Phthalic acid derivatives

Some phthalic acid derivatives with bulky substituents in the 1,4-positions (e.g., 8124, 9125 and 10126) do not form phthalocyanines due to steric hindrance but have found major interest in the preparation of unsymmetrical phthalocyanines (see pp 736, 737). 

Treatment of 4-substituted phthalic acid derivative 3 with cobalt(II) sulfate, urea, ammonium chloride and ammonium molybdate(VI) in nitrobenzene at 180°C for six hours provided phthalocyanine 4 in 80% yield.421... 

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. 

Korhonen A, Hemminki K, Vainio H. 1983a. Embryotoxic effects of phthalic acid derivatives, phosphates and aromatic oils used in the manufacturing of rubber on three day chicken embryos. Drug Chem Toxicol 6 191-207. 

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-... 

Because of their more positive cathode potentials, phthalic acid derivatives are considerably easier to reduce. 1,2-Dihydrophthalic acid 400) was produced industrially by BASF for many years by electrochemical reduction of phthalic acid ... 

Literature references on the ozonation of A07 indicate that the molecule in such an oxidative degradation is cleaved at the point where the azo bond is attached to the naphthalene moiety giving rise to the intermediate, 1,2 naphthoquinone (NQ) [260,261]. This intermediate is oxidized subsequently to a phthalic acid derivative. The spectrum of the photolyzed A07 was found to be similar, especially in the area of 1400 to 1800 cm-1, to the spectra of the photolyzed naphthoquinone samples. It is reasonable to conclude therefore that naphthoquinone is an intermediate from the photosensitized degradation of A07 on Ti02. The naphthoquinone then undergoes further degradation to form a phthalic acid derivative. The end product of oxidation of A07 is an aromatic carboxylic acid as characterized from the peak at 1700 cm-1. 

Diacylbenzenes with hydrazine form phthalazines 409. Monoxo compounds of type 410 result from 0-acylbenzoic acids and hydrazine or hydroxylamine, and dioxo derivatives 411 from phthalic acid derivatives with N2H4, NH2OH, or H202. Phthalodinitrile is converted by methanolic hydrazine into 1,4-diaminophthalazine 412 <1968JHC111>. 

Ring fission to the phthalic acid derivative has been observed [155] (Figure 9.64). 

Stetter et al. reacted phthaloyl chloride with ED and OPD and reported the products as diazocines 69 (R = H) and 57, respectively (58CB1775). However, Paudler and Zeiler have disputed these and earlier reports of 1,4-diazocine formation by reaction of 1,2-diamines with phthalic acid derivatives, and claim that the compound reported (58CB1775) as 57 is really bisphthalimide 70, and have themselves prepared authentic 57 by the reaction of OPD with diethyl phthalate in the presence of sodium hydride (69JOC2138). Wolfe and Hasan repeated the synthesis of 69 (R = H) by... 

General acid-catalyzed hydrolysis of carboxylic acid derivatives has been observed mostly in intramolecular catalysis. In phthalic acid derivatives the mechanism changes from general acid to nucleophilic... 

Examples for cyclization reactions via extrusion of partial constituents of the ortho function are the well-known decompositions of phthalic acid derivatives, 85,... 

Pyrolytic scission of cyclobutenes leads to a diene which promises to be useful in a Diels Alder approach to catechols. Heating of the sllyl derivative of the acyloin product from dimethyl glutarate in the presence of dlenophiles affords adducts of the transient diene. The adduct obtained with dimethyl acetylene dicarboxylate was converted in several steps to phthalic acid derivative. ... 

Rearrangement of phthalic acid derivatives. Treatment of phthalic anhydride with ammonia and NaOH leads to phthalamic acid (8), which rearranges with NaOCl to IA.33,34 The same result can be achieved starting with phthalimide (7)8,23,35-38 or N-chlorophthalimide (9).39 Similar reactions starting with phthalic acid or anhydride via the azide (5) also give IA6,40,41 (see Scheme l). 

Some of the simplest compounds are the phthalic acid derivatives (Fig. 4). They consist of a phenyl group and two or more carboxylic acid groups. 

Lastly, a convenient fcw-crown ether derivative of triaminotriazine, prepared from a phthalic acid derivative of a polyether macrocycle, would make an excellent reagent in the preparation of dendrimers desirous of surface crown ether(s) <97BCSJ671>. 

Rearrangement of phthalic acid derivatives. Treatment of phthalic an-... 

A COMPREHENSIVE REVIEW ON AROMATIC POLYESTERS OF N-OXYBENZOIC AND PHTHALIC ACID DERIVATIVES... 

Laminated polyolefin Drug product SPE concentration, residue reconstituted in ethanol LiChrosorb C18 ODS-2, 250 X 4.6 mm, 5 pm MEOH/water (70 30) 280 20 pi Caprolactam, butylhydroxytoluene, phthalic acid derivative [7]... 

Gratzel M, Halmann M (1990) Photosensitized oxidation of bromide to bromine with phthalic acid derivatives in aqueous solutions. Solar Energy Mater 20 117-129. doi 10.1016/0165-1633(90)90023-T... 

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