US3716532A - Process for preparing crystalline forms of 4,4'-bis[(4-anilino-6-morpholino-1,3,5-triazin-2-yl)-amino]-stilbene-2,2'-disulfonic acid - Google Patents

Process for preparing crystalline forms of 4,4'-bis[(4-anilino-6-morpholino-1,3,5-triazin-2-yl)-amino]-stilbene-2,2'-disulfonic acid Download PDF

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US3716532A
US3716532A US00027587A US3716532DA US3716532A US 3716532 A US3716532 A US 3716532A US 00027587 A US00027587 A US 00027587A US 3716532D A US3716532D A US 3716532DA US 3716532 A US3716532 A US 3716532A
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disulfonic acid
bis
anilino
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morpholino
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M Schwarz
R Pichler
C Tscharner
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0025—Crystal modifications; Special X-ray patterns
    • 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
    • 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
    • D06L4/664—Preparations of optical brighteners; Optical brighteners in aerosol form; Physical treatment of optical brighteners

Definitions

  • the fluorescent whitening is effected today not only by the textile producer or finisher including the manufacturers of synthetic materials but, to an increasing extent, also by the housewife who washes her laundry with detergents and/or soaps containing fluorescent whitening materials.
  • fluorescent whitening agents are incorporated into a washing agent during the production of such agents.
  • Canadian Pat. No. 783,566 relates to a salt of 4,4- bis(4-anilin0-6-morpholino-s-triazin-Z-ylamino)-2,2'- stilbenedisulfonic acid and more particularly, to a novel crystalline form of the disodium salt of the aforesaid acid.
  • the aforesaid novel crystalline material is characterized by improved properties as an optical bleaching agent.
  • the disodium salt that is, disodium 4,4'-bis(4- anilino-6-morpholino-s-triazin-2-ylamino)-2,2'-stilbenedisulfonate is a known compound having valuable properties as a fluorescent optical bleaching agent and which is used as a whitening and brightening agent in detergent compositions for laundering textile goods.
  • the aforesaid known compound has been found to be objectionable because of its light sensitivity and this light sensitivity is objectionable especially when the product is incorporated into white detergents.
  • the novel procedure for preparing the aforesaid new crystalline material involves heating, at a temperature between about and 200 C, amorphous disodium 4,4'-bis (4-anilinomorpholino-s-triazin-Z-ylamino)-2,2-stilbenedisulfonate with one-half to five molecular proportions of aniline or morpholine in an aqueous medium having an initial pH of about 8 to 12 until approximately 80 to percent of the disodium 4,4'-bis(4-anilino-6-- morpholino-s-triazin-2-ylamino)-2,2-stilbenedisulfonate is in the form of crystalline needles.
  • the novel crystalline material is also characterized by a series objectionable feature that is, its unsuitability for use in detergent or laundering compositions, at low temperatures.
  • the whitening effect of practically all fluorescent whitening agents is substantially reduced at low temperatures.
  • low temperature whitening agents yield yellow speckles in detergent on recycling the detergent through the spray tower.
  • the present invention relates to new crystalline forms of 4,4'-bis[(4-anilino-6-morpholino-l,3,5- triazin-2-yl)-aminol-stilbene-2,g disulfonic m acid, cmmoNnossz, having the following chemical structural formula;
  • the new crystalline material possesses unusual and most surprising properties. Specifically, as indicated above, while the effectiveness of most fluorescent whitening agents is substantially reduced at low temperatures, the fluorescent whitening effect at low temperatures of the novel crystalline forms of 4,4-bis-[(4- anilino-o-morpholino-l ,3 ,5-triazin-2-yl)-amino]-stilbene-2,2'-disulfonic acid are substantially unaffected. In addition to the aforesaid unusual property of extremely high whitening effect at temperature, the novel crystalline material of the present invention is characterized by excellent bleach stability.
  • the novel crystalline material of the present invention does not yield yellow speckles.
  • the novel crystalline forms of 4,4'-bis[(4-anilino-6- morpholino-l ,3 ,5-triazin-2-yl)-amino]-stilbene-2,2 disulfonic acid possess the rare and most unusual combination of properties namely (1) detergent powder whitener, (2) excellent fluorescent whitening effects even when used at low temperatures, (3) excellent bleach stability and (4) freedom from formation of yellow speckles.
  • the present invention also includes within its scope the use of the aforesaid fluorescent whitening agent in detergents, soaps and other laundry products such as bleaches, softeners, and the like.
  • disulfonic acid disodium salt product is recovered, by conventional procedures and suitably, by filtration.
  • the product is then washed, acidified to a pH between about 2 and 6 and preferably between about 2 and 3.
  • the reaction involving the acidification of the disodium salt is illustrated as follows:
  • the starting materials used in preparing the novel product of the present invention are produced by known methods similar to those described, for example, in U.S. Pat. No. 2,762,801 or Swiss Pat. No. 321,109.
  • the procedure involves condensing 1 mol of disodium 4,4'diaminostilbene-2,2-disulfonate or alternatively, the free acid that is, 4,4'-diaminostilbene- 2,2'-disulfonic acid (DAS) with 2 mols of cyanuric chloride (CC) at a low temperature that is, at a temperature between about -l0 and C and preferably, between about 6 to +5C.
  • DAS 4,4'-diaminostilbene- 2,2'-disulfonic acid
  • CC cyanuric chloride
  • a suitable solvent and illustratively, methylethylketone, for cyanuric chloride is used in this step.
  • the resulting intermediate product, disodium 4,4-bis(4,6- dichloro-s-triazin -2ylamino)-2,2'-stilbenedisulfonate (CC/DAS) is then reacted with aniline (2 mol equivalent to 1 mol of DAS) at a temperature between about 5 and 50C and this step is followed by converting the remaining 2 chlorines in the 4,4'-bis- ⁇ 2"-phenylamino-4"-chloro-striazinyl-(6")-amino1-stilbene-2,2'-disulfonic acid by heating the reaction mixture at a temperature between about 50 and 90C with morpholine.
  • the above steps in the process are performed continuously that is, without isolating the intermediate products.
  • the novel step in the process involves acidifying the reaction mixture to obtain the desired product, i.e., 4,4'-bis[(4- anilino-fi-morpholino-l ,3 ,5-triazin-2-yl )-amino 1 stilbene-2,2 '-disulfonic acid.
  • the new crystalline forms of 4,4'-bis[(4-anilino-6- morpholino-l ,3 ,5triazin-2-yl)-amino]-stilbene-2,2 disulfonic acid are obtained either, as indicated above, by acidifying the reaction mixture to a pH ranging between about 2 and 6 and preferably, between about 2 and 3 or alternatively, following the reaction with morpholine, the resulting 4,4-bis[(4-anilino-6- morpholino-l ,3 ,5 -triazin-2-yl)-amino1-stilbene-2,2
  • the desired product precipitates our of solution and said product is then recovered by conventional means such as, for example, by filtration. On drying, the desired product is obtained in the form of a crystalline material.
  • novel crystaliine products of the present invention provide outstanding superior performance characteristics as compared with known fluorescent whitening agents since, the present compound provides the rare combination of unusually excellent detergent whitening ability coupled with excellent low temperature performance. ln addition to this unusual combination, the present novel crystalline material does not form yellow speckels in detergents on recycling the latter through the spray tower and further, the products of the present invention are also characterized by excellent bleach stability.
  • the crystalline material of the present invention is capable of going into solution at an extremely rapid rate and therefore can be drawn on to fibers at low temperatures that is, at temperatures between about 35 and 60 C. Since the present product is available to exhaust on to the fabric even at low temperatures, its effectiveness at cold water washing is essentially equivalent to that of warm water washing. Consequently, the present product is ideally suitable for use in household laundering.
  • Solid detergents including soaps and the like laundering compositions, to which the fluorescent whitening agents, according to the present invention, can be added at any step of their production
  • anionic detergents such as alkali metal salts of alkyl-aryl sulfonates especially alkyl-benzene and alkyl-naphthalene sulfonates, alkali metal salts of sulfates of higher fatty alcohol or alkali metal salts of higher fatty acids, in which the cation portion consists preponderantly of sodium ions.
  • anionic detergents such as alkali metal salts of alkyl-aryl sulfonates especially alkyl-benzene and alkyl-naphthalene sulfonates, alkali metal salts of sulfates of higher fatty alcohol or alkali metal salts of higher fatty acids, in which the cation portion consists preponderantly of sodium ions.
  • the present fluorescent whitener agent can also be included in nonionic detergent formulations and a typical formulation of this type is as follows:
  • the amount of fluorescent whitener agent added is usually at least about 0.1 percent up to about 1.0 by weight of the detergent, soap, softener, or like material.
  • the crystalline product of this example is characterized by an X-ray diffraction diagram having the following characteristic lines expressed in 2 9:
  • FIG. 1 The X-ray pattern for this crystalline material is shown in accompanying FIG. 1.
  • EXAMPLE I1 400 parts of water are heated, accompanied by agitation, at a temperature of 80C. To this solution is added a solution of parts of 4,4-bis-[(4-anilino-6- morpholino-1,3 ,5-triazin-2-yl)-amino]-stilbene-2,2'- disulfonic acid disodium salt dissolved in 400 parts of water; Concurrently, a 1.0 normal solution of hydrochloric acid in water is added at such a rate that the pH of the resultant solution is maintained at 6. After the addition of the brightener solution,the temperature is kept at 80C and the pH is maintained at 6 for an additional hour. The reaction mixture is then cooled to room temperature and filtered. The precipitate is washed with cold water to remove the salt and then dried at 100C in vacuum to obtain the desired crystalline product.
  • the crystalline product is characterized by an X-ray diffraction diagram having the following characteristic lines expressed in 2 0:
  • the crystalline product is characterized by an X-ray diffraction diagram having the following characteristic lines expressed in 2 0:
  • EXAMPLE IV 700 Parts by weight of cyanuric chloride are added to 6,000 parts by weight of methylethylketone and 6,000 parts by weight of icewater. A solution of 785 parts by weight of the sodium salt of 4,4'-diaminostilbene-2,2-disulfonic acid and 200 parts by weight of sodium carbonate in 6,000 parts by weight of water is poured, within 1 hour, accompanied by stirring, at a temperature of 0.5C into the cyanuric chloride suspension thus obtained. 353 parts by weight of aniline are added all at once and then the pH is held at 6-8 by the addition of 155 parts by weight of sodium hydroxide dissolved in 155 parts by weight of water.
  • the yellowish suspension is then stirred and heated to 50C until all the aniline has disappeared. 665 Parts by weight of morpholine are added and the reaction is heated, accompanied by agitation, to distill the methethylketone at a temperature of about 100C. The reaction mixture is allowed to cool to -90C and held at this temperature while 300 parts by weight of sulfuric acid (98 percent) are added, to a pH of 2-3 accompanied by agitation, within the one hour. The yellow slurry is cooled and the solid material is recovered by filtration.
  • the wet product is dried at 100C in vacuum to obtain the desired product, 4,4'-bis[(4- anilino-6-morpholino-l ,3 ,5-triazin-2-yl )-amino ]-stilbene-2,2'-disulfonic acid.
  • the crystalline product is characterized by an X-ray diffraction diagram identical with the product of Example 1 supra.
  • the detergent whitening characteristics of this product were examined.
  • the procedure used involved incorporating measured concentrations of the aforesaid whitener product into a typical anionic heavy duty detergent illustrated above by slurrying the detergent and whitener with about 1N NaOH until a smooth, homogeneous paste is obtained.
  • the paste is dried in a gravity convection oven at C and the resulting dried detergent cake is ground through a 20 mesh screen.
  • the powder is sieved through a 60 mesh screen and the fines are discarded.
  • the detergent powder is then allowed to stand overnight at about 85 percent relative humidity before color measurement.
  • the hue of the powder is measured on a Hunter Color Difference Meter, Model D-25, using L", a, and b units.
  • Example 1V SPECKLING As compared with other low temperature whiteners some of which are presently being sold, the crystalline material of Example 1V does not cause yellow speckling of detergent upon recycle of the detergent in spray drying operations.
  • the novel crystalline material of the present invention is superior to the dis- 8 odium 4,4'-bis(4-anilino-6-morpholino-s-triazin-2- ylamino)-2,2-stilbenedisulfonate disclosed in Canadian Pat. No. 783,566 in that the last mentioned compound is unsuitable for use as a whitening agent in detergent or laundering compositions at low temperatures.
  • the comparison data set out above clearly indicates the superiority of the crystalline material of the present invention both in detergent whitening, high and low temperature performance as well as bleach stability.
  • the X-ray patterns of the crystalline material referred to above were obtained by the well known pAowder technique described for instance, by Krug and lexander m -ray Diffraction Procedures for Polycrystalline and Amorphous Materials," published by John Wiley and Sons, New York, N.Y. (1954), especially on pages 235 et seq., using a Proportional- Counter equipped Goniometer made by N.V. Philips Gloeilampen Fabrieken, Eindhoven, Netherlands. The instrument does actually record the intensity of the diffracted ray along the vertical axis in relation to the diffraction angle 26 using CuK radiation.
  • the values given are accurate within 2 percent and in most cases, particularly with d values of less than 10 A, variation is less than 1 percent. Therefore, this variation should be taken into account when interpreting the specification and appendant claims.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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US00027587A 1970-04-13 1970-04-13 Process for preparing crystalline forms of 4,4'-bis[(4-anilino-6-morpholino-1,3,5-triazin-2-yl)-amino]-stilbene-2,2'-disulfonic acid Expired - Lifetime US3716532A (en)

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US (1) US3716532A (enrdf_load_stackoverflow)
CA (1) CA973181A (enrdf_load_stackoverflow)
DE (1) DE2117455A1 (enrdf_load_stackoverflow)
FR (1) FR2089425A5 (enrdf_load_stackoverflow)
GB (1) GB1301429A (enrdf_load_stackoverflow)
NL (1) NL7104795A (enrdf_load_stackoverflow)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5656760A (en) * 1994-09-21 1997-08-12 Ciba-Geigy Corporation Fluorescent whitening agents
EP1253191A1 (en) * 2001-04-27 2002-10-30 3V SIGMA S.p.A Detergent compositions

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1565202A (en) * 1975-07-25 1980-04-16 Hickson & Welch Ltd Aqueous dispersions of optical brighteners
GB1542907A (en) * 1976-09-20 1979-03-28 Procter & Gamble Activated perbleach detergent composition containing stilbene brightener
DE3064762D1 (en) 1979-09-21 1983-10-13 Procter & Gamble Washing and softening compositions and methods for their manufacture

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2612501A (en) * 1947-10-14 1952-09-30 Ici Ltd Triazine substances for textile treatment
FR1485673A (fr) * 1966-05-10 1967-06-23 Sterling Drug Inc Nouvelle forme cristalline du sel de sodium de l'acide 4, 4'-bis (4-anilino-6-morpholino-s-triazin-2-ylamino)-2, 2'-stilbènedisulfonique et son procédé de préparation
GB1093507A (en) * 1966-05-13 1967-12-06 Sterling Drug Inc Crystalline disodium 4, 4'-bis(4-anilino-6-morpholino-s-triazin-2-ylamino)-2, 2'-stilbene disulphonate
US3392122A (en) * 1964-02-24 1968-07-09 Sumitomo Chemical Co Washing agents containing optical brightening agents
US3532692A (en) * 1967-05-02 1970-10-06 Bayer Ag Brightening agents of the bistriazinylaminostilbene series
US3546218A (en) * 1966-06-29 1970-12-08 Geigy Chem Corp Substituted bis-triazinylamino stilbene compounds and compositions thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2612501A (en) * 1947-10-14 1952-09-30 Ici Ltd Triazine substances for textile treatment
US3392122A (en) * 1964-02-24 1968-07-09 Sumitomo Chemical Co Washing agents containing optical brightening agents
FR1485673A (fr) * 1966-05-10 1967-06-23 Sterling Drug Inc Nouvelle forme cristalline du sel de sodium de l'acide 4, 4'-bis (4-anilino-6-morpholino-s-triazin-2-ylamino)-2, 2'-stilbènedisulfonique et son procédé de préparation
GB1093507A (en) * 1966-05-13 1967-12-06 Sterling Drug Inc Crystalline disodium 4, 4'-bis(4-anilino-6-morpholino-s-triazin-2-ylamino)-2, 2'-stilbene disulphonate
US3546218A (en) * 1966-06-29 1970-12-08 Geigy Chem Corp Substituted bis-triazinylamino stilbene compounds and compositions thereof
US3532692A (en) * 1967-05-02 1970-10-06 Bayer Ag Brightening agents of the bistriazinylaminostilbene series

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5656760A (en) * 1994-09-21 1997-08-12 Ciba-Geigy Corporation Fluorescent whitening agents
EP1253191A1 (en) * 2001-04-27 2002-10-30 3V SIGMA S.p.A Detergent compositions

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NL7104795A (enrdf_load_stackoverflow) 1971-10-15
DE2117455A1 (de) 1971-11-04
CA973181A (en) 1975-08-19
GB1301429A (enrdf_load_stackoverflow) 1972-12-29
FR2089425A5 (enrdf_load_stackoverflow) 1972-01-07

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