INVESTIGATION OF SYNTHESIS VERSUS REËNTRY IN TWO ORGANIC NITROGEN CONTAINING SYSTEMS UNDER NEUTRON IRRADIATION<sup>1</sup>

Wolf, Alfred P.; Gordon, B. E.; Anderson, Robbin C.

doi:10.1021/ja01592a103

Cited by 18 publications

(9 citation statements)

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“…In liquid systems, radical reactions, possibly by CH, CH 2 and CH 3 radicals, were suggested to occur due to either direct hydrogen displacement in the molecules of the medium or to interactions with different fragments formed in the irradiated matrix [10][11][12][13][14][15]. Insertion reactions by carbon atoms, methyne [16] and methylene radicals were also suggested as occurring in irradiated liquid systems [12,[16][17][18], Studies of reactions of recoil carbon atoms in solid systems should be much more complicated than in simple gaseous or liquid systems [19]. Although the subject has been treated in some publications [20][21][22][23][24][25][26][27][28] our understanding of the chemistry of recoil carbon atoms in solid systems is as yet far from complete.…”

Section: Introductionmentioning

confidence: 99%

Chemical Effects Associated with the Thermal Neutron Irradiation of Solid Acetanilide (Antifibrin)

Barakat¹,

Zahran

1972

Radiochimica Acta

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Reactions of recoil carbon-14 atoms have been studied in neutron irradiated acetanilide system. The reaction mechanisms in solid systems are discussed with reference to those occurring in simple gaseous and liquid systems. The "random fragmentation" hypothesis seems to oifer an adequate explanation. Most of the products identified were the result of different recombination processes between fragments formed by the severe fragmentation of the irradiated material. 14 Clabelled acetanilide was obtained with the highest radiochemical yield. The radiochemical yields of the simple synthetic products were higher than those of more complicated products. Labelled methyl derivatives were not detected. The infra red spectrum of the polymer separated showed a marked similarity, in absorption bands, to the spectrum of pure acetanilide except for the possible appearance of -CH 2 -groups in the polymer spectrum. ZusammenfassungReaktionen von KohlenstofF-14-Rückstoßatomen sind in einem mit Neutronen bestrahlten Acetanilidsystem untersucht worden. Die Reaktionsmechanismen in Festkörpersystemen werden in bezug auf die in einfachen gasförmigen und flüssigen Systemen auftretenden Mechanismen behandelt. Die Hypothese der "statistischen Zertrümmerung" scheint eine ausreichende Erklärung zu bieten. Die meisten identifizierten Produkte stammten aus verschiedenen Rekombinationsprozessen zwischen Bruchstücken, die durch die starke Zertrümmerung des bestrahlten Materials entstanden waren. Mit 14 C markiertes Acetanilid wurde mit der höchsten radiochemischen Ausbeute erhalten. Die radiochemischen Ausbeuten der einfachen synthetischen Produkte waren höher als die der komplizierteren Produkte. Markierte Methylderivate wurden nicht festgestellt. Das Infrarotspektrum des abgetrennten Polymers deutete auf eine bemerkenswerte Ähnlichkeit in den Absorptionsbanden mit den im Spektrum von reinem Acetanilid nachgewiesenen, mit der Ausnahme des möglichen Auftretens von -CH 2 -Gruppen im Polymerspektrum. RésuméOn a étudié les réactions des atomes de recul de carbone-14 sur l'acétanilide irradié aux neutrons. Les mécanismes des réactions intervenant pour la forme solide sont discutés et comparés aux mécanismes observés pour les formes de gaz et liquide. L'hypothèse de la «fragmentation au hasard» semble offrir une explication adéquate. La plupart des produits identifiés résultent de différents processus de recombinaison qui se sont produits entre les radicaux formés à la suite d'une importante fragmentation du produit irradié. L'acétanilide marqué au 14 C a été obtenu avec un rendement radiochimique élevé. Les rendements radiochimiques étaient plus grands pour les produits synthétiques simples que pour les produits plus compliqués. On n'a pas trouvé de dérivés méthyliques marqués. En ce qui concerne les bandes des spectres d'adsorption, l'analyse infrarouge du polymère isolé a mis en évidence une ressemblance profonde avec les polymères observés dans le spectre de l'acétanilide pur, exception faite de l'apparition éventuelle de groupes -CH S -dans le sp...

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Section: Introductionmentioning

confidence: 99%

Chemical Effects Associated with the Thermal Neutron Irradiation of Solid Acetanilide (Antifibrin)

Barakat¹,

Zahran

1972

Radiochimica Acta

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“…On the other hand, in nitrogen-free compounds such as benzene or toluene there was always the necessity to use a nitrogen-containing additive in order to supply nitrogen atoms to the system [11,[13][14][15][16][17][18]. However, irradiation of binary homogeneous organic mixtures could not be assumed to afford a means for studying the true behaviour of the recoil carbon-14 atoms in a given hydrocarbon medium.…”

Section: Introductionmentioning

confidence: 99%

Investigation of the Reactions of the Recoil Carbon-14 Atoms in Some Heterogeneous Mixtures

Barakat¹,

Zahran²

1970

Radiochimica Acta

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“…Degradative evidence led WOLF et al [5], to postulate an insertion reaction, i. e., by methylene [CH 2 :], as a possible pathway for the formation of certain recoil labeled molecules. MACKAY et al [6], postulated insertion by carbon atoms in order to account for the labeled acetylene and ethylene arising from reaction between carbon-11 and low molecular weight hydrocarbons.…”

Section: Introductionmentioning

confidence: 99%

Mechanisms and Isotope Effects in the Reactions of Energetic Carbon Atoms with Hydrocarbons and Alkylfluorides

1969

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Carbon-ll-atoms were allowed to react with specifically deuterated and perdeuterated hydrocarbons and also with specifically deuterated and perdeuterated alkylfluorides, all in the presence of oxygen scavenger. In addition the reactions of carbon-11 atoms with protonated and perdeuterated hydrocarbons or protonated and perdeuterated alkylfluorides in 1:1 mixtures containing oxygen scavenger were studied. The major fraction (>90% in the 1:1 mixtures) of the acetylene-u C formed in these reactions was in the form of the specifically labeled acetylenes, H"C=CH and D ll C=CD. The overall isotope effect as measured by the ratio of yield, H 11 C=CH/D 11 C=CD varies from 1.05 for aromatice such as benzene to 1.27 for aliphatics such as methane.Increased isotopie mixing observed in acetylene-n C yields from specifically labeled hydrocarbons reflects both the intramolecular nature of the reaction and the lifetime and excitation energy of the carbon-11 containing intermediate. The isotope effects and mixing effects are discussed in light of the current hot-carbon-atom reaction hypothesis.

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INVESTIGATION OF SYNTHESIS VERSUS REËNTRY IN TWO ORGANIC NITROGEN CONTAINING SYSTEMS UNDER NEUTRON IRRADIATION¹

Cited by 18 publications

References 0 publications

Chemical Effects Associated with the Thermal Neutron Irradiation of Solid Acetanilide (Antifibrin)

Chemical Effects Associated with the Thermal Neutron Irradiation of Solid Acetanilide (Antifibrin)

Investigation of the Reactions of the Recoil Carbon-14 Atoms in Some Heterogeneous Mixtures

Mechanisms and Isotope Effects in the Reactions of Energetic Carbon Atoms with Hydrocarbons and Alkylfluorides

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INVESTIGATION OF SYNTHESIS VERSUS REËNTRY IN TWO ORGANIC NITROGEN CONTAINING SYSTEMS UNDER NEUTRON IRRADIATION1

Cited by 18 publications

References 0 publications

Chemical Effects Associated with the Thermal Neutron Irradiation of Solid Acetanilide (Antifibrin)

Chemical Effects Associated with the Thermal Neutron Irradiation of Solid Acetanilide (Antifibrin)

Investigation of the Reactions of the Recoil Carbon-14 Atoms in Some Heterogeneous Mixtures

Mechanisms and Isotope Effects in the Reactions of Energetic Carbon Atoms with Hydrocarbons and Alkylfluorides

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INVESTIGATION OF SYNTHESIS VERSUS REËNTRY IN TWO ORGANIC NITROGEN CONTAINING SYSTEMS UNDER NEUTRON IRRADIATION¹