Allyl acrylate

Methyl, ethyl and allyl acrylate were first prepared in 1873 by Caspary and Tollens, and of these materials the last was observed to polymerise. In 1880 Kahlbaum reported the polymerisation of methyl acrylate and at approximately the same time Fittig found that methacrylic acid and some of its derivatives readily polymerised. 

Figure 3.4 Relative reactivity of indicated site towards /-butoxy radicals for allyl methacrylate (99) and allyl acrylate (100)...

Morken et al. developed a reductive Claisen rearrangement of substituted allyl acrylates. The reaction of ( )-hex-2-enyl acrylate 175 was catalyzed by [Rh(COD)Cl]2 (0.25 mol %) and Me-DuPhos (0.5 mol %) with C MeSiH in benzene at 22 °C to give y,8-unsaturated ester 176 with high diastereoselect-ivity, 11 1 (Scheme 46) [80]. The reaction was carried out on a 10 g scale to provide a 70% yield of 176. This reaction was applied to allylic ester 177 to provide 178, which is a key intermediate in the total synthesis of inos-tamycin [24],... 

Hydroxamic acids constitute an important class of siderophores, which play a major role in iron solubilization and transport. Some of them are important as therapeutic agents. The Michael addition of nitroacetyl proline esters to allyl acrylate followed by Pd(0)-catalyzed intramolecular allyl transfer and subsequent reduction of the nitro group yields a novel class of cyclic hydroxamic acids related to pyroglutamic acid (Scheme 5.9).85... 

Acetylenic acrylates have been used to reduce side reactions in the preparation of acrylic sil(ox)anes by hydrosilylation [13,14], Allylic acrylates are known to result in addition products with both types of double bonds. Elimination of propene under loss of the allylic group is a major concern, because this path yields acryloxy silicone compounds with SiOC linkages of low hydrolytic stability. 

Allyl acrylates have been reacted with the combination of ClMe2SiH/ [(cod)RhCl]2/Me-DuPHOS (l,2-bis(2,5-dimethylphospholano)benzene) to bring about reduction of the ,/l-unsaturated ester followed by a Claisen rearrangement to the y,8-unsaturated carboxylic acid (Eq. 293)474 Other silanes did not perform as well in this sequence. 

Allyl acrylate n-Butyl acrylate Methyl acrylate Methacrylonitrile Methyl isopropenyl ketone N-Vinyl pyrrolidone 2-Vinyl pyrrolidone Vinylidene chloride... 

Methacrylic acid Acrylic acid Di-isobutylene Acrylonitrile Allyl acrylate Allyl methacrylate n-Butyi acrylate n-Butyl methacrylate isobutyl methacrylate 2-Chloroethyl methacrylate -Ethoxyethyl methacrylate Ethyl acrylate 2-Ethylhexyl acrylate Ethyl methacrylate Lauryl methacrylate Nonyl methacrylate N-Vinyl pyrrolidone Octyl acrylate 2-Vinyl pyridine... 

Acrylonitrile Allyl acrylate Allyl methacrylate n-Butyl acrylate n-Butyl methacrylate Isobutyl methacrylate Divinyl benzene 2-Choroethyl methacrylate Ethyl acrylate /i-Ethoxyethyl methacrylate 2-Ethylhexyl methacrylate Ethyl methacrylate Methyl methacrylate Methylisopropenylketone Methyl vinyl ketone N-Vinyl pyrrolidone Styrene Vinylpyridine Acrylonitrile Allyl acrylate Allyl methacrylate... 

The cross-linking rate of EPR by radiation comes close to that of polypropylene. EPDM terpolymers exhibit an enhanced cross-linking rate, and it increases with the diene content. However, not only the cross-linking rate, but also a greater yield of scissions results from the addition of the third monomer. Cross-linking of EPR can be promoted by the addition of a variety of additives, particularly by those that were found effective in polypropylene. Tetravinyl silane, chlorobenzene, nitrous oxide, allyl acrylate, neopentyl chloride, and N-phenyl maleimide were reported to promote the process. 

Cross-linking of EPR can be promoted by the addition of a variety of additives, particularly by those that were found effective in polypropylene. Tetravinyl silane, chlorobenzene, nitrous oxide, allyl acrylate and neopentyl chloride,191192 and biphenyl maleimide177 were reported to promote the process. 

Allyl methacrylate and allyl acrylate are difunctional monomers, triallyl phosphate is a trifunctional monomer, and polyethylene glycol dimethacrylate is a polyfunctional monomer. All these lead to cross-linked graft copolymers. 

Usually, one would expect that an acrylate ester would be prepared by the acylation of an alcohol with acryloyl chloride. Jonathan M.J. Williams of the University of Bath reports (Tetrahedron Lett. 44 5523,2003) that this acylation can also be effected with the mild combination of Ph,P and maleic anhydride. The acrylate esters so prepared are interesting as polymerization precursors, and as Diels-Alder dienophiles. The allylic acrylates invite tandem conjugate addition / Ireland Claisen rearrangement. 

Figure 12.2 Synthesis of Allyl acrylate and Allyl methacrylate...

E.A. Youngman and F.F. Rust, Production of allyl acrylate from acrolein, CA Patent 708634, assigned to Shell Oil Co., April 27,1965. 

Several ester monomers have also been studied. In methanol solution, methyl acrylate (16,21), ethyl acrylate (21,54), 2-ethyl hexyl acrylate (55), allyl acrylate (44), glycidyl acrylate (56,57) usually in methanol solution, have been extensively studied. Methyl methacrylate (19, 21, 28, 30, 36, 39, 58) in diversified media composition, has been successfully grafted on polyamides. Vinyl acetate is reported also for grafting on polyamide backbone (19, 28, 35, 58), as well as n-butyl maleate in methanol solution (55). Diallyl maleate as cross-linking agent for polyamide chains is reported (44). Other less usual ester monomers have been mentioned in the literature to form grafts (41,59,60). 

The literature reports direct grafting by gamma-rays exposure of Nylon fibers or films to the following monomers carbon monoxide (/65), ethylene (157), propylene (157), acetylene (166), butadiene (157.162,163), styrene (158, 161,163,167,168), vinyl chloride (157,163), vinyl fluoride (169-172), vinyl acetate (161,163,173), vinyl propionate (161), vinyl butyrate (161), vinyl crotonate (161), vinyl 2-ethyl hexanoate (161), acrylic add (173,174), methyl acrylate (162, 163), ethyl acrylate (162,163), allyl acrylate (163), methyl methacrylate (28,161, 163,164), butyl methacrylate (161), acrylamide (158), methylol acrylamide (163), acrylonitrile (157,160-163, 167, 175-179), divinyl sulfone (161), vinyl pyridine (167,173), vinyl pyrrolidone (28) and triallyl cyanurate (158). 

Multicomponent tandem addition reactions have been investigated by Russell and coworkers. Addition of t-butyl radical to the allyl acrylate 70 with termination from dimethyldisulfide furnishes butyrolactone 71 as a diastereomeric mixture (remote center). However, the ring junction stereochemistry is exclusively trans [95JA3645],... 

The drawback of allylic, acrylic and vinylic polymerizable groups is their tendency to ho-mopolymerize. Allylic derivatives, furthermore, are susceptible to degradative chain transfer. 

Maleate Surfmers. Surfmers with allylic, acrylic and vinylic moieties tend to homopoly-merize and produce water-soluble polyelectrolytes if used above their CMC. This has shifted researchers attention to maleic derivatives that do not homopolymerize at normal temperatures because their ceiling temperature is too low. Tauer and co-workers have pioneered the synthetic work [4,15] which led originally to compounds like those given in Figure 6.49. An example of maleic-derived Surfmer used in emulsion polymerization lattices is reported in [16] and the advantages provided in commercial paint formulations are discussed later. 

An interesting extension of the cyclopolymerization strategy is the polymerization of allyl acrylate quaternary ammonium salts, where the resulting ester precursor of 7 is easily hydrolyzed by trifluoroacetic acid to the polybetaine [23]. Polyampholyte 8 was prepared by copolymerization with a high excess of DADMAC [24]. 

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