3-Methoxy-2- acrylate

The key step in the total synthesis of rhizobitoxine is the Pd-catalyzed exchange reaction of the methyl alkenyl ether moiety in 4 with the functionalized alcohol, although the yield is low[3]. The enol pyruvate 6 (a-ethoxyacrylic acid) is prepared by the reaction of methyl a-methoxyacrylate or a-methoxy-acrylic acid (5) with ethanol catalyzed by PdCl2(PhCN)2 at room temperature in the presence of CuCli and NaH2P04[4],... 

However, a careful HPLC analysis of the mixture arising from the photo-stimulated reaction between a-methoxydeoxybenzoin and methyl ot-methoxy-acrylate at room temperature demonstrated that a considerable number of products are formed during this reaction [62]. Besides the expected products, some were found to result from the addition of a captodative (methoxy)-(methoxycarb-onyl)alkyl radical to the captodative olefin itself, i.e. a propagation step. The HPLC analysis was not quantitative, but the presence of these products even at high olefin/initiator ratio (2/1) implies that a propagation step cannot be ruled out for all the above experiments only on the basis of the isolation of low-molecular weight products in good yields. As we will show the polymerizability of captodative olefins is confirmed by an analysis of the literature. 

Benzenethiol (9) itself can partake in 1,4-addition to the methyl ester 10 of 2-fluoro-3-methoxy-acrylic acid to yield the nionothioacetal ll. ... 

The skeletal structure of oxindoles of the secoyohimbane type, typified by rhynchophylline and isorhynchophylline, rests on a mass of chemical and physical evidence which has been discussed in earlier volumes. Some physical properties of members of this group are presented in Table II. The UV spectra of all the oxindole alkaloids are closely related (Table III) and are satisfactorily explained on the basis of contributions of an oxindole and a -methoxy acrylic ester... 

Scheme 11.2 Reaction equations and the corresponding activation energies and pre-experimental factors (MA = methyl acrylate, 3MAC = 3-methoxy acrylate.

Synonyms Acrylic acid, 2-methoxyethyl ester Ethanol. 2-methoxy-, acrylate Ethylene glycol monomethyl ether acrylate Glycol monomethyl ether acrylate 2-Methoxyethanol acrylate 2-Methoxyethyl acrylate P-Methoxyethyl acrylate Methyl Cello lve acrylate 2-PrDpenoic acid, 2-methoxyethyl ester Classification Monomer Empirical CsHioO,... 

Amongst other 1,3-dicarbonyl equivalents which will serve for interaction wifli thioglycolates are 3-chloro-enones [94] and 3-chloro-enals [95, 96] (illustrated in Schemes 61 and 62 - the latter also showing the use of a nitro group in lieu of an ester, leading to a 2-nitrothiophene), 3-amino-enones [94], 3-methoxy-acrylates [97] 3,3-bis(methylthio)-enones (producing 5-methylthio-products) [98] and 3-phenylthio-enones [99]. 

When methyl 2-(indol-2-yl)acrylate derivative (22a) reacted with A-methoxy-carbonyl-l,2-dihydropyridine (8a) in refluxing toluene, in addition to the dimer of 22a (25%), a mixture of the expected isoquinculidine 23a and the product 24a (two isomers) was obtained in 7% and 45% yields, respectively (81CC37). The formation of 24a indicates the involvement of the 3,4-double bond of dihydropyridine. Similarly, Diels-Alder reaction of methyl l-methyl-2-(indol-2-yl)acrylate (22b) with 8a gave, in addition to dimer of 22b, a mixture of adducts 23b and 24b. However, in this case, product 23b was obtained as a major product in a 3 2 mixture of two isomers (with a- and (3-COOMe). The major isomer shows an a-conhguration. The yields of the dimer, 23b, and 24b were 25%, 30%, and 6%, respectively. Thus, a substituent on the nitrogen atom or at the 3-position of indole favors the formation of the isoquinuclidine adduct 23. 

The Diels-Alder reactions of the methyl or ethyl ester of benzenesulfonylindole-2-acrylic acid with several l-alkoxycarbonyl-l,2-dihydropyridines are reported and only a single stereoisomer was obtained, as in the case of l-methoxy(ethoxy)-carbonyl-1,2-dihydropyridines. However, when the Diels-Alder reaction of 17 was carried out with 8g[R = (CHsjsC], a mixture of two stereoisomers 18gand25were obtained in a 1 1 ratio (65% total yield). The bulky rerr-butyl group creates sufficient steric interference with the indole ring to cause the loss of stereochemistry ... 

Reaction of 2,3-dihydro-3-hydroxy-3-methyl- 240 (R = Me), or a mixture of 2,3-dihydro-3-hydroxy-3-aryl-57/-pyrido[l,2,3-dfe]-l,4-benzoxazin-5-ones 240 (R = Ar) and (8-aroylmethoxy)quinolin-2(l//)-ones 241 (R = Ar) with ethyl 2-(bromomethyl)acrylate in the presence of activated Zn and hydroquinone gave 8-[(2,3,4,5-tetrahydro-4-methylidene-5-oxo-2-furanyl)-methoxy]quinolin-2(l//)-ones (242) (97HCA1161). 6,7-Dihydro derivatives of 240 reacted similarly (00HCA349). 

Cycloaddition reactions of (E)-l-acetoxybutadiene (18a) and (E)-l-methoxy-butadiene (18b) with the acrylic and crotonic dienophiles 19 were studied under high pressure conditions [9] (Table 5.1). Whereas the reactions of 18a with acrylic dienophiles regioselectively and stereoselectively afforded only ortho-enJo-adducts 20 in fair to good yields, those with crotonic dienophiles did not work. Similar results were obtained in the reactions with diene 18b. The loss of reactivity of the crotonic dienophiles has been ascribed to the combination of steric and electronic effects due to the methyl group at the )S-carbon of the olefinic double bond. 

Table 5.1 High pressure Diels-Alder reactions of (E)-l-acetoxy- (18a) and (E)-l-methoxy butadiene (18b) with acrylic and crotonic dienophiles...

The application of 3-aminopropyl phosphine (3) [41,46] as a building block for incorporation into -COOH functionalized frameworks provides an excellent example of the utility of preformed primary phosphine frameworks (Scheme 8) [46]. The reactions involved Michael addition of ferf-butyl acrylate to malonic acid dimethyl ester to produce the intermediate adduct, 2-methoxycarbonyl-pentanedioc acid 5-ferf-butyl ester 1-methyl ester, which upon treatment with trifluro-acetic acid (TFA) produced the corresponding diester acid,2-methoxy-carbonyl-pentanedioic acid 1-methyl ester, in near quantitative yield. It is remarkable to note that the reaction of NH2(CH2)3PH2 (3) with the diester acid is highly selective as the -COOH group remained unattacked whereas the reaction occurred smoothly and selectively at the -COOMe groups to pro-... 

All cements that contain eugenol inhibit the polymerization of acrylates, and those of EBA-eugenol are no exception. In order to remedy this and other defects, Brauer and his coworkers examined alternatives to eugenol (Figure 9.7). These included the esters of vanillic acid (3-methoxy-4-hydroxybenzoic acid, HV) and syringic acid (3,5-dimethoxy-4-hydroxy-benzoic acid). Both are 3-methoxy-4-hydroxy compounds and are thus chemically related to eugenol and guaiacol. Both are solids and have to be dissolved in EBA where they form satisfactory cements with EBA zinc oxide powder. The vanillate (EBA-HV) cements are the more important. 

Thus, [HRh(C0)(TPPTS)3]/H20/silica (TPPTS = sodium salt of tri(m-sulfophenyl)phopshine) catalyzes the hydroformylation of heavy and functionalized olefins,118-122 the selective hydrogenation of a,/3-unsaturated aldehydes,84 and the asymmetric hydrogenation of 2-(6 -methoxy-2 -naphthyl)acrylic add (a precursor of naproxen).123,124 More recently, this methodology was tested for the palladium-catalyzed Trost Tsuji (allylic substitution) and Heck (olefin arylation) reactions.125-127... 

Figure 12.10 Pyrogram of acrylic emulsion paints containing different organic pigments (a) PR5 (b) PR112 (c) PR4 (d) PY3 (e) PR 251 (f) PY74. Peak assignments 1, EA 2, MMA 3, nBA 4, 4 chloro 2 nitro benzenamine 5, 2 chloro benzenamine 6, 1 chloro 2 isocya nato benzene 7, 2 methoxy 4 nitro benzenamine 8, 2 methoxy benzenamine 9, 1 isocya nato 2 methoxy benzene 10, 1 chloro 4 nitro benzenamine 11,1 chloro 2 nitro benzene 12, 2 naphthalenol 13, 3 amino 4 methoxy N,N diethyl benzenesulfonamide 14, 4 meth oxy N,N diethyl benzenesulfonamide 15, 5 chloro 2,4 demethoxy benzenamine 16, 2,4,5 trichloro benzenamine 17, 1,3,4 trichloro benzene 18, 2 methyl benzenamine 19,...

There are several new methodologies based on the Julia olefination reaction. For example, 2-(benzo[t/Jthiazol-2-ylsulfonyl)-j -methoxy-i -methylacetamide 178, prepared in two steps from 2-chloro-iV-methoxy-jV-methylacetamide, reacts with a variety of aldehydes in the presence of sodium hydride to furnish the ajl-unsaturated Weinreb amides 179 <06EJOC2851>. An efficient synthesis of fluorinated olefins 182 features the Julia olefination of aldehydes or ketones with a-fluoro l,3-benzothiazol-2-yl sulfones 181, readily available from l,3-benzothiazol-2-yl sulfones 180 via electrophilic fluorination <06OL1553>. A similar strategy has been applied to the synthesis of a-fluoro acrylates 185 <06OL4457>. 

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