Reaction with Trichloroisocyanuric Acid

The reaction of trichloroisocyanuric acid (204) with tryptophan led to the formation of an oxindole derivative (74). This oxidation which is complete at pH 7.0 in proteins may be useful for cleavage at 

The reagents that are used most widely for the chemical modification of tryptophan in proteins are limited to simple, readily available 

A critical reading of the book by Sundberg S94) on the chemistry of indoles could suggest to the reader useful and in principle new techniques for the modification of tryptophan containing peptides and 

Xylose Reaction with tryptophan at 160° in aqueous solution affords p-carboline derivatives 58) 

Bisulfite In the presence of bisulfite and oxygen, tryptophan gives three unidentified products. The reaction shows a free radical mechanism 201) 

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Ethers in which at least one group is primary alkyl can be oxidized to the corresponding carboxylic esters in high yields with ruthenium tetroxide.297 Cyclic ethers give lactones. The reaction, a special case of 9-16, has also been accomplished with CrO, in sulfuric acid.39" with benzyltriethylammonium permanganate,299 and with trichloroisocyanuric acid in the presence of an excess of water.300 In a similar reaction, cyclic tertiary amines (e.g., 28) can... 

Most aromatic compounds, whether of high or low reactivity, can be nitrated, because a wide variety of nitrating agents is available. For benzene, the simple alkylbenzenes, and less reactive compounds, the most common reagent is a mixture of concentrated nitric and sulfuric acids,but for active substrates, the reaction can be carried out with nitric acid alone, or in water, acetic acid, acetic anhydride, or chloroform.Nitric acid in acetic anhydride/trifluoroacetic anhydride on zeolite H-(3 was used to convert toluene to 2,4-dinitrotoluene, and AcONOi on clay converted ethylbenzene to ortho-para nitro ethylbenzene. " In fact, these milder conditions are necessary for active compounds, such as amines, phenols, and pyrroles, since reaction with mixed nitric and sulfuric acids would oxidize these substrates. With active substrates, such as amines and phenols, nitration can be accomplished by nitrosation under oxidizing conditions with a mixture of dilute nitrous and nitric acids.A mixture of N02/02/Fe(acac)3 can be used for active compounds, as can NaN02 with trichloroisocyanuric acid on wet silica gel, or N2O4 and silica acetate. Trimethoxybenzenes were nitrated easily with ceric ammonium nitrate on silica gel, and mesitylene was nitrated in an... 

Chlorination of ketones, along with a number of other functional groups, may be achieved with trichloroisocyanuric acid and per-a-chlorinated ketones may be prepared by reaction of manganese(III) acetate with ketones in the presence of lithium chloride. ... 

Atassi, M. Z. Reaction of Amino Acids and Proteins with Trichloroisocyanuric Acid. Tetrahedron Letters 49, 4893-4896 (1973). 

Dichlorine monoxide, generated in situ in the presence of CCl by reaction of CO2 and NaOCl, has been used in preparation of substituted hydra2ines (48). Dichlorine monoxide reacts with finely divided cyanuric acid in a fluidized bed forming dichloro- and trichloroisocyanuric acids (49) and with sodium cyanurate monohydrate yielding sodium dichloroisocyanurate monohydrate (50) (see Cyanuric and isocyanuric acids). 

In a 200-ml round-bottom flask equipped with a magnetic stirrer and a thermometer is placed a mixture of 50 ml of di- -butyl ether and 25 ml of water. The flask is immersed in an ice bath and the mixture is cooled to 5°. In one portion is added 23.2 g (0.1 moles) of trichloroisocyanuric acid (Chapter 17, Section IV), and stirring in the ice bath is continued for 12 hours. The ice bath is removed and the mixture is stirred at room temperature for an additional 8 hours. The reaction mixture is then filtered to remove solids. The water is separated from the organic layer, which is then washed with two additional portions of water, dried with anhydrous sodium sulfate, filtered, and fractionated as above. 

As mentioned before a PEG-supported TEMPO proved to be very efficient in the oxidation of 1-octanol to octanal not only with sodium hypochlorite, but also in combination with different terminal oxidants such as bis(acetoxy)iodobenzene and trichloroisocyanuric acid. This reaction could be extended to acyclic and cyclic primary and secondary alcohols with excellent results. It is remarkable that the PEG-supported TEMPO maintained the good selectivity for primary vs secondary ben-zylic alcohol oxidation typical of non-supported TEMPO. 

Later on, Liang and coworkers successfully employed trichloroisocyanuric acid (TCCA) as a new type of stoichiometric oxidant for the asymmetric epoxidation of acyclic enones in the presence of 10 mol% of catalyst 4 (Scheme 5.6) [9]. The desired epoxy ketones were obtained in good yields (69-93%) with high enantioselectivities (73-93% ee) under nonaqueous solid-liquid conditions [9b]. In this reaction, TCCA reacts with an inorganic base (KOH) to form a hypochlorite salt, which is transferred to the organic phase by the phase-transfer catalyst and oxidizes... 

Contact with alkaline materials causes decomposition to dichlorvos, which is corrosive to iron and steel. TRICHLOROISOCYANURIC ACID (87-90-1) C3CI3N3O3 Reacts with water releasing toxic chlorine gas. A powerful oxidizer accelerates the burning of combustible materials. Violent reaction with reducing agents, including hydrides, nitrides, and sulfides ammonium compounds ... 

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