C-Br Bonds

Step 2 of the mechanism m Figure 6 12 is a nucleophilic attack by Br at one of the carbons of the cyclic bromonium ion For reasons that will be explained m Chapter 8 reactions of this type normally take place via a transition state m which the nude ophile approaches carbon from the side opposite the bond that is to be broken Recall mg that the vicinal dibromide formed from cyclopentene is exclusively the trans stereoisomer we see that attack by Br from the side opposite the C—Br bond of the bromonium ion intermediate can give only trans 1 2 dibromocyclopentane m accordance with the experimental observations... 

The reaction proceeds in the direction indicated because a C—F bond is much stronger than a C—Br bond... 

If the addition of Br to the alkene results in a bromonium ion, the anti stereochemistry can be readily eiqilained. Nucleophilic ring opening by bromide ion would occur by backside attack at carbon, with rupture of one of the C—Br bonds, giving overall anti addition. 

Sonication conditions were used with several CF3CXYZ (X = F, Cl, Br, Y = F, Cl, Br, H Z = Cl, Br) compounds and zinc and carbon dioxide to give CF3CXYCO2H [62] in moderate yields Hydrogenolysis of the C-Cl and C-Br bonds in CF3CFCICO2H and CF3CFBrC02H afforded CF3CFHCO2H [62]... 

Bromide ion donates an electron pair to the positively charged carbon atom, forming a C-Br bond and yielding the neutral addition product. 

First, look at the reaction and identify the bonding changes that have occurred. In this case, a C—Br bond has broken and a C-C bond has formed. The formation of the C-C bond involves donation of an electron pair from the nucleophilic carbon atom of the reactant on the left to the electrophilic carbon atom ol CH Br, so we draw a curved arrow originating from the lone pair on the negatively charged C atom and pointing to the C atom of CH3Br. At the same time the C—C bond forms, the C-Br bond must break so that the octet rule is not violated. We therefore draw a second curved arrow from the C-Br bond to Br. The bromine is now a stable Br- ion. 

As the reaction proceeds, ethylene and HBr must approach each other, the ethylene tt bond and the H—Br bond must break, a new C—H bond must form in the first step, and a new C—Br bond must form in the second step. 

We call the carbocation, which exists only transiently during the course of the multistep reaction, a reaction intermediate. As soon as the intermediate is formed in the first step by reaction of ethylene with H+, it reacts further with Br in a second step to give the final product, bromoethane. This second step has its own activation energy (AG ), its own transition state, and its own energy change (AG°). We can picture the second transition state as an activated complex between the electrophilic carbocation intermediate and the nucleophilic bromide anion, in which Br- donates a pair of electrons to the positively charged carbon atom as the new C-Br bond starts to form. 

We won t study the details of this substitution reaction until Chapter 11 but for now can picture it as happening by the pathway shown in Figure 8.6. The nucleophilic acetylide ion uses an electron pair to form a bond to the positively polarized, electrophilic carbon atom of bromomethane. As the new C-C bond forms, Br- departs, taking with it the electron pair from the former C-Br bond and yielding propyne as product. We call such a reaction an alkylation because a new alkyl group has become attached to the starting alkyne. 

The nucleophilic acetylide anion uses its electron lone pair to form a bond to the positively polarized, electrophilic carbon atom of bromomethane. As the new C-C bond begins to form, the C-Br bond begins to break in the transition state. 

As other examples, the reaction of an alkene with Br2 to yield a 1,2-dibro-mide is an oxidation because two C-Br bonds are formed, but the reaction of an alkene with HBr to yield an alkyl bromide is neither an oxidation nor a reduction because both a C-H and a C—Br bond are formed. 

Neither oxidation nor reduction One new C-H bond and one new C-Br bond formed... 

Q The nucleophile OH uses its lone-pair electrons to attack the alkyl halide carbon 180° away from the departing halogen. This leads to a transition state with a partially formed C-OH bond and a partially broken C-Br bond. 

O An electron pair from the benzene ring attacks the positively polarized bromine, forming a new C-Br bond and leaving a nonaromatic carbocation intermediate. 

Figure 18-4 illustrates the mechanism chemists have deduced for this reaction. This picture shows (A) the approach of the hydroxide ion, (B) the atomic arrangement thought to be the activated complex, and (C) the final products. In the activated complex the O—C bond is beginning to form and the C—Br bond is beginning... 

The synthesis of the trisubstituted cyclohexane sector 160 commences with the preparation of optically active (/ )-2-cyclohexen-l-ol (199) (see Scheme 49). To accomplish this objective, the decision was made to utilize the powerful catalytic asymmetric reduction process developed by Corey and his colleagues at Harvard.83 Treatment of 2-bromocyclohexenone (196) with BH3 SMe2 in the presence of 5 mol % of oxazaborolidine 197 provides enantiomeri-cally enriched allylic alcohol 198 (99% yield, 96% ee). Reductive cleavage of the C-Br bond in 198 with lithium metal in terf-butyl alcohol and THF then provides optically active (/ )-2-cyclo-hexen-l-ol (199). When the latter substance is treated with wCPBA, a hydroxyl-directed Henbest epoxidation84 takes place to give an epoxy alcohol which can subsequently be protected in the form of a benzyl ether (see 175) under standard conditions. 

X-ray diffraction analysis of crystalline poly(schiff base)s and their low molecular models shows that the formation of molecular complexes is accompanied by an increase in interplanar distances and, in a number of cases, by complete amor-phization. Molecular complexes of poly(schiff base)s with Br2 decompose with time, because of the bromination of the donor components, forming C—Br bonds. Substitution of hydrogen by bromine in phenyl groups occurs only in cases in which these groups are not included into the main polymeric chain. 

Electrochemical methods allowed to shed light on the different reaction mechanisms, both in homogeneous and heterogeneous (Ag20 promoted) systems. Furthermore, electroreduction reverses the C-Br bond polarity, allowing the formation of a C-C bond with an electrophile (f.ex. CO2). 

This paper reviews the recent studies in the field of radical reactions of organobromine compounds. A special attention is paid to the use of metal-complex systems based on iron pentacarbonyl as catalysts this makes it possible to perform the initiation and chain transfer reactions selectively at C-Br bond. 

The less efficient dibromomethane also reacts presumably with C-Br bond rapture, although some examples of reacting at a C-H bond are known (ref. 1). 

The easy homolysis of C-Br bond in CBr4 allowed us to conduct the radical chain reaction of CBr4 with 3,3,3-trifluoropropene under common conditions (benzoyl peroxide), although in this case the strong electrophiles are used as reagents (an addend and a monomer), i.e. a very unfavorable combination of polar factors for proceeding the process takes place (ref. 6). 

The occurrence of the CF3 group adjacent to the radical center gives the radical a strongly electrophilic character and only the energetically easy homolysis of C-Br bond in CBr4 allows us to conduct the following process as a chain one. 

The authors (ref. 19) managed to perform this reaction selectively as telomerization at the C-Br bond of bromoform using initiating system Fe(CO)5 + DMF, which facilitates a bromine transfer at a step of a chain transfer (ref. 19). In this case only one row of telomers is formed which contain three bromine atoms in molecules ... 

The use of metal-complex initiating systems proved to be especially promising in carrying out the reactions with acrylic monomers which can be easily polymerized, when the common initiators of radical reactions are excepted. The use of Fe(CO)s -I- DMFA system allows us to perform homolytical addition of bromoform to acrylic monomers selectively at C-Br bond with no essential polymerization (ref. 10). 

The structure of the adducts obtained (addition resulted from homolysis of C-Br bond) is an indirect evidence for radical character of the process. Ionic addition of haloforms is known to occur at C-H bond (ref. 11), this leads to adducts with CX3 group. The highest yield of the adduct with bromoform was obtained for... 

The estimation of reactivity of polyhalomethanes in the reactions with the same monomer shows that the quantity of halogen atoms in a molecule is the most essential factor affecting the easiness of homolysis of even one C— Br bond in molecule, and the influence of the halogen nature (chlorine or bromine) is of less significance. For instance, the analysis of the data on relative kinetics of some polyhalomethanes reactions with vinyl chloride allows us to grade the studied polyhalomethanes according to their reactivity, as follows ... 

Polybromochloromethanes containing two or even one C— Br bond are thus seen to be more efficient chain transfer agents than bromoform with three bromine atoms in molecule. 

Of bromochloromethanes reacting mainly at C— Br bonds, bromotrichloro-methane has been the most investigated compound. Both the various monomers and diversified routes of initiations were used in the studies of CCl3Br. The addition of bromotrichloromethane to a-olefines under common conditions of radical initiation has been described by a number of examples (ref. 3). 

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