Dicarboxylic acid esters imides

Dimalone [bicyclo-(2.2.1)-5-heptene-2,3-dicarboxylic acid dimethyl ester] and Octa-cide 264 [the V-octyl imide of bicyclo-(2.2.1)-5-heptene-2,3-dicarboxylic acid] do produce a red color with an absorption maximum in the same region as that obtained in the analysis of Compound 118. However, because Dimalone is an insect repellent and Octacide 264 is a pyrethrum synergist, neither of these products is likely to be encountered in commercial mixtures of Compound 118. The response to the colorimetric test for Compound 118 of some chemicals commonly used for insect control is listed in Table V. 

Procedures have been reported to convert 67 into the corresponding imide (74) (73USP3736299), dicarboxylic acid (75), anhydride (76), and a variety of acid/esters (77) and diesters (78) (75USP3915974). Chromic acid oxidation of 2,3-dichloroquinoxaline has also been reported as a route to 75 (58RTC842). 

Azo compounds like esters or imides of azo dicarboxylic acid act as reactive dienophiles in normal electron demand hetero Diels-Alder reactions due to the strong activation caused by two electron-withdrawing moieties. In the last years, considerable attention has focused on alkyl and phenyl derivatives of 1,2,4-tria-zoline-3,5-diones since their cycloadditions to chiral dienes proceed with often excellent facial selectivities. Thus, when reacting an oxapropellane derived diene with N -methyltriazolinedione, Paquette et al. obtained the cycloadduct as single diastereomer, but both maleic anhydride and N-phenyl maleimide were distinctly less reactive and turned out to undergo cycloadditions with poor selectivities [289]. 

R) - and (S)-l-phenylethylamine to the diethyl esters of fumaric and maleic acid which are carried out by heating the pure compounds, without solvent, to 115-120 °C for three days (see Table 1). The reaction mixtures are then hydrolyzed and hydrogenated to give aspartic acids in high yields (85-87%) but very low optical purities (6.3-12.2%). A number of intermediates and by-products arc isolated, especially amides and imides of the dicarboxylic acids participating in the reaction. This may explain the low overall diastereoselectivity which can be calculated from the low optical rotation of the isolated aspartic acids. However, any discussion of the reaction mechanism remains difficult because the structures of the substrates and products of the actual addition step itself are not known with certainty. It is known that... 

Sulfur tetrafluoride fluorination of aryl perfluoroalkyl esters provides a route to stable aryl perfluoroalkyl ether compounds (1). By using nitrophenyl esters of perfluoroalkyl-ene and perfluoroalkylene ether dicarboxylic acids, a, w-bis (m-nitrophenoxy) perfluoroalkylene ether intermediates were prepared. The conversion of these products to the corresponding amino and isocyanatophenoxy derivatives is described. Reaction of the diamines with benzophenone-tetracarboxylic dianhydride resulted in formation of poly-imides. Cyclotrimerization of the diisocyanate intermediates formed polyisocyanurates. Both the imide and iso-cyanurate polymers have high thermal, oxidative, and hydrolytic stability. 

Table 22 lists four polymer series of PEIs which contain an ether, sulphone or carbonyl linked diphenyl tetracarboxylimide unit [36]. Each of the four series contains two imide and two ester groups and have four aromatic co-monomers. Polymer series 7 and 9 also contain two units of p-aminophenol in conjunction with a bicyclic aromatic dicarboxylic acid, whereas polymer series 6 and 8 are based on m-aminophenol. The Mesogenic Index correctly predicts that series 6, 8 and 9 give rise to isotropic copolymers. However, in the case of series 7, in which the variable monomer was based on ether or thioether diphenol derivatives, thermotropic phases were observed in all three cases. When all four series are viewed as a whole it is clear that an MI value of 9.5 represents a borderline condition for a mesophase to occur. It also corresponds with the minimum value for a mesophase observed in NCPT-based PEIs. 

Asymmetric hydrocarboxylation has also been applied to heterofunctionalized alkenes, such as vinyl imides, giving chiral amino acids. Similarly, methacrylic esters give chiral dicarboxylic acids and allylic alcohols give chiral y-butyrolactones. The results of these conversions are compiled in Tabic 12. 

Lactams from dicarboxylic acid amide esters via dicarboxylic acid imides by decarbonylation... 

Dicarboxylic acid imides, N-carbaryloxy-a,/3-Ethylene-a-nitro-carboxylic acid esters... 

The studies of the crosslinking reaction of a nadic end-capped imide, N, N -(ox-ydi-3,4 -phenylene)bis(5-norbornene-2,3-dicarboximide) in thermal and micro-wave processes were performed by Scola at al. (Fig. 14) [80]. The investigated starting resin (RP-46) consisted of polyimide precursors, 3,3, 4,4 -benzophenonetet-racarboxylic acid methyl ester (BTDE), 3,4 -oxydianiline (3,4 -ODA), and end capping reagent, 5-norbornene-2,3-dicarboxylic acid monomethyl ester (NE). The cure process proceeds in two steps imidization (1) and a thermally induced (retro-diene Diels-Alder) decomposition-recombination crosslinking step (2) (Fig. 14). 

There are cyclic esters (known as lactones), cyclic amides (known as lactams), cyclic anhydrides, and cyclic imides. The structures for these derivatives are presented in Chapter 20, Section 20.6.5. The chemical reactions associated with derivatives of dicarboxylic acids are discussed in Chapter 20 as well. 

Kinetic and mechanistic studiesoftheimidizationreactionhave been made and the effects of amine activators, catalysts, and palladium " have all been studied. Imide plastics have also been produced by the reaction of diamine-esters of poly(dicarboxylic acid) on filler surfaces in a quasi reaction-injection moulding process. ... 

Polyanhydride structures can be modified by the addition of aminoacids, linked via imide bonds at the amino terminus, so that the carboxylic acid terminus remains available for the interaction with acetic anhydride [459]. These poly(anhydride-imides) degrade in a similar way as the simple polyanhydride polymers. Other modifications that can take place are copolymers linked with esters. In that way, the polymer contains two types of hydrolytically cleavable bonds. In the presence of water, both types of bonds are hydrolyzed, releasing the dicarboxylic acid and the ester [460]. An example of a poly(anhydride-ester) with application in the medicinal field includes sebacic acid and salicylic acid, a therapeutically useful compound. The release of sebacic acid in the body opens up a variety of potential applications. 

The chemistry involved in curable poly(ester imide) formulations is well established, and it is still based on trimellitic anhydride, methylene dianiline, and low molecular weight polyesters of aromatic dicarboxylic acids and glycols, along with a classical heterocyclic triol, 2,4,6-trishydroxyethyl isocyanurate (THEIC), as it is shown in Scheme (29). The composition is formulated in a way that the final polymers, although linear, contain free —OH groups, both as chain ends and as side reactive groups. At the moment of... 

Diacids.—Succinic acid derivatives can be obtained in good yields by coupling lithium a-lithiocarboxylates (or ester enolates) with lithium a-halocarboxylates, or a-halo-esters/ Carboxylic acid dianions also react with isocyanates and iso thiocyanates to give malonamic acids (13 X = O) and 3-thiomalonamic acids (13 X = S), respectively/ A route to c/5-cyclobutane-l,2-dicarboxylic acids (16), which could be of some generality, consists of photocyclization of acryl-imides (14) to maleimides (15) and hydrolysis/ Yields of (15), as judged by n.m.r. spectra, are between 45 and 82%. 

Carboxylic acid imides Cyanoformic acid esters Diacyl amines l,r-Di(alkoxy)amines a, a-Dialkoxynitriles Dicarboxylic acid imides... 

Yinylogous dicarboxylic acid imides from y-oximinocarboxylic acid esters and acetylene derivs. via carbalkoxyisoxazoles... 

Dicarboxylic acid imides from dicarboxylic acid amide esters Dicarboxylic acid monothioimides from dicarboxylic acid thiamide esters... 

The concept of norbomene-terminated oligo-imides was further studied at the NASA Lewis Research Center by researchers who developed the polymerization of monomeric reactants (PMR) approach. The method, represented in Fig. 9.18, involves a blend of both the dimethyl ester of 3,3 -benzophenonetetracarboxylic acid 42 and the mono-methylester of 5-norbomene-2,3-dicarboxylic acid 41 with 4,4 -methylenebisbenzeneamine 34 in solution in methanol. 

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