Fumaric acid diesters

The cycloaddition of allenes to symmetrically disubstituted alkenes gives mixtures of cyclobutanes with stereochemical equilibration of the substituents. The reaction of 1,3-dimethylallenc with either diethyl fumarate or diethyl maleate produces a mixture of the /raw.v-bis(ethoxycar-bonyl)cyclobutanes.s The same nonstereoselectivity was observed for phenylallene and 1,1-dimelhylallene cycloadditions to maleic and fumaric acid diesters.9 10... 

Ketcnc equivalents, such as ketene acetals and thioacetals, can be used in cycloadditions to electron-deficient alkenes (see Sections 1.3.2.1. and 1.3.2.2.). In an example of a fumaric acid diester fitted with two chiral alcohol auxiliary groups, the aluminum(III)-catalyzed cycloaddition of 1,1-dimethoxyethene with di-(—)-menthyl fumarate (9) proceeds with > 99% diastereomeric excess. Intermediate 10 can be readily converted to cyclobutanone derivatives.17, 18... 

Use as a Chiral Auxiliary. (5)-Ethyl lactate has been used as a chiral auxiliary in a variety of simple Diels-Alder reactions. As the fumaric acid diester, the de employing cyclopentadiene can almost be completely reversed by addition of Titanium(IV) Chloride (eq 8). In general, superior de values are achieved using (R)-Pantolactone in this context, and also for base-mediated addition to ketenes. ... 

Water Insoluble Polymers. There are a number of polymeric substances reported to have functionality as defoamers. These include fatty acid modified alkyloid resins, copolymers of vinyl acetate and long-chain maleic and fumaric acid diesters, as well as polypropylene and butylene oxide polymers and addition products [19-21],... 

Whereas free radically initiated polymerization yields polymers characterized by an essentially random distribution of monomeric units, block-like polymeric products are obtained in the cationic copolymerization of NVC with alkyl vinyl ethers. The possible formation of preferential aggregates of the vinyl aromatic monomer or a possible control of the homopropagation process connected with the bulkiness of the monomers has been suggested as responsible for such polymer structures . A random distribution of monomeric units is conceivable in copolymers based on the spaced-carbazole-containing monomers 11-14, whilst a quasi alternating distribution is observed in copolymers from NVC and fumaric acid diesters . ... 

For the diester of fumaric acid, EtAlCl2 was the most effective catalyst and the reaction proceeded with more than 90% diastereoselectivity.87... 

All-trans unsaturated ester oligomers have been synthesized by lipase-catalyzed polymerization of diesters of fumaric acid and 1,4-butanediol.217 No isomerization of the double bond was observed, as opposed to the extensive isomerization found during chemical polycondensations. Crystallinity was found in the enzymatically formed unsaturated oligoesters prepared in acetonitrile, whereas industrial unsaturated polyesters are amorphous. 

A previous publication of the attempted photoaddition of fumaric acid to stilbene reported the failure of the reaction.1 2 Green and Retjo1 8 have reexamined the reaction and have found that a 46% yield of the diester (238) of / -truxinic acid is obtained when / / -stilbene is irradiated (Pyrex) in benzene solution with dimethyl fumarate. Trace amounts of dimethyl 8-truxinate (239) and dimethyl neo-truxinate (240) are also formed. 

Shea and co-workers (109,110) were the first to try this approach. They prepared polymers from the optically active (-)-trans-l,2-cyclobutanedicarboxylic diester 15 and obtained cavities after splitting off the template containing two benzyl alcohols each. To these cavities fumaric acid could be bound. It was reacted with a methylene-transfer reagent [(dimethylamino)methyl-phenyl-oxosulfonium tetrafluoroborate]. The cyclopropanedicarb-... 

CAS 141-02-6 EINECS/ELINCS 205-448-2 220-835-6 Synonyms Bis (2-ethylhexyl) 2-butenedioate Bis (2-ethylhexyl) fumarate 2-Butenedioic acid bis (2-ethylhexyl) ester Di (2-ethylhexyl) fumarate DOF 2-Ethylhexyl fumarate Definition Diester of 2-ethylhexanol and fumaric acid Empirical CaHssO,... 

Definition Diester of isostearyl alcohol and fumaric acid... 

Diester derivatives of maleic and fumaric acid (see Chapter 3) are not easily polymerized. However, they do yield soft, tacky thermoplastics with free-radical generating initiators such as BPO. Diethyl fumarate, for example, polymerizes to an 89% yield of poly (ethyl succinate) when heated in the presence of 2% BPO for 7 Liquid-phase (neat) reaction at high pressure (5000 psi) improves the yield.Polymers of higher softening point and higher molecular weight may be prepared by emulsion-polymerization techniques. 

In some cases, one of the precursors contributes to the formation of both the hard and the soft blocks. Aleksandrovic and Djonlagic [23] copolycondensed a mixture of diesters of terephthalic and fumaric acids, 1,4-butanediol and a,o>-dihydroxy-poly(oxytetramethylene) in the presence of tetrabutoxytitanium... 

Table 1. Aspartic Acid Derivatives by Addition of Nonracemic Amines to Fumaric and Maleic Acids and Their Diesters...

When two parts of (3) and one part of (1) are heated with copper at 75°, the product is the pure Irons,trans-ester (2). When (1) or (3) is heated separately with copper and benzoic acid, the major product is diethyl fumarate or diethyl maleate, respectively. These diesters are probably formed by protonolysis of an organocopper intermediate, with complete retention of configuration. 

Won et al. [19], have reported synthesis of polyesters with valine, leucine, isoleucine, methionine, and phenylalanine (Table 12.1). This three-step process involves synthesis of a diester and a dinitro compound that are copolymerized [19], An amino acid is first coupled with a diol (with 3, 4, or 6 methylene groups) in the presence of tosyl to yield a diester with acid salts of diamine at the terminal ends. The second monomer, di-p-nitrophenyl ester of carboxylic acids, is synthesized by a condensation reaction of adipoyl or se-bacoyl chloride with p-nitro phenol. The final polymerization step involves an arduous condensation reaction in the presence of a strong proton abstractor between acid salt of bis(amino acid-alkyne diester) and di-p-nitrophenyl ester of dicarboxylic acids. Following along the same lines, Chu and Guo [22] have copolymerized a mixture of nitro phenyl ester of succinate, adipate, or sebacate and nitrophenyl fumarate with toluenesulfonic acid salt of phenylalanine butane-1,4-diester. The addition of fumarate derivative to the monomer mixture provides an unsaturated double bond in the polymer backbone that can be functionalized for specific biomedical... 

In another invention, plasticizers are prepared from a mixture of acids (acrylic, maleic, and fumaric) and alcohols having 6 to 18 carbon atoms. Mono and diesters are obtained during manufacturing process. The composition of stock is controlled to obtain plasticizer which has good electrical insulation properties, water extraction resistance, and fogging resistance. ... 

All starting materials and solvents were obtained from commercial sources (Sigma-Aldrich, Fisher Scientific Int.). Active di-esters (of Formula I) di-p-nitrophenyl adipate, I.l (1), di-p-nitrophenyl sebacate, 1.2 (1), di-p-nitrophenyl fumarate, 1.3 (10), and bis-nucleophilic monomers (of general Formula II) di-p-toluenesulfonic acid salts of bis(a-aminoacyl)-a,(o-alkylene diesters (1, 2), and di-p-toluenesulfonic acid salt of L-lysine benzyl ester (11,12) were prepared as described previously. 

The reaction of diazomethane with dimethyl fumarate was reported by Von Pechmann to give the diester of 2-pyrazoline-4,5-dicarboxylic acid 25 (21,26) product was isolated as the acid after hydrolysis. 

Natural Cyclopropanes.—In extensions of their earlier investigations of the synthesis of chrysanthemic acid (25) based on elaboration of the cyclopropane ring by reaction between the isopropyl ylide (22) and alkene substrates (see Volume 1, p. 292), Krief and his co-workers have now shown that the ylide (22) can be added to both maleate and fumarate, leading to the frans-cyclo-propanedicarboxylate (23). Conversion of the diester into the aldehydo-ester (24) and Wittig reaction then completes a new synthesis of chrysanthemic acid (Scheme 5). 

The most common examples of this class are diesters of 2-ethylhexanol. However, there are commercial products which are monoesters, diesters, or mixtures of the two. The alcohol portion of the ester may be fatty alcohol, fatty acid alkanolamide, or ethoxylated fatty amine. They are typically synthesized by forming the ester or amide with maleic anhydride, followed by reaction of the alkyl fumarate with sodium bisulfite. The monoesters are often used in cosmetics and shampoos. 

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