Esters epoxy

This reaction involves the condensation of an aldehyde or ketone with an a-halo ester in the presence of a basic condensing agent (sodium ethoxlde, sodamide, finely divided sodium or potassium iert.-butoxide) to give a glycldio (or ap-epoxy) ester. Thus acetophenone and ethyl chloroacetate yield phenyl-methylglycidic ester (I) ... 

Varnishes were widely used in the nineteenth and early twentieth centuries. They have been replaced almost completely by a wide variety of other products, especially alkyds, epoxy esters, and urethane oils. The term varnish has come to be used for transparent coatings, such as trade sales varnishes, even though few of them are varnishes in the original meaning of the word. 

The products of these reactions with maleic anhydride, termed maleated oils, react with polyols to give moderate mol wt derivatives that dry faster than the unmodified oils. For example, maleated, esterified soybean oil is a drying oil with a drying rate comparable to that of a bodied linseed oil with a similar viscosity. Maleated linseed oil can be converted to a water-dilutable form by hydrolysis with aqueous ammonium hydroxide to convert the anhydride groups to ammonium salts of the diacid. Such products have not found significant commercial use, but similar reactions with alkyds and epoxy esters are used on a large scale to make water-dilutable derivatives. 

Condensations of aldehydes or ketones with a-halo esters give a,P-epoxy esters. This is called the Dar2ens condensation. 

Asphalt, unmodified Coal tar Coal tar— epoxy Coal tar— nretlianes Epoxy phenolic- baked Epoxy amine- cnred Epoxy ester Fnrfnryl alcohol Phenolics, baked Polyesters (nnsati i-rated) Polyvinyl cliloracetates Vinyl ester Urethanes Vinylidene cliloride Clilorinated rubber... 

High phenyl content resins are compatible with organic resins of the P-F, U-F, M-F, epoxy-ester and oil-modified alkyd types but are not compatible with non-modified alkyds. Silicone resins are highly water repellent. 

The complementary ABO ester (2,7,8-trioxabicyclo[3.2.1]octyl ester) is prepared from the epoxy ester by rearrangement with Cp2ZrCl2/AgC104. The OBO ester is more easily cleaved by Brpnsted acids than is the ABO ester, but the ABO ester is cleaved more easily by Lewis acids, thus forming an orthogonal set. The ABO ester can be cleaved with PPTS (MeOH, H2O, 22°, 2 h LiOH) the OBO ester is cleaved at 0° in 2 min. ... 

Darzens glycidic ester condensation generally involves the condensation of an aldehyde or ketone 2 with the enolate of an a-halo ester 1 which leads to an a,P-epoxy ester (a glycidic ester) (3). Thus the reaction adds two carbons to the electrophile however, the reaction has been primarily developed as a one-carbon homologation method. That is, subsequent to the condensation, the ester is saponified and decarboxylation ensues to give the corresponding aldehyde or ketone 5.2... 

Silicone alkyds Urethane alkyds Epoxy esters Tung oil phenolic... 

Epoxy ester Epoxy esters are a type of alkyd where a high molecular weight resin is reacted with alkyd resin. The curing mechanism remains primarily through the oil-oxidation reaction and their properties are in no way similar to the chemically reacted epoxies. They have similar properties to alkyds although with improved chemical resistance but inferior appearance. They form a reasonably hard, oil-resistant coating, which can sometimes be suitable for machinery enamels, but are primarily for interior use, since they tend to chalk rapidly on exteriors. Their best use is for chemical or water resistance where circumstances dictate that finishes that are more superior cannot be used. 

Thin coatings These pigmented materials, commonly known as floor paints, are often based on chlorinated rubber (see Section 12.3.2) or epoxy ester (see Section 12.3.1). They have limited life in heavy traffic but are easy to apply. 

Epoxide resins can be esterified with fatty acids to give media ranging from air-drying to stoving types. The presence of fatty acid reduces the chemical resistance to the same order as that of the alkyds. It is nevertheless sometimes found advantageous to use an epoxy ester for certain specialised purposes. 

This provides excellent adhesion to the metal. The PVB will crosslink in the presence of the acid with phenolic resin, and epoxy or epoxy ester resin... 

The esterification reaction is also used to prepare epoxy esters from epoxy resins having an n value of 4 and vegetable oil fatty acids. They may be used in the same way as alkyds where better chemical resistance and adhesion are required. Unlike the alkyds, the epoxy esters contain virtually no acid groups. 

The Darzens reaction involves a two-step, base-catalyzed condensation of ethyl chloroacetate with a ketone to yield an epoxy ester. The first step is a carbonyl condensation reaction, and the second step is an SK2 reaction. Write both steps, and show their mechanisms. 

There have been two general approaches to the direct asymmetric epoxidation of carbonyl-containing compounds (Scheme 1.2) ylide-mediated epoxidation for the construction of aryl and vinyl epoxides, and a-halo enolate epoxidation (Darzens reaction) for the construction of epoxy esters, acids, amides, and sulfones. 

Epoxy Esters, Amides, Acids, Ketones, and Sulfbnes 1.2.3.1 Sulfur Ylide-mediated Epoxidation... 

Additionally, the sulfonamide precursor to 75 could be recovered and recycled to regenerate the bromoborane 75 [36], The resulting aldols could then be cyclized to the epoxy esters by treatment with potassium tert-butoxide (Scheme 1.22). 

The procedure is outlined in Scheme 8.33, starting from the generic allylic alcohol 125. SAE on 125 would provide epoxide 126, which could easily be transformed into the unsaturated epoxy ester 127 by oxidation/Horner-Emmonds olefmation (two-carbon extension). This operation makes the oxirane carbon adjacent to the double bond more susceptible to nucleophilic attack by a hydride, so reductive opening (DIBAL) of 127 provides, with concomitant ester reduction, diol 128. Pro-... 

Aldehydes and ketones condense with a-halo esters in the presence of bases to give ot,p-epoxy esters, called glycidic esters. This is called the Darzens condensation. The reaction consists of an initial Knoevenagel-type reaction (16-41), followed by an internal Sn2 reaction (10-13) ° ... 

Figure 5. HPGPC chromatogram of a model compound of epoxy-ester...

---