One-electron photooxidation of N-ethylcarbazole in the presence of carbon tetrachloride. Products and mechanism of the photochemical reaction

1985 ◽  
Vol 63 (7) ◽  
pp. 1654-1665 ◽  
Author(s):  
Bogumil Zelent ◽  
Gilles Durocher
Keyword(s):  
Carbon Tetrachloride ◽  
Photochemical Reaction ◽  
Reaction Medium ◽  
Chloride Ion ◽  
Photochemical Reactions ◽  
The Other ◽  
Main Process ◽  
Reaction Products ◽  
Solvent Cage ◽  
Ct Complex

The mechanism of the photodecomposition of N-ethylcarbazole (NEC) in the presence of carbon tetrachloride has been discussed on the basis of the photoproducts identified. The photodissociation of the N-ethyl bond and the electron transfer in the transiently formed ex-CT complex, [Formula: see text], have been proposed as the primary photochemical processes involved irr the singlet excited NEC molecule. The latter, treated as the main process, leads to the radical cation of NEC, chloride ion, and trichloromethyl radical in the solvent cage, [NEC+•Cl−ĊCl3]. The other reactions in the system studied are analysed following the decomposition of NEC+• in the presence of Cl− and ĊCl3, which can occur by the N-ethyl group and (or) by the aromatic ring. The formation of intermediate products such as[Formula: see text]in the solvent cage gives rise to secondary photochemical reactions in the system studied. The polarity and chemical activity of the reaction media used strongly influence the nature of the secondary photochemical transformations both in and outside the solvent cage. The formation mechanism of the photochemical reaction products in CCl4 when ammonia was used, after and during irradiation, has been explained mainly by the transformations of the radical αr and cation αk as well as by the carbazyl radical β, which is also formed in the reaction medium. On the other hand, reaction of the cation [Formula: see text] explains the formation of the photoproducts in the irradiated solution of NEC with CCl4 in ethanol. These photochemical results have been compared to the photochemical reactions involved in the carbazole–CCl4 system.

One-electron photooxidation of carbazole in the presence of carbon tetrachloride. Part I. Carbon tetrachloride and ethanol used as reaction media

1982 ◽  
Vol 60 (8) ◽  
pp. 945-956 ◽  
Author(s):  
Bogumil Zelent ◽  
Gilles Durocher
Keyword(s):  
Electron Transfer ◽  
Carbon Tetrachloride ◽  
Photochemical Reaction ◽  
Ethanol Solution ◽  
Photochemical Reactions ◽  
Reaction Products ◽  
Solvent Cage ◽  
Ct Complex ◽  
Heterolytic Dissociation ◽  
Reaction Media

The photochemical reaction products of carbazole with carbon tetrachloride in ethanol have been isolated and identified along with photoproducts in the irradiated solution of carbazole in pure CCl4 using water and ethanol added after the irradiation. This allowed us to discuss the complex mechanism of secondary photochemical changes in the carbazole–CCl4 system. We propose that the electron transfer from carbazole to CCl4 molecule in the excited CT complex, [Formula: see text] is the primary photochemical reaction followed by an heterolytic dissociation of a C—Cl bond which gives rise to the primary photoproducts in the solvent cage [C+•Cl−ĊCl3]. Secondary photochemical reactions initiate transformation of the radical cation of carbazole in the solvent cage giving rise to the following intermediate species:[Formula: see text]The probability of formation and further transformations of these Transient products: α, β, and γi, depends strongly on the nature of the reaction media. Thermodynamically stable products are formed depending on the reaction media; (carboethoxy)carbazoles, (carbo-N-carbazyl)carbazoles, and carbazole – carboxylic acids can serve as a proof for the formation of the above listed intermediates. All the results reported on the secondary photochemical reactions strongly support the electron-transfer primary mechanism used to explain the fluorescence quenching of carbazole by CCl4.These results also explain the changes observed in the fluorescence spectrum of carbazole when the ethanol solution of carbazole in the presence of CCl4 is irradiated.

One-electron photooxidation of carbazole in the presence of carbon tetrachloride. Part II. Carbon tetrachloride as a reaction medium. Use of ammonia after irradiation and during irradiation

1982 ◽  
Vol 60 (19) ◽  
pp. 2442-2450 ◽  
Author(s):  
Bogumil Zelent ◽  
Gilles Durocher
Keyword(s):  
Carbon Tetrachloride ◽  
Photochemical Reaction ◽  
Reaction Medium ◽  
Radical Cations ◽  
Mechanism Of Formation ◽  
Ammonia Gas ◽  
Solvent Cage ◽  
Determining Factors ◽  
Primary Photochemical Reaction ◽  
Reaction Media

In part I of this series of papers we proposed the mechanism of electron transfer as the primary photochemical reaction in the carbazole – carbon tetrachloride system along with a secondary photochemical reaction initiated by transformations of the radical cation of carbazole in the solvent cage resulting in intermediates:[Formula: see text]In this paper we discuss the influence of ammonia, used after and during irradiation, on the mechanism of secondary transformation and the formation of thermodynamically stable products in the system studied. Such compounds as N-cyanocarbazole, 1-cyanocarbazole, and 3-cyanocarbazole have been formed as the main products during neutralization of the photolyte solution by ammonia gas. The mechanism of formation of these compounds has been explained by the chemical reaction of ammonia with cations α and γi. If ammonia is present in the solution of carbazole in CCl4 during irradiation, such products as N,N′-dicarbazyl and N-cyanocarbazole are mainly formed along with 3-(N-carbazyl)carbazole, 3,9-di-(N-carbazyl)carbazole, and N-cyano-3-(N-carbazyl)carbazole. In such a case, reactions of radicals β are the determining factors in the secondary photochemical transformations. Radicals β are formed by the reaction involving ammonia with radical cations of carbazole. All the results in this paper have been discussed taking under consideration the influence of the reaction media on the mechanism of photochemical transformation of carbazole.

scholarly journals Sunscreen-Assisted Selective Photochemical Transformations

Molecules ◽  
2020 ◽  
Vol 25 (9) ◽  
pp. 2125
Author(s):  
Or Eivgi ◽  
N. Gabriel Lemcoff
Keyword(s):  
Photochemical Reaction ◽  
Reaction Pathway ◽  
General Procedure ◽  
Molar Absorptivity ◽  
Photochemical Reactions ◽  
The Other ◽  
Protecting Group ◽  
Selective Reaction ◽  
Photochemical Transformations ◽  
Photolabile Protecting Group

In this review, we describe a simple and general procedure to accomplish selective photochemical reaction sequences for two chromophores that are responsive to similar light frequencies. The essence of the method is based on the exploitation of differences in the molar absorptivity at certain wavelengths of the photosensitive groups, which is enhanced by utilizing light-absorbing auxiliary filter molecules, or “sunscreens”. Thus, the filter molecule hinders the reaction pathway of the least absorbing molecule or group, allowing for the selective reaction of the other. The method was applied to various photochemical reactions, from photolabile protecting group removal to catalytic photoinduced olefin metathesis in different wavelengths and using different sunscreen molecules. Additionally, the sunscreens were shown to be effective also when applied externally to the reaction mixture, avoiding any potential chemical interactions between sunscreen and substrates and circumventing the need to remove the light-filtering molecules from the reaction mixture, adding to the simplicity and generality of the method.

scholarly journals Laser-Induced Photochemical Reaction of Maleic Acid Solutions in the Presence of Hydrogen Peroxide

1997 ◽  
Vol 17 (2) ◽  
pp. 97-108 ◽  
Author(s):  
Yuichi Shimizu ◽  
Shun'ichi Sugimoto ◽  
Shunichi Kawanishi ◽  
Nobutake Suzuki
Keyword(s):  
Hydrogen Peroxide ◽  
Maleic Acid ◽  
Photochemical Reaction ◽  
Room Temperature ◽  
Direct Synthesis ◽  
Reaction Scheme ◽  
Photochemical Reactions ◽  
The Other ◽  
Acid Solutions ◽  
Selective Formation

Targeting the selective and direct synthesis of tartaric acid (TA), the photochemical reactions of maleic acid (MA) solutions containing H2O2. in various solvents have been investigated using four wavelengths in the UV region between 193 and 351 nm, with high intensity from an excimer laser. All the laser irradiations in H2O resulted in the direct synthesis of TA with lower selectivity and it was found that, with XeF-laser (351 nm) irradiation in 1,4-dioxane, TA is selectively and directly synthesized from MA containing H2O2 of lower concentration at room temperature. On the other hand, none of the irradiations in methanol, N,N-dimethylformamide, acetonitrile, and tetrahydrofuran gave the selective formation of TA. On the basis of these results, the reaction scheme for the selective formation of TA is discussed.

Photochemical Reactions of Bromoanthracenes with N,N-Dimethylaniline in Solution

1981 ◽  
Vol 36 (7) ◽  
pp. 846-851 ◽  
Author(s):  
Jan Fulara ◽  
Tadeusz Latowski
Keyword(s):  
Photochemical Reaction ◽  
Photochemical Reactions ◽  
Medium Effect ◽  
Reaction Products ◽  
Photochemical Transformations

AbstractMajor products of the photolysis of 9-bromoanthracene and 9,10-dibromoanthracene in benzene and acetonitrile as well as photochemical reaction products of the two bromoanthracenes with N,N-dimethylaniline in these solvents have been isolated and identified. The mechanisms of partial reactions are discussed and attention is paid to the medium effect on the photochemical transformations.

Photochemical reactions of bacteriorhodopsin in Triton X-100 solution studied by low temperature spectrophotometry

1985 ◽  
Vol 63 (7) ◽  
pp. 1891-1898 ◽  
Author(s):  
Tatsuo Iwasa ◽  
Fumio Tokunaga ◽  
Tỏru Yoshizawa
Keyword(s):  
Low Temperature ◽  
Thermal Equilibrium ◽  
Photochemical Reaction ◽  
Membrane Structure ◽  
Purple Membrane ◽  
Photochemical Reactions ◽  
The Other ◽  
Other Hand ◽  
Triton X

The photochemical reaction of purple membrane solubilized with Triton X-100 (T-BR) was investigated by low temperature spectrophotometry. The batho- and meta-intermediates of T-BR were observed to resemble bacteriorhodopsin in native purple membrane. Two photoproducts characteristic of the T-BR system were found, which were named the "490-nm complex" and the "380-nm complex". The 490-nm complex was in thermal equilibrium with T-BR in the dark. Cooling T-BR to low temperature favoured the 490-nm complex, which was photoinsensitive. On the other hand, the 380-nm complex was produced by warming the batho-intermediate and reverted to the original T-BR. The meta-intermediate of T-BR may possibly be in thermal equilibrium with the 380-nm complex. On the basis of the above results, the possible role of the membrane structure was discussed

Paraquat (Methylviologen): Its Interference with Primary Photochemical Reactions

1993 ◽  
Vol 48 (3-4) ◽  
pp. 374-378 ◽  
Author(s):  
Tetsuo Hiyama ◽  
Akira Ohinata ◽  
Shin-ichi Kobayashi
Keyword(s):  
Reaction Center ◽  
Electron Donor ◽  
Photosystem I ◽  
Photochemical Reaction ◽  
Photochemical Reactions ◽  
The Other ◽  
Primary Photochemical Reaction

Paraquat(methylviologen), a widely used nonspecific herbicide, is ptoreduced in the primary photochemical reaction of photosystemI. Using two types of the photosystem I reaction center preparations, i.e. one with FeSA/FeSB and the other without, the immediate electron donor to methylviologen was determined to be FeSx (P430) rather than FeSA/FeSB.

Mutagenicity assays of photochemical reaction products of biphenyl (BP) and o-phenylphenol (OPP) with NOx

Chemosphere ◽  
1981 ◽  
Vol 10 (2) ◽  
pp. 223-228 ◽  
Author(s):  
Teruhisa Hirayama ◽  
Motoshi Nohara ◽  
Hirohiko Shindo ◽  
Shozo Fukui
Keyword(s):  
Photochemical Reaction ◽  
Reaction Products

scholarly journals Control of the setting reaction and strength development of slag-blended volcanic ash-based phosphate geopolymer with the addition of boric acid

2021 ◽  
Author(s):  
Jean Noël Yankwa Djobo ◽  
Dietmar Stephan
Keyword(s):  
Blast Furnace ◽  
Boric Acid ◽  
Blast Furnace Slag ◽  
Volcanic Ash ◽  
Strength Development ◽  
Main Process ◽  
Reaction Products ◽  
Setting Times ◽  
Granulated Blast Furnace Slag ◽  
Furnace Slag

AbstractThis work aimed to evaluate the role of the addition of blast furnace slag for the formation of reaction products and the strength development of volcanic ash-based phosphate geopolymer. Volcanic ash was replaced by 4 and 6 wt% of ground granulated blast furnace slag to accelerate the reaction kinetics. Then, the influence of boric acid for controlling the setting and kinetics reactions was also evaluated. The results demonstrated that the competition between the dissolution of boric acid and volcanic ash-slag particles is the main process controlling the setting and kinetics reaction. The addition of slag has significantly accelerated the initial and final setting times, whereas the addition of boric acid was beneficial for delaying the setting times. Consequently, it also enhanced the flowability of the paste. The compressive strength increased significantly with the addition of slag, and the optimum replaced rate was 4 wt% which resulted in 28 d strength of 27 MPa. Beyond that percentage, the strength was reduced because of the flash setting of the binder which does not allow a subsequent dissolution of the particles and their precipitation. The binders formed with the addition of slag and/or boric acid are beneficial for the improvement of the water stability of the volcanic ash-based phosphate geopolymer.

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