Perylene-3, 4, 9, 10-tetracarboxylic acid

Perylene pigments include the dianhydride and diimide of perylene tetracarboxylic acid along with derivatives of the diimide while perinone pigments are derived from naphthalene tetracarboxylic acid. 

Most pigments derived from vat dyes are structurally based on anthraquinone derivatives such as indanthrone, flavanthrone, pyranthrone, or dibromoan-thanthrone. There are other polycyclic pigments which may be used directly in the form in which they are manufactured. This includes derivatives of naphthalene and perylene tetracarboxylic acid, dioxazine (Carbazole Violet), and tetrachloro-thioindigo. Quinacridone pigments, which were first introduced in 1958, and recently DPP pigments have been added to the series. 

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. 

Unsymmetrically substituted perylene pigments are a comparatively recent novelty. Selective protonation of the tetra sodium salt of perylene tetracarboxylic acid affords the monosodium salt of perylene tetracarboxylic monoanhydride in high yield. Stepwise reaction with amines produces unsymmetrically substituted perylene pigments [2],... 

The dianhydride of perylene tetracarboxylic acid is converted into the pigment form by preparing the corresponding alkali salt and then reprecipitating the compound with an acid. The dianhydride is formed after separating the acid by thermal aftertreatment at 100 to 200°C, possibly under pressure, with an organic solvent. The list of suitable media includes alcohols, ketones, carboxylic acid esters, hydrocarbons, and dipolar aprotic solvents. 

Perylene tetracarboxylic acid dimethylimide may also be prepared by methylating the corresponding diimide. 

Various Other Perylene Tetracarboxylic Acid Pigments... 

Dibromoanthanthrone is a vat type pigment which demonstrates excellent fastness properties, a feature which is an asset in high grade paints. It provides a clean yellowish shade of scarlet, somewhere between that of P.O.43, a naphthalene tetracar-boxylic acid derivative, and those of yellowish perylene tetracarboxylic acid type pigments. 

Zhu, G., Zhang, X., Gai, P., Zhang, X., and Chen, J. (2012) fi-Cyclodextrin non-covalently functionalized single-walled carbon nanotubes bridged by 3,4,9,10-perylene tetracarboxylic acid for ultrasensitive electrochemical sensing of 9-anthracenecarboxylic acid. Nanoscale, 4, 5703. 

Several methods have been reported for the monofunctionaUzation of PDI [6] including one-pot imidization (route A) or a base-promoted coupling reaction between naphthalene monoimide derivatives (route B) [7], as shown in Scheme 2. We found the one-pot imidizatitMi reaction (route A) to be more practical than route B route B consisted of five steps and the open-form product 6b was labile under the basic reaction conditions required to produce the closed product 6a. The one-pot imidization, route A, was simple and 3 could easily be recovered via column chromatography because the use of an excess amount of 3 was necessary. Concerning the solubility and reactivity of perylene tetracarboxylic acid dianhydride (PDA) 4, the imidization of 4 was, first, carried out with 2,6-ditsopropylaniline (5) in imidazole then 3 in propionic acid solution was added to produce the closed product PDI 6a. 

Metal complexes of 2,9,16,23-tetrasulfophthalocyanines Riboflavin 5 -phosphate N, N -Bis(ethylenesulfate)-3,4,9,10-perylene tetracarboxylic acid diimide Ru(NCS) Me2bpy)(2,2 5, 2"-terpy-4-phosphonic acid) " "... 

Another, less direct, approach to manipulate molecules on a surface is through the use of chemical self-assembly principles derived from X-ray crystallographic work. A two-dimensional hydrogen bonding motif derived from crystal-engineering studies has been used to assemble a two-dimensional honeycomb lattice based on the hydrogen bonded triad motif formed between perylene tetracarboxylic acid diimide (5.1) and melamine (5.2). The honeycomb... 

Perylenes are chemically diimides of perylene tetracarboxylic acid. The shade change is dependent on the substitution of the imide nitrogen (4). 

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

The third reaction stage is the most important and complex in the sequence, and is an alkaline 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 nucleophilic substitution in the presence of molten alkali at temperatures in excess of 200 C. The resulting alkaline 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 lenco form is represented with the general formula (5). 

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

Dori N, Menon M, Kilian L, Sokolowski M, Kronik L, Umbach E (2006) Valence electronic structure of gas-phase 3,4,9,10-perylene tetracarboxylic acid dianhydride experiment and theory. Phys Rev B 73 195208... 

Zhao HM et al (2009) Understanding ground- and excited-state properties of perylene tetracarboxylic acid bisimide crystals by means of quantum chemical computations. J Am Chem Soc 131 15660-15668... 

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