Color formers

A group of aminoxanthenes, ie, pyra2oloxanthenes, is used as color formers ia pressure or heat-sensitive imaging papers (43). These compounds are colorless, but, upon contact with acidic electron-accepting material, are converted to resonance forms that are lightly colored. An example is stmcture [58294-05-6] (35), which forms upon the condensation of A[,A/-diethyl-y -aminophenol with phthalic anhydride, followed by addition of 6-hydroxyinda2ole ia 80% sulfuric acid (44). 

Ai- 4-(bis[4-(phenylamino)phenyl]methylene)-2,5-cyclohexadien-l-ykdene -3-methyl-ben2eneaminesulfate [57877-94-8] (20) have been claimed as positive CCAs (65). The absorption spectra of the triaryknethane dyes can be extended into the near-infrared region. The use of triaryknethane dyes as infrared absorbers for optical information recording media (66) and as infrared color formers in carbonless copy paper has been claimed. 

Although leuco quinones have been studied as color formers, their use in color-forming recording media has not been studied extensively due to their instability. 

Synthesis and Properties of Phthalide-Type Color Formers... 

Since the introduction of carbonless copying papers, CVL has undoubtedly found the most widespread use as a phthalide color former. Hence, it is appropriate to describe in detail the various approaches to its synthesis, particularly as they are representative of the preparations of various other phthalides described herein. 

The most versatile route to lactone color formers is based on the elegant synthesis of Malachite Green lactone described by Haller and Guyot in 1899.24 Scheme 3 illustrates the application of this route for the preparation of CVL. 

However, despite the commercial importance of CVL as a color former, the product possesses a number of disadvantages, notably poor lightfastness especially in combination with clay developers, and low solubility in organic solvents. Hence, it is not surprising that a vast number of variations on the basic structure have been described in the patent literature, typical examples of which are structures 3-5 (see also for example Ref. 26). 

Phthalic anhydride condenses with the aniline derivative in the presence of zinc or aluminum chlorides to yield the intermediate benzoyl-benzoic acid, which subsequently reacts with l,3-bis-V,V-dimethylaniline in acetic anhydride to yield the phthalide. The above compound gives a violet-gray image when applied to a clay developer. Clearly this synthesis is also very flexible and variations in shades of color formers have been obtained by varying the aniline components and also by using phthalic anhydrides substituted, for example, by nitro groups or chlorine atoms. Such products have excellent properties as color formers and have been used commercially. Furthermore, this synthetic route is of great importance for the preparation of heterocyclic substituted phthalides, as will be seen later. 

All of these phthalides in which the phthalide ring is not substituted by electron-donating groups are yellow to orange color formers, and useful as... 

Only one report45 of monoarylmethane color formers has appeared to date, the synthetic route being shown in Scheme 6. These compounds in combination with clay developers give yellow images with good light stability. 

Finally, a number of heterocycles such as quinolines, indoles, and diazines in which the heterocyclic ring is hydrogenated have been reacted as shown in Scheme 7 to produce a number of green color formers such as 15.68... 

Color formers such as 16 and 17 and their mixtures are commonly known as Pyridyl Blues and are excellent products in combination with organic developers, yielding intense blue images with very high fastness properties. However, it has been observed71 that, for some applications, the 7-azaisomer is too reactive and hence it was desirable to modify the... 

Azaphthalides carrying indolyl and indolizinyl substituents have been shown65 to produce blue color formers, while the combination of indoles... 

Introduction of an ethylene bridge between the maso-carbon atom and one of the diaminophenyl groups of a triarylmethane-type phthalide results in a considerable bathochromic shift, thus producing color formers exhibiting absorption in the near infrared region of the electromagnetic spectrum. 

Reaction of 2-formylbenzoic acids with 1, 1-bisdialkylaminoethylenes in acetic anhydride has been found91 to yield phthalides such as 21. These color formers are claimed to yield blue to green images, but have also been described92 as intermediates for the preparation of divinyl phthalides by a route identical to that described in Scheme 3, for which they are probably of more significance. (See Section 4.6.2.)... 

Introduction of two diaminophenylethylene moieties at the 3-position of the phthalide ring naturally also produces color formers exhibiting infrared absorption. As in Section 4.6.1, the first report93 encompasses a vast number of compounds such as 22 which was prepared by treating phthalic anhydride with 2 mol of 1,1-bisdimethylaminophenylethylene in acetic anhydride. 

Finally, bisindolylethylenes have also been reacted with tetrahaloph-thalic anhydrides to yield color formers showing absorption in the near infrared.99 The chief advantage over the diarylethylenes is the availability of the starting materials. The bisindolylethylenes may be prepared in situ by reaction of an indole with acetyl chloride and then converted directly to the phthalide without isolation. 

Fusion of the two arylamino groups of a triarylmethane phthalide color former results in the formation of spirofluorene phthalides. Due to the increased planarity of this system, a bathochromic shift results leading also to color formers showing infrared absorption when developed. This was first exemplified in 1983102 by preparation of phthalide 26 as shown in Scheme... 

One further example of this principle of bridging the aryl groups of a triarylmethane phthalide was reported in 1986.108 Thus, treatment of phthalide 27 with aluminum chloride results in the formation of the spirobenzanthracene 28 as shown in Scheme 11. These color formers also exhibit absorption in the near infrared spectral region, but no further reports of such compounds have since been published. 

Reaction of pyromellitic anhydride with 1,1-bisdimethylaminophenyl-ethylene has been shown110 to yield a mixture of the bisphthalides 31 and 32 which are infrared-absorbing color formers on clay. 

Finally, 1-ethyl-2-methyl indole was reacted111 with pyromellitic anhydride to give a mixture of keto acids, as in Scheme 12, which was then treated with diphenylamines to yield bisphthalides such as 33 and 34. These color formers produce orange images on development, as also do those in which the indole residue is replaced by a 4-dialkylaminophenyl group. 

Direct oxidation of diphenylmethanes is of little practical value as color formers. In liquid sulfur dioxide, leuco diphenylmethane 12 (Scheme 2) undergoes hydride abstraction by triphenylcarbenium perchlorate at the benzylic amine position to form immonium ion7 13, whereas in acetonitrile... 

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