Halogenation—Addition of Halogen

Mechanism 10.2 Electrophilic Addition of H2O to an Alkene—Hydration Step [1] Addition of the electrophile (H ) to the n bond 

The n bond attacks H3O, thus forming a new C - H bond while breaking the H-0 bond. Because the remaining carbon atom of the original double bond is left with only six electrons, a carbocation intermediate is formed. This step is rate-determining because two bonds are broken but only one bond is formed. 

H Removal of a proton with a base (H2O) forms a neutral 

Problem 10.22 What two alkenes give rise to each alcohol as the major product of acid-catalyzed hydration  

Problem 10.23 What stereoisomers are formed when 1-pentene is treated with H2O and H2SO4  

Halogenation is the addition of halogen X2 (X = Cl or Br) to an alkene, forming a vicinal dihalide. 

Halogenation is synthetically useful only with CI2 and Br2, because the addition of I2 is often too slow iind the addition of F2 is too explosive. The dichlorides and dibromides formed in this reaction serve as starting materials for the synthesis of alkynes, as we learned in Section 8.10. 

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MarkownikofT s rule The rule states that in the addition of hydrogen halides to an ethyl-enic double bond, the halogen attaches itself to the carbon atom united to the smaller number of hydrogen atoms. The rule may generally be relied on to predict the major product of such an addition and may be easily understood by considering the relative stabilities of the alternative carbenium ions produced by protonation of the alkene in some cases some of the alternative compound is formed. The rule usually breaks down for hydrogen bromide addition reactions if traces of peroxides are present (anti-MarkownikofT addition). 

Bromination of fatty acids in the a-position can be effected quite readily in the presence of phosphorus trichloride, red phosphorus or pyridine as catalysts or halogen carriers with acetic acid, the addition of acetic anhydride (to ensure the absence of water) improves the yield and facilitates the bromination. Examples are —... 

The reaction must be carried out in the absence of direct sunlight, since sunlight causes direct addition of the halogen to the hydrocarbon, particularly if the latter is warm benzene, for example, yields the hexahalide ... 

Sulphur, as sulphide ion, is detected by precipitation as black lead sulphide with lead acetate solution and acetic acid or with sodium plumbite solution (an alkaLine solution of lead acetate). Halogens are detected as the characteristic silver halides by the addition of silver nitrate solution and dilute nitric acid the interfering influence of sulphide and cyanide ions in the latter tests are discussed under the individual elements. 

The halogen in the 5-position of 2-aminothiazoles is usually reactive and is used for further reaction (see Chapter V). The reaction may take place in the same medium as thiocyanation (437-440), rhodanation (441). or reaction with NaNO (435). Similarly, a mixture of 2-amino-4-methylthiazole and thiourea in H2O yields 5,5 -thiobis(2-amino-4-methyDthiazole (202) after addition of iodine (Scheme 128) (442). 

With the exception of the nuclear amination of 4-methylthiazole by sodium amide (341, 346) the main reactions of nucleophiles with thiazole and its simple alkyl or aryl derivatives involve the abstraction of a ring or substituent proton by a strongly basic nucleophile followed by the addition of an electrophile to the intermediate. Nucleophilic substitution of halogens is discussed in Chapter V. 

It is also possible to start from chloroacetaldehyde derivatives such as 1,2-dihalogeno ethyl acetate yields can reach 90% (356). These compounds can be easily obtained by addition of halogen to the double bond of vinylacetate at 0 to 10°C. 

Many of the features of the generally accepted mechanism for the addition of halogens to alkenes can be introduced by referring to the reaction of ethylene with bromine... 

Table 6 3 shows that the effect of substituents on the rate of addition of bromine to alkenes is substantial and consistent with a rate determining step m which electrons flow from the alkene to the halogen Alkyl groups on the carbon-carbon double bond release electrons stabilize the transition state for bromonium ion formation and increase the reaction rate... 

Addition of halogens (Sections 6 14-6 16) Bromine and chlorine add to alkenes to form vicinal dihalides A cy clic halonium ion is an intermediate Stereospecific anti addition is observed... 

Halogenation (Section 9 13) Addition of 1 mole of chlorine or bromine to an alkyne yields a trans dihaloalkene Atetrahalide is formed on addition of a second equivalent of the halogen... 

Halonium ion (Section 6 16) A species that incorporates apos itively charged halogen Bridged halonium 10ns are inter mediates in the addition of halogens to the double bond of an alkene... 

Addition of halogens proceeds stepwise, sometimes accompanied by oxidation. Iodine forms 2,3-diiodo-2-butene-l,4-diol (53). Depending on conditions, bromine gives 2,3-dibromo-2-butene-l,4-diol, 2,2,3,3-tetrabromobutane-l,4-diol, mucobromic acid, or... 

Addition of approximately 40% of the halogen flame retardants are needed to obtain a reasonable degree of flame retardancy. This usually adversely affects the properties of the plastic. The efficiency of the halogens is enhanced by the addition of inorganic flame retardants, resulting ia the overall reduction of flame-retardant additive package and minimising the adverse effects of the retardants. 

Alumina trihydtate is also used as a secondary flame retardant and smoke suppressant for flexible poly(vinyl chloride) and polyolefin formulations in which antimony and a halogen ate used. The addition of minor amounts of either zinc borate or phosphoms results in the formation of glasses which insulate the unbumed polymer from the flame (21). 

Unsaturated Polyesters. There are two approaches used to provide flame retardancy to unsaturated polyesters. These materials can be made flame resistant by incorporating halogen when made, or by adding some organic halogen compound when cured. In either case a synergist is needed. The second approach involves the addition of a hydrated filler. At least an equal amount of filler is used. 

Olefin Polymers. The flame resistance of polyethylene can be increased by the addition of either a halogen synergist system or hydrated fillers. Similar flame-retarder packages are used for polypropylene (see Olefin polymers). Typical formulations of the halogen synergist type are shown in Table 15 the fiUer-type formulations are in Table 16. 

Historically, the discovery of one effective herbicide has led quickly to the preparation and screening of a family of imitative chemicals (3). Herbicide developers have traditionally used combinations of experience, art-based approaches, and intuitive appHcations of classical stmcture—activity relationships to imitate, increase, or make more selective the activity of the parent compound. This trial-and-error process depends on the costs and availabiUties of appropriate starting materials, ease of synthesis of usually inactive intermediates, and alterations of parent compound chemical properties by stepwise addition of substituents that have been effective in the development of other pesticides, eg, halogens or substituted amino groups. The reason a particular imitative compound works is seldom understood, and other pesticidal appHcations are not readily predictable. Novices in this traditional, quite random, process requite several years of training and experience in order to function productively. 

Halogenation and Hydrohalogenation. Halogens add to the triple bond of acetylene. FeCl catalyzes the addition of CI2 to acetylene to form 1,1,2,2-tetrachloroethane which is an intermediate in the production of the industrial solvents 1,2-dichloroethylene, trichloroethylene, and perchloroethylene (see Chlorocarbons and chlorohydrocarbons). Acetylene can be chlorinated to 1,2-dichloroethylene directiy using FeCl as a catalyst... 

The binder system of a plastic encapsulant consists of an epoxy resin, a hardener or curing agent, and an accelerating catalyst system. The conversion of epoxies from the Hquid (thermoplastic) state to tough, hard, thermoset soHds is accompHshed by the addition of chemically active compounds known as curing agents. Flame retardants (qv), usually in the form of halogens, are added to the epoxy resin backbone because epoxy resins are inherently flammable. 

Phosphate Esters. The principal advantage of phosphate esters is the improved fire retardancy relative to phthalates. The fire performance of PVC itself, relative to other polymeric materials, is very good due to its high halogen content, but the addition of plasticizers reduces this. Consequendy there is a need, in certain demanding appHcations, to improve the fire-retardant behavior of dexible PVC. 

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