Methyl acrylate, reaction with

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... 

The first iridium-catalyzed reductive aldol reaction was reported in 2001.422 Methyl acrylate reacts with certain aldehydes and diethylmethylsilane with high enantio- and diastereoselectivies (Equation (69)). 

Wamhoff and Huang obtained alkyl 2,3,4,9-tetrahydro-6-oxo-67/-pyrido[l,2-a]pyrimidine-9-carboxylates 237 in the reaction of 3-(hexahy-dropyrimidin-2-ylidene)-2(3.//)-furanones 235 (R3 = H) and methyl propi-olate in a refluxing alcohol in excellent yields (Scheme 17) (84CB1856). When the reactions were carried out in benzene or dioxane, addition products 236 could be isolated, which then were transformed in quantitative yields to tetrahydro-6-oxo-6//-pyrido[ 1,2-a ]pyrimidine-9-carboxyl-ates 237 by stirring in an alcohol at ambient or elevated temperature. When 3-(hexahydropyrimidin-2-ylidene)-2(3//)-furanones 235 (R3 = Me) were reacted with methyl acrylate or with dimethyl acetylenedicarboxy-late, hexahydro- and tetrahydropyridopyrimidin-6-ones 238 and 239, respectively, were obtained in good yields (84CB1926). 

Adaptation of these cyclization reactions allows for the introduction of new C-C-bonded substituents so that, for example, when the bromoethyl glycoside 216 is activated with radicals generated with allyltributyltin (in place of the tributyltin hydride), the main product is the 3-C-allyl compound 218. Otherwise, branching can be introduced by carrying out the radical-promoted reactions in the presence of radical-trapping species such as methyl acrylate.218 With appropriate compounds, the initial organic radicals formed during intramolecular cyclization can be trapped by... 

In an ideal world all chemical reactions would be carried out in water because solvent is the main by-product of all chemical processes and is difficult to recycle. For many reactions water as solvent is virtually impossible as reagents and/or catalysts are incompatible and/or insoluble in water. But Diels-Alder reactions are faster and more stereoselective in water even though the reagents generally don t dissolve.11 So cyclopentadiene 24 adds to methyl acrylate 59 with poor endo selectivity in cyclopentadiene as solvent. The selectivity improves in ethanol but is... 

The production of a,m-diesters from fatty esters can be realized via their SM as already explained, but it can also be performed by CM with methyl acrylate. The bulk CM of several unsaturated fatty acid methyl esters containing double bonds in different positions with methyl acrylate was studied by Rybak and Meier (Scheme 6) [43], C4 and C5 displayed very good activities with high conversions and CM selectivities. Among them, C5 showed the best performance for both methyl oleate (97% conversion, 92% selectivity, with 0.2 mol%) and methyl 10-undecenoate (99% conversion, 99% selectivity, with 0.1 mol%). The same conditions were successfully applied to methyl erucate and methyl petroselinate. The reaction conditions were further optimized, also considering the effect of 1,4-benzoquinone as additive for the reduction of double-bond isomerization [39], The CM of methyl 10-undecenoate and methyl acrylate worked with full conversions and high selectivity if five- to tenfold excess of methyl acrylate is used. Furthermore, using a 1 1 ratio between both reactants led, after optimization of the reaction... 

Methyl acrylate reacts with the enediamine 230 to yield the spiro-tetrahydroimidazo-pyridone 232 via the transient intermediate 231120. The reaction with methyl propiolate gives an analogous intermediate 233, which, however, is stable. It is transformed into the bicyclic dihydropyridone 234 by the action of methanol121 (equation 98). 

The reaction of poly(methyl acrylate)-Br with 2-aminoethanol was expected to result in multiple substituted products. This result was ascribed to the fact that after the substitution of the bromine by 2-aminoethanol, formation of a six-membered ring could occur (Scheme 18). Afterwards, ring opening by attack of a second 2-aminoethanol molecule could lead to the double-substituted product. The a-bromo poly(methyl acrylate) could be suppressed by using 4-aminobutanol instead of 2-aminoethanol as a nucleophile, without side reactions (Scheme 18). For example, the yield of functionalization of poly( -butyl acrylate) with 5-amino-l-pentanol is close to 96% [197]. 

Phosphonate analogues of Reissert compounds (76) have been prepared and converted into 1-alkyl-isoquinolines (Scheme 49). Treatment of a number of A -methylisocarbostyrils with mercuric acetate gave rise to 4-mercuri-ated derivatives, which underwent insertion reactions with methyl acrylate and with styrenes in the presence of palladium chloride (Heck reaction). 

Table 2 gathers the results obtained from the reaction of methyl acrylate (1) with cyclopentadiene (2) (Figure 1). Except for Na(l) exchanged clay, whose structure collapses upon calcination, calcination improves both catalytic activity and endo/exo selectivity. 

Subsequent work in the Markd group has shown that under high-pressure reaction conditions, methyl acrylate reacts with 2-pyrone to yield a mixture of all four possible isomeric bicyclic lactones. The identification of the major reaction product as the syn-endo isomer 28 was established by X-ray crystallographic analysis. This methodology was subsequently employed to synthesize dialdehyde 29 as an entry into the tricyclic core of gibberellic acid and zizaene. ... 

Under similar conditions, polymerization of methyl acrylate (MA) with AIBN as an initiator under microwave irradiation was carried out by Chia et al. [36]. To prepare samples for polymerization, 4.1 mg of AIBN (0.85 wt%) was taken in a 4-ml sample vial of 15 mm diameter together with 0.5 ml (478 mg) of MA. The reaction rate enhancement of microwave polymerization compared to thermal method was found to be as follows 500 W, 275% 300 W, 220% and 200 W 138%. Even though the comparable temperature at variable power was the same, 52 °C, the reaction rate enhancement increased with increase in microwave power indicating a significant correlation between the reaction rate enhancements and the level of microwave power used [36]. 

The regiospecificity of the olefin cycloaddition reaction depends on the substituent groups present on the double bond. Thus, acrylonitrile and methyl acrylate react with various nitrile ylides to give only the 4-substituted regio-isomers (i.e., 16). Photocycloaddition of arylazirines to a-methylacrylo-nitrile and methyl methacrylate, on the other hand, give adducts of type 33 and 34 in a 3 2 ratio. ... 

Bipyridyl(diethyl)platinum(ii) reacts with methyl acrylate with release of ethylene and formation of [Pt CH(Me)C02Me 2(bipy)]. No ethane was detected in the products and ethyl radicals are considered unlikely intermediates in the reaction. This contrasts with earlier studies of [Pt(R)2(L)2] complexes which react with diethyl fumarate to give [Pt(CHC02Et)a(L)J with release of alkyl radicals which could be trapped by Bu NO. Second-order kinetics were followed in the methyl acrylate reaction and if the stationary-state approximation is made for the intermediate [Pt(Et)2(CH2=CHCOaMe)] (19) in Scheme 10 the rate expression is... 

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