318. The kinetics of chlorine, iodine chloride, and bromine chloride addition to olefinic compounds

White, E. P.; Robertson, P. W.

doi:10.1039/jr9390001509

Cited by 27 publications

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“…Bromine is formed by electrolysis at the anode 2Br---> Br2 + 2e- [1] Because in saturated propylene solution the rate for addition of bromine to propylene is over 200 times larger than that for bromine hydrolysis (19,20), the reaction of dissolved propylene was assumed to occur exclusively with molecular bromine to form propylene bromohydrin (20)(21)(22)(23)(24) OH Br~ + CH3CH--CH~ + OH---+ CH3CH--CH~Br + Br- [2] Electrolysis of water occurs at the cathode 2H=,O + 2e--~ H2 + 2 OH- [3] Propylene oxide is formed by base-promoted dehydrohalogenation of the vicinal bromohydrin (25)(26)(27)(28) O OH / \ CH3CH--CH2Br + OH-~ CH3CH--CH2 + H20 + Br- [4] The desired overall cell reaction is Bromine is formed by electrolysis at the anode 2Br---> Br2 + 2e- [1] Because in saturated propylene solution the rate for addition of bromine to propylene is over 200 times larger than that for bromine hydrolysis (19,20), the reaction of dissolved propylene was assumed to occur exclusively with molecular bromine to form propylene bromohydrin (20)(21)(22)(23)(24) OH Br~ + CH3CH--CH~ + OH---+ CH3CH--CH~Br + Br- [2] Electrolysis of water occurs at the cathode 2H=,O + 2e--~ H2 + 2 OH- [3] Propylene oxide is formed by base-promoted dehydrohalogenation of the vicinal bromohydrin (25)(26)(27)(28) O OH / \ CH3CH--CH2Br + OH-~ CH3CH--CH2 + H20 + Br- [4] The desired overall cell reaction is…”

Section: System Chemistrymentioning

confidence: 99%

“…However, iodine reaction with propylene is slower and is reversible (28); also, reaction of bromohydrin to propylene oxide is more rapid than that of chlorohydrin, and is of comparable magnitude to that of iodohydrin (26). The halogen species does not appear in the overall reaction.…”

Section: System Chemistrymentioning

confidence: 99%

“…High bromide ion concentrations are known to catalyze addition of molecular bromine to olefins (28). High bromide ion concentrations are known to catalyze addition of molecular bromine to olefins (28).…”

Section: System Chemistrymentioning

confidence: 99%

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Incorporation of Complex Reaction Sequences in Engineering Models of Electrolytic Cells: I . Paired Synthesis of Propylene Oxide in an Undivided Cell

Alkire

Lisius

1985

J. Electrochem. Soc.

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A reaction sequence involving 11 chemical species was incorporated into a mathematical model of an electrolytic cell consisting of an undivided parallel-plate reactor operating under steady, continuous flow conditions. The set of coupled, nonlinear, stiff differential equations was solved numerically by dynamic simulation. The technique was applied to the paired synthesis of propylene oxide from propylene-saturated bromide electrolyte. For this system, the eigenvalues associated with the jacobian ranged over ten orders of magnitude. The effect of pH, [Br-], mass transfer, space time, and current density were explored to understand their influence on yield, selectivity, conversion, current efficiency, and cell voltage. ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 141.217.58.200 Downloaded on 2015-04-08 to IP ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 141.217.58.200 Downloaded on 2015-04-08 to IP Vol. 132,No. 8 COMPLEX REACTION SEQUENCES ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 141.217.58.200 Downloaded on 2015-04-08 to IP Vol. 132, No. 8 COMPLEX REACTION SEQUENCES ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 141.217.58.200 Downloaded on 2015-04-08 to IP

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Section: System Chemistrymentioning

confidence: 99%

Section: System Chemistrymentioning

confidence: 99%

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Incorporation of Complex Reaction Sequences in Engineering Models of Electrolytic Cells: I . Paired Synthesis of Propylene Oxide in an Undivided Cell

Alkire

Lisius

1985

J. Electrochem. Soc.

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“…Entretanto, essa reação é reversível 8 , embora seja possível deslocar o equilíbrio para a formação de produtos utilizando um excesso de substrato 9 . A adição de iodo a compostos insaturados é muito lenta, quando comparada com as adições de Cl 2 , Br 2 ou halogênios mistos 10 . Além disso, diiodo-compostos vicinais são instáveis em certas condições, podendo ocorrer reações de substituição ou eliminação.…”

Section: Introductionunclassified

Coiodação de alquenos com nucleófilos oxigenados: reações intermoleculares

et al. 2001

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Recebido em 6/7/00; aceito em 15/1/01 COIODINATION OF ALKENES WITH OXYGENATED NUCLEOPHILES: INTRAMOLECULAR REACTIONS. A review on the electrophilic addition of iodine to alkenes in the presence of oxygen containing nucleophiles (cohalogenation reaction) is presented. The intermolecular reactions are discussed with emphasis in methods of reaction and synthetic applications of the resulting vicinal iodofunctionalized products (iodohydrins, β-iodoethers and β-iodocarboxylates).

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“…Despite such widespread use, little work has been done on the kinetics and mechanism of this addition of ICl to alkenes and some of the work is contradictory. White and Robertson (1) reported that the addition of IC1 to allyl acetate in acetic acid follows an overall third-order rate law, first order in alkene and second order in ICl. A similar rate law was reported by Viswanathan and co-workers (2) for ICl addition to some allyl and vinyl compounds in acetic acid, and by Sergeev and Smirnov (3) for the addition of ICl to both cyclohexene and 1-hexene in CCld.…”

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Evidence for molecular complexes in the mechanism of additions of iodine mono-chloride to alkenes

Sçhmid¹,

Gordon²

1984

Can. J. Chem.

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. 62, 2526 (1984).Immediately upon mixing ICI and 2,3-dimethyl-2-butene in CC1, at 25'C a new absorption band due to an alkene-IC1 molecular complex appears at 295 ? 5 nm and decreases rapidly with time. The rate law under conditions of (alkene),, > > (ICl),, for the electrophilic addition of IC1 to 2,3-dimethyl-2-butene, E-and Z-2-butene, and E-and Z-I-phenylpropene is -d(ICl)/dt = k,,p,(alkene)(~C1)3/{l + ~~,(alkene)}j where KAD is the equilibrium constant for the formation of a I : 1 alkene-IC1 molecular complex. The addition of IC1 to the Z and E isomers of 2-butene and 1-phenylpropene occurs by anti-stereospecific addition. The negative enthalpy of activation for the addition of ICI to 2,3-dimethyl-2-butene is evidence that one or more complexes are involved on the reaction coordinate prior to the rate-determining step. On the basis of analysis of the enthalpy changes during the reaction, it is proposed that both a I : I and a 1 :2 alkene-IC1 molecular complex is involved in the mechanism prior to the rate-determining step. GEORGE H. SCHMID et JAMES W. GORDON. Can. J. Chem. 62, 2526Chem. 62, (1984.Des que l'on mtlange du ICl et du dimtthyl-2,3 butene-2 dans du CCL B 25"C, il y a apparition, B 295 ? 5 nm, d'une nouvelle bande d'absorption qui est due i un complexe molCculaire alcene-1C1; I'intensitC de cette bande diminue rapidement avec le temps. La loi de vitesse qui s'applique, si (alcene),, > > (ICI),,, pour l'addition Clectrophile de 1C1 sur le dimethyl-2,3 butene-2, sur les butenes-2 (E ou Z) ou sur les phtnyl-l propenes (ou K,, est la constante d'tquilibre pour la formation d'un complexe molCculaire 1 : 1 alckne-ICI. La sttrtochimie de l'addition du IC1 sur les isomtres E et Z du butene-2 et du phtnyl-1 propene est sttrCosptcifiquement anti. Le fait que l'enthalpie d'activation de l'addition du IC1 sur le dimtthyl-2,3 butkne-2 soit ntgative est une preuve qu'un ou plusieurs complexes sont impliquCs dans les coordonnCes de la rCaction avant d'atteindre l'ttape dtterminante. Sur la base d'une analyse des changements d'enthalpie au cours de la riaction, on propose que des complexes molCculaires alcene-IC1 1 : 1 ainsi que 1 :2 sont impliquCs dans le mCcanisme avant d'atteindre l'ttape diterminante.[Traduit par le journal]The stoichiometry of the addition of iodine monochloride (ICl) to alkenes is 1 : I in a number of solvents (1 -5). Because of this fact, solutions of IC1 in acetic acid (Wijs' solution) are used to determine iodine values of fats and oils (6). Despite such widespread use, little work has been done on the kinetics and mechanism of this addition of ICl to alkenes and some of the work is contradictory. White and Robertson (1) reported that the addition of IC1 to allyl acetate in acetic acid follows an overall third-order rate law, first order in alkene and second order in ICl. A similar rate law was reported by Viswanathan and co-workers (2) for ICl addition to some allyl and vinyl compounds in acetic acid, and by Sergeev and Smirnov (3) for the addition of ICl to both cyclohexene and 1-he...

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318. The kinetics of chlorine, iodine chloride, and bromine chloride addition to olefinic compounds

Cited by 27 publications

References 0 publications

Incorporation of Complex Reaction Sequences in Engineering Models of Electrolytic Cells: I . Paired Synthesis of Propylene Oxide in an Undivided Cell

Incorporation of Complex Reaction Sequences in Engineering Models of Electrolytic Cells: I . Paired Synthesis of Propylene Oxide in an Undivided Cell

Coiodação de alquenos com nucleófilos oxigenados: reações intermoleculares

Evidence for molecular complexes in the mechanism of additions of iodine mono-chloride to alkenes

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