Telomerisation of Buta‐1,3‐diene and Methanol: Superiority of Chromanyl‐Type Phosphines in the Dow Process for the Industrial Production of 1‐MOD

Tschan, Mathieu J.‐L.; Launay, H.; Hagen, Henk; Benet‐Buchholz, Jordi; Leeuwen, Piet W. N. M. van

doi:10.1002/chem.201100684

Cited by 16 publications

(14 citation statements)

References 33 publications

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“…By variation of the base concentration, a strong influence on the reaction rate was observed resembling a first-order dependency in the base concentration. This strong influence was already discussed in the literature [13]. Furthermore, the variation of the base strength showed that the Pd-IMes catalyst seems to be only efficiently activated by a strong base such as KOMe.…”

Section: Imes Ligandsupporting

confidence: 59%

“…Compared to the traditional phosphine-modified systems, higher chemo-and regioselectivity and significantly higher activity have been reported. To the best of our knowledge, all previously reported telomerization catalysts have been applied to either pure 1,3-butadiene feedstock or a technical diluted feed [1,[10][11][12][13][14][15][16]. Here we present for the first time a comparative study of both phosphine and NHC-modified palladium catalysts with pure and mixed butadiene feed.…”

Section: Introductionmentioning

confidence: 99%

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Pd-catalyzed telomerization of butadiene and methanol with direct catalyst recycling using a liquid-ionic liquid biphasic, continuous process

Völkl

Geburtig

Kiermaier

et al. 2016

Chemical Engineering and Processing: Process Intensification

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Comparison between phosphine and NHC-modified Pd catalysts in the telomerization of butadiene with methanol ndash a kinetic study combined with model-based experimental analysis, Chemical Engineering and Processing http://dx.doi.org/10. 1016/j.cep.2015.07.007 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.Comparison between phosphine and NHC-modified Pd catalysts in the telomerization of butadiene with methanol -a kinetic study combined with model-based experimental analysis The telomerization of butadiene with methanol was investigated in the presence of different palladium catalysts modified either with triphenylphosphine (TPP) or 1,3-dimesityl-imidazol-2-ylidene (IMes) ligand. When pure butadiene was used as substrate, a moderate selectivity for the Pd-TPP catalyst toward the desired product 1-methoxy-2,7-octadiene (1-Mode) of around 87 % was obtained, while the IMes carbene ligand almost exclusively formed 1-Mode with 97.5 % selectivity. The selectivity remained unchanged when the pure butadiene feed was replaced by synthetic crack-C 4 (sCC 4 ), a technical feed of 45 mol % butadiene and 55 mol % inerts (butenes and butanes). The TPP-modified catalyst showed a lower reaction rate, which was attributed to the expected dilution effect caused by the inerts. Surprisingly, the IMes-modified catalyst showed a higher rate with sCC 4 compared to the pure feed. By means of a model-based experimental analysis, kinetic rate equations could be derived. The kinetic modeling supports the assumption that the two catalyst systems follow different kinetic rate equations. For the Pd-TPP catalyst, the reaction kinetics were related to the Jolly mechanism. In contrast, the Jolly mechanism had to be adapted for the Pd-IMes catalyst as the impact of the base seems to differ strongly from that for the Pd-TPP catalyst. The Pd-IMes system was found to be zero order in butadiene at moderate to high butadiene concentrations and first order in base while the nucleophilicity of the base is influenced by the methanol amount resulting in a negative reaction order for methanol.

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Section: Imes Ligandsupporting

confidence: 59%

Section: Introductionmentioning

confidence: 99%

Pd-catalyzed telomerization of butadiene and methanol with direct catalyst recycling using a liquid-ionic liquid biphasic, continuous process

Völkl

Geburtig

Kiermaier

et al. 2016

Chemical Engineering and Processing: Process Intensification

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“…The 1 H, 13 C, 11 B, 31 P, and 19 FNMR spectra were recorded on Bruker AvanceI II HD nanobay 400 MHz or Bruker AvanceI II 500 MHz spectrometer at ambient temperature and referenced internally to residual protio-solvent ( 1 H) or solvent ( 13 C) resonances and are reported relative to tetramethylsilane (d = 0ppm), 31 Pr esonances are referenced externally to H 3 PO 4 (85 %), 19 Fc hemical shifts to CF 3 COOH, and 11 Bc hemical shifts to BF 3 ·Et 2 O. Solvents were degassed by sparging with argon and dried by passing through ac olumn of the appropriate drying agent and stored over potassium or 4 sieves.…”

Section: Methodsmentioning

confidence: 99%

Reversible C−H Activation, Facile C−B/B−H Metathesis and Apparent Hydroboration Catalysis by a Dimethylxanthene‐Based Frustrated Lewis Pair

Vasko

Zulkifly

Fuentes

et al. 2018

Chemistry A European J

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Ad imethylxanthene-based phosphine/borane frustrated Lewis pair (FLP) is shown to effect reversible CÀH activation, cleaving phenylacetylene, PhCCH, to give an equilibrium mixture of the free FLP and phosphoniuma cetylide in CD 2 Cl 2 solution at room temperature. This systema lso reacts with BÀHb onds although in ad ifferentf ashion:r eactions with HBpin and HBcatp roceed via CÀB/BÀHm etathe-sis, leading to replacement of the -B(C 6 F 5 ) 2 Lewis acid component by -Bpin/-Bcat, and transfer of HB(C 6 F 5 ) 2 to the phosphine Lewis base. Thist ransformationu nderpins the ability of the FLP to catalyze the hydroboration of alkynes by HBpin: the active species is derived from the HB(C 6 F 5 ) 2 fragment generated in this exchangep rocess.Scheme1.Stoichiometric reactions( a) between 1a and PhCCH;a nd (b) between 1b and PhCCH.

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“…Subsequent work demonstrated that mono‐ as well as diphosphines based on a dibenzodioxocin backbone ( L7 ) are capable of comparable activities under the same conditions . Furthermore, this group was able to demonstrate that chromanyl backbones lead to very effective ligands, for example ( L8 ) …”

Section: Catalystsmentioning

confidence: 99%

The Telomerization of 1,3‐Dienes – A Reaction Grows Up

2019

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Telomerization is a versatile tool for synthesizing unsaturated ethers, amines and other molecules starting from 1,3‐dienes and respective nucleophiles. The homogeneously catalyzed reaction has been the subject of academic and industrial research for over 50 years, offering a broad variety of substrates, catalysts and process concepts. This Minireview presents the advances and developments in this field over the last decade. The focus was on the conversion of renewable resources, the synthesis of promising new products and the development of efficient process concepts to combine these.

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Telomerisation of Buta‐1,3‐diene and Methanol: Superiority of Chromanyl‐Type Phosphines in the Dow Process for the Industrial Production of 1‐MOD

Cited by 16 publications

References 33 publications

Pd-catalyzed telomerization of butadiene and methanol with direct catalyst recycling using a liquid-ionic liquid biphasic, continuous process

Pd-catalyzed telomerization of butadiene and methanol with direct catalyst recycling using a liquid-ionic liquid biphasic, continuous process

Reversible C−H Activation, Facile C−B/B−H Metathesis and Apparent Hydroboration Catalysis by a Dimethylxanthene‐Based Frustrated Lewis Pair

The Telomerization of 1,3‐Dienes – A Reaction Grows Up

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