Phthalimides phthalic acids

The two-step procedure includes formation of a N-substituted phthalimide 3, and its subsequent cleavage to the primary amine 5. Phthalimide (which can be obtained from reaction of phthalic acid with ammonia) shows NH-acidity, since the negative charge of the phthalimide anion (the conjugated base) is stabilized... 

A further alkylation of the nitrogen is not possible. In a second step the TV-substituted phthalimide 3 is hydrolyzed to give the desired amine 5 and phthalic acid 4 ... 

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... 

Phthalocyanines have been synthesized with nearly all metals of the periodic table.77 Normally they are formed in a single-step reaction from available derivatives of phthalic acid, in particular phthalic acid (see Section 2.1.1.1.), phthalic anhydride (see Section 2.1.1.2.), phthalimide (see Section 2.1.1.3.), 2-cyanobenzamide (see Section 2.1.1.4.), phthalonitrile (see Section 2.1.1.5.), isoindolinediimine (see Section 2.1.1.6.), or 1,2-dibromobenzene (see Section 2.1.1.7.), usually in a high-boiling solvent or by heating the neat components.1 4... 

Fig. 23 Microwave-promoted SPOS of substituted phthalimides. Reagents and conditions a phthalic acid (R = H, F, Br, CH3, C4H4), DIAD, PPha, THF, rt, 24h b primary amine (R =C3H6Ph, CH(CH3)C2H4Ph, CsH, 4-CH3 0Bn,4-ClBn, C5H9) amine, EDC HCl, HOAt, CH2CI2, rt, 18 h c MW, DMF, 170 °C, 20 min, closed vessel...

The independent preparation of potassium phthalimide (from a solution of phthalimide in absolute ethanol and potassium hydroxide in 75 per cent, ethanol) may be avoided in many cases by boiling phthalimide with the halide in the presence of anhydrous potassium carbonate. The N-substituted phthalimide (I) is frequently cleav with difficulty this is often facilitated by reaction with hydrazine hydrate to give an intermediate product, which is easily decomposed by hydrochloric acid to yield the insoluble hydrazide of phthalic acid (II) and the primary amine (III) ... 

The transformation and metabolism products of pesticides in plants may not only be of acute toxicity, but also may have other properties. Phosmet, for example, transforms into phthalimide and phthalic acid, teratogenic substances [21]. 

Phthalic acid, 32, 67 Phthalic anhydride, 32, 19 PHTHALIMIDE, N-2-BROMOETHYL-, 32, 18 PlMELIC ACID, 7-0X0-, DIETHYL ESTER,... 

For the cydative cleavage step, it turned out that aprotic conditions were definitely superior to the use of protic media. Thus, employing N,N-dimethylformamide as solvent at somewhat elevated temperatures furnished the desired compounds in high yields and excellent purities. Having established the optimized conditions, various phthalic acids and amines were employed to prepare a set of phthalimides (Scheme 7.51). However, the nature of the amine was seen to have an effect on the outcome of the reaction. Benzyl derivatives furnished somewhat lower yields, probably due to the reduced activities of these amines. Aromatic amines could not be included in the study as auto-induced ring-closure occurred during the conversion of the polymer-bound phthalic acid. 

The baking process has remained much the same until the present day at a stoichiometric ratio of 1 4, phthalic anhydride or phthalic acid reacts with an ammonia releasing compound. The reaction may also start from other suitable materials, such as phthalic acid derivatives, including phthalic acid esters, phthalic acid diamide, or phthalimide. Appropriate ammonia releasing agents include urea and its derivatives, such as biuret, guanidine, and dicyanodiamide. The fact that a certain amount of urea decomposes to form side products makes it necessary to use excess urea. Approximately 0.2 to 0.5, preferably 0.25 equivalents of copper salt should be added for each mole of phthalic anhydride. 0.1 to 0.4 moles of molybdenum salt per mole of phthalic anhydride is sufficient. The reaction temperature is between 200 and 300°C. 

The phthalocyanines, naphthalocyanines, and certain of their metal derivatives (Figure 6.17) are infrared fluorophores. 61"64 As a class, they are exceptionally stable compounds, with copper (Cu) phthalocyanine (not a fluorophore) remaining intact above 300 °C in air. First used for textile dyeing in the last century and still widely used, there is a rich chemistry of phthalocyanines. Most derivatives can be made by prolonged heating of a phthalimide or phthalic acid derivative with a metal in powder or salt form at elevated temperature. Several derivatives absorb in the near-IR, and either fluoresce or phosphoresce. The electronic transitions of phthalocyanines are complex and have been extensively studied, at least in part because the symmetry of the molecule makes theoretical calculations of its spectroscopic behavior more tractable. Unsubstituted phthalocyanines and naphthalocyanines are, as a class, very insoluble in solvents other than, for instance, nitrobenzene. Sulfonated phthalocyanines are water soluble and exhibit spectra comparable to the parent derivative. Photolumines-cent phthalocyanines (Pcs) include SiPc, ZnPc, and PC itself. These compounds have been little used for practical infrared fluorometry to date however, Diatron Corpora-... 

Phthalimidoacetic ester is obtained by the action of chloracetic ester upon potassium phthalimide this is first hydrolysed by alkali to glyco-coll phthaloylic acid, and then by 20 per cent, hydrochloric acid to glycocoll and phthalic acid —... 

Carboxy carbons of methyl benzoates are shielded by electron-withdrawing substituents in the oposition of the benzene ring [320] (Table 4.38). Carbonyl shifts of phthalic acid diesters and phthalimide are larger than those of phthalic anhydride [321]. fi effects of the O-alkyl group in the esters and hydrogen bonding of the imide are the obvious reasons. 

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). 

Keywords nitrile, phthalic acid, microwave irradiation, hydrolysis, phthalimide... 

In a typical run, the nitrile 1 (30 mmol) and phthalic acid 2 (36 mmol) were introduced into the reactor, and heated under stirring. In the kinetic studies, time zero is taken at complete dissolution of the phthalic acid. At the desired reaction time, the reactor was rapidly cooled in a water-ice mixture and then chloroform (30 mL) was added. The mixture was stirred for 5 min and then the solid was filtered off. The chloroform solution contains the unchanged nitrile 1, the amide and the carboxylic acid 3. The residual solid contains unchanged phthalic acid 2, phthalimide 4, and as the major component, phthalic anhydride 5. The volume of the chloroform solution was adjusted to 50 mL and naphthalene was added as an internal standard. The resulting solution was analyzed by GLC. 

For the preparation of anthranilic acid the starting material is phthalimide, the cyclic imide ring of which is opened by alkaline hydrolysis in the first step of the reaction to give the sodium salt of phthalimidic acid (the half amide of phthalic acid). The intermediate undergoes the Hofmann reaction in the manner outlined on p. 783 yielding o-aminobenzoic acid (anthranilic acid). 

With the exception of tetrachlorophthalic acid, substituted phthalic acids, phthalimides, or phthalonitriles are industrially not readily accessible in pure form. 

Substitution. Copper phthalocyanine is preferred as starting material. Very little is known about the position of substitution. With the exception of hexadeca-chloro CuPc, all commercial Pc substitution products, as well as the tetrasubsti-tuted derivatives synthesized from monosubstituted phthalic acids, are mixtures of isomers. Despite the 16 hydrogen atoms that can be substituted, only two different monosubstituted Pc s are possible. The number of disubstituted isomers is higher. Mono- to heptasubstituted Pc derivatives have not yet been isolated in isomerically pure form. In addition, only a limited number of isomers are accessible in pure form by synthesis. Only symmetrically substituted phthalic acids, phthalimides, or phthalodinitriles (3,6-di-, 4,5-di-, or 3,4,5,6-tetrasubstituted derivatives) yield pure isomers of octa- or hexadecasubstituted phthalocyanine derivatives. All other substituted phthalic acids give mixtures of isomers. 

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