Bromine atoms, reaction

Figure 2.3. Potential energy changes during progress of reaction the methane-bromine atom reaction.

Most of the Arrhenius parameters listed in Table 7 for the bromine atom reactions have been determined in competitive experiments... 

The first stage (a) of the reaction represents the dissociation of bromine into bromine atoms. Both steps (b) and (c) lead to production of HBr, and since bromine atoms are... 

This method follows the ASTM D 1159 and D 2710 procedures and the AFNOR M 07-017 standard. It exploits the capacity of the double olefinic bond to attach two bromine atoms by the addition reaction. Expressed as grams of fixed bromine per hundred grams of sample, the bromine number, BrN, enables the calculation of olefinic hydrocarbons to be made if the average molecular weight of a sufficiently narrow cut is known. 

Although the transition to difhision control is satisfactorily described in such an approach, even for these apparently simple elementary reactions the situation in reality appears to be more complex due to the participation of weakly bonding or repulsive electronic states which may become increasingly coupled as the bath gas density increases. These processes manifest tliemselves in iodine atom and bromine atom recombination in some bath gases at high densities where marked deviations from TronnaF behaviour are observed [3, 4]. In particular, it is found that the transition from Lto is significantly broader than... 

Bromobenzene is a colourless liquid of b.p. 156°, and d, 1 50 it has a faint agreeable odour. The bromine atom, being directly joined to the benzene ring, is very inert, and the only common reactions in which it is split off from the ring are the Fittig reaction (p. 288) and the Grignard reagent (pp. 280-284). 

The reaction of chlorine and bromine with cycloalkenes illustrates an important stereo chemical feature of halogen addition Anti addition is observed the two bromine atoms of Br2 or the two chlorines of CI2 add to opposite faces of the double bond... 

The relative rates of reaction of ethane toluene and ethylbenzene with bromine atoms have been measured The most reactive hydrocarbon undergoes hydrogen atom abstraction a million times faster than does the least reactive one Arrange these hydrocarbons in order of decreasing reactivity... 

Introduction of a 3-bromosubstituent onto thiophene is accompHshed by initial tribromination, followed by reduction of the a-bromines by treatment with zinc/acetic acid, thereby utilizing only one of three bromines introduced. The so-called halogen dance sequence of reactions, whereby bromothiophenes are treated with base, causing proton abstraction and rearrangement of bromine to the produce the most-stable anion, has also been used to introduce a bromine atom at position 3. The formation of 3-bromotbiopbene [872-31-1] from this sequence of reactions (17) is an efficient use of bromine. Vapor-phase techniques have also been proposed to achieve this halogen migration (18), but with less specificity. Table 3 summarizes properties of some brominated thiophenes. 

Such a reaction is controlled by the rate of addition of the acid. The two-phase system is stirred throughout the reaction the heavy product layer is separated and washed thoroughly with water and alkaU before distillation (Fig. 3). The alkaU treatment is particularly important and serves not just to remove residual acidity but, more importantiy, to remove chemically any addition compounds that may have formed. The washwater must be maintained alkaline during this procedure. With the introduction of more than one bromine atom, this alkaU wash becomes more critical as there is a greater tendency for addition by-products to form in such reactions. Distillation of material containing residual addition compounds is ha2ardous, because traces of acid become self-catalytic, causing decomposition of the stiU contents and much acid gas evolution. Bromination of alkylthiophenes follows a similar pattern. 

These reactions occur on the benzylic hydrogens because these hydrogens are much more reactive. Competition experiments show, for example, that at 40°C a benzylic hydrogen of toluene is 3.3 times as reactive toward bromine atoms as the tertiary hydrogen of an alkane and nearly 100 million times as reactive as a hydrogen of methane. 

Hydrogen haHde addition to vinyl chloride in general yields the 1,1-adduct (50—52). The reactions of HCl and hydrogen iodide [10034-85-2], HI, with vinyl chloride proceed by an ionic mechanism, while the addition of hydrogen bromide [10035-10-6], HBr, involves a chain reaction in which a bromine atom [10097-32-2] is the chain carrier (52). In the absence of a transition-metal catalyst or antioxidants, HBr forms the 1,2-adduct with vinyl chloride (52). HF reacts with vinyl chloride in the presence of stannic chloride [7646-78-8], SnCl, to form 1,1-difluoroethane [75-37-6] (53). 

Methyl bromide slowly hydrolyzes in water, forming methanol and hydrobromic acid. The bromine atom of methyl bromide is an excellent leaving group in nucleophilic substitution reactions and is displaced by a variety of nucleophiles. Thus methyl bromide is useful in a variety of methylation reactions, such as the syntheses of ethers, sulfides, esters, and amines. Tertiary amines are methylated by methyl bromide to form quaternary ammonium bromides, some of which are active as microbicides. 

Many anthraquinone reactive and acid dyes are derived from bromamine acid. The bromine atom is replaced with appropriate amines in the presence of copper catalyst in water or water—alcohol mixtures in the presence of acid binding agents such as alkaU metal carbonate, bicarbonate, hydroxide, or acetate (Ullmaim condensation reaction). 

Other mechanisms must also operate, however, to account tor the fact that 5-10% of the product is formed with retained configuration at the chiral center. Isotopic labeling studies have also demonstrated that the 3-bromo-2-butyl radical undergoes reversible loss of bromine atom to give 2-butene at a rate which is competitive with that of the bromination reaction ... 

It is assumed that these alkaloids are formed by junetion at C that is, in the par -position to the hydroxyl group in ring I, beeause (1) the diazo-reaction in the two bimoleeular alkaloids is much less intense than with sinomenine, and (2) neither of the monobromosinomenines, in which the bromine atom is assumed to be at C, can be oxidised to a bimolecular... 

Bromination of 3 -hydroxy-B-homo-5a-cholestan-7-one acetate (54b) in the presence of hydrobromic acid gives a single thermodynamically stable monobromo ketone. To determine the position of the bromine atom, the sequence of reactions was repeated with compounds selectively deuterated in the 5a-position. 

The next major bonded phase project was the development of the GBR resin, which stands for modified glucose bonded on both the backbone and the ring of basic PDVB gels. The manufacture of this product was ultimately achieved, as outlined later. The gel is first brominated, which places bromine atoms on both tertiary hydrogens of the PDVB. The brominated gel is then reacted with chlorosulfonic acid, and a specially treated reduced D-glucosamine is coupled to the gel. This process has the potential to covalently bond up to three sugar residues to each available divinylbenzene residue in the PDVB polymer. The exact reaction conditions used are proprietary however, the surface of the finished product is believed to look similar to Figs. 13.11 and 13.12. 

In the reactions of 2,5-disubstituted thiophenes elimination of an a-substituent occurs to a much greater extent than in the benzene series. The Friedel-Crafts acetylation of 5-bromo-2-ethylthiophene in the presence of SnCE gives 2-ethyl-5-acetyIthiophene. Elimination of an a-bromine occurs also in the chloromethylation of 2,5-di-bromothiophene, leading to a mixture of 2-bromo-5-chloromethyIthio-phene and 2,5-dibromo-3-chloromethyIthiophene. Bromine atoms at both the and -position are exchanged for chlorine in the... 

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