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Yicheng Zhang - One of the best experts on this subject based on the ideXlab platform.

Pinhua Li - One of the best experts on this subject based on the ideXlab platform.

Stojan Stavber - One of the best experts on this subject based on the ideXlab platform.

  • Lodination of Organic Compounds Using the Reagent System Ι2-30% aq. H2O2 under Organic Solvent-Free Reaction Conditions
    Acta Chimica Slovenica, 2020
    Co-Authors: Jasminka Pavlinac, Marko Zupan, Stojan Stavber
    Abstract:

    Lodine was efficiently introduced into the methoxy substituted aromatic compounds, acetophenone, 1-indanone and 1-tetralone using the elemental iodine / 30% aq. H 2 O 2 system under organic Solvent-Free Reaction conditions (SFRC) and two types of iodo-functionalisation through an electrophilic process were observed. Iodination of the aromatic ring in the case of dimethoxy- and trimethoxy benzenes took place, while aryl alkyl ketones were regioselectively iodinated at the alkyl position next to a carbonyl group. Based on the ratio of substrate : I 2 : H 2 O 2 required for the most efficient iodo-transformation, two different roles of H 2 O 2 in the Reaction route can be distinguished. Different forms of H 2 O 2 as mediators of iodination, namely 30% aq. H 2 O 2 and two solid forms urea-H 2 O 2 and sodium percarbonate (2Na 2 CO 3 . 3H 2 O 2 ), were comparatively evaluated in terms of efficiency under SFRC. Reactions using 30% aq. H 2 O 2 as the mediator of iodination under SFRC were compared with those performed in water as Reaction medium.

  • direct halogenation of alcohols with halosilanes under catalyst and organic Solvent Free Reaction conditions
    Tetrahedron Letters, 2016
    Co-Authors: Njomza Ajvazi, Stojan Stavber
    Abstract:

    Abstract A chemoselective method for the direct halogenation of different types of alcohols with halosilanes under catalyst- and Solvent-Free Reaction conditions (SFRC) is reported. Various primary, secondary and tertiary benzyl alcohols and tertiary alkyl alcohols were directly transformed to the corresponding benzyl and alkyl halides, respectively, using chlorotrimethylsilane (TMSCl) and bromotrimethylsilane (TMSBr).

  • Towards Greener Fluorine Organic Chemistry: Direct Electrophilic Fluorination of Carbonyl Compounds in Water and Under Solvent-Free Reaction Conditions
    Advanced Synthesis & Catalysis, 2010
    Co-Authors: Gaj Stavber, Stojan Stavber
    Abstract:

    Selective and efficient fluorination of organic 1,3-dicarbonyl compounds was achieved using the electrophilic fluorinating reagents Selectfluor ™ F-TEDA-BF 4 (1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis-tetrafluoroborate) in aqueous medium or Accufluor ™ NFSi (N-fluorobenzene-sulfonimide) under Solvent-Free Reaction conditions (SFRC). Under both Reaction conditions cyclic 1,3-dicarbonyl compounds were transformed into 2-fluoro-substituted derivatives and acyclic analogues into 2,2-difluoro-substituted compounds, while the Reactions of 1-trifluoromethyl-substituted 1,3-dicarbonyls in water resulted in the formation of 2,2-difluoro-3,3-dihydroxy-1-one derivatives. The reactivity of the starting material in water was found to be dependent on its enolizability, hydrophobic interactions and aggregate state at the Reaction temperature. Reactions under SFRC proceeded in the molten eutectic phase of the reactants. The technique of competitive reactivity was used in order to evaluate and better understand the effects of Reaction conditions on the course of these Reactions.

  • visible light promoted wohl ziegler functionalization of organic molecules with n bromosuccinimide under Solvent Free Reaction conditions
    Helvetica Chimica Acta, 2009
    Co-Authors: Marjan Jereb, Marko Zupan, Stojan Stavber
    Abstract:

    The visible-light-induced transformation of toluenes with N-bromosuccinimide (NBS) under Solvent-Free Reaction conditions (SFRC) was studied. The Reaction took place in spite of the very restricted molecular motion; toluenes could be regioselectively converted to benzyl bromides. Selective radical-chain Reactions with NBS were carried out in liquid/liquid and in solid/solid systems; furthermore, Reactions could be performed in the presence of air. The radical scavenger TEMPO (=2,2,6,6-tetramethylpiperidin-1-yloxy) completely suppressed the side-chain bromination of toluenes with NBS under SFRC. Electron-withdrawing groups decreased the reactivity of the toluenes, and the Hammett Reaction constant ρ+=−1.7 indicated involvement of polar radical intermediates with electrophilic character.

  • Visible‐Light‐Promoted Wohl–Ziegler Functionalization of Organic Molecules with N‐Bromosuccinimide under SolventFree Reaction Conditions
    Helvetica Chimica Acta, 2009
    Co-Authors: Marjan Jereb, Marko Zupan, Stojan Stavber
    Abstract:

    The visible-light-induced transformation of toluenes with N-bromosuccinimide (NBS) under Solvent-Free Reaction conditions (SFRC) was studied. The Reaction took place in spite of the very restricted molecular motion; toluenes could be regioselectively converted to benzyl bromides. Selective radical-chain Reactions with NBS were carried out in liquid/liquid and in solid/solid systems; furthermore, Reactions could be performed in the presence of air. The radical scavenger TEMPO (=2,2,6,6-tetramethylpiperidin-1-yloxy) completely suppressed the side-chain bromination of toluenes with NBS under SFRC. Electron-withdrawing groups decreased the reactivity of the toluenes, and the Hammett Reaction constant ρ+=−1.7 indicated involvement of polar radical intermediates with electrophilic character.

Lei Wang - One of the best experts on this subject based on the ideXlab platform.

Marjan Jereb - One of the best experts on this subject based on the ideXlab platform.

  • Chemistry of Organo Halogenic Molecules. Part 229. The Role of Iodine in Acetyl Group Transfer to Oxygen-containing Molecules under Solvent-Free Reaction Conditions
    Acta Chimica Slovenica, 2020
    Co-Authors: Marjan Jereb, Dejan Vrazic, Marko Zupan
    Abstract:

    Iodine was shown to be an efficient catalyst for the conversion of phenyl-substituted aldehydes to the corresponding 1,1-diacetate derivatives under Solvent-Free Reaction conditions (SFRC), which are superior to the classical solution conditions. It was demonstrated that the order of the addition of reactants was of fundamental importance; the ability of substituents on the phenyl ring modified reactivity irrespectively to electronic properties, the pentafluorophenyl group significantly reduced reactivity of the aldehyde. Alcohols yielded acetates; acetic anhydride was found to be the most ef- ficient reagent; isopropenyl acetate and vinyl acetate were less reactive; however the pentafluorophenyl group enhanced reactivity with the latter two reagents. Beside the esterification of benzyl alcohol and its pentafluorophenyl analogue, the formation of acetals was also observed.

  • iodine catalyzed disproportionation of aryl substituted ethers under Solvent Free Reaction conditions
    Organic and Biomolecular Chemistry, 2013
    Co-Authors: Marjan Jereb, Dejan Vrazic
    Abstract:

    Iodine was demonstrated to be an efficient catalyst for disproportionation of aryl-substituted ethers under Solvent-Free Reaction conditions. Variously substituted 1,1,1′,1′-tetraaryldimethyl ethers were transformed into the corresponding diarylketone and diarylmethane derivatives. I2-catalyzed transformation of 4-methoxyphenyl substituted ethers yielded mono- and dialkylated Friedel–Crafts products as well. Treatment of trityl alkyl and trityl benzyl ethers with a catalytic amount of iodine produced triphenylmethane and the corresponding aldehydes and ketones. The electron-donating substituents facilitated the Reaction, while the electron-withdrawing groups retarded it; the difference in reactivity is not very high. Such an observation may be in favour of hydride transfer, predominantly from the less electron rich side of the ether with more stable carbocation formation. With the isotopic studies it was established that a substantial portion of the C–H bond scission took place in the rate-determining step, while the carbonyl oxygen atom originated from the starting ether, and not from the air. The transformation took place under air and under argon, and HI was not a functioning catalyst.

  • Highly atom economical uncatalysed and I2-catalysed silylation of phenols, alcohols and carbohydrates, using HMDS under Solvent-Free Reaction conditions (SFRC)
    Tetrahedron, 2012
    Co-Authors: Marjan Jereb
    Abstract:

    Abstract An uncatalysed silylation of phenols, regardless on the aggregate state and nature of the substituents with 0.55 equiv of HMDS under Solvent-Free Reaction conditions (SFRC) at room temperature is reported. Sterically hindered phenols, carbohydrates and most of the alcohols additionally required a catalytic amount (up to 2 mol %) of iodine. The Reaction protocol is very simple; obtaining a pure product, particularly of uncatalysed Reactions, was frequently a completely Solvent-Free process.

  • Dual behavior of alcohols in iodine-catalyzed esterification under Solvent-Free Reaction conditions
    Tetrahedron Letters, 2009
    Co-Authors: Marjan Jereb, Dejan Vrazic, Marko Zupan
    Abstract:

    Abstract The dual behavior phenomenon of alcohols in iodine-catalyzed esterification under Solvent-Free Reaction conditions (SFRCs) is described; the governing factor is the stability of the carbonium ion generated from the alcohol; high concentration Reaction conditions (HCRCs) or dilute solutions are much less suitable. In the case of benzylic alcohols, loss of optical activity was noted, whereas alkyl alcohols furnished a product with retention of stereochemistry.

  • visible light promoted wohl ziegler functionalization of organic molecules with n bromosuccinimide under Solvent Free Reaction conditions
    Helvetica Chimica Acta, 2009
    Co-Authors: Marjan Jereb, Marko Zupan, Stojan Stavber
    Abstract:

    The visible-light-induced transformation of toluenes with N-bromosuccinimide (NBS) under Solvent-Free Reaction conditions (SFRC) was studied. The Reaction took place in spite of the very restricted molecular motion; toluenes could be regioselectively converted to benzyl bromides. Selective radical-chain Reactions with NBS were carried out in liquid/liquid and in solid/solid systems; furthermore, Reactions could be performed in the presence of air. The radical scavenger TEMPO (=2,2,6,6-tetramethylpiperidin-1-yloxy) completely suppressed the side-chain bromination of toluenes with NBS under SFRC. Electron-withdrawing groups decreased the reactivity of the toluenes, and the Hammett Reaction constant ρ+=−1.7 indicated involvement of polar radical intermediates with electrophilic character.