Ethyl acrylate, acylation with

Esters, acylation of aminothiazoles, 47, 53 with aminothiazoles, 119 Ethoxy carbonylisothiocyanate, 126 Ethyl acrylate, acylation with. 54 Ethyl chloroformate, to carbamate, 51. 96, 97... 

Treatment of O-acyl esters (2) with l,l-dichloro-2,2-difluoroethylene provides a,a-difluorocarboxylic acids (37) through photolysis, followed by the hydrolysis of the adducts (36) with AgN03 (eq. 8.17) [53]. Eq. 8.18 shows the preparation of a-keto carboxylic acids (40) from carboxylic acids, by means of the radical addition to ethyl acrylate, oxidation to the sulfoxides by mCPBA, the Pummerer reaction with... 

Microwave irradiation of a mixture of an acid anhydride, an amine adsorbed on silica gel, and TaCl5/Si02 is a solvent-free method for the synthesis of A-alkyl and A-aryl-imides [47]. Ni(II) promotes the conversion of an acrylamide to ethyl acrylate via a Diels-Alder adduct with (2-pyridyl)anthracene [48], Aromatic carboxylic acids [49] and mandelic acid [50] are efficiently esterified with Fc2(S04)3 XH2O as catalyst. Co(II) perchlorate in MeOH catalyzes the methanolysis of acetyl imidazole and acetyl pyrazole [51]. Hiyama et al. used FeCb as a catalyst for the acylation of a silylated cyanohydrin. The resulting ester was then cyclized to 4-amino-2(5H)-furanones (Sch. 5) [52]. 

When lithium aluminum hydride was applied, besides reduction of the C-4—N-5 double bond, the ester group was converted to a hydroxymethyl group. S By reaction with dry formic acid under reflux conditions, the pyrroloquinazoline-2-carboxylates 63 yielded the 6-formyl-5,6-dihydro derivatives 65. S The formyl group was transformed into a methyl group by diborane. S The NH group of the dihydro derivatives 64 was acylated by ethyl chloroformate. Reaction with ethyl acrylate and acrylonitrile involved a Michael addition.The ethoxycarbonyl moiety in position 2 and on the side chain in position 6 was hydrolyzed to a carboxylic group by the action of potassium hydroxide in aqueous methanol and was reduced to a hydroxymethyl group by lithium aluminum hydride in ether. 

With a, p-un saturated esters, competition between cydopropa nation (l,4addition) and acylation (1,2-addition) becomes acute. With ethyl acrylate (63) and ethyl crotonate (64), the small R groups on the p-carbon atom permit facile conjugate addition leading to good yields (60-65%) of the corresponding cyclopropane derivatives (67) (Scheme 25). On the... 

Bakuzis has explored the use of an interesting (B-acrylate anion equivalent in his synthesis of 9 (Scheme 4.5) ° The Grignard reagent from 3-bromopropyl phenyl sulfide was condensed with acetaldehyde and the resulting alkoxide was acylated to procure 24 (70%). Oxidation of the sulfide to aldehyde 25 proceeded in 74% yield. Reaction of 25 with ethyl 3-nitropropionate followed by elimination of HNO2 from the intermediate afforded 26. The latter step, equivalent to the addition of the p-carbanion of ethyl acrylate, occurred in 38% yield. Oxidation of alcohol 26, protection of the resulting ketone, and saponification gave 17. This intermediate was then dimerized as previously described to a mixture of 9 and its meso diastereomer. 

Various immobilized lipases were tested in the transesterification of 1-O-octyl a-D-glucopyranoside (1) with ethyl acrylate, using the latter compound both as reactant and solvent. By far the best results were obtained with lipase preparations of the Candida antarctica type (see Table 1). Acylation occurred mainly at the 6-0 position, in line with the usual preference of lipases for primary alcohol functions. The resulting 6-O-acryl ester may serve as a starting material for specialty polymers. Acylation at the 2-O-position was the main side-reaction. The selectivity and rate of the C. antarctica lipase catalyzed reaction could be improved substantially by adding zeolite CaA which selectively adsorbs water and ethanol . ... 

The most important shampoo hair conditioners are the alkylamido alkylamines. As a rule, they are complex mixtures derived from the reaction of alkyl-substituted imidazolines with chlo-roacetic acid or ethyl acrylate [8]. Similar to the acylated protein derivatives, these amphoteric surfactants exhibit detergency, are compatible with anionic detergents, and reportedly form complex salts with anionics. These complexes reportedly do not sting the eyes and are employed in baby shampoos. These amphoterics in combination with anionic detergents leave the hair conditioned after rinsing. 

In the late nineteenth century, Michael found that the enolate anion (46) derived from diethyl malonate reacts with ethyl acrylate at the P-carbon (as shown in the illustration) to give an enolate anion, 47, as the product. Remember from Chapter 22 (Section 22.7.4) that the a-proton of a 1,3-dicarbonyl compound such as diethyl malonate is rather acidic (pK of about 11), and even a relatively weak base will deprotonate to form the enolate anion. Michael addition of 46 with ethyl acrylate will give enolate anion 47, and aqueous acid workup leads to the isolated product, 48. Attack at the -carbon is possible because that carbon is less hindered than the acyl carbon, so reaction at the C=C unit is somewhat faster than attack at the acyl carbon. Michael addition occurs with relatively stable carbanion nucleophiles, such as malonate derivative 46 and some other common nucleophiles. Other conjugated carbonyl derivatives react similarly. 

DipolarophUes such as ethyl acrylate exhibit regiochemical preference for meta acyl or carhoxyl groups (eq 7) With one exception (entry 6), all cases are consistent with FMO approximation in which the largest dipole HOMO coefficient is at the... 

As shown in Scheme 5, the scope of the reaction with respect to the chalcone component is broad. Electron-withdrawing and electron-donating substituents are well tolerated and afford the 1,4-diketone in good yields. Interestingly, methyl vinyl ketone and ethyl acrylate are suitable partners in the acyl silane addition reaction. 

Cobalt. The rate law for carbonylation of Schiff bases, catalysed by Co2(CO)8, has been reported. Dicobalt octacarbonyl also catalyses reaction between aldehydes, for instance formaldehyde or acetaldehyde, amides, for example acetamide or benzamide, and carbon monoxide. The products are iV-acyl-amino-acids. The main product from the reaction of acetylene with carbon monoxide in the presence of CoH(CO)4 is ethyl acrylate. Characterization of the intermediates permits suggestions to be made as to the mechanism of this reaction. Initial reactions between the acetylene and two molecules of catalyst may give (106), in equilibrium with its isomer (107) the carbon monoxide inserts into the cobalt-carbon bonds of the latter. Further information about Coa(CO)8-catalysed hydro-formylation of acrylonitrile and of 3-methyl[3- H]hex-l-ene has led... 

The complete transformation of a racemic mixture into a single enantiomer is one of the challenging goals in asymmetric synthesis. We have developed metal-enzyme combinations for the dynamic kinetic resolution (DKR) of racemic primary amines. This procedure employs a heterogeneous palladium catalyst, Pd/A10(0H), as the racemization catalyst, Candida antarctica lipase B immobilized on acrylic resin (CAL-B) as the resolution catalyst and ethyl acetate or methoxymethylacetate as the acyl donor. Benzylic and aliphatic primary amines and one amino acid amide have been efficiently resolved with good yields (85—99 %) and high optical purities (97—99 %). The racemization catalyst was recyclable and could be reused for the DKR without activity loss at least 10 times. 

Oxoindolizines are obtained by reaction of ethyl pyrrolidinylideneacetate with several acyclic unsaturated carbonyl compounds by cyclization of the formed Michael adducts104 (equation 73). When this reaction was modified by changing the ring size of the enaminoester, the substitution pattern of the enone structure and by varying the conditions, different products were isolated105. N-acylation could be accomplished by reaction of acyl chlorides in the presence of pyridine. Bicyclic lactams are yielded by Michael addition of acrylic esters and NaH (equation 74). 

Butyl-i-methylimidazolium tetrafluoroborate [BMIMJBF as the eco-friendly reaction medium could also be applied to the 0-acylation reaction of dehydroabietic acid chloride with 2-hydroxyethyl acrylate to yield dehydroabietic acid (2-acryloloxy) ethyl ester. This new method showed the advantages of mild reaction conditions, short reaction times, good yields, and recyclable solvent [121]. 

---