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Masakatsu Matsumoto - One of the best experts on this subject based on the ideXlab platform.

  • intramolecular charge transfer induced decomposition promoted by an aprotic Polar Solvent for bicyclic dioxetanes bearing a 4 benzothiazol 2 yl 3 hydroxyphenyl moiety
    Journal of Organic Chemistry, 2011
    Co-Authors: Masatoshi Tanimura, Nobuko Watanabe, Hisako K Ijuin, Masakatsu Matsumoto
    Abstract:

    Bicyclic dioxetanes 3a−d bearing a 4-(benzothiazol-2-yl)-3-hydroxyphenyl group decomposed to give the corresponding keto esters 4a−d accompanied by the emission of bright light when simply dissolved in an aprotic Polar Solvent such as N-methylpyrrolidone (NMP) or DMF at 50−100 °C. This Solvent-promoted decomposition (SPD) was effectively a chemiluminescence process caused by the hydrogen bonding of a phenolic OH with a Solvent molecule(s). The characteristics of the chemiluminescence in SPD resembled those in base-induced decomposition (BID), which occurs through an oxidoaryl-substituted dioxetane 5 by an intramolecular charge-transfer-induced decomposition (CTID) mechanism. Both free energies of activation, ΔG⧧SPD and ΔG⧧BID, increased in the order 3a < 3b < 3c < 3d, and were linearly correlated with each other. However, SPD showed features different from those of BID in terms of enthalpy of activation and entropy of activation. SPD had large negative values for ΔS⧧ (ca. −71 J mol−1 K−1) regardless of th...

  • Solvent promoted chemiluminescent decomposition of a bicyclic dioxetane bearing a 4 benzothiazol 2 yl 3 hydroxyphenyl moiety
    Tetrahedron Letters, 2008
    Co-Authors: Masakatsu Matsumoto, Masatoshi Tanimura, Nobuko Watanabe, Taichi Akimoto, Hisako K Ijuin
    Abstract:

    An aprotic Polar Solvent such as N-methylpyrrolidone (NMP) promoted the thermal decomposition of bicyclic dioxetane bearing a 4-(benzothiazol-2-yl)-3-hydroxyphenyl moiety 1 without the addition of any base. This Solvent-promoted decomposition (SPD) gave light as effectively as the base-induced decomposition (BID) in an aprotic Polar Solvent. SPD caused intramolecular CT-induced chemiluminescence similar to BID, but, in contrast to BID, SPD proceeded through a pathway with a large negative entropy of activation. Dioxetane 1 was also shown to give light due to excited state intramolecular proton transfer (ESIPT) upon heating in p-xylene.

Hisako K Ijuin - One of the best experts on this subject based on the ideXlab platform.

  • intramolecular charge transfer induced decomposition promoted by an aprotic Polar Solvent for bicyclic dioxetanes bearing a 4 benzothiazol 2 yl 3 hydroxyphenyl moiety
    Journal of Organic Chemistry, 2011
    Co-Authors: Masatoshi Tanimura, Nobuko Watanabe, Hisako K Ijuin, Masakatsu Matsumoto
    Abstract:

    Bicyclic dioxetanes 3a−d bearing a 4-(benzothiazol-2-yl)-3-hydroxyphenyl group decomposed to give the corresponding keto esters 4a−d accompanied by the emission of bright light when simply dissolved in an aprotic Polar Solvent such as N-methylpyrrolidone (NMP) or DMF at 50−100 °C. This Solvent-promoted decomposition (SPD) was effectively a chemiluminescence process caused by the hydrogen bonding of a phenolic OH with a Solvent molecule(s). The characteristics of the chemiluminescence in SPD resembled those in base-induced decomposition (BID), which occurs through an oxidoaryl-substituted dioxetane 5 by an intramolecular charge-transfer-induced decomposition (CTID) mechanism. Both free energies of activation, ΔG⧧SPD and ΔG⧧BID, increased in the order 3a < 3b < 3c < 3d, and were linearly correlated with each other. However, SPD showed features different from those of BID in terms of enthalpy of activation and entropy of activation. SPD had large negative values for ΔS⧧ (ca. −71 J mol−1 K−1) regardless of th...

  • Solvent promoted chemiluminescent decomposition of a bicyclic dioxetane bearing a 4 benzothiazol 2 yl 3 hydroxyphenyl moiety
    Tetrahedron Letters, 2008
    Co-Authors: Masakatsu Matsumoto, Masatoshi Tanimura, Nobuko Watanabe, Taichi Akimoto, Hisako K Ijuin
    Abstract:

    An aprotic Polar Solvent such as N-methylpyrrolidone (NMP) promoted the thermal decomposition of bicyclic dioxetane bearing a 4-(benzothiazol-2-yl)-3-hydroxyphenyl moiety 1 without the addition of any base. This Solvent-promoted decomposition (SPD) gave light as effectively as the base-induced decomposition (BID) in an aprotic Polar Solvent. SPD caused intramolecular CT-induced chemiluminescence similar to BID, but, in contrast to BID, SPD proceeded through a pathway with a large negative entropy of activation. Dioxetane 1 was also shown to give light due to excited state intramolecular proton transfer (ESIPT) upon heating in p-xylene.

Masatoshi Tanimura - One of the best experts on this subject based on the ideXlab platform.

  • intramolecular charge transfer induced decomposition promoted by an aprotic Polar Solvent for bicyclic dioxetanes bearing a 4 benzothiazol 2 yl 3 hydroxyphenyl moiety
    Journal of Organic Chemistry, 2011
    Co-Authors: Masatoshi Tanimura, Nobuko Watanabe, Hisako K Ijuin, Masakatsu Matsumoto
    Abstract:

    Bicyclic dioxetanes 3a−d bearing a 4-(benzothiazol-2-yl)-3-hydroxyphenyl group decomposed to give the corresponding keto esters 4a−d accompanied by the emission of bright light when simply dissolved in an aprotic Polar Solvent such as N-methylpyrrolidone (NMP) or DMF at 50−100 °C. This Solvent-promoted decomposition (SPD) was effectively a chemiluminescence process caused by the hydrogen bonding of a phenolic OH with a Solvent molecule(s). The characteristics of the chemiluminescence in SPD resembled those in base-induced decomposition (BID), which occurs through an oxidoaryl-substituted dioxetane 5 by an intramolecular charge-transfer-induced decomposition (CTID) mechanism. Both free energies of activation, ΔG⧧SPD and ΔG⧧BID, increased in the order 3a < 3b < 3c < 3d, and were linearly correlated with each other. However, SPD showed features different from those of BID in terms of enthalpy of activation and entropy of activation. SPD had large negative values for ΔS⧧ (ca. −71 J mol−1 K−1) regardless of th...

  • Solvent promoted chemiluminescent decomposition of a bicyclic dioxetane bearing a 4 benzothiazol 2 yl 3 hydroxyphenyl moiety
    Tetrahedron Letters, 2008
    Co-Authors: Masakatsu Matsumoto, Masatoshi Tanimura, Nobuko Watanabe, Taichi Akimoto, Hisako K Ijuin
    Abstract:

    An aprotic Polar Solvent such as N-methylpyrrolidone (NMP) promoted the thermal decomposition of bicyclic dioxetane bearing a 4-(benzothiazol-2-yl)-3-hydroxyphenyl moiety 1 without the addition of any base. This Solvent-promoted decomposition (SPD) gave light as effectively as the base-induced decomposition (BID) in an aprotic Polar Solvent. SPD caused intramolecular CT-induced chemiluminescence similar to BID, but, in contrast to BID, SPD proceeded through a pathway with a large negative entropy of activation. Dioxetane 1 was also shown to give light due to excited state intramolecular proton transfer (ESIPT) upon heating in p-xylene.

Jiamin Shieh - One of the best experts on this subject based on the ideXlab platform.

Nobuko Watanabe - One of the best experts on this subject based on the ideXlab platform.

  • intramolecular charge transfer induced decomposition promoted by an aprotic Polar Solvent for bicyclic dioxetanes bearing a 4 benzothiazol 2 yl 3 hydroxyphenyl moiety
    Journal of Organic Chemistry, 2011
    Co-Authors: Masatoshi Tanimura, Nobuko Watanabe, Hisako K Ijuin, Masakatsu Matsumoto
    Abstract:

    Bicyclic dioxetanes 3a−d bearing a 4-(benzothiazol-2-yl)-3-hydroxyphenyl group decomposed to give the corresponding keto esters 4a−d accompanied by the emission of bright light when simply dissolved in an aprotic Polar Solvent such as N-methylpyrrolidone (NMP) or DMF at 50−100 °C. This Solvent-promoted decomposition (SPD) was effectively a chemiluminescence process caused by the hydrogen bonding of a phenolic OH with a Solvent molecule(s). The characteristics of the chemiluminescence in SPD resembled those in base-induced decomposition (BID), which occurs through an oxidoaryl-substituted dioxetane 5 by an intramolecular charge-transfer-induced decomposition (CTID) mechanism. Both free energies of activation, ΔG⧧SPD and ΔG⧧BID, increased in the order 3a < 3b < 3c < 3d, and were linearly correlated with each other. However, SPD showed features different from those of BID in terms of enthalpy of activation and entropy of activation. SPD had large negative values for ΔS⧧ (ca. −71 J mol−1 K−1) regardless of th...

  • Solvent promoted chemiluminescent decomposition of a bicyclic dioxetane bearing a 4 benzothiazol 2 yl 3 hydroxyphenyl moiety
    Tetrahedron Letters, 2008
    Co-Authors: Masakatsu Matsumoto, Masatoshi Tanimura, Nobuko Watanabe, Taichi Akimoto, Hisako K Ijuin
    Abstract:

    An aprotic Polar Solvent such as N-methylpyrrolidone (NMP) promoted the thermal decomposition of bicyclic dioxetane bearing a 4-(benzothiazol-2-yl)-3-hydroxyphenyl moiety 1 without the addition of any base. This Solvent-promoted decomposition (SPD) gave light as effectively as the base-induced decomposition (BID) in an aprotic Polar Solvent. SPD caused intramolecular CT-induced chemiluminescence similar to BID, but, in contrast to BID, SPD proceeded through a pathway with a large negative entropy of activation. Dioxetane 1 was also shown to give light due to excited state intramolecular proton transfer (ESIPT) upon heating in p-xylene.