US 12,359,069 B2
Azacyanine dyes and use thereof
Riccardo Sinisi, Lausanne (CH); Alma Rosa Morales Morales, Lausanne (CH); Elena A. Goun, Lausanne (CH); Rajendra Singh, Lausanne (CH); and Pavlo Khodakivskyi, Columbia, MO (US)
Filed by Ecole Polytechnique Fédérale de Lausanne (EPFL), Lausanne (CH)
Filed on Feb. 26, 2020, as Appl. No. 16/802,476.
Application 16/802,476 is a continuation of application No. 15/928,074, filed on Mar. 21, 2018, granted, now 10,633,542.
Prior Publication US 2021/0040326 A1, Feb. 11, 2021
This patent is subject to a terminal disclaimer.
Int. Cl. C09B 23/01 (2006.01); A61K 41/00 (2020.01); A61K 49/00 (2006.01)
CPC C09B 23/0075 (2013.01) [A61K 41/0057 (2013.01); A61K 49/0032 (2013.01); A61K 2123/00 (2013.01)] 12 Claims
 
1. A fluorescent dye of formula A:

OG Complex Work Unit Chemistry
or a salt thereof, wherein
Z is selected from the group consisting of NR17 and +NR17R18;
Q is selected from the group consisting of Cl, Br, I, and R19U, —OR19U, —SR19U, —NHR19U, and NR19R20U, wherein R19 and R20 are independently selected from the group consisting of: linear and branched, non-cyclic and cyclic, substituted and unsubstituted C1-20 alkyl, wherein the alkyl group can be single or multiple substituted by a homocyclic or heterocyclic C5-, C6- or C7-aromatic ring which can be substituted by a linear or branched C1-C6 alkyl group and —(CH2—O—CH2)xCH2—; and U is selected from the group consisting of: —(CH2)mSO3−, —(CH2)mC(O)O−, —(CH2)mP(O)O22−, —(CH2)mNH2, —(CH2)mNHR32, and —(CH2)mNR32R33; and wherein in case of —(CH2)mNH2, —(CH2)mNHR32, and —(CH2)mNR32R33 the N atom may be bound to a further substituent R34 to form a quaternary N atom, and wherein R34 is in all the above cases independently selected from H and an alkyl group having from 1-12 C atoms,
R1 and R2 are selected from the group consisting of absent, H, and linear and branched, non-cyclic and cyclic, substituted and unsubstituted C1-20 alkyl, wherein the alkyl group can be single or multiple substituted by homocyclic and heterocyclic 5-, 6- and 7-membered aromatic rings which can be substituted by a linear or branched C1-C6 alkyl group;
R17 and R18 are absent or are independently selected from the group consisting of H and linear and branched, non-cyclic or cyclic, substituted and unsubstituted C1-20 alkyl, wherein the alkyl group can be single or multiple substituted by homocyclic and heterocyclic 5-, 6-, and 7-membered aromatic rings which can be substituted by a linear or branched C1-C6 alkyl group;
A6 and A10 are C, N, or +N;
A7, A8, A9, and A11, A12, A13 are C, and form a 6-membered aromatic ring which together with the pyrrolin derived ring to which they are attached form an indol or an azaindol system, and, optionally, to which indol or azaindol system a further 6-membered ring is annulated which is formed by R5 and R6, and R9 and R10;
R4 and R8 are independently H;
R3 and R7, and also R5, R6, R9, and R10 when they are not annulated with the further 6-membered ring, are independently selected from the group consisting of absent, H, Cl, Br, I, R25H, and OR25H;
R25 is selected from the group: linear and branched, non-cyclic and cyclic, substituted and unsubstituted C1-20 alkyl, wherein the alkyl group can be single or multiple substituted by a homocyclic or heterocyclic 5-, 6-, or 7-membered aromatic group which can be substituted by a linear or branched C1-C6 alkyl group;
m is an integer from 0 to 6;
x is an integer from 1 to 50;
R32 and R33 are independently of each other an alkyl group having from 1-12 C atoms;
X and Y are CR29R30, where R29 and R30 are each independently selected from H, and unsubstituted and substituted linear or branched, cyclic or non-cyclic C1-C6 alkyl; and
E and E′ are independently selected from H, and unsubstituted and substituted linear or branched, cyclic or non-cyclic C1-C6 alkyl.