Trihaloisocyanuric acids as convenient reagents for regioselective halogenation of β-dicarbonyl compounds

Mendonça, Gabriela F.; Sindra, Haryadylla C.; Almeida, Leonardo S. de; Esteves, Pierre M.; Mattos, Marcio C. S. de

doi:10.1016/j.tetlet.2008.11.045

Cited by 48 publications

(21 citation statements)

References 27 publications

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“…IR:

\overset{ν}{true}

=579, 617, 826, 907, 926, 1005, 1063, 1194, 1229, 1317, 1395, 1418, 1456, 1732, 1755, 2872, 2930, 2967, 3030 cm −1 . The 1 H and 13 C NMR data are consistent with those reported in the literature …”

Section: Methodssupporting

confidence: 90%

The Multiple Reactions in the Monochlorodimedone Assay: Discovery of Unique Dehalolactonizations under Mild Conditions

2015

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The monochlorodimedone assay hasb een widely used as an assayo ft he brominating activity of halogenating enzymes;h owever, the assumed product was found to spontaneously decompose during the measurement. The decompositionm echanism and systematic error in the assay were explained by five reactions in their multiple reactions.We discoveredu nique dehalolactonizations of halogenated d-keto acids in aqueous solutiona mong many reactions in the assay.I ts reactionm echanism wass uggested as the cyclization via ac yclopropanone intermediate produced by the intramolecular catalysis of the carboxylate anion. Figure 1. (a) MCD assay and (b) caldoriomycin biosynthesis.[a] H.

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“…IR:

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Section: Methodssupporting

confidence: 90%

The Multiple Reactions in the Monochlorodimedone Assay: Discovery of Unique Dehalolactonizations under Mild Conditions

2015

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“…Among the chlorinating reagents considered, trichloroisocyanuric acid (TCCA) is a stable and convenient reagent that has been previously used for the chlorination of a variety of substrates, including deactivated benzenes (e.g., nitrobenzene) in good yields. 8 Inspired by these reports, we investigated the reactivity of BODIPY 1 in the presence of TCCA, at room temperature in different solvents. Our optimized conditions involved the treatment of BODIPY 1 with increasing amounts of TCCA in acetic acid, for 10 min at room temperature, as shown in Scheme 1; this methodology is significantly faster, cheaper, greener, and more efficient than previously reported methods for halogenation of BODIPYs.…”

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confidence: 99%

Stepwise Polychlorination of 8-Chloro-BODIPY and Regioselective Functionalization of 2,3,5,6,8-Pentachloro-BODIPY

et al. 2015

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An effective, stepwise methodology for polychlorination of BODIPY using trichloroisocyanuric acid (TCCA) in acetic acid was developed. In this way, selectively substituted di-, tri-, tetra-, and pentachloro-BODIPYs 2–5 were prepared. The pentachloro-BODIPY is shown to undergo regioselective Pd(0)-catalyzed Stille and Suzuki coupling reactions, first at the 8-position followed by the 3,5- and then the 2,6-positions; nucleophilic substitution reactions occur first at the 8-followed by the 3,5-positions, while the 2,6 are unreactive.

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“…Finally, the chlorination was carried out by treatment of the reduced products with trichloro-isocyanuric acid (5) in acetone at room temperature. The use of trichloro-isocyanuric acid was motivated by its very low price, since it is a very cheap material used for treatment of water in swimming pools, and by its reported use as a very effective chlorinating [22][23][24] and oxidizing compound. 25 This chlorination reaction was carried out at room temperature with acetone as solvent, and the use of reflux conditions gives the same results with a better yield.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and in vivo evaluation of 5-chloro-5-benzobarbiturates as new central nervous system depressants

Vieira¹,

Gomes²,

Matheus³

et al. 2011

J. Braz. Chem. Soc.

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Uma nova família de barbituratos, ácidos 5-cloro-5-benzilbarbitúricos, foi preparada usando um método simples e eficiente a partir de aldeídos aromáticos e ácido barbitúrico, seguido de redução e cloração usando ácido tricloroisocianúrico, com rendimento global de 53 a 70%. Por avaliação in vivo com camundongos, os produtos apresentaram atividade tranqüilizante.A new family of barbiturates, 5-chloro-5-benzylbarbituric acids, was prepared using a simple efficient synthetic method from aromatic aldehydes and barbituric acid, followed by reduction and chlorination with trichloro-isocyanuric acid, affording overall yields of 53 to 70%. The in vivo evaluation with mice showed that these compounds present tranquilizing activity.Keywords: 5-chloro-5-benzylbarbituric acids, tranquilizers, benzylidenebarbiturates, trichloroisocyanuric acid, rota-rod tests IntroductionBarbiturates are very well known drugs with activity at the central nervous system (CNS), with specific activity as anticonvulsants, anxiolytics, tranquilizers and sedatives-hypnotics. 1 The mechanism of action of barbiturates at the CNS is not well known, but it has been shown that they are able to interfere with acetylcholine, norepinephrine and glutamate activity and also that they can inhibit the calcium uptake of nerve terminals, thus allowing their use as analgesics. 2,3 In fact, today barbiturates are commonly used to induce anesthesia in surgery procedures. They are also known as GABA-mimetics, thus functioning as agonists of GABA receptors. 3,4 For many years the barbiturates were the main drugs used to cause effects on the CNS. However, after the discovery of the very effective benzodiazepines, their use became less common simply because benzodiazepines have less potential for lethal overdoses. 5,6 The main cause of death by overdoses of barbiturates is respiratory failure, because they are very potent respiratory depressants. Today, the main uses of barbiturates are the induction of anesthesia and for the treatment of refractory status epilepticus. 7 Regarding the significant historical and actual use of barbiturates as neurological drugs, and the importance of this type of disease in the actual condition of mankind, we developed a very simple new family of barbiturates with CNS activity. Interestingly, 5-chlorobarbituric acid and their derivatives have been rarely investigated. The only similar compounds that have been reported as anticonvulsants are the 5-chloro-5-phenyl barbiturates. 8 Surprisingly, 5-benzyl-5-chlorobarbituric acids have not been reported in the literature. We developed a very simple and efficient method for the preparation of this new family of barbiturates as potential tranquilizers. Results and DiscussionOur strategy for the preparation of 5-benzyl-5-chlorobabiturates was based on the use of benzylidenebarbiturates as intermediates, which are very easy to prepare. [9][10][11][12] Benzylidenebarbiturates are employed in several well known reactions in the literature 10,13-17 and have even been used as methionine aminopeptidas...

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Trihaloisocyanuric acids as convenient reagents for regioselective halogenation of β-dicarbonyl compounds

Cited by 48 publications

References 27 publications

The Multiple Reactions in the Monochlorodimedone Assay: Discovery of Unique Dehalolactonizations under Mild Conditions

The Multiple Reactions in the Monochlorodimedone Assay: Discovery of Unique Dehalolactonizations under Mild Conditions

Stepwise Polychlorination of 8-Chloro-BODIPY and Regioselective Functionalization of 2,3,5,6,8-Pentachloro-BODIPY

Synthesis and in vivo evaluation of 5-chloro-5-benzobarbiturates as new central nervous system depressants

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