Thermal Reactions of Highly Fluorinated CycloHexadienes

Gething, Bill; Patrick, C. R.; Tatlow, J. C.; Banks, R. E.; Barbour, A. K.; Tipping, A. E.

doi:10.1038/183586a0

Cited by 26 publications

(1 citation statement)

References 7 publications

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“…he Pure Oil Co. process for the manufacture of aliphatic mercaptans is based on an old reaction, discovered by Sabatier in 1910 (13), adapted to a new process and an active and selective catalyst. The process involves the reaction of aliphatic monohydric alcohols and hydrogen sulfide to form corresponding mercaptans at high yields and selectivities per pass according to the reaction ROH + H2S -* RSH + H20 Kramer and Reid in 1921 (11) found that the reaction of alcohols and hydrogen sulfide progressed over thoria-type catalysts. However, the reaction system had disadvantages 1 Deceased.…”

mentioning

confidence: 99%

Production of Aromatic Polyfluoro Compounds from Chlorofluorocyclohexanes

Johncock¹,

Mobbs²,

Musgrave³

1962

Ind. Eng. Chem. Proc. Des. Dev.

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mentioning

confidence: 99%

Production of Aromatic Polyfluoro Compounds from Chlorofluorocyclohexanes

Johncock¹,

Mobbs²,

Musgrave³

1962

Ind. Eng. Chem. Proc. Des. Dev.

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Introduction of Fluorine

Kirsch

2013

Modern Fluoroorganic Chemistry

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Shortly after their first isolation of elemental fluorine in 1886, Moissan and his co-workers treated several organic substrates with this highly reactive gas. All these experiments, either at room temperature or at liquid nitrogen temperature, resulted in sometimes violent explosions. No major defined reaction products could be isolated.A plausible, first explanation for these discouraging results was proposed by W. Bockemüller in the 1930s, on the basis of thermochemical considerations. The energy released by formation of the highly stable carbon-fluorine bonds (∼116 kcal mol −1 ) is considerably greater than the energy needed for dissociation of carbon-carbon (∼83 kcal mol −1 ) or carbon-hydrogen bonds (∼99 kcal mol −1 ) [1]. A second problem is the extremely low homolytic dissociation energy of elemental fluorine (only 37 kcal mol −1 ), which allows the ready initiation of uncontrollable radical chain reactions, even at low temperatures and in the absence of light [2].The first defined fluoroaliphatic compounds obtained by direct fluorination of organic substrates in liquid reaction media were characterized by Bockemüller [3] in the early 1930s and published with his thermochemical analysis. To control the immense reaction enthalpy, the fluorine gas was diluted with nitrogen or carbon dioxide. The organic substrate was dissolved in a cooled inert solvent, for example, CCl 4 or CF 2 Cl 2 . A similar line of work was pursued in the United States by L. A. Bigelow [4], who studied the reaction of arenes with fluorine gas.In an alternative approach, volatile organic substrates were fluorinated in the gas phase on contact with a copper mesh. This work was pioneered by K. Fredenhagen and G. Cadenbach in the early 1930s [5] and then continued by N. Fukuhara and L. A. Bigelow [6] as part of the Manhattan Project (Figure 2.1). Vapor-phase fluorination finally permitted the preparation of (relatively) defined polyfluorination products from aliphatic hydrocarbons, benzene, or acetone.A modern, improved version of this general method, the LaMar (Lagow-Margrave) process, uses a nickel reactor with different temperature zones and Modern Fluoroorganic Chemistry: Synthesis, Reactivity, Applications, Second Edition. Peer Kirsch.

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Fluorierungen organischer Verbindungen mit Chlortrifluorid, I. Einwirkung von Chlortrifluorid auf Benzol in der Gasphase

1965

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Durch möglichst schnelle und gründliche Durchmischung von mit Stickstoff verdünntem Benzoldampf und Chlortrifluorid wurde in einer kontinuierlich arbeitenden Apparatur die Fluorierung des Benzols in der Gasphase erreicht. Außer Fluorbenzol wurden Chlorierungsprodukte erhalten, im besten Falle 40–50%, berechnet auf eingesetztes Benzol. Nichtaromatische Verbindungen traten nur bis zu etwa 1.5% als flüchtige Substanzen auf; je nach den angewandten Mengenverhältnissen und Temperaturen (60–300°) wurden die Reaktions‐produkte in verschiedenem Verhältnis gefunden. — Die mit Benzol erhaltenen Ergebnisse wurden durch gleichartige Umsetzung von Fluorbenzol ergänzt.

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Thermal Reactions of Highly Fluorinated CycloHexadienes

Cited by 26 publications

References 7 publications

Production of Aromatic Polyfluoro Compounds from Chlorofluorocyclohexanes

Production of Aromatic Polyfluoro Compounds from Chlorofluorocyclohexanes

Introduction of Fluorine

Fluorierungen organischer Verbindungen mit Chlortrifluorid, I. Einwirkung von Chlortrifluorid auf Benzol in der Gasphase

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