko

2020

Polymers

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Coordination catalysis is a highly efficient alternative to more traditional acid catalysis in the oligomerization of α-olefins. The distinct advantage of transition metal-based catalysts is the structural homogeneity of the oligomers. Given the great diversity of the catalysts and option of varying the reaction conditions, a wide spectrum of processes can be implemented. In recent years, both methylenealkanes (vinylidene dimers of α-olefins) and structurally uniform oligomers with the desired degrees of polymerization have become available for later use in the synthesis of amphiphilic organic compounds and polymers, high-quality oils or lubricants, and other prospective materials. In the present review, we discussed the selective dimerization and oligomerization of α-olefins, catalyzed by metallocene and post-metallocene complexes, and explored the prospects for the further applications of the coordination α-olefin dimers and oligomers.

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Section: Catalytic Transformations Of Methylenealkanesmentioning

confidence: 99%

Fair Look at Coordination Oligomerization of Higher α-Olefins

Nifant’ev

Ivchenko

2020

Polymers

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“…Therefore, it is important to study the structure and reactivity of the hydride intermediates formed upon the reaction of the transition metal complex with OACs and activators. The use of metallocenes not only provides high rate and selectivity of dimerization and/or oligomerization [19][20][21][22][23][24][25][26][27], but also enables monitoring of intermediates by NMR spectroscopy, the most informative method, because metallocene complexes are readily soluble in organic solvents and the atoms present in the η 5 -ligands give rise to signals in the characteristic low-eld region, which most often do not overlap with signals of the σ-ligands.…”

Section: Introductionmentioning

confidence: 99%

Activation of metallocene hydride intermediates by methylaluminoxane in alkene dimerization and oligomerization

Parfenova,

Kovyazin,

Bikmeeva

et al. 2023

Reac Kinet Mech Cat

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Homogeneous catalytic systems based on metallocenes, organoaluminum compounds, and activators proved to be e cient in alkene dimerization, oligomerization, and polymerization reactions. Metal hydrides can act as highly reactive species of these catalytic systems. Despite the large number of experimental and theoretical studies in this eld, the effect of the activator on the structure and dynamics of hydride intermediates is an open question. In order to elucidate the dependence of the structure and reactivity of the bimetallic hydride intermediates formed in the systems metal complex -OAC -activator on the nature of the transition metal atom and ligand environment, we used NMR spectroscopy to study reactions of a series of L 2 MCl 2 complexes (M = Hf, Zr; L 2 = Cp 2 , CpMe 2 , ansa-(Me 2 C) 2 Cp 2 , ansa-Me 2 CInd 2 ) with HAlBu i 2 and ММАО-12 activator. As a result, M,Al-bimetallic intermediates containing [L 2 ZrH 3 ] and [(L 2 Zr) 2 H 3 ] type moieties were detected for both hafnium and zirconium complexes with cyclopentadienyl ligands. The [L 2 ZrH 3 ] type structure predominates in the system based on the ansa-linked bis-indenyl zirconium complex. The detected complexes provide associates with ММАО-12 and, hence, they can act as precursors of active sites determining the alkene dimerization and oligomerization routes.

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“…СО выделяют из синтез-газа, который может быть получен не только из нефти и природного газа, но и каменного угля, а также отходов биомассы -возобновляемого сырьевого источника. В алкоксикарбонилировании алкенов гомогенные палладий-фосфиновые каталитические системы считаются наиболее активными и селективными, поскольку позволяют получать целевые продукты -сложные эфиры -в мягких условиях с высокими выходами [1][2][3][4][5][6][7][8][9]. Побочными продуктами в этих реакциях являются, как правило, лишь изомерные сложные эфиры.…”

Section: Introductionunclassified

Combined process of cyclohexyl cyclohexanecarboxylate synthesis from cyclohexanol and CO catalyzed by the Pd(OAc)2–PPh3–p-toluenesulfonic acid system

Sevostyanova

Баташев

Rodionova

2023

Fine Chem. Technol.

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Objectives. To study the possibility of combining acid-catalytic cyclohexanol dehydration and alkoxycarbonylation of the formed cyclohexene with cyclohexanol and carbon(II) oxide in a single reactor in order to achieve high yields of the target cyclohexyl cyclohexanecarboxylate product under mild conditions using the Pd(OAc)2–PPh3–p-toluenesulfonic acid catalytic system.Methods. The combined process took place in a toluene medium in a periodic steel reactor designed to operate at elevated pressure, equipped with a glass insert, a magnetic stirrer, and a sampler, as well as gas input and discharge devices. The reaction mass with the components of the catalytic system was placed in a glass reactor inside a steel autoclave. The reaction mass samples obtained during the combined process were analyzed by gas–liquid chromatography with a flame ionization detector.Results. The possibility of combining cyclohexanol dehydration catalyzed by p-toluenesulfonic acid monohydrate and formed cyclohexene alkoxycarbonylation with cyclohexanol and CO during catalysis by the Pd(OAc)2–PPh3–p-toluenesulfonic acid system in a single reactor was demonstrated. Under mild conditions (temperature 110°C; CO pressure 2.1 MPa), the target product yield reached 64.8% in 5 h. However, the combined process is complicated by the formation of a cyclohexanecarboxylic acid by-product formed as a result of the cyclohexyl cyclohexanecarboxylate hydrolysis and the cyclohexene hydroxycarbonylation.Conclusions. The reactions of intramolecular acid-catalytic cyclohexanol dehydration and formed cyclohexene alkoxycarbonylation catalyzed by the Pd(OAc)2–PPh3–p-toluenesulfonic acid system can be combined in a single reactor. p-Toluenesulfonic acid can simultaneously act as a catalyst for the cyclohexanol dehydration and a co-catalyst of the palladium–phosphine system of cyclohexene alkoxycarbonylation. The involvement of cyclohexene, representing a product of reversible cyclohexanol dehydration, in the alkoxycarbonylation reaction is a factor in shifting the dehydration reaction equilibrium towards the formation of cyclohexene. Cyclohexanecarboxylic acid is a by-product of the proposed combined process. A factor in the reduction of target product yield is water formed as a result of cyclohexanol dehydration due to the involvement of the latter in the hydrolysis reaction and the course of the cyclohexene hydroxycarbonylation.

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Methylenealkane-Based Low-Viscosity Ester Oils: Synthesis and Outlook

Cited by 11 publications

References 41 publications

Fair Look at Coordination Oligomerization of Higher α-Olefins

Fair Look at Coordination Oligomerization of Higher α-Olefins

Activation of metallocene hydride intermediates by methylaluminoxane in alkene dimerization and oligomerization

Combined process of cyclohexyl cyclohexanecarboxylate synthesis from cyclohexanol and CO catalyzed by the Pd(OAc)2–PPh3–p-toluenesulfonic acid system

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