Halogenating agents

Preparation of the reagent [116, 118] Amberlyst A26 Ch form 125 (35 g) was washed with aqueous sodium hydroxide and water. The polymer was then suspended in 1 m aqueous HBr (200 mb), stirred overnight, filtered, and washed with water, acetone and Et20. The dried resin 139 (14.9 g) was suspended in ecu (160 mb) and a solution of bromine (2.8 mb) in CCU (28 mb) was slowly added. After 7 h, the resin was filtered off and washed extensively with ecu, THF, and Et20 to give 22.3 g of 138. 

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The conversion of indoles to oxindoles can be achieved in several ways. Reaction of indoles with a halogenaling agent such as NCS, NBS or pyridin-ium bromide perbromide in hydroxylic solvents leads to oxindoles[l]. The reaction proceeds by nucleophilic addition to a 3-haloindolenium intermediate. 

Use of an excess of the halogenating agent results in halogenation at the 3-position of the oxindole[3,4]. The halogenation and hydrolysis can be carried out as two separate steps. One optimized procedure of this type used NCS as the halogenating agent and it was found that 70% phosphoric acid in 2-mcthoxycthanol was the most effective medium for hydrolysis[2]. If the halogenation is carried out in pyridine, the intermediate is trapped as an... 

Various halogenating agents have been used to replace hydroxyl with chlorine or bromine. Phosphoms trihaUdes, especially in the presence of pyridine, are particularly suitable (17,18). Propargyl iodide is easily prepared from propargyl bromide by halogen exchange (19). 

Primary and secondary phosphines can be treated with halogenating agents to produce halophosphines. 

V-Chlorosuccinimide [128-09-6] mp 150—151°C, forms orthorhombic crystals and has a chlorine-like odor it is prepared from succinimide and hypochlorous acid (114,115). Because of its powerhil germicide properties, it is used ia disiafectants for drinking water. Like its bromine derivative, it is also a halogenating agent. 

Chloroform reacts readily with halogens or halogenating agents. Chlorination of the irradiated vapor is beUeved to occur by a free-radical chain reaction (7). 

Generally these derivatives are rather unstable and behave as oxidizing and halogenating agents. 1-Iodoimidazoles are more stable than other analogs. 

This rate law could correspond to formation of a CI2-AICI3 complex that acts as the active halogenating agent but is also consistent with a rapid equiUbrium involving formation of C1+ ... 

Molecular iodine is not a very powerful halogenating agent. Only very reactive aromatics such as anilines or phenolate anions are reactive toward iodine. Iodine monochloride can be used as an iodinating agent. The greater electronegativity of the... 

Fire Hazards - Flash Point Not flammable Flammable Limits in Air (%) Not flammable Fire Extinguishing Agents Use water, foam, or dry chemical on adjacent flres Fire Extinguishing Agents Not to be Used Any agent with an acid reaction (e.g. carbon dioxide or halogenated agents) will... 

Direct halogenation at C-21 of a A -20-ketopregnane with the common reagents e.g., bromine) is ordinarily not possible. However, by the use of cupric bromide as halogenating agent, a modest yield of the 21-bromo compound can be obtained ... 

In addition to the applications indicated on p. 858. hypohalous acids are useful halogenating agents for Ixjth aromatic and aliphatic compounds. HOBr and HOI are usually generated in silii. The ease of aromatic halogenation increa.ses in the sequence OCl < OBr < Ol and is facilitated by salts of Pb or Ag. Another well-known reaction of hypohalites is their cleavage of methyl ketones to form carboxylates and haloform ... 

The preparation of isothiazolidin-3-one 5-oxide and 5,5-dioxide derivatives of azetidin-3-ones was described (99EUP100069), starting from penicillanic acid sulfoxide amides in the presence of halogenating agents in anhydrous inert solvents or even without them. Through rearrangement and oxidation with conventional methods, compounds 73 could be obtained. For some derivatives the usefulness, as intermediates for the preparation of novel p-lactam analogs or active substances in formulations for antimicrobial therapy, is claimed. 

Chlorination and bromination of chlorins can be carried out with aqueous hydrochloric or hydrobromic acid in the presence of hydrogen peroxide, but also with free chlorine or bromine in solution. Depending on the stoichiometric amount of halogenation agent, mono-or bishalogenated products are selectively formed as in the case of octaethylchlorin 15, Attempts to iodinate chlorins have been unsuccessful. 

With bromine monochloride at 0°C in a variety of solvents, 1 was converted into addition products, the product distribution being a function of solvent. A change in halogenating agent also altered the product ratio. (Scheme 4) Nucleophilic displacement reactions between these products and silver fluoride was found to cause preferential bromine substitution (83G149). 

It becomes clear that in all these compounds it is the conjugate base that takes part in the substitution proper. For mono- and particularly 1,3-dicarbonyl compounds this result actually removes the problem of whether it is the keto or the enol form which enters into an electrophilic substitution by diazonium ions, halogenating agents, and many other reagents. The keto and the enol form are distinct species, but they have one (common) conjugate base This was made clear quite early, but even today there are many chemists who seem not to be aware of it. 

Acetoxylation is found to accompany nitration of fairly reactive aromatics by nitric acid in acetic anhydride and gives rise to zeroth-order kinetics76. The electrophile is believed to be protonated acetyl nitrate the formation of which is rate-determining, hence the kinetic order (see p. 37). Acetoxylation can also accompany halogenation by positive halogenating agents in acetic acid solvent, especially in the presence of sodium acetate137, but no kinetic studies have been carried out. 

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