Synthesis of Perylenes

Conversion of Perylenes Acenaphthene to Perylene Tetracarboxylic Acid Diimide (PTCI, Pigment Violet 29) 

The process to manufacture the perylene chromophore is basically unchanged since its discovery in the early 1900s. The reaction sequence begins with catalyzed air oxidation of a coal tar extract, acenaphthene (2), to produce naphthalic acid anhydride (3). There are several catalysts, such as V2O5, that are used commercially in this oxidation reaction. Naphthalic acid anhydride is available from several global suppliers in a range of purities. 

In the second stage of the process, (3) is condensed with aqueous ammonia to yield naphthalimide (4). The reaction is quantitative and the purity is high [4]. 

The imide can also be prepared by using of ammonium sulfate. 

The third reaction stage is the most important and complex in the sequence, and is an alkahne fusion reaction. This is the synthesis stage in which the perylene chromophore is chemically formed, as well as the step in which many of the important physical properties of perylene tetracarboxylic acid diimide (PTCI) are determined. In the fusion reaction, (4) is fused with itself via a bimolecular nucleophiUc substitution in the presence of molten alkah at temperatures in excess of 200 °C. The resulting alkahne mass is then precipitated by slowly mixing into water. The subsequent slurry contains perylene in its reduced (leuco) form or salt One of the several possible isomers of the leuco form is represented with the general formula (5). 

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SCHEME 2.51 Synthesis of perylene-fluorene and a-cyanostilbene-fluorene copolymers via Yamamoto coupling. (From Klarner, G., Lee, J.-I., Davey, M.H., and Miller, R.D., Adv. Mater., 11, 115, 1999.)... 

The primary starting material for the synthesis of perylene tetracarboxylic acid pigments is the dianhydride 71. It is prepared by fusing 1,8-naphthalene dicar-boxylic acid imide (naphthalic acid imide 69) with caustic alkali, for instance in sodium hydroxide/potassium hydroxide/sodium acetate at 190 to 220°C, followed by air oxidation of the molten reaction mixture or of the aqueous hydrolysate. The reaction initially affords the bisimide (peryldiimide) 70, which is subsequently hydrolyzed with concentrated sulfuric acid at 220°C to form the dianhydride ... 

A different route proceeds by alkali fusion of the corrspondingly substituted naphthalic acid imide. This pathway parallels the synthesis of perylene tetracarboxylic acid diimide 70 (Sec. 3.4.1.1). The method is particularly suited to aliphatic amines. 

Perhaps the most important class of vat pigments introduced by Harmon Colors is the perylene family with new members being introduced frequently (35). Scheme XI outlines the general synthesis of perylene pigments, and it is of interest that even the dianhydride. Pigment Red 224, is of commercial importance and is sold for use in automotive finishes. The other perylenes find broad use in architectural, plastic, and industrial finishes and vary from red to violet in hue. 

Li, F., Yang, H., Shan, C., Zhang, Q., Han, D., Ivaska, A, and Niu, L. (2009). The synthesis of perylene-coated graphene sheets decorated with Au nanoparticles and its electrocatalysis toward oxygen reduction. J. Mater. Chem, 23, pp. 4022-4025. 

Scheme 13.19 Synthesis of perylene diimide 68 according to Kardos.

Loewe, R.S., K. Tomizaki, W.J. Youngblood, Z. Bo, and J.S. Lindsey (2002). Synthesis of perylene-porphyrin building blocks and rod-like oligomers for light-harvesting applications. J. Mater. Chem. 12(5), 3438-3451. 

Synthesis of Perylene Tetracarboxylic Acid Dianhydride (PTCA) by Hydrolysis of PTCI to PTCA, and PTCA as a Pigment (Pigment Red 224)... 

Synthesis of Perylene Pigments and Mixed Crystals by Condensation of PTCA with Amines... 

Scheme 27. Synthesis of perylene based discogens [99], Reagents (a) R COCl (b) NHjNHj HCI/base (c) Bf2 (d) BuLi, -78 C (e) B(0- Pr>3 (f) HjO (g) Pd(0)/PPh3/K2C03/toluene, reflux (h) K/DME (i) xylene, reflux.

SCHEME 3 Oxidative dimerization of an aryllithium intermediate in the synthesis of perylene-quinone natural products. 

Scheme 4.20 Synthesis of perylene bisimides (i) RNH2/ArNH2, Zn(OAc>2, quinoline, 130-180 °C, 2-3 h or RNH2, pyridine, 100-125 °C...

Mullen and co-workers extended the synthesis of perylene discotics to various other core-enlarged perylene dyes, such as terrylene and quaterrylene diimides [158]. An example of quaterrylene diimides synthesis is shown in Scheme 4.24. 

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