EP-4735570-A1 - BLEACH CATALYSTS

Abstract

The present invention relates to bleach catalysts comprising at least one metal ion coordinated to at least one ligand based upon a common structural element of (4,5-Dihydro-1,3-oxazol-2-yl)benzene and more preferably upon a o-(4,5-Dihydro-1,3-oxazol-2-yl)phenol core structure: which may be ring substituted with ancillary groups, esterified, or etherified. The catalysts are suitable for catalysing oxidative bleaching. The compounds are biodegradable and thus prevent catalyst build up in the environment.

Inventors

• ELLISON, Jack Robert
• GRANT, SIMON JONATHON
• WATSON, Cleo
• RIBIERE, Patrice Georges Antonin
• ANDERSON, CRAIG
• PETRIS, Rusalim-Antoniu

Assignees

• Thomas Swan&Co. Ltd.

Dates

Publication Date

20260506

Application Date

20240627

Claims (1)

1. P13308WO TSW Bleach (GFI0304) CLAIMS 1. A bleach catalyst comprising at least one metal coordinated to at least one ligand of formula (I) having the structure: wherein m is 1 or 2; n is 1 or 2; the or each R independently represents H, CH 3 , C 2 H 5 , C 3 H 7 , C 4 H 9 or OH; or OR 1 wherein R 1 represents CH 3 (CH 2 ) v , wherein v is 0 to 17, which chain may be hydroxy- or alkoxy- terminated; or NR 2 2 , wherein: R 2 represents H or CH 3 (CH 2 ) w , wherein w is 0 to 17; or R 2 represents alkoxyalkyl; R’ represents H, CH 3 , CH 2 CH 3, CH(CH 3 ) 2 , (CH 2 ) y OH or (CH 2 ) y COOH, wherein y is 0 to 17; R’’ represents H, CH 3 , CH 2 CH 3, CH 2 OH, CH 2 CH 2 OH, CH 2 OCH 3 or CH 2 CH 2 OCH 3 ; R’’’ represents: H; or C(O)R 3 , wherein R 3 represents(CH 2 ) z R 4 , wherein z is from 1 to 18 and R 4 is H, OH or COOH; or –R 5 –R 6 ; wherein R 5 represents C 1 to C 4 alkyl; and R 6 represents H, CH 3 , OH, COOH, OCH 3 , OCH 2 CH 2 OH or OCH 2 CH 2 OCH 3 ; or CH(OH)CH 2 OH. 2. The bleach catalyst according to claim 1 wherein: a. the or each R is H, CH(CH 3 ) 2 , C(CH 3 ) 3 , CH 2 CH 3 or OH; b. the or each R is H; c. where the or each R represents NR 2 2, R 2 is H or CH 3 (CH 2 ) w ; d. where the or each R represents NR 2 2 and R 2 is CH 3 (CH 2 ) w , w is 0; e. where the or each R represents NR 2 2 and R 2 represents alkoxyalkyl, the alkoxyalkyl is hydroxyethyl or hydroxypropyl; f. R is located in positions 4, 5 or 6 of the aromatic ring; g. R’ is H; h. R’’ is H; i. where R’’’ represents C(O)R 3 , R 3 is (CH 2 ) z R 4 ; j. R 4 is OH; or k. where R’’’ represents -R 5 -R 6 , R 5 is methylene. 3. The bleach catalyst of claim 1 or claim 2, wherein the metal is selected from iron (Fe), manganese (Mn), copper (Cu), or cobalt (Co). P13308WO TSW Bleach (GFI0304) 4. The bleach catalyst according to claim 3, wherein the transition metal ions is iron(II), iron(III), manganese(II), manganese(III), copper(II), cobalt(II) or cobalt(III). 5. The bleach catalyst of any one of claims 1 to 4, being a chelate. 6. The bleach catalyst of claim 5 being a hexadentate complex. 7. The chelate according to claim 5 or claim 6, wherein the chelate further comprises one or more further ligands other than those according to claims 1 or 2, optionally wherein the further ligand(s) is or are selected from H 2 O, carbonate, hydroxide, a halide or an organic acid. 8. The bleach catalyst or chelate according to any one of claims 1 to 7, formulated for use as a bleach catalyst, optionally wherein the compound or chelate is formulated for use as an oxidative bleach catalyst. 9. The bleach catalyst or chelate according to claim 8 comprising part of a bleach catalyst or chelate formulation, wherein the formulation additionally comprise at least one ancillary compound, optionally selected from one or more of surfactant(s), detergent(s), bleach(es), bleach activator(s), carrier compound(s), stabilizer(s) and/or dispersant(s). 10. Use of the compounds of formula (I) or chelates thereof in any one of claims 1 to 9 as bleach catalysts. 11. A method for bleach catalysis comprising contacting the compound of formula (I) with a bleach under conditions effective to allow the compound to enhance a bleaching process.

Description

P13308WO TSW Bleach (GFI0304) BLEACH CATALYSTS TECHNICAL FIELD The present invention concerns bleach catalysts and certain applications. BACKGROUND Industry standard bleach catalysts in the dishwashing detergent industry include CAS 640-67-5 (manganese oxalate), CAS 6556-16-7 (manganese oxalate dihydrate), CAS 116633-53-5 (Mn-Me3-tacn), and certain cobalt-based complexes. These and other conventional bleach catalysts suffer from one or more of the following disadvantages: 1. They are conventionally manufactured from fossil fuels; 2. They are non-biodegradable; 3. They are toxic; 4. They are damaging to some materials, such as textiles; and 5. Their performance is not as good as other industry standards characterised by one or more of the aforesaid disadvantages. The present invention aims to provide improved bleach catalysts in at least one of these respects. There is some recognition in the prior art that certain oxazoline-derived ligands can be useful in certain types of catalysis. US2023/203211 discloses organometallic Ziegler-Natta catalysts derived from oxazoline compounds for the production of higher molecular weight polyethylenes. Living cationic ring-opening polymerization of 2-oxazolines initiated by rare-earth metal triflates are disclosed in RSC Adv., 2014,4, 59917-59926. Additionally, other ring-opened oxazoline derivatives are disclosed in EP1390340. GB2422832A discloses Group 3B, 4B and rare earth metal precursors for chemical vapour deposition comprising a metal and at least one ligand having oxygen and nitrogen available for co-ordination with the metal, the oxygen and nitrogen being separated by 2 or 3 carbon atoms in the ligand and having sterically hindering groups on the nitrogen and/or the oxygen and/or a carbon adjacent to nitrogen and/or oxygen. WO02/102707A2 discloses methods for carrying out nucleophilic addition reactions using oxo-, sulfido- or amido-complexes of transition metals as reaction catalysts. Nucleophilic addition reactions that can be catalysed using the present methods include silylation, hydrosilylation, hydroamination, silylmetallation, carbometallation, aldol reactions, hydro- and carbometallation initiated cyclization/polymerization, and epoxide/aziridine opening. The disclosure also pertains to novel transition metal complexes that have utility in catalysing such reactions. P13308WO TSW Bleach (GFI0304) US2005/0235428A1 discloses the use of metal complex compounds as oxidation catalysts. The present invention relates also to formulations comprising such metal complex compounds, to novel metal complex compounds and to a method of catalysing oxidations, wherein at least one complex compound according to the invention is added to the oxidising agent. Other relevant disclosures include: Stereoisomers and functional groups in oxidorhenium(V) complexes: effects on catalytic activity, Dalton Trans., 2019, 48, 8106-8115. Iron complexes of chiral phenol-oxazoline ligands: Structural studies and oxidation catalysis, Inorganica Chimica Acta, 360 (2007) 1954–1960. Arene–ruthenium complexes with salicyloxazolines: diastereoselective synthesis, configurational stability, and applications as asymmetric catalysts for Diels–Alder reactions, Dalton Trans., 2004, 1481- 1492. A mild catalytic synthesis of 2-oxazolines via oxetane ring-opening: rapid access to a diverse family of natural products, Chem. Sci., 2019,10, 9586-9590. Titanium and Vanadium Catalysts with 2-Hydroxyphenyloxazoline and Oxazine Ligands for Ethylene- Norbornene (co)Polymerization, Catalysts 2019, 9(12), 1041. Palladium and copper complexes with oxygen–nitrogen mixed donors as efficient catalysts for the Heck reaction, Inorganica Chimica Acta 383 (2012) 46–51. Electrochemical and Catalytic Properties of Novel Manganese(III) Complexes with Substituted 2-(2ʹ- Hydroxyphenyl)oxazoline Ligands − X-ray Structures of Tris[5-methyl-2-(2ʹ- oxazolinyl)phenolato]manganese(III) and Tris[5-chloro-2-(2ʹ-oxazolinyl)phenolato]manganese(III), European J. Inorg. Chem., (2002), 377-387. Synthesis, Structure, and Catalytic Properties of V-IV, Mn-III, Mo-VI, and U-VI Complexes Containing Bidentate (N, O) Oxazine and Oxazoline Ligands, Inorganic Chemistry, (2004), 43(18), 5704-5713. C 2-Symmetric Group 4 Metal Complexes Adorned with Chiral N,O Chelates: Synthesis and Structural Characterization of Helical Hexacoordinate Metal Dichlorides Derived from 6-Isopropyl-3-methyl-2-(4- isopropyl-4,5-dihydrooxazol-2-yl)phenol Ligands, Z. Anorg.Allg. Chem., (2009), 635 (9-10), 1435-1441. Synthesis, Structures, and Magnetism of Three 1D Mn-III Chains with Oxazoline-Based Ligands, Inorganic Chemistry, (2010), 49, 5868-5875. A general and convenient route to oxazolyl ligands, Tetrahedron Letters, (2011), 52, 5120-5123. P13308WO TSW Bleach (GFI0304) Bleach catalysts are effective to enhance the activity of peroxygen bleaches such as hydrogen peroxide, hydrogen peroxide liberating or generating compounds, and/or inorganic and organic peroxyacids. None o