Chlorine addition reactions with

Addition reactions with bromine, chlorine, hydrogen bromide or hydrogen chloride are very vigorous and may be explosive if uncontrolled. 

These complexes, which are readily synthesized by transmetalation see Transmetalation) from the appropriate Cp metal and MX4 (L = U) or (jj -L)MX3 (L L ), represent a large family of qnite always air-stable componnds. The bromides and iodides are also obtained from chlorine exchange reactions with the appropriate boron trihalide. The flnorides can be obtained by metathesis see Metathesis) of chlorides derivatives with MesSnF. With only one equivalent of tin reagent per mole of dichloride, partial fluorination occms affording mixed hahde metallocenes. The fluorides are also prepared by chloride/fluoride, by chloride/NMe2 followed by NMe2/fluoride exchange, and by oxidative addition see Oxidative Addition). ... 

The decrease of the excitation energy required to form the pentavalent state of phosphorus as compared with nitrogen and its greater electropositive character, explains the readiness with which the tertiary phosphines undergo addition reactions with chlorine and sulphur. 

Oxidation was performed in aqueous acetic acid in the presence or absence of additives of strong mineral acids and chloride ions. CBT under these conditions may exist in an a-protonated form and act as an oxidant or it may give other oxidants with positively charged chlorine by reactions with the components of the reaction mixture. 

The reactions of the non-5-chlorinated 1,3,2,4,6-dithiatriazines are, in fact, reactions of the dimers. These undergo addition reactions with alkenes to give adducts (85CC929,85MCLC447,861C47, 86IC2119,91CB39>. 

The stereochemistry of certain thermal reactions involving atom addition processes and resultant radical intermediates can also be studied conveniently by recoil techniques. In this type of experiment the recoil atom used to initiate the process must be thermalized before reaction, by diluting the system with a large concentration of nonreactive bath molecules. Two recently reported results on geometric isomerization serve as examples of the type of processes that can be studied (55,56). Both involve recoil chlorine atom reactions with unsaturated substrates. 

Acetylene reacts with fluorine with explosive violence. Reactions with other halogens, chlorine, bromine, and iodine are violent, too. Acetylene chloride, which is formed from addition reaction with chlorine, explodes spontaneously. It forms unstable acetylides with metals such as copper,... 

Chlorine also reacts readily with tropolone by substitution, entering the 5-position more readily than does bromine [291,293]. Trichlorotropolones undergo addition reactions with more chlorine to give adducts which rearrange with formation of a six-membered ring [294]... 

Alkynes show the same kind of addition reactions with chlorine and bromine that alkenes do. 

Acetylene and other substances containing a carbon-carbon triple bond are very reactive. They readily undergo addition reactions with chlorine and other reagents, and they are classed as unsaturated substances. 

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 reaction can also be carried out with oleum, distilling the chlorosulfuric acid as it forms. Reaction with oxidizing oxyacids such as HNO Hberates chlorine. Anhydrous sulfates of the heavy metals form addition compounds with HCl that can be released by heating the complex to elevated temperatures. The complex CuSO 2HC1 has been used for storage and transport of HCl (23). 

Chlorine can be removed by either activated carbon adsorption or by reaction with olefins such as ethylene over-activated carbon at temperatures of 30—200°C (44). Addition of Hquid high boiling paraffins can reduce the chlorine content in the HCl gas to less than 0.01% (45). 

---