Cyclic succinic anhydride

The preparation of the cyclic ketone a-tetralone possesses a number of interesting features. Succinic anhydride is condensed with pure benzene in the presence of anhydrous aluminium chloride (slightly over two equivalents see 1 above) to yield (3-benzoylpropionlc acid ... 

Succinic anhydride the structure of which is shown is a cyclic... 

With a mixed anhydride two different arylketones may be formed. Reaction of a cyclic anhydride of a dicarboxylic acid, e.g. succinic anhydride, leads to formation of an arylketo acid. ... 

Succinic anhydride yields the cyclic imide succinimide when heated with ammonium chloride at 200 °C. Propose a mechanism for this reaction. Why do you suppose such a high reaction temperature is required ... 

Reactions of wood with cyclic anhydrides do not yield a by-product, leaving the modified wood polymers with a covalently bonded carboxylic group an example is reaction with succinic anhydride (SA) (Figure4.1a). With reactions above 100°C there is some formation of diester observed (Figure 4.1b), resulting in cross-linking within the cell wall matrix (Matsuda, 1987). 

Apart from the alkenyl succinic anhydrides, other cyclic anhydrides are solids, requiring the use of a delivery solvent, or a solid-state reaction. Apart from succinic anhydride, phthalic (PA) (Figure 4.2a) (Risi and Arseneau, 1958) and maleic anhydride (MA) have also been extensively studied (Figure 4.2b) (Clemons etal., 1992). Goethals and Stevens (1994) have reported reaction of wood with glutaric (Figure 4.2c) or cyclohexane-1,2-dicarboxylic anhydride (Figure 4.2d) and subsequent reaction with epichlorohydrin. 

Suitable cyclic carboxylic anhydrides for this process are for example cz5-l,2-cyclohexane-dicarboxylic anhydride (HHPA), cz5-l,2-cyclohex-4-ene-dicarbo-xylic anhydride (THPA), phthalic anhydride (PA), succinic anhydride (SA), 1-oct-2-ene-succinic anhydride (OSA), and glutaric anhydride (GA) - see Fig. 9. 

The diacylation of isopropenyl acetate with anhydrides of dicarboxylic acids is applicable for the synthesis of several other cyclic jS-triketones in moderate yield. - It has been used for the synthesis of 2-acetylcyclohexane-l,3-dione (40% yield), 2-acetyl-4-methylcyclopentane-l,3-dione (10% yield), 2-acetyl-4,4-dimethylcyclopentane-l,3-dione (10% yield), 2-acetyl-5,5-dimethylcyclohexane-l,3-dione (10% yield), 2-acetylcyclo-heptane-l,3-dione (12% yield) and 2-acetylindane-l,3-dione (26% yield). Maleic anhydrides under more drastic conditions give acetylcyclopent-4-ene-l,3-diones in yields from 5% to 12%. The corresponding acylation of the enol acetate of 2-butanone with succinic anhydride has been used to prepare 2-methylcyclopentane-l,3-dione, an important intermediate in steroid synthesis. - ... 

Potassium carboxylate groups introduced onto the surface of carbon fibers initiated anionic polymerization of epoxides (e.g., styrene oxide, epichlorohydrin, and glycidyl phenyl ethers) and cyclic acid anhydrides (e.g., maleic anhydride, succinic anhydride, and phthalic anhydride) in the presence of 18-crown-6 [41]. 

Friedel-Crafts acylation can be carried out with cyclic anhydrides,272 in which case the product contains a carboxyl group in the side chain. When succinic anhydride is used, the product is ArCOCH2CH2COOH. This can be reduced (9-37) to A1CH2CH2CFLCOOH, which can then be cyclized by an internal Friedel-Crafts acylation. The total process is called the Haworth reaction 173... 

XVII XVII, 1st Supplement (combined with Volumes XVIII and XIX) XVII, 2nd Supplement 1933 1934 1952 2359-2503 2359-3031 2359-2503 One Cyclic Oxygen (S, Se or Te). Stem nuclei Furan, 27. Thiophene, 29. Hydroxy compounds Furfuryl alcohol, 112. Carbonyl compounds Butyrolactone, 234. Furfural, 272. 2-Aeetyl-thio-phene, 287. Xanthone, 355. Succinic anhydride, 404. Phthalic anhydride, 469. 

Succinic anhydride, the structure of which is shown, is a cyclic anhydride often used in Friedel-Crafts acylations. Give the structure of the product obtained when benzene is acylated with succinic anhydride in the presence of aluminum chloride. 

Maleic acid is a linear four-carbon molecule with carboxylate groups on either end, similar to succinic acid, but with a double bond between the central carbon atoms. The anhydride of maleic acid is a cyclic molecule containing five atoms in its ring. Although the reactivity of maleic anhydride is similar other such reagents like succinic anhydride, the products of maleylation are much more unstable toward hydrolysis, and the site of unsaturation lends itself to additional side reactions. Acylation products of amino groups with maleic anhydride are stable at neutral pH and above, but they readily hydrolyze at acid pH values (around pH 3.5) (Butler etal., 1967). Maleylation of sulfhydryls and the phenolate of tyrosine are even more sensitive to hydrolysis. 

Cyclic anhydrides of dibasic acids such as succinic or glutaric acid are readily prepared by dehydrating the acid with an excess of acetic anhydride, e.g. as in the preparation of succinic anhydride, Expt 5.141 cf. 3-nitrophthalic anhydride, Expt 6.162. 

A number of cyclic systems have produced bis-carboxonium dications (Table 1, entries 6-9). In the case of succinic anhydride (82), however, the product formed at — 80°C in FS03H-SbF5-S02 solution was the acyl-carboxonium dication (96, eq 26).37... 

There are some important cyclic compounds such as the lactone 75, succinic anhydride 76, furan 77, and many substituted furans, particularly furfuraldehyde 78, a by-product of breakfast cereal manufacture, and its reduction product 79 and maleic anhydride 80. 

It might be anticipated that, if a racemic unsymmetrically substituted cyclic anhydride were to be used as a substrate for asymmetric alcoholysis, a KR would ensue. In fact, Deng has shown that for monosubstituted succinic anhydrides, because both carbonyl groups have comparable reactivity, what actually occurs on subjection to his (DHQD)2AQN-catalyzed asymmetric alcoholysis conditions, is a PKR [188]. Thus, the reaction of 2-methyl succinic anhydride (39a) with 2,2,2-trifluoroethanol (10 equiv.) in ether at —24 °C in the presence of (DHQD)2AQN (15 mol%) provided a mixture of two regioisomeric hemiesters... 

Indium-mediated allylation of cyclic and acyclic acid anhydrides gives w-diallyl esters.203,204 Examples are shown in Scheme 48 the allylation of succinic anhydride or phthalic anhydride with allyl bromide in DMF in the presence of indium metal results in the formation of diallylbutenolides or diallylphthalides. In contrast, monoallylated hydroxy esters are formed exclusively with y-substituted allylic halides. 

Half of an anhydride s acid units are lost as leaving groups. If the acid is expensive, we would not use the anhydride as an activated form to make a derivative. The acid chloride is a more efficient alternative, using chloride as the leaving group. Anhydrides are used primarily when the necessary anhydride is cheap and readily available. Acetic anhydride, phthalic anhydride, succinic anhydride, and maleic anhydride are the ones we use most often. Diacids commonly form cyclic anhydrides, especially if a five- or six-membered ring results. 

Cyclic anhydrides can be used to make keto-acids. Either carbonyl group is used for the acylation and the other becomes an AICI3 complex until work-up. Thus 3-benzoylpropanoic acid can be prepared from benzene and succinic anhydride. 

Problem 16.36 Give the structural formula and name for the product formed when 1 mol of succinic anhydride, the cyclic anhydride of succinic acid (Problem 16.22), reacts with (a) 1 mol of CH3OH (b) 2 mol of NH3 and (c) 1 mol of C6H6 with A1C13. M... 

Cyclic anhydrides react well with trimethyl(trifluoromethyl)silane however, a stoichiometric amount of tctrabutylammonium fluoride is required. - For example, succinic anhydride undergoes efficient addition of trimethyl(trifluoromethyl)silane to initially form an adduct, which upon hydrolysis aflbrds the trifluoromethyl-substiluted 0x0 carboxylic acid 27. Simple amides, such as benzamide and acetamide, do not react with trimetliyl(trifluoromethyl)silane even when a molar quantity of tetrabutylainmonium fluoride is used. Furthermore, lactams, such as caprolactam, do not react with trimethyl(trifluoromethyl)silane under similar conditions. An activated amide carbonyl, such as that in A -methylsuccinimide. however, reacts smoothly to afford an interesting adduct, which upon acid hydrolysis affords the hcmiaminal 28. 

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