EP0766677A1 - Derives de s-triazinylaminostilbene et leur utilisation en tant qu'agents d'azurage optique - Google Patents

Derives de s-triazinylaminostilbene et leur utilisation en tant qu'agents d'azurage optique

Info

Publication number
EP0766677A1
EP0766677A1 EP95922602A EP95922602A EP0766677A1 EP 0766677 A1 EP0766677 A1 EP 0766677A1 EP 95922602 A EP95922602 A EP 95922602A EP 95922602 A EP95922602 A EP 95922602A EP 0766677 A1 EP0766677 A1 EP 0766677A1
Authority
EP
European Patent Office
Prior art keywords
compound
alkyl
phenyl
halogen
substituted
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP95922602A
Other languages
German (de)
English (en)
Inventor
John Dennis Thompson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clariant Finance BVI Ltd
Original Assignee
Hickson International PLC
Clariant Finance BVI Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hickson International PLC, Clariant Finance BVI Ltd filed Critical Hickson International PLC
Publication of EP0766677A1 publication Critical patent/EP0766677A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40—Dyes ; Pigments
    • C11D3/42—Brightening agents ; Blueing agents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40—Nitrogen atoms
    • C07D251/54—Three nitrogen atoms
    • C07D251/68—Triazinylamino stilbenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/60—Optical bleaching or brightening
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
    • D06P1/382—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes reactive group directly attached to heterocyclic group
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/30—Luminescent or fluorescent substances, e.g. for optical bleaching

Definitions

  • the present invention relates to novel s-triazinylaminostilbene derivatives, processes and intermediates for their preparation and their use as optical whitening agents (OWAs) for whitening natural, synthetic and semi-synthetic polymers.
  • OWAs optical whitening agents
  • s-triazinylaminostilbene OWAs The area of use covered by s-triazinylaminostilbene OWAs is very broad, but of particular interest is the whitening of paper and textile substrates by the class of triazinylaminostilbene derivatives known as the "hexasulphonated" compounds resulting from the use of aniline-2,5-disulphonic acid as one of the substituents.
  • OWA to cellulose for example is generally a function of the number of solubilising groups (particularly sulphonic acids) present.
  • the disulphonic acid derivatives such as 4,4'-bis(6"-phenylamino-4 ,1 -morpholino- l",3 ,5"-triazin-2"-yl)aminostilbene-2,2'-disulphonic acid
  • the tetrasulphonic acid derivatives such as 4,4'-bis[6"-(4'"-suIphophenylamino)- 4 " - morpholino-1 " ,3" ,5"-triazin-2"-yl]aminostilbene-2,2'-disulphonic acid
  • the hexasulphonic acid derivatives such as 4,4'-bis[6"-
  • tetrasulphonic acids are thus especially useful for application to paper either alone, or in combination with other optical whitening agents, dyestuffs, pigments or other additives by size press or other surface application methods, and to textiles by padding, either alone or in combination with other typical textile finishing additives e.g. acid resins, crease- and water-proofmg agents, or specialist finishes, or during laundering processes as part of detergent or fabric conditioner compositions.
  • typical textile finishing additives e.g. acid resins, crease- and water-proofmg agents, or specialist finishes, or during laundering processes as part of detergent or fabric conditioner compositions.
  • novel s-triazinylaminostilbene derivatives according to the invention are compounds of formula (1)
  • Y is halogen (e.g. fluoro, chloro or bromo), alkoxy (e.g. C alkoxy) or -NR 2 R 3 [ where R 2 and R 3 are the same or different and are H, alkyl (e.g. C alkyl), hydroxy ⁇ alkyl (e.g. C M hydroxyalkyl), or aryl (e.g. phenyl, optionally substituted), or together with the nitrogen atom form a substituted or unsubstituted cyclic amino group having 5-7 ring members, e.g. morpholino or piperidino],
  • R 2 and R 3 are the same or different and are H, alkyl (e.g. C alkyl), hydroxy ⁇ alkyl (e.g. C M hydroxyalkyl), or aryl (e.g. phenyl, optionally substituted), or together with the nitrogen atom form a substituted or unsubstituted cyclic amino group having 5-7 ring members,
  • R is H, aryl (e.g. phenyl), which is unsubstituted or substituted (e.g. by one or more electron releasing groups such as C alkyl and/or C M alkoxy),
  • R 1 is H or alkyl (e.g. C M alkyI, optionally substituted),
  • Z is an electron-withdrawing group (e.g. CN, -SO ⁇ ),
  • x 2 or 3
  • M is H, a metal cation (e.g. alkali metal, such as Na, K or Li) or -N + R R 5 R 6 R 7 (where R 4 -R 7 are the same or different and are H, alkyl (e.g. C M alkyl), aralkyl (e.g. phenyl(C j . 6 )-alkyl) or hydroxyalkyl (e.g. C M hydroxyalkyl)).
  • Y is preferably bis(2-hydroxyethyl)amino or morpholino.
  • R is preferably phenyl or substituted phenyl, e.g.
  • R 1 is preferably H or -CH 3 and Z is preferably -S0 3 M (particularly where M is an alkali metal cation such as Na) or CN.
  • a compound of particular importance is the compound in which Y is bis(2- hydroxyethyl)amino, R is phenyl, R 1 is H and Z is -S0 3 Na.
  • the compounds of formula (1) can be prepared by reacting a compound of formula (2)
  • X is halogen (e.g. fluoro, chloro or bromo)
  • Y is halogen (e.g. fluoro, chloro or bromo) or alkoxy (e.g. C ⁇ alkoxy) and N(R)CHR f Z is as defined above) with 4,4'- diaminostilbene-2,2'-disulphonic acid.
  • the reaction can be carried out at any convenient temperature (e.g. 20-60°C or to reflux) in a suitable solvent (e.g. water or aqueous acetone), preferably in the presence of an acid binding agent such as sodium bicarbonate or carbonate.
  • a suitable solvent e.g. water or aqueous acetone
  • the compounds of formula (2) which also form part of the invention, may be prepared by reacting a cyanuric halide of formula (3)
  • the amines (4) may be prepared by reacting an amine RNH 2 with an alcohol HOCHR'Z, for example in a neutral aqueous or aqueous alcoholic medium at 20- 60°C.
  • a soluble cyanide e.g. NaCN, KCN
  • me compounds of formula (1) lie in the optical whitening of paper and textiles under conditions normally used for me "hexasulphonic acid derivatives" referred to above.
  • diey may also be used to treat any other cellulosic or otfier natural, synmetic or semi- syndietic materials to which optical brightening is relevant.
  • Tetra-sodium 4.4'bis ⁇ 6"-N-phenyl-N-sulphonatomethylamino-4''-bis( ' 2" , - hydroxyethyl)amino-l".3".5"-triazin-2"-yl]aminostilbene-2.2'-disulphonate To a solution of sodium N-phenyl-N-(2,4-dichloro-l,3,5-triazin-6-yl)aminomemane sulphonate (37.5g, 0.105g.
  • the starting material is prepared as follows:
  • a solution of cyanuric chloride (19.4g, 0.105. mol.) in acetone (200ml) containing sodium bicarbonate (8.8g, 0.105g.mol.) is cooled to -10°C, and an ice-cold solution of sodium ⁇ -anilinomethane sulphonate (23.0g, OJlOg.mol.) in water (175ml) is added as rapidly as possible and me mixture is allowed to warm up to room temperature.
  • the reaction may be followed by means of HPLC using detection at 265nm to enable visualisation of all me starting products and final products, (including any by-products) to be observed.
  • the resulting solution of me title compound may then be used for further condensations wim nucleophiles, e.g. 4,4'- diaminostilbene-2,2'-disulphonic acid and other amines as required.
  • the solution of sodium ⁇ -anilinomethane sulphonate is prepared as follows. Aniline (10.2g, 0.110 g.mol) is added to a stirred solution of the sodium salt of the formaldehyde bisulphite addition complex (15.4g, 0.115 g.mol) in water (100ml) at 25-30°C. Formation of the sodium phenylaminomethane sulphonate is complete within 90 minutes (less at higher temperatures) and the solution may then be diluted and cooled and used as described above.
  • Tetra-sodium 4.4 ' -b isf ⁇ " -N-phenyl-N-sulphonatomethylamino-4 " -morpholino- 1 " .3 ⁇ 5"-triazin-2 w -yl1aminostilbene-2.2'-disulphonate
  • the above compound is prepared by me method of Example 1 except that the diethanolamine is replaced witii morpholine (lO.Og, 0.115g. mol.) to give the corresponding morpholine derivative.
  • the product may be isolated by salting followed by filtration.
  • aniline used in the preparation of the starting material in Examples 1 and 2 may be replaced by p-toluidine (11.8g, O.llOg.mol.) or p-anisidine (13.5g, O.llOg.mol.) to give the corresponding derivatives.
  • Cyanuric chloride (18.5g) is added all at once to a stirred, ice-cold slurry of phenylaminoacetonitrile (13.9g) in water (150ml) containing sodium bicarbonate (8.4g) and the mixture is allowed to warm up to room temperature.
  • the resulting slurry of the title compound may then be used for further condensations wim nucleophiles, e.g. 4,4'-diaminostilbene-2,2'-disulphonic acid and other amines as required.
  • the slurry of phenylaminoacetonitrile is prepared as follows. Aniline (9.8g) is added to a stirred solution of glycolonitrile (55% aqueous solution, 11.5g) in water (100ml) at 20°C, warmed up to 60°C and maintained at mat temperature until the reaction is complete (ca. 1 hour). The resulting oily dispersion may then be cooled and diluted and used as described above.
  • Blank handsheets (comprised of 27.2% bleached kraft softwood, 52.8% bleached kraft hardwood and 20% calcium carbonate filler internally sized wim alkyl ketene dimer) are passed through 9% clear starch solution at pH 6 containing 30, 40 and 50 g/1 of OWA (optical strength (E ll ⁇ t )62) and then fed through a size press to squeeze out me excess liquor.
  • OWA optical strength
  • Patterns of 80 x 80 bleached cotton fabric are passed through solutions of OWAs containing 5,10,15 and 20 g/1 of OWA of optical strength (E ⁇ ) adjusted to 65, and men fed tiirough a padding mangle at constant pressure to give 100% wt/wt pick-up of liquor.
  • the padding solutions contain (in addition to the OWA) 100 g/1 Fixapret 00 CPN and 10 g/1 magnesium chloride.
  • the OWAs used are (i) that of Example 2 and (ii) a "hexa-sulpho" OWA based on aniline- 2,5-disulphonic acid and morpholine. The patterns are dried for 5 minutes at 140°C

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Paper (AREA)

Abstract

Dérivés de s-triazinylaminostilbène représentés par la formule (1) dans laquelle Y représente halogène, alcoxy ou-NR?2R3 (R2 et R3¿ étant semblables ou différents et représentant H, hydroxyalkyle ou aryle ou, avec l'atome d'azote, constituant un groupe amino cyclique substitué ou insubstitué possédant 5-7 éléments), R représente H, aryle substitué ou insubstitué (par exemple, par un ou plusieurs groupes de libération d'électrons, tels que alkyle C¿1-4? et/ou alcoxy C1-4), R?1¿ représente H ou alkyle, Z représente un groupe de retrait d'électrons (par exemple, CN, -SO¿x?M), x est 2 ou 3 et M représente -H, un cation de métal ou N?+R4R5R6R7 (R4-R7¿ étant semblables ou différents et représentant H, alkyle, aralkyle ou hydroxyalkyle). Ces composés sont efficaces en tant qu'agents d'azurage optique pour du papier ou des textiles.
EP95922602A 1994-06-24 1995-06-19 Derives de s-triazinylaminostilbene et leur utilisation en tant qu'agents d'azurage optique Withdrawn EP0766677A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB9412756A GB9412756D0 (en) 1994-06-24 1994-06-24 Chemical compounds
GB9412756 1994-06-24
PCT/GB1995/001428 WO1996000220A1 (fr) 1994-06-24 1995-06-19 Derives de s-triazinylaminostilbene et leur utilisation en tant qu'agents d'azurage optique

Publications (1)

Publication Number Publication Date
EP0766677A1 true EP0766677A1 (fr) 1997-04-09

Family

ID=10757297

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95922602A Withdrawn EP0766677A1 (fr) 1994-06-24 1995-06-19 Derives de s-triazinylaminostilbene et leur utilisation en tant qu'agents d'azurage optique

Country Status (5)

Country Link
EP (1) EP0766677A1 (fr)
GB (1) GB9412756D0 (fr)
IL (1) IL114228A0 (fr)
WO (1) WO1996000220A1 (fr)
ZA (1) ZA955278B (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19706238B4 (de) * 1997-02-18 2005-09-01 Bayer Chemicals Ag Verfahren zur Herstellung von substituierten 4,4'-Diaminostilben-2,2'-disulfonsäuren
PL353873A1 (en) 1999-09-10 2003-12-01 Ciba Specialty Chemicals Holding Inc.Ciba Specialty Chemicals Holding Inc. Triazinylaminostilbene derivative as fluorescent whitening agents
US7270771B2 (en) * 2002-07-05 2007-09-18 Ciba Specialty Chemicals Corporation Triazinylaminostilbene disulphonic acid mixtures
WO2004046293A2 (fr) * 2002-11-19 2004-06-03 Ciba Specialty Chemicals Holding Inc. Agents de blanchiment fluorescents amphoteres
JP2011515547A (ja) 2008-03-26 2011-05-19 クラリアント・ファイナンス・（ビーブイアイ）・リミテッド 改善された光学的増白組成物
DE602008004328D1 (de) * 2008-06-11 2011-02-17 Kemira Germany Gmbh Zusammensetzung und Verfahren zur Papierbleichung
US8262744B2 (en) 2010-05-18 2012-09-11 Milliken & Company Optical brighteners and compositions comprising the same

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1350757A (en) * 1970-05-18 1974-04-24 Ici Ltd Optical brightening agents
JPS4910216A (fr) * 1972-05-26 1974-01-29
JPS4932923A (fr) * 1972-07-27 1974-03-26
JPH0221014A (ja) * 1988-07-08 1990-01-24 Osaka Gas Co Ltd ねじ

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9600220A1 *

Also Published As

Publication number Publication date
WO1996000220A1 (fr) 1996-01-04
GB9412756D0 (en) 1994-08-17
ZA955278B (en) 1996-12-27
IL114228A0 (en) 1995-10-31

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