Alkyl fumarates

Additives acting on the pour point also modify the crystal size and, in addition, decrease the cohesive forces between crystals, allowing flow at lower temperatures. These additives are also copolymers containing vinyl esters, alkyl acrylates, or alkyl fumarates. In addition, formulations containing surfactants, such as the amides or fatty acid salts and long-chain dialkyl-amines, have an effect both on the cold filter plugging point and the pour point. 

Esterification. Both mono- and dialkyl maleates and fumarates are obtained on treatment of maleic anhydride or its isomeric acids with alcohols or alkoxides (25). An extensive review is available (59). Alkyl fumarates (18) often are made from isomeri2ation of the corresponding maleate (19) (60). 

Alkyl dimethyl glycinates, 24 148 Alkyl diphenyl phosphates, 11 494 Alkyl dithiocarbazate esters, 13 568 Alkyleneamine, pK values, 8 487t Alkylenediamines, 8 485 Alkylene terephthalate polymers, 20 32 Alkyl ether phosphates, 24 146 Alkyl ethers, 10 574, 575 uses for, 10 580-581 Alkyl fumarates, 15 491... 

Alkenes activated by electron-withdrawing groups at both ends of the double bond are more easily reduced than the analogous singly substituted alkenes, and the radical anions formed are less reactive. Examples include fumarodinitrile compared to acrylonitrile and dialkyl fumarates compared to alkyl acrylates. Fumarodinitrile (51) [2,35,36,48,55,70,71, 124] and simple alkyl fumarates (52) [7,10,15,55,70,125,126] have therefore been the subjects of a number of mechanistic studies as models for acrylonitrile and alkyl acrylates. Examples of the formation of LHDs on a preparative scale are given later, in Table 12. 

Di (Cl2-15) alkyl dimethyl ammonium chloride. See Ditridecyidimonium chloride Di-C12-15 alkyl fumarate CAS 142104-11-8... 

Cycloethoxymethicone Cyclomethicone Cypress (Cupressus sempervirens) oil Decyl isostearate Decyl myristate Decyl oleate Decyl succinate 2-Decyl-1-tetradecanol Dibutyl sebacate Di-C12-15 alkyl fumarate... 

Bis (9-acridinyl) heptane Greatcure 1717 142104-11-8 Di-C12-15 alkyl fumarate Marrix SF 142747-39-5... 

Decene or styrene Dodecyl fumarate Dodecyl fumarate Octadecyl fumarate. Alkyl fumarates Lauryl fumarate... 

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. 

In a similar manner diethyl maleate (actually diethyl fumarate since the basic enamine catalyzes the maleate s isomerization upon contact) forms unstable 1,2 cycloadducts with enamines with hydrogens at temperatures below 30°C (37). At higher temperatures simple alkylated products are formed (41). Enamines with no )3 hydrogens form very stable 1,2 cycloadducts with diethyl maleate (36,37,41). The two adjacent carboethoxy groups of the cyclobutane adduct have been shown to be Irons to one another (36,37). 

Examples of polyfunctional carboxylic acids esterified by this method are shown in Table I. Yields are uniformly high, with the exception of those cases (maleic and fumaric acids) where some of the product appears to be lost during work-up as a result of water solubility. Even with carboxylic acids containing a second functional group (e.g., amide, nitrile) which can readily react with the oxonium salt, the more nucleophilic carboxylate anion is preferentially alkylated. The examples described in detail above illustrate the esterification of an acid containing a labile acetoxy group, which would not survive other procedures such as the traditional Fischer esterification. 

The initially expected (75) cis-hydrometallation or olefin-insertion step with fumarate (R = C02Me) yields the threo isomer 8, which then undergoes the k2 step with retention to give racemic 1,2-dideuterosuccinate. Such retention is necessary to give the usually observed (7, p. 407) overall cis addition of H2 to olefinic bonds, but this study provided the first direct experimental proof, the difficulty being the scarcity of stable metal alkyl-hydride intermediates. The Cp2MoH2 complex also catalyzes hydrogenation of 1,3- or 1,4-dienes to monoenes (197). 

Pd(II)-catalyzed dialkoxy- or dihydroxycarbonylation of alkynes (Eq. 22, R = alkyl or H, respectively) with formation of maleic and fumaric esters or acids (and, in the case of acetylene, of muconic esters too), has been reported to occur in the presence of CuCl2 and/or 02 as oxidant [73-79] electrochemical reoxidation of Pd(0) has also been described [80]. 

Particularly significant results have been obtained in the oxidative carbonylation of simple and functionalized alkynes. Thus, the PdI2/KI-catalyzed oxidative carbonylation of simple alkyl- or arylacetylenes, as well as of propy-nyl alcohol and propynyl acetate, carried out in alcoholic solvents under mild conditions (15-25 atm of CO, 4-9 atm of air, 25-80 °C), led to the formation of maleic derivatives (together with small amounts of fumaric derivatives) and 5,5-dialkoxyfuran-2(5H)-ones, in high yields and with unprecedented catalytic efficiencies for this kind of reaction (up to ca. 4000 mol of product... 

DAP was cocured in bulk with vinyl monomers having long-chain alkyl groups, including vinyl laurate (VL), dioctyl fumarate (DOF), lauryl methacrylate (LMA), and stearyl methacrlate (SMA) (12). 

The hydrogen transfer photosensitization has been applied to the diastereo-selective alkylation of chiral fumaric acid derivatives, where again the mild conditions of the photochemical method are advantageous (Figure 3.8). ... 

Figure 3.8 Diastereoselective alkylation of chiral fumaric acid derivatives.

Uses. In the manufacture of polyester resins, fumaric acid, agricultural pesticides, and alkyl... 

Copolymers of ethylene vinylacetate are the most commonly utilized fuel wax crystal modifiers. Other compounds such as vinyl acetate-fumarate copolymers, styrene-ester copolymers, diester-alphaolefin copolymers, as well as alkyl carbamate compounds are effective wax crystal modifiers. These compounds differ in both chemical structure and in the extent of performance provided. See FIGURES 6-7 and 6-8. 

Barker and Copeland have reported a slightly modified process for the preparation of 3 (Scheme 10). 29 was reacted with phenylchloroformate to give carbamate 33. The ring closure was affected by heating 33 in polyphosphoric acid at 100 °C to provide 31. The imino chloride 32, formed as in Scheme 9, was treated with piperazine in refluxing toluene to give 34. The piperazine 34 was then alkylated with 2-chloroethoxyethanol in the presence of Nal and Na2CO3 to afford quetiapine, which was isolated as the fumarate... 

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