Derivatives Anhydrides

The carbonylation of 2-methyl-3-butyn-2-oI (50) in benzene gives teraconic anhydride (51). Fulgide (53) (a dimethylenesuccinic anhydride derivative), which is a photochromic compound, can be prepared by the carbonylation of 2,5-dimethyl-3-hexyne-2,5-diol (52)[21], The reaction proceeds under milder conditions when PdlOAc) is used as a catalyst in the presence of iodine [23],... 

All lation. Maleic anhydride reacts with alkene and aromatic substrates having a C—H bond activated by a,P-unsaturation or an adjacent aromatic resonance (31,32) to produce the following succinic anhydride derivatives. 

Halogenation. Halogens add directly to the double bond of maleic anhydride to give dihalo succinic acids. However, different procedures are used for dihalomaleic anhydride derivatives. Fluorinated substrates offer access to difluoromaleic anhydride [669-78-3] (64). 

Isomerization. Maleic acid is isomerized to fumaric acid by thermal treatment and a variety of catalytic species. Isomerization occurs above the 130 to 140°C melting point range for maleic acid but below 230°C, at which point fumaric acid is dehydrated to maleic anhydride. Derivatives of maleic acid can also be isomerized. Kinetic data are available for both the uncatalyzed (73) and thiourea catalyzed (74) isomerizations of the cis to trans diacids. These data suggest that neither carbonium ion nor succinate intermediates are involved in the isomerization. Rather, conjugate addition imparts sufficient single bond character to afford rotation about the central C—C bond of the diacid (75). 

Reduction. Heterogeneous catalytic reduction processes provide effective routes for the production of maleic anhydride derivatives such as succinic anhydride [108-30-5] (26), succinates, y-butyrolactone [96-48-0] (27), tetrahydrofuran [109-99-9] (29), and 1,4-butanediol [110-63-4] (28). The technology for production of 1,4-butanediol from maleic anhydride has been reviewed (92,93). 

Lubrication oil additives represent another important market segment for maleic anhydride derivatives. The molecular stmctures of importance are adducts of polyalkenyl succinic anhydrides (see Lubrication and lubricants). These materials act as dispersants and corrosion inhibitors (see Dispersants Corrosion and corrosion control). One particularly important polyalkenyl succinic anhydride molecule in this market is polyisobutylene succinic anhydride (PIBSA) where the polyisobutylene group has a molecular weight of 900 to 1500. Other polyalkenes are also used. Polyalkenyl succinic anhydride is further derivatized with various amines to produce both dispersants and corrosion inhibitors. Another type of dispersant is a polyester produced from a polyalkenyl succinic anhydride and pentaerythritol [115-77-5]. 

L. H. Flett and W. H. Gardner, Maleic Anhydride Derivatives, John Wiley Sons, Inc., New York, 1952. 

Polymers based on trimellitic anhydride are widely used in premium electromagnetic wire enamels requiring high temperature performance. Several types of trimellitic anhydride-derived polymers are used as wire enamels poly(amide—imide)s (133), poly(ester—imide)s (134), and poly(amide—imide— ester)s (135). Excellent performance characteristics are imparted by trimellitic anhydride-based polymers for wire enamel requirements of flexibiUty, snap, burnout, scrap resistance, heat shock, and dielectric strength. 

This anhydride can then be esterified with polyols yielding a polyester with a residual double bond available for further reaction. AppHcations for chlorendic anhydride derivatives are in polymers for building materials, paints, and other coatings. 

Little is known concerning the tautomerism of glutaric anhydrides and related compounds, although a recent report claims the isolation of the two tautomeric forms (18 and 19) of a glutaconic anhydride derivative, which appears improbable. 

Cyclic 1,3-diacetoxy-l,3-dienes can be generated in situ from cyclic 1,3-diketones under the influence of isopropenyl acetate. The dienes then undergo Diels-Alder reactions with maleic anhydride giving as products 1-acetoxybicycloalkane dicarboxylic anhydride derivatives (10). The procedure is also successful with cyclic 1,2- and 1,4-diketones as well as cyclic a,j3-unsaturated ketones. The products, after hydrolysis to... 

Phthalic anhydride derivatives are also not typical precursors in phthalocyanine formation. Their use is of interest in cases where the substituents prohibit conversion of the anhydride to nitrogen-containing derivatives like phthalimides or phthalonitriles. 

Milbemectin consists of two active ingredients, M.A3 and M.A4. Milbemectin is extracted from plant materials and soils with methanol-water (7 3, v/v). After centrifugation, the extracts obtained are diluted to volume with the extraction solvent in a volumetric flask. Aliquots of the extracts are transferred on to a previously conditioned Cl8 solid-phase extraction (SPE) column. Milbemectin is eluted with methanol after washing the column with aqueous methanol. The eluate is evaporated to dryness and the residual milbemectin is converted to fluorescent anhydride derivatives after treatment with trifluoroacetic anhydride in 0.5 M triethylamine in benzene solution. The anhydride derivatives of M.A3 and M.A4 possess fluorescent sensitivity. The derivatized samples are dissolved in methanol and injected into a high-performance liquid chromatography (HPLC) system equipped with a fluorescence detector for quantitative determination. 

The anhydride derivatives obtained as above are dissolved in an appropriate volume of methanol, and a 10-pL aliquot of each solution is injected into the pre-conditioned HPLC system. The peak heights of the fluorescent derivatives of M.A3 and M.A4 are converted to weight using a calibration curve corresponding to each chemical. 

Quantitation is performed by the calibration technique. A standard solution containing 0.1 mgkg of both M.A3 and M.A4 is prepared and 1, 2.5, 5 and 7.5mL of this solution are pipetted into around-bottom flask separately and evaporated. Each sample is converted into the fluorescent anhydride derivative according to the procedures described above. Each sample is dissolved in lOmL of methanol for injection into the HPLC system. The calibration curves are obtained by plotting the peak heights against the amounts of M.A3 and M.A4. The derivatives for preparing the calibration curve should be freshly prepared on a daily basis prior to quantitation. 

A potential liability associated with such reductive hydroacylations resides in the fact that only one acyl residue of the symmetric anhydride is incorporated into the coupling product. For more precious carboxylic acids, selective acyl transfer from mixed anhydrides is possible. Mixed anhydrides derived from pivalic acid are especially convenient, as they may be isolated chromato-graphically in most cases. In practice, mixed anhydrides of this type enable completely branch-selective hydroacylation with selective delivery of the aromatic and a,()-unsalurated acyl donors (Scheme 19). 

Scheme 19 Selective acyl transfer in reductive hydroacylations involving mixed carboxylic anhydrides derived from pivalic acid...

Whereas imidazolides of nucleotides react only in organic solvents with phosphates or pyrophosphates to give the corresponding anhydride derivatives in high yield, ATP can also be formed enzymatically in aqueous solution from AMP-Im with inorganic pyrophosphate in the presence of valyl-f-RNA synthetase.[66] A variant of this method is the one-pot reaction of a nucleoside with phosphoryltristriazole and tributylammonium pyrophosphate. 671 An a-methylphosphonyl-/ ,y-diphosphate of a thymidine derivative has been synthesized in a similar way t681... 

The naphthalimide 11.23 is manufactured from acenaphthene by sulphonation, oxidation to the naphthalic anhydride derivative and conversion to 4-methoxy-N-methylnaphthal-imide as outlined in Scheme 11.14. 

Williams and Rastetter also accomplished an elegant synthesis of ( )-hyalodendrin (83) in 1980 [39]. Beginning with the sarcosine anhydride-derived enolic aldehyde 78, silyl protection of the enal enabled alkylation of the glycine center with benzyl bromide and thiolation using LDA and monoclinic sulfur a la Schmidt. After protection of the thiol with methylsulfenyl chloride and deprotection of the silyl ether, the enol was sulfenylated with triphenylmethyl chlorodisulfide to afford bis(disulfide) 82 as a 2 1 mixture of diastereomers favoring the anti isomer. Reduction of the disulfides with sodium borohydride and oxidation with KI3 in pyridine afforded ( )-hyalodendrin (83) in 29 % yield (Scheme 9.4). 

The corresponding hydroxyazaquinones appear to exist mainly in their trioxo tautomeric forms. The only structure of this type, which has been described in subsequent trapping reactions (Scheme 8), is compound 4c (59JA6049). This compound when treated with o-phenylenediamine in acetic acid provided pyrido[2,3-6]quinoxaline 24. Reduction of 4c with zinc in acetic anhydride provided triacetoxypyridine derivative 25. Acidic hydrolysis of the azaquinone provided maleic anhydride derivative 27, probably via intermediate 26. 

Neither has oxidation, with lead tetraacetate, of the sirup obtained by dehydration of the D-galactose condensate VIII so far resulted in isolation of the expected dialdehyde. On the other hand, when the anhydride from the D-glucose condensate (XXXIV) was oxidized with lead tetraacetate, an appreciable amount of dialdehyde (XXXVI) was isolated. This discrepancy in behavior is probably attributable to the trans position of the hydroxyl groups of the anhydride derived from D-galactose as compared with the cis configuration for the anhydride from D-glucose. 

The mixed carbonic anhydride procedure8-7 has been useful in the preparation of amide linkages and thiol esters. Mixed carbonic anhydrides have successfully acylated, under very mild conditions, the carb-anions derived from diethyl ethylmalonate and diethylcadmium.8 The latter gives as a product the corresponding ketone. Mixed anhydrides derived from acetic and acetylsalicylic acids give results similar to those described here.8... 

The heptafluorobutyric anhydride derivative of pseudoephedrine and electron capture detector have been used to enhance the sensitivity of the gas chromatographic method. Lin and co-workers36 and Cummins and Fourier37 extracted basefied urine or serum with benzene. Heptafluorobutyric anhydride is added to the benzene extract. The heptafluoro-ibutyric anhydride derivative extracted was chromatographed... 

See also Josephson entries Low temperature superconductors (LTS) Lube basestocks, dewaxing of, 16 844 Lube oil additives, maleic anhydride derivatives as, 15 512. See also Lubricant (lube) additives Lube oil sulfonates... 

Saalfrank, Hoffmann and co-workers performed a number of reactions with tetra-alkoxyallenes such as 196 (Scheme 8.47) [1, 41, 105, 114—116] and demonstrated that this class of donor-substituted allenes can serve as a 1,3-dianion equivalent of malonic acid. Treatment of 196 with cyclopropyldicarboxylic acid dichloride 197 produces 2,4-dioxo-3,4-dihydro-2H-pyran 198 through release of two molecules of ethyl chloride [115]. Similarily, the reaction of this allene 196 with oxalyl chloride gives 3-chloromalonic acid anhydride derivative 199. This intermediate is a reactive dieno-phile which accepts 2,3-dimethyl-l,3-butadiene in a subsequent [4+2] cycloaddition to afford cycloadduct 200 in good yield [116]. 

The reaction is believed to begin with the metalation of the substrate via aromatic electrophilic substitution (SEAr) followed by CO insertion and nucleophilic displacement by water or another protic nucleophile such as tri-fluoroacetic acid (TFFA) to give, respectively, the aromatic carboxylic acid or its mixed anhydride derivative, from which the acid is freed by hydrolysis (Scheme 24). 

Figure 9.3 / schematic showing a possibie future acetyiation process, with acetic anhydride derived from wood and energy suppiied by biomass. 

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