Diarylamino groups

Fluoran compounds having two diarylamino groups at 3 - and 6 -positions generally develop blue tone colors. For example, 3, 6 -bis-(diphenylamino)fluoran (34 R1, R2 = H)29 develops reddish blue color, and 3 -diphenyl amino-6 -di-/ -tolylaminofluoran (34 R1 = H, R2 = CH3)29 and 3, 6 -bis(di-/i-tolylamino)fluoran (34 R1, R2 = CF13)29 blue color. 

In this compound the electron donor is the diarylamino group and the acceptor is the nitro group. They are connected by an azobenzene bridge. In the above polymer the chromophore is present in every repeat unit and accounts for more that 50 % of the polymer s weight. 

Imahori H, Matsubara Y, lijima H et al (2010) Effects of me o-diarylamino group of porph5oins as sensitizers in dye-sensitized solar cells on optical, electrochemical, and photovoltaic properties. J Phys Chem C 114(23) 10656-10665... 

Fig. 3. Synthesis of quinacridones where (1) is dialkyl 2,5-diarylamino-3,6-dihydroterephthalate. See Table 6 for representative groups.

According to method K (p. 87), one of the amino groups in 1.1-bis-diarylamino-or l.l-bis-dialkylamino-2.4.6-triphenyl-A -phosphorins can be replaced by an alkoxy group by treatment with alcohols in the presence of trifluoroacetic acid. If thio-alcohols are used, both amino groups are exchanged by alkylthio groups. Compounds of type 153 or 154 (p. 85) are also accessible to these exchange reactions. 

Diphenylphosphino moieties have been investigated as auxiliary donor groups for the tailoring of potential second- and third-order NLO-phores, although their jr-donating ability is clearly much lower than that of diarylamino units. The P-based systems are prepared using classical synthetic transformations (e.g. Wittig... 

Acylation of 3-amino-5-methylamino-l,2,4-thiadiazole (28) with benzoyl chloride (or arenesulfonyl chlorides) introduces one acyl group when one equivalent is employed, and three when a large excess is used to produce (29) and (30), respectively (Scheme 16). With acetic anhydride, however, acylation terminates with the formation of the 3-monoacyl derivative (65AHC(5)ll9). For the mechanism of acylation, see Scheme 3. In the case of 3,5-diarylamino-l,2,4-thiadiazoles, no triacyl derivative is obtained even when excess of acylating agent is employed. Acetyl and benzoyl chlorides give monoacyl derivatives and p-toluenesulfonyl chloride forms 3,5-di(p-toIuenesulfonyl) derivatives (65AHC(5)119). 

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