Kinetic study of the reaction of triphenylphosphine with acrylic acid in alcohol media

Salin, Alexey V.; Sobanov, A. A.; Bakhtiyarova, Yu. V.; Khabibullin, Azat A.; Галкин, В. И.

doi:10.1134/s1070363210090033

Cited by 15 publications

(16 citation statements)

References 3 publications

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“…Another advantage is that there is no restriction in solubility of substrates in solvents of different classes. The use of the monocarboxylic acid is also preferred, since it allows to avoid the complication of the reaction kinetics due to appearance of the parallel channels of proton transfer, as observed for the dicarboxylic acids [a].…”

Section: Resultsmentioning

confidence: 99%

“…Despite the above restrictions, the scope of solvents suitable for the kinetic study remains sufficiently broad; this allowed us to expand considerably the series of seven aprotic solvents used previously [d] by adding ethylene carbonate, propylene carbonate, methyl acetate, ethyl formate, propionitrile, 1,4‐dioxane, 1,3‐dioxolane, 1,2‐dimethoxyethane, and THF.…”

Section: Resultsmentioning

confidence: 99%

“…When unsaturated carboxylic acid is used as a substrate, and if the addition of tertiary phosphine proceeds in an aprotic solvent, the reaction obeys third‐order kinetics, being first order in the phosphine and second order in the unsaturated acid [d, f]. However, previous conclusions were based on a relatively limited number of the solvents used for the kinetic study.…”

Section: Introductionmentioning

confidence: 91%

“…Much less information is available about the mechanism of the phospha‐Michael reaction, where tertiary phosphine acts as a nucleophile. To fill up the gap in the theory of the Michael‐type additions, we have recently started a systematic study of the mechanism of the reaction of tertiary phosphines with unsaturated carboxylic acids and their derivatives . In comparison with amines, phosphines are stronger nucleophiles, but have weaker basic character (e.g., p K a for the conjugate acid of PPh 3 in water is 2.7 ).…”

Section: Introductionmentioning

confidence: 96%

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Solvent Effect on Kinetics and Mechanism of the Phospha‐Michael Reaction of Tertiary Phosphines with Unsaturated Carboxylic Acids

Salin

Fatkhutdinov

II'in

et al. 2014

Heteroatom Chemistry

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In aprotic solvents, kinetics of the reaction of triphenylphosphine with acrylic acid is second order in the acid and first order in the phosphine. To find the most suitable model to describe the solvent effect on this reaction, the third‐order rate constants in a series of 16 aprotic solvents were analyzed using one‐ and multiparameter regressions within the framework of the Kamlet–Taft, the Catalán, the Gutmann–Mayer, and the Koppel–Palm equations. The best result gives a two‐parameter model constructed on the basis of the Reichardt polarity ET and the basicity B from the Koppel–Palm equation, with the weak positive effect of the ET parameter on the reaction rate and very strong negative effect of the B parameter. The results obtained give further evidence to the previously suggested a stepwise mechanism, which involves the initial formation of a zwitterionic intermediate, followed by the proton transfer from the second molecule of acrylic acid to the generated carbanionic center in the rate‐determining step.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 91%

Section: Introductionmentioning

confidence: 96%

See 2 more Smart Citations

Solvent Effect on Kinetics and Mechanism of the Phospha‐Michael Reaction of Tertiary Phosphines with Unsaturated Carboxylic Acids

Salin

Fatkhutdinov

II'in

et al. 2014

Heteroatom Chemistry

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“…The system shows similarities to the reaction of cinnamaldehyde with THPP in water (or D 2 O), which finally generates two isomeric self-condensation aldehyde products with co-production of the phosphine oxide (Scheme 1) [11]. Kinetic and mechanistic details have recently been published by Galkin's group on the related but simpler reactions of α,β-unsaturated carboxylic acids with Ph 3 P where, for example, acrylic acid in acetic acid media gives just the phosphonium acetate [Ph 3 P + CH 2 CH 2 CO 2 H]OAc - [19], while in alcohol media the Ph 3 P + CH 2 CH 2 CO 2 -zwitterion is formed [20].…”

Section: VImentioning

confidence: 97%

Lignin-type, α,β-unsaturated aldehydes of lignin-type in organic solvents

2012

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A 1:1 reaction of [HO(CH 2 ) 3 ] 3 P with 4-hydroxy-3-methoxy-cinnamaldehyde (coniferaldehyde) or 3,5-dimethoxy-4-hydroxycinnamaldehyde (sinapaldehyde) in acetone at room temperature affords phosphonium zwitterions of the type R 3 P + CH(4-O --Ar)CH 2 CHO; other phosphines [R = Et, n-Bu, (CH 2 ) 2 CN, and p-Tol] do not react under the same conditions. In alcohols R'OH(D) [R' = CD 3 , Et, (CD 3 ) 2 CD, s-Bu, HOCH 2 CH 2 ], the above phosphines (except the cyano-derivative) and those where R = i-Pr, Cy, Me 2 Ph, MePh 2 do react within an equilibrium established between the reactants and the zwitterion-hemiacetal products R 3 P + CH(4-O --Ar)CH 2 CH(OH)(OR') that are formed as a mixture of two diastereomers. The nature of the phosphine and the alcohol affects the equilibrium and the diastereomeric ratio.Our group has been involved in investigating interactions of phosphines with unsaturated compounds in aqueous media, the interest evolving from discovery of the use of the water-soluble phosphine (HOCH 2 ) 3 P for the bleaching of pulps [1][2][3][4]. The topic is also of interest within homogeneous catalysis in aqueous media involving unsaturated organic substrates using transition metal-phosphine systems [5,6]. A review covering both these aspects of the chemistry of this specific phosphine has appeared recently [7]. We have reported previously studies on the reactions of tertiary phosphines with substituted benzaldehydes [8], benzyl and cinnamyl alcohols [9], and quinones [10].Prior to our detailed studies on the interaction of α,β-unsaturated aldehydes with tertiary phosphines in aqueous media [11,12], these systems were not well understood, the relevant literature being summarized in our reports. The studies revealed that the reactions with aromatic α,β-unsaturated aldehydes depend on substituents present in the aromatic ring. Thus, cinnamaldehyde, in the presence of tris(hydroxypropyl)phosphine, [HO(CH 2 ) 3 ] 3 P (THPP), undergoes self-condensation into the two isomeric products shown in Scheme 1, the reaction being initiated by nucleophilic attack of the phosphine at the C-atom adjacent to the Ph group [11]; however, lignin-type aldehydes, which contain a p-OH-group, react with tertiary phosphines to afford bisphosphonium zwitterion products via the same nucleophilic phosphine attack (Scheme 2) [12].Reactions of α,β-unsaturated aldehydes such as ArCH=CHCHO (Ar = aryl) with tertiary phosphines in organic media have been investigated recently, but only with (α-hydroxy)phosphines [e.g. Ph 2 PCH(OH)R, where R = H, alkyl or aryl], which readily decompose reversibly to RCHO and Ph 2 PH. The secondary phos-

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Effect of Anchimeric Assistance in the Reaction of Triphenylphosphine with α,β‐Unsaturated Carboxylic Acids

Salin

Fatkhutdinov

Il'in

et al. 2014

Int J of Chemical Kinetics

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Quaternization of triphenylphosphine with maleic and cis-aconitic acids is strongly accelerated by participation of the cis-carboxyl group in stabilization of the phosphonium zwitterion intermediate by intramolecular hydrogen bonding, in spite of steric hindrance by the acid's reaction center. A similar effect for trans-isomeric acids is not observed, which can be rationalized on the basis of spatial structures of the generated zwitterions, implying an electrostatic interaction between the phosphonium center and carbonyl oxygen atom. The effect of anchimeric assistance decreases when the intramolecular hydrogen bonding disfavors attack of the phosphine on the sterically less hindered carbon atom of the C=C bond, as observed for cis-aconitic acid. C

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Kinetic study of the reaction of triphenylphosphine with acrylic acid in alcohol media

Cited by 15 publications

References 3 publications

Solvent Effect on Kinetics and Mechanism of the Phospha‐Michael Reaction of Tertiary Phosphines with Unsaturated Carboxylic Acids

Solvent Effect on Kinetics and Mechanism of the Phospha‐Michael Reaction of Tertiary Phosphines with Unsaturated Carboxylic Acids

Lignin-type, α,β-unsaturated aldehydes of lignin-type in organic solvents

Effect of Anchimeric Assistance in the Reaction of Triphenylphosphine with α,β‐Unsaturated Carboxylic Acids

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