Primary bromine

All this business of swapping out bromine would be a lot easier if that bromine were at the end of that aliphatic chain which would make it a primary bromine (don t ask). As it so happens, the bromine in bromo-safrole is at a secondary position which means that... 

The 2,5-dibromo-2,5-dideoxy-D-xylono-1,4-lactone (6) (Scheme 2) can also be selectively reduced to give 5-bromo-2,5-dideoxy-D-fhreo-pentonolactone (7) by reaction with either aqueous hydrazine as mentioned above, or by consumption of 1 mole of hydrogen [ 14]. Further reaction with hydrogen and Pd/C leads to 3-hydroxypentanoic acid by an initial reductive elimination [15]. Reduction of the primary bromine in these cases can be obtained by means of tributyltin hydride [25] to give 8. 

Also, the fact that these products tend to dissolve faster than BCDMH can give rise to an effect similar to providing shock chlorine with a background of bromine. The primary bromine delivery system is tablets and feeders, the same as for BCDMH, which has found considerable favor with operators due to the simplicity and convenience. 

Synthesis of 3-alkylated piperidine derivatives could of course be performed most directly by alkylation of 2-deoxyaldono- 1,5-lactams, as outlined in Scheme 8. After unsucessfull experiments due to solubility problems, we turned our interest to the alkylation at C-2 of unprotected 2-deoxy- -bromodeoxyaldonolactons. This strategy requires set-up of a dianion in the presence of a primary bromine, followed by stereoselective alkylation at C-2, two possible doubtful reactions (Scheme 9). Gratifyingly, both reactions could be performed satisfactory. 

The mechanism for this remarkable selectivity is based on the hydrogen bonding between the reagent and the substrate. Two routes have been proposed (equation 102). This reaction has been used in a catalytic process in which NBS is the primary brominator and diisopropylamine is the catalyst (equation 103)757. 

The starting substance ClmeaSiCFbBr (primary bromination product of me3SiCl) leads to compound 1 by phenylation with C6HsMgBr, which is then converted to compound 2 by adding a Li suspension in diethylether at -20 °C. 

Mono-substitution products of primary amines cannot easUy be prepared by direct action of the appropriate reagent for example, bromination of aniline yields largely the 2 4 6-tribomo derivative and nitration results in much oxidation. If, however, the amino group is protected as in acetanilide, smooth substitution occurs. Thus with bromine, />-bromoacetanilide is the main product the small quantity of the ortlio isomeride simultaneously formed can be easily eliminated by crystallisation. Hydrolysis of p-bromoacetanilide gives/ -bromoaniline ... 

It consists in treating a solution of sodium iodide in pure acetone with the organic compound. The reaction is probably of the S 2 type involving a bimolecular attack of the iodide ion upon the carbon atom carrying the chlorine or bromine the order of reactivities of halides is primary > secondary > tertiary and Br > Cl. 

In practice this means that when an alkane contains primary secondary and tertiary hydrogens it is usually only the tertiary hydrogen that is replaced by bromine... 

Addition of a bromine atom to C 2 gives a primary alkyl radical... 

A secondary alkyl radical is more stable than a primary radical Bromine therefore adds to C 1 of 1 butene faster than it adds to C 2 Once the bromine atom has added to the double bond the regioselectivity of addition is set The alkyl radical then abstracts a hydrogen atom from hydrogen bromide to give the alkyl bromide product as shown m... 

Octabromodiphenyl Oxide. Octabromodiphenyl oxide [32536-52-0] (OBDPO) is prepared by bromination of diphenyl oxide. The degree of bromination is controlled either through stoichiometry (34) or through control of the reaction kinetics (35). The melting poiat and the composition of the commercial products vary somewhat. OBDPO is used primarily ia ABS resias where it offers a good balance of physical properties. Poor uv stabiUty is the primary drawback and use ia ABS is being supplanted by other brominated flame retardants, primarily TBBPA. 

TetrabromobisphenolA. TBBPA is the largest volume reactive flame retardant. Its primary use is in epoxy resins (see Epoxyresins) where it is reacted with the bis-glycidyl ether of bisphenol A to produce an epoxy resin having 20—25% bromine. This brominated resin is typically sold as a 80% solution in a solvent. TBBPA is also used in the production of epoxy oligomers which are used as additive flame retardants. 

The reactions of trialkylboranes with bromine and iodine are gready accelerated by bases. The use of sodium methoxide in methanol gives good yields of the corresponding alkyl bromides or iodides. AH three primary alkyl groups are utilized in the bromination reaction and only two in the iodination reaction. Secondary groups are less reactive and the yields are lower. Both Br and I reactions proceed with predominant inversion of configuration thus, for example, tri( X(9-2-norbomyl)borane yields >75% endo product (237,238). In contrast, the dark reaction of bromine with tri( X(9-2-norbomyl)borane yields cleanly X(9-2-norbomyl bromide (239). Consequentiy, the dark bromination complements the base-induced bromination. 

Occurrence. Magnesium bromide [7789-48-2] MgBr2, is found in seawater, some mineral springs, natural brines, inland seas and lakes such as the Dead Sea and the Great Salt Lake, and salt deposits such as the Stassfurt deposits. In seawater, it is the primary source of bromine (qv). By the action of chlorine gas upon seawater or seawater bitterns, bromine is formed (see Chemicals frombrine). 

The same products may be made from primary alkoxides by the violent reaction with elementary chlorine or bromine. A radical mechanism has been proposed to account for the oxidation of some of the alkoxy groups (54) ... 

Bromine or chlorine dissolved in hexamethylphosphoric triamide [680-31-9] (HMPT) with a base, eg, NaH2PO, present, oxidizes primary and secondary alcohols to carbonyl compounds in high yield (38). 

Bromine compounds are found ia the atmosphere ia small amounts the sea is a primary source. Rainfall over the Pacific and Indian Oceans has been found to contain 60—80 f-lg/L of bromine (46). Approximately 10 parts per trillion (v/v) of bromine is found ia the stratosphere (47). 

Traditional Processes. The two primary stripping vapors are steam and air. Steam is used when the concentration of bromine in brine is greater than 1000 ppm. The advantage is that bromine can be condensed direcdy from the steam. Air is used when seawater is the source of bromine because very large volumes of stripping gas are needed and steam would be too expensive. When air is used the bromine needs to be trapped in an alkaline or reducing solution to concentrate it. 

Zinc—bromine storage batteries (qv) are under development as load-leveling devices in electric utilities (64). Photovoltaic batteries have been made of selenium or boron doped with bromine. Graphite fibers and certain polymers can be made electrically conductive by being doped with bromine. Bromine is used in quartz—haUde light bulbs. Bromine is used to etch aluminum, copper, and semi-conductors. Bromine and its salts are known to recover gold and other precious metals from their ores. Bromine can be used to desulfurize fine coal (see Coal conversion processes). Table 5 shows estimates of the primary uses of bromine. 

Bromination has been shown not to exhibit a primary kinetic isotope effect in the case of benzene, bromobenzene, toluene, or methoxybenzene. There are several examples of substrates which do show significant isotope effects, including substituted anisoles, JV,iV-dimethylanilines, and 1,3,5-trialkylbenzenes. The observation of isotope effects in highly substituted systems seems to be the result of steric factors that can operate in two ways. There may be resistance to the bromine taking up a position coplanar with adjacent substituents in the aromatization step. This would favor return of the ff-complex to reactants. In addition, the steric bulk of several substituents may hinder solvent or other base from assisting in the proton removal. Either factor would allow deprotonation to become rate-controlling. 

Important differences are seen when the reactions of the other halogens are compared to bromination. In the case of chlorination, although the same chain mechanism is operative as for bromination, there is a key difference in the greatly diminished selectivity of the chlorination. For example, the pri sec selectivity in 2,3-dimethylbutane for chlorination is 1 3.6 in typical solvents. Because of the greater reactivity of the chlorine atom, abstractions of primary, secondary, and tertiary hydrogens are all exothermic. As a result of this exothermicity, the stability of the product radical has less influence on the activation energy. In terms of Hammond s postulate (Section 4.4.2), the transition state would be expected to be more reactant-like. As an example of the low selectivity, ethylbenzene is chlorinated at both the methyl and the methylene positions, despite the much greater stability of the benzyl radical ... 

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