Fumaric epoxide

Michael addition to maleates, 66 Dialkyl alkoxysuccinates, maleates in synthesis, 229 Dialkyldisulfides, adduct with MA, 52 Dialkyl o, )3-epoxysuccinate, from fumarate epoxidation, 69 Dialkyl succinates... 

With regard to the use of tungsten-based systems, Payne and Williams reported on the selective epoxidation of maleic, fumaric, and crotonic acids with a catalytic amount of sodium tungstate (2mol%) in combination with aqueous hydrogen... 

A general type of chemical reaction between two compounds, A and B, such that there is a net reduction in bond multiplicity (e.g., addition of a compound across a carbon-carbon double bond such that the product has lost this 77-bond). An example is the hydration of a double bond, such as that observed in the conversion of fumarate to malate by fumarase. Addition reactions can also occur with strained ring structures that, in some respects, resemble double bonds (e.g., cyclopropyl derivatives or certain epoxides). A special case of a hydro-alkenyl addition is the conversion of 2,3-oxidosqualene to dammara-dienol or in the conversion of squalene to lanosterol. Reactions in which new moieties are linked to adjacent atoms (as is the case in the hydration of fumarate) are often referred to as 1,2-addition reactions. If the atoms that contain newly linked moieties are not adjacent (as is often the case with conjugated reactants), then the reaction is often referred to as a l,n-addition reaction in which n is the numbered atom distant from 1 (e.g., 1,4-addition reaction). In general, addition reactions can take place via electrophilic addition, nucleophilic addition, free-radical addition, or via simultaneous or pericycUc addition. 

Domb, A. J., Manor, N., Elmalak, O. (1996). Biodegradable bone cement compositions based on acrylate and epoxide terminated poly(propylene fumarate) oligomers and calcium salt compositions. Biomaterials, 77,411-417. 

The formation of carbanions, according to Scheme 6, has been much studied but has proved to be of little preparative use. The benzyl anion, generated from benzyl-dimethylsulphonium tosylate, reacted with acrylonitrile but the addition product was formed in only low yield Similarly the reactive ylid formed by deprotonation of trimethylsulphonium salts has been cathodically generated and trapped by several aldehydes and ketones as well as ethyl maleate and fumarate examples are given in Scheme 7. For the best case (benzophenone), the epoxide was formed in 40%... 

The 2-oxoacid p-hydroxyphenylpyruvate is decar-boxylated by the action of a dioxygenase (Eq. 18-49). The product homogentisate is acted on by a second dioxygenase, as indicated in Fig. 25-5, with eventual conversion to fumarate and acetoacetate. A rare metabolic defect in formation of homogentisate leads to tyrosinemia and excretion of hawkinsin97 a compound postulated to arise from an epoxide (arene oxide) intermediate (see Eq. 18-47) which is detoxified by a glutathione transferase (Box 11-B). 

Salts and organic by-products, mostly the diol resulting from hydrolysis of the epoxide, from dry cationization are left in the starch. Trimethylamine, if formed, can be detected by its odor. It can be neutralized by subsequent addition of acid. Addition of a slightly soluble organic acid, such as fumaric or adipic acid, during the cationization both eliminates the odor and aids scale control in starch cooking equipment.44... 

Payne and Williams found that maleic, fumaric, and crotonic acid are very resistant to attack by peracetic or perbenzoic acid but are converted into their epoxides in yields of 77, 50, and 50% by hydrogen peroxide-sodium tungstate at pH 4-5.5. Addition of the peroxide initiates an exothermal reaction which is... 

The double bonds in diethyl maleate and fumarate are very electron deficient olefins. These were indeed the most difficult compounds to epoxidize. The usual treatment with slight excess of oxidant for short periods of time did not result in any reaction. With a large excess, however (5-10 molequivalent) progress could be monitored at room temperature and after 12 hours about 90% conversion was achieved. Thus cis and traits diethyl epoxysuccinate were obtained in 65% and 50% yield respectively. These epoxides are important intermediates in many syntheses, immuno-pharmacological studies and polymerization processes and are always made stepwise by indirect methods. A full retention of configuration was observed and neither epoxide was contaminated with the other (figure 12). 

Applications of chirally modified titanium Lewis acids have been reported most cases use various acetal diols derived from tartrate as the chiral auxiliary26 33,31 90. Various methods of catalyst preparation are known, as well as the use of different types of dienes (open-chained, cyclopentadiene) and dienophiles (acroleins, acrylates, crotonates, fumarates and amides derived from oxazolidinone), including intramolecular cycloaddition30. Addition of 4 A molecular sieves can improve asymmetric induction31,34 (as observed with the Sharpless epoxidation, loc. cit 31 in ref 6) and shows remarkable solvent effects on enantioselectivity. This method has been applied to the asymmetric Diels-Alder cycloaddition of cyclopentadiene and open-chain dienes to acrylamides28, 35. 

Unsaturated maleic/fumaric acid-containing polyesters (UPEs) dissolved in styrene, (2) acrylate/methacrylate systems, (3) thiol/ene systems, and (4) epoxide- or vinyl ether-containing systems. In the case of systems (l)-(3), free radical polymerizations are operative, while in case (4) cationic species are involved (see Chapter 10). Regarding thiol/ene systems, the mechanism of free radical thiol/aUcene polymerization outlined in Scheme 11.1 is assumed to be operative... 

PP poly(propylene), PS poly(styrene), MAH maleic anhydride, MA methacrylic acid, S styrene, PE poly(ethylene), PPE poly(phenylene ether), LDPE low-density PE, EPDM ethylene-propylene-diene terpolymer, SAN styrene-acrylonitrile copolymer, EPR ethylene-propylene copolymer, NMAC A -methacrylyl caprolactam, GMA glycidyl methacrylate, FA fumaric acid, AEFO anhydride and epoxide functionalized olefin copolymer, SEBS styrene/ethylene-butylene/styrene copolymer, HDPE high-density PE, AN acrylonitrile, and S-MAH-MMA styrene-maleic anhydride-methyl methacrylate copolymer. 

Domb, A.J., Manor, N. and Elmalak, O. (1996) Biodegradable Bone Cement Compositions Based on Acrylate and Epoxide Terminated Poh (Propylene Fumarate) Oligomers and Calcium Salt Compositions, Bio-materials, 17, 411-417. 

Epoxidation of fumaric acid can be achieved by using ozone in water at neutral pH in quantitative yield. 

D3 BISPHENOL-A, EPOXIDE, VINYL CYANATE ESTERS AND FUMARIC BASED... 

Databook - Section D3 Bisphenol - A, Epoxide, Vinyi Cyanate Esters Fumaric Based... 

---