A-halogenated products

Hell-VoLhard-Zelinskii (HVZ) reaction, in which an acid is treated with Bc2 and PBr3. The a-halogenated products can then undergo base-induced E2 elimination to yield a,j6-unsaturated carbonyl compounds. 

The combination of X2/protic acid (X2=Cl2,Br2> I2) is usually ineffective for reactions of conjugate addition, due to formation of significant amounts of a halogenation product. However, addition of a Lewis acid may alter the course of the reaction. For example, fluorosulfate 44 was isolated in 84% yield in the reaction of HFP with C12/H0S02F catalyzed by SbF5, but in the absence of the catalyst no formation of 44 was observed [82] ... 

When potassium platinocyanide in aqueous solution is acted upon by chlorine or bromine, a halogenated product of composition corresponding to the formula 3 (in the case of bromine)... 

We thus obtain a tri-halogen substitution product of the saturated hydrocarbon. These reactions may be repeated, yielding, each time, a halogen product of the saturated hydrocarbon containing one more halogen atom. We may thus pass from di-halogen ethane to hexa-halogen ethane. The entire series of reactions is as follows ... 

Carbonyl compounds are in a rapid equilibrium with their enols, a process called keto-enol tautomerism. Although enol tautomers are normally present to only a small extent at equilibrium and can t usually be isolated in pure form, they nevertheless contain a highly nucleophilic double bond and react with electrophiles, for example, aldehydes and ketones are rapidly halogenated at the a position by reaction with CI2 Br2, or I2 in acetic acid solution. Alpha bromination of carboxylic acids can be similarly accomplished by the Hell-Volhard-Zelinskii (HVZ) reaction, in which an acid is treated with Bi and PHr3. The a-halogenated products can then undergo base-induced E2 elimination to yield ,jS-unsaturated carbonyl compounds. 

The halogenation of an alkane occurs by a free radical mechanism. The first step is the formation of a halogen radical, which subsequently abstracts a hydrogen atom from the alkane. These steps yield a carbon radical, which reacts with the halogen molecule to give a halogenated product. 

That looks simple and direct don t it If safrole was used as the alkene one would get safrole-azide as product. Just one teensy little reduction away from MDA. Strike also found some azide papers that, with a little work, will get safrole-azide in a totally different way. Strike came across a lot of work where groups were using dinucleophilic addition to get an azide and a halogen added across a double bond. The azide would always go to the beta secondary carbon and the halogen to the primary carbon (just what one would want if safrole was the substrate). 

Thus a second method was envisaged, the reaction of a nitrile, hydrogen selenide, and an a-halogenated ketone in the presence of a condensation catalyst, which can be POCl, or POCI3 with a Lewis acid such as PCI3 or anhydrous ZnCl. The use of fresh AICI3 leads to the formation of tarry side-products. 

Another factor potentially affecting the market for halogenated fire retardants is the waste disposal of plastics (see Wastes, industrial). As landfiU availabihty declines or becomes less popular, two alternatives are incineration and recycling (qv). The nature of the combustion products from halogenated products requires carefiil constmction and maintenance of incinerators (qv) to avoid damage to the incinerator itself and a pubHc health problem from the exhaust. The ease of recycling used products also has a potential effect on fire retardants. 

Stannous fluoride probably was first prepared by Scheele in 1771 and was described by Gay-Lussac and Thenard in 1809. Commercial production of stannous fluoride is by the reaction of stannous oxide and aqueous hydrofluoric acid, or metallic tin and anhydrous hydrogen fluoride (5,6). Snp2 is also produced by the reaction of tin metal, HP, and a halogen in the presence of a nitrile (7). 

The limitations of this reagent are several. It caimot be used to replace a single unactivated halogen atom with the exception of the chloromethyl ether (eq. 5) to form difluoromethyl fluoromethyl ether [461 -63-2]. It also caimot be used to replace a halogen attached to a carbon—carbon double bond. Fluorination of functional group compounds, eg, esters, sulfides, ketones, acids, and aldehydes, produces decomposition products caused by scission of the carbon chains. 

For reaction with hydrogen haUdes, the substitution reaction with haUde ion easily occurs when a cuprous or cupric compound is used as the catalyst (23) and yields a halogenated aHyl compound. With a cuprous compound as the catalyst at 18 °C, the reaction is completed in 6 h. Zinc chloride is also a good catalyst (24), but a by-product, diaHyl ether, is formed. 

Displacement of the hydroxyl group is exemplified by the production of isopropyl haUdes, eg, isopropyl bromide [75-26-3] by refluxing isopropyl alcohol with a halogen acid, eg, hydrobromic acid [10035-10-6] (12). 

Meta.1 Oxides. Halogen-containing elastomers such as polychloropreae and chlorosulfonated polyethylene are cross-linked by their reaction with metal oxides, typically ziac oxide. The metal oxide reacts with halogen groups ia the polymer to produce an active iatermediate which then reacts further to produce carbon—carbon cross-links. Ziac chloride is Hberated as a by-product and it serves as an autocatalyst for this reaction. Magnesium oxide is typically used with ZnCl to control the cure rate and minimize premature cross-linking (scorch). 

Dkect synthesis is the preparative method that ultimately accounts for most of the commercial siUcon hydride production. This is the synthesis of halosilanes by the dkect reaction of a halogen or haUde with siUcon metal, siUcon dioxide, siUcon carbide, or metal sihcide without an intervening chemical step or reagent. Trichlorosilane is produced by the reaction of hydrogen chloride and siUcon, ferrosiUcon, or calcium sihcide with or without a copper catalyst (82,83). Standard purity is produced in a static bed at 400—900°C. 

The usual containers for shipping are glass for small quantities, and steel cans, dmms, or tank cars for bulk items. Over a period of time, moisture passes through the walls of some plastic containers. If this occurs, the more hydrolytically unstable borate esters may hydroly2e. Thus caution should be used when storing borate esters in plastic. In addition, shipping in metal cans or dmms is not acceptable where hydrolysis can lead to a corrosive product, such as a halogenated alcohol. 

The addition of HX, where X is a halogen, has been thoroughly investigated (32,33). Whether 1,2- or 1,4-product dominates depends on reaction... 

The chloride is readily available as a by-product of benzyl chloride [100-44-7] production (see Chlorocarbon and chlorohydrocarbons-BENZYL chloride, BENZAL CHLORIDE, AND benzotrichloride). The yield is comparable to the Perkin-based process, but the difficulty associated with removal of trace halogenated impurities makes the resultant cinnamic acid less desirable for many appHcations. 

The reaction of an alcohol with a hydrogen halide is a substitution. A halogen, usually chlorine or bromine, replaces a hydroxyl group as a substituent on carbon. Calling the reaction a substitution tells us the relationship between the organic reactant and its product but does not reveal the mechanism. In developing a mechanistic picture for a particular reaction, we combine some basic principles of chemical reactivity with experimental observations to deduce the most likely sequence of steps. 

Initiation step (Section 4.17) A process which causes a reaction, usually a free-radical reaction, to begin but which by itself is not the principal source of products. The initiation step in the halogenation of an alkane is the dissociation of a halogen molecule to two halogen atoms. 

Acetophenone.—The Fnedel-Crafts reaction, of which this pieparation is a type, consists in the use of anhydious aluminium chlonde for effecting combination between an aromatic hydrocarbon or its deiivative on the one hand, and a halogen i,Cl 01 Bi) compound on the othei. The leaction 13 always accompanied by the evolution of hydiochloiic or hydio-bromic acid, and the product is a compound with AlCl-j, which decomposes and yields the new substance on the addition of watei. This reaction has been utilised, as in the present case, (r) for the prepaiation of ketones, in which an acid chloiide (aliphatic or aromatic) is employed,... 

Thiophenedithiol (170) has been prepared by halogen-metal interconversion between the lithium salt of 4-bromo-3-thiophenethiol and n-butyllithium at —70°C, followed by reaction with sulfur/ IR, NMR, and UV spectra showed that this compound exists in the dithiol form (170). The compound obtained as a by-product in the... 

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