T Butyl acrylate

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. 

OVS tube t-Butyl acrylate. Ethylene glycol-dimethacrylate... 

PtBA-b-PCEMA poly(t-butyl acrylate)-block-poly(2-cinnamoyloxyethyl) methacrylate... 

In some reactions, the choice of PTC can actually alter the distribution of products for example, the reaction of t-butyl acrylate with chloroform under basic phase transfer conditions gives two major products, as illustrated in Scheme 5.8, the amounts of which are catalyst dependent [46],... 

Fig. 11 Chemical formulas of poly(acryl amide) (PAAm), poly(methyl methacrylate) (PMMA), poly(2-hydroxyethyl methacrylate) (PHEMA), poly(t-butyl acrylate) (PtBA), and poly(acrylic acid) (PAA), and poly(dimethyl aminoethyl methacrylate) (PDMAEMA)...

Various Ln amides have already been described in Sections 4.3.5 and 4.3.6 as catalysts for polymerisation of ethylene," I38,i4i i43 jjex-l-ene, isoprene,styrene, " methyl methacrylate or other polar monomers such as t-butyl acrylate or acrylonitrile, . 138,143,152,177 nng-opening polymerisation catalysts for e-caprolactone or... 

It is reported that methyl acrylate, allyl acetate, vinyl acetate and dimethyl maleate give only low yields of oligomers with butyllithium under all experimental conditions (31). Furukawa and coworkers (32) confirm that vinyl acetate will not polymerize and that n-butyl-vinyl-ether will not either. High polymers can be formed from isopropyl acrylate (39) in toluene at —70° and from t-butyl acrylate (65). The reported failure of methyl acrylate and butyl acrylate to yield high polymers could reflect a genuine difference in behaviour connected with the side group or. could simply result from failure to choose the most favourable conditions for polymerization. Vinyl acetate can be polymerized by lithium metal (49) but co-polymerization experiments suggest that the polymer is formed by a radical mechanism. 

The asymmetric addition of glycine enolates to acrylates was also achieved by use of the tartaric acid-derived phase-transfer catalysts 27 and 28 (Scheme 4.9). Arai, Nishida and Tsuji [13] showed that the C2-symmetric ammonium cations 27a,b afford up to 77% ee when t-butyl acrylate is used as acceptor. The cations 28 are the most effective/selective PTC identified by broad variation of the substituents present on both the acetal moiety and nitrogen atoms [14], In this study by Shibasaki et al. enantiomeric excesses up to 82% were achieved by use of the catalyst 28a (Scheme 4.9) [14], Scheme 4.9 also shows the structure of the guanidine 29 prepared by Ma and Cheng in the absence of additional base this also catalyzes the Michael addition of the glycine derivative 22 to ethyl acrylate, albeit with modest ee of 30% [15],... 

Merck has used the L-phenylalanine-derived Evans oxazolidinone to make matrix metalloproteinase inhibitors such as 45 (Scheme 23.14) (see also Chapter 2).62 The mixed anhydride of 4-butyric acid was reacted with the lithium anion of the oxazolidinone. This was enolized with the standard titanium reagents. An enantioselective Michael addition was then carried out by the addition of t-butyl acrylate at low temperature. The auxiliary was removed with LiOH/peroxides to give the acid, which was further derivatized over multiple steps to yield the desired drug. 

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

Polymers consisting of t-butyl acrylate, methacrylic acid, sodium ether dodecyl sulfate, and n-dodecylthiol were prepared by Drohmann [4] and used in hairsprays. 

The Ziegler-Natta catalyst trimethylammonium o-methyl-1-(2-hydroxy Icy do hexyl)-carborane zirconium chloride has been prepared and affixed to a Merrifield resin. When used as a polymerization catalyst for vinyl chloride, t-butyl acrylate, styrene, or ethylene, oligomers with molecular weights <6000 daltons were obtained. 

Emulsion terpolymerization of t-butyl acrylate, methacrylic acid, and dimethi-cone in the presence of n-decanethiol resulted in an odorless product that was used in cosmetic formulations by Drohmann [3]. 

Figure 4.2 Frequency vs temperature for a poly(t-butyl acrylate)-coated FPW device showing a slope change at the static (low-frequency) Tg. (Reprinted with permission. See Ref. [S6]. 1992 American Chemical Society.)...

GansSuer et al. studied the tandem titanocene-mediated cyclization/inter-molecular addition to Michael acceptors [132]. After treatment with t-butyl acrylate in the presence of Zn, collidine hydrochloride and catalytic amounts of titanocene [133], epoxide 143 yielded the desired bicycUc product 144 in reasonable yield and high diastereoselectivity (Scheme 46). Remarkably, alkyne 145 led to the first example of an intermolecular addition involving a vinylic radical. The success of this reaction was attributed by the authors... 

Fig. 8 (a) SEC curves of the PS macromonomer (PS-MA curve 1), the crude (curve 2) and the purified (curve 3) poly( ter t-butyl acrylate-gra/f-styrene) (PTBA-g-PS), and the esterified polymethylacrylate (PMA curve 4) backbone, (b) H NMR spectra of the macromonomer PSMA, the graft copolymer PTBA-g-PS and the final purified reaction product poly(acrylic acid-gra/f-styrene) (PAA-g-PS)... 

Poly(t-butyl acrylate) 128.17 Poly(vinyl ec-butyl ether) 100.16... 

The Norrish type I and type II reactions were found with a number of polymers such as polyketones [Refs. 15, 258, 259, 271, 381, 676], polyolefins [Refs. 122, 123, 149, 205, 206, 278, 623], ethylene—carbon monoxide copolymer [Refs. 258, 270, 284, 286] and poly(t-butyl-acrylate) [430]. 

The stracture-property correlation of different copolymers with n-butyl acrylate and isobomyl acrylate units have been studied. The primary goal was to compare thermomechanical properties of block, gradient and statistical copolymers of nBA and IBA with various acrylate homopolymers (Scheme 1). The choice of nBA and IBA was dictated by very different thermal properties of the resulting homopolymers, glass transition temperature (Tg) of PnBA is -54°C while the Tg of PIBA is 94°C. Thus, their copolymerization with carefully selected ratios should result in polymers with thermal properties, i.e., Tg similar to acrylate homopolymers poly(t-butyl acrylate) (PtBA), poly(methyl acrylate) (PMA), poly(ethyl acrylate) (PEA) and poly(n-propyl acrylate) (PPA). 

Synthesis of Polystyrene-A-Poly(t-Butyl Acrylate) (PSt-A-PtBA) via ARGET ATRP... 

Sn2 Reactions. Methyl a-(t-butyl)acrylate is obtained from reaction of the 2-chIoromethyI-3-methyl-2-butenoic ester with a methylcopper/zinc reagent. Higher-order zinc cuprates or vinyl-ZnCl (with catalytic Cu salt) effect displacement reactions on y-mesyloxy a,/3-enoates, whereas reduction is observed with vinyl-Cu(CN)M or (vinyl)2Cu(CN)M2. ... 

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