Dyes with phosphinic acid, phosphinate, phosphonate and phosphonamidate substituents as auxochromic groups and methods for preparing the same

Patent metadata

Field	Value
Publication number	US-10174202-B2
Application number	US-201815886494-A
Country	US
Kind code	B2
Filing date	Feb 1, 2018
Priority date	Feb 3, 2017
Publication date	Jan 8, 2019
Grant date	Jan 8, 2019

Abstract

Compounds of formula I are disclosed:

wherein X 1 , X 2 , X 3 , X 4 are independently H, F, Cl, Br, I, CN, NO 2 , OR 1 , SR 1 , NR 1 R 2 , COR 1 , COOR 1 , CONR 1 R 2 , PO 3 R 1 R 2 , SO 2 R 1 , SO 3 R 1 or R 3 ; R 1 and R 2 are, e.g., H, alkyl or aryl or optionally a ring; R 3 is, e.g., alkyl, alkenyl, alkynyl, aryl or cycloalkyl; Y is OR 1 , NR 1 R 2 , or NR 1 R 3 ; Q is O, S, SO 2 , NR, C(R 3 ) 2 , Si(R 3 ) 2 , Ge(R 3 ) 2 , P(═O)R 3 or P(═O)OR 3 ; Q and X 1 can optionally form part of a ring; L and M are independently OR 1 , SR 1 , NR 1 R 2 and R 3 ; L and M can optionally form part of a ring; Z is O, S, NR 1 , CR 1 R 3 or aryl; and Z and X 4 can optionally form part of a ring.

First claim

The invention claimed is:

1. A compound which is a fluorescent dye and has the structural formula:

wherein:
each of X 1 , X 2 , X 3 and X 4 is a member independently selected from the group consisting of H, F, Cl, Br, I, CN, NO 2 , OR 1 , SR 1 , NR 1 R 2 , COR 1 , COOR 1 , CONR 1 R 2 , PO 3 R 1 R 2 , SO 2 R 1 , SO 3 R 1 and R 3 , where:
R 1 and R 2 are independently selected from H, alkyl, aryl or heteroaryl, and R 1 and R 2 can optionally form together a substituted or unsubstituted 4-7 membered ring;
R 3 is alkyl, alkenyl, alkynyl, aryl or cycloalkyl, optionally substituted with one or more heteroatoms independently selected from N, O, S, F, Cl, Br, I, N 3 , amine, OH, OR 1 , OCOR 1 , aryl, COOR 1 , CONR 1 R 2 , PO 3 H 2 and SO 3 H, where R 1 and R 2 are defined as above;

Y is selected from OR 1 , NR 1 R 2 , or NR 1 R 3 , where R 1 , R 2 and R 3 are defined as above;
Q is selected from O, S, SO 2 , NR 3 , C(R 3 ) 2 , Si(R 3 ) 2 , Ge(R 3 ) 2 , P(═O)R 3 , or P(═O)OR 3 , where R 3 is defined as above, and wherein Q and X 1 , taken together with the atoms to which they are bonded, can optionally form a substituted or unsubstituted 5-7 membered ring;
L and M are independently selected from OR 1 , SR 1 , NR 1 R 2 or R 3 , where R 1 , R 2 and R 3 are defined as above, and wherein L and M, taken together with the atoms to which they are bonded, can optionally form a substituted or unsubstituted 5-7 membered ring; and
Z is selected from O, S, NR 1 , CR 1 R 3 or aryl, where R 1 and R 3 are defined as above, and wherein Z and X 4 , taken with the atoms to which they are bonded, can optionally form a substituted or unsubstituted 5-7 membered ring.

2. The compound according to claim 1 , wherein the amine is a member selected from the group consisting of NH 2 , NH(alkyl), NH(aryl), N(alkyl)(aryl) and N(alkyl) 2 .

3. The compound according to claim 1 , where Z and X 4 , taken with the atoms to which they are bonded, form a substituted or unsubstituted 5-7 membered ring, substituted with at least one additional heteroatom selected from the group consisting of N, O and S and/or at least one substituent selected from the group consisting of F, Cl, Br, I, CN, N 3 , B(OR 1 )(OR 2 ), OR 1 , SR 1 , NR 1 R 2 , COR 1 , COOR 1 , CONR 1 R 2 , PO 3 R 1 R 2 , SO 2 R 1 , SO 3 R 1 and R 3 , where R 1 , R 2 , R 3 are defined as in claim 1 .

4. The compound according to claim 1 , having one of the following formulae Ia-Is:

wherein:
each substituent X is a member independently selected from the group consisting of: H, F, Cl, Br, I, CN, NO 2 , OR 1 , SR 1 , NR 1 R 2 , COR 1 , COOR 1 , CONR 1 R 2 , PO 3 R 1 R 2 , SO 2 R 1 , SO 3 R 1 and R 3 , where R 1 , R 2 , R 3 are defined as in claim 1 ;
the substituent R′ is selected from H and R 3 , where R 3 is defined as in claim 1 ;
Q′ is selected from O, S, SO 2 , NR 3 , C(R 3 ) 2 , Si(R 3 ) 2 , Ge(R 3 ) 2 , P(═O)R 3 , and P(═O)OR 3 , where R 3 is defined as in claim 1 ,
L, M, R 1 , R 2 are defined as in claim 1 ;

wherein the substituents L, M, and R 1 are defined as in claim 1 ,
the substituents Q′, R′ and X are defined as above;

wherein the substituents L, M, R 1 and R 2 are defined as in claim 1 ,
the substituents Q′, R′ and X are defined as above;

wherein:
R 1a and R 2a are independently selected from H, alkyl, aryl or heteroaryl, and wherein R 1a and R 2a can optionally form together a substituted or unsubstituted 4-7 membered ring;
R 1b and R 2b are independently selected from H, alkyl, aryl or heteroaryl, and wherein R 1b and R 2b can optionally form together a substituted or unsubstituted 4-7 membered ring;
L and M are defined as in claim 1 ,
Q′ and X are defined as above,
and a positive charge is delocalized among atoms of the conjugated system in alternating positions such that structure Id above represents only one possible mesomeric structure;

wherein:
R 1a and R 2a are independently selected from H, alkyl, aryl or heteroaryl, and wherein R 1a and R 2a can optionally form together a substituted or unsubstituted 4-7 membered ring;
R 1b and R 2b are independently selected from H, alkyl, aryl or heteroaryl, and wherein R 1b and R 2b can optionally form together a substituted or unsubstituted 4-7 membered ring;
L and M are defined as in claim 1 ,
Q′ and X are defined as above,
and a positive charge is delocalized among atoms of the conjugated system in alternating positions such that structure Ie above represents only one possible mesomeric structure;

wherein the substituents L, M, R 1 and R 2 are defined as in claim 1 ,
Q′, R′ and X are defined as above,
and a positive charge is delocalized among atoms of the conjugated system in alternating positions such that structure If above represents only one possible mesomeric structure;

wherein the substituents L and M are defined as in claim 1 ,
Q′ and X are defined as above,
R a , R b and R c are independently selected from H and R 3 , where R 3 is defined as in claim 1 ;

wherein the substituents L and M are defined as in claim 1 ,
Q′ and X are defined as above,
R a , R b and R c are independently selected from H and R 3 , where R 3 is defined as in claim 1 ;

wherein the substituents L and M are defined as in claim 1 ,
Q′ and X are defined as above,
R a , R b and R c are independently selected from H and R 3 , where R 3 is defined as in claim 1 ;

wherein the substituents L and M are defined as in claim 1 ,
Q′ and X are defined as above,
R a , R b , R c and R d are independently selected from H and R 3 , where R 3 is defined as in claim 1 ,
and a positive charge is delocalized among atoms of the conjugated system in alternating positions such that structure Ij above represents only one possible mesomeric structure;

wherein the substituents L and M are defined as in claim 1 ,
Q′ and X are defined as above,
R a , R b , R c and R d are independently selected from H and R 3 , where R 3 is defined as in claim 1 ,
and a positive charge is delocalized among atoms of the conjugated system in alternating positions such that structure Ik above represents only one possible mesomeric structure;

Assignees

• Max Planck Gesellschaft

Inventors

• Sednev Maksim
• Butkevich Alexey
• Shojaei Heydar
• Belov Vladimir
• Hell Stefan
• Wurm Christian
• Kamin Dirk

Classifications

• C07F9/65586

  at least one of the hetero rings does not contain nitrogen as ring hetero atom · CPC title

• C07F9/4419

  Amides of aromatic acids (P-C aromatic linkage) · CPC title

• C09B5/2436

  only nitrogen-containing hetero rings · CPC title

• C07F9/6561

  containing systems of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring or ring system, with or without other non-condensed hetero rings · CPC title

• C09B57/00

  Other synthetic dyes of known constitution · CPC title