Phthalic anhydride, reaction with amines

The benzenedisulfonic acids are of little interest, except that benzene-1,3-disulfonic acid is a source of 1,3-dihydroxybenzene (see Chapter 4). The benzene dicarboxylic acids are more important. Benzene-1,2-dicarboxylic acid (phthalic acid, 8) can be converted into phthalic anhydride (9), which is a typical acid anhydride, reacting with amines and alcohols and also taking part in Friedel-Crafts reactions. Phthalimide (10), produced by reaction of the anhydride with ammonia, is weakly acidic and forms a potassium salt with ethanolic potassium hydroxide. 

C. Phthalic Anhydride reacts with many I and II aminos very readily, even without heating III amines show no reaction. 

Phosphine(s), chirality of, 314 Phosphite, DNA synthesis and, 1115 oxidation of, 1116 Phospholipid, 1066-1067 classification of, 1066 Phosphopantetheine, coenzyme A from. 817 structure of, 1127 Phosphoramidite, DNA synthesis and, 1115 Phosphoranc, 720 Phosphoric acid, pKa of, 51 Phosphoric acid anhydride, 1127 Phosphorus, hybridization of, 20 Phosphorus oxychloride, alcohol dehydration with. 620-622 Phosphorus tribromide, reaction with alcohols. 344. 618 Photochemical reaction, 1181 Photolithography, 505-506 resists for, 505-506 Photon, 419 energy- of. 420 Photosynthesis, 973-974 Phthalic acid, structure of, 753 Phthalimide, Gabriel amine synthesis and, 929... 

The activated carbonyl of anhydrides can acylate alcohols or amines at the temperatures necessary for polymer processing. These reactions have been verified by HPLC using the polymer system described in Table 2. An examination of the HPLC chromatograms in Fig. 25 indicates that the phthalic anhydride peak (3.2 min) diminishes with increasing injection-molding temperatures and that two new peaks (4.6 and 6.9 min) increase in intensity. These new peaks corresponded to the half phthalate esters of 1,6-hexanediol and trans-... 

This study was prompted by a report that phthalimidoacetic acid (R = CH2C02H, see also Scheme 4.11, vide supra) could be synthesized by the reaction of phthalic anhydride with glycine in the absence of solvent, which involves the reaction between two solids [56], However, in this study [45], it was established that the synthesis of phthalimides under solvent-free reactions requires at least one liquid reactant in order to occur. This was possible when reacting a liquid amine (e.g. R = CH2Ph) or a solid with a sufficiently low melting point to melt rapidly under MW (e.g. R = (CH2)6OH, m.p. 56-58). In these cases, the reaction temperature was typically over 135 °C after 2 or 3 min of MW heating resulting in dissolution of phthalic anhydride in the molten... 

The antibacterial sulfonamide phthalazole 268 is obtained free of imide and bisamide side products (that occur upon reaction in solution or in the melt) if stoichiometric solid-state milling of the reactants 266 and 267 is performed for the acylation [95] (Scheme 38). Numerous solid arylamines and heterocyclic amines react correspondingly with phthalic anhydride upon stoichiometric milling and provide 100% yield without any workup requirement [22]. 

Inride (N) condensation products that are wax-like are those of the condensation reaction of one mole of phthalic anhydride with one mole of a primary aliphatic amine to produce a phthalimide. Phthalimide waxes are used in polishes and carbon paper. 

Carboxylic acids react with aryl isocyanates, at elevated temperatures to yield anhydrides. The anhydrides subsequently evolve carbon dioxide to yield amines at elevated temperatures (70—72). The aromatic amines are further converted into amides by reaction with excess anhydride. Ortho diacids, such as phthalic acid [88-99-3], react with aryl isocyanates to yield the corresponding N-aryl phthalimides (73). Reactions with carboxylic acids are irreversible and commercially used to prepare polyamides and polyimides, two classes of high performance polymers for high temperature applications where chemical resistance is important. Base catalysis is recommended to reduce the formation of substituted urea by-products (74). 

Second-order kinetics with respect to the amine and epoxide was also found by Antipova et al. 65) for the curing of epoxy resins with hexahydrophthalic anhydride, by Sorokin et al.321 for the reaction of phenylglycidyl ether with phthalic anhydride in the presence of butanol, Luston and Manasek 45 74) for the copolymerization of 2-hydroxy-4-(2,3-epoxypropoxy)benzophenone with phthalic anhydride in the absence or in the presence of proton donors, and Kudyakov et al. 98) for the curing of epoxy resins with maleic anhydride. 

These may be prepared from a primary amine by reaction with phthalic anhydride. The general procedure described in Section 9.6.21, p. 1276 uses glacial acetic acid reaction conditions using chloroform as the solvent medium have been reported.235 Deprotection using hydrazine is described in Expt 5.198. 

The phthalimlde group is typically introduced by reaction of a primary amine with phthalic anhydride in chloroform at 70 °C for 4 h (85-93% yield)1 or phthaloyl chloride in the presence of triethylamine [Scheme 8.10].20 2-Ch oro-carbonylbenzoic acid methyl ester in the presence of base [Scheme 8.11JT21-22 or N-ethoxycarbonylphthalimide23 have also been used with the latter reagent being especially useful for the -protection of a-amino acids [Scheme 8 12] m. 24... 

A vessel was charged with bisphenol A dianhydride (490 kg), diaminodiphenyl sulfone (245 kg), phthalic anhydride (11.0 kg), 1,287 liters of o-dichlorobenzene, and sodium phenyl phosphinate (360 g) as the reaction catalyst. The mixture was heated to 150°C to 180°C with removal of water, and the reaction was analyzed for residual amine and anhydride end groups. Additional bisphenol A dianhydride or... 

Cyclic anhydrides of dibasic acids react with ammonia and certain amines to give cyclic imides, such as phthalimide (97%) and a-ethyl-glutarimide (85%). Aqueous ammonia, ammonium carbonate, and dry ammonia gas have been used. 2-Aminopyridine and phthalic anhydride react at 180° to yield N-(2 pyridyl)-phthalimide (76%). t-Butylphthali-mide is made by the action of phthalic anhydride on /-butylurea at 200-240°. The use of alkylureas in this reaction is general. ... 

Several methods have been developed for phthaloylation of primary amines. Originally, the phthaloyl group was introduced by treatment of anoino acids with phthalic anhydride at elevated temperatures of around The harsh reaction conditions of this... 

Chlorobenzene is employed in the synthesis of certain amino-containing vat dye intermediates. When reacted with phthalic anhydride, the product is 2-chloroanthraquinone, which, with ammonia, is converted readily into 2-aminoanthraquinone (61). Other routes include replacement of halogen by amino groups, with ammonia or ammonium salts of urea, and alkyl- and aryl amines to afford secondary amines. Modification of the amino group by alkylation, with dimethyl sulfate, alkyl halides or esters of toluenesul-fonic acids, is of synthetic value. Arylation of the amino groups is of importance only in the reaction between aminoanthraquinones and nitro- or chloroanthraquinones to yield dianthraquinonylamines, or anthrimides48. For example, the reaction between 62 and 63 yields 64, which can then be converted into carbazole 65, Cl Vat Brown R (Scheme 14). Amination of haloanthraquinones such as l-amino-4-bromoanthraquinone-2-sulfonic acid (bromamine acid) (66), prepared from 1-aminoanthraquinone, is of industrial use. 

There are two options for the other component of an epoxy resin system. Use of mono- or di-anhydrides as curing agents, usually catalyzed by a tertiary amine, causes reactions with the residual secondary hydroxyls in the repeating unit of the prepolymer forming esters and free carboxylic acids. The carboxylic acids formed also react with the epoxide end groups forming cross-links and further free secondary hydroxyl groups. Maleic anhydride, phthalic anhydride, or pyromellitic dianhydride are suitable for this process (Eq. 21.27). 

Purification. R. Breslow and J. Posner [Org. Syn., 47,62 (1967)] recommend that commercial triethylamine be purified to remove primary and secondary amines and water either by distillation from acetic anhydride and then from barium oxide or by reaction with phenyl isocyanate. F. F. Rogers, Jr., R. J. Albers, and D. F. DeTar (procedure submitted to Org. Syn.) recommend refluxing with phthalic anhydride followed by distillation. 

Phthalic anhydride reacts in situ with the hydroxyl groups of polyether polyols forming an half ester of phthalic acid. The formed acidic group neutralises the tertiary amine under the form of quaternary ammonium salt (reaction 13.33). 

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