Maleic anhydride alkylated

In studies on hydrophobic interactions and conformational transitions of selected hydrolyzed maleic anhydride-alkyl vinyl ether copolymers (I, 2), we found that under certain conditions neutralization by base caused phase separation in aqueous solutions of the hexyl and octyl copolymers. Both the hexyl and octyl copolymers are insoluble at low pH and require partial neutralization by a base for complete dissolution. Under certain conditions, these copolymers will again precipitate as their degree of neutralization is raised with more base. Insolubility at low pH has been reported for other polyacids (3, 4). However, the phase separation at high pH contradicts the wealth of data indicating that neutralization increases the water affinity of polyacids. 

A.lkyl Sulfosuccinate Half Asters. These detergents are prepared by reaction of maleic anhydride and a primary fatty alcohol, followed by sulfonation with sodium bisulfite. A typical member of this group is disodium lauryl sulfosucciaate [26838-05-1]. Although not known as effective foamers, these surfactants can boost foams and act as stabilizers when used ia combination with other anionic surfactants. In combination with alkyl sulfates, they are said to reduce the irritation effects of the latter (6). 

Endo adducts are usually favored by iateractions between the double bonds of the diene and the carbonyl groups of the dienophile. As was mentioned ia the section on alkylation, the reaction of pyrrole compounds and maleic anhydride results ia a substitution at the 2-position of the pyrrole ring (34,44). Thiophene [110-02-1] forms a cycloaddition adduct with maleic anhydride but only under severe pressures and around 100°C (45). Addition of electron-withdrawiag substituents about the double bond of maleic anhydride increases rates of cycloaddition. Both a-(carbomethoxy)maleic anhydride [69327-00-0] and a-(phenylsulfonyl) maleic anhydride [120789-76-6] react with 1,3-dienes, styrenes, and vinyl ethers much faster than tetracyanoethylene [670-54-2] (46). 

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). 

Poly(phenylene oxide)s undergo many substitution reactions (25). Reactions involving the aromatic rings and the methyl groups of DMPPO include bromination (26), displacement of the resultant bromine with phosphoms or amines (27), lithiation (28), and maleic anhydride grafting (29). Additional reactions at the open 3-position on the ring include nitration, alkylation (30), and amidation with isocyanates (31). 

Another important use of BCl is as a Ftiedel-Crafts catalyst ia various polymerisation, alkylation, and acylation reactions, and ia other organic syntheses (see Friedel-Crafts reaction). Examples include conversion of cyclophosphasenes to polymers (81,82) polymerisation of olefins such as ethylene (75,83—88) graft polymerisation of vinyl chloride and isobutylene (89) stereospecific polymerisation of propylene (90) copolymerisation of isobutylene and styrene (91,92), and other unsaturated aromatics with maleic anhydride (93) polymerisation of norhornene (94), butadiene (95) preparation of electrically conducting epoxy resins (96), and polymers containing B and N (97) and selective demethylation of methoxy groups ortho to OH groups (98). 

Although benzene prices have escalated in recent years, a concurrent need for butenes for use in alkylates for motor fuel has also increased and butane prices have also escalated. As a result, a search for alternative feedstocks began and Amoco Chemical Co. commercialized a process in 1977 to produce maleic anhydride from butane. A plant in JoHet came on-stream in 1977 with a capacity of 27,000 t/yr (135,136). No new plants have been built in the United States based on butenes since the commercialization of butane to maleic anhydride technology. In Europe and particularly in Japan, however, where butane is in short supply and needs for butenes as alkylation feed are also much less, butenes may become the dominant feedstock (see Maleic anhydride). 

The refined grade s fastest growing use is as a commercial extraction solvent and reaction medium. Other uses are as a solvent for radical-free copolymerization of maleic anhydride and an alkyl vinyl ether, and as a solvent for the polymerization of butadiene and isoprene usiag lithium alkyls as catalyst. Other laboratory appHcations include use as a solvent for Grignard reagents, and also for phase-transfer catalysts. 

The most useful syntheses of pyridazines and their alkyl and other derivatives begins with the reaction between maleic anhydride and hydrazine to give maleic hydrazide. This is further transformed into 3,6-dichloropyridazine which is amenable to nucleophilic substitution of one or both halogen atoms alternatively, the halogen(s) can be replaced by hydrogen as shown in Scheme 110. In this manner a great number of pyridazine derivatives are prepared. 

Isoindole itself gives normal Diels-Alder addition products, (107 and 108), with maleic anhydride and A-phcnylmaleimide, these derivatives constituting the main evidence for forma,tion of the parent substance. 2-Alkyl- and 2-arylisoindoles also give normal addition products with these two dienophiles.Although only one product is generally isolated, it seems likely, in view of the known tendency of several Diels-Alder adducts of isoindoles to dissociate to their components (see below), that both exo and endo stereoisomers might be formed in certain cases. The reaction between 2-p-tolyl-isoindole and A-phenylmaleimide has been shown to give both e,xo (109) and endo (110) addition products. ... 

All attempts to prepare other [2 + 4] cycloadducts of sulfoxides 115 with dienophiles such as maleic anhydride, ethyl azodicarboxylate, etc., have failed60. A method for preparing ordinary alkyl-substituted thiirene oxides (e.g. 18 R1 = R2 = alkyl) is still lacking. 

Thiophene 1,1-dioxide (61) is too unstable to isolate and dimerizes with loss of S02 to give 3a, 7a-dihydrobenzothiophene 1,1-dioxide (172) in 34%113. However, alkyl-substituted thiophene 1,1-dioxides can serve as dienes in the Diels-Alder reaction, since the aromatic properties of the thiophene nucleus are lost completely and the n-electrons of the sulfur atom are used for forming the bond with oxygen. The sulfones 173-178 are found to react with two moles of maleic anhydride at elevated temperature to give bicyclic anhydrides114. Thus, at high reaction temperature, S02 is split off to give cyclohexadiene... 

A common reaction sequence is shown in the schemes printed above. The sulfosuccinate monoesters are produced by a two-step reaction. In the first step 1 mol of maleic anhydride is reacted with a hydroxyl group-bearing component. In the second step the monoester is reacted with sodium sulfite (or sodium bisulfite) to form the disodium alkyl sulfosuccinate. At the so-called halfester stage, there are two possibilities for an electrophilic attack [61] (Michael-type reaction) at the double bond (Scheme 6). Reactivity differences between the two vinylic carbons should be very small, so that probably an exclusive formation of one single regioisomer can be excluded. 

In copolymers containing the styrene sulfonate moiety and maleic anhydride units, the maleic anhydride units can be functionalized with alkyl amine [1411-1416]. The water-soluble polymers impart enhanced deflocculation characteristics to the mud. Typically, the deflocculants are relatively low-molecular-weight polymers composed of styrene sodium sulfonate monomer maleic anhydride, as the anhydride and/or the diacid and a zwitterionic functionalized maleic anhydride. Typically the molar ratio of styrene sulfonate units to total maleic anhydride units ranges from 3 1 to 1 1. The level of alkyl amine functionalization of the maleic anhydride units is 75 to 100 mole-percent. The molar concentrations of sulfonate and zwitterionic units are not necessarily equivalent, because the deflocculation properties of these water-soluble polymers can be controlled via changes in their ratio. 

Maleic acid imides (maleimides) are derivatives of the reaction of maleic anhydride and ammonia or primary amine compounds. The double bond of a maleimide may undergo an alkylation reaction with a sulfhydryl group to form a stable thioether bond (Chapter 2, Section 2.2). Maleic anhydride may presumably undergo the same reaction with cysteine residues and other sulfhydryl compounds. 

The data presented here constitute part of the results attained in the development of a research project funded by the European Community (EC) and performed in cooperation with three independent European companies [6]. Hybrid polymeric materials based on intimate blends of human serum albumin (HSA), alkyl hemiesters of alternating copolymers of maleic anhydride (MAn), and vinyl ethers of monomethoxyoligoethylene glycols (PEGVE) were selected as biocompatible matrices for the formulation of the nanoparticles. 

The preparation and characterization of alternating copolymers of Maleic anhydride (MAn) and poly (ethylene glycol-vinyl ether) as well as their chemical conversions to provide various alkyl hemiesters (Scheme 1) have been described elsewhere [7]. The matrices are quoted as PAMm z, where m represent the number of oxyethylene units in R and n the number of carbon atoms in R. Human serum albumin (HSA) was provided by Isti-tuto Sierovaccinogeno Italiano SpA, Italy. 

Maleic anhydride derivatives are readily making it possible to perform their transformations into photochromic N-alkyl-substituted dithienylma-leimides with primary amines. This method was used to prepare cyclic imides 187 in anhydrous methanol or ethanol at 20-80°C in 67-90% yields (02ZOR1390) and N-alkyl(aryl) derivatives 188 based on thieno[3,2-b]pyr-role (03IZV1719) in 70-90% yields. 

The polymerization of alkyl vinyl ethers is of some commercial importance. The homopolymers, which can be obtained only by cationic polymerization, are useful as plasticizers of other polymers, adhesives, and coatings. (The copolymerization of vinyl ethers with acrylates, vinyl acetate, maleic anhydride, and other monomers is achieved by radical polymerization but not the homopolymerizations of alkyl vinyl ethers.)... 

In addition to the regioselectivity of the cycloaddition, there also exists a question of stereoselectivity. This issue involves the location of the substituent X on the dipolarophile in either an exo or endo fashion (Scheme 2.3). In the case of simple alkyl nitronates bearing an electron-withdrawing substituent, the stereoselectivity is highly dependent on both the nature of the dipolarophile and the configuration of the nitronate (Scheme 2.5) (96). In the case of nitronate 47, either a mixture of diastereomers or only the exo adduct is observed. However, the cycloaddition of maleic anhydride with 47 provides only the endo stereoisomer (97). 

Alkyl monoesters of poly(vinyl methyl ether-maleic anhydride) (PVM-MA) are bioerodible acidic polymers that are used to control drug release. In biological fluids with poor buffering capacity, drug release from the polymers and their dissolution are slowed owing to the lower pH on the polymer surface. We studied whether the release of timolol from matrices of monoisopropyl ester of PVM-MA in vitro and in vivo in rabbits eyes could be affected by disodium phosphate in the matrices. Addition of disodium phosphate to the matrices doubled the release rate of timolol in vitro, but it did not affect the bulk pH of the dissolution medium. On the basis of the timolol concentrations in the tear fluid and in systemic circulation, disodium phosphate seems to accelerate drug release in vivo also. Disodium phosphate probably affects the rate of dmg release by increasing the microenvironmental pH on the polymer surface. 

Bioerodible alkyl monoesters of poly(vinyl methyl ether-maleic anhydride) (PVM-MA) (Fig. 1) can be used to control drug release. Being acidic, ionizable polymers the pH of the disolution medium affects the rate of polymer dissolution [1]. 

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