Trichloroisocyanuric Acid Research Articles

Metal‐Free Decarboxylative Trichlorination of Alkynyl Carboxylic Acids: Synthesis of Trichloromethyl Ketones

Abstract2,2,2‐Trichloroacetophenone derivatives were synthesized via decarboxylative trichlorination from arylpropiolic acids and trichloroisocyanuric acid (TCCA). The reaction was performed in the presence of water at room temperature, and the desired products were obtained in good yields. The reaction showed good functional group tolerance towards halide, cyano, nitro, ketone, ester and aldehyde groups. In addition, the 2,2,2‐trichloroacetophenone derivatives were readily transformed into esters, amides, and hydrazides. Based on experiments with H218O (water‐18O), we proposed a cationic reaction pathway as the mechanism and suggested two different pathways for producing aryl‐ and alkyl‐substituted propiolic acids.magnified image

Trichloroisocyanuric Acid as an Efficient Reagent for the Synthesis of Phosphoroamidates via Atherton–Todd Reaction under Base-Free Conditions

A simple, efficient, and novel method is developed for the synthesis of phosphoroamidates via an Atherton–Todd coupling reaction of amines with dialkyl H-phosphite using trichloroisocyanuric acid as an efficient and safe reagent. Treatment of amines with dialkyl H-phosphite and trichloroisocyanuric acid under base-free conditions gives phosphoroamidates in moderate to good yields. The reaction proceeded effectively to afford the corresponding phosphoroamidates via a dehydrogenative coupling of H-phosphonates with amines. This method is easy, rapid, and good-yielding for the synthesis of phosphoroamidates.

Asymmetric Hydrogenation of Isoquinolines and Pyridines Using Hydrogen Halide Generated in Situ as Activator.

By employing halogenide trichloroisocyanuric acid as a traceless activation reagent, a general iridium-catalyzed asymmetric hydrogenation of isoquinolines and pyridines is developed with up to 99% ee. This method avoids tedious steps of installation and removal of the activating groups. The mechanism studies indicated that hydrogen halide generated in situ acted as an activator of isoquinolines and pyridines.

Regioselective Chlorination and Suzuki–Miyaura Cross‐Coupling of 4‐Alkoxycoumarins, 4‐Alkoxy‐2‐pyrones, and Related Heterocycles

Chlorination of the coumarin framework was achieved by using trichloroisocyanuric acid, which has several advantages over N‐chlorosuccinimide, particularly with respect to cost‐effectiveness and toxicity. The Suzuki–Miyaura cross‐coupling of the chlorinated 4‐alkoxycoumarins with a range of aryl‐ and heteroarylboronic acids was then carried out in the presence of Pd(OAc)2 and 2‐(dicyclohexylphosphino)‐2′,6′‐dimethoxybiphenyl (SPhos) in an environmentally benign solvent. This transformation afforded the coupled products in yields up to 99 %. Sensitive functional groups such as aldehydes and nitriles were tolerated under the reaction conditions, and the protocol could be performed on a gram scale. The cross‐coupling method was also successfully extended to related 2‐pyrone, 2‐pyridone, and 2‐quinolone derivatives to give yields up to 96 %. This is the first time cross‐coupling conditions have been shown to be general across this range of heterocyclic substrates. The demethylation of the Suzuki–Miyaura products allowed for access to 3‐aryl‐4‐hydroxycoumarins.

Symmetrical Trichlorotriazine Derivatives as Efficient Reagents for One-Pot Synthesis of 3-Acetyl-2-chloroquinolines from Acetanilides under Vilsmeier–Haack Conditions

Symmetrical trichlorotriazine derivatives such as 2,4,6-trichloro-1,3,5-triazine and trichloroisocyanuric acid were explored as Vilsmeier–Haack type reagents in the presence of N,N-dimethylacetamide for the effective synthesis of 3-acetyl-2-chloroquinolines from acetanilides. Ultrasonication led to shorter reaction times than conventional heating and gave yields comparable to those obtained under reflux conditions.

Mesoporous ZSM-5 Zeolites in Acid Catalysis: Top-Down vs. Bottom-Up Approach

A top-down desilication of Al-rich ZSM-5 zeolites and a bottom-up mesopores creating method were evaluated in this study. Three liquid–solid and one gas–solid heterogeneously-catalysed reactions were chosen to establish relationships between zeolites textural properties and their catalytic behavior in acid-catalysed model reactions that are influenced by shape selectivity: Diels-Alder cyclization between isoprene and methylacrylate, Methanol-to-Olefins (MTO) reaction, chlorination of iodobenzene with trichloroisocyanuric acid (TCCA), and Friedel-Crafts acylation of anisole by carboxylic acids with differing sizes. It is found amongst others that no optimal mesoporosity for all the different reactions can be easily obtained, but depending on the chosen application, a specific treatment has to be set to achieve high activity/selectivity and stability.

Mise Au Point D’un Protocole De Sterilisation D’explants Nodaux D’alchornea Cordifolia Avec De L’acide Triclororoisocyanurique

Trichloroisocyanuric acid is a swimming pool disinfectant and is readily accessible. As a result, there is the need to use it as a substitute for conventional disinfectants in in vitro culture. Nodal explants of Alchornea cordifolia, harvested in a natural environment, have been rinsed abundantly with Dettol under running water. Then it was soaked in Talo Plus (550 g/l carbendazim and 100 g/l Chlorothalonil) at 5 ml/liter, which is a broad spectrum fungicide. After then, it was immersed in 70% alcohol for 10 minutes before being soaked in different solutions of trichloroisocyanuric acid to: 6, 4, 3, 2, 1, 0.3, 0.1, and 0.08%. The explants were disinfected completely of all contaminating bacterial and fungal exogenous. This was after a treatment in solutions of acidic trichloroisocyanurique of 6 to 0.08%. The results showed that the losses of active chlorine remained low during storage at temperatures of 4 to 18 ± 2°C. They reach only 5.29% after 72 hours. At room temperature of 27 ± 2 ° C, these losses are more than 30% after three days. Concentrations of 0.1 to 0.3% are effective for the disinfection of explants. This protocol of explants disinfection in vitro culture could therefore be advantageously substituted using the hypochlorite of calcium or the chloride of mercury.

A rapid and convenient oxidation of secondary alcohols

A rapid (normally 20 min to 2 h) and selective oxidation of secondary alcohols to ketones can be achieved using 0.4 equivalents trichloroisocyanuric acid and 1.2 equivalents pyridine at room temperature in ethyl acetate. A likely mechanism for the reaction is proposed.

Metal-free oxidative self-coupling of aldehydes or alcohols to symmetric carboxylic anhydrides

Abstract A metal-free synthesis of symmetrical anhydrides has been developed starting from aldehydes, both aliphatic and aromatic or primary benzylic alcohols. The reaction occurs at room temperature and makes use of trichloroisocyanuric acid (TCCA) as an oxidant providing the desired carboxylic anhydrides in satisfactory yields.

Hypochlorite solution for root canal irrigation that lacks a chlorinated odor.

Objectives:This is an in vitro study to develop a formulation of a hypochlorite solution for root canal irrigation that lacks a chlorinated odor. The antibacterial effect, tissue dissolution efficacy, and the cytotoxicity of the solution were assessed in cell culture and were compared with those of commercial sodium hypochlorite (NaOCl) solutions.Materials and Methods:Trichloroisocyanuric acid (TCA) was used as the source of hypochlorite ions in solution. All required properties of the NaOCl irrigant were evaluated and compared with those of original 2.5% NaOCl solutions currently in use.Results:Our results revealed that a TCA 3.5% + 1/6 Buffer-1 solution passed the short-term stability test. Moreover, no odor of chlorine gas was detected by three independent observers. The hypochlorite ion content and pH were stable over an incubation period of 4 weeks. The new solution did not differ from commercial products in terms of the dissolution property on bovine pulpal tissue (P > 0.05). Moreover, the antibacterial effect of this solution on Enterococcus faecalis did not differ from that of the commercial products (P > 0.05). In addition, our biocompatibility analysis demonstrated no difference among the tested solutions (P > 0.05).Conclusions:According to the results of all properties tested, TCA 3.5% + 1/6 Buffer-1 could be considered an option for NaOCl irrigation with the benefit of no detectable chlorine odor.

Mild Aliphatic and Benzylic Hydrocarbon C-H Bond Chlorination Using Trichloroisocyanuric Acid.

We present the controlled monochlorination of aliphatic and benzylic hydrocarbons with only 1 equiv of substrate at 25-30 °C using N-hydroxyphthalimide (NHPI) as radical initiator and commercially available trichloroisocyanuric acid (TCCA) as the chlorine source. Catalytic amounts of CBr4 reduced the reaction times considerably due to the formation of chain-carrying ·CBr3 radicals. Benzylic C-H chlorination affords moderate to good yields for arenes carrying electron-withdrawing (50-85%) or weakly electron-donating groups (31-73%); cyclic aliphatic substrates provide low yields (24-38%). The products could be synthesized on a gram scale followed by simple purification via distillation. We report the first direct side-chain chlorination of 3-methylbenzoate affording methyl 3-(chloromethyl)benzoate, which is an important building block for the synthesis of vasodilator taprostene.

Trichloroisocyanuric Acid Promoted Cascade Cyclization/Trifluoromethylation of Allylic Oximes: Synthesis of Trifluoromethylated Isoxazolines.

Cheap and commercially available trichloroisocyanuric acid has been used to promote trifluoromethylation by using TMSCF3 as the trifluoromethyl source. The method provides a novel and efficient protocol for the construction of CF3-containing 4,5-dihydroisoxazoles from allylic oximes in good to excellent yields.

Anhydrides from aldehydes or alcohols via oxidative cross-coupling

A novel type of oxidative cross-coupling was developed to prepare symmetrical and mixed anhydrides from aldehydes or alcohols using trichloroisocyanuric acid (TCCA).

A new system for cyclohexane functionalization employing iron(iii) catalysts and trichloroisocyanuric acid

Herein, dinuclear and mononuclear iron complexes were investigated as catalysts in the reaction of cyclohexane chlorination employing trichloroisocyanuric acid as oxidant.

Efficient one-pot construction of unsymmetrical disulfide bonds with TCCA

We report herein a one-pot synthesis of unsymmetrical disulfides with trichloroisocyanuric acid (TCCA) as an oxidant. Under facile conditions, aromatic-aromatic disulfides and aromatic-aliphatic disulfides were synthesized in good to excellent yields even without base. For the construction of the challenging aliphatic-aliphatic disulfides, good yields of the desired products were also obtained with slightly modified conditions. Additionally, the reactions demonstrated a wide range of substrate scope, very short reaction time (<5min), and convenient procedures.

Synthesis of 1, 4-dihydropyridines (DHP) Catalyzed by Trichloroisocyanuric Acid (TCCA) in Aqueous Media

An array of 1, 4-dihydropyridines (DHP) derivativeswas synthesized by Hantzsch three-component reaction of aromatic aldehydes, ethyl acetoacetate and ammonium acetate using trichloroisocyanuric acid (TCCA) as an efficient catalyst in aqueous media. The proposed method was operationally simple and to make the process benign for the environment, water used as a reaction medium. No aromatization of dihydropyridinesproducts was done in the presence of TCCA as an oxidant.

Anthelmintic efficacies of three common disinfectants and extracts of four traditional Chinese medicinal plants against Gyrodactylus kobayashii (Monogenea) in goldfish (Carassius auratus)

Gyrodactylids are commonly occurring fish ectoparasites that cause high host mortality and considerable economic losses in aquaculture. With the goal of finding safe and effective alternative agents to control monogenean infections in aquaculture, we investigated the anthelmintic efficacy of three common disinfectants (trichloroisocyanuric acid, glutaraldehyde and potassium permanganate) and crude extracts of four herbal medicines (Cortex meliae, Radix zanthoxyli, Semen aesculi and Macleaya cordata) against Gyrodactylus kobayashii in goldfish. Also, we compared the anthelmintic efficacy of the above agents with formaldehyde, which is one of the most frequently-used agents to treat gyrodactyliasis. After 48-h exposure, trichloroisocyanuric acid had the EC50 value of 0.12mg/L and EC90 value of 0.65mg/L, and exhibited a 100% efficacy against G. kobayashii at 1.0mg/L. Glutaraldehyde and potassium permanganate were less effective, with EC50 values of 4.0 and 2.9mg/L, and EC90 of 5.0 and 3.6mg/L, respectively. For the extracts of herbal medicines, EC50 and EC90 values of methanol extract of M. cordata were 8.6 and 25.5mg/L, respectively, after 48-h exposure, and EC100 of ethyl acetate and petroleum ether extracts of M. cordata were 80 and 100mg/L, respectively. The remaining extracts were either highly toxic to fish, or exhibited very weak anthelmintic efficacy, even at higher concentrations. Acute toxicity assay indicated that the LC50 of the promising agents (trichloroisocyanuric acid, glutaraldehyde, potassium permanganate and methanol extract of M. cordata) against goldfish after 48-h exposure were 4.1, 8.8, 5.9 and 81.4mg/L, which were 6.3, 1.8, 1.6 and 3.2 times higher than the corresponding EC90. The LC50/EC90 ratio for formaldehyde (2.1-fold) was higher than for glutaraldehyde and potassium permanganate, but lower than for trichloroisocyanuric acid and methanol extract of M. cordata. These results suggested that trichloroisocyanuric acid and methanol extract of M. cordata are both viable alternatives for formaldehyde in aquaculture. Statement of relevanceThe objective of the present study was motivated by the urgent need to find safe and effective alternative agents to control monogenean infections in aquaculture.

Interference of laboratory disinfection with trichloro-isocyanuric acid on cardiac troponin I measurement using the Vitros immunoassay system.

Interference of laboratory disinfection with trichloro-isocyanuric acid on cardiac troponin I measurement using the Vitros immunoassay system.

A Simple and Expedient Procedure for the Preparation of Gabapentin Lactam (2-Aza-spiro[4,5]decan-3-one)

A novel process has been described on 100 g scale for the preparation of gabapentin lactam which is a penultimate intermediate for the preparation of gabapentin, comprising a Hofmann reaction of 1,1-cyclohexanediacetic acid monoamide using chlorinating agents such as trichloroisocyanuric acid, sodium dichloroisocyanurate, 1,3-dichloro-5,5-dimethylhydantoin, and N-chlorosuccinimide, which have not been employed so far for making this molecule. Reactions done in aqueous alkali on the 1,1-cyclohexanediacetic acid monoamide led to a solution of gabapentin sodium salt which on heating led to the formation of the gabapentin lactam in good yield.

Design and synthesis of a novel lanthanide fluorescent probe (EuIII-dtpa-(bis)melamine) and application in melamine detection in milk products

EuIII-dtpa-bis(melamine) was designed and synthesized as a novel targeting fluorescence probe for melamine detection in milk products. The ligand field change around EuIII caused by melamine leads to a highly selective fluorescence “turn-on” response. The competitive assay showed that the presence of other analogues (cyanuric acid, cyanuric chloride, trichloroisocyanuric acid and acetoguanamine) rarely affected the turn-on fluorescence intensity in probing melamine. The obtained results displayed a linear correlation beteewn melamine concentration and fluorescence intensity. The linear equation was y=38.68x+568.32 (R2=0.9972) with melamine concentration ranged from 5 to 100μmol/L. When melamine concentration reaches 100μmol/L, the fluorescence intensity becomes the maximum. The formed EuIII-dtpa-bis(melamine)-melamine complex was extremly stable with the stability constant (k) of 9.90×106 and the complexation ratio was 1:1. The detection limit (LOD) was 0.3743μmol/L. The recoveries ranged from 99.80 to 100.50%, when melamine was detected in some milk products. It can be confirmed that EuIII-dtpa-bis(melamine) shows high selectivity, sensitivity, targeting and recognition ability in melamine detection.