Chlorinated dicarboxylic acid

Amino fatty acids can he treated wilh a mixture of nitric oxide and chlorine to produce the corresponding chloroacid. Mono- and dichlorosuccinic acids are examples of chlorinated dicarboxylic acids. 

The saturated dicarboxylic acids act as modifiers. While aliphatic dicarboxylic acids can be used, the most common one is orthophthalic acid (added to the reaction mixture as an anhydride). The acid improves compatibility with styrene that is polymerized in the presence of the polyester to form hard, rigid, crosslinked materials. Other modifiers are used to obtain special properties. When a flexible product is needed, adipic or sebacic acids may be used instead. For better heat resistance endomethylene tetrahydrophthalic anhydride (nadic anhydride) may be utilized. Hame retardancy is achieved by using chlorinated dicarboxylic acids, like tetrachlorophthalic. 

Brahmbhatt, V. V., C. J. Albert, D. S. Anbukumar, B. A. Cunningham, W. L. Neumann, and D. A. Ford. 2010. Omega -oxidation of alpha -chlorinated fatty acids Identification of alpha -chlorinated dicarboxylic acids. 285(53) 41255-69. 

Treatment of bipyridine-dicarboxylic acid 191 in alcohols with thionyl chloride and gaseous chlorine furnished the corresponding trichloroindolizines 193 through the intermediary of diesters 192 (Scheme 6) <2002J(P 1) 1688, 2002MI1, 2002MOL628>. 

Cycloalkanones are oxidatively cleaved to yield dicarboxylic acids, together with their chlorinated derivatives [23]. The initial a-chlorination is followed by solvolysis... 

Of the wide array of platinum derivatives, carboplatin is the only compound except cisplatin that is used in medical practice, and it differs from cisplatin in the replacement of two chlorine atoms with a cyclobutan-l,l-dicarboxylic acid fragment. Like cisplatin, carboplatin also reacts with DNA to form both internal and external cross-bonds. The range and indications of use are practically analogous to cisplatin. Synonyms of this drug are paraplatin and others. 

The selective carbonylation of 4,7-dichloroquinoline proceeds readily and the chlorine in the more active 4-position reacts preferentially to give quinolinecarboxylic acid derivatives in excellent yield (7.65.), The carbon-chlorine bond in the 7-position is so unreactive that attempts at the preparation of dicarboxylic acid derivatives were only moderately successful.86... 

Furthermore, di- and polychlorination are much less prevalent. Dicarboxylic acids are predominantly chlorinated in the middle of the chain,99 and adamantane and bicy-clo[2.2.2]octane at the bridgeheads100 by this procedure. The reasons for the high to - 1 specificity are not clearly understood.101 Alkyl bromides can be regioselectively chlorinated... 

Furan-2,5-dicarboxylic acid reacts similarly, but a temperature of 150°C is required for the reactions to proceed. Again, reaction in the presence of disulfur dichloride gives exclusively the fluorinated product, 2,5-difluoro-2,5-bis(trifluoromethyl)-2,5-dihydrofuran (21), while in the presence of chlorine a mixture of chlorofluoro derivatives 22 and 23 is formed.245... 

The diacid components for the manufacture of poly( -phenyleneisophthalamide) and poly( -phenyleneterephthalamide) are produced by one of two processes. In the first, the diacid chlorides are produced by the oxidation of >% -xylene [108-38-3] orxylene [106 -2-3] followed by the reaction of the diacids with phosgene [75-44-5]. In the second, process m- or p-xylene reacts with chlorine initiated by ultraviolet light to form the m- or % he x achl o r o xylene. This then reacts with the respective aromatic dicarboxylic acid to form the diacid chloride. 

More than 100 organochlorines have been identified and structurally characterized in the laboratory chlorination of terrestrial humic acid, although the major products are chloroform and trichloroacetic acid, followed by dichloroacetic acid and chlorinated C-4 dicarboxylic acids (324). In addition, other products that form in the chlorination of both humic acid and the model compound 3,4-dihydroxybenzoic acid are shown in Scheme 3.11. A more recently discovered source of natural organically bound chlorine is peat, reaching to 0.2% of the dry weight, and estimated to have accumulated globally to the extent of 280-1,000 million tons (169). 

Plasticizers include the esters of a few aliphatic and aromatic mono and dicarboxylic acids, aliphatic and aromatic phosphorus acid esters, ethers, alcohols, ketones, amines, amides, and non-polar and chlorinated hydrocarbons. These additives are used in various mixtures. For their separation and qualitative detection, thin-layer chromatography (TLC) is preferred. Usually Kieselgur plates, 0.25 mm thick, activated at 110°C for 30 min, in the saturated vapor are used. Methylene chloride and mixtures of diisopropyl ether/petether at temperatures between 40 to 60°C have been successfully used as the mobile phase. Refer to Table 1. 

Oxidation reactions included the use of alkaline permanganate, alkaline copper(II)oxide, and aqueous chlorine (Schnitzer and Khan, 1972 Christman et al., 1989).The degradation products consisted of aromatic and aliphatic acids. Aliphatic dicarboxylic acids ranging from ethanedioic to decanedioic acids were identified. Methylation prior to oxidation prevented phenolic groups from degradation and allowed gas chromatography (GC) analysis. 

Onodera et al. [8] examined the applicability of isotachophoresis to the identification and determination of chlorinated mono- and dicarboxylic acids in chlorinated effluents. Four electrolyte systems for the separation of acids were evaluated. The potential unit values in each system were determined for the chlorinated acids. A mechanism for the reaction of phenol with hypochlorite in dilute aqueous solutions is suggested, based on results from the isotachophoretic analysis of diethyl ether extracts taken from phenol treated with hypochlorite. 

Fig. 8-15. Possible carboxyl group structures formed in cellulose during chlorine and hypochlorite stages. 1, Arabinonic acid 2, erythronic acid 3, glucuronic acid 4, dicarboxylic acid.

Phenoxy-5,13-pentacenequinone (IV) was obtained by the replacement of chlorine atoms with phenoxy groups in 5-chloro-6,13-pentacenequinone in a phenol-phenoxide melt (Scheme 7).57 5-Chloro-6,13-pentacenequinone was synthesized by cyclization of 2-(l-chloro-2-naphthoyl)-3 naphthoic acid, which was prepared by acylation of a-naphthol with anhydrous naphthalene-2,3-dicarboxylic acid and by the subsequent treatment of the resultant 2-(l-oxy-2-naphthoyl)-3 naphthoic acid with phosphorus pentachloride. 

The reaction of furancarboxylic acids with sulfur tetrafluoride leads to the corresponding trifluoromethyl-substituted furans in good yields (see examples in Table 6). A number of furancarboxylic acids, mainly furan-2-carboxylic acids, and furan-2,5- and -3,4-dicarboxylic acids, show a different behavior. Here highly fluorinated dihydrofurans, e g. 25, are formed. This class of compounds is also obtained with the reagent system sulfur tetrafluoride/hydrogen fluoridc/chlorine or sulfur tetrafluoride/hydrogen fluoride/sulfuryl chloride. In some cases chlorine-containing products are found. 

A conjugated chlorofluorination of furan-2,5-dicarboxylic acid (1) occurs on heating with the sulfur tetrafluoride/hydrogen fluoride/chlorine system. 

Silver salts of carboxylic acids react with bromine or chlorine in an inert solvent to give carbon dioxide, a silver halide, and the halide containing one less carbon atom than the acid. The method has been reviewed. " Both low- and high-molecular-weight aliphatic bromides have been prepared. "t i i The degradation of silver salts of aromatic acids is complicated by nuclear halogenation." The procedure is valuable as a step in the synthesis of oi-bromo esters (C, to C,) from dicarboxylic acids. ... 

Preparation of (R)-l involves the chlorination of (R)-l,l-bina-phthyl-2,2-dicarboxylic acid with scc-BuLi and hexachloro-ethane. Condensation of the resulting dichorinated product with 3-chloro-2-chloromethyl-l-propene, followed by oxidative cleavage of the olefin moiety with ruthenium trichlorde affords (R)-l in modest yields. 

Some thermosets are made with maleic anhydride only, or with other unsaturated 1,2-dicarboxylic acids or anhydrides such as itaconic acid or methylenesuccinic acid [7], chlorendic acid or 1,4.5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic acid (or anhydride), 1,4.5,6,7-pentachloro-5-norbornene-2,3-dicarboxylic acid anhydride or 1,4.5,6-tetrachloro-5-norbornene-2,3-dicarboxylic acid anhydride. These norbomene derivatives can be obtained from the Diels-Alder condensation of the chlorinated cyclopenta-1,3-dienes and maleic anhydride, as shown in the following reaction ... 

Stevens, C. V., Vanderhoydonck, B. Use of acylphosphonates forthe synthesis of a-chlorinated carboxylic and a,a -dichloro dicarboxylic acids and their derivatives. Tetrahedron 2001, 57, 4793-4800. 

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