Pulse radiolysis and 77 K matrix. gamma. irradiation of dimethyl truxinates and trans-methyl cinnamate in 2-methyltetrahydrofuran

Takamuku, S; Kigawa, H; Suematsu, H; Susumu, T; Tsumori, K; Sakurai, H

doi:10.1021/j100207a025

Title: Pulse radiolysis and 77 K matrix. gamma. irradiation of dimethyl truxinates and trans-methyl cinnamate in 2-methyltetrahydrofuran

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Abstract

One-electron reduction of dimethyl ..mu..-truxinate (..mu..-DMT), dimethyl ..beta..-truxinate (..beta..-DMT), and dimethyl ..cap alpha..-truxillate (..cap alpha..-DMT) has been investigated by pulse radiolysis and 77 K matrix ..gamma.. irradiation of the 2-methyltetrahydrofuran solutions. Cycloreversion of the radical anions formed by an electron attachment to these cyclobutanes was observed in all cases, even at 77 K. The orientation of the cycloreversion was dependent on the stereochemistry of the cyclobutanes, and the selectivity was reasonably explained by a so-called cis effect; the best possible release of steric hindrance decides the primary step of the reaction. In 77 K matrix ..gamma.. irradiation of ..cap alpha..-DMT, an intense IR absorption was found after the photobleaching of trapped electrons with light > 690 nm. In other DMTs, the IR absorption band was not observed while the cycloreversion of DMT by mobile electrons occurred. Thus, the IR band in the case of ..cap alpha..-DMT was assigned to an associated dimer anion due to the interaction between the radical anion and the neutral molecule pair of trans-methyl cinnamate orginally formed by the cycloreversion of ..cap alpha..-DMT. The dimer anion was presumed to be oriented in a head-to-tail structure in a solvent cage on the basis of the original configurationmore » of ..cap alpha..-DMT.« less

Authors:: Takamuku, S; Kigawa, H; Suematsu, H; Susumu, T; Tsumori, K; Sakurai, H

Publication Date:: Thu May 13 00:00:00 EDT 1982

Research Org.:: Osaka Univ., Japan

OSTI Identifier:: 6592193

Resource Type:: Journal Article

Journal Name:: J. Phys. Chem.; (United States)

Additional Journal Information:: Journal Volume: 86:10

Country of Publication:: United States

Language:: English

Subject:: 38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CYCLOALKANES; RADIOLYSIS; STEREOCHEMISTRY; ABSORPTION SPECTRA; CHEMICAL REACTIONS; ELECTRON BEAMS; ELECTRON CAPTURE; EXPERIMENTAL DATA; GAMMA RADIATION; LOW TEMPERATURE; MTHF; PULSED IRRADIATION; RADICALS; REDUCTION; ALKANES; BEAMS; CAPTURE; CHEMICAL RADIATION EFFECTS; CHEMISTRY; DATA; DECOMPOSITION; ELECTROMAGNETIC RADIATION; FURANS; HETEROCYCLIC COMPOUNDS; HYDROCARBONS; INFORMATION; IONIZING RADIATIONS; IRRADIATION; LEPTON BEAMS; NUMERICAL DATA; ORGANIC COMPOUNDS; ORGANIC OXYGEN COMPOUNDS; PARTICLE BEAMS; RADIATION CHEMISTRY; RADIATION EFFECTS; RADIATIONS; SPECTRA; TETRAHYDROFURAN; 400600* - Radiation Chemistry; 400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987); 400200 - Inorganic, Organic, & Physical Chemistry

Citation Formats


                    Takamuku, S, Kigawa, H, Suematsu, H, Susumu, T, Tsumori, K, and Sakurai, H. Pulse radiolysis and 77 K matrix. gamma. irradiation of dimethyl truxinates and trans-methyl cinnamate in 2-methyltetrahydrofuran.  United States: N. p., 1982. 
        Web.  doi:10.1021/j100207a025.

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                    Takamuku, S, Kigawa, H, Suematsu, H, Susumu, T, Tsumori, K, & Sakurai, H. Pulse radiolysis and 77 K matrix. gamma. irradiation of dimethyl truxinates and trans-methyl cinnamate in 2-methyltetrahydrofuran.  United States.  https://doi.org/10.1021/j100207a025

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                    Takamuku, S, Kigawa, H, Suematsu, H, Susumu, T, Tsumori, K, and Sakurai, H. 1982.  
        "Pulse radiolysis and 77 K matrix. gamma. irradiation of dimethyl truxinates and trans-methyl cinnamate in 2-methyltetrahydrofuran".  United States.  https://doi.org/10.1021/j100207a025.

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@article{osti_6592193,

  title        = {Pulse radiolysis and 77 K matrix. gamma. irradiation of dimethyl truxinates and trans-methyl cinnamate in 2-methyltetrahydrofuran},

  author       = {Takamuku, S and Kigawa, H and Suematsu, H and Susumu, T and Tsumori, K and Sakurai, H},

  abstractNote = {One-electron reduction of dimethyl ..mu..-truxinate (..mu..-DMT), dimethyl ..beta..-truxinate (..beta..-DMT), and dimethyl ..cap alpha..-truxillate (..cap alpha..-DMT) has been investigated by pulse radiolysis and 77 K matrix ..gamma.. irradiation of the 2-methyltetrahydrofuran solutions. Cycloreversion of the radical anions formed by an electron attachment to these cyclobutanes was observed in all cases, even at 77 K. The orientation of the cycloreversion was dependent on the stereochemistry of the cyclobutanes, and the selectivity was reasonably explained by a so-called cis effect; the best possible release of steric hindrance decides the primary step of the reaction. In 77 K matrix ..gamma.. irradiation of ..cap alpha..-DMT, an intense IR absorption was found after the photobleaching of trapped electrons with light > 690 nm. In other DMTs, the IR absorption band was not observed while the cycloreversion of DMT by mobile electrons occurred. Thus, the IR band in the case of ..cap alpha..-DMT was assigned to an associated dimer anion due to the interaction between the radical anion and the neutral molecule pair of trans-methyl cinnamate orginally formed by the cycloreversion of ..cap alpha..-DMT. The dimer anion was presumed to be oriented in a head-to-tail structure in a solvent cage on the basis of the original configuration of ..cap alpha..-DMT.},

  doi          = {10.1021/j100207a025},

  url          = {https://www.osti.gov/biblio/6592193},
  journal      = {J. Phys. Chem.; (United States)},
number       = ,

  volume       = 86:10,

  place        = {United States},

  year         = {Thu May 13 00:00:00 EDT 1982},

  month        = {Thu May 13 00:00:00 EDT 1982}

}

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