Reaction maleic anhydride

Concerted Nonpolar Reactions. Maleic anhydride exemplifies the model dienophile for cycloaddition with dienes such as 1,3-butadiene... 

Furan [110-00-9] - [BUTADIENE] (Vol 4) - [FURANDERIVATIVES] (Supplement) -from butenediol [ACETYLENE-DERIVED CHEMICALS] (Voll) -Diels-Alder reaction [MALEIC ANHYDRIDE, MALEIC ACID AND FUMARIC ACID] (Vol 15) -from waste combustion [FUELS FROM WASTE] (Vol 12)... 

Keywords solid-gas reaction, Diels-Alder reaction, maleic anhydride, 1,3-cyclo-hexadiene, quantitative, stereospecific... 

Keywords solid-solid reaction, Diels-Alder reactions, maleic anhydride, fumaro-dinitrile, fumarodinitrile, fulvenes, orthoquinone, 9-methylanthracene, ball mill, stereospecific, stereospecific... 

The crude phthalic anhydride is heated and held at 260 C to allow some byproduct reactions to go to completion. Purification is by continuous distillation in two columns. In the first column, maleic anhydride and benzoic and toluic acids are removed overhead. In the second column, pure phthalic anhydride is removed overhead. High boiling residues are removed from the bottom of the second column. 

Represented by its abbreviation, MAV, the Maleic Anhydride Value Is based on the fact that olefinic conjugated double bonds can be added to maleic anhydride by the reaction below m]... 

Derivatives of polyisobutylene (6. in Figure 9.1) offer the advantage of control over the molecular weight of the polyisobutylene obtained by cationic polymerization of isobutylene. Condensation on maleic anhydride can be done directly either by thermal activation ( ene-synthesis reaction) (2.1), or by chlorinated polyisobutylene intermediates (2.2). The condensation of the PIBSA on polyethylene polyamines leads to succinimides. Note that one can obtain mono- or disuccinimides. The mono-succinimides are used as... 

Since the octatetrene contains two CH CH-CH CH units, it will readily combine with two molecules of maleic anhydride and other adducts by the Diels-Alder reaction (p. 292). 

The Diels-Alder Reaction consists in the direct combination of a compound containing a conjugated diene system u ith a reagent which possesses a double or triple bond activated bj suitable adjacent groups. Examples of such reagents are maleic anhydride, p-benzoquinone, acraldehyde and acetylene dicarboxylic esters. Combination always occurs at the 1,4 positions of the diene system ... 

In the following preparation, this reaction is exemplified by the union of anthracene with maleic anhydride, to form 9,io-dihydroanthracene-9,io-e do-a -succinic anhydride note that as a result of this reaction both the outer rings of the anthracene system become truly aromatic in character. 

A. Maleic acid. Assemble the apparatus shown in Fig. Ill, 28, 1. Place 45 g. of dry mahc acid in the 200-250 ml. distilling flask and cautiously add 63 g. (57 ml.) of pure acetyl chloride. Warm the flask gently on a water bath to start the reaction, which then proceeds exothermically. Hydrogen chloride is evolved and the malic acid passes into solution. When the evolution of gas subsides, heat the flask on a water bath for 1-2 hours. Rearrange the apparatus and distil. A fraction of low boiling point passes over first and the temperature rises rapidly to 190° at this point run out the water from the condenser. Continue the distillation and collect the maleic anhydride at 195-200°. Recrystallise the crude maleic anhydride from chloroform (compare Section 111,93) 22 g. of pure maleic anhydride, m.p. 54°, are obtained. 

The mechanism of the diene synthesis appears to involve an electron transfer from the diene to the dienophile, .e., it is initiated by an ionic reaction. The following scheme may represent the addition of 2 3-dimethylbutadiene to maleic anhydride ... 

The Dieb-Alder reaction is a purely cia addition the relative positions of the substituents are retained in the adduct (compare anthracene and maleic anhydride above). ... 

Another class of reaction where you can see at once that the disconnection is the reverse of the reaction is Pericychc Reactions. An example would be the Diels-Alder reaction between butadiene and maleic anhydride. Draw the mechanism and the product. 

Carbonyiation of butadiene gives two different products depending on the catalytic species. When PdCl is used in ethanol, ethyl 3-pentenoate (91) is obtained[87,88]. Further carbonyiation of 3-pentenoate catalyzed by cobalt carbonyl affords adipate 92[89], 3-Pentenoate is also obtained in the presence of acid. On the other hand, with catalysis by Pd(OAc)2 and Ph3P, methyl 3,8-nonadienoate (93) is obtained by dimerization-carbonylation[90,91]. The presence of chloride ion firmly attached to Pd makes the difference. The reaction is slow, and higher catalytic activity was observed by using Pd(OAc) , (/-Pr) ,P, and maleic anhydride[92]. Carbonyiation of isoprcne with either PdCi or Pd(OAc)2 and Ph,P gives only the 4-methyl-3-pentenoate 94[93]. 

Like butadiene, allene undergoes dimerization and addition of nucleophiles to give 1-substituted 3-methyl-2-methylene-3-butenyl compounds. Dimerization-hydration of allene is catalyzed by Pd(0) in the presence of CO2 to give 3-methyl-2-methylene-3-buten-l-ol (1). An addition reaction with. MleOH proceeds without CO2 to give 2-methyl-4-methoxy-3-inethylene-1-butene (2)[1]. Similarly, piperidine reacts with allene to give the dimeric amine 3, and the reaction of malonate affords 4 in good yields. Pd(0) coordinated by maleic anhydride (MA) IS used as a catalyst[2]. 

The cyclohexadiene derivative 130 was obtained by the co-cyclization of DMAD with strained alkenes such as norbornene catalyzed by 75[63], However, the linear 2 1 adduct 131 of an alkene and DMAD was obtained selectively using bis(maleic anhydride)(norbornene)palladium (124)[64] as a cat-alyst[65], A similar reaction of allyl alcohol with DMAD is catalyzed by the catalyst 123 to give the linear adducts 132 and 133[66], Reaction of a vinyl ether with DMAD gives the cyclopentene derivatives 134 and 135 as 2 I adducts, and a cyclooctadiene derivative, although the selectivity is not high[67]. 

Maleic anhydride condenses with 2-aminothiazole-4-carboxylic acid giving the raaleimide 107 (269) another report claims, however, that the reaction of 2-amino-4-methylthiazole with this anhydride gives the N-substituted maleamic acid (108) (Scheme 73) (270). 

Furthermore, if the structural unit to be polymerized is a vinyl group, mixed reactions can be carried out with a second compound such as a vinyl derivative or maleic anhydride. 

Unsaturated Polyesters. Unsaturated polyesters are produced by reaction between two types of dibasic acids, one of which is unsaturated, and an alcohol to produce an ester. Double bonds in the body of the unsaturated dibasic acid are obtained by using maleic anhydride or fumaric acid. 

Diels-Alder reaction TALEIC ANHYDRIDE, MALEIC ACID AND FUMARIC ACID] (Vol 15) -from waste combustion [FUELS FROM WASTE] (Vol 12)... 

The balance between aromatic and aUphatic reactivity is affected by the type of substituents on the ring. Furan functions as a diene in the Diels-Alder reaction. With maleic anhydride, furan readily forms 7-oxabicyclo [2.2.1]hept-5-ene-2,3-dicarboxyhc anhydride in excellent yield [5426-09-5] (4). 

Furan and maleic anhydride undergo the Diels-Alder reaction to form the tricycHc 1 1 adduct, 7-oxabicyclo [2.2.1]hept-5-ene-2,3-dicarboxyHc anhydride (4) in exceUent yield. Other strong dienophiles also add to furan (88). Although both endo and exo isomers are formed initially, the former rapidly isomerize to the latter in solution, even at room temperature. The existence of a charge-transfer complex in the system has been demonstrated (89,90). 

Chlorendic Acid. Chlorendic acid [115-28-6] and its anhydride [115-27-5] are widely used flame retardants. Chlorendic acid is synthesized by a Diels-Alder reaction of maleic anhydride and hexachlorocyclopentadiene (see CyclopentadlENE and dicyclopentadiente) in toluene followed by hydrolysis of the anhydride using aqueous base (60). The anhydride can be isolated directly from the reaction mixture or can be prepared in a very pure form by dehydration of the acid. The principal use of chlorendic anhydride and chlorendic acid has been in the manufacture of unsaturated polyester resins. Because the esterification rate of chlorendic anhydride is similar to that of phthalic anhydride, it can be used in place of phthalic anhydride in commercial polyester... 

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). 

A large variety of bisimides and polymers containing maleimide and citraconimide end groups have also been reported (21—26). Thus polymers based on bisimidobenzoxazoles from the reaction of maleic anhydride and citraconic anhydride with 5-aniino-2-(p-aniinophenyl)benzoxazole and 5-aniino-2(y -aniinophenyl)benzoxazole are found to be thermally stable up to 500°C in nitrogen. 

Reactions of /l-Butane. The most important industrial reactions of / -butane are vapor-phase oxidation to form maleic anhydride (qv), thermal cracking to produce ethylene (qv), Hquid-phase oxidation to produce acetic acid (qv) and oxygenated by-products, and isomerization to form isobutane. 

Reactions. Mahc acid undergoes many of the characteristic reactions of dibasic acids, monohydric alcohols, and a-hydroxycarboxyUc acids. When heated to 170—180°C, it decomposes to fumaric acid and maleic anhydride which sublimes on further heating (see Maleic anhydride, maleic acid, AND FUMARIC acid). MaUc acid forms two types of condensation products linear malomalic acids and the cycHc dilactone or maUde it does not form an anhydride. 

Bitumen Ionomers. Moisture-resistant asphalts (qv) have been prepared by reaction of metal oxides with acid-functionalized bitumens (75). Maleic anhydride or sulfur trioxide/trimethylamine complexes have been used successfully for introduction of acid groups into asphaltic bitumens. 

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