The Chemistry of Organo Halogenic Molecules. 155. The Role of Reagent Structure in Halogenation of 9-Substituted Phenanthrenes

9-Substituted phenanthrenes were used as target molecules in investigations of the effect of the reagent structure and reaction conditions on halogenation with bromine (1), CsSO4F (2) and F-TEDA (1-chloromethyl-4-fluoro-1,4-diazoniabicycloe[2,2,2]octane bis(tetra- fluoroborate), (3). 9-Methoxyphenanthrene (4) was converted to 9- bromo-10-methoxyphenanthrene (6a) and 9-bromo-10-hydroxy- phenanthrene (7a), while the amount of dealkylation depended on the solvent and was more pronounced in methanol than in acetonitrile, but no adduct was observed. Addition reaction became a major process in fluorination with CsS04F (2) in methanol and 88% of 9-fluoro-10,10-dimethoxy-9,10-dihydrophenanthrene (8b) was formed, while dealkylation occurred in acetonitrile. The course of fluorination of 9-methoxyphenanthrene with F-TEDA (3) could be completely manipulated by the choice of solvent and 9,9-difluoro- 10-oxo-9,10-dihydrophenanthrene (9b) was formed in acetonitrile, 9-fluoro-10-methoxyphenanthrene (6b) in trifluoroacetic acid and 9-fluoro-10,10-dimethoxy-9,10-dihydrophenanthrene (8b) in methanol. Bromination of 9-hydroxyphenanthrene (5) in acetonitrile resulted only in the substitution process, while 9-fluoro-10-hydroxyphenanthrene (7b) formed in the reaction with CsSO4F and F-TEDA was more reactive than the starting hydroxy derivative and, using a 2 molar ratio of F-TEDA, only 9,9-difluoro-10-oxo- 9,10-dihydrophenanthrene (9b) was formed

Microwave Assisted Esterification of Aryl/Alkyl Acids Catalyzed by N-Fluorobenzenesulfonimide

The susceptibility of the carbonyl group towards nucleophilic attack affords the construction of various organic compounds. Thus, investigations of carbonyl activation applying greener methodologies are highly important. In the present work, among the investigated N-halo compounds, N-fluorobenzenesulfonimide (NFSi) has been found as an efficient and selective catalyst in the reaction of direct esterification of aryl and alkyl carboxylic acids supported by microwave (MW) irradiation. The comprehensive esterification of different benzoic acids and mono-, di-and tri-carboxy alkyl derivatives was performed, whereby significant reaction time reductions were achieved. The presented method used NFSi as an easily manipulatable, non-metal, water-and air-tolerant catalyst, allowing simple synthetic and isolation procedures and energy saving, compared to conventional methodologies. Importantly, in contrast to esterification under thermal conditions, where N-halo compounds behave as pre-catalysts, in the MW-supported protocol, a distinct reaction mechanism has been proposed that assumes NFSi as a sustainable catalyst. Moreover, a scale-up of the industrially important derivative was performed

Recent Advances in the Application of Selectfluor TM F-TEDA-BF4 as a Versatile Mediator or Catalyst in Organic Synthesis

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Electrophilic Iodination of Organic Compounds Using Elemental Iodine or Iodides: Recent Advances 2008–2021: Part I

The iodination of organic compounds is of great importance in synthetic organic chemistry. It opens comprehensive approaches for the synthesis of various biologically active compounds. The recent advances in iodination of organic compounds using elemental iodine or iodides, covering the last thirteen years, are the objective of the present review

Transformation of Tertiary Benzyl Alcohols into the Vicinal Halo-Substituted Derivatives Using N-Halosuccinimides

The efficiency of direct conversion of tertiary alcohols bearing a β-hydrogen atom to vicinal halohydrins—chlorohydrins and bromohydrins—under green reaction conditions was tested preliminarily on model tertiary benzyl alcohols. Tertiary alcohols were successfully directly halogenated to vicinal halohydrins with N-halosuccinimide in aqueous media. The efficiency of the reaction in water was significantly improved in the presence of sodium dodecyl sulphate as the surfactant

<i>N</i>-Iodosuccinimide as a Precatalyst for C–N Bond-Forming Reactions from Alcohols under Mild Reaction Conditions

We report an efficient and selective methodology for the direct cross-coupling of alcohols with N-nucleophiles mediated by N-iodosuccinimide (NIS) as the non-metal, commercially available, low-cost, and most effective precatalyst among the N-halosuccinimides (NXSs) under mild reaction conditions enhancing the green chemical profiles of these reactions. The scale-up procedure was accomplished with almost quantitative yield, verifying the presented method’s synthetic applicability and potential for industrial application

Direct Cross-Coupling of Alcohols with O-Nucleophiles Mediated by N-Iodosuccinimide as a Precatalyst under Mild Reaction Conditions

We report N-iodosuccinimide as the most efficient and selective precatalyst among the N-halosuccinimides for dehydrative O-alkylation reactions between various alcohols under high-substrate concentration reaction conditions. The protocol is non-metal, one-pot, selective, and easily scalable, with excellent yields; enhancing the green chemical profiles of these transformations

N-Halosuccinimides as Precatalysts for C-, N-, O-, and X-Nucleophilic Substitution Reactions of Alcohols under Mild Reaction Conditions

N-halosuccinimides (chloro, bromo, and iodo, respectively) were introduced, tested, and applied as efficient and non-metal precatalysts for C-, N-, O-, and X-nucleophilic substitution reactions of alcohols under solvent-free reaction conditions (SFRC) or under high substrate concentration reaction conditions (HCRC) efficiently and selectively, into the corresponding products