Bleach catalysts

Patent metadata

Field	Value
Publication number	US-9533296-B2
Application number	US-201615005288-A
Country	US
Kind code	B2
Filing date	Jan 25, 2016
Priority date	Dec 13, 2010
Publication date	Jan 3, 2017
Grant date	Jan 3, 2017

Abstract

The present invention relates to specific acylhydrazone compounds, their use as oxidation catalysts and to a process for removing stains and soil on textiles and hard surfaces. The compounds are substituted with a specific cyclic ammonium group adjacent to the acyl group. Further aspects of the invention are compositions or formulations comprising such compounds.

First claim

The invention claimed is:

1. A method of oxidizing a compound comprising contacting the compound with a catalyst for oxidation reactions wherein the catalyst is at least one compound of formula (1)

wherein
R 1 , R 2 , R 3 , R 4 independently from each other are hydrogen, unsubstituted or substituted C 1 -C 28 alkyl, C 1 -C 28 alkoxy, C 2 -C 28 alkenyl, C 2 -C 22 alkinyl, C 3 -C 12 cycloalkyl, C 3 -C 12 cycloalkenyl, C 7 -C 9 aralkyl, C 3 -C 20 heteroalkyl, C 3 -C 12 cycloheteroalkyl, C 5 -C 16 heteroaralkyl, unsubstituted or substituted phenyl or naphthyl, wherein the substituents for the radicals are selected from the group consisting of C 1 -C 4 alkyl; C 1 -C 4 alkoxy; hydroxy; sulfo; sulfato; halogen; cyano; nitro; carboxy; amino; N-mono- or N,N-di-C 1 -C 4 alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety; N-phenylamino; N-naphthylamino wherein the amino groups may be quaternised; phenyl; phenoxy and naphthyloxy;
or R 1 , R 2 , R 3 , R 4 independently from each other are OR 11 , NR 11 R 12 , NO 2 or halogen;
or
R 1 and R 2 , R 2 and R 3 or R 3 and R 4 are linked together to form 1, 2 or 3 carbocyclic or heterocyclic rings, which may be uninterrupted or interrupted by one or more —O—, —S— or —NR 13 — and or which may be further fused with other aromatic rings and/or which may be substituted with one or more C 1 -C 6 akyl groups;
R 5 is hydrogen, unsubstituted or substituted C 1 -C 28 alkyl, C 2 -C 28 alkenyl, C 2 -C 22 alkinyl, C 3 -C 12 cycloalkyl, C 3 -C 12 cycloalkenyl, C 7 -C 9 aralkyl, C 3 -C 20 heteroalkyl, C 3 -C 12 cycloheteroalkyl, C 5 -C 16 heteroaralkyl, unsubstituted or substituted phenyl, or unsubstituted or substituted heteroaryl; wherein the substituents for the radicals are selected from the group consisting of C 1 -C 4 alkyl; C 1 -C 4 alkoxy; hydroxy; sulfo; sulfato; halogen; cyano; nitro; carboxy; amino; N-mono- or N,N-di-C 1 -C 4 alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety; N-phenylamino; N-naphthylamino wherein the amino groups may be quaternised; phenyl; phenoxy and naphthyloxy;
R 6 is hydrogen, C 1 -C 28 alkyl, C 2 -C 28 alkenyl, C 2 -C 22 alkinyl, C 3 -C 12 cycloalkyl, C 3 -C 12 cycloalkenyl, C 7 -C 9 aralkyl, C 3 -C 20 heteroalkyl, C 3 -C 12 cycloheteroalkyl, C 5 -C 16 heteroaralkyl, unsubstituted or substituted phenyl or naphthyl, or unsubstituted or substituted heteroaryl; wherein the substituents for the radicals are selected from the group consisting of C 1 -C 4 alkyl; C 1 -C 4 alkoxy; hydroxy; sulfo; sulfato; halogen; cyano; nitro; carboxy; amino; N-mono- or N,N-di-C 1 -C 4 alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety; N-phenylamino; N-naphthylamino wherein the amino groups may be quaternised; phenyl; phenoxy and naphthyloxy;
R 7 is a group

 each group with an anion A − ;
k is an integer from 1 to 4;
A − is an anion;
R 10 is hydrogen, C 1 -C 28 alkyl, C 2 -C 28 alkenyl, C 2 -C 22 alkinyl, C 3 -C 12 cycloalkyl, C 3 -C 12 cycloalkenyl, C 7 -C 9 aralkyl, C 3 -C 20 heteroalkyl, C 3 -C 12 cycloheteroalkyl, C 5 -C 16 heteroaralkyl;
R 11 , R 12 independently are hydrogen, C 1 -C 15 alkyl or phenyl; or R 11 and R 12 together with the nitrogen atom to which they are bonded form a 5 or 6 membered-ring which may contain a further N, O or S atom; and
R 13 is hydrogen or C 1 -C 18 alkyl,
together with a peroxide or a peroxide precursor.

2. The method according to claim 1 wherein the at least one compound of formula (1) is further used as catalysts together with O 2 and/or air.

3. The method according to claim 1 wherein a bleach activator is present.

4. The method according to claim 1 wherein additionally a metal chelating agent is present.

5. The method according to claim 2 for oxidizing of stains or soiling on textile materials in a washing process or by the direct application of a stain remover or for the cleaning of hard surfaces.

6. The method according to claim 5 wherein a bleach activator is present.

7. The method according to claim 5 wherein additionally a metal chelating agent is present.

8. The method according to claim 6 wherein additionally a metal chelating agent is present.

9. The method of claim 1 wherein, in the compound of formula (1),
R 1 , R 2 , R 3 , R 4 independently from each other are hydrogen, C 1 -C 8 alkyl, C 1 -C 8 alkoxy, halogen, OR 11 or NR 11 R 12 ;
R 5 is hydrogen or C 1 -C 18 alkyl;
R 6 is hydrogen or C 1 -C 18 alkyl;
R 7 is a group

 each group with an anion A − ;
k is an integer from 1 to 4;
A − is Cl − , Br − , ClO 4 − , NO 3 − , HSO 4 − , BF 4 − or PF 6 − ;
R 10 is hydrogen or C 1 -C 18 alkyl;
R 11 , R 12 independently are hydrogen, C 1 -C 18 alkyl or phenyl; and
R 13 is hydrogen or C 1 -C 4 alkyl.

10. The method of claim 1 wherein, in the compound of formula (1),
R 1 , R 2 , R 3 , R 4 independently from each other are hydrogen, OH, methoxy, halogen or methyl;
R 5 is hydrogen or methyl;
R 6 is hydrogen or methyl;
R 7 is a group

 each group with an anion A − ;
k is an integer from 1 to 2;
A − is Cl − , Br − , ClO 4 − , NO 3 − , HSO 4 − , BF 4 − or PF 6 − ; and
R 10 is hydrogen or C 1 -C 4 alkyl.

11. The method of claim 1 wherein, in the compound of formula (1),
R 1 , R 2 , R 3 , R 4 independently from each other are hydrogen, OH, or methyl;
R 5 is hydrogen;
R 6 is hydrogen;
R 7 is a group

 each group with an anion A − ;
k is 1;
A − is Cl − , Br − , ClO 4 − , NO 3 − , HSO 4 − , BF 4 − or PF 6 − ; and
R 10 is methyl.

12. The method of claim 1 wherein, in the compound of formula (1),
R 1 , R 2 , R 3 , R 4 are hydrogen;
R 5 is hydrogen;
R 6 is hydrogen;
R 7 is a group

 each group with an anion A − ;
k is 1;
A − is Cl − or Br − ; and
R 10 is methyl.

13. A method of oxidizing a compound comprising contacting the compound with a catalyst for oxidation reactions wherein the catalyst is at least one compound of formula (1)

wherein
R 1 , R 2 , R 3 , R 4 independently from each other are hydrogen, unsubstituted or substituted C 1 -C 28 alkyl, C 1 -C 28 alkoxy, C 2 -C 28 alkenyl, C 2 -C 22 alkinyl, C 3 -C 12 cycloalkyl, C 3 -C 12 cycloalkenyl, C 7 -C 9 aralkyl, C 3 -C 20 heteroalkyl, C 3 -C 12 cycloheteroalkyl, C 5 -C 16 heteroaralkyl, unsubstituted or substituted phenyl or naphthyl, wherein the substituents for the radicals are selected from the group consisting of C 1 -C 4 alkyl; C 1 -C 4 alkoxy; hydroxy; sulfo; sulfato; halogen; cyano; nitro; carboxy; amino; N-mono- or N,N-di-C 1 -C 4 alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety; N-phenylamino; N-naphthylamino w

Assignees

• Basf Se
• Henkel Ag & Co Kgaa

Inventors

• Rohwer Hauke
• Winkler Barbara
• Wendeborn Frédérique
• Misteli Katharina

Classifications

• C11D7/3263

  Amides or imides · CPC title

• C11D3/3917

  Nitrogen-containing compounds · CPC title

• D06L4/10

  using agents which develop oxygen (D06L4/20 takes precedence) · CPC title

• C11D7/3281

  Heterocyclic compounds · CPC title

• B01J31/0202

  Alcohols or phenols · CPC title