US2715630A - Fluorescent whitening agents - Google Patents

Fluorescent whitening agents Download PDF

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Publication number
US2715630A
US2715630A US469293A US46929354A US2715630A US 2715630 A US2715630 A US 2715630A US 469293 A US469293 A US 469293A US 46929354 A US46929354 A US 46929354A US 2715630 A US2715630 A US 2715630A
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parts
acid
amino
compound
water
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US469293A
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Inventor
Sartori Mario Francesco
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EIDP Inc
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EI Du Pont de Nemours and Co
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Priority to BE533344D priority Critical patent/BE533344A/xx
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to US469293A priority patent/US2715630A/en
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Publication of US2715630A publication Critical patent/US2715630A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings

Definitions

  • an agent to be commercially successful must be capable of being synthetized economically from readily available materials, and must have suflicient fluorescent power (often referred to as tinctorial strength?) to give the desired eflect at a minimum cost. It is also desirable that the agent should have good build-up qualities; in other words, repeated treatments with a bath of the same concentration, should continually increase the whiteness of the treated fabric, up to a maximum.
  • the agent must also have aflinity for the fiber that is to be treated and must possess sufficient Water-solubility to be applicable from an aqueous bath in the concentrations that would normally be used.
  • novel compounds of my invention may be defined by the general formula XII wherein Y designates a member of the group consisting of O, S and NH (oxygen, sulfur and the mine radical), X is a sulfo group, while n stands for an integer not greater than 2.
  • These compounds may be synthesized by tetrazotizing a member of the group consisting of 6-amino-2(p- .aminophenyl) benzoxazole, 6-amino-2(p-aminophenyl) benzthiazole and 6-amino-2(p-aminophenyl benzimidazole, then coupling in acid medium to two moles of an aminonaphthalene monoor di-sulfonic acid wherein the NH2 group is located in one of the positions 1 and 2 while the other of said two positions is free, and oxidizing the resulting bis-orthoaminoazo compound to the corresponding di(naphthotriazole) derivative.
  • the latter step may be achieved by heating the bisorthoaminoazo compound in an aqueous solution of cupric ammonium sulfate or of sodium hypochlorite until the color of the intermediate disazo dye has disappeared.
  • the product is then recovered in the desired physical or chemical form, for instance in the form of its sodium, potassium or ammonium salt.
  • aqueous reaction mass prior to salting out of the final product, contains residual color, the latter may be destroyed by treating the reaction mass with dilute hypochlorite solution or with a decolorizing charcoal.
  • l-aminonaphthalene-4-sulfonic acid (naphthionic acid); l-aminonaphthalene-5-sulfonic acid, (Laurents acid); l-aminonaphthalene-4,6-disulfonic acid; l-aminonaphthalene-4,7-disulfonic acid; l-aminonaphthalene-4,8-disulfonic acid; l-aminonaphthalene-S,S-disulfonic acid; 2-aminonaphthalene-4-sulfonic acid; 2-aminonaphthalene-6-sulfonic acid, (Broenners acid); 2-aminonaphthalene-3,6-disulfonic acid, (amino-R acid); Z-aminonaphthalene-4,8-disulfcnic acid; Z-aminonaphthalene-5,7-disulfonic acid, (amino-J-acid);
  • Example 1 4.5 parts (0.02 mol) of 6-amino-2(p-aminophenyl) benzoxazole were tetrazotized in diluted hydrochloric acid, and the resulting tetrazo compound was coupled with 9.8 parts (0.04 mol) of Broenners acid sodium salt. The acidity was adjusted to slightly acid on Congo Red paper by the addition of sodium acetate. ⁇ Vhen the coupling was completed, the mixture was made alkaline to Brilliant Yellow paper by the addition of 30% sodium hydroxide, and the disazo dye was salted out and filtered ofi.
  • the obtained wet dye was slurried in 200 parts of water at 60 C.
  • reaction mass was filtered.
  • the cake was slurried in water, treated with an excess of sodium sulfide solution (as shown by test with lead acetate paper), boiled a few minutes and filtered hot.”
  • the filtrate was decolorized with an aqueous solution of sodium hypochloride, and the product was salted out with sodium chloride. It was a pale tan powder, soluble 'in water with blue fluorescence.
  • the absorption maximum of this compound in-aqueous solution is located at 375 millimicrons.
  • the product i builds up to a strong White when applied to cellulosic textiles in serial Washes in the presence of a soap or detergent.
  • Example 3 W Y 5.6 parts (0.025 mol) of 6-amino-2(p-aminophenyl) benzimidazole [Kym, 0., Ber. 32, 2180 (1899)] were tetrazotized in dilute hydrochloric acid, and the resulting tetrazo compound was coupled with 12.5 parts (0.05 mol) of napthionic acid sodium salts The further details of coupling and isolation were as in Example 1.
  • the wet dye was slurried in 500 parts of water at 60 C.
  • the final product was a light tan powder soluble in water with bluish fluorescence. The absorption maximum of this compound in aqueoussolution is located at 373' millimicrons.- Its'properties are similar to those of-the product of Example 3.
  • Example 5 2.4 parts 0.01 mol) of 6 -amino-2(p-arninophenyl) benzothiazole were tetrazotized in dilute hydrochloric acid and the resulting .tetraz o compound was coupled with 4.9 parts (0.02 mol) of naphthionie acid sodium salt, and followed by further treatment and isolation as in Example 1.- i V a
  • the obtained wet dye was slurried in 300'parts of water at60 C. A solution of 10 parts of CuSO4-5H2O in parts of water and parts of 28% aqueous ammonia was added. The mixture-was thenheated to reflux for 24 hours and thereafter filtered hot and washed.
  • the wet cake was slurried in 200 parts of dilute hydrochloric acid (10%) and the slurry was boiled for '1 hour and filtered hot. The obtained cake was washed with hot water and After further treatment and isolation as in Example 1, a light yellow powder was obtained, which was soluble intwater with blue fluorescence. The absorption maximum of this compound in aqueous solution is located at 385 millimicrons.
  • the end product is considered to have the formula:
  • 6-arnino-2-(p-ami! lopheriyll benzothiazole was obtained by' nitrating Z-(p-nitrophenyl) benzothiazole, according to the process described by Bogert, M. T. in I. Am. Chem. Soc. 44, 832 (1922) for the preparation of 6-nitro-2-phenylbenzothiazole.
  • the 6-nitro-2-(p-nitrophenyl) benzothiazole thus obtained was reduced to the desired product by treatment with stannous chloride and hydrochloric acid, as described by Rivier, 1-1., in Helv. Chim. Acta 20, 703 (1937) for the preparation of 6-amino-2-phenylbenzothiazole.
  • the products obtained in the above examples have been isolated as the sodium salts of the sulfonic acids.
  • potassium hydroxide and potassium salts in lieu of sodium hydroxide and sodium salts, throughout, the products may be obtained as potassium sulfonates. Isolation as the free sulfonic acids can be effected by acidification of the condensation mass, and the products thus obtained may be reacted with ammonium hydroxide or any suitable organic or inorganic base, to yield the corresponding salts.
  • Cotton cloth was entered into an aqueous bath containing a heavy duty detergent in quantity corresponding to 0.15% of the Weight of the cloth, and 10 parts of the fluorescent agent per million parts of cloth.
  • the heavy duty detergent was a commercial detergent composed, by weight, of approximately of the active ingredient (i. e., a long chain alkyl aryl sulfonate), 2% of carboxy methyl cellulose and 68% of sodium polyphosphate. After stirring at 130 F. for 20 minutes, the cloth was removed from the bath, rinsed and dried. The fluorescence of the cloth thus treated was measured by spectrophotometric methods. Then the same cloth was subjected to four additional, identical treatments.
  • the practical merits of my invention will now be readily apparent.
  • the compounds of this invention are suitable for incorporation into soap or synthetic detergents, and endow a fluorescent or whitening eflect to cotton fabric laundered with such soap or detergent.
  • my novel compounds may also be used fo various other purposes where fluorescence or absorption of ultra-violet light is desirable, for instance to achieve novel effects on photographic paper, as ultraviolet filters when impregnated on cellulosic films which are used for wrapping materials, etc.
  • R is the 6,4'-radical of Z-phenyl-benzimidazole, while each Q is a l,2-naphthylene radical carrying a sulfo group in the 6-position.
  • a compound of the formula lF-NR-N-1fi1' Q Q wherein R is the 6,4-radical of 2-phenyl-benzothiazole, while each Q is a 1,2-naphthylene radical carrying a sulfo group in the 4-position.
  • the process of producing a fluorescent agent of bluish fluorescence and good bleach-fastness which comprises coupling a tetrazotized diamine selected from the group consisting of 6-amino-2(p-arninophenyl) benzoxazole, 6-amino-2(p-arninophenyl) benzthiazole and 6- amino-2(p-aminophenyl) benzimidazole to two molecules of an aminonaphthalene sulfonic acid of the formula wherein one of the members Z, Z is NHz while the other one is hydrogen, X is a sulfo group and n is a numeral not greater than 2, and oxidizing the resulting bis-orthoarninoazo compound to produce the corresponding bistriazole.
  • a tetrazotized diamine selected from the group consisting of 6-amino-2(p-arninophenyl) benzoxazole, 6-amino-2(p-arninophenyl) benzthi

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US469293A 1954-11-16 1954-11-16 Fluorescent whitening agents Expired - Lifetime US2715630A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
BE533344D BE533344A (enrdf_load_stackoverflow) 1954-11-16
US469293A US2715630A (en) 1954-11-16 1954-11-16 Fluorescent whitening agents

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1047163B (de) * 1957-08-14 1958-12-24 Bayer Ag Optische Aufhellungsmittel
US4000148A (en) * 1974-11-14 1976-12-28 Eastman Kodak Company Polychromophoric heterocyclic ultraviolet stabilizers and their use in organic compositions
US20120307344A1 (en) * 2011-05-30 2012-12-06 Boe Technology Group Co., Ltd. Electronic paper display device and displaying method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1047163B (de) * 1957-08-14 1958-12-24 Bayer Ag Optische Aufhellungsmittel
US4000148A (en) * 1974-11-14 1976-12-28 Eastman Kodak Company Polychromophoric heterocyclic ultraviolet stabilizers and their use in organic compositions
US4065427A (en) * 1974-11-14 1977-12-27 Eastman Kodak Company Polychromophoric heterocyclic ultraviolet stabilizers and their use in organic compositions
US20120307344A1 (en) * 2011-05-30 2012-12-06 Boe Technology Group Co., Ltd. Electronic paper display device and displaying method

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Publication number Publication date
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