Brominated butyl compound

This compound can give a smooth extrusion. Butyl compounds are slow curing. Brominated butyl compound (Table 10.13)... 

Lonza Ltd in Visp, Switzerland, developed at the beginning of the 1990s a process for the halogen exchange of a brominated aromatic compound with butyl lithium followed by the C—C coupling to a ketone [44]. 

Phenylmercuric borate is 0.08 % soluble in water. Mercury is in this compound covalently bound to the phenyl group. It is incompatible with many anions, including halides. However a 0.004 % solution is compatible with up to 0.7 % sodium chloride. The active concentration is 0.002 %, but a concentration up to 0.004 % may be used to compensate losses by adsorption on the membrane filter, etc. Eye drop bottles with chlorine and bromine butyl rubber droppers cannot be used with phenylmercuric salts, because a precipitate will be formed. An alternative is packaging the eye drops in a bottle with a polypropylene dropper (see Sect. 24.4.2). Phenylmercuric borate causes few hypersensitivity reactions, but with prolonged use, there might be a risk of mercury deposition in the lens. 

A pyridinyl-functionalized ionic liquid, iV-butyl-]V -(4-pyridyIhept-yl)imidazolium bromide, cf. Figure 2.38, has been S5mthesized and applied as an additive for dye-sensitized solar cells (129). In comparison to a volatile organic additive, 4-tert-butyl pyridine, the bromine-containing compound can be used at a very low concentration for high overall power conversion efficiency cells, which shows an overall power conversion efficiency of 5.67% under the simulated air... 

Benzylic Bromination. Toluene and substituted methylben-zenes undergo benzylic bromination using CuBt2 and tcrt-butyl hydroperoxide in acetic acid or anhydride (eq 14). While the yields (43-95%) are not quite as high as those obtained using A-bromosuccinimide, the copper(II) bromide procedure allows the benzylic bromination of compounds which are insoluble in nonpolar solvents. 

Vulcanization rates are higher than for normal butyl rubber because the presence of allylic halide increases the reactivity of the unsaturated sites. Brominated butyl rubber shows higher vulcanization rates than chlorinated butyl rubber. Halogenated butyl rubbers can be vulcanized with various reagents, e.g. diamines, dihydroxy aromatic compounds and zinc oxide. 

Peptisers, too, are seldom needed in butyl rubber compounding. It is usually simpler to buy a grade of butyl rubber that already has the viscosity required, than to break down a higher-viscosity grade the improvements in extrusion properties that peptisers produce can usually be achieved more economically with process oils. However, when a peptiser is needed, various organic peroxides, substituted aromatic mercaptans and chlorothiophenols are effective. Peroxides are very efficient peptisers for standard butyl rubbers but act as curatives for crosslinked and brominated butyl rubbers. 

With mercuric acetate (Hg(OOCCH2)2), olefins and / fZ-butyl hydroperoxide form organomercury-containing peroxides (66,100). The organomercury compound can be treated with bromine or a mild reducing agent, such as sodium borohydride, to remove the mercury. 

In order to induce the free-radical chain reaction, a starter compound such as dibenzoyl diperoxide, azo-Zj -(isobutyronitrile) or tcrt-butyl hydroperoxide or UV-light is used. The commercially available, technical grade N-bromosuccinimide contains traces of bromine, and therefore is of slight red-brown color. Since a small amount of elemental bromine is necessary for the radical... 

Bromination of 7-ter/-butyl, 2-mcthyl 5-methyl-4//-azepine-2,7-dicarboxylate (7) with 1 equivalent of jV-bromosuccinimide yields 2-terf-butyl,7-methyl 4-(bromomethylene)-4,5-dihvdro-l//-azepinc-2,7-dicarboxylate (8) as a 1 2 mixture of the E- and Z-isomers.113 With an excess of reagent the dibromomethylene compound 9 results. 

Treatment with NCS in carbon tetrachloride converted the parent into the 2,3-dichloro derivative. The 2,3-dibromo compound was made similarly with NBS (74BSF2239), or with bromine in chloroform in the presence of sodium acetate (72CHE13). Monobromination is possible, but generally mixtures form with 2- and 3-bromo products in ratios of the order of 1 3 (72CHE13). It was possible to prepare 3-bromobenzo[h]sele-nophene by reaction of the 2,3-dibromo derivative with butyl lithium followed by hydrolysis. Four moles of bromine gave the 2,3,6-tribromo derivative from benzo[h]selenophene (74BSF2239). 

The presence of chlorine and/or bromine is easily detected by their characteristic isotopic patterns (see Appendix 11). As in many aliphatic compounds, the abundance of the molecular ion decreases as the size of the R group increases. For example, in the El mass spectra of methyl chloride and ethyl chloride, the molecular ion intensities are high, whereas in compounds with larger R groups such as butyl chloride, the molecular ion peak is relatively small or nonexistent. 

A kinetic isotope effect, kH/kD = 1.4, has been observed in the bromination of 3-bromo-l,2,4,5-tetramethylbenzene and its 6-deuterated isomer by bromine in nitromethane at 30 °C, and this has been attributed to steric hindrance to the electrophile causing kLx to become significant relative to k 2 (see p. 8)268. A more extensive subsequent investigation304 of the isotope effects obtained for reaction in acetic acid and in nitromethane (in parentheses) revealed the following values mesitylene, 1.1 pentamethylbenzene 1.2 3-methoxy-1,2,4,5-tetramethyl-benzene 1.5 5-t-butyl-1,2,3-trimethylbenzene 1.6 (2.7) 3-bromo-1,2,4,5-tetra-methylbenzene 1.4 and for 1,3,5-tri-f-butylbenzene in acetic acid-dioxan, with silver ion catalyst, kH/kD = 3.6. All of these isotope effects are obtained with hindered compounds, and the larger the steric hindrance, the greater the isotope... 

The reaction of bromine with optically active sec-butyltin compounds Bu SnRs, to give sec-butyl bromide, can give retention or inversion in the sec-butyl group, depending on the natime of the group R... 

The most prevalent approach to achieve long-lasting and nonstaining ozone protection of rubber compounds is to use an inherently ozone-resistant, saturated backbone polymer in blends with a diene rubber. The ozone-resistant polymer must be used in sufficient concentration (minimum 25 phr) and must also be sufficiently dispersed to form domains that effectively block the continuous propagation of an ozone-initiated crack through the diene rubber phase within the compound. Elastomers such as ethylene-propylene-diene terpolymers, halogenated butyl mbbers, or brominated isobutylene-co-para-methylstyrene elastomers have been proposed in combination with NR and/or butadiene rubber. 

In this method, Furstner converts N-BOC protected pyrrole to the 2,5-dibromo compound (122) with NBS and this is followed by metalation and carbomethoxylation with t-butyl lithium in THF and subsequent trapping of the metalated species with methyl chloroformate to yield a pyrrole diester (123). Bromination of this diester at positions 3 and 4 with bromine in water followed by Suzuki cross-coupling with 3,4,5-trimethoxyphenyl boronic acid yields the symmetrical tetrasubstituted pyrrole (125). Base-mediated N-alkylation of this pyrrole with 4-methoxyphenethyl bromide produces the key Boger diester (126) and thereby constitutes a relay synthesis of permethyl storniamide A (120). 

Photolytic. When a dilute aqueous solution (1-10 mg/L) of bromacil was exposed to sunlight for 4 months, the TV-dealkylated photoproduct, 5-bromo-6-methyluracil, formed in small quantities. This compound is less stable than bromacil and upon further irradiation, the de-brominated product, 6-methyluracil was formed (Moilanen and Crosby, 1974). Acher and Dunkelblum (1979) studied the dye-sensitized photolysis of aerated aqueous solutions of bromacil using sunlight as the irradiation source. After 1 h, a mixture of diastereoisomers of 3-5ec-butyl-5-acetyl-5-hydroxyhydantoin formed in an 83% yield. In a subsequent study, another minor intermediate was identified as a 5,5 -photoproduct of 3-5ec-butyl-6-methyluracil. In this study, the rate of photooxidation increased with pH. The most effective sensitizers were riboflavin (10 ppm) and methylene blue (2-5 ppm) (Acher and Saltzman, 1980). Direct photodegradation of bromacil is not significant (Acher and Dunkelblum, 1979 Ishihara, 1963). 

Instead of bromobenzophenone (see Scheme 5.1), 4-bromobenzonitrile may also be used as a substrate (Pinson and Saveant 1978). The latter two compounds carry not only bromine, but also other electrochemically active groups, that is, C=0 or C N. These groups do not inhibit the substitution. Along with the thiophenyl, the thiomethyl or thio-tert-butyl groups can be introduced as substituting fragments. The yields of the substitution products are high (from 60 to 95%), and one electron is consumed for every 20-30 molecules of substrate. The reactions proceed at an ambient temperature and do not take place when a potential difference is not set up. 

Interestingly, if the tribromo compound is treated with five equivalents of n-BuLi, then tetralithiation occurs, as was shown by the isolation of an a-butyl-2,4,5-trimethylthio derivative after reaction with excess dimethyl-disulfide [87JCS(P1)1453]. The a-butyl group in the product is derived from reaction of the a-benzyl carbanion with the n-butyl bromide produced by the initial bromine-lithium exchange reaction (Scheme 59). However,... 

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