Poly halogenation reaction

Di- and poly-halogenated aliphatic hydrocarbons. No general procedure can be given for the preparation of derivatives of these compounds. Reliance must be placed upon their physical properties (b.p., density and refractive index) and upon any chemical reactions which they undergo. 

Furan reacts vigorously with chlorine and bromine at room temperature to give poly-halogenated products. Low temperature (-40 °C) reaction of furan with chlorine in dichloromethane yields mainly 2-chlorofuran and reaction of furan with dioxane dibromide at 0 °C affords 2-bromofuran in good yield. 2-Iodofuran is obtained by treatment of 2-furoic acid with iodine and potassium iodide in aqueous sodium hydroxide. 

Little is known about the tolerance of 1 with unsaturated (poly)halogen compounds. Hydrozirconation of chloroalkenes can lead to competitive cycUzation, and simple reduction of both C=C and C-Cl bonds [98, 222], However addition of 1 to an alkenyl- or propargyl bromide led to the expected product as the sole product of the reaction in excellent yield (Scheme 8-30) [134, 223]. 

Porphyrinatoiron(IV) carbenes, including that resulting from the reaction of l,l-bis(p-chlorophenyl)-2,2,2-trichloroethane (DDT), are produced by reaction of poly-halogenated hydrocarbons with PFe (equation 57) i588,i589... 

A convenient method for the preparation of penta- and hexacoordinate silicon complexes was recently developed and reported [1]. The synthesis was based on an exchange reaction between poly-halogenated silanes with the O- or A-trimethylsilylated acylhydrazines and led to the formation of (0-Si)- and (N-Si)- mono and bis- chelate complexes (Scheme 1). 

The addition of elemental halogen or hydrogen halides to C-C multiple bonds is the most important halogenation reaction in industrial chemistry. At present, 1,2-dichloroethane (DCE, by chlorination of ethylene) is among those chemicals with the highest production rates and is now used as a starting material for the production of poly (vinyl chloride) (PVC, Scheme 2) [6], Vinyl chloride monomer (VCM) can be achieved by three different routes. 

Sulphones are blessed with high thermal and chemical stability so that oxidation of these species requires extreme, forcing conditions in most cases. However, poly-halogenated sulphones can be oxidized relatively easily to sulphonyl halides and these reactions will be discussed here. 

Halogenation reactions of unsaturated polymers follow two simultaneous paths, ionic and free radical. Ionic mechanisms give soluble products from chlorination reactions of polybutadiene." The free-radical mechanisms, on the other hand, cause crosslinking, isomerization, and addition products. If the free-radical reactions are suppressed, soluble materials form. Natural rubber can be chlorinated in benzene with addition of as much as 30% by weight of chlorine without cycliza-tion. " Also, chlorination of polyalkenamers, both cis and trans, yields soluble polymers. X-rays show that the products are partly crystalline. The crystalline segments obtained from 1,4-trans-polyisoprene are diisotactic poly( 0 /rw-dichlorobutamer)s while those obtained from the 1,4-cis isomer are diisotactic polyOAfieo-l,2-dichlorobutamer)s. ... 

Halogenation and hydrohalogenation of elastomers have been reported extensively in the literature [26]. The main problems with these reactions are the cyclization and chain scission that occur parallel to the halogenation reaction. These introduce difficult problems in the characterization of the resulting products. Despite these problems, several products have been prepared and commercialized. Chlorination of poly(l, 4-butadiene) to prepare a product similar to poly(vinyl chloride) has been reported by several workers [27]. This process had extensive side reactions and chain degradation. The chlorination of butyl rubber and conjugated diene-butyl rubbers gives end products that are used in the tire industry as inner liners for air retention. 

The mechanism exhibited in Fig. 7 is also applicable to the sMMO-catalyzed oxygenation of terminal olefins. The formation of primary alcohol and epoxide from terminal olefin is reasonably explained by applying the reaction mechanism for the poly halogenated ethene as shown in Scheme 5. Formation of a carbonium cation at the tertiary carbon must be predominant, because a carbonium cation at the primary carbon is very unstable. The predominant intermediate gives both primary alcohol and epoxide. The minor intermediate, a carbonium cation at the primary carbon, gives only epoxide. Secondary alcohol having a terminal olefin can not be formed via these intermediates. Therefore, this mechanism explains the formation of the primary alcohol from terminal olefins better than the radical mechanism. 

Halogen Displacement. Poly(phenylene oxide)s can also be prepared from 4-halo-2,6-disubstituted phenols by displacement of the halogen to form the ether linkage (48). A trace of an oxidizing agent or free radical initiates the displacement reaction. With 4-bromo-2,6-dimethylphenol, the reaction can be represented as in equation 10 ... 

Ethers, esters, amides and imidazolidines containing an epithio group are said to be effective in enhancing the antiwear and extreme pressure peiformance of lubricants. Other uses of thiiranes are as follows fuel gas odorant (2-methylthiirane), improvement of antistatic and wetting properties of fibers and films [poly(ethyleneglycol) ethers of 2-hydroxymethyl thiirane], inhibition of alkene metathesis (2-methylthiirane), stabilizers for poly(thiirane) (halogen adducts of thiiranes), enhancement of respiration of tobacco leaves (thiirane), tobacco additives to reduce nicotine and to reduce phenol levels in smoke [2-(methoxymethyl)thiirane], stabilizers for trichloroethylene and 1,1,1-trichloroethane (2-methylthiirane, 2-hydroxymethylthiirane) and stabilizers for organic compounds (0,0-dialkyldithiophosphate esters of 2-mercaptomethylthiirane). The product of the reaction of aniline with thiirane is reported to be useful in the flotation of zinc sulfide. 

The reaction takes place above 20 atms press and above 482°, with suitable H2 partial press and contact time necessary to obtain destructive hydrogenation without the formation of poly merized material. The resulting hydroformed naphthas may be halogenated, sulfonated or nitrated... 

The Ullman reaction has long been known as a method for the synthesis of aromatic ethers by the reaction of a phenol with an aromatic halide in the presence of a copper compound as a catalyst. It is a variation on the nucleophilic substitution reaction since a phenolic salt reacts with the halide. Nonactivated aromatic halides can be used in the synthesis of poly(arylene edier)s, dius providing a way of obtaining structures not available by the conventional nucleophilic route. The ease of halogen displacement was found to be the reverse of that observed for activated nucleophilic substitution reaction, that is, I > Br > Cl F. The polymerizations are conducted in benzophenone with a cuprous chloride-pyridine complex as a catalyst. Bromine compounds are the favored reactants.53,124 127 Poly(arylene ether)s have been prepared by Ullman coupling of bisphenols and... 

Recently, Baneijee et al. prepared a series of difluoro monomers with pendent trifluoromethyl groups using a Pd(0)-catalyzed cross-coupling reaction (Scheme 6.32).242,243 These monomers were converted to poly(arylene ether)s by nucleophilic displacement of the halogen atoms on the benzene ring with several... 

Polv(Arvloxyphosphazene) Elastomers. Poly(aryloxyphosphazene) elastomers, III, prepared by the reaction of chloropolymer with mixed phenoxides, offer excellent fire resistance without the incorporation of halogens in the polymer or as an additive. In addition, in a fire situation smoke evolution from these polymers... 

Table IV compares the X-ray exposure characteristics (at 8.3 X, Al Kai,2 emission line) of the halogenated resists and of PMMA Elvacite 20U1. It can be seen that poly(2-ehloroethyl methacrylates) and poly(2-bromoethyl methacrylates) exhibit a low sensitivity unlike poly(2-fluoroethyl methacrylates) and poly(2-, 2-,2-trifluoroethyl methacrylates) which are more sensitive than PMMA as shown in Figures 2a, 2b, 2c, 2d where the dose-thickness curves of these resists are plotted. The low sensitivity of the PC1EMA and PBrEMA samples may be explained by some competing crosslinking reactions which could occur during exposure as a result of C-Cl and C-Br homolytic bond scissions as noted by Tada...

Organo halogen compounds (RX, where X = Cl, Br) on heating generate HX by reaction with the polymer (poly-H) ... 

The most important process so far has been the reductive elimination of halogens with the formation of Si-Si bonds. Kipping used this reaction and discovered the first perphenylated cyclosilanes, yielding polysilanes as a by-product [8]. Similarly dodecamethylcyclohexasilane was found using dimethyldichlorosilane as a starting material for this reaction by Burkhardt in 1949, but 90% of the yield appeared as poly silane by-products [9]. 

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