Esters methyl acrylate

In 1979, Schollkopf et al. " formed a-isocyano- 3-dimethylamino-acryl methyl esters 86, and Bienayme prepared many similar isocyanides,which can undergo a variety of heterocycles, forming reactions like the synthesis of 88 from 84-87 (Scheme 1.20). 

Poly(acrylic acid) and Poly(methacrylic acid). Poly(acryHc acid) (8) (PAA) may be prepared by polymerization of the monomer with conventional free-radical initiators using the monomer either undiluted (36) (with cross-linker for superadsorber appHcations) or in aqueous solution. Photochemical polymerization (sensitized by benzoin) of methyl acrylate in ethanol solution at —78° C provides a syndiotactic form (37) that can be hydrolyzed to syndiotactic PAA. From academic studies, alkaline hydrolysis of the methyl ester requires a lower time than acid hydrolysis of the polymeric ester, and can lead to oxidative degradation of the polymer (38). Po1y(meth acrylic acid) (PMAA) (9) is prepared only by the direct polymerization of the acid monomer it is not readily obtained by the hydrolysis of methyl methacrylate. 

Acrylic acid, -(3-benzo[f>]thienyl)-a -mercapto-reaction with iodine, 4, 764 Acrylic acid, o -cyano-y3-(2-thienyl)-ring opening, 4, 807 Acrylic acid, -formyl-in pyridazinone synthesis, 3, 46 Acrylic acid, furyl-rotamers, 4, 545 synthesis, 4, 658 Acrylic acid, 2-hydroxybenzoyl-chroman-4-one synthesis from, 3, 850 Acrylic acid, 5-(l-propynyl)-2-thienyl-methyl ester occurrence, 4, 909 Acrylonitrile... 

Chemical Designations - Synonyms Acrylic acid, methyl ester Methyl 2-propenoate Chemical Formula CH2=CHCOOCH3. 

The addition of diazomethane to unsaturated esters (1), as ethyl acrylate, methyl crotonate and ethyl cinnamate, was investigated by Auwers who showed that the primary addition product is a A -pyrazoline (2) which rearranges spontaneously to the conjugated A -pyrazoline (3). 

Eberle and Schaub (93EUP571326) describe the synthesis of a large series of 3-hydroxy-2-(2-methyl-4-prop-l-ynyl-2//-pyrazol-3-yl)acrylic acid methyl esters 26 and methoxyimino-(2-methyl-4-prop-l-ynyl-2//-pyrazol-3-yl)acetic acid methyl esters 27 by dehydrohalogenation of the corresponding chloroolefins 25 under the action of bases. In this case, the functional groups in position 5 of the pyrazole ring undergo dehydrobromination (Scheme 34). 

The 2-phenyl-2-ethyl-pentane-1,5-diacid-mononitrile-(1) of melting point 72° to 76°C, used as starting material in this process, can be produced for example from o-phenyl-butyric acid nitrile by condensation with acrylic acid methyl ester and subsequent hydrolysis of the thus-obtained 2-phenyl-2-ethyl-pentane-1,5-diacid-monomethyl ester-mononltrile-(l) of boiling point 176° to 185°C under 12 mm pressure. 

Triethylamine (8) Ethanamine, N,N-diethyl- (9) (121-44-8) Methyl acrylate Acrylic acid, methyl ester (8) 2-Propenoic acid, methyl ester (9) (96-33-3)... 

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-... 

Fig. 6.7. Viscosity sensitive fluorophores molecular rotors. DCVJ = 9-(dicyanovinyl)-julolidine, CCVJ = 9-(carboxy-2-cyano)vinyl julolidine, CMAM = 2-cyano-3-(p-dimethyl-aminophenyl)acrylic acid, methyl ester.

Similarly, methyl methacrylate reacts with ketones and TMSH/RuCE-SlEO to give /l-trimethylsiloxy-2,2-dimethyl methyl esters in good yields. A lactone example is shown in Eq. 292.473 Methyl acrylate, trans methyl ( )-cinnamate, and 3,4-dehydro-S-lactone react in an analogous manner, albeit in lower yields.473... 

Table 1 Asymmetric hydrogenation of (Z)-2-(acetamido) cinnamic acid, 2-(acetamido) acrylic acid and their methyl esters...

When assessing catalytic results reported for new ligands, one must bear in mind that their quality and relevance differ widely. For most new ligands only experiments with selected model test substrates carried out under standard conditions are available, and very few have already been applied to industrially relevant problems. The test substrates for alkenes used most frequently are Aceta-mido Cinnamic Acid (ACA) or its methyl ester (MAC), Methyl Acetamido Acrylate (MAA), ITaconic Acid or DiMethyl ITaconate (ITA, DMIT) and selected aryl enamides (Fig. 25.3). 

In reactions in which methyl acrylate is used as the dienophile (Scheme 6.33), cycloadditions occur with lower levels of enantioselection (23% ee, as compared to 53 % observed for acrolein), but with significantly higher degrees of diastereoselectivity (17 1, endo-.exo). Improved levels of endo selectivity are observed in the case of the methyl ester (Scheme 6.33) this is perhaps because, at least in part, the dienophile p-system is oriented towards the t-butoxy ligand, where the steric influence of the bulky substituent is expected to be more pronounced. As before, formation of the endo isomer may occur to a greater extent, since the transition structure that leads to the exo isomer would involve energetically unfavorable interactions between the diene... 

The reaction of //-protected dehydroalanine methyl esters (e.g. 56, 59) with other indoles 58 can also be effected to give the corresponding dehydrotryptophans 60, invariably as the Z-isomers [81]. Murakami, Yokoyama and co-workers also studied oxidative couplings of acrylates, acrylonitrile, and enones with 2-carboethoxyindole, 1-benzylindole, and l-benzyl-2-carboethoxyindole and PdCfe and CuCk or Cu(OAc) 2 to give C-3 substitution in 50-84% yields [82, 83]. 

The vinyl triflate of Komfeld s ketone has been subjected to Heck reactions with methyl acrylate, methyl methacrylate, and methyl 3-(Af-rerf-butoxycarbonyl-lV-methyl)amino-2-methylenepropionate leading to a formal synthesis of lysergic acid [259]. A similar Heck reaction between l-(phenylsulfonyl)indol-5-yl triflate and dehydroalanine methyl ester was described by this research group [260]. Chloropyrazines undergo Heck couplings with both indole and 1-tosylindole, and these reactions are discussed in the pyrazine Chapter [261], Rajeswaran and Srinivasan described an interesting arylation of bromomethyl indole 229 with arenes [262]. Subsequent desulfurization and hydrolysis furnishes 2-arylmethylindoles 230. Bis-indole 231 was also prepared in this study. 

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