R-Butyl acrylate

Scheme 5.8 Reaction of r-butyl acrylate with chloroform under basic phase transfer conditions...

In the reductive aldol reaction r-butyl acrylate is formally transformed into an enolate of the propanoate ester. Such a reaction requires Phi in addition to Ni(cod)2 and... 

The enolate of (2S,4R)-1 can also undergo Michael addition to r-butyl acrylate. The yield is low, but the adduct is obtained in 98% ee. This reaction provides a route to a derivative of 2-methylglutamic acid (equation 1). 

FIGURE 5.5 Schematic representation of the growth of the poly(r-butyl acrylate) star by the arm-first approach. (From Matyjaszewski, K., Polym. Int., 52, 1559, 2003. With permission... 

Sodium dispersions in hexane yield syndiotactic poly(methyl methacrylate). A 60-65% conversion is obtained over a 24-hour period at a reaction temperature of 20-25 C. Lithium dispersions, butyllithium, and Grignard reagents " "yield crystalline isotactic poly(r-butyl acrylate). The reactions take place in bulk and in hydrocarbon solvents. Isotactic poly(isopropyl acrylate) forms with Grignard reagents. ... 

The resolution of the system is moderate and the stability after irradiation is poor. However, it is used for the 243 nm domain due to its sensitivity. Derivatives of this resist system have also been proposed, e.g., a copolymer of 4-hydroxystyrene with a r-butyl acrylate and a phenyloxysuccinimid as the acid photogenerator. This resist is more stable during processing (Figure 6.16). 

MA is methyl acrylate, MMA is methyl methacrylate, and BA is r -butyl acrylate. 

The other important direct alkylation processes involve reaction of electron-rich olefinic compounds with either tin metal or stannous chloride (tin(II) chloride) in the presence of stoichiometric amounts of hydrogen chloride (22). Butyl acrylate (R = C Hg) was used commercially in this process to prepare the estertin or P-carboalkoxyethyltin chlorides as iHustrated in the foUowing. 

Papageorgiou and Benezra204 treated chiral r-butyl (-)-(S)- and ( + )-(R)-2-(p-tolylsulfinyl)propionate with an aldehyde, then pyrolyzed the mixture and obtained chiral a-(hydroxyalkyl)acrylate in 75% e.e. Similarly, condensation of the anion of ( + )-(R)-3-(p-tolylsulfinyl)propionic acid 159 with aldehydes was found to give the diastereomeric [i-sulfinyl-y-lactones, (+)-(Sc4,Rc5,Ps)-160a and ( + )-( c4,Sc5,l s)-160b in an approximate ratio of 60 40205. 

Recently, the chiral Pt(0) precatalyst Pt[(R, R)-Me-Duphos](trows-stilbene) (11) has been used to prepare enantiomerically enriched chiral phosphines via hydrophosphination of acrylonitrile, t-butyl acrylate and related substrates. This chemistry is summarized in Scheme 5-13. 

Product Identification was by GC/MS, NMR, and IR. Fundamental crosslinking chemistry was explored using swell measurements on simple solution copolymers and swell and tensile measurements with vinyl acetate (VAc), vinyl acetate/butyl acrylate (VAc/BA) or vinyl acetate/ethylene (VAE) emulsion copolymers. Polymer synthesis 1s described In a subsequent paper (6). Homopolymer Tg was measured by DSC on a sample polymerized In Isopropanol. Mechanistic studies were done 1n solution, usually at room temperature, with 1, 2 and the acetyl analogs 1, 2 (R =CH3). 

The first three components were mixed at room temperature and heated at 65°C In a 250 ml round bottom flask equipped with a magnetic stirring bar, reflux condenser and Na blanket. The AIBN was then added to start the reaction. Monitoring of the unreacted free monomers (butyl acrylate and comonomer) was done by GLPC. Additional 10 mg amounts of AIBN were added as needed. The temperature was also Increased to 75 C to finish the polymerization. Host of the reactions took longer than 24 h to reduce the free monomer below 0.7%. A control BA homopolymer and copolymers with butoxymethylacrylamide (BNMA), 2 (R = Et AEP), acrylamidoacetaldehyde dimethyl acetal (AADMA), and N-ethyl-1 (Et-ABDA, 13) were prepared In this way. 

R= n°2, H or COCH3 [Pd] = (PPh3)2PdCI2 or Pd(OAc)2 Scheme 1. The Heck reaction of halogenoarenes with butyl acrylate. 

Some terminal alkenes are oxidized to aldehydes depending on their structure. As described before, acrylonitrile and acrylate are oxidized to acetals of aldehydes in alcohols or ethylene glycol.Selective oxidation of terminal carbons in 4-hydroxy-1-alkenes (18) gave the five-membered hemiacetals (19), which can be converted to y-butyrolactones by PCC oxidation (Scheme 4). Formation of a tricyclic six-membered hemiacetal (62%) from a 5-hydroxy-1-alkene system was used for the synthesis of rosa-ramicin. Formation of aldehydes as a major product from terminal alkenes using (MeCN)2Pd(Cl)(N02) and CuCU in r-butyl alcohol under selected conditions was reported. The vinyl group in the -lactam was oxidized mainly to the aldehyde as shown below (equation 12). ... 

Fig. 18. Rate R %/rainl versus conveision dependence during polymerizatMn of (i) methyl acrylate <2) ethyl acrylate and (3) butyl acrylate in the presence of SDDS (A) and AAOES (B). The graphs are plotted from the kinetic curves in F g, 9- Initiator benzoyl peroxide.

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