[go: up one dir, main page]

EP0766677A1 - S-triazinylaminostilbene derivatives and their use as optical whitening agents - Google Patents

S-triazinylaminostilbene derivatives and their use as optical whitening agents

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Withdrawn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)
French (fr)
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/en
Withdrawn legal-status Critical Current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

S-Triazinylaminostilbene derivatives of formula (1) are described in which Y is halogen, alkoxy or -NR2R3 (where R?2 and R3¿ are the same or different and are H, alkyl, hydroxyalkyl or aryl or together with the nitrogen atom form a substituted or unsubstituted cyclic amino group having 5-7 ring members), R is H, aryl, which is unsubstituted or substituted (e.g. by one or more electron releasing groups such as C¿1-4?alkyl and/or C1-4alkoxy), R?1¿ is H or alkyl, Z is an electron-withdrawing group (e.g. CN, -SO¿x?M), x is 2 or 3 and M is H, a metal cation or -N?+R4R5R6R7¿ (where R4-R7 are the same or different and are H, alkyl, aralkyl or hydroxyalkyl). The compounds are useful as optical whitening agents for paper or textiles.

Description

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.
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. The substantivity- (i.e. the natural affinity of the substance for the fibre) of this class of
OWA to cellulose for example, is generally a function of the number of solubilising groups (particularly sulphonic acids) present. in the molecule: thus, 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, are very substantive, 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, are moderately substantive, and the hexasulphonic acid derivatives, such as 4,4'-bis[6"-
(2'" ,5" '-disulphophenylamino)-4"-morpholino-l " ,3 " ,5 "-triazin-2"-yl]aminostilbene-
2,2'-disulphonic acid, are hardly substantive.
We have now found a new group of s-triazinylaminostilbenes which contain a solubilising group (such as sulphonic acid) attached to a methylamino substituent on the triazine ring. This contrasts to the tetra- and hexasulphonic acid derivatives referred to above in which the sulphonic acid substituents are attached to phenylamino groups. Surprisingly, these compounds are stable to acid hydrolysis and have different properties compared to the known tetrasulphonic acid derivatives. In particular we have found that these tetrasulphonic acid derivatives have the substantivity properties of the hexasulphonic acid derivatives of the prior art OWAs. These 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.
The novel s-triazinylaminostilbene derivatives according to the invention are compounds of formula (1)
in which:
Y is halogen (e.g. fluoro, chloro or bromo), alkoxy (e.g. C alkoxy) or -NR2R3 [ where R2 and R3 are the same or different and are H, alkyl (e.g. C alkyl), hydroxy¬ alkyl (e.g. CMhydroxyalkyl), 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 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 CMalkoxy),
R1 is H or alkyl (e.g. CMalkyI, optionally substituted),
Z is an electron-withdrawing group (e.g. CN, -SO^ ),
x is 2 or 3 and
M is H, a metal cation (e.g. alkali metal, such as Na, K or Li) or -N+R R5R6R7 (where R4-R7 are the same or different and are H, alkyl (e.g. CMalkyl), aralkyl (e.g. phenyl(Cj.6)-alkyl) or hydroxyalkyl (e.g. CM hydroxyalkyl)). Y is preferably bis(2-hydroxyethyl)amino or morpholino. R is preferably phenyl or substituted phenyl, e.g. o, m- or p_-tolyl, anisyl, xylyl or cresyl. R1 is preferably H or -CH3 and Z is preferably -S03M (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, R1 is H and Z is -S03Na.
The compounds of formula (1) can be prepared by reacting a compound of formula (2)
(where 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)CHRfZ is as defined above) with 4,4'- diaminostilbene-2,2'-disulphonic acid.
To ensure complete reaction, at least 2 moles of the compound (2) should be added per mole of the 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.
When a compound in which Y is -NR2R3 is required, a compound of formula (1) in which Y is halogen can be reacted with an amine HNR2R3, in generally the same manner as for the preparations of other compounds of formula (1).
The compounds of formula (2), which also form part of the invention, may be prepared by reacting a cyanuric halide of formula (3)
(where X and Y are as defined for formula (2) above) with an amine of formula (4), RNHCHR'Z. This reaction may be performed as described above for die preparation of the compounds (1), preferably at 0-25°C.
The amines (4) may be prepared by reacting an amine RNH2 with an alcohol HOCHR'Z, for example in a neutral aqueous or aqueous alcoholic medium at 20- 60°C.
Alternatively, die compounds of formula (4), (Z=CN) may be prepared from die compound of formula (4) (Z=S03Na) by treatment with a soluble cyanide (e.g. NaCN, KCN).
The main applications of me compounds of formula (1), particularly the preferred compounds, lie in the optical whitening of paper and textiles under conditions normally used for me "hexasulphonic acid derivatives" referred to above. However, diey may also be used to treat any other cellulosic or otfier natural, synmetic or semi- syndietic materials to which optical brightening is relevant.
The following Examples illustrate the invention.
EXAMPLE 1
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. mol.) in aqueous acetone (375ml) at 20°C containing sodium bicarbonate (8.8g, 0.105 g.mol.) is added a solution of sodium 4,4'- diaminostilbene-2,2'-disulphonate (20.7g, 0.05 g.mol.) in water (140ml) at 20°C. The mixture is then heated up to 50°C and maintained at mat temperature until me reaction is complete (ca. 1 hour). Diethanolamine (12. lg, 0.115 g.mol.) and sodium bicarbonate (8.8g, 0.105 g.mol.) are men added and me solution is heated to 100°C whilst distilling off the acetone and maintained at that temperature for 2 hours. The resulting solution may be used as is, or may be desalinated and concentrated by ultrafiltration to give the title compound as a concentrated solution.
The starting material is prepared as follows:
Sodium N-phenyl-N-(2.4-dichloro-1.3.5-triazin-6-yD aminomethane sulphonate
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 ω -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 ω -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. EXAMPLE 2
Tetra-sodium 4.4 ' -b isfό " -N-phenyl-N-sulphonatomethylamino-4 " -morpholino- 1 " .3\5"-triazin-2w-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.
EXAMPLES 3-6
The 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.
The following is a further example of a compound of formula (2).
EXAMPLE 7
N-Phenyl-N-(2.4-dichloro-l .3.5-triazin-6-yl') aminoacetonitrile
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.
The following Examples illustrate me use of the compounds of Examples 1 and 2.
Examples A - Size Press Application
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 (Ell^t)62) and then fed through a size press to squeeze out me excess liquor. The OWAs used are (i) me compound of Example 1 and (ii) Photine m SLC Standard (a proprietary brand of "hexa-sulpho" OWA). The sheets are dried (4 minutes at 105°C), conditioned (1 hour at room temperature and 70% R.H.) and men the fluorescence is measured on a Harrison Meter and me brightness on an ICS Q MM 2000 meter, with and without UV filter. To check on the shade and overall appearance, a visual assessment of me two sets of patterns is also made. Typical readings of brightness lift (e-f) obtained are:-
Concentration (g/1 Product from Photine m of 62) Example 1 SLC
30 13.1 15.9 40 16.0 16.9 50 17.3 16.8
Visual Assessment
Equivalent to the Photine m SLC patterns. Example B - Padding Application
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. Where a resin finish is employed, the padding solutions contain (in addition to the OWA) 100 g/1 Fixapret00 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
10 and conditioned for 1 hour at room temperature and 70% R.H. The fluorescence is then measured using a Harrison fluorescence meter and the ISO whiteness by means of a ICS Q MM 2000 meter. Typical readings obtained are:-
(a) Harrison Meter 15
Concentration Water Resin
(g/1 of JjJJ, 65) Product from Hexa-sulpho Product from Hexa-sulpho Example 2 OWA Example 2 OWA
5 309 316 317 335
10 338 347 362 366
15 365 373 382 383
20 369 396 391 386
5 (b) ISO Brightness
Concentration Water Resin
Product from Hexa-sulpho Product from Hexa-sulpho Example 2 OWA Example 2 OWA
5 111.9 113.1 111.5 112.1
10 113.8 114.7 114.9 115.0
15 115.9 117.5 115.8 116.8
20 116.4 119.3 115.5 115.9
10 These results show mat the compound of Example 2 is comparable in performance to me hexa-sulpho compound.

Claims

CLAIMS :
1. s_-Triazinylaminostilbene derivatives of formula (l)
in which :
Y is halogen, Cλ.4 alkoxy or -NR2R3 (where R2 and R3 are the same or different and are H, C1.4alkyl, C1_4hydroxyalkyl or 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, or phenyl, which is unsubstituted or substituted by one or more electron releasing groups such as Cx.4 alkyl and/or C1.4alkoxy,
R1 is H or C1-4alkyl, optionally substituted,
Z is an electron-withdrawing group such as CN or -SOxM,
x is 2 or 3 and
M is H, a metal cation or -N+R4R5R6R7 (where R4-R7 are the same or different and are H, Cx-4alkyl , phenyl (Ci-g) -alkyl or Cx-4 hydroxyalkyl) .
2. Compounds as claimed in claim 1 in which:
Y is bis(2-hydroxyethyl)amino or morpholino,
R is phenyl, o_, m- or β-tolyl, anisyl, xylyl or cresyl,
R1 is H or -CH3 and
Z is -S03M (where M is an alkali metal cation such as Na) or CN.
3. A compound as claimed in claim 1 in which Y is bis(2-hydroxyethyl)amino, R is phenyl,R1 is H, Z is - S03Na and M is Na.
4. A process for the preparation of a compound as claimed in claim 1 which comprises reacting a compound of formula (2)
(where X is halogen, Y is halogen or Ci.galkoxy and N(R)CHR1Z is as defined in claim 1) with 4,4'- diaminostilbene-2,2' -disulphonic acid.
5. A composition for the whitening of paper or textiles which contains a compound as claimed in claim 1 as an optical whitening agent.
6. A composition as claimed in claim 5 which includes an aqueous medium.
7. The use of a compound as claimed in any of claims l to 3 for the whitening of natural, synthetic or se i- synthetic polymeric materials.
8. The use of a compound as claimed in any of claims 1 to 3 for application to paper, for example by surface application from an aqueous medium which can include starch, carboxymethylcellulose, polyvinyl alcohol or other natural or synthetic polymeric binders.
9. The use of a compound as claimed in any of claims 1 to 3 for application to textiles, for example by padding, either alone or in combination with other textile finishing additives.
10 The use of a compound as claimed in any of claims 1 to 3 as an optical brightening additive in a laundry detergent, for example a liquid detergent, or in a fabric conditioner composition.
EP95922602A 1994-06-24 1995-06-19 S-triazinylaminostilbene derivatives and their use as optical whitening agents Withdrawn EP0766677A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB9412756 1994-06-24
GB9412756A GB9412756D0 (en) 1994-06-24 1994-06-24 Chemical compounds
PCT/GB1995/001428 WO1996000220A1 (en) 1994-06-24 1995-06-19 S-triazinylaminostilbene derivatives and their use as optical whitening agents

Publications (1)

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

Family

ID=10757297

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95922602A Withdrawn EP0766677A1 (en) 1994-06-24 1995-06-19 S-triazinylaminostilbene derivatives and their use as optical whitening agents

Country Status (5)

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

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19706238B4 (en) * 1997-02-18 2005-09-01 Bayer Chemicals Ag Process for the preparation of substituted 4,4'-diaminostilbene-2,2'-disulfonic acids
IL148105A0 (en) * 1999-09-10 2002-09-12 Ciba Specialty Holding Inc Triazinylaminostilbene derivative as fluorescent whitening agents
US7270771B2 (en) * 2002-07-05 2007-09-18 Ciba Specialty Chemicals Corporation Triazinylaminostilbene disulphonic acid mixtures
BR0316400A (en) * 2002-11-19 2006-02-21 Ciba Sc Holding Ag amphoteric fluorescent whitening agents
WO2009118247A1 (en) * 2008-03-26 2009-10-01 Clariant International Ltd Improved optical brightening compositions
ES2359359T3 (en) 2008-06-11 2011-05-20 Kemira Germany Gmbh COMPOSITION AND PROCESS FOR WHITENING PAPER.
BR112012029133A2 (en) 2010-05-18 2016-09-13 Milliken & Co 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 (en) * 1972-05-26 1974-01-29
JPS4932923A (en) * 1972-07-27 1974-03-26
JPH0221014A (en) * 1988-07-08 1990-01-24 Osaka Gas Co Ltd Screw

Non-Patent Citations (1)

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

Also Published As

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

Similar Documents

Publication Publication Date Title
JP4060352B2 (en) Optical brightener
JP4696296B2 (en) Triazinylaminostilbene disulfonic acid mixture
JP4550419B2 (en) Improvements on optical brighteners
RU2241703C2 (en) Method for preparing liquid composition containing stilbene compounds
US3600385A (en) Bis-(triazinylamino) stilbene derivatives for optical brightening
CA2773768A1 (en) Disulfo-type fluorescent whitening agent compositions
CA2610518A1 (en) Storage stable solutions of optical brighteners
SU429593A3 (en) METHOD OF PREPARING THE AMBASSY: Fenledenediamine sulfonic acid. Method 10 consists in condensing cyanuric chloride with a diamine and a dye compound. However, the dyes obtained by this method have a low fixation on cellulose 15 fibers and unsatisfactory durability with respect to wet treatments. a new starting material 20 is used, phenylenediaminodisulfonic acid. The proposed new dye has the general formula where R is hydrogen or alkyl; D is the residue of the amino-amino compound in which molecule nitrogen atoms are bonded to carbon atoms of a homocyclic aromatic radical; X is a residue of a colorless organic acid, the molecule of which contains cellulose-reactive substituents, for example —C1, or X is a dichloro-sym.-triazine group. that one mole of cyanuric chloride is condensed with one mole of a coloring compound of the formula DNHR
CA2562777C (en) Improvements relating to optical brightening agents
US4025507A (en) Bis-(triazinylamino) stilbene compounds
WO1996000220A1 (en) S-triazinylaminostilbene derivatives and their use as optical whitening agents
US6143888A (en) Use of triazine-based UVAs for use as quenchers in paper-making processes
US3728275A (en) Preparations containing concentrated aqueous asymmetrically substituted bis-triazinylaminostilbenes and the use of the preparations for optical brightening
US3464886A (en) Das-triazine brighteners and paper made therewith
CA2782729C (en) Concentrated storage-stable aqueous optical brightening solutions
RU2772022C2 (en) Optical bleach for paper
DE2051718A1 (en) Concentrated aqueous preparations containing asymmetrically substituted bis triazinyl amino stilbenes and their use for optical brightening
AU2003246605B9 (en) Triazinylaminostilbene disulphonic acid mixtures
RU2495972C2 (en) Improved optical bleaching compositions
JPH0859659A (en) Water-soluble triazine dye
HK1116175B (en) Improvements relating to optical brightening agents
CH285750A (en) Process for the preparation of an optical brightening agent.
MXPA98010234A (en) Use of triazine-based grapes to be used as neutralizers in processes for elaboration ofpa
CH286341A (en) Process for the preparation of an optical brightening agent.

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19970120

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE ES FR GB IT LI NL SE

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: CLARIANT FINANCE (BVI) LIMITED

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 19990105