Phthalic acid, reactions

According to this new reaction network, the starting material is converted to the wanted product PA by three parallel routes via phthalic aldehyde and phthalic acid (reactions 8,9,10), via tolylic acid and phthalide (reactions 5,6,7) and via phthalide (reactions 4 and 7). Phthalic anhydride when formed is very stable but it is converted in part via bencoic acid (reaction 26) over a rather complex reaction scheme to maleic anhydride (MA). Maleic anhydride is formed directly from o-xylene via tolylic aldehyde (reaction 1) and toluene (reaction 11) by two routes and via dimethylben-zochinone (DMBQ) (reaction 15). Toluene and DMBQ are converted over a series of reaction steps to acetic acid. The main by-products, CO and CO2, are predominantly formed directly from o-xylene according to this mechanistic study. 

Phthalein reaction. Fuse together carefully in a dry test-tube a few crystals of phthalic acid or of a phthalate and an equal quantity of ph tol moistened with 2 drops of cone. H2SO4. Cool, dissolve in water and add NaOH solution in excess the bright red colour of phenolphthalein in alkaline solution is produced. 

Reactions of the Methyl Groups. These reactions include oxidation, polycondensation, and ammoxidation. PX can be oxidized to both terephthahc acid and dimethyl terephthalate, which ate then condensed with ethylene glycol to form polyesters. Oxidation of OX yields phthaUc anhydride, which is used in the production of esters. These ate used as plasticizers for synthetic polymers. MX is oxidized to isophthaUc acid, which is also converted to esters and eventually used in plasticizers and resins (see Phthalic acids and otherbenzenepolycarboxylic acids). 

The diacids are characterized by two carboxyHc acid groups attached to a linear or branched hydrocarbon chain. AUphatic, linear dicarboxyhc acids of the general formula HOOC(CH2) COOH, and branched dicarboxyhc acids are the subject of this article. The more common aUphatic diacids (oxaUc, malonic, succinic, and adipic) as weU as the common unsaturated diacids (maleic acid, fumaric acid), the dimer acids (qv), and the aromatic diacids (phthaUc acids) are not discussed here (see Adipic acid Maleic anhydride, maleic acid, and fumaric acid Malonic acid and derivatives Oxalic acid Phthalic acid and OTHERBENZENE-POLYCARBOXYLIC ACIDS SucciNic ACID AND SUCCINIC ANHYDRIDE). The bihinctionahty of the diacids makes them versatile materials, ideally suited for a variety of condensation polymerization reactions. Several diacids are commercially important chemicals that are produced in multimillion kg quantities and find appHcation in a myriad of uses. 

The phthalic acid and benzoic acid are reacted to form a reaction intermediate. The reaction intermediate is dissolved in sulfuric acid, which precipitates terephthalic acid (TPA). Fifty percent of the TPA is sold as a product and 50 percent is further processed at your facility into polyester fiber. The TPA Is treated with ethylene glycol to form an intermediate product, which is condensed to polyester. 

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... 

In much the same vein, reaction of the heterocycle, 145 (obtainable from phthalic acid and hydrazine), with phosphorus oxychloride gives the dichloride, 146. Double displacement of halogen by means of hydrazine leads to dihydralazine (147)... 

The detection of phthalic acid by fusion with resorcin has been found to be unreliable as a fluorescein reaction is frequently obtained with pure oils. 

The following example illustrates in detail the preparation of amino benzoic acids from the hot reaction product obtained by the oxidation of a xylene and containing a mixture of salt, amide salt and diamide of a phthalic acid. 

It is prepared by reaction of ethylene glycol with 1,4-benzenedicarboxylic acid (tere-phthalic acid). Draw the structure of PET. 

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... 

Zinc phthalocyanine (PcZn) is prepared from phthalonitrile in solvents with a boiling point higher than 200 C, e.g. quinoline277,278 or 1-bromonaphthalene,137 or without solvent in a melt of phthalonitrile.83,116 The zinc compound normally used is zinc(ll) acetate or zinc powder. The reaction of zinc(II) acetate with phthalic acid anhydride, urea and ammonium mo-lybdate(VI) is also successful.262 The metal insertion into a metal-free phthalocyanine is carried out in an alcohol (e.g.. butan-l-ol).127,141,290 This reaction can be catalyzed by an alkali metal alkoxide.112,129... 

Hajek et al. [173] have reported a detailed kinetic study of the solid phase decomposition of the ammonium salts of terephthalic and iso-phthalic acids in an inert-gas fluidized bed (373—473 K). Simultaneous release of both NH3 molecules occurred in the diammonium salts, without dehydration or amide formation. Reactant crystallites maintained their external shape and size during decomposition, the rate obeying the contracting volume equation [eqn. (7), n = 3]. For reaction at 423 K of material having particle sizes 0.25—0.40 mm, the rate coefficients for decompositions of diammonium terephthalate, monoammonium tere-phthalate and diammonium isophthalate were in the ratio 7.4 1.0 134 and values of E (in the same sequence) were 87,108 and 99 kJ mole-1. 

Phosphorus pentachloride, for conversion of pentaacetylgluconic add to add chloride, 41, 80 for oxidation of cycloheptatriene to tropylium fluoborate, 43, 101 with cyanoacetic acid, 41, 5 Phosphorus tribromide, reaction with 1.5-hexadien-3-ol, 41, 50 Phthalic anhydride, reaction with L-phenylalanine to yield N-phthalyl-L-phenylalanine, 40, 82 Phthalic monoperacid, 42, 77 N-Phthalyl-i.-alanine, 40, 84 N-Phthalyl-/3-alanine, 40, 84 N-Phthalylglycine, 40, 84 N-Phthalyl-l-/5-phenylalanine, 40, 82... 

Hie most representative member of this class of polyesters is the low-molar-mass (M 1000-3000) hydroxy-terminated aliphatic poly(2,2/-oxydiethylene adipate) obtained by esterification between adipic acid and diethylene glycol. This oligomer is used as a macromonomer in the synthesis of polyurethane elastomers and flexible foams by reaction with diisocyanates (see Chapter 5). Hydroxy-terminated poly(f -caprolactonc) and copolyesters of various diols or polyols and diacids, such as o-phthalic acid or hydroxy acids, broaden the range of properties and applications of polyester polyols. 

Figure 27 shows that the release rate of CBP from the polymer decreased with increasing injection-molding temperatures. Samples with decreased levels of phthalic anhydride and increased levels of the phthalate half ester erode at slower rates presumably because the phthalic acid (pKai = 2.9 and pKa2 = 5.5) is a stronger acid than its alkyl half ester (estimated pKa = 3.6) and because the concentration of acidic groups is reduced by the esterification reaction. 

The introduction of phthalic acid into sodium nitrite caused the medium to detonate. This was put down to the reaction below that leads to an unstable compound ... 

Note that in these three examples involving hydrogen peroxide, chromium trioxide and sodium nitrite, dangerous reactions have been described for carboxyiic acids (see on p.316-317). They all referred to the three following systems acetic acid-/hydrogen peroxide, acetic acid/chromium trioxide and o-phthalic acid/sodium nitrite. One can ask oneself whether the same reactions did not take place after the acetic and phthalic anhydride hydrolysis. 

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 solution is allowed to cool, and the di- -butylamine hydrobromide, which separates in the course of the reaction, is removed by means of a suction filter (Note 2). The filtrate is transferred to a 500-ml. distilling flask, and the xylene is removed by distillation. The crude y-di-w-butylaminopropylphthalimide, a brown oil, is transferred to a 500-ml. round-bottomed flask with a ground-glass joint and treated with 20 ml. of water and 120 ml. of 12 N hydrochloric acid. The flask is fitted with a reflux condenser, and the solution is heated for 6 hours in an oil bath maintained at 140-150°. After the solution has cooled to room temperature, the precipitated phthalic acid is removed by filtration and washed with four 25-ml. portions of cold water. The combined filtrates are transferred to a 600-ml. beaker and heated on a steam bath to evaporate the water and hydrochloric acid. 

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