Dinitriles diamines from

Then in a series of chemical transformations the diamine or lactam can be prepared from brassyUc acid (177,178). The diamine is formed as described above for the 12-carbon diamine, ie, diacid —> diamide —> dinitrile —> diamine. The lactam is made from the dinitrile as follows. 

In a process developed by Lummus, / -xylene and ammonia are converted to terephthalonitrile in a fluidized bed at 450°C. A supported vanadium pentoxide catalyst is used and gives about 50% conversioa The vanadium pentoxide is reduced during the reaction and can be reoxidized with air in a separate reactor. The dinitrile is then hydrolyzed to terephthalic acid. The process has not been used in polyester production, although a similar process used in Japan produces diamines from terephthalonitrile or isophthalonitriles. 

Its manufacture begins with the formation of dodecanedioic acid produced from the trimeri2ation of butadiene in a process identical to that used in the manufacture of nylon-6,12. The other starting material, 1,12-dodecanediamine, is prepared in a two-step process that first converts the dodecanedioic acid to a diamide, and then continues to dehydrate the diamide to the dinitrile. In the second step, the dinitrile is then hydrogenated to the diamine with hydrogen in the presence of a suitable catalyst. 

PAs can also be formed from dinitriles and diamines in die presence of water18 ... 

Ammoxidation is also used for the manufacture of isophthalonitrile from m-xylene. The catalysts claimed in the patents are mixed oxides, e.g., of Mo, V, and Sb. The dinitrile is hydrogenated to m-xylylene diamine and m-diamino-dimethylcyclohexane, used for the production of the corresponding diisocyanates that are less toxic than toluene diisocyanate TDL A different use is for the production of tetrachloroisophthalonitrile, a potent fungicide. 

The hydrogenation of the benzene ring is carried out on the diamine before phosgen-ariocL Hydrogenated diamine can be obtained directly from the dinitrile. 

C-C by-products formation occurs during the hydrogenation of dinitrile into aminonitrile, while C-N by-products are formed during the second stage of the hydrogenation ie from aminonitrile to diamine. 

The diamines were synthesized through the aromatic nucleophilic substitution of corresponding diols with / -chloronitrobenzene or /7-fluoronitrobenzene in the presence of potassium carbonate, followed by catalytic reduction with hydrazine monohydrate and Pd/C (such as synthesis of DBAPB and DBTFAPB in Scheme 2.6). As illustrated in Scheme 2.7, bis(ether anhydride)s were prepared by a three-stage synthetic procedure starting from the nucleophilic nitrodisplacement reaction of 4-nitrophthalonitrile with diols (15A 15F, Scheme 2.7) in dry DMF in the presence of potassium carbonate at room temperature. Use of high temperature (in excess of 100 °C) was avoided as it led to dark colored products in the case of 16A 16F. The nitrodisplacement reactions led to a series of new bis(ether nitrile)s (16A 16F, Scheme 2.7). The bis(ether dinitrile)s were then hydrolyzed in an alkaline solution in the presence of hydrogen peroxide to obtain the corre-... 

Only one fiber and a series of thermoplastic copolyureas are manufactured commercially. For the fiber, one starts with 1,9-nonane diamine, obtained in the following way Rice-bran oil contains a large amount of oleic acid, (CH3—(CH2)7—CH=CH—(CH2)7—COOH), and linoleic acid, (CH3—azelaic acid (HOOC—(CH2)7—COOH). Ammonia is added to this, then water is eliminated during the formation of 1,7-heptane dinitrile, and 1,9-nonane diamine is obtained from this by hydrogenation. Polynonane urea has a melting point of 240 C and possesses better resistance to alkalis than, for example, poly(ethylene terephthalate). It can be dyed satisfactorily with acid dyestuffs. 

R.A. Brand, M. Bruma, R. Kellman, C.S. Marvel, Low-molecular-weight polybenzimidazoles from aromatic dinitriles and aromatic diamines, J. Polym. Sci. Part A Polym. Chem. 16 (9) (1978) 2275-2284. 

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