Acryloyl

Pentanedioyl, see Glu-taryl CH2—CH2— pynyl Propenoyl, see Acryloyl 1-Propenyl CH3—CH=CH—... 

Property AcryHc acid Acrolein AcryHc anhydride Acryloyl chloride Acrylamide... 

Carboxylic Acid Functional Group Reactions. Polymerization is avoided by conducting the desired reaction under mild conditions and in the presence of polymeriza tion inhibitors. AcryUc acid undergoes the reactions of carboxyUc acids and can be easily converted to salts, acryhc anhydride, acryloyl chloride, and esters (16—17). 

Jicyylic anhydride is formed by treatment of the acid with acetic anhydride or by reaction of acrylate salts with acryloyl chloride. Jicryloylchloride is made by reaction of acryhc acid with phosphorous oxychloride, or benzoyl or thionyl chloride. Neither the anhydride nor the acid chloride is of commercial interest. 

Monomethylacryloyl and vinylbenzyl derivatives of sucrose have been prepared as intermediates for polymers, and preparation of a range of copolymers of styrene and O-methjiacryloylsucrose has been described (114). Synthesis of 4- and 6-0-acryloylsucrose has been achieved by acid-catalyzed hydrolysis of 4,6-0-(l-ethoxy-2-propenyhdene)sucrose (76). These acryloyl derivatives have been polymerized and copolymerized with styrene (qv). 

Acylation of the enamine (113) with a,/9-unsaturated acid chlorides has been shown (57) to give bicyclo(3.3.1)nonan-2,9-diones. Acryloyl ehloride on reaction with the enamine (113) and subsequent hydrolysis gave bicyelo-(3.3.1)nonan-2,9-dione (123). Mechanistic studies suggest that C alkylation by the olefin precedes acylation (87). 

Acryloyl chloride can be used to cause ring enlargement with the production of a bicyclodiketone when it is treated with a cyclohexanone enamine. This is shown by the reaction of acryloyl chloride (25) with 1-N-morpholino-1-cyclohexene (26), affording diketone 27 upon hydrolysis (32,33). 

Kanemasa et al. discovered an asymmetric Diels-Alder reaction of acryloyl-oxazolidi-none and cyclopentadiene catalyzed by a chiral aqua complex of 4,6-dibenzofurani-dyl-2,2 -bis(4-phenyloxazoline) 16 (vide infra) [22]. Unlike the Diels-Alder reaction of acryloyloxazolidinone, for which NiBr2/AgC104 and Znl2/AgC104 are the most suitable sources of the central metal, the best for the Diels-Alder reaction of a-bromo-... 

Corey et al. reported that the catalyst 19, prepared from trimethylaluminum and the bis-trifluorosulfonamide of stilbenediamine (stien), with generation of methane, is a suitable catalyst for the Diels-Alder reaction of 3-acryloyl, and 3-crotonoyl-l,3-oxazo-lidin-2-ones, giving the cycloadducts in high optical purity [28] (Scheme 1.35, Table 1.14). X-ray structure analysis of the catalyst and and NMR studies revealed that... 

A quinoline-phosphine ligand has been developed by Buono et ah, and its complex 29 with Cu(OTf)2 found to be an effective catalyst for the Diels-Alder reaction between acryloyl-oxazolidinone and cyclopentadiene, affording the cycloadduct... 

The Diels-Alder reaction catalyzed by this chiral titanium catalyst 31 has wide generality (Scheme 1.53, 1.54, Table 1.22, 1.23). Acryloyl- and fumaroyl-oxazolidinones react with isoprene giving cycloadducts in high optical purity. 2-Ethylthio-l,3-buta-diene can also be successfully employed as the diene [42]. 

The TiX2-TADD0Late-catalyzed 1,3-dipolar q cloaddition reactions were extended to include an acrylate derivative [66]. In the absence of a catalyst, the reaction between nitrones 1 and acryloyl oxazolidinone 19b proceeded to give a mixture all eight regio-and stereoisomers (Scheme 6.23). However, application of in this case only 10 mol% of Ti(OTs)2-TADDOLate 23d as catalyst for the reaction of various nitrones 1 with alkene 19b, led to complete regioselectivity and high endo selectivity in the reaction and the endo products 21 were obtained with 48-70% ee (Scheme 6.23) [66]. 

The complexation procedure included addition of an equimolar amount of R,R-DBFOX/Ph to a suspension of a metal salt in dichloromethane. A clear solution resulted after stirring for a few hours at room temperature, indicating that formation of the complex was complete. The resulting solution containing the catalyst complex was used to promote asymmetric Diels-Alder reactions between cyclopen-tadiene and 3-acryloyl-2-oxazolidinone. Both the catalytic activity of the catalysts and levels of chirality induction were evaluated on the basis of the enantio-selectivities observed for the endo cycloadduct. 

Although the aqua nickel(II) complex A was confirmed to be the active catalyst in the Diels-Alder reaction, no information was available about the structure of complex catalyst in solution because of the paramagnetic character of the nickel(II) ion. Either isolation or characterization of the substrate complex, formed by the further complexation of 3-acryloyl-2-oxazolidinone on to the l ,J -DBFOX/ Ph-Ni(C104)2 complex catalyst, was unsuccessful. One possible solution to this problem could be the NMR study by use of the J ,J -DBFOX/Ph-zinc(II) complex (G and H, Scheme 7.9) [57]. 

We are the first group to succeed with the highly enantioselective 1,3-dipolar cycloadditions of nitronates [75]. Thus, the reaction of 5,6-dihydro-4H-l,2-oxazine N-oxide as a cyclic nitronate to 3-acryloyl-2-oxazilidinone, at -40 °C in dichloro-methane in the presence of MS 4 A and l ,J -DBFOX/Ph-Ni(II) complexes, gave a diastereomeric mixture of perhydroisoxazolo[2,3-fe][l,2]oxazines as the ring-fused isoxazolidines in high yields. The J ,J -DBFOX/Ph aqua complex prepared from... 

Unfortunately the reaction of trimethylsilyldiazomethane with 2-acryloyl-2-oxa-zolidinone led to a racemic result. Since 2-acryloyl-2-oxazolidinone has a terminal-... 

Acryloyl chloride (0.2 mol) in dry benzene (60 ml) was added over 0.5 hour with mechanical stirring to pentane-1,5-diol (0.1 mol), triethylamine (0.2 mol) and pyrogallol (0.1 g) in dry benzene (100 ml). Further dry benzene (ca 100 ml) was added followed by triethylamine (10 ml), and the mixture stirred at 50°C for 0.5 hour. The triethylamine hydrochloride was fii-tered off and the solvent removed In vacuo to leave a yellow oil which was distilled in the presence of a trace of p-methoxyphenol, excluding light, to give 1,5-pen tarn ethylene diacrylate (12.9g 61% BP90°to95°C/0,01 mm Hg),... 

Benzoctamine HCI ChlorthenoxazIne Hydroxytryptophan Letosteine Methionine Acrylonitrile Fenproporex Acryloyl chloride... 

Free amino acids can be derivatized with isothiocyanates to phenyl- or methyl-thiohydantoin derivatives. The thiohydantoins can be separated on a CSP with poly-[Af-acryloyl-L-phenylalanine ethylester] (Chiraspher ) as a chiral selector [25]. This CSP offers a known selectivity for many five-membered heterocyclic rings. 

Urea has no promoting effect on the A AM polymerization initiated with Ce(lV) ion. Recently, Qiu et al. [24] have studied the effect of N-acryloyl-N -4-tolylurea (ATU), N-methacryloyl-N -4-tolylurea (MTU), and N-acetyl-N -4-tolylurea (AcTU) on A AM polymerization initiated with Ce(IV) ion and found that these three urea compounds have a high promoting effect on the polymerization of AAM. The data are cited in Table 4. 

Qiu et al. [241 have reported the synthesis of macromolecules having 4-tolylureido pendant groups, such as poly(N-acryloyl-N -4-tolylurea-cvi ethyl acrylate) [po-ly(ATU-co-EA)] 18, and poly(N-methacryloyl-A/ -4-tol-ylurea-co-EA) [poly(MTU-co-EA)] 19, from the copolymerization of ATU and MTU with EA, respectively. Graft copolymerization of acrylamide onto the surface of these two copolymer films took place using the Ce(lV) ion as initiator. The graft copolymerization is proposed as Scheme (12). 

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