Phthalic nitrile

Extension of the Kunii-Levenspiel bubbling-bed model for first-order reactions to complex systems is of practical significance, since most of the processes conducted in fluidized-bed reactors involve such systems. Thus, the yield or selectivity to a desired product is a primary design issue which should be considered. As described in Chapter 5, reactions may occur in series or parallel, or a combination of both. Specific examples include the production of acrylonitrile from propylene, in which other nitriles may be formed, oxidation of butadiene and butene to produce maleic anhydride and other oxidation products, and the production of phthalic anhydride from naphthalene, in which phthalic anhydride may undergo further oxidation. 

Benzonitrile also can be prepared by this method in comparable yields, but a longer reaction time (7 hours) is required. The method was found to be unsatisfactory for the preparation of the nitriles of azelaic and phthalic acids from the corresponding diamides. 

Many substances can be partially oxidized by oxygen if selective catalysts are used. In such a way, oxygen can be introduced in hydrocarbons such as olefins and aromatics to synthesize aldehydes (e.g. acrolein and benzaldehyde) and acids (e.g. acrylic acid, phthalic acid anhydride). A selective oxidation can also result in a dehydrogenation (butene - butadiene) or a dealkylation (toluene -> benzene). Other molecules can also be selectively attacked by oxygen. Methanol is oxidized to formaldehyde and ammonia to nitrogen oxides. Olefins and aromatics can be oxidized with oxygen together with ammonia to nitriles (ammoxidation). 

Rubbers. Plasticizers have been used in mbber processing and formulations for many years (8), although phthalic and adipic esters have found litde use since cheaper alternatives, eg, heavy petroleum oils, coal tars, and other predominantly hydrocarbon products, are available for many types of mbber. Esters, eg, DOA, DOP, and DOS, can be used with latex mbber to produce large reductions in T. It has been noted (9) that the more polar elastomers such as nitrile mbber and chloroprene are insufficiently compatible with hydrocarbons and require a more specialized type of plasticizer, eg, a phthalate or adipate ester. Approximately 50% of nitrile mbber used in Western Europe is plasticized at 10—15 phr (a total of 5000—6000 t/yr), and 25% of chloroprene at ca 10 phr (ca 2000 t/yr) is plasticized. Usage in other elastomers is very low although may increase due to toxicological concerns over polynuclear aromatic compounds (9). 

Some references covet direct preparation of the different crystal modifications of phthalocyanines in pigment form from both the nitrile-urea and phthalic anhydridc-urca process. Mctal-free phthalocyanine can be manufactured by reaction of o-phthalodinitrile with sodium amylate and alcoholysis of the resulting disodium phthalocyanine. The phthalic anhydridc-urca process can also be used. Other sodium compounds or an electrochemical process have been described. Production of the different crystal modifications has also been discussed. 

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. 

Plasma polymerizations allow some interesting variations when the monomers are themselves products of plasma reactions, for example, the fragmentation of phthalic anhydride to dehydrobenzene which under certain reaction conditions can polymerize to polyphenyl 24>. Also, the isomerization of some nitrogen heterocyclics gives unsaturated nitriles which polymerize easily 19). 

Tho contents of tlio tube aro then transferred to water, filtered from any insoluble matter, aud tlio nitrile precipitated by sulphuric acid. When filtered, it is hydrolysed by boiling with 30 por cent, potash till no more ammonia is evolved, after which homo-phthalic acid is precipitated by sulphuric acid. M.p. 175°. 

The catalytic oxidation in the presence of various heteropoly compounds of lower olefins to unsaturated aldehydes and subsequent conversion into unsaturated nitriles are described in Ref.225-231. Copper phthalocyanine is produced in 92% yield from phthalic anhydride in the presence of 12-molybdophosphoric acid232. ... 

Aromatic nitriles are also prepared by heating amides with phosphorus pentoxide, phosphorus oxychloride, phosphorus pentachloride, thionyl chloride, and ammonium sulfamate. In addition, the action of a double salt of aluminum and sodium chlorides, NaCl- AlClj, gives excellent yields of nitriles from both aliphatic and aromatic amides. Heating an amide with phthalic anhydride causes dehydration. A novel synthesis consists in treating a mixture of an aromatic acid and p-toluene-sulfonamide with phosphorus pentachloride the yields of nitriles range from 63% to 79%. ... 

By fusion of naphthalene sulphonic acids with potassium cyanide the corresponding cyano naphthalenes are obtained. These compounds are nitriles of naphthalene acids. The mono-carboxyl acids are known as naphthoic acids while the di-carboxyl acids are termed naphthalic acids. The naphthoic acids are similar to benzoic acid and the naphthalic acids are like the phthalic acids. The naphthalic acid... 

Most dicarboxylic acids are prepared by adaptation of methods used to prepare monocarboxylic acids. Where hydrolysis of a nitrile yields a monocarboxylic acid, hydrolysis of a dinitrile or a cyanocarboxylic acid yields a dicarboxylic acid where oxidation of a methylbenzene yields a benzoic acid, oxidation of a di-methylbenzene yields a phthalic acid. For example ... 

Retention of ester groups. Equimolar amounts of startg. nitrile and tetrafluorophthalic acid heated at 135° for 4 days in a heavy-walled glass pressure tube product. Y 56%. Work-up is simple since no solvent is required. F.e.s. W.D. Rounds, G.W. Gribble, Tetrahedron Letters 29, 6557-60 (1988) from carboxylic acid amides with tetrachloro-or tetrafluoro-phthalic anhydride s. ibid. 6553-6. 

The Desmocoll polymers show compatibility with some or all of the following polymers to the extent that they give clear solutions and films phthalic resins, xylene-formaldehyde resin, cyclohexanone-formaldehyde resin, highly chlorinated terphenyl, terpene-phenolic resin, acetyl cellulose, nitrocellulose, nitrile rubber, chlorinated PVC, vinyl chloride-vinyl acetate copolymer, rosin esters and coumarone resin. 

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