Chloro compounds

C-Cl St 830- 600 Strong, often broad (rotational isomers), absent in ehloroaromaties 

Other 1100-1020 Strong, narrow or of medium width chloroaro-matics 

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The diazonium hydrogen sulphate is used in preference to the diazonium chloride, because the latter gives small quantities of the chloro compound as a by-product ... 

Health and Safety Factors. Fluorocarbons containing bromine or iodine are more toxic than the corresponding chloro compounds. When the ratio of the fluorine to other halogens is high, the toxicity can be quite low, especially for bromofluorocarbons. Perfluoro-l-bromooctane [423-55-2] has an LD q of greater than 64 mL/kg when adininistered into the gastrointestinal tract, and has Htde effect when instilled into the lungs (49). Other examples are included in Table 7. 

The first three classes are called available chlorine compounds and are related to chlorine by the equilibria in equations 1—4. These equilibria are rapidly established in aqueous solution (6), but the dissolution of some hypochlorite salts and A/-chloro compounds can be quite slow. 

In solutions, the concentration of available chlorine in the form of hypochlorite or hypochlorous acid is called free-available chlorine. The available chlorine in the form of undissociated A/-chloro compounds is called combined-available chlorine. Several analytical methods can be used to distinguish between free- and combined-available chlorine (8). Bleaches that do not form hypochlorite in solution like chlorine dioxide and nonchlorine bleaches can be characterized by thek equivalent available chlorine content. This can be calculated from equation 5 by substituting the number of electrons accepted divided by two for the number of active chlorine atoms. It can also be measured by iodomettic titration. 

OtherH-Chloro Compounds. Sodium N-chlorobenzenesulfonamide (chloramine B) [127-52-6] (4), sodium A/-chloro-/)-toluenesulfonamide (chloramine T) [127-65-1] (5), /V-cb1orosuccinimide [128-09-6] (6), and tricbloromelamine [12379-38-3] (7) have also had minor roles as bleaching agents. 

Chlorine dioxide is usually used in aqueous solution. It is a weaker oxidant than hypochlorite. Unlike chlorine it does not react with water to form hypochlorite or with amines to form A/-chloro compounds. Thus chlorine dioxide is easily removed from solutions by passing air through the solution or its headspace. Chlorine dioxide solutions decompose by equation 12 ... 

Ureas. Chlorination of aqueous urea yields unstable A/-chloro compounds. With excess C10 decomposition yields CO2, N2O, and NCl the latter decomposes further to NO (96). Only two soHd derivatives have been isolated A/-chlorourea [3135-74-8] mp 74—76°C, and N,lSf-dichlorourea [2959-01-5] which decomposes at its mp of 83°C with evolution of NCl. As an amide, urea also undergoes the Hofmann reaction yielding hydrazine. This route to hydrazine was once employed commercially. 

Hypochlorous acid reacts very rapidly and quantitatively with a slight excess of free ammonia forming monochloramine, NH2CI, which reacts at a slower rate with additional HOCl forming dichloramine, NHCI2. Trichloramine is formed when three moles of HOCl are added per mole of ammonia between pH 3—4 (100). Hypochlorous acid in the form of chlorine or hypochlorite is used in water treatments to oxidize ammonia by the process of break-point chlorination, which is based on formation of unstable dichloramine. The instabiHty of NHCI2 is caused by presence of HOCl and NCl (101,102). The reaction is most rapid at a pH of about 7.5 (103). Other nitrogen compounds such as urea, creatinine, and amino acids are also oxidized by hypochlorous acid, but at slower rates. Unstable iV-chloro compounds are intermediates in deammination of amino acids (104,105). 

Stable A/-chloro compounds are formed by reaction of hypochlorous acid and appropriate N—H compounds. For example, HOCl, formed in situ via chlorine hydrolysis, converts di- or trisodium cyanurates to dichloro- and trichloroiso-cyanuric acids, respectively (114). Chloroisocyanurates can also be prepared from isocyanuric acid or monosodium cyanurate and preformed HOCl (115—117). Hydrolysis of chloroisocyanurates provide HOCl for use in swimming pool disinfection and in bleaching appHcations. 

Alkoxyl tion. The nucleophilic replacement of an aromatic halogen atom by an alkoxy group is an important process, especially for production of methoxy-containing iatermediates. Alkoxylation is preferred to alkylation of the phenol wherever possible, and typically iavolves the iateraction of a chloro compound, activated by a nitro group, with the appropriate alcohol ia the presence of alkaU. Careful control of alkaU concentration and temperature are essential, and formation of by-product azoxy compounds is avoided by passiag air through the reaction mixture (21). 

When chloro compounds are treated with sodium azide in ethanol or aqueous acetone the corresponding azides or tetrazolo[l,5-6]pyridazines are obtained. For example, 3-azido-and 4-azido-pyridazine 1-oxides are obtained from the corresponding chloro compounds ... 

Where direct amination of chloro compounds has proved unsatisfactory, 4-alkoxy or 4-phenoxy intermediates have sometimes been used for reactions with amines or hydrazine. 

CPB1457), whilst with azide ion the chloro compound (107) underwent ring opening and reclosure to give the 2-tetrazolyl-3-aminopyridine (108) (74CR(C)(278)l42l). 

In addition to conversion to chloro compounds, -ones and diones have given thiones with phosphorus pentasulfide, whilst in some cases replacement by amine of alkoxy groups in preference to a chloro group has been observed (68JHC13). 

In comparison to N—S bond formation, O—N bond formation by essentially oxidative procedures has found few applications in the synthesis of five-membered heterocycles. The 1,2,4-oxadiazole system (278) was prepared by the action of sodium hypochlorite on A(-acylamidines (277) (76S268). The A -benzoylamidino compounds (279) were also converted into the 1,2,4-oxadiazoles (280) by the action of r-butyl hypochlorite followed by base. In both cyclizations A -chloro compounds are thought to be intermediates (76BCJ3607). 

Hydroxy-l,2-benzisoxazoles show a variety of reactions. With POCla/EtaN the 3-chloro compound is formed (see Section 4.16.3.3 for further discussion). 

Chloro compounds are aromatic in character, but 5-chloro compounds and 3-chloro-... 

Bromo-3-methyl-4-nitroisothiazole can be converted into the 5-iodo analogue by reaction with sodium iodide in acetone (65AHC(4)107). Halogen exchange also takes place when 4-bromo-3-methylisothiazole-5-diazonium chloride is treated with methyl methacrylate and hydrolyzed, giving the chloro compound (150) (72AHC(14)l). 

Benzisothiazoles can be prepared by the reaction of aromatic chloro compounds with sulfur and ammonia. Thus, 2,6-dichlorobenzylidene chloride gives 4-chloro-l,2-benzisothiazole (72AHC(14)43), and 2-chlorobenzophenone gives 3-phenyl-l,2-benziso-thiazole (79GEP27 34866). 

There is some evidence for the formation of unstable benzazetidines from [2 + 2] cycloaddition of benzyne to imines (75BCJ1063). A novel formation of a benzazetidine is reported in the solvolysis of the exo iV-chloro compound (297). Neighbouring group participation by the benzene ring leads to the cation (298), which is intercepted by methanol to give the benzazetidine (299) (81CC1028). 

The magnitude of the anomeric effect depends on the nature of the substituent and decreases with increasing dielectric constant of the medium. The effect of the substituent can be seen by comparing the related 2-chloro- and 2-methoxy-substituted tetrahydropy-rans in entries 2 apd 3. The 2-chloro compound exhibits a significantly greater preference for the axial orientation than the 2-methoxy compound. Entry 3 also provides data relative to the effect of solvent polarity it is observed that the equilibrium constant is larger in carbon tetrachloride (e = 2.2) than in acetonitrile (e = 37.5). 

Acridine and compounds Aniline and compounds Benzanthrone and compounds Benzidine and compounds Chloro compounds... 

It has been claimed that the elimination of tosylates of 3a-alcohols in 5jS-series gives 3-oleflns with high selectivity. However, the homogeneity of these products is questionable, in view of recent findings concerning the ehmination of 3-chloro compounds (see below) and Fieser s results with the elimination of methyl lithocholate tosylate (ref. 232, cf. ref. 233). Neutral alumina may also be used to effect elimination of tosylates of 3j5-alcohols if the alumina is pretreated with potassium hydroxide the inverted alcohol is the predominant product. 

While the dehydrohalogenation of 3-halo-5a-steroids gives the A -olefin selectively, it has been shown that in the 5j5-series dehydrochlorination of 3j5-chloro compounds with quinoline gives a mixture of A - and A -olefins in a 45 55 ratio. 

Halogen-substituted olefins may be obtained from hydrazones by the action ofN-halocompounds. 327, /. 328.372 (Chloro compounds of this type may also be made by the direct action of phosphorous pentachloride on the ketone, e.g. ref. 329, 330.)... 

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