Chemistry of singlet oxygen. 47. 9,10-Dicyanoanthracene-sensitized photooxygenation of alkyl-substituted olefins

Araki, Yasunori; Dobrowolski, Diane C.; Goyne, Thomas; Hanson, Douglas C.; Jiang, Zhi Qin; Lee, Kenneth J.; Foote, Christopher S.

doi:10.1021/ja00328a045

Cited by 55 publications

(26 citation statements)

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“…This means that reaction sequences (10) and (11) do not contribute to the ene-product formation from 1 and 4. (For similar observations with simple alkyl-substituted olefins, see Araki et al, 1984 andAlbini andSpreti, 1985).…”

mentioning

confidence: 59%

9, 10‐DICYANOANTHRACENE‐SENSITIZED PHOTOOXYGENATION OF Α,α′‐DIMETHYLSTILBENES. MECHANISM AND KINETICS OF THE COMPETING SINGLET OXYGEN AND ELECTRON TRANSFER PHOTOOXYGENATION REACTIONS

Gollnick¹,

Schnatterer²

1986

Photochem & Photobiology

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Abstract— The 9, lodicyanoanthracene‐sensitized photooxygenation of 2‐methyl‐2‐butene and (+)‐limonene proceeds via the singlet oxygen pathway in carbon tetrachloride as well as in acetonitrile, although the fluorescence of the sensitizer in acetonitrile is quenched by these olefins in an electron transfer quenching mechanism. The 9, 10‐dicyanoanthracene‐sensitized photooxygenation of cis‐ and trans‐ä, ä′‐dimethylstilbenes occurs exclusively via the singlet oxygen pathway in carbon tetrachloride; in acetonitrile, however, singlet oxygen and electron transfer photooxygenation reactions compete with one another. Addition of tetra‐n‐butyl ammonium bromide and increasing oxygen concentrations favor the formation of the singlet oxygen product, whereas addition of anisole, increasing substrate concentrations and decreasing oxygen concentrations favor the electron transfer photooxygenation products. In carbon tetrachloride, exciplexes of the sensitizer and the dimethylstilbenes are formed which give rise to cidrrans‐isomerization of the substrates. In acetonitrile, neither exciplex formation nor cisltrans‐isomerization are observed. A mechanism is proposed which allows us to calculate product distributions of the competing singlet oxygen/electron transfer photooxygenation reactions and thus to determine the efficiencies with which encounters between the singlet excited sensitizer and the substrates finally result in electron transfer photooxygenation products. Using (I) these efficiencies, (2) the β‐value obtained from singlet oxygen photooxygenation sensitized by rose bengal, and (3) the appropriate k‐values determined from fluorescence quenching of 9, 10‐dicyanoanthracene in MeCN by oxygen and the stilbene, allows the calculation of the quantum yield of oxygen consumption by this stilbene. The quantum yield thus calculated is strictly proportional to the rate of oxygen consumption experimentally obtained; this result is considered as convincing evidence for the mechanism proposed.

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mentioning

confidence: 59%

9, 10‐DICYANOANTHRACENE‐SENSITIZED PHOTOOXYGENATION OF Α,α′‐DIMETHYLSTILBENES. MECHANISM AND KINETICS OF THE COMPETING SINGLET OXYGEN AND ELECTRON TRANSFER PHOTOOXYGENATION REACTIONS

Gollnick¹,

Schnatterer²

1986

Photochem & Photobiology

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“…In light of these experimental data, it seems rather strange that the kinetics of DCA fluorescence quenching are consistent with an electron-transfer process [207]. Several possible explanations can be advanced for the apparent lack of radical ion chemistry in this system.…”

Section: (43)mentioning

confidence: 79%

“…(43), seems to be the major mechanistic pathway for singlet oxygen production. Cyanoaromatic-sensitized photooxygenation of single olefins, such as 1-methylcyclohexene, 90, 1,2-dimethylcydohexene, 91, cholesterol, 92, and several others [119], afford complex reaction mixtures, indistinguishable from those obtained in the singlet oxygenations of the same substrates [207] (Scheme 15).…”

Section: (43)mentioning

confidence: 99%

Photoinduced electron transfer oxygenations

Lopez

1990

Topics in Current Chemistry

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“…The participation of OT, which was proposed by Foote et al for the photooxygenation of trans-stilbene (Eriksen et al, 1977(Eriksen et al, , 1980Lewis et al, 1985;Goodson and Schuster, 1984) (Scheme 2) cannot be ruled out at present but seems to be unlikely, because the dependence of the selectivity on added Mg(C104)* cannot be explained on the basis of this assumption (see below). Participation of singlet oxygen is also unlikely, although Araki et al (1984) reported the generation of lo2 in the DCA-sensitized photooxygenation (Scheme 2 ) . In fact, the methyleneblue sensitized photooxygenation of l a in CHzClz under O2 did not give any oxidation products, and l a was recovered unchanged.…”

Section: Mechanistic Pathways Of the Photooxygenationmentioning

confidence: 99%

PHOTOOXYGENATION OF BIPHENYL AND ITS DERIVATIVES via PHOTOINDUCED ELECTRON TRANSFER: EFFECT OF Mg(CIO₄)₂ ON PHOTOOXYGENATION

Tamai

Mizuno

Hashida

et al. 1991

Photochem & Photobiology

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The 9,10‐dicyanoanthracene (DCA)‐sensitized photooxygenation of biphenyl derivatives in the presence of Mg(CIO4)2 in acetonitrile produces benzoic acid and its derivatives in high yields. In the absence of Mg(CIO4)2, the rates for the consumption of biphenyl derivatives decrease by a factor of 0.5‐0.8, compared with those in the presence of Mg(CIO4)2. In these cases, however, both biphenyls and DCA are oxygenated to give benzoic acids and anthraquinone, respectively, indicating that the addition of Mg(CIO4)2 retards the photooxygenation of DCA. With 4‐methylbiphenyl, the photooxygenation proceeds efficiently without added Mg(CIO4)2, and benzene rings and methyl groups are competitively oxygenated to give benzoic acid, 4‐methylbenzoic acid, 4‐phenylbenzoic acid, and 4‐phenylbenzaldehyde. The addition of Mg(CIO4)2 facilitates the oxidation of benzene rings, giving benzoic acid and 4‐methylbenzoic acid as major products. These photooxygenations are initiated by a one‐electron transfer from biphenyls to the excited singlet DCA and proceed via the radical cations of biphenyls and the radical anion of DCA.

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Chemistry of singlet oxygen. 47. 9,10-Dicyanoanthracene-sensitized photooxygenation of alkyl-substituted olefins

Cited by 55 publications

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9, 10‐DICYANOANTHRACENE‐SENSITIZED PHOTOOXYGENATION OF Α,α′‐DIMETHYLSTILBENES. MECHANISM AND KINETICS OF THE COMPETING SINGLET OXYGEN AND ELECTRON TRANSFER PHOTOOXYGENATION REACTIONS

9, 10‐DICYANOANTHRACENE‐SENSITIZED PHOTOOXYGENATION OF Α,α′‐DIMETHYLSTILBENES. MECHANISM AND KINETICS OF THE COMPETING SINGLET OXYGEN AND ELECTRON TRANSFER PHOTOOXYGENATION REACTIONS

Photoinduced electron transfer oxygenations

PHOTOOXYGENATION OF BIPHENYL AND ITS DERIVATIVES via PHOTOINDUCED ELECTRON TRANSFER: EFFECT OF Mg(CIO₄)₂ ON PHOTOOXYGENATION

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Chemistry of singlet oxygen. 47. 9,10-Dicyanoanthracene-sensitized photooxygenation of alkyl-substituted olefins

Cited by 55 publications

References 0 publications

9, 10‐DICYANOANTHRACENE‐SENSITIZED PHOTOOXYGENATION OF Α,α′‐DIMETHYLSTILBENES. MECHANISM AND KINETICS OF THE COMPETING SINGLET OXYGEN AND ELECTRON TRANSFER PHOTOOXYGENATION REACTIONS

9, 10‐DICYANOANTHRACENE‐SENSITIZED PHOTOOXYGENATION OF Α,α′‐DIMETHYLSTILBENES. MECHANISM AND KINETICS OF THE COMPETING SINGLET OXYGEN AND ELECTRON TRANSFER PHOTOOXYGENATION REACTIONS

Photoinduced electron transfer oxygenations

PHOTOOXYGENATION OF BIPHENYL AND ITS DERIVATIVES via PHOTOINDUCED ELECTRON TRANSFER: EFFECT OF Mg(CIO4)2 ON PHOTOOXYGENATION

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PHOTOOXYGENATION OF BIPHENYL AND ITS DERIVATIVES via PHOTOINDUCED ELECTRON TRANSFER: EFFECT OF Mg(CIO₄)₂ ON PHOTOOXYGENATION