Novel Chromogenic Esters of ortho‐Phenylazonaphthols

Abstract

We have prepared the photo‐labile benzoic acid esters and the acid‐labile tert‐butoxycarbonyl esters of Sudan I and Sudan Red B, two representatives of the ortho‐phenylazonaphthol dye family, exhibiting hydroxyazo–hydrazone tautomerism with the hydrazone as the strongly favored form. The chromophores obtained are “locked” in an exclusive azo configuration and exhibit absorbance spectra which are dramatically blue‐shifted (more than 100 nm) and have strongly reduced extinction coefficients when compared to their parent chromophores. Thus, the esters of the orange dye Sudan I exhibit an absorption maximum in the ultraviolet (UV) regime, and the esters of the red dye Sudan Red B appear yellow. Depending on the nature of the ester moiety, by irradiation with UV light or by exposure to preferentially photochemically released acidic species at elevated temperatures, these esters can be reverted to the parent, highly tinctured Sudan I and Sudan Red B, respectively. Unlike conventional chromogenic systems, these dyes are compatible with melt‐processible polymers and do not require any wet‐chemical development. In polymer films comprised of these chromogenic dyes, color patterns can be produced directly by masked irradiation. We here report on the synthesis, spectral properties, and conversion kinetics of these novel chromogenic dyes, which may be potentially suitable for marking and labeling goods in a lithographic process and for optical data storage and sensing applications.

Photocatalytic disassembly of tertiary amine-based dendrimers to monomers and their application to the ‘catch and release’ of a dye in aqueous solution

“…The solution was then filtered (0.2 mm) and the concentration of solubilized Sudan I was identified by recording its absorbance at 479 nm (e = 16 300 M À1 cm À1 ). 30 The amounts of Sudan I solubilized were found to be 4.6 mM, 8.8 mM and 17.7 mM for the first (1), second (2) and third (3) generation dendrimers, respectively. The above solubilities represent 90, 172 and 350 fold increases for first, second and third generation dendrimers containing aq.…”

Photocatalytic disassembly of tertiary amine-based dendrimers to monomers and their application to the ‘catch and release’ of a dye in aqueous solution

“…The solution was then filtered (0.2 mm) and the concentration of solubilized Sudan I was identified by recording its absorbance at 479 nm (e = 16 300 M À1 cm À1 ). 30 The amounts of Sudan I solubilized were found to be 4.6 mM, 8.8 mM and 17.7 mM for the first (1), second (2) and third (3) generation dendrimers, respectively. The above solubilities represent 90, 172 and 350 fold increases for first, second and third generation dendrimers containing aq.…”

Ruthenium‐Catalyzed Regioselective Direct Ortho‐Acyloxylation of Azoarenes with Carboxylic Acids via C–H Bond Activation

“…The residue was purified by column chromatography (n-hexane/EtOAc, 8:1) to yield the desired product. 5, 154.0, 141.5, 132.4, 129.9, 129.6, 127.2, 122.9, 122.1, 34.2, 21.5, 21.5, 16 8,137.1,132.2,130.5,130.4,130.4,129.9,129.6,127.5,127.3,126.2,123.6,122.9,122.2,117.1,116.5,114.4,40.4,21.5,21.4;MS (EI): m/z (%) = 342 (21) [M + ], 265 (15), 225 (31), 117 (41), 105 (100), 91 (64), 77 (47). C 22 H 20 N 2 O 2 (344.41): calcd.…”

“…C 76.72, H 5.85, N 8.13; found C 76.89, H 5.89, N 8.17. 8,151.0,148.8,142.6,142.1,137.1,132.2,130.5,130.4,130.4,129.9,129.6,127.5,127.3,126.2,123.6,122.9,122.2,117.1,39.0,21.5,21.4,19.8;MS (EI): m/z (%) = 356 (7) H 6.19, N 7.82; found C 77.30, H 6.14, N 7.87.…”

“…Table 1, entries[8][9][10][11]. The reaction was also monitored with different catalyst loadings, and theTable 1.…”

50th Anniversary Perspective: Solid-State Multistimuli, Multiresponsive Polymeric Materials

“…The approach should be readily applicable to other types of responsive photonic crystals, such as multilayer films or responsive PCs based on a (thermally or otherwise triggered) shape-memory polymer . Moreover, other types of responsive molecules can be used in this context, e.g., photoreactive chromogenic compounds , or chemical sensor molecules …”

Photocatalytic disassembly of tertiary amine-based dendrimers to monomers and their application to the ‘catch and release’ of a dye in aqueous solution

“…The solution was then filtered (0.2 mm) and the concentration of solubilized Sudan I was identified by recording its absorbance at 479 nm (e = 16 300 M À1 cm À1 ). 30 The amounts of Sudan I solubilized were found to be 4.6 mM, 8.8 mM and 17.7 mM for the first (1), second (2) and third (3) generation dendrimers, respectively. The above solubilities represent 90, 172 and 350 fold increases for first, second and third generation dendrimers containing aq.…”

Ruthenium‐Catalyzed Regioselective Direct Ortho‐Acyloxylation of Azoarenes with Carboxylic Acids via C–H Bond Activation

“…The residue was purified by column chromatography (n-hexane/EtOAc, 8:1) to yield the desired product. 5, 154.0, 141.5, 132.4, 129.9, 129.6, 127.2, 122.9, 122.1, 34.2, 21.5, 21.5, 16 8,137.1,132.2,130.5,130.4,130.4,129.9,129.6,127.5,127.3,126.2,123.6,122.9,122.2,117.1,116.5,114.4,40.4,21.5,21.4;MS (EI): m/z (%) = 342 (21) [M + ], 265 (15), 225 (31), 117 (41), 105 (100), 91 (64), 77 (47). C 22 H 20 N 2 O 2 (344.41): calcd.…”

“…C 76.72, H 5.85, N 8.13; found C 76.89, H 5.89, N 8.17. 8,151.0,148.8,142.6,142.1,137.1,132.2,130.5,130.4,130.4,129.9,129.6,127.5,127.3,126.2,123.6,122.9,122.2,117.1,39.0,21.5,21.4,19.8;MS (EI): m/z (%) = 356 (7) H 6.19, N 7.82; found C 77.30, H 6.14, N 7.87.…”

“…Table 1, entries[8][9][10][11]. The reaction was also monitored with different catalyst loadings, and theTable 1.…”

50th Anniversary Perspective: Solid-State Multistimuli, Multiresponsive Polymeric Materials

“…The approach should be readily applicable to other types of responsive photonic crystals, such as multilayer films or responsive PCs based on a (thermally or otherwise triggered) shape-memory polymer . Moreover, other types of responsive molecules can be used in this context, e.g., photoreactive chromogenic compounds , or chemical sensor molecules …”

Photocatalytic disassembly of tertiary amine-based dendrimers to monomers and their application to the ‘catch and release’ of a dye in aqueous solution

“…The solution was then filtered (0.2 mm) and the concentration of solubilized Sudan I was identified by recording its absorbance at 479 nm (e = 16 300 M À1 cm À1 ). 30 The amounts of Sudan I solubilized were found to be 4.6 mM, 8.8 mM and 17.7 mM for the first (1), second (2) and third (3) generation dendrimers, respectively. The above solubilities represent 90, 172 and 350 fold increases for first, second and third generation dendrimers containing aq.…”

Ruthenium‐Catalyzed Regioselective Direct Ortho‐Acyloxylation of Azoarenes with Carboxylic Acids via C–H Bond Activation

“…The residue was purified by column chromatography (n-hexane/EtOAc, 8:1) to yield the desired product. 5, 154.0, 141.5, 132.4, 129.9, 129.6, 127.2, 122.9, 122.1, 34.2, 21.5, 21.5, 16 8,137.1,132.2,130.5,130.4,130.4,129.9,129.6,127.5,127.3,126.2,123.6,122.9,122.2,117.1,116.5,114.4,40.4,21.5,21.4;MS (EI): m/z (%) = 342 (21) [M + ], 265 (15), 225 (31), 117 (41), 105 (100), 91 (64), 77 (47). C 22 H 20 N 2 O 2 (344.41): calcd.…”

“…C 76.72, H 5.85, N 8.13; found C 76.89, H 5.89, N 8.17. 8,151.0,148.8,142.6,142.1,137.1,132.2,130.5,130.4,130.4,129.9,129.6,127.5,127.3,126.2,123.6,122.9,122.2,117.1,39.0,21.5,21.4,19.8;MS (EI): m/z (%) = 356 (7) H 6.19, N 7.82; found C 77.30, H 6.14, N 7.87.…”

“…Table 1, entries[8][9][10][11]. The reaction was also monitored with different catalyst loadings, and theTable 1.…”

50th Anniversary Perspective: Solid-State Multistimuli, Multiresponsive Polymeric Materials

“…The approach should be readily applicable to other types of responsive photonic crystals, such as multilayer films or responsive PCs based on a (thermally or otherwise triggered) shape-memory polymer . Moreover, other types of responsive molecules can be used in this context, e.g., photoreactive chromogenic compounds , or chemical sensor molecules …”