Trichloroisocyanuric Acid Research Articles

Antibacterial, Antifungal, Anti-Oxidant, Anti-Inflammatory and Anti-Hypertensive Activities of N-Chloropyrazinamide

N-chloropyrazinamide was prepared by the chlorination of pyrazinamide using trichloroisocyanuric acid. The experimental results ascertained that the tested N-chloropyrazinamide showed good antimicrobial activities when compared to standard drug. It was found that N-chloropyrazinamide at different concentrations exhibited significant dose dependent anti-oxidant, anti-inflammatory and anti-hypertensive activity.

ChemInform Abstract: Halonium Ion Mediated Synthesis of 2‐Halomethylene‐3‐oxoketoxime Derivatives from Isoxazoline N‐Oxides.

A protocol for the N-bromosuccinimide (NBS)- and trichloroisocyanuric acid (TCCA)-mediated synthesis of novel 2-halomethylene-3-oxoketoximes via one-pot halogenation/oxidation of isoxazoline N-oxide derivatives is described here. The keto functionality of 3-ketoximes was selectively reduced by lithiumaluminum hydride to synthesize an unprecedented type of Baylis–Hillman oxime, which underwent N–O coupling to produce new isoxazoline N-oxide derivative.

Antibacterial, Antifungal, Anti-Oxidant, Anti-Inflammatory and Anti-Hypertensive Activities of N-Chloropyrazinamide

N-chloropyrazinamide was prepared by the chlorination of pyrazinamide using trichloroisocyanuric acid. The experimental results ascertained that the tested N-chloropyrazinamide showed good antimicrobial activities when compared to standard drug. It was found that N-chloropyrazinamide at different concentrations exhibited significant dose dependent anti-oxidant, anti-inflammatory and anti-hypertensive activity.

Efficient racemization of 1-phenylethylamine and its derivatives

We report on simple and efficient procedure for the racemization of 1-phenylethylamine and its derivatives. In the presence of trichloroisocyanuric acid, N-chloroimine derivative is formed as the intermediates, with subsequent hydrogenation catalyzed by Pd-C leading to the racemic product.

ChemInform Abstract: One‐Pot Synthesis of Hypervalent Iodine Reagents for Electrophilic Trifluoromethylation.

AbstractA simplified synthesis of hypervalent iodine reagents (IV) and (VI) is elaborated using trichloroisocyanuric acid for the first step instead of reported oxidants like sodium metaperiodate or tert‐butyl hypochlorite.

Enantiospecific Total Synthesis of (+)-Tanikolide via a Key [2,3]-Meisenheimer Rearrangement with an Allylic Amine N-Oxide-Directed Epoxidation and a One-Pot Trichloroisocyanuric Acid N-Debenzylation and N-Chlorination

The enantiospecific total synthesis of the δ-lactonic marine natural product (+)-tanikolide (1), isolated from Lyngbya majuscula , was achieved using a [2,3]-Meisenheimer rearrangement as the key reaction. During this rearrangement, we discovered that the allylic amine N-oxide could direct the m-CPBA double-bond epoxidation to the syn position. The resulting syn product 8 underwent epoxide ring opening under the m-CBA conditions to give the five- and six-membered cyclic ether amine N-oxides, which we further treated with Zn and conc. HCl to obtain the reduced bisbenzyl tertiary amines 23 and 22, respectively. When 23 and 22 were treated with trichloroisocyanuric acid (TCCA) in dichloromethane, oxidation at the benzyl position occurred, forming iminium ions. These intermediates were trapped by intramolecular reaction with the hydroxyls, and the resulting intermediates were then oxidized or shifted to afford 25 and 24, respectively. The entire one-pot process involves N-debenzylation, N-chlorination, and hemiacetal oxidation. The amine N-oxide-directed epoxidation complements Davies' ammonium-directed epoxidation. Thus, TCCA N-debenzylation is described for the first time and might be a useful N-debenzylation technique.

ChemInform Abstract: (PhIO)n Mediated Annulations of Aromatic Aldehyde N‐Acylhydrazones for the Synthesis of 1,3,4‐Oxadiazoles.

Oxadiazole as a class of five-membered heterocycles has been reported to be biologically versatile compounds due to their metabolic profile. Amongst these heterocycles, 1,3,4oxadiazole has become an important construction motif for the development of new drugs, furamizole as antibiotics, tiodazosin as antihypertensive agent and raltegravir as antiretroviral agent have been on market. In addition, 2,5-disubstituted-1,3,4-oxadiazole derivatives have also been used as electron conducting and hole blocking (ECHB) materials for electron deficient and good electron transport properties of oxadiazole rings. The most common synthetic approach to 1,3,4-oxadiazoles involves cyclodehydration of 1,2-diacylhydrazines 3 (Scheme 1). Typically, this reaction is carried out by using SOCl2, 5 POCl3, 6 as well as others. Although these methods are very useful for the preparation of large quantities of materials due to the ready availability of diacylhydrazines, hydrazides, and hydrazones as starting materials, the reaction conditions tend to be harsh and long reaction times are generally needed. An alternative route to 1,3,4-oxadiazoles 2 by oxidative cyclization from the corresponding aldehyde N-acylhydrazones 1 proceeds (a) with transition metal oxidants such as Pb, Mn, Fe, Ce or Cu et al.; (b) with chloramine T, Trichloroisocyanuric Acid, iodobenzene diacetate (IBD), Dess–Martin reagent (DMP) or other oxidants; (c) electrochemical methods (Scheme 1). To the best of our knowledge, preparation of 1,3,4-oxadiazoles utilizing iodosobenzene as the oxidizing agent has not been reported yet. In our continuous research program of the oxidation of hypervalent iodine, we were interested in the development of robust and general method to access functionalized 2,5-disubstituted-1,3,4-oxadiazoles. It was found that aromatic aldehyde N-acylhydrazones 1 reacted with (PhIO)n/BF3·Et2O at room temperature to efficiently afford 2,5-disubstituted-1,3,4-oxadiazoles 2 in mild to good yields (Scheme 2). The polymeric character of iodosobenzene makes it less suitable as oxidant than other hypervalent reagents, mainly because of its insolubility in ordinary solvents. Its utility is, however, greatly enhanced when it is used with catalysts, notably boron trifluoride. The electrophilic character of iodine in iodosobenzene is greatly increased by the addition of boron trifluoride, probably because of the in-situ formation of the monomeric dipole PhI+-OBF3 −. N'-Benzylidenefuran-2-carbohydrazide (1a) was chosen as the substrate in initial studies (Table 1). When the substrate

Halonium Ion Mediated Synthesis of 2-Halomethylene-3-oxoketoxime Derivatives from Isoxazoline N-Oxides

A protocol for the N-bromosuccinimide (NBS)- and trichloroisocyanuric acid (TCCA)-mediated synthesis of novel 2-halomethylene-3-oxoketoximes via one-pot halogenation/oxidation of isoxazoline N-oxide derivatives is described here. The keto functionality of 3-ketoximes was selectively reduced by lithiumaluminum hydride to synthesize an unprecedented type of Baylis-Hillman oxime, which underwent N-O coupling to produce new isoxazoline N-oxide derivative.

Modular CeCl3·7H2O-catalyzed multi-component synthesis of 1,2,3,4-tetrasubstituted pyrroles under microwave irradiation and their further trichloroisocyanuric acid-mediated conversion into 5-sulfenylpyrrole derivatives

A modular, multicomponent synthesis of 1,2,3,4-tetrasubstituted pyrroles promoted by the inexpensive CeCl3·7H2O, is reported. The reaction was carried out under microwave irradiation, affording good yields of products in short time. Scope and limitations were explored and a plausible reaction mechanism is discussed. The resulting heterocycles were smoothly and efficiently converted into their corresponding 5-arylsulfenyl derivatives by reaction with diaryl disulfides and trichloroisocyanuric acid in EtOAc.

(PhIO)nMediated Annulations of Aromatic Aldehyde N-Acylhydrazones for the Synthesis of 1,3,4-Oxadiazoles

Oxadiazole as a class of five-membered heterocycles has been reported to be biologically versatile compounds due to their metabolic profile. Amongst these heterocycles, 1,3,4oxadiazole has become an important construction motif for the development of new drugs, furamizole as antibiotics, tiodazosin as antihypertensive agent and raltegravir as antiretroviral agent have been on market. In addition, 2,5-disubstituted-1,3,4-oxadiazole derivatives have also been used as electron conducting and hole blocking (ECHB) materials for electron deficient and good electron transport properties of oxadiazole rings. The most common synthetic approach to 1,3,4-oxadiazoles involves cyclodehydration of 1,2-diacylhydrazines 3 (Scheme 1). Typically, this reaction is carried out by using SOCl2, 5 POCl3, 6 as well as others. Although these methods are very useful for the preparation of large quantities of materials due to the ready availability of diacylhydrazines, hydrazides, and hydrazones as starting materials, the reaction conditions tend to be harsh and long reaction times are generally needed. An alternative route to 1,3,4-oxadiazoles 2 by oxidative cyclization from the corresponding aldehyde N-acylhydrazones 1 proceeds (a) with transition metal oxidants such as Pb, Mn, Fe, Ce or Cu et al.; (b) with chloramine T, Trichloroisocyanuric Acid, iodobenzene diacetate (IBD), Dess–Martin reagent (DMP) or other oxidants; (c) electrochemical methods (Scheme 1). To the best of our knowledge, preparation of 1,3,4-oxadiazoles utilizing iodosobenzene as the oxidizing agent has not been reported yet. In our continuous research program of the oxidation of hypervalent iodine, we were interested in the development of robust and general method to access functionalized 2,5-disubstituted-1,3,4-oxadiazoles. It was found that aromatic aldehyde N-acylhydrazones 1 reacted with (PhIO)n/BF3·Et2O at room temperature to efficiently afford 2,5-disubstituted-1,3,4-oxadiazoles 2 in mild to good yields (Scheme 2). The polymeric character of iodosobenzene makes it less suitable as oxidant than other hypervalent reagents, mainly because of its insolubility in ordinary solvents. Its utility is, however, greatly enhanced when it is used with catalysts, notably boron trifluoride. The electrophilic character of iodine in iodosobenzene is greatly increased by the addition of boron trifluoride, probably because of the in-situ formation of the monomeric dipole PhI+-OBF3 −. N'-Benzylidenefuran-2-carbohydrazide (1a) was chosen as the substrate in initial studies (Table 1). When the substrate

One-Pot Synthesis of Hypervalent Iodine Reagents for Electrophilic Trifluoromethylation

Simplified syntheses suited for large scale preparations of the two hypervalent iodine reagents 1 and 2 for electrophilic trifluoromethylation are reported. In both cases, the stoichiometric oxidants sodium metaperiodate and tert-butyl hypochlorite have been replaced by trichloroisocyanuric acid. Reagent 1 is accessible in a one-pot procedure from 2-iodobenzoic acid in 72% yield. Reagent 2 was prepared via fluoroiodane 11 in a considerably shorter reaction time and with no need of an accurate temperature control.

Gas-phase chlorination of aromatics over FAU- and EMT-type zeolites

Abstract Three FAU-structure type zeolites (EMC-1, USY and USY without EFAl) with different Si/Al molar ratio and their pure hexagonal analogue, the EMC-2 zeolite (EMT-structure type) were prepared and thoroughly characterized. Their catalytic properties were examined in the non-conventional gas–solid reaction requiring a strong acidity. A deeper focus was paid to the difference in activity/selectivity of these zeolites toward the continuous chlorination of aromatics (nitrobenzene and toluene) using trichloroisocyanuric acid (TCCA, C 3 N 3 O 3 Cl 3 ) as chlorination agent.

Electrophilic chlorination of arenes with trichloroisocyanuric acid over acid zeolites

Trichloroisocyanuric acid (TCCA) reacts with arenes and its reactivity is highly affected by the acid strength of the reaction medium. Deactivated arenes are efficiently chlorinated by TCCA in solid acids. Our experimental results, along with DFT calculations show that chlorination using solid acid catalysis is feasible, thus leading to possible replacement of strong liquid acids used to promote this superelectrophilic reaction. We have tested several solid acids, showing the synergic need for acid strength and pore size for promoting the reaction.

The “Mushroom Cloud” Demonstration Revisited

A revisitation of the classical “mushroom cloud” demonstration is described. Instead of aniline and benzoyl peroxide, the proposed reaction involves household chemicals such as α-pinene (turpentine oil) and trichloroisocyanuric acid (“Trichlor”) giving an impressive demonstration of oxidation and combustion reactions that can be useful either as part of a “chemistry show” or as a lecture demonstration for a general, inorganic, or organic chemistry course.

ChemInform Abstract: Phosphonium Chloride as a Non‐Volatile Chlorinating Reagent: Preparation and Reaction in No Solvent or Ionic Liquid.

AbstractPhosphonium chloride PPC prepared in situ from trichloroisocyanuric acid and triphenylphosphine is used for the conversion of hydroxyheterocycles to chloroheterocycles, of carboxylic acids to esters or amides and of amides to nitriles.

Bacteriological examination of digital X-ray imaging device before and after disinfection

The digital X-ray imaging device was disinfected with trichloro-isocyanuric acid solution. The samples were taken with cotton swab pouring method before and 1, 2, 3 and 6 h after disinfection and the bacteriological examination was performed. Before disinfection the colony count of samples was all above the standard (>10 cfu/cm2) with bacilli and gram-positive cocci predominantly. The highest count was detected in the X-ray photographic bed (58 cfu/cm2) and the lowest was in the exposure button (19 cfu/cm2). After disinfection the colony count in radiation suits still exceeded the standard, the colony count in diagnosis bed 2 h after disinfection, that in all parts of device 3 h after disinfection was off levels. The results indicate that the chlorine disinfectants can only achieve short-term effect in disinfection of digital X-ray imaging device. Key words: Equipment contamination; Radiography; Disinfection

Direct and facile synthesis of acyl azides from carboxylic acids using the trichloroisocyanuric acid–triphenylphosphine system

A mild, efficient, and practical method for the one-step synthesis of acyl azides from carboxylic acids using a safe and inexpensive mixed reagent, trichloroisocyanuric acid–triphenylphosphine, is described.

One-Pot Racemization Process of 1-Phenyl-1,2,3,4-tetrahydroisoquinoline: A Key Intermediate for the Antimuscarinic Agent Solifenacin

(S)-(+)-1-Phenyl-1,2,3,4-tetrahydroisoquinoline, which is the key intermediate in preparing the urinary antispasmodic drug solifenacin, was racemized in quantitative yield by a simple one-pot procedure through N-chlorination with trichloroisocyanuric acid, conversion of the N-chloroamine into the imine hydrochloride, and reduction of the imine double bond. The racemized amine was successfully resolved by d-(−)-tartaric acid obtaining (S)-1-phenyl-1,2,3,4-tetrahydroisoquinoline in 81% yield and with 96.7% ee and, from the crystallization mother liquors, the R enriched form. This was racemized by the same one-pot process and resolved by d-(−)-tartaric acid with the same efficiency. Such an approach to the racemization of 1-phenyl-1,2,3,4-tetrahydroisoquinoline can be industrially useful to recycle the waste R enantiomer resulting from the classical resolution used to obtain the S enantiomer on a large scale.

Trichloroisocyanuric acid (TCCA): an efficient green reagent for activation of thioglycosides toward hydrolysis

Trichloroisocyanuric acid (TCCA), an inexpensive, commercially available, and non-toxic reagent has been used for the activation of thioglycosides toward their hydrolysis to the corresponding hemiacetals in high to excellent yields. The methodology provides a mild reaction condition for dealing with compounds containing acid sensitive functional groups.

One-pot tandem reactions for direct conversion of thiols and disulfides to sulfonic esters, and Paal–Knorr synthesis of pyrrole derivatives catalyzed by TCCA

A convenient synthesis of sulfonic esters from thiols and disulfides is described. In situ preparation of sulfonyl chlorides from thiols is accomplished by oxidation with trichloroisocyanuric acid (TCCA), tetra-butylammonium chloride (t-Bu4NCl), and water. The sulfonyl chlorides are then further allowed to react with phenol derivatives in the same reaction vessel. Also, a facile synthesis of N-substituted pyrroles by the reaction of hexane-2,5-dione with primary amines has been accomplished using TCCA as a catalyst under mild condition with excellent yields.