Bis-(triazinylamino)-stilbene derivatives

Patent metadata

Field	Value
Publication number	US-9376405-B2
Application number	US-201214113686-A
Country	US
Kind code	B2
Filing date	Apr 17, 2012
Priority date	Apr 27, 2011
Publication date	Jun 28, 2016
Grant date	Jun 28, 2016

Abstract

The instant invention relates to novel water soluble bis-(triazinylamino)-stilbene optical brightening agents, a process for their preparation and their use for whitening natural and synthetic materials.

First claim

The invention claimed is:

1. An optical brightening agent of formula (I)

wherein
the anionic charge on the brightener is balanced by a cationic charge composed of one or more identical or different cations selected from the group consisting of hydrogen, an alkali metal cation, alkaline earth metal, ammonium, ammonium that is mono-, di-, tri- or tetrasubstituted by a C 1 -C 4 linear or branched alkyl radical, ammonium that is mono-, di-, tri- or tetrasubstituted by a C 1 -C 4 linear or branched hydroxyalkyl radical, ammonium that is, di-, tri- or tetrasubstituted by a mixture of C 1 -C 4 linear or branched alkyl radical and linear or branched hydroxyalkyl radical, and mixtures thereof,
R1 and R1′ are the same or different and are each a radical of formula (II)

or R1 together with R1′ are each a radical of formula (III)

or R1 together with R1′ are each a radical of formula (IV)

or mixtures thereof,
R2 and R2′ are the same or different and are selected from the group consisting of hydrogen, C 1 -C 4 linear or branched alkyl, C 2 -C 4 linear or branched hydroxyalkyl, —CH 2 CO 2 − , —CH 2 CH 2 CONH 2 , and —CH 2 CH 2 CN,
or R2 and R2′ are each a radical of formula (II)
or R2 together with R2′ are each a radical of formula (III),
or R2 together with R2′ are each a radical of formula (IV),
or R2 and R2′ are each a radical of formula (V),

and mixtures thereof,
R3 and R3′ are the same or different and are selected from the group consisting of hydrogen, C 1 -C 4 linear or branched alkyl, C 2 -C 4 linear or branched hydroxyalkyl, —CH 2 CO 2 − , —CH(CO 2 − )CH 2 CO 2 − , —CH(CO 2 − )CH 2 CH 2 CO 2 − , —CH 2 CH 2 SO 3 − , —CH 2 CH 2 CO 2 − , —CH 2 CH(CH 3 )CO 2 − , benzyl,
and mixtures thereof,
or R2 and R3 and/or R2′ and R3′ together with the neighboring nitrogen atom are each a morpholine, a piperidine, a piperazine, a pyrrole, or a pyrrolidine ring or mixtures thereof,
R12 and R13 are the same or different and are selected from the group consisting of hydrogen, C 1 -C 6 linear or branched alkyl radical, halogen, —SR14, —OR15, —NR16R17, —CONR18R19, —COR20, —SO2NR21R22, —CN, —CO 2 − , —SO 3 − ,
and mixtures thereof,
R4, R5, R6, R7, R8, R9, R10, R11, R14, R15, R16, R17, R18, R19, R20, R21 and R22 are the same or different and are selected from the group consisting of hydrogen, phenyl or C 1 -C 25 linear and branched alkyl radical,
x, y, and z are the same or different and are each in the range of from 0 to 200, with the proviso that x+y+z≧5, if R1 together with R1′ are each a radical of formula (III), or with the proviso that x+y≧5, if R1 and R1′ are the same or different and are each a radical of formula (II), or R1 together with R1′ are each a radical of formula (IV),
n is in the range of from 0 to 4,
or mixtures thereof.

2. The optical brightening agent according to claim 1 , wherein in formula (I) the anionic charge is balanced by a cationic charge composed of one or more identical or different cations selected from the group consisting of hydrogen, Li, Na, K, Ca, Mg, ammonium, ammonium that is mono-, di-, tri- or tetrasubstituted by a C 1 -C 4 linear or branched alkyl radical, ammonium that is mono-, di-, tri- or tetrasubstituted by a C 1 -C 4 linear or branched hydroxyalkyl radical, ammonium that is, di-, tri- or tetrasubstituted by a mixture of C 1 -C 4 linear or branched alkyl radical and linear or branched hydroxyalkyl radical, and mixtures thereof,
R1 and R1′ are the same or different and are each a radical of formula (II)
or R1 together with R1′ are each a radical of formula (III)
or R1 together with R1′ are each a radical of formula (IV)
or mixtures thereof,
R2 and R2′ are the same or different and are selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, 2-hydroxyethyl, 2-hydroxypropyl, —CH 2 CO 2 − , —CH 2 CH 2 CONH 2 , and —CH 2 CH 2 CN,
or R2 and R2′ are each a radical of formula (II)
or R2 together with R2′ are each a radical of formula (III)
or R2 together with R2′ are each a radical of formula (IV)
or R2 and R2′ are each a radical of formula (V),
and mixtures thereof,
R3 and R3′ are the same or different and are selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, 2-hydroxyethyl, 2-hydroxypropyl, —CH 2 CO 2 − , —CH(CO 2 − )CH 2 CO 2 − , —CH(CO 2 − )CH 2 CH 2 CO 2 − , —CH 2 CH 2 SO 3 − , —CH 2 CH 2 CO 2 − , —CH 2 CH(CH 3 )CO 2 − , benzyl,
and mixtures thereof,
or R2 and R3 and/or R2′ and R3′ together with the neighboring nitrogen atom are each a morpholine, a piperidine or a pyrrolidine ring
or mixtures thereof,
R12 and R13 are the same or different and are selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 2-ethylhexyl, F, Cl, Br, I, —SR14, —OR15, —NR16R17, —CONR18R19, —COR20, —SO2NR21R22, —CN, —CO 2 − , —SO 3 − ,
and mixtures thereof,
R4, R5, R6, R7, R8, R9, R10, R11, R14, R15, R16, R17, R18, R19, R20, R21 and R22 are the same or different and are selected from the group consisting of hydrogen, phenyl or C 1 -C 20 and branched alkyl radical,
x, y, and z are the same or different and are each in the range of from 0 to 200, with the proviso that x+y+z≧5, if R1 together with R1′ are each a radical of formula (III), or with the proviso that x+y≧5, if R1 and R1′ are the same or different and are each a radical of formula (II), or R1 together with R1′ are each a radical of formula (IV),
n is in the range of from 0 to 4,
or mixtures thereof.

3. The optical brightening agent according to claim 1 , wherein in formula (I), the anionic charge is balanced by a cationic charge composed of one or more identical or different cations selected from the group consisting of hydrogen, Na, K, ammonium, triethanolamine, dimethylaminoethanol, and mixtures of said compounds thereof,
R1 and R1′ are the same or different and are each a radical of formula (II)
or R1 together with R1′ are each a radical of formula (III),
R2 and R2′ are the same or different and are selected from the group consisting of hydrogen, methyl, ethyl, 2-hydroxyethyl, 2-hydroxypropyl, —CH 2 CO 2 − , —CH 2 CH 2 CONH 2 , and —CH 2 CH 2 CN,
or R2 and R2′ are each a radical of formula (II)
or R2 together with R2′ are each a radical of formula (III)
or R2 and R2′ are each a radical of formula (V),
R3 and R3′ are the same or different and are selected from the group consisting of methyl, ethyl, 2-hydroxyethyl, 2-hydroxypropyl, —CH 2 CO 2 − , —CH(CO 2 − )CH 2 CO 2 − , —CH 2 CH 2 SO 3 − ,
and mixtures thereof,
or R2 and R3 and/or R2′ and R3′ together with the neighboring nitrogen atom are each a morpholine ring,
R12 and R13 are the same or different and are selected from the group consisting of hydrogen, —CO 2 − , and —SO 3 − ,
R4, R5, R6, R7, R8, R9, R10, R11, R14, R15, R16, R17, R18, R19, R20, R21 and R22 are the same or different and are selected from the group consisting of hydrogen, C 1 -C 20 linear, and branched alkyl radical,
x, y, and z are the same or different and are each in the range of from 0 to 150, with the proviso that x+y+z≧5, if R1 together wit

Assignees

• Klein Cedric
• Reveaud Frederic
• Jackson Andrew Clive
• Atkinson David
• Clariant Int Ltd

Inventors

• Klein Cedric
• Reveaud Frederic
• Jackson Andrew Clive
• Atkinson David

Classifications

• C07D251/50

  with a halogen atom attached to the third ring carbon atom · CPC title

• C07D251/54 Primary

  Three nitrogen atoms · CPC title

• C07D251/44 Primary

  with halogen atoms attached to the two other ring carbon atoms · CPC title

• C07D251/68 Primary

  Triazinylamino stilbenes · CPC title

• D21H21/30

  Luminescent or fluorescent substances, e.g. for optical bleaching (D21H21/40 takes precedence) · CPC title