Oxidation of substituted styrene by thallium triacetate

Ouellette, Robert J.; Kordosky, G.; Levin, Charles; Williams, S. B. C.

doi:10.1021/jo01264a074

Cited by 27 publications

(17 citation statements)

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“…Presence of electron-releasing substituents on alkene double bond increases the rate of oxythallation -it is in accordance with Ads character of this reaction [2][3][4][5]. In earlier papers of this series we showed that oxidation of alkenes by an aqueous solution of thallic salts suits Taft's equation, and isokinetic relationship, too [6][7][8].…”

supporting

confidence: 59%

“…A good correlation between the rate constants and the ionization potentials of alkenes was found. It was found that inductive effects were the most important in the oxythallation of RCH -CH2 and RiR2C = CH2 alkenes.From earlier studies [1,2] it is obvious that the rate determining step of the oxidation of alkenes by thallic salts is the formation of the intermediate oxythallation adduct according to Eq (1):( 1) where R = H and/or alkyl (aryl).Presence of electron-releasing substituents on alkene double bond increases the rate of oxythallation -it is in accordance with Ads character of this reaction [2][3][4][5]. In earlier papers of this series we showed that oxidation of alkenes by an aqueous solution of thallic salts suits Taft's equation, and isokinetic relationship, too [6][7][8].…”

mentioning

confidence: 71%

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Substituent Effects in the Oxythallation of Alkenes

Strašák¹

1978

Zeitschrift Für Naturforschung B

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confidence: 59%

mentioning

confidence: 71%

Substituent Effects in the Oxythallation of Alkenes

Strašák¹

1978

Zeitschrift Für Naturforschung B

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“…To a mixture of thallium(II1) oxide (2.741 g, 0.00600 mol), acetic anhydride (2.04 g, 0.02 mol), and 40 ml of dry glacial acetic acid (i.e., the it1 sifu preparation of thallium(1II) acetate) (20) was added 1 (0.816 g, 0.00400 nlol), and the heterogeneous mixture was stirred for 24 h at 80 "C. The thallium oxide dissolved after 12 h to form a clear yellow solution. The reaction mixture was poured into 40 ml of water and the product was extracted with ether.…”

Section: Reaction 041 With Tiralliurn(li1) Aceratementioning

confidence: 99%

The metal-ligand oxidations of dibenzobicyclo[2.2.2]octatriene by lead tetraacetate – hydrogen fluoride, lead tetraacetate, thallium(III) acetate, and mercuric acetate

Tanner¹,

Bostelen²,

Lai³

1976

Can. J. Chem.

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The isoelectronic series lead tetraacetate -hydrogen fluoride, lead tetraacetate, thallium(II1) acetate, and mercuric acetate were used to oxidize the bicyclic olefin dibenzobicyclo[2.2.2]-octatriene. The stereochemistry of the products formed from these reactions substantiates the proposal that the first formed intermediate in these oxidations is the cis-molecular addition product of the metal and its ligand to the bicyclic olefin. Subsequent stereospecific rearrangement of the adducts in the case of the lead and thallium reagents verified the absence of the involvement of homolytic processes in the formation or decomposition of the adducts. DENNIS D. TANNER, PETER B. VAN BOSTELEN et MATHEW LAI. Can. J. Chenl. 54, 2004 (1976.On a utilisC les series isoClectroniques tetraacktate de plomb -f uorure d'hydrogene. tetraacetate de plomb. acetate de thalliurn(lI1) et acetate mercurique pour oxyder l'olefine bicyclique dibenzobicyclo[2.2.2.]octatri6ne. La sterkochimie des produits formis 2 partir de ces reactions supporte la proposition que la premier intermediaire form6 dam ces oxydations est le produit d'addition molCculaire cis du metal et de son ligand a I'olCfine bicyclique. Un rearrangement sterCospCcifique ulttrieur des adduits dans le cas des rCactifs du plomb et du thallium a permis de verifier l'absence d'une implication des processus homolytiques dans la formation ou la dCcomposition des adduits.[Traduit par le journal]

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“…In most cases, the formation of the organo-thallic adduct has been proposed as the rate-determining step of the Tl(II1) oxidation of olefins (13,14); this was also the case of T1-(NO3), oxidation of styrene i11 methanol and in methanol-water mixtures (1 7). It appears however, that at least in this case, the nature of the rate-determining step depends on the conceritrations used.…”

Section: Resultsmentioning

confidence: 99%

“…However, Henry's first kinetic measurements (13) suggested interesting mechanistic implica-[2bl TI+ + CH2-CHR + H + tions and thus prompted several recent kinetic I I studies (14)(15)(16)(17)(18)(19). The kinetics and product distri- OH OH bution for the oxidation of manysimple olefins by TI (111) in aqueous acid solutions have been Reaction 1 represents the formation of an orinterpreted by Henry in terms of the following gano-thallic intermediate (1); it is followed by mechanism : the decomposition of 1 into the final products reactions (2a and 2b).…”

Section: I/mentioning

confidence: 99%

Thallic Ion Oxidation of Styrene: Kinetics of Decomposition of the Oxythallation Adduct C₆H₅—CH(OCH₃)—CH2Tl(OAc)₂

Nadon¹,

Zador²

1974

Can. J. Chem.

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LOUISE NADON and MIKLOS ZADOR. Can. J. Chem. 52, 2667 (1974) The kinetics of decomposition of the organo-thallic adduct formed in methanol between styrene and TI(OAC)~, (C6H,-CH(OCH,)-CHZ-T1(OAc)Z) has been studied in a watermethanol solvent. The reaction follows a first order rate law. The organo-thallic compound, RTI(OAC)~, is shown to be dissociated at low concentrations yielding two reactive specles, RTIOH+ and RTl2+. The influence of acidity on the rate of decomposition shows that RT12+ is much more reactive than RTIOHt. The kinetic parameters have been determined. The implication of the results on the rate-determining step of TI(II1) oxidation of styrene is discussed.LOUISE NADON et MIKLOS ZADOR. Can. J. Chem. 52, 2667Chem. 52, (1974. La cinetique de decomposition du compose organo-thallique forrne dans le methanol entre le styrene et TI(OAc),, (C,H,-CH(OCH,)-CHZ-Tl(OAc),) a ete etudiee dans un melange eau-methanol. La cinetique de la reaction est du premier ordre. Le compose organo-thallique, RTI(OAc),, se dissocie a faible concentration et conduit a deux especes reactives RTIOHt et RT12 + . L'influence de I'acide sur la vitesse de dCcomposition montre que RTIZ + est b e a u c o~~p plus reactif que RTIOH+. Les pararnetres cinetiques ont ete determines. Les consequences de ces resultats sur I'etape determinante de I'oxydation thallique du styrene sont discutees. Several workers have ~reviouslv described the 0 oxidation of a variety ofolefins b i thallium (111)

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Oxidation of substituted styrene by thallium triacetate

Cited by 27 publications

References 3 publications

Substituent Effects in the Oxythallation of Alkenes

Substituent Effects in the Oxythallation of Alkenes

The metal-ligand oxidations of dibenzobicyclo[2.2.2]octatriene by lead tetraacetate – hydrogen fluoride, lead tetraacetate, thallium(III) acetate, and mercuric acetate

Thallic Ion Oxidation of Styrene: Kinetics of Decomposition of the Oxythallation Adduct C₆H₅—CH(OCH₃)—CH2Tl(OAc)₂

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Oxidation of substituted styrene by thallium triacetate

Cited by 27 publications

References 3 publications

Substituent Effects in the Oxythallation of Alkenes

Substituent Effects in the Oxythallation of Alkenes

The metal-ligand oxidations of dibenzobicyclo[2.2.2]octatriene by lead tetraacetate – hydrogen fluoride, lead tetraacetate, thallium(III) acetate, and mercuric acetate

Thallic Ion Oxidation of Styrene: Kinetics of Decomposition of the Oxythallation Adduct C6H5—CH(OCH3)—CH2Tl(OAc)2

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Thallic Ion Oxidation of Styrene: Kinetics of Decomposition of the Oxythallation Adduct C₆H₅—CH(OCH₃)—CH2Tl(OAc)₂