Chloroalkylation

In addition to the above, cyclic polymers, e.g. (RjSiOln, and also three-dimensional polymers can be formed. The exact nature of the polymer (its structure, and whether it is liquid or solid at room temperatures) will depend upon the substituted chloroalkyl-(or aryl-)silicane, or mixture of substituted silicanes, used and upon the experimental conditions. 

Pentabromodiphenyl Oxide. Pentabromodiphenyl oxide [32534-81-9] (PBDPO) is prepared from diphenyl oxide by bromiaation (36). It is primarily used as a flame retardant for flexible polyurethane foams. For this appHcation PBDPO is sold as a blend with a triaryl phosphate. Its primary benefit ia flexible polyurethanes is superior thermal stabiUty, ie, scorch resistance, compared to chloroalkyl phosphates (see Phosphate esters). 

The question as to whether a flame retardant operates mainly by a condensed-phase mechanism or mainly by a vapor-phase mechanism is especially comphcated in the case of the haloalkyl phosphoms esters. A number of these compounds can volatilize undecomposed or undergo some thermal degradation to release volatile halogenated hydrocarbons (37). The intact compounds or these halogenated hydrocarbons are plausible flame inhibitors. At the same time, thek phosphoms content may remain at least in part as relatively nonvolatile phosphoms acids which are plausible condensed-phase flame retardants (38). There is no evidence for the occasionally postulated formation of phosphoms haUdes. Some evidence has been presented that the endothermic vaporization and heat capacity of the intact chloroalkyl phosphates may be a main part of thek action (39,40). 

Cross-linked macromolecular gels have been prepared by Eriedel-Crafts cross-linking of polystyrene with a dihaloaromatic compound, or Eriedel-Crafts cross-linking of styrene—chloroalkyl styrene copolymers. These polymers in their sulfonated form have found use as thermal stabilizers, especially for use in drilling fluids (193). Cross-linking polymers with good heat resistance were also prepared by Eriedel-Crafts reaction of diacid haUdes with haloaryl ethers (194). 

Isoprene reacts with a-chloroalkyl ethers in the presence of ZnCl in diethyl ether from 0—10°C. For example,a-chloromethyl methyl ether at 10°C gives a 6 1 ratio of the 1,4-adduct, (F)4-chloro-l-methoxy-2-methyl-2-butene, to the 1,2-adduct, 2-chloro-l-methoxy-2-methyl-3-butene. Other a-chloroalkyl ethers react in a similar manner to give predominately the 1,4-addition product. A wide variety of aHyUc chlorides and bromides and a-chloroethers and esters add primarily 1,4- to isoprene in the presence of acid catalysts (8). 

Olefins react with tert-huty hydroperoxide in the presence of tert-huty hypochlorite, forming tert-huty P-chloroalkyl peroxides (66) ... 

Phosphoms compounds are effective flame retardants for oxygenated synthetic polymers such as polyurethanes and polyesters. Aryl phosphates and chloroalkyl phosphates are commonly used, although other compounds such as phosphonates are also effective. The phosphoms compounds can promote char formation, thereby inhibiting further ignition and providing an efficient thermal insulation to the underlying polymer. 

Sulfur dichloride undergoes many of the same reactions with organic compounds as described for sulfur monochloride. Addition to olefins affords a route to bis(2-chloroalkyl) sulfides and, ia certain cases, heterocycHc sulfides (159,160). 

P-Ghloroalkoxy Titanates. The reaction of TiCl with epoxides, such as ethylene or propylene oxide (qv), gives P-chloroalkyl titanates (8,9). One example is Ti(OCH2CH2Cl)4 [19600-95-5]. The P-chloroalkoxy titanates can be used to biad refractory powders and ia admixture with diethanolamine to impart thixotropy to emulsion paints (10). 

Protonated /V-chloroalkyl amines under the influence of heat or uv light rearrange to piperidines or pyrroHdines (Hofmann-Lriffler reaction) (88). The free-radical addition of alkyl and dialkyl-/V-chloramines to olefins and acetylenes yields P-chloroalkji-, P-chloroalkenyl-, and 8-chloroalkenylamines (89). Various N-hiomo- and N-chloropolyfluoroaLkylarnines have been synthesized whose addition products to olefinic double bonds can be photolyzed to fluoroazaalkenes (90). 

The kinetics of formation and hydrolysis of /-C H OCl have been investigated (262). The chemistry of alkyl hypochlorites, /-C H OCl in particular, has been extensively explored (247). /-Butyl hypochlorite reacts with a variety of olefins via a photoinduced radical chain process to give good yields of aUyflc chlorides (263). Steroid alcohols can be oxidized and chlorinated with /-C H OCl to give good yields of ketosteroids and chlorosteroids (264) (see Steroids). /-Butyl hypochlorite is a more satisfactory reagent than HOCl for /V-chlorination of amines (265). Sulfides are oxidized in excellent yields to sulfoxides without concomitant formation of sulfones (266). 2-Amino-1, 4-quinones are rapidly chlorinated at room temperature chlorination occurs specifically at the position adjacent to the amino group (267). Anhydropenicillin is converted almost quantitatively to its 6-methoxy derivative by /-C H OCl in methanol (268). Reaction of unsaturated hydroperoxides with /-C H OCl provides monocyclic and bicycHc chloroalkyl 1,2-dioxolanes. 

Isoxazoles are presently known to undergo hydrogen exchange, nitration, sulfonation, halogenation, chloroalkylation, hydroxymethylation, Vilsmeier-Haack formylation, and mercuration. The Friedel-Crafts reaction on the isoxazole nucleus has not yet been reported. 

Chloroalkyl ethersf (chloromethyl, chloroethyl, and mixed ethers)... 

BLANC QUELLET Chtoroalkylation Lewis acid catalyzed aromatic chloromethylation (Blanc) chloroalkylation (Quellet)... 

On the organic side of the interface, chemical bonds are formed between the organofunctional R group of the silane and the reactive species in the polymer matrix. For example, a methacrylate- or styryl-functional silane reacts with polyesters copolymerized with styrene or similar monomers, while amino- or chloroalkyl-functional silanes are unsuitable in this particular case. Polybutadiene... 

The synthesis of fluoroalkyl and chloroalkyl fluoromethyl ketones is achieved by oxidation of the corresponding alcohols by sodium dichromate and sulfunc acid in methylene chlonde in the presence of a phase transfer catalyst [49] (equation 45)... 

In analogy to alkylation with chloroalkyl ethers, methyl ot-methoxyperfluoro-propionate reacts with 2,6-dimethylphenol to give the bispheiiol [7] (equation 7)... 

Trichloroethyl, 397 2-Haloethyl, 397 ft)-Chloroalkyl, 398 2-(Trimethylsilyl)ethyl, 399 2-Methylthioethyl, 400 1,3-Dithianyl-2-methyl, 400 2-(p-Nitrophenylsulfenyl)ethyl, 400 2-(p-Toluenesulfonyl)ethyl, 401 2-(2 -Pyridyl)ethyl, 401 2-(p-Methoxyphenyl)ethyl, 402 2-(Diphenylphosphino)ethyl, 402... 

An interesting intermediate 30 was proposed to result from the sequential addition of pyridine to tetrachlorocyclopropene (31). Compound 30 represents an alkyl nitrogen ylide with two 1-chloroalkyl pyridinium moieties in the same molecule. Pyridines with electron-withdrawing groups and heterocycles with an electron-deficient nitrogen, for example, pyridine-3-carbaldehyde or quinoline, react with 31 to yield the corresponding mono-substituted products 32a and 32b (83JOC2629) (Scheme 8). 

From a practical point of view, literature data indicate that it is not necessary in most cases to isolate the title salts prior to their reaction. Tliis can be readily understood since their preparation is nearly quantitative and sulfur dioxide is the sole product evolved during their formation. In fact, it is highly advisable to recourse to a two-step procedure during the reactions between A -(l-chloroalkyl)pyridinium chlorides and amino acids (Section IV,C,6) (97BSB383). 

It has been proposed (89JOC4808) that the first step of a reaction between an amine and an N-(l-chloroalkyl)pyridinium chloride 33 is a simple substitution of the halogen atom yielding a mixed bisonium salt 55 (pathway a in Scheme 19). Tliis is the final product when various nitrogen het-... 

Tliere is only one report concerning the reaction of A -(l-chloroalkyl)-pyridinium chlorides with secondary diamines (92BSB233). 2-Substituted 1,3-dimethyl- and 1,3-diphenyl-imidazolidines 79 have been prepared (75-95% yields) starting from either -dimethyl- or A, A -diphenylethane-1,2-diamines, respectively (Scheme 25). Reactions are particularly fast for the preparation of the 1,3-dimethylimidazolidines. Reaction times as short as 5 min have been claimed. 

Reactions between A -(l-chloroalkyl)pyridinium chlorides 33 and amino acids in organic solvents have a low synthetic value because of the low solubility of the amine partner. A special protocol has been designed and tested in order to circumvent this drawback. Soon after the preparation of the salt, an aqueous solution of the amino acid was introduced in the reaction medium and the two-phase system obtained was heated under reflux for several hours. However, this was not too successful because sulfur dioxide, evolved during the preparation of the salt, was converted into sulfite that acted as an 5-nucleophile. As a result, A -(l-sulfonatoalkyl)pyridinium betaines such as 53 were obtained (Section IV,B,3) (97BSB383). To avoid the formation of such betaines, the salts 33 were isolated and reacted with an aqueous solution of L-cysteine (80) to afford thiazolidine-4-carboxylic acids hydrochlorides 81 (60-80% yields). 

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