US3817990A - Triazole brighteners - Google Patents

Triazole brighteners Download PDF

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Publication number
US3817990A
US3817990A US00047112A US4711270A US3817990A US 3817990 A US3817990 A US 3817990A US 00047112 A US00047112 A US 00047112A US 4711270 A US4711270 A US 4711270A US 3817990 A US3817990 A US 3817990A
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US
United States
Prior art keywords
triazole
compounds
styrylphenyl
amino
aminostilbene
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.)
Expired - Lifetime
Application number
US00047112A
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English (en)
Inventor
A Strobel
M Whitehouse
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GAF Corp
Original Assignee
GAF Corp
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Filing date
Publication date
Application filed by GAF Corp filed Critical GAF Corp
Priority to US00047112A priority Critical patent/US3817990A/en
Priority to GB2780171A priority patent/GB1331682A/en
Priority to GB465173A priority patent/GB1331683A/en
Priority to DE19712129855 priority patent/DE2129855A1/de
Priority to CH875571A priority patent/CH534729A/de
Priority to CA115,756A priority patent/CA963464A/en
Priority to FR7122000A priority patent/FR2099153A5/fr
Application granted granted Critical
Publication of US3817990A publication Critical patent/US3817990A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • 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
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/04—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles
    • C07D249/06—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles with aryl radicals directly attached to ring atoms

Definitions

  • Such later techniques i.e., those employing said fluorescent optical bleaching agents and/or brighteners can be performed either by, utilizing said fluorescent optical bleaching agents or brighteners either as additives to soap or detergent or used in the dye bath and/or in so-called melt incorporation techniques wherein said materials are incorporated into the plastic mass prior to shaping.
  • Said fluorescent optical bleaching agents perform the desired function by virtue of their characteristic absorption of ultraviolet radiation and the subsequent conversion of the energy to light energy within the visible spectrum. This converted and emitted energy within the visible spectrum tends to neutralize any yellowness of the material and thereby increases the, apparent whiteness thereof.
  • X represents hydrogen or a lower alkyl group such as methyl, ethyl, propyl and butyl
  • Y Y and Y represent hydrogen, lower alkyl such as methyl and ethyl, lower alkoxy, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec. butoxy, cyano, chloro and the like.
  • Y may be COOMe and SO Me
  • Y, and Y may be SO Me, wherein Me is hydrogen, ammonium, sodium or potassium.
  • the instant invention is directed to those 5-amino-2-( 4-styrylphenyl )-2H- 1 ,2,3-triazole-4- carboxamide compounds which have the formula:
  • the object of the instant invention is to provide a new class-of compounds which are either fluorescent pigments and/or brightening agents.
  • a further object of the-instant invention is to provide 2-(4-styrylphenyl)-2H-v-triazole[4,5-dlpyrimidin-7-ol compounds, which compounds are fluorescent pigments and, in addition, have brightening agent characteristics.
  • a still further object of the instant invention is to provide 5-amino-2-(4-styrylphenyl)-2l-l-1 ,2,3-triazole-4- carboxamides which compounds have brightening characteristics.
  • a still further object of the instant invention is to provide 5-amino-2-(4-styrylphenyl)-2H-1,2,3-triazole-4- carboxamide compounds which compounds are useful in the preparation of 2-(4-styrylphenyl)-2H-vtriazole[4,5d pyrimidin-7-ol compounds.
  • the instant invention is directed to 2- 4-styr'ylphenyl )-2H-v -triazole [4,5-d pyrimidin- 7-01 compounds which have the general fonnula:
  • those compounds without the above-noted solubilizing groups have been found to be particularly useful for mass application in connection with synthetic fibers. That is to say, that such compounds, i.e., those without I solubilizing groups, may be incorporated into the melt ments and as a result, they have specialized uses, particularly when they are dissolved in organic solvents, resin solutions, or ink formulations and applied to numerous bases for marking purposes. As a result of such application from solution said 2-(4-styrylphenyI)-2l-l-vtriazole[4,5-dlpyrimidin-7-ol compounds are useful in detecting, on exposure, ultraviolet light.
  • U.S. Pat. No. 2,543,333 discloses a 5-amino-2-( 4-styrylphenyl )-2H-v-triazole 4,5- dlpyrimidin compound. It is noted, however, that such compound in all instances is disclosed to have an amino group in the 5-position as distinguished from the subject compounds of the instant invention. Such an amino substituent has a bathochromic effect and hence the compounds disclosed in the above-noted patent will have their absorption maximum in the visible rather than the ultraviolet range. As a result, such a compound cannot be an effective brightening agent and, in fact, such compounds are disclosed to be useful .for effecting the growth of neoplasms and myelogenous leukemia. Therefore, while one might suspect that such compounds having such a structure would have fluorescent brightening properties, this is not supported by the above-noted disclosure.
  • the subject compounds of the instant invention and in particular the 5-amino-2-(4-styrylphenyl)-2H-l,2,3- triazole-4-carboxamide compounds may be prepared according to the following reaction scheme.
  • a molar quantity of cyanoacetic acid, lower alkyl ester, e.g., ethyl ester, and a molar quantity to about a 10 percent excess of a lower alkyl alcohol, e.g., ethyl alcohol, isopropyl alcohol, methyl alcohol and the like, are mixed preferably in an inert solvent and then cooled to from about above -l to +l0C. Hydrogen chloride gas is then passed into this mixture in molar quantity or up to an excess of about l0 percent and then the charge maintained at l0 to +l0C. usually for about 10-36 hours.
  • the B-amino-B-ethoxy-acrylic acid, ethyl ester, hydrochloride precipitates and is filtered, and washed with the organic solvent and/or alcohol.
  • a molar quantity of this product is then slurried with a lower aliphatic alcohol, e.g., ethyl alcohol, and ammonia gas is passed therethrough at about 20 35C. After precipitation is complete the malonamamidine hydrochloride is filtered, washed with ethyl alcohol and dried.
  • a lower aliphatic alcohol e.g., ethyl alcohol
  • a molar amount of a 4-aminostilbene is then diazotized in a known manner and combined with an approximately-molar amount, although an excess of either intermediate up to about l0 percent may be used, of the malonamamidine hydrochloride, at a temperature preferably of about 10 30C. It is desirable to warm the charge up to as high as about C; for several hours, before the charge is adjusted to very slight alkalinity (Pale Congo Blue) with sodium acetate or other suitable alkalizing agent. The charge is maintained at 40 50C for a suitable time, e.g., about 6 to 24 hours while maintaining the pH just to alkaline neutrality. The product is then filtered, washed and dried, thus producing (4-styrylphenyl)azomalonamamidine hydrochloride.
  • This azo dye is then oxidized in known manner to form a triazole by dissolving in a suitable solvent, usually pyridine or picoline with a small amount of water, and treating same with an excess of cupric salt, e.g., cupric chloride, cupric sulfate pentahydrate and the like.
  • a suitable solvent usually pyridine or picoline
  • cupric salt e.g., cupric chloride, cupric sulfate pentahydrate and the like.
  • This treatment is preferably carried out at elevated temperatures, at about C to the-reflux.
  • sodium sulfide is added to precipitate the copper salt, and said copper salt is filtered and washed with warm pyridine or picoline.
  • the filtrate is steam distilled, the residue cooled, filtered, washed with alcohol and dried.
  • the material may be sufficiently insoluble in the pyridine or picoline solution that it is precipitated and can be recovered by filtering without stripping off the solvent by evaporation.
  • a 5- amino-2-(4-styrylphenyl )-2H- 1 ,2,3-triazole-4- carboxamide is thus formed.
  • Said 5-amin0-2-( 4-styrylphenyl )-2l-l-l ,2,3-triazole-4- carboxamide is in and of itself a brightening agent. In addition, however, it may also be utilized in the formation of the subject 2( 4-styrylphenyl)-2H-vtriazole[4,5-d]pyrimidin-7-ol compounds according to the following reaction scheme.
  • the 5-amino-2-(4- styrylphenyl)-2H- 1 ,2,3-triazole-4-carboxamide formed above may be refluxed for approximately 2 10 hours in an excess of lower alkyl orthocarboxylate such as, for example, ethyl orthoforrnate in acetic anhydride.
  • the subject compounds' may also be prepared according to the general method disclosed in Hua Hsueh Hsueh Pao 30 (1) 8890 (1964),'described in Chemical Abstracts 38, l865g. According to the method disclosed therein, a 4amino-6-hydroxypyrimidine is coupled with 4-aminostilbene diazo and oxidized in boiling pyridine or picoline to give a 2-(4-styry1phenyl)-2H-vtriazole[4,5-Cllpy imidin-7-ol compound.
  • EXAMPLE 1 5-amino-2-(4-styrylphenyl)-2H-1,2,3-triazole-4- carboxamide was prepared as follows. Step 1 Preparation of B-amino-B-ethoxyacrylic acid, ethyl ester, hydrochloride.
  • drochloric acid (36.5 percent HCl).
  • the charge was covered and heated on a steam bath for 1 hour, stirring occasionally.
  • the steam bath was replaced by an ice bath and the beaker was fitted with stirrer, thermometer and dropping funnel.
  • To the diazo solution was added a solution of 52.8 g. malonamamidine hydrochloride (0.384; mole) in cc. water. The charge was stirred at room temperature for l hour and then at 40 45C for 4 hours.
  • EXAMPLE 3 The steps of Examples 1 and 2 were repeated with the exception that the 0.348 mole of 4-aminostilbene was replaced by 0.348 mole 4-methoxy-4- aminostilbene.
  • the azo dye resulting from 3,4-[4- (methoxystyryl)phenyllazomalonamamidine hydrochloride, had a m.p. l92.0-200C., and an A,,,,,, 74.3 at 410 mp.
  • the triazole product which resulted from step 4 was 5-amino-2-[4-(4-methoxystyryl)phenyll- 2H-l,2,3-triazole-4-carboxamide.
  • the resultant 2-[4- (4-methoxystyryl )phenyl l -2H-v-triazole[ 4,5- dlpyrimidin-lol thus produced has a m.p. 352355C.
  • EXAMPLE 4 The steps of Examples 1 and 2 were repeated with the exception that 0.348 moles of 4-aminostilbene was replaced 'by 0.348 moles of 4-amino-4'-chloro-2- cyanostilbene.
  • 2-[4-(4-chlorostyryl-2- cyanophenyl)l-2H-v-triazolo[4,5-dlpyrimidin-7-ol was prepared which had a melting point of 355-356.4C and an A,,,,, of 128.1 at 352 mu. 1
  • EXAMPLE 5 The steps of Examples 1 and 2 were repeated with the exception that the 0.348 mole 4-aminostilbene was substituted by 0.348 mole 4-amino-Z-stilbenesulfonic acid.
  • the 2-[4-styryl-(3-sulfophenyl)]-5-amino- 2H,1,2,3,-triazole-4-carboxamide which resulted had an A,, 96.4 at 352 mu.
  • the 2[4-styryl-(3- sulfophenyl) l-21-l-v-triazole[4,5-d pyrimidin-7-ol had an A 89.9 at 348 mu.
  • EXAMPLE 8 50 milligrams of the 4-(styrylphenyl)-5-amino- 2H,1,2,3,-triazolecarboxamide was dissolved in moles of dimethylformamide. 1.0 ml. of the resulting solution was added to mls. of 0. 1% Peregal 0." solution (commercially available ethylene oxide condensation product) as a dispersing agent. This total formulation was poured into a launderometer jar together with a 5.0 gram swatch of cellulose acetate fabric together with 10 steel balls. The material was heated at 200F for 45 minutes. The swatch was removed, rinsed and dried. A comparison of this piece of cloth against a piece similarly treated, with the exception that no brightening compound was added, visibly showed an improved brightness of the treated cloth.
  • EXAMPLE 1O Marking inks, luminescent under ultraviolet light, were prepared by milling differing amounts of the compound of Example 2 into a commercial ink vehicle. Markings were made from this ink on linoleum and other floor-covering materials and the samples were exposed to ultraviolet light. These samples showed intense fluorescence of a yellow-green hue.
  • X is selected from the group consisting of a hydrogen and a lower alkyl
  • Y and Y are selected from the group consisting of hydrogen, lower alkyl, lower alkoxy, cyano, halogen, and SO Me
  • Me is selected from the group consisting of hydrogen, ammonium, sodium or potassium
  • Y is selected from the group consisting of hydrogen, lower alkyl, lower alkoxy, cyano, halogen, COOMe and SO Me, wherein Me is selected from the group consisting of hydrogen, ammonium, sodium and potassium.
  • dIpyrimidin-7-ol Compound of claim 1 wherein said compound is 2-[4-(4-methoxystyryl)phenyll-2H-v- 5 triazolo[ 4,5-d Py imidin-7-0l.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Luminescent Compositions (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
US00047112A 1970-06-17 1970-06-17 Triazole brighteners Expired - Lifetime US3817990A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
US00047112A US3817990A (en) 1970-06-17 1970-06-17 Triazole brighteners
GB2780171A GB1331682A (en) 1970-06-17 1971-03-30 Triazole derivatives
GB465173A GB1331683A (en) 1970-06-17 1971-06-14 Trizaole derivatives
DE19712129855 DE2129855A1 (de) 1970-06-17 1971-06-16 Neue Styrole und ihre Verwendung als optische Aufheller
CH875571A CH534729A (de) 1970-06-17 1971-06-16 Fluoreszierendes Mittel für Markierungszwecke
CA115,756A CA963464A (en) 1970-06-17 1971-06-16 4-styrylphenyl-triazole (4,5-d) pyrimidin-7-ol compounds
FR7122000A FR2099153A5 (enExample) 1970-06-17 1971-06-17

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US00047112A US3817990A (en) 1970-06-17 1970-06-17 Triazole brighteners

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US3817990A true US3817990A (en) 1974-06-18

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US00047112A Expired - Lifetime US3817990A (en) 1970-06-17 1970-06-17 Triazole brighteners

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US (1) US3817990A (enExample)
CA (1) CA963464A (enExample)
CH (1) CH534729A (enExample)
DE (1) DE2129855A1 (enExample)
FR (1) FR2099153A5 (enExample)
GB (2) GB1331682A (enExample)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4113937A (en) * 1977-03-25 1978-09-12 Ciba-Geigy Corporation Stilbene compounds
US4302586A (en) * 1979-01-19 1981-11-24 Ciba-Geigy Corporation V-Triazolyl-[4,5-d]-pyrimidines
WO2005093007A1 (de) * 2004-03-23 2005-10-06 Basf Aktiengesellschaft Triazolderivate und verwendung von triazolderivaten in organischen leuchtdioden (oleds)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2543333A (en) * 1950-02-02 1951-02-27 American Cyanamid Co Derivatives of upsilon-triazolo (d) pyrimidine and methods of preparing the same
US3222371A (en) * 1962-04-19 1965-12-07 American Cyanamid Co Pyridotriazole brighteners
US3453268A (en) * 1966-01-18 1969-07-01 Bayer Ag Substituted v-triazolyl-2-stilbenes and their use for brightening materials
US3459744A (en) * 1965-01-09 1969-08-05 Bayer Ag V-triazole-(2)-stilbenes

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2543333A (en) * 1950-02-02 1951-02-27 American Cyanamid Co Derivatives of upsilon-triazolo (d) pyrimidine and methods of preparing the same
US3222371A (en) * 1962-04-19 1965-12-07 American Cyanamid Co Pyridotriazole brighteners
US3459744A (en) * 1965-01-09 1969-08-05 Bayer Ag V-triazole-(2)-stilbenes
US3453268A (en) * 1966-01-18 1969-07-01 Bayer Ag Substituted v-triazolyl-2-stilbenes and their use for brightening materials

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Richter et al., J. Am. Chem. Soc., Vol. 78, pp. 5848 5852, (1956). *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4113937A (en) * 1977-03-25 1978-09-12 Ciba-Geigy Corporation Stilbene compounds
US4302586A (en) * 1979-01-19 1981-11-24 Ciba-Geigy Corporation V-Triazolyl-[4,5-d]-pyrimidines
WO2005093007A1 (de) * 2004-03-23 2005-10-06 Basf Aktiengesellschaft Triazolderivate und verwendung von triazolderivaten in organischen leuchtdioden (oleds)
US20070188078A1 (en) * 2004-03-23 2007-08-16 Basf Aktiengesellschaft Triazole derivatives and use thereof in organic light-emitting diodes (oleds)
US7750556B2 (en) 2004-03-23 2010-07-06 Basf Aktiengesellschaft Triazole derivatives and use thereof in organic light-emitting diodes (OLEDs)

Also Published As

Publication number Publication date
CH534729A (de) 1973-03-15
GB1331683A (en) 1973-09-26
CA963464A (en) 1975-02-25
FR2099153A5 (enExample) 1972-03-10
GB1331682A (en) 1973-09-26
DE2129855A1 (de) 1971-12-23

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