Chloromaleic anhydride

Maleic anhydride has been used in many Diels-Alder reactions (29), and the kinetics of its reaction with isoprene have been taken as proof of the essentially transoid stmcture of isoprene monomer (30). The Diels-Alder reaction of isoprene with chloromaleic anhydride has been analy2ed using gas chromatography (31). Reactions with other reactive hydrocarbons have been studied, eg, the reaction with cyclopentadiene yields 2-isopropenylbicyclo[2.2.1]hept-5-ene (32). Isoprene may function both as diene and dienophile in Diels-Alder reactions to form dimers. 

Dibasic acids and derivatives chloromaleic anhydride, R = Cl maleic anhydride, R = H... 

Chlorohydroxotricyclohexylantimony, 3 7 7 /V-Chloroimines, 73 102 Chloroisocyanurates, 73 114, 115 Chloromaleic anhydride, Diels-Alder adduct from cyclopentadiene, 8 222t Chloromethane(s)... 

The kinetic method in GC was used for the first time in 1960 by Gil-Av and Herzberg-Minzly [40], who identified cis and trans isomers of conjugated dienes on the basis of their different reactivities in a reaction with chloromaleic anhydride, which was used as the liquid stationary phase. 

Such a method was used for the first time by Gil-Av and Herzberg-Minzly in studying the reaction of conjugated dienes with chloromaleic anhydride [40]. 

Fig. 2.2 [64] shows chromatograms of commercial-grade 1,3-pentadiene, obtained on two columns connected in series, the first column containing a saturated solution of silver nitrate in ethylene glycol and the second containing chloromaleic anhydride reacting with a trans isomer. As a result of the reaction the relative content of the irons isomer decreases. The pseudo-first-order rate constant varied from 2.0-10 to 1.4 10 sec (the half-time of transformation changed from 30 to 100 sec) [64]. 

Fig. 2.2. Chromatograms of 1,3-pentadiene on a composite column containing silver nitrate (column 1) and a column reactor containing chloromaleic anhydride (column 2) at40°C [64]. Carrier gas (helium) flow-rate (A) 77ml/min (B) 11.4ml/min. First peak area (trans isomer) (A) 60% (B) 31%. From ref. 64.

The possibility of identifying cis- and trans-isomers of 1,3-dienes, based on the fact that the trans-isomer reacts faster than the c/s-isomer with the dienophilic chloromaleic anhydride, was demonstrated by Gil-Av and Herzberg-Minzly [93]. They proposed the use of comparatively slow chemical reactions for identifying the peaks of unknown compounds. As a result of these reactions the zones of the reacting compounds are subtracted only partially ( partial subtraction method ). The reagent used, as a Uquid stationary phase, was chloromaleic anhydride, which reacts selectively with dienes. Later this method was also used successfully by Alekseeva and Solomatina [94]. 

Other compounds reacting similarly via activated double bonds (excluding here block or graft copolymerization) include maleic acid, A-methyl-maleimide, chloromaleic anhydride, fumaric acid, y-crotonolactone,/7-benzoquinone, and acrylonitrile. Other polymers with unsaturated backbones, such as polybutadiene, copolymers of butadiene with styrene and with acrylonitrile, and butyl rubber, react in similar ways, but the recorded reaction with poly(vinyl chloride) is largely mechanochemical in nature (discussed later). 

Plates from AcOH. M.p. l9l-2°. Sol. HgO, EtOH, EtjO. Spar. sol. CgHg. Sublimes. Boil —> chloromaleic anhydride. NaHg — > succinic acid, k (first) = 1-72 X 10- (second) = 155 X 10. ... 

MegCO. par. sol. CeHg, ligroin. Cold KOH —> chlorofumaric acid. Boiling aq. Na salt chloromaleic acid Na salt. ACgO at 150 — chloromaleic anhydride. 

In a series of more recently published papers, solvent effects, kinetics, steric effects, and ultraviolet initiation in the region of absorption of the complex were studied. Guilbault and Butler [41] found chloromaleic anhydride to copolymerize with divinyl... 

A closely related reaction is observed with chloromaleic anhydride (218), which gives the apparent aryne adduct 216 with tetracyclone (151) but stops at the Diels-Alder adduct 219 with other dienes such as cyclopentadiene (146b), butadiene (146e), and anthracene (147). Not only does this result suggest the absence of an elimination-addition mechanism via the aryne (23) in this system. 

Little has been published on techniques for achieving the homopolymerization of mono or disubstituted MA monomers (see Chapter 3). Thamm and Hensinger recently showed that y irradiation of dichloromaleic anhydride (DCMA) in benzene produced a polymer as the main product. The yield and molecular weight of the polymer increased with radiation dose. The polymer backbone contained chlorophenylsuccinic anhydride residues. It was shown that chlorophenylmaleic anhydride was produced during the reaction. Under the same conditions, dimethylmaleic anhydride (DMMA) failed to polymerize with free-radical, ionic, and UV initiation with sensitizers.Presumably, techniques may be found for the homopolymerization of chloro or phenyl-maleic anhydride. Chloromaleic anhydride (CMA) reacts with methyl radicals more readily than MA and much more readily than DCMA. " This, coupled with halogen activation and ring coplanarity, should allow CMA to be homopolymerized. It is known that CMA will copolymerize with styrene, methyl methacrylate, butadiene, cyanoacrylates, and other olefins. 

MA copolymerization, 538 synthesis from dichlorosuccinic acid, 61 Chloromaleic anhydride applications, 63 grafting to polyethylene, 462 radical copolymerization, 263, 280, 326 synthesis route, 60... 

In connection with a wider study on new indigoid dyes, the trichochrome-like chromophore (55) (see Vol. 2, pp. 772—776) has been obtained by a novel one-step inverse indigo synthesis involving the reaction of 1 mole of 2,3-di-chloromaleic anhydride (53) with 2 moles of 2-aminothiophenol or its zinc salt... 

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