Acrylates Experimental Procedure

The experimental procedures were essentially the same as reported (Figure 1, (16, 17)). Reagents other than those described in (16. 17) were as follows. Acrylic acid(Wako Pure Chemicals) was distilled once under reduced pressure under a nitrogen stream. Solvents(acetonitrile, n-hexane, and benzene) were purified by accepted procedures. 

The reaction of acceptor-substituted carbene complexes with alcohols to yield ethers is a valuable alternative to other etherification reactions [1152,1209-1211], This reaction generally proceeds faster than cyclopropanation [1176], As in other transformations with electrophilic carbene complexes, the reaction conditions are mild and well-suited to base- or acid-sensitive substrates [1212], As an illustrative example, Experimental Procedure 4.2.4 describes the carbene-mediated etherification of a serine derivative. This type of substrate is very difficult to etherify under basic conditions (e.g. NaH, alkyl halide [1213]), because of an intramolecular hydrogen-bond between the nitrogen-bound hydrogen and the hydroxy group. Further, upon treatment with bases serine ethers readily eliminate alkoxide to give acrylates. With the aid of electrophilic carbene complexes, however, acceptable yields of 0-alkylated serine derivatives can be obtained. 

This experimental procedure must be followed carefully to avoid partial decomposition of ethyl a-(hydroxymethyl)acrylate. The reaction is stopped rapidly after the addition of the carbonate solution (5 min) to prevent formation of high molecular weight by-products which result from transesterification and Michael addition, both of which occur in the basic medium. However, about 25% of the product is lost. Addition of diethyl ether during cooling minimizes side reactions. 

Reactions involving a variety of terpene-derived, chiral acrylic amides and esters at least partly lead to equally remarkable yields and diastereoselectivities (Table 2). A more detailed discussion including experimental procedures is available. ... 

Pentachlorophenyl acrylate, (1), was terpolymerized with methyl methacrylate (MMA) and n-butyl acrylate (nBA) (Scheme III) to give a latex containing 537 solids and a pll of 4.7 which was adjusted to 6.8 by adding aqueous NaOH. The latex was stable up to pH =10. A small aliquot vzas coagulated and the resulting polymer purified. Its intrinsic viscosity was 3.1 /g and analysis indicated 2 mole percent (1), 587 CIA and 40" nBA. Similar terpolyner latices were prepared from acrylates (2) and (3) (Scheme III). Another terpolymer latex made from (3), vinyl acetate, and 2-ethylhexyl acrylate contained 547 solids. Tliese latices and their compositions are summarized in the Table 1 and a sample experimental procedure is given in the experimental section. 

The experimental procedure described here for the preparation of Ru(ti -methyl acrylate)(C0)4 is applicable to a variety of other olefins as manifested by the syntheses of Ru(Ti -olefin)(CO)4 complexes of, for example, dimethyl fumarate, dimethyl maleate, allyl acrylate, methyl vinyl ketone (3-butene-2-one), and acrylonitrile. ... 

Tables 3 and 4 display an overview of the majority of organic styrene- or acryl-based monomers used in molecular imprinting to date. As can be seen, many of those are commercially available, whereas most others can be accessed following the experimental procedures in the literature, or via the general guidelines outlined in this chapter. The building blocks have been divided into structural- and functional...

A technique for the preparation of Eudragit RL-100 acrylic resin microcapsules was developed, which was based on the principle of solvent evaporation. Diclofenac sodium was used as a model drug for encapsulation. A solution of drug and Eudragit dissolved in acetone-isopropyl alcohol was sprayed in liquid paraffin. The microcapsules obtained were unifonu and free flowing particles. The release rate was more sustained by increasing the polymer coneentration. The experimental procedure provided a rapid and eonvenient method for the preparation of Eudragit microcapsules. 8 refs. 

The intra-intermolecular Heck reaction of dienediol bisnonaflates containing an (O-alkenyl substituent with an external alkene such as an acrylate gives rise to the formation of a bicyclic tetraene by an intramolecular coupling followed by an intermolecular Heck or Sonogashira-type reaction (Scheme 5-30, Experimental Procedure below).It should be noted that the alkynylation proceeds in absence of copper additives. 

Experimental procedure for the preparation of (S)-2,2,2-trifluoroethyl cyclohex-3-enecarboxylate 5 To freshly prepared catalyst 3 (10mol%) in a heavy-walled Pyrex (World Kitchen LLC, Rosemont, IL) botde was added successively 1,3-butadiene 1 (ca. lOmL) and 2,2,2-trifluoroethyl acrylate 2 (12.2g, 78.5mmol) at —78°C. The pressure bottle was sealed with a screw cap and was stirred at 23°C for 30 hours and then quenched by the addition of 1 mL of EtsN. The residue was concentrated in vacuo and purified by flash column chromatography to give the desired ester 5 (15.8 g, 97%) as a colorless oil [o ]o - 68.8 (c 1.0, CHCI3, 97% ee). Enantioselectivity was determined to he >97% ee hy gas chromatography (GC) analysis with the retention times of 29.50 minutes (the desired ester 5) and 30.15 minutes (the enantiomer). 

Brandt [200] has extracted tri(nonylphenyl) phosphite (TNPP) from a styrene-butadiene polymer using iso-octane. Brown [211] has reported US extraction of acrylic acid monomer from polyacrylates. Ultrasonication was also shown to be a fast and efficient extraction method for organophosphate ester flame retardants and plasticisers [212]. Greenpeace [213] has recently reported the concentration of phthalate esters in 72 toys (mostly made in China) using shaking and sonication extraction methods. Extraction and analytical procedures were carefully quality controlled. QC procedures and acceptance criteria were based on USEPA method 606 for the analysis of phthalates in water samples [214]. Extraction efficiency was tested by spiking blank matrix and by standard addition to phthalate-containing samples. For removal of fatty acids from the surface of EVA pellets a lmin ultrasonic bath treatment in isopropanol is sufficient [215]. It has been noticed that the experimental ultrasonic extraction conditions are often ill defined and do not allow independent verification. 

Experimental apparatus and procedure. Figure 1 is a schematic diagram of the experimental apparatus. The crystallizer was a 1 liter stirred tank reactor made of acrylic resin and is considered to be a continuous MSMPR reactor. The reactor was 0.1m in diameter and the liquid height 0.14m. The impeller used was of the 6-blade turbine type and operated at 450 rpm to... 

Reactivity ratios between acrylated lignin model compound (Fig. 2), defined as Mi, with either MM A or S, defined as M2, were determined experimentally in accordance with standard procedures (15). These involve mixing two different vinyl monomers in various molar ratios with catalyst (i.e., benzoyl peroxide) and solvent, heating the mixture to achieve polymerization, and recovering the polymer by the addition of non-solvent, and centrifugation. The respective molar monomer fractions of the copolymer were determined by UV-spectroscopy in the cases where MMA served as M2, and by methoxyl content analysis in those cases in which S was the M2-species. The results were subjected to numerical treatments according to the established relationships of Kelen-Tiidos (17) and Yezrielev-Brokhina-Roskin (YBR) (18), and this is described elsewhere (15). 

The procedure for the elimination of HBr from the dibromo ester is a modification of the method of Lawton and co-workers for sui generis generation of the methyl or ethyl ester during a reaction. Methyl a-(bromomethyl)acrylate has also been prepared by bromination of methyl methacrylate in 700°C steam and by dehydrohalogenation with sodium acetate in acetic acid. Ethyl a-(bromomethyl)acrylate has been prepared by dehydrohalogenation with the monosodium salt of ethylene glycoP and ethyl diisopropylamine." The latter reaction was reported by Ohler et al. with no experimental details for the elimination reaction. The use of triethylamine as reported in this procedure appears to be the most efficient and convenient method for dehydrobromination to these acrylate esters. 

The experimental difficulties involved with the controlled use of Grignard initiators were recognized early on. The exact nature of the species present in the reaction media is often unclear. In many instances, it is difficult to obtain reproducible kinetic data. The polymerizations are very sensitive to the presence of small concentrations of impurities. Finally, the polymerization of acrylic and methacrylic esters is further complicated by side reactions involving the carbonyl group. Consequently, it is not uncommon for two workers in the same laboratory to prepare different products using the same procedure [9,10]. 

In the following we present an experimental set up which allows the simultaneous determination of the gas phase composition and the oxygen activity of the solid catalyst under operating conditions along a tubular fixed bed reactor. Preliminary results of the partial oxidation of acrolein to acrylic acid at an oxidic catalyst illustrate the possibilities of the procedure. 

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