Acrylates 2-substituted

The reaction of methoxybutenyne with diethylcarbonate gives a mixture of substituted acrylates 119 and 120 (yield about 50%), which quantitatively form, with... 

Yuki, H. and Hatada, K. Sterospecific Polymerization of Alpha-Substituted Acrylic Acid Esters. Vol. 31, pp. 31, pp. 1—45. 

Tabic 1.3 Relative Rate Constants for Reactions of Radicals with Alkyl-Substituted Acrylate Esters CHR CFEcOaCHs"... 

Outcomes from the reactions of radicals with substituted acrylate esters depend on the attacking radical (refer Table 1.3 and Scheme 1.4). The results may be summarized as follows (the methyl substituent is usually considered to be electron donating - Section 1.2.2) ... 

There have heen many studies on the polymerizability of a-substituted acrylic monomers.3jU35 33S It is established that the ceiling temperature for a-alkoxyacrylates decreases with the size of the alkoxy group. 35 However, it is of interest that polymerizations of a-(alkoxymethyl)acrylates (67)3 15 and a-(acyloxymethyl)acrylates (68)and captodative substituted monomers (69, 70) 39 appear to have much higher ceiling temperatures than the corresponding a-alkylacrylates methyl ethacrylate, MEA). For example, methyl a-... 

Hydrostannation of chiral menthyl esters of substituted acrylic acids proceeds stereoselectiveiy, providing a route to optically active alkyl-... 

The work of Charton and Meislich (15) has already been referred to. Hogeveen (58) has reported a correlation of pKa values for tra s-3-substituted acrylic acids. Hogeveen (50) and Sandris (49) have studied the pKa values of 3-substituted cinnamic acids. Bowden (59) has also studied pKa values of frflns-3-substituted acrylic acids. 

As was noted previously, Hine and Bailey (16, 17) have obtained correlation of rate data for the reaction of tra s-3-substituted acrylic acids and diphenyl-diazomethane with the Hammett equation. Bowden has reported correlation of rate data for the reaction of tra s-3-substituted acrylic acids with diphenyl-diazomethane (59) and the alkaline hydrolysis of trans-3-substituted methyl acrylates (69) with the Hammett equation. Sufficient data are available for nine sets of rate studies. The sets studied are reported in Table VIII. The results of the correlations are given in Table IX. Of the nine sets studied, seven gave... 

Ionization constants of czs-3-substituted acrylic acids have been correlated with the Hammett equation by Hogeveen (58) and by Charton (60). Charton has correlated ionization constants for a number of other c/s-vinylene sets with the Hammett equation (60). Charton and Charton have correlated some cw-vinylene sets with the extended Hammett equation [eq. (2)] (73). Sufficient data are available for twelve sets of cis-vinylene equilibria, of which four sets represent ionization constants of hydroxy compounds (sets 12-1 to 12-4) and eight sets represent ionization constants of carboxylic acids (sets 12-5 to 12-12). All sets have been correlated with eq. (24) and eq. (2). Sets studied are reported in Table XII. Results of the correlations are reported in Table XIII. Sets designated A were correlated with eq. (24), sets designated B were correlated with eq. (2). In the case of the second ionization constant of 2,3,5,6-tetrahydroxy-l,4-benzoquinone (set 12-3), it is uncertain which hydroxyl group ionizes therefore, the value for X = OH was excluded from the correlation. All of the sets 12-1 to 12-4 gave significant correlations with both eq. (24) and eq. (2),... 

With regard to the composition of the electrical effects, values of pj for the sets studied are reported in Table XIV. The sets in which the hydroxyl group is the reaction site generally exhibit a Pr value of about 39. The cis-3-substituted acrylic acids show a p value of 39 in aqueous solution. The value of 71 obtained in 50% aqueous ethanol seems too large. 

Data are extant in the literature for two other sets of ethynylene compounds. The sets studied are reported in Table XXXIII. Results of correlation are set forth in Table XXXIV and values of Pr in Table XXXV. The ionization constants of 3-substituted propiolic acids, which were first correlated with the Hammett equation by Charton (18), gave an excellent correlation with eq. (2) (set 22-27-1). The results are very much improved by the elimination of the value for X = H (set 33-27-2). The composition of the electrical effect corresponds approximately to that of the Op constants. The magnitude of the electrical effect is significantly less than that observed for the rrans-3-substituted acrylic acids. 

Ru/(S)-BINAP Hydrogenation of substituted acrylic acid 5-Naproxcn Pharmaceutical 97... 

Brittelli, D.R., Preparation of Dialkyl- and Diarylphosphonoalkanoic Acids and Substituted Acrylic Acids, U.S. Patent 4,307,232, 1981. 

A general route to [l,2,4]triazolo[3,2-A][l,3]thiazines was discovered by Britsun etal. <2001ZOR1102, 2004KGS1256, 2004ZOR260>. In these publications, reaction of triazole thiones 332 with various substituted acrylic chlorides was reported to yield a series of ring-closed products 333 with the substituent of the reagent in the six-membered ring at the position adjacent to the sulfur atom. 

A wide range of a,fi-unsaturated carboxylic acids, including substituted acrylic acids, undergo enantioselective homogeneous hydrogenation when catalyzed by... 

A large number of substituted acrylic acids, R-CH=CHC02H, are known to yield in the solid the c/j-l,2-dicarboxylic acids of type 91. This is true, for example, when R = phenyl, substituted phenyl, naphthyl, or styryl. Thus a ring-opening reaction analogous to the above may provide an avenue to iso-merically pure cis,trans-dienes, trans,cis,trans-trienes, and so on. 

Yamamoto and colleagues showed that very high enantioselectivities and yields were obtained in the cycloadditions of cyclopentadiene with several a-substituted acrylic aldehydes using binaphthol catalyst 387 (equation 116). 

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