Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
  • C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
  • C07D249/18—Benzotriazoles
  • C07D249/20—Benzotriazoles with aryl radicals directly attached in position 2

Definitions

• This invention relates to new, useful and outstanding stilbene triazole compounds, and in particular, di-substituted oxy benzotr-iazolyl stilbenesulfonic acid compounds with their outstanding optical brighteners or whitening agents.
• brightening agents for use in laundering operations in conjunction with the conventional detergents are generally characterized by the pres ence of ionic or water-solubilizing groups which are preferably sulfonic acid groups in order to obtain the necessary afiinity for the cotton material.
• ionic or water-solubilizing groups which are preferably sulfonic acid groups in order to obtain the necessary afiinity for the cotton material.
• Such compounds may or may not also be eliective with other synthetic textile fibers such as nylon and acetate rayon and the like, and while this is obviously desirable in many instances, such ionic brighteners which are useful with cotton may only be partially satisfactory with nylon and the like.
• N 0H (F) in which R is selected from the group consisting of hydrogen, chloro, bromo and lower alkyl.
• oXy benzotriazole brighteners have unique brightness strength on cotton from non-ionic detergent baths in the presence of hypochlorite. For instance, only half as much of H H o01n l OCHa S O Na N (A) is required to produce the same whitening effect on cotton from commercial Ad and All, both non-ionic detergents, in the presence of sodium hypochlorite as of the most widely used commercial product:
• nonsulfonated, mono-sulfonated, di-sulfonated, are trisu'lfonated brightener from all the mono-triazole, ditriazole, bis-benzoxazole, bis-benzimidazole, stilbeneamine-cyanuric amide, stilbene amine-benzoylamide, pyrazoline, coumarin, etc. classes which has anywhere near equal whitening power from non-ionic detergents with sodium hypochlorite on cotton.
• the new brightening compounds of this invention have the following general formula:
• R and R are independently lower alkyl, and preferably alkyl of 1 to 4 carbon atoms, carboxy lower alkyl and preferably carlboxy methyl, or together R and R may be methylene; m and n have the values 0 or and the sum of m: and n is 1 or 2; M is hydrogen or a saltforming cation, preferably an alkali metal (sodium, potassium or lithium and the like), ammonium, or substituent ammonium such as an amine and the like.
• the preferred compounds are those containing one sulfo group, and this preferably in the benzene ring of the stilbene moiety remote from the triazole ring.
• the most preferred compounds are those having the following formula:
• R R and M are as defined above.
• novel compounds of this invention are characterized by excellent fiber substantivity, particularly for cellulosic and similar hydrophilic fibers, and esthetically desirable hue, an outstanding apparent whiteness, excellent resistance to bleaching agents such as chlorine, and extremely excellent light fastness characteristics. While the compounds are most preferred for use in detergent systems for application to the textile during laundering operations, the compounds may, nevertheless, be employed using techniques for incorporation into organic material.
• the compounds may be added to spinning solutions of cellulose acetate, they may be used to impregnate paper, they may be incorporated into paper by addition to the pulp in the beater stage or at any point prior to the drying of the paper, and they may, in general, be added to waxes, gums, resins and the like to effect a whitening thereof.
• the compounds of this invention are prepared generally in the conventional manner known to the art which involves coupling a diazotized sulfo stilbene to the selected substituted dioxyaniline compound and thereafter oxidizing the resultant azoamino compound to the corresponding triazole.
• the procedure for the latter oxidation may vary depending upon the choice of the oxidizing agent.
• the resultant by-products of such reagent may be removed by adjustment of the pH of the solution, i.e., the reduction products of the oxidizing agents may be solubilized by making the solution more acidic, so that the by-products are removed in the filtrate by a filtration step.
• the lay-products may be removed in the filtrate by making the reaction medium alkaline with ammonia (pH 11) prior to filtration.
• metallic (ic-ous ozidizing agents such as copper sulfate, ferric chloride, ferric NH SO do
• metallic (ic-ous ozidizing agents such as copper sulfate, ferric chloride, ferric NH SO do
• hydrogen peroxide KMnO K Cr O CaCOl
• Na perborate oxygen, etc.
• the general procedure for testing the compounds is as follows. 50 mg. of brightener compound is dissolved in 10 ml.
• i SO3NB yields a product with a brightness value of 66.
• Example 3 Example 2 is repeated except that in place of All, the detergent employed is Alfionol, a biodegradable nonionic compound based on the reaction of ethylene oxide and an aliphatic alcohol.
• the brightener of Example 1 gave a reading of 68 when used at a concentration of 0.0032% based on the weight of the fiber whereas the commercial brightener (i.e., the sulfostilbylnaphthotriazole shown in Example 2) gives a brightness value of 59 at a concentration of 0.0064% (based on the weight of the fiber).
• the commercial brightener i.e., the sulfostilbylnaphthotriazole shown in Example 2 gives a brightness value of 59 at a concentration of 0.0064% (based on the weight of the fiber).
• Example 4 and the resultant swatch has a brightness value of 65.
• Example 5 Example 2 is again repeated employing the compound of Example 1 at the same concentration used in Example 2 and in place of the commercial brightener comparison of Example 2, there is used 0.0064% based on the weight of the fiber of the compound of the formula:
• Example 2 N ooH3 NHCOCH S OaNa N/ which compound is described in Example 4 of US. Patent 2,713,057.
• the All of Example 2 is replaced by Tide (anionic alkyl aryl sultonate).
• the swatch laundered with the compound of Example 1 has a brightness of 87 whereas the swatch laundered with the com- 8 pound of Example 4 of US. Patent 2,713,057 has a value of 32.
• This compound is prepared in the manner of Example 1 with the exceptions that the 4-amino-Z-stilbenesulfonic acid is replaced by 4-amino-2-stilbenesulfonic acid and the 3,4-dimethoxyaniline is replaced by 19 g. 3,4-methylenedioxyaniline.
• the brightener is then produced in the manner of Example 1 with the exception that the 3,4- dimethoxyaniline is replaced by 14.9 g. of 3-amino-6- methoxyphenoxyacetic acid.
• the 3,4- dimethoxyaniline is replaced by 14.9 g. of 3-amino-6- methoxyphenoxyacetic acid.
• Example 11 Preparation of stilbenedisulfonic acid. When applied to cotton in the manner of Example 1, excellent results are obtained.
• Example 12 Example 6 is repeated except that 4'-amino-2-stilbenesulfonic acid is replaced by 4-amino-2-stilbenesulfonic acid. Excellent results are obtained when applied to cotton following the procedure of Example 1.
• Example 13 Example 11 is repeated except that the 3,4-dimethoxyaniline is replaced by 3-methoxy-4-ethoxyaniline. Excellent results are obtained when applied to cotton by the procedure of Example 1.
• Example 14 The preceding example is further repeated except that in place of the aniline thereof, an equivalent weight of 3,4-methylene dioxyaniline is employed.
• Example 15 The preceding example is further repeated except that the aniline compound used is an equivalent weight of 1,2-(4-aminophenylene)bisoxy acetic acid.
• Example 16 The procedure of Example 9, is repeated except that in place of the stilbenesulfonic acid of that example, an equivalent amount of 4-amino-2,2'-stilbenedisulfonic acid is used.
• the compounds of this invention may be used generally for brightening cellulosic materials and cellulose derivative materials as well as other textile products also.
• the compounds may further be employed with any organic substrate to improve the brightness thereof.
• the amount of brightener to be used is not critical, and may be varied Within wide limits. As little as 0.001% has been found to give eifective results with the upper limit being goverened solely by practical considerations of compatibility and price. In general, it has been found that no more than by weight based on the weight of organic material is necessary under the most adverse con ditions.
• the compounds of this invention are used in conjunction With detergent products, it is advantageous to employ the brighteners in amounts ranging from about 0.1% to about 3% by weight thereof based on the weight of the detergent material.
• R and R together are methylene; m and n have values from 0 to 1 and the sum of m .and rt is at least 1; M is a member selected from the group consisting of hydrogen and a salt-forming cation.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Detergent Compositions (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Coloring (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Priority Applications (7)

Applications Claiming Priority (1)

Publications (1)

Family

ID=23711957

Family Applications (1)

Country Status (6)

Citations (3)

• 1965
  • 1965-02-09 US US431442A patent/US3410847A/en not_active Expired - Lifetime
• 1966
  • 1966-01-27 DE DE1695057A patent/DE1695057C3/de not_active Expired
  • 1966-01-28 CH CH120966A patent/CH478281A/de not_active IP Right Cessation
  • 1966-01-31 GB GB4205/66A patent/GB1141921A/en not_active Expired
  • 1966-02-04 ES ES0322605A patent/ES322605A1/es not_active Expired
  • 1966-02-08 NL NL6601562A patent/NL6601562A/xx unknown

Patent Citations (3)

Also Published As

Similar Documents