Near-infrared fluorescent dyes and uses thereof

Patent metadata

Field	Value
Publication number	US-10351706-B2
Application number	US-201615756734-A
Country	US
Kind code	B2
Filing date	Aug 30, 2016
Priority date	Sep 1, 2015
Publication date	Jul 16, 2019
Grant date	Jul 16, 2019

Abstract

The invention relates to a near-infrared fluorescent dye and use thereof, and particularly relates to compounds represented by following Formulae A, B and C, wherein each group in the Formulae is described in the specification. Further provided are a dye composition comprising the compound represented by Formula A or Formula B, and a preparation method of the compound represented by Formula A or Formula B. The compound has a maximum absorption wavelength of 880 nm, considerably exceeding maximum absorption wavelengths of the majority of small-molecule near-infrared fluorescent dyes in the prior art. Moreover, the structure thereof does not aggregate even if the concentration thereof is excessively high, thereby having considerably high chemical stability and light stability.

First claim

The invention claimed is:

1. A compound of Formula A:

wherein:
R a is NR 14 R 15 ;
R b is NR 14 R 15 ;
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 are each independently selected from the group consisting of H, hydroxyl, amino, C1-4 alkoxyl, halogen, cyano, carboxyl, C2-4 alkenyl, —SO 3 − , —SO 2 X, —SO 2 NH 2 , nitro and C1-4 alkyl optionally substituted by one or two substituents selected from the group consisting of C1-4 alkoxyl, halogen, azido, amino and thiol;
R 14 and R 15 are each independently selected from the group consisting of H, C1-4 alkyl and C2-4 alkenyl; or R 14 , together with N, C1 and C3 to which it attaches or together with N, C4 and C5 to which it attaches, forms a 6-membered nitrogen-containing heterocycle, and/or R 15 , together with N, C1 and C2 to which it attaches or together with N, C5 and C6 to which it attaches, forms a 6-membered nitrogen-containing heterocycle;
X is halogen; and
A − is selected from the group consisting of F − , Cl − , Br − , I − , OAc − , HSO 4 − , H 2 PO 4 − , ClO 4 − , F 3 CCOO − , CH 3 SO 3 − , CF 3 SO 3 − , BF 4 − , PF 6 − and NO 3 − .

2. The compound according to claim 1 , wherein the compound has a structure as shown in Formula AI, AII or AIII:

wherein in each of the Formulae, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 are each independently selected from the group consisting of H, hydroxyl, amino, C1-4 alkoxyl, halogen, cyano, carboxyl, C2-4 alkenyl, —SO 3 − , —SO 2 X, —SO 2 NH 2 , nitro and C1-4 alkyl optionally substituted by one or two substituents selected from the group consisting of C1-4 alkoxyl, halogen, azido, amino and thiol; R 14 and R 15 are each independently selected from the group consisting of H, C1-4 alkyl and C2-4 alkenyl; and A − is those as defined in claim 1 .

3. The compound according to claim 1 , wherein R 1 , R 2 , R 3 and R 4 are each independently selected from the group consisting of H, —SO 3 − , —SO 2 X and halogen; R 5 , R 6 , R 7 and R 8 are each independently selected from the group consisting of H, —SO 3 − , —SO 2 X and halogen; R 9 , R 10 , R 11 , R 12 and R 13 are each independently selected from the group consisting of H, —SO 3 − , —SO 2 X, halogen, carboxyl, C1-4 alkoxyl, C2-4 alkenyl and C1-4 alkyl optionally substituted by one or two substituents selected from the group consisting of C1-4 alkoxyl, halogen, azido, amino and thiol; or
in each of the Formulae, R 1 , R 2 , R 4 , R 5 , R 7 , R 8 , R 10 and R 11 are H; R 3 is selected from the group consisting of H, —SO 3 − , —SO 2 X and halogen; R 6 is selected from the group consisting of H, —SO 3 − , —SO 2 X and halogen; R 9 is selected from the group consisting of H, carboxyl, C1-4 alkoxyl, C2-4 alkenyl and C1-4 alkyl optionally substituted by one or two substituents selected from the group consisting of C1-4 alkoxyl, halogen, azido, amino and thiol; R 12 is selected from the group consisting of H, —SO 3 − , —SO 2 X and halogen; and R 13 is selected from the group consisting of H and C1-4 alkyl;
wherein X is halogen.

4. The compound according to claim 2 , wherein in each of the Formulae, R 1 , R 2 , R 3 and R 4 are each independently selected from the group consisting of H, —SO 3 − , —SO 2 X and halogen; R 5 , R 6 , R 7 and R 8 are each independently selected from the group consisting of H, —SO 3 − , —SO 2 X and halogen; R 9 , R 10 , R 11 , R 12 and R 13 are each independently selected from the group consisting of H, —SO 3 − , —SO 2 X, halogen, carboxyl, C1-4 alkoxyl, C2-4 alkenyl and C1-4 alkyl optionally substituted by one or two substituents selected from the group consisting of C1-4 alkoxyl, halogen, azido, amino and thiol; or
in each of the Formulae, R 1 , R 2 , R 4 , R 5 , R 7 , R 8 , R 10 and R 11 are H; R 3 is selected from the group consisting of H, —SO 3 − , —SO 2 X and halogen; R 6 is selected from the group consisting of H, —SO 3 − , —SO 2 X and halogen; R 9 is selected from the group consisting of H, carboxyl, C1-4 alkoxyl, C2-4 alkenyl and C1-4 alkyl optionally substituted by one or two substituents selected from the group consisting of C1-4 alkoxyl, halogen, azido, amino and thiol; R 12 is selected from the group consisting of H, —SO 3 − , —SO 2 X and halogen; and R 13 is selected from the group consisting of H and C1-4 alkyl;
wherein X is halogen.

5. The compound according to claim 2 , wherein:
in Formula AI, R 14 and R 15 are each independently selected from the group consisting of C1-4 alkyl and C2-4 alkenyl; R 1 , R 2 , R 3 and R 4 are each independently selected from the group consisting of H, —SO 3 − , —SO 2 X and halogen; R 5 , R 6 , R 7 and R 8 are each independently selected from the group consisting of H, —SO 3 − , —SO 2 X and halogen; R 9 , R 10 , R 11 , R 12 and R 13 are each independently selected from the group consisting of H, —SO 3 − , —SO 2 X, halogen, carboxyl, C1-4 alkoxyl, C2-4 alkenyl and C1-4 alkyl optionally substituted by one or two substituents selected from the group consisting of C1-4 alkoxyl, halogen, azido, amino and thiol;
in Formula AII, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are H; R 9 , R 10 , R 11 , R 12 and R 13 are independently selected from the group consisting of H and C1-4 alkyl;
in Formula AIII, R 1 , R 2 , R 4 , R 5 , R 7 , R 8 , R 10 and R 11 are H; R 3 is selected from the group consisting of H, —SO 3 − , —SO 2 X and halogen; R 6 is selected from the group consisting of H, —SO 3 − , —SO 2 X and halogen; R 9 is selected from the group consisting of H, carboxyl, C1-4 alkoxyl, C2-4 alkenyl and C1-4 alkyl optionally substituted by one or two substituents selected from the group consisting of C1-4 alkoxyl, halogen, azido, amino and thiol; R 12 is selected from the group consisting of H, —SO 3 − , —SO 2 X and halogen; and R 13 is selected from the group consisting of H and C1-4 alkyl.

6. The compound according to claim 5 , wherein:
in Formula AI, R 14 and R 15 are each independently selected from the group consisting of C1-4 alkyl and C2-4 alkenyl; R 1 , R 2 , R 4 , R 5 , R 7 , R 8 , R 10 and R 11 are H; R 3 is selected from the group consisting of H, —SO 3 − , —SO 2 X and halogen; R % is selected from the group consisting of H, —SO 3 − , —SO 2 X and halogen; R 9 is selected from the group consisting of H, carboxyl, C1-4 alkoxyl, C2-4 alkenyl and C1-4 alkyl optionally substituted by one or two substituents selected from the group consisting of C1-4 alkoxyl, halogen, azido, amino and thiol; R 12 is selected from the group consisting of H, —SO 3 − , —SO 2 X and halogen; and R 13 is selected from the group consisting of H and C1-4 alkyl;
in Formula AII, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 10 , R 11 , R 12 and R 13 are H; R 9 is selected from the group consisting of H and C1-4 alkyl.

7. The compound according to claim 5 , wherein, in Formula AI, R 14 and R 15 are each independently selected from the group consisting of C1-4 alkyl and C2-4 alkenyl; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 10 , R 11 , R 12 and R 13 are H; R 9 is selected from the group consisting of H and C1-4 alkyl optionally substituted by one or two substituents selected from the group consisting of C1-4 alkoxyl and halogen.

8. A compound of Formula B:

wherein:
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R

Assignees

• Univ East China Science & Tech

Inventors

• Yang Youjun
• Li Xinran
• Lei Zuhai
• Li Yi

Classifications

• C09B23/0025

  the substituent being bound through an oxygen atom · CPC title

• C09B11/10 Primary

  Amino derivatives of triarylmethanes · CPC title

• C09B23/0066

  the polymethine chain being part of a carbocyclic ring,(e.g. benzene, naphtalene, cyclohexene, cyclobutenene-quadratic acid) · CPC title

• C09B11/24

  Phthaleins containing amino groups {; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes} · CPC title

• C07D491/20

  Spiro-condensed systems · CPC title