Photocycloaddition of thiocarbonyl compounds to olefins. Reaction of thiobenzophenone with various types of olefins. V.

Ohno, Atsuyoshi; Ohnishi, Yutaka; Tsuchihashi, Gen-ichi

doi:10.1021/ja01046a018

Cited by 62 publications

(24 citation statements)

References 2 publications

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“…Four substances, numbered according to ease of elution on chromatographic separation, were obtained. This contrasts with the irradiation at shorter wavelength, reported [6] to give XVIII in very high yield, an observation which we have confirmed.…”

Section: Acrylonitrilecontrasting

confidence: 55%

“…Of the eight substituted olefines listed, the slowest regeneration was observed for acrylonitrile, which also gave a high percentage of such regeneration. Acrylonitrile is, under the Tsuchihashi -Ohno nomenclature, a Type ii olefine, i.e., it has an electron-withdrawing substituent, and was, in fact, one of the substances studied by these workers [6]. We were therefore surprised to observe that reaction with thiobenzophenone did occur, not only at wavelengths from 300 nm upwards, but also from 500 nm upwards: that is from both 'IT, 'IT* and n, 'IT* excitation.…”

Section: Tetramethylethylenementioning

confidence: 99%

“…This was followed, in 1962, by the description of both the photochemical oxidation and reduction of thiobenzophenone. This work, by Oster, Citarel and Goodman [2] ,contained, in addition, the first report However, the distinction between Classes i and iii as defined is indistinct since these authors have shown that there is concentration dependence: when the concentration of the thiobenzophenone was lowered in reaction with styrene (Class i) it exhibited Class iii behaviour [6]. This latter particular distinction has been supposed to be steric.…”

Section: Introductionmentioning

confidence: 99%

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Thione Photochemistry: On Thiobenzophenone Photoannelation

Mayo

Nicholson

1972

Israel Journal of Chemistry

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The photochemistry of the reaction of thiobenzophenone with acrylonitrile, following excitation into both the n, π* and π, π* absorption bands, has been examined. The products obtained are different, indicating dual mechanisms. It has been shown that the thietane is not a primary product, but is the result of thermal decomposition of a 1,3‐dithiane which can be isolated at low temperatures. This is the main product at the shorter wavelengths, but at longer wavelengths a 1,4‐dithiane and a thiatetrahydronaphthalene are obtained. A disulphide is also produced as a result of a secondary photochemical attack of thiobenzophenone on the thietane. The mechanistic implications of these results are discussed.

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Section: Acrylonitrilecontrasting

confidence: 55%

Section: Tetramethylethylenementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Thione Photochemistry: On Thiobenzophenone Photoannelation

Mayo

Nicholson

1972

Israel Journal of Chemistry

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“…[7] Cycloaddition and photoreaction of thiobenzophenone with 2a gave benzothiopyran derivatives. [8,9] To the best of our knowledge, however, there is no report on the formation of 3, thiodioxenone, through the reaction between thiones and propiolic acid in a [4ϩ2] manner.…”

Section: Resultsmentioning

confidence: 99%

First Isolation of Thione‐Propiolic Acid Adducts − Synthesis of Thiodioxenones

et al. 2003

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Treatment of adamantane‐2‐thione (1a) with propiolic acid (2a) afforded a novel type of cycloadduct, spiro[adamantane‐2,2′‐[1,3]oxathiin]‐6‐one (3a), in quantitative yield. The reaction proceeds through a concerted process, as was confirmed by kinetic analysis. Treatment of 1a with butynoic acid or phenylpropiolic acid gave the corresponding adducts regioselectively. Interestingly, only one isomer was obtained by treatment of thiofenchone with propiolic acid, suggesting that the reaction proceeded stereospecifically. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

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“…The generally high ground state reactivity of these substances has hampered their investigation however and, to the present, substantial work has been done only on the most stable thiones. Thus, studies have been made of the thermal (1, 2) and photochemical (3)(4)(5)(6) cycloaddition reactions of thiocarbonyls, particularly thiobenzophenone, the internal photocyclization of aromatic thiobenzoyl compounds (7), and the photothioenolization of some bicyclic thiones (8). Measurement of the electronic absorption (9. 10) and emission (3,11) spectra of only a limited number of thiones and thials in condensed media has been possible.…”

Section: Introductionmentioning

confidence: 99%

Photolysis of Thietane–Cyclopentadiene Mixtures. Reactions of Monomeric Thioformaldehyde

Dice¹,

Steer²

1974

Can. J. Chem.

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. Can. J. Chem. 52,3518 (1974) The 313 nm photolysis of thietane-cyclopentadiene mixtures in the vapor phase at temperatures between 25 and 235 "C has been studied. 2-Thiabicyclo[2.2.1]hept-5-ene (TBH) results from the concerted, thermal, 1,4-Diels-Alder cycloaddition of thioformaldehyde to cyclopentadiene. Other products arise via nonconcerted processes involving biradical intermediates. Thioformaldehyde is scavenged quantitatively with high added pressures of cyclopentadiene and thus the yield of TBH may be used as a measure of the amount of monomeric CH2S produced in the system. DAVID R. DICE et RONALD P. STEER. Can. J. Chem. 52,3518 (1974). On a CtudiC la photolyse, a 313 nm en phase vapeur et ii des temperatures allant de 25 a 235 *C, de melanges de thietane avec du cyclopentadiene. Le thia-2 bicyclo[2.2.1]hept8ne-5 (TBH) qui se forme resulte d'une reaction Diels-Alder-1,4 (cycloaddition concertee et thermique) du thioformaldehyde sur le cyclopentadiene. D'autres produits proviennent de processus nonconcertes impliquant des intermidiaires biradicalaires. Le thioforn~aldChyde est piege quantitativement lorsque du cyclopentadiene sous haute pression est utillsk; les rendements en TBH obtenu peuvent donc etre utilises comme une mesure de la quant~te de CH,S, sous forme monomerique, produite dans le systeme.[Traduit par le journal]

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Photocycloaddition of thiocarbonyl compounds to olefins. Reaction of thiobenzophenone with various types of olefins. V.

Cited by 62 publications

References 2 publications

Thione Photochemistry: On Thiobenzophenone Photoannelation

Thione Photochemistry: On Thiobenzophenone Photoannelation

First Isolation of Thione‐Propiolic Acid Adducts − Synthesis of Thiodioxenones

Photolysis of Thietane–Cyclopentadiene Mixtures. Reactions of Monomeric Thioformaldehyde

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