Alkyl itaconates

The effect of the length of the side chain and the presence of the carboxylic group have been taken into account to explain the particular conformational behavior of some of these poly(itaconate)s [191,192], The effect of the length of the side group and the presence of the carboxylic group are the responsible of the particular conformational behavior of some poly(monoitaconate)s [191, 192], On the other hand poly(di-n-alkyl itaconate)s obtained from diester of itaconic acid and lower unbranched alcohols, show important changes in both solution and the solid state properties [182-185],... 

Allylstarch can be blended with lower alkyl itaconates in the ratio from 2 1 to 10 1 and then copolymerized with a variety of coating materials to enhance coating plasticity, drying, and hardening.1028 Allylstarch can be polymerized into insoluble products using either sulfur chloride or disulfur dichloride.1029 The reaction product of allylstarch with propylene oxide was utilized as a dispersant for petroleum emulsions.1030 Novel resinous materials have been obtained from adducts of unsaturated esters of dienophilic dioic acids and cyclic polyenic hydrocarbons with mono- and di-allyl starch.1031... 

Poly(di-n-alkyl itaconate)s have the general structure ... 

Mono-n-alkyl itaconate Vinylpyridine Single Tg FTIR I had an alkyl group of methyl, ethyl, /i-iMopyl, /i-butyl, /i-pentyl, or /i-hexyl II was 2- or 4-vinylpyridine Velada et al. (1996a, b)... 

Fig. 1. Variation of the glass transition and crystallization temperatures of poly(di-/ -alkyl itaconate)s plotted as a function of the number of carbon atoms in one side chain. Single Tg (O) Tg ( ) Tg ( ) melting temperatures (A) poly(di-oleyl itaconate) Tg (V) small melting endotherm ( ). ("Reproduced from J.M.G. Cowie, Z. Haq, I.J. McEwen, and J. Velickovic, Polymer, 22, 327 (1981), by permission of the publishers, Buttenvorth and Co. (Publishers) Ltd. "). 

J.M.G. Cowie Well, I d like to make the following comment. When we made the equivalent ethylene oxide side chain polymers, we did not see the same phraomena. You only see the phenomenon in the alkyl itaconates when there are 7-11 carbon atoms in the long chain, and our interpretation of that is as follows. 

Sedimentation velocity Turbidimetric titration -CO-acrylonitrile-CO-methyl methacrylate) Fractional precipitation i-CO-di-n-alkyl itaconates) (General)... 

The reaction can be applied to allyl malonates. Alkylation of diallyl mal-onate (734) with bromoacetate and acetoxymethylation afford the mixed triester 735. Treatment of the tricster 735 with Pd catalyst affords allyl ethyl itaconate (736). In a similar way, a-methylene lactone and the lactam 737 can be prepared[462]. 

Fluoroalkyl Acrylates—Alethacrylates—Itaconates—AIesoconates. Fluoroalkyl acrylates have been copolymerized with alkyl acrylates... 

Methylsuccinic acid has been prepared by the pyrolysis of tartaric acid from 1,2-dibromopropane or allyl halides by the action of potassium cyanide followed by hydrolysis by reduction of itaconic, citraconic, and mesaconic acids by hydrolysis of ketovalerolactonecarboxylic acid by decarboxylation of 1,1,2-propane tricarboxylic acid by oxidation of /3-methylcyclo-hexanone by fusion of gamboge with alkali by hydrog. nation and condensation of sodium lactate over nickel oxide from acetoacetic ester by successive alkylation with a methyl halide and a monohaloacetic ester by hydrolysis of oi-methyl-o -oxalosuccinic ester or a-methyl-a -acetosuccinic ester by action of hot, concentrated potassium hydroxide upon methyl-succinaldehyde dioxime from the ammonium salt of a-methyl-butyric acid by oxidation with. hydrogen peroxide from /9-methyllevulinic acid by oxidation with dilute nitric acid or hypobromite from /J-methyladipic acid and from the decomposition products of glyceric acid and pyruvic acid. The method described above is a modification of that of Higginbotham and Lapworth. ... 

Mention should also be made of the DuPhos-type hybrid 10 that works well for the reductions of itaconic acids [62]. A recent addition to the general class is trichickenfootphos (11) this has been developed for the reduction of enamides, dehydroamino acids and a,/ -unsaturated nitriles [63, 64]. (Throughout this chapter, R in generic structures denotes an alkyl group unless otherwise stated.)... 

A PYRPHOS ligand was found to be effective for the hydrogenation of a / -aryl- or alkyl-substituted monoamido itaconate [107]. A MeO-BIPHEP-Ru catalyst was successfully applied for the enantioselective hydrogenation of an intermediate for the drug candoxatril in a mixed solvent (THF/H20) (Scheme 26.12) [108]. 

Since the formation of Complex 11 from 10b is a second-order process and the formation of product from Complex 11 is a first-order process, their entropies of activation will be very different. A value of AS f = -121 J mol 1deg 1 has been reported for hydrogen addition to Yaska s compound, carbonylchloro bis-triphenylphosphineiridium(I) (12). As pointed out by Halpern (II), formation of the alkyl will be favored at low temperatures and it is observed to decay rapidly above -40°C. The observation and characterization of Complex 11 proved to be both fortunate and fortuitous, since we were unsuccessful in all of our attempts to form alkyls from chiraphos or DIOP, or from DiPAMP with itaconic acid derivatives. 

Fig. 1.20 Comparison of theory and experiment for the preferential adsorption coefficient, X, of poly(dialkyl itaconates) in 1,4-dioxane/methanol (pBO = methanol volume fraction). Points experimental results for PDMI (o), (alkyl = Me) PDEI (A) (Et) PDPI ( ) (nPr) PDBI (.) (nBu). Curves Association equilibria theory calculated with the set of parameter values shown in Table II. (From ref. [122])...

The effect of the side chain structure on the relaxational behavior of poly (itaconate)s was studied by Diaz Calleja and coworkers [238] in a family of poly(di-n-alkyl and diisoalkylitaconate)s. Specifically in poly(dimethyl itaconate) (PDMI), poly(diethylitaconate) (PDEI), poly(di-n-propyl itaconate) (PDPI), poly (di-n-butylitaconate) (PDIBI), poly(diisopropylitaconate) (PDIPI) and poly (diisobutylitaconate) (PDIBI). These systems show three dielectric relaxation processes, labelled as a, /3 and y. Nevertheless, in some polymers a poor resolution of... 

Rhodium and palladium catalysts that contain 4 display high enantioselectivities for the asymmetric hydrogenation of enamides, itaconates, P-keto esters, asymmetric hydroboration, and asymmetric allylic alkylation,80 82 but this ligand system distinguishes itself from other chiral bisphos-phines in the asymmetric reduction of tetrahydropyrazines and tetrasubstituted olefins (see also Chapter 15). The reduction of tetrahydropyrazines produces the piperazine-2-carboxylate core,... 

Some other interesting copolymers having properties of PVC thermal stabUizers, like poly[Af-(a-benzothiazolonylmethyl)methacrylate-co-methyl methacrylate] [45], of flame retardants like a terpolymer of styrene, acrylonitrile and a polymerizable perbrominated phenol [76] or poly[4-methacryloyloxy-2,3,5,6-tetrabromobenzyldi-phenyl phosphonate-co-methyl methacrylate] [104] (93), bioddes, mostly copolymers of monomers containing tris(n-butyl tin) or triphenyl tin moieties and alkyl acrylates, methacrylates, vinyl acetate, acrylonitrile, styrene or A-vinylpyrrolidone [105], e.g. a terpolymer of styrene, MMA and tri(n-butyl tin) itaconate [106] (94),... 

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