High temperature bromination

In the course of studying the bromination reactions of the bicyclic systems we noticed that the reaction temperature has a dramatic influence on the product distribution. Increasing of the temperature gives non-rearranged reaction products (refs. 1,2). For this reason, we submitted 1 to high temperature bromination. To a solution of 1 in decalin at 150 C was added a hot solution of bromine in decalin in one portion. The colour of bromine disappeared immediately. After silica gel chromatography followed by fractional crystallization we isolated four products 2-6 in yields 8, 35, 37, and 9 % respectively. The structure of these compounds has been elucidated on the basis of spectral data by iH NMR and NMR experiments and by comparison with those reported in the literature. Symmetrical endo-c/5-isomer 6 has been observed for the first time. Studies concerning the mechanism of syn-addition show that the syn-adduct can arise either from direct... 

Next we studied high temperature bromination of benzobarrelene at 150 C. NMR analysis indicated that the reaction mixture was very complex and consisted of at least ten products. After repeated column chromatography combined with fractional crystallization we have been able to separate 18 compounds (Scheme 6). Four of them were bromoalcohol compounds 18, 12, 22 and 2fl. After high temperature bromination we expected three isomeric non-rearranged products with benzobarrelene skeleton and isolated 22, 22, and 24 in yields of 34, 9.3, and 6.2 %, respectively. Because of the very close structural similarity we were not able to make a clear-cut differentiation between the stereochemistry of 22 and 24-Therefore, we carried out an X-ray analysis (ref. 9) of the isomer 22-... 

Finally, we would like to conclude that high temperature bromination of bicyclic systems gives more non-rearranged products. If the molecule is more strained, the tendency to rearrange decreases as in the case of benzonorbornadiene. On the other hand, substituents at double bond of benzobarrelene retards also rearrangement (ref. 1). 

Scipioni et al (58) report a somewhat different set of impurities for halothane made by high temperature bromination of 2-chloro-1,1,1-trifluoroethane on a laboratory scale, and they also investigated the changes in concentrations with changes in reaction temperature and contact time. 

The exquisite imaging capabilities of STM have been applied to a wide range of surface chemistry and physics problems. Figure 5 shows a 40 nm x 40 nm image of a silicon surface that was exposed to bromine vapor (Bra) at 800 K. At this high temperature, bromine reacts with... 

Bromoacetic acid can be prepared by the bromination of acetic acid in the presence of acetic anhydride and a trace of pyridine (55), by the HeU-VoUiard-Zelinsky bromination cataly2ed by phosphoms, and by direct bromination of acetic acid at high temperatures or with hydrogen chloride as catalyst. Other methods of preparation include treatment of chloroacetic acid with hydrobromic acid at elevated temperatures (56), oxidation of ethylene bromide with Aiming nitric acid, hydrolysis of dibromovinyl ether, and air oxidation of bromoacetylene in ethanol. 

Halogenated intermediates based on chlorendic anhydride and alkoxylated, brominated bisphenol are quite stable and are used extensively in flame-retarded high temperature compositions, but brominated aUcychcs, such as dibromotetrahydrophthahc resin, are rapidly dehydrohalogenated at lower temperatures. 

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). 

Addition to the Double Bond. Chlorine, bromine, and iodine react with aHyl chloride at temperatures below the inception of the substitution reaction to produce the 1,2,3-trihaLides. High temperature halogenation by a free-radical mechanism leads to unsaturated dihalides CH2=CHCHC1X. Hypochlorous and hypobromous acids add to form glycerol dihalohydrins, principally the 2,3-dihalo isomer. Dehydrohalogenation with alkah to epicbl orobydrin [106-89-8] is ofgreat industrial importance. 

Pyrazolesulfonic acids, like (493), have high melting points (Table 24) and probably exist as the zwitterions (497). They are very stable to hydrolysis and only afford pyrazolones at high temperatures. The replacement of the SO3H group by bromine has also been reported (B-76MI40402). Pyrazole-3-, -4- and -5-sulfonic acids react with phosphorus pentachloride to form sulfonyl chlorides. 

Other routes are the thermal decomposition of (NH4)2Cr207, the reaction of NH3 with bromine water, or the high-temperature reaction of NH3... 

Bromination at 450°C hardly occurs, but when the pumice is impregnated with ferrous or cuprous bromide a much better yield of 2,4,6-tribromopyridine is obtained. When pyridine is brominated at 180°C in the presence or absence of impregnated pumice only 2-bromo- and 2,6-dibromopyridine are formed. These facts are not consistent with an electrophilic substitution, which should take place at the 3-position, On the other hand, the high temperature coefficient of the reaction (cf. Table XV) and the fact that ultraviolet light has no effect on the reaction argue against a simple free-radical sub-stitutiond ... 

De la Mare and Maxwell199 measured the rate of bromination of biphenyl by hypobromous acid in 75 % aqueous acetic acid, in some cases catalysed by perchloric acid, at temperatures between —3.78 and +20.1 °C. They showed that whereas when mineral acid is present the brominating species is Br+ (or a solvate), in the absence of mineral acid it is BrOAc which is a highly reactive brominating species giving Ea = 7.9 (this value is only approximate since it also includes a contribution from bromination by HOBr), and the appropriate kinetic equation is then... 

Because of their low reactivity, a Diels-Alder reaction of 2-pyrones usually requires such a high temperature that the initial bicyclic lactone adducts often undergo cycloreversion [30,33] with loss of CO2. In some cases this limitation has been overcome by carrying out the reaction imder high pressure conditions. Posner and coworkers have shown [34-36] that the presence of a tolylthio group or a bromine atom at the 3- or 5-position increases the reactivity of 2-pyrones. 3-Bromo-2-pyrone (35) (Scheme 2.15), as well as its regioisomer 5-bromo (36)... 

Alkoxybenzenes were highly regioselectively halogenated by use of copper(II) halides supported on alumina to give 4-halo-alkoxybenzenes in high yield. Bromination of alkoxybenzenes with alumina-supported copper(II) bromide occurred at lower temperature than chlorination with alumina-supported copper(II) chloride (ref. 14). 

HIGH TEMPERATURE BROMBVATION IVC f D. BROMINATION OF BENZONORBORNADIENE AND BENZOBARRELENE... 

Lastly, we isolated a tetrabromo compound 21 (ref. 10) which is derived from solvent. IH and NMR spectra of 21 indicates the formation of a highly symmetrical compound whose configuration is not known. Possible configurations are given on scheme 10. On an independent reaction we treated decalin with bromine at high temperature and obtained 21 in high yield. 

However this solution is not always convenient and may prevent high productivity and/or the production of intricate forms which require high temperature processing. Fortunately, some fire retardants dramatically increase the flowability of fire retardant plastics melts. For example ABS, flame retarded with F-2016 or F-2016M (brominated epoxy) has much higher flowability, melt flow index (MFI), and spiral flow index, than virgin ABS (Fig. 1). 

When chlorination or bromination is carried out at high temperatures (e.g., 300-400°C), ortho-para directing groups direct meta and vice versa. " A different mechanism operates here, which is not completely understood. It is also possible for bromination to take place by the SeI mechanism, (e.g., in the r-BuOK catalyzed bromination of 1,3,5-tribromobenzene). ... 

A greater hindrance for paleoclimate studies, however, is that the traditional method required reduction in an all metal vacuum line at high temperature (in externally-heated nickel reaction vessels) with bromine pentafluoride (BrFs), a highly reactive gas (Clayton and Mayeda 1963). Handling this material in anything other than a dedicated geochemistry laboratory has proven extremely difficult and dangerous (Chivas 1984). 

The bromination of meta-nitrotoluene is an example for a high-temperature, high-pressure (high p,T) side-chain bromination of alkylaromatics [25]. 

The key structural features of compound 1 are the chiral cis-diaryl benzox-athiin fused ring system, two phenols, and one phenol ether linkage with the pyrrolidinylethanol. Originally, SERM 1 was prepared by medicinal chemists from a key ketone intermediate 5 shown in Scheme 5.1. Compound 5 was prepared in four steps with rather low yield [4a], Among these steps, the high temperature de-methylation step and the use of extremely toxic MOM-C1 were not particularly suitable for scale-up. The ketone 5 was then brominated with PhMe3NBr3 (PTAB) and coupled with thiophenol 7 to produce adduct 8. The key step of the synthesis was the conversion of adduct 8 to cis-diaryl benzoxathiin 9 under the Kursanov-Parne reaction conditions (TFA/Et3SiH). This novel reaction allowed the formation... 

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