Bromine, oxidation with

Sulfur-containing pyrimidines are frequent intermediates in substitution reactions. Several methods exist for exchange of the thiol group with hydrogen, either by hydrogenolysis, especially by the use of Raney Nickel, or by oxidative desulfurization which involves a sulfinic acid intermediate. Oxidation may also lead to a sulfonic acid. The 2- and 4-/6-thiones are considerably more stable to air oxidation than 5-thiol derivatives. Disulfides are conveniently formed by oxidation with bromine. Oxidation with chlorine at low temperature can be used to prepare sulfonyl chlorides. These reactions have been summarized [Pg.187]

Within the cubane synthesis the initially produced cyclobutadiene moiety (see p. 329) is only stable as an iron(O) complex (M. Avram, 1964 G.F. Emerson, 1965 M.P. Cava, 1967). When this complex is destroyed by oxidation with cerium(lV) in the presence of a dienophilic quinone derivative, the cycloaddition takes place immediately. Irradiation leads to a further cyclobutane ring closure. The cubane synthesis also exemplifies another general approach to cyclobutane derivatives. This starts with cyclopentanone or cyclohexane-dione derivatives which are brominated and treated with strong base. A Favorskii rearrangement then leads to ring contraction (J.C. Barborak, 1966). 

Sn Citrate, C20 , 2,3-dimercaptopropanol, EDTA, F , E, OH , oxidation with bromine water,... 

Furan can be catalyticaHy oxidized in the vapor phase with oxygen-containing gases to maleic anhydride (93). Oxidation with bromine or in an electrochemical process using bromide ion gives 2,5-dimethoxy-2,5-dihydrofuran [332-77-4] (19) which is a cycHc acetal of maleic dialdehyde (94—96). 

DecabromodiphenylOxide. Decabromodiphenyl oxide [1163-19-5] (decabrom) is the largest volume bromiaated flame retardant used solely as an additive. It is prepared by the bromination of diphenyl oxide ia neat bromine usiag AlCl as a catalyst (32). The bromination may also be carried out ia an iaert solvent such as methylene dibromide [74-95-3] (33). The commercially available grades are >98% decabromodiphenyl oxide with the remainder being the nonabromo species. 

The oxidation may be carried out with an inert solvent thermally (35), with a sensitizer such as bromine (36), with uv radiation (37), or over a suitable catalyst (38). Principal by-products of all these oxidation processes are the acyl fluoride products derived from oxidative cleavage of the perfluoroaLkene (eq. 

Chlorine and Bromine Oxidizing Compounds. The organo chlorine compounds shown in Table 6 share chemistry with inorganic compounds, such as chlorine/77< 2-3 (9-j5y and sodium hypochlorite/7 )< /-j5 2-5 7. The fundamental action of chlorine compounds involves hydrolysis to hypochlorous acid (see Cm ORiNE oxygen acids and salts). 

The aHphatic iodine derivatives are usually prepared by reaction of an alcohol with hydroiodic acid or phosphoms trHodide by reaction of iodine, an alcohol, and red phosphoms addition of iodine monochloride, monobromide, or iodine to an olefin replacement reaction by heating the chlorine or bromine compound with an alkaH iodide ia a suitable solvent and the reaction of triphenyl phosphite with methyl iodide and an alcohol. The aromatic iodine derivatives are prepared by reacting iodine and the aromatic system with oxidising agents such as nitric acid, filming sulfuric acid, or mercuric oxide. 

Eastman Chemical Co. uses only cobalt and bromine, and lower temperature oxidations are held at 175—230°C (83). Solution of 4-formylbenzoic acid is obtained by using hydroclones to replace the mother hquor from the first oxidation with fresh acetic acid. A residence time of up to 2 h is used in order to allow for sufficient digestion to take place and to reduce the 4-formylbenzoic acid content to 40—270 ppm (83). Recovery of dry terephthahc acid is as described above. 

Com and rice starches have been oxidized and subsequently cyanoethylated (97). As molecular size decreases due to degradation during oxidation, the degree of cyanoethylation increases. The derivatized starch shows pseudoplastic flow in water dispersion at higher levels of cyanoethylation the flow is thixotropic. Com and rice starches have been oxidized and subsequently carboxymethylated (98). Such derivatives are superior in the production of textile sizes. Potato starch has been oxidized with neutral aqueous bromine and fully chemically (99) and physically (100) characterized. Amylose is more sensitive to bromine oxidation than amylopectin and oxidation causes a decrease in both gelatinization temperature range and gelatinization enthalpy. 

Bromine reacts with some metal oxides, eg, thorium oxide, at high temperatures in the presence of reducing agents to form bromides (18). Certain nonhydrated metal haUdes can be formed by precipitation. These include AgBr, CuBr, AuBr, HBr, PbBr2, PtBr2, and Hg2Br2 (19). 

Bromine oxidizes carbon and reacts with carbon monoxide to form carbonyl bromide [593-95-3]. 

When tertiary alcohols are oxidized with bromine and a silver salt, tetrahydrofutan derivatives result (34). 

Detection of Bromine Vapor. Bromine vapor in air can be monitored by using an oxidant monitor instmment that sounds an alarm when a certain level is reached. An oxidant monitor operates on an amperometric principle. The bromine oxidizes potassium iodide in solution, producing an electrical output by depolarizing one sensor electrode. Detector tubes, usefiil for determining the level of respiratory protection required, contain (9-toluidine that produces a yellow-orange stain when reacted with bromine. These tubes and sample pumps are available through safety supply companies (54). The usefiil concentration range is 0.2—30 ppm. 

Acids nd Sa.lts. The oxygen acids of bromine are strong oxidants but at ordinary temperatures are stable only in solution. An aqueous solution of hypobromous acid [13517-11-8] may be prepared by treating bromine water with silver oxide or mercuric oxide (69) ... 

Tetracyanoquinodimethane [1518-16-7] (5), 2,2 -(2,5-cyclohexadiene-l,4-diyhdene)bispropanedinitrile (TCNQ), is prepared by condensation of 1,4-cyclohexanedione with malononittile to give l,4-bis(dicyanomethylene)cyclohexane [1518-15-6] which is oxidized with bromine (31). 

A -Pyrazolines are converted into pyrazoles by oxidation with bromine or Pb(OAc)4 and... 

The 2-thienylthiourea (245) on oxidation with bromine in acetic acid gave the thieno[3,2-djthiazole (247). It has been suggested that the intermediate electrophilic sulfenyl bromide adds to the 2,3-bond of the thiophene ring to form (246) when then loses HBr to give (247) (71AJC1229, 78JHC81). Pyrazolo(3,4- /]thiazoles are formed in a similar fashion (76GEP2429195). 

Ethylene bromohydrin has been prepared by the reaction between ethylene glycol and hydrobromic acid and phosphorus tribromide. It has also been prepared by the direct addition of hypobromous acid to ethylene, and by the reaction between ethylene and dilute bromine water. With ethylene oxide now available at a reasonable price, the method described is probably the best because of the high yields and the convenience of reaction. 

Similar oxidation with bromine of alkenes having branched perfluoroalkyls in the allylic position gives bromohydrm regioisomcrs and a dibromo derivative [J5] (equation 27)... 

Oxidation with bromine (Section 25.19) When a preparative method for an aldonic acid is required, bromine oxidation is used. The aldonic acid is formed as its lactone. More properly described as a reaction of the anomeric hydroxyl group than of a free aldehyde. 

Bromine oxide trifluoride, p3BrO, is made by reaction of K[p4BrO] with a weak Lewis acid ... 

This method can be considered as a general one except when the preparation of methylmercapto derivatives is not possible, e.g., with 6-benzyl-2,4-dimethyl-3-thioxo-5-oxo-2,3,4,5-tctrahydro-l,2,4-tri-azine which was converted to the corresponding, dioxotriazine derivative by oxidation with bromine in an alkaline solution. ... 

The benzylic position of an alkylbcnzene can be brominated by reaction with jV-bromosuccinimide, and the entire side chain can be degraded to a carboxyl group by oxidation with aqueous KMnCfy Although aromatic rings are less reactive than isolated alkene double bonds, they can be reduced to cyclohexanes by hydrogenation over a platinum or rhodium catalyst. In addition, aryl alkyl ketones are reduced to alkylbenzenes by hydrogenation over a platinum catalyst. 

---