Nitriles, aromatic

The purpose of the present investigation was to study the trimerization of aromatic nitriles under the conventional resin/fiber composite fabrication conditions using p-toluenesulfonic acid as a catalyst. Trimerization parameters investigated included reaction temperature, pressure, time, and concentration of catalyst. The influence of the nature of aromatic nitriles on trimerization was also studied. Also presented are preliminary results on the use of the catalytic trimerization of the nitrile-terminated imide oligomers to fabricate graphite fiber reinforced composites. 

Materials. All of the aromatic nitriles except p-cyanophthalanil used in this study were purchased from commercial sources and used as received. The p-cyanophtha-lanil was synthesized by a method similar to that used for synthesizing N-phthalyl-L-yj-phenylalanine (9) except that p-aminobenzonitrile was used instead of L-phenylalanine. 

Catalytic Trimerization. About 0.01 mole of the aromatic nitrile togethter with 0.5 to 5.0 mole percent of the p-toluenesulfonic acid (PTSA) catalyst was introduced into a +5-milliliter stainless steel pressure vessel. The vessel was flushed with nitrogen gas and the initial 2 pressure in the vessel was varied from 0 to 2.76 MH/m (0 to 1400 psi). The vessel was then heated to temperatures in the range of 100 to 316°C. The selected temperature was maintained for 2i4 to 90 hours. The PTSA catalyst and unreacted nitrile were then removed from the product by washing with water followed by distillation under reduced pressure. The product was then recrystallized from xylene or glacial acetic acid. Melting point and infrared spectrum were determined for identification purposes. 

Trimerization Study. Bengelsdorf flOl reported that 

ACS Symposium Series American Chemical Society Washington, DC, 1974. 

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Aromatic nitriles (or aryl cyanides) can be obtained by methods (1) and (3). but not by method (2). In addition, aromatic nitriles can be prepared by two other methods, (a) from the corresponding diazo compound by Sandmeyer s Reaction (p. 189), (b) by fusing the corresponding sulphonic acid (or its salts)... 

This method has the great advantage over method (A) in that it can be applied in particular to those aromatic nitriles in which the aryl group is readily sulphonated clearly, it can also be applied to nitriles in which the alkyl or aryl portion contains groups which are in any other way affected by concentrated sulphuric acid, or by concentrated aqueous alkalis. 

Almost insoluble in cold water. Higher alcohols (including benzyl alcohol), higher phenols (e.g., naphthols), metaformaldehyde, paraldehyde, aromatic aldehydes, higher ketones (including acetophenone), aromatic acids, most esters, ethers, oxamide and domatic amides, sulphonamides, aromatic imides, aromatic nitriles, aromatic acid anhydrides, aromatic acid chlorides, sulphonyl chlorides, starch, aromatic amines, anilides, tyrosine, cystine, nitrocompounds, uric acid, halogeno-hydrocarbons, hydrocarbons. 

Aromatic nitriles are generally liquids or low melting point solids, and usually have characteristic odours. They give no ammonia with aqueous sodium hydroxide solution in the cold, are hydrolysed by boiling aqueous alkali but more slowly than primary amides ... 

The physical properties of some typical aromatic nitriles are collected in Table IV, 195. 

Aromatic nitriles are converted into a methyl group with ammonium for-mate[109]. Aldehydes and ketones are reduced to alcohols[l 10],... 

Reactions that employ copper(I) salts as reagents for replacement of nitrogen m diazo mum salts are called Sandmeyer reactions The Sandmeyer reaction using copper(I) cyanide is a good method for the preparation of aromatic nitriles... 

Aromatic nitriles or nitrogen heterocycles Indicates either CHO or C2H5 Indicates either CH2O or NO Thiols... 

In 1987, Toray Industries, Inc., announced the development of a new process for making aromatic nitriles which reportedly halved the production cost, reduced waste treatment requirements, and reduced production time by more than two-thirds, compared with the vapor-phase process used by most producers. The process iavolves the reaction of ben2oic acid (or substituted ben2oic acid) with urea at 220—240°C ia the presence of a metallic catalyst (78). 

Even ia 1960 a catalytic route was considered the answer to the pollution problem and the by-product sulfate, but nearly ten years elapsed before a process was developed that could be used commercially. Some of the eadier attempts iacluded hydrolysis of acrylonitrile on a sulfonic acid ion-exchange resia (69). Manganese dioxide showed some catalytic activity (70), and copper ions present ia two different valence states were described as catalyticaHy active (71), but copper metal by itself was not active. A variety of catalysts, such as Umshibara or I Jllmann copper and nickel, were used for the hydrolysis of aromatic nitriles, but aUphatic nitriles did not react usiag these catalysts (72). Beginning ia 1971 a series of patents were issued to The Dow Chemical Company (73) describiag the use of copper metal catalysis. Full-scale production was achieved the same year. A solution of acrylonitrile ia water was passed over a fixed bed of copper catalyst at 85°C, which produced a solution of acrylamide ia water with very high conversions and selectivities to acrylamide. 

H-Bond Acceptor (HBA) Acyl chlorides Acyl fluorides Hetero nitrogen aromatics Hetero oj gen aromatics Tertiary amides Tertiary amines Other nitriles Other nitros Isocyanates Peroxides Aldehydes Anhydrides Cyclo ketones Ahphatic ketones Esters Ethers Aromatic esters Aromatic nitriles Aromatic ethers Sulfones Sulfolanes... 

The cyano group in aromatic nitriles can be converted directly to a methyl group in vapor phase over 30% Ni-on-AljOj prereduced by hydrogen i>i situ... 

Molecular ion The mass spectra of aromatic nitriles and dinitriles show intense molecular ions (see Figure 21.3). 

Cyano-de-diazoniations of the Sandmeyer type have been used for the synthesis of aromatic nitriles for many decades (example Clarke and Reed, 1964), as cyanide ions are comparable to bromide and iodide in many respects. A homolytic cyano-de-diazo-niation that does not use metal ions as reductant or ligand transfer reagent was described by Petrillo et al. (1987). They showed that substituted diazosulfides (XC6H4 — N2 — SC6H5), either isolated or generated in situ from arenediazonium tetrafluoroborates and sodium benzenethiolate, react with tetrabutylammonium cyanide in dimethylsulfoxide under photon stimulation, leading to nitriles (XC6H4CN). The method worked well with eleven benzenediazonium ions substituted in the 3- or 4-position, and was also used for the synthesis of phthalo-, isophthalo-, and tere-... 

This synthetic process is applicable to the preparation of other aromatic nitriles from aldehydes. The submitters have used it to prepare 5-bromoindole-3-carbonitrile, 7-azaindole-3-carboni-trile, j)-chlorobenzonitrile, 3,4,5-trimethoxybenzonitrile, and p-N,N-dimethylaminobenzonitrile.9 There are several advantages to its use. They include (a) readily available and inexpensive reagents, (b) a simple, time-saving procedure, and (c) fair to good yields of nitrile obtained by a one-step method. 

Regarding the series of hetero aromatic pentacyclic compounds with three heteroatoms, an accelerated synthesis of 3,5-disubstituted 4-amino-1,2,4-triazoles 66 under microwave irradiation has been reported by thermic rearrangement of dihydro-1,2,4,5 tetrazine 65 (Scheme 22). This product was obtained by reaction of aromatic nitriles with hydrazine under microwave irradiation [53]. The main limitation of the method is that exclusively symmetrically 3,5-disubstituted (aromatic) triazoles can be obtained. 

In the presence of anunonium bromide cobalt (ref. 22) and manganese (ref. 23) have been shown to catalyze the ammoxidation of methylaromatics to the corresponding aromatic nitriles (Fig. 20). It is interesting to compare this homogeneous, liquid phase system with the more well-known vapour phase ammoxidation of alkylaromatics over oxidic catalysts (ref. 4). 

The other way of reducing nitriles to aldehydes involves using a metal hydride reducing agent to add 1 mol of hydrogen and hydrolysis, in situ, of the resulting imine (which is undoubtedly coordinated to the metal). This has been carried out with LiAlH4, LiAlH(OEt)3, LiAlH(NR2)3, and DIBAL-H. The metal hydride method is useful for aliphatic and aromatic nitriles. 

From the point of view of the synthetic organic chemist, the importance of aromatic thallation, and the remarkable degree of orientation control which can be exercised over this process, lies in the ease with which the resulting ArTlXj compounds can be converted into substituted aromatic derivatives in which the new substituent group has entered the ring at the position to which thallium was originally attached. Syntheses of phenols, nitroso compounds, biaryls, aromatic nitriles, thiophenols, and deuterated aromatic compounds have all been achieved these results are summarized briefly below. 

A further demonstration of the efficacy of photolysis of ArTlXj compounds is the recently described synthesis of aromatic nitriles by photolysis of solutions of arylthallium ditrifluoroacetates in aqueous potassium cyanide... 

The NHase responsible for aldoxime metabolism from the i -pyridine-3-aldoxime-degrading bacterium, Rhodococcus sp. strain YH3-3, was purified and characterized. Addition of cobalt ion was necessary for the formation of enzyme. The native enzyme had a Mr of 130000 and consisted of two subunits (a-subunit, 27 100 (3-subunit, 34500). The enzyme contained approximately 2 mol cobalt per mol enzyme. The enzyme had a wide substrate specificity it acted on aliphatic saturated and unsaturated as well as aromatic nitriles. The N-terminus of the (3-subunit showed good sequence similarities with those of other NHases. Thus, this NHase is part of the metabolic pathway for aldoximes in microorganisms. 

Peijnenburg WJGM, KGM de Beer, HA den Hollander, MHL Stegeman, H Verboom (1993) Kinetics, products, mechanisms and QSARs for the hydrolytic transformation of aromatic nitriles in anaerobic sediment slurries. Environ Toxicol Chem 12 1149-1161. 

Harper DB (1977) Microbial metabolism of aromatic nitriles. Enzymology of C-N cleavage by Nocardia sp. (Rhodochrous group) NCIB 11216. Biochem J 165 309-319. 

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