CH356435A - Process for the preparation of an optical brightening agent - Google Patents
Process for the preparation of an optical brightening agentInfo
- Publication number
- CH356435A CH356435A CH356435DA CH356435A CH 356435 A CH356435 A CH 356435A CH 356435D A CH356435D A CH 356435DA CH 356435 A CH356435 A CH 356435A
- Authority
- CH
- Switzerland
- Prior art keywords
- parts
- aryl radical
- brightening agent
- preparation
- optical brightening
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 6
- 230000003287 optical effect Effects 0.000 title claims description 4
- 238000005282 brightening Methods 0.000 title description 3
- 150000005840 aryl radicals Chemical group 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 239000007850 fluorescent dye Substances 0.000 claims description 5
- GTBIOFHVLDFRDA-UHFFFAOYSA-N 4-(5-phenyl-1,3-dihydropyrazol-2-yl)benzoic acid Chemical compound C(=O)(O)C1=CC=C(C=C1)N1NC(=CC1)C1=CC=CC=C1 GTBIOFHVLDFRDA-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001555 benzenes Chemical class 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 239000000344 soap Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- OCGXIMRXKNSVSN-UHFFFAOYSA-N 4-[5-(4-chlorophenyl)-1,3-dihydropyrazol-2-yl]benzoic acid Chemical compound C(=O)(O)C1=CC=C(C=C1)N1NC(=CC1)C1=CC=C(C=C1)Cl OCGXIMRXKNSVSN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 125000004494 ethyl ester group Chemical group 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- XHLQMKQBCHYRLC-UHFFFAOYSA-N 4-hydrazinylbenzoic acid;hydron;chloride Chemical compound Cl.N[NH2+]C1=CC=C(C([O-])=O)C=C1 XHLQMKQBCHYRLC-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- -1 aryl hydrazines Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- QEYMMOKECZBKAC-UHFFFAOYSA-N 3-chloropropanoic acid Chemical compound OC(=O)CCCl QEYMMOKECZBKAC-UHFFFAOYSA-N 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 125000004442 acylamino group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- DQFBYFPFKXHELB-UHFFFAOYSA-N chalcone Chemical compound C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Landscapes
- Plural Heterocyclic Compounds (AREA)
Description
Verfahren zur Herstellung eines optischen Auf hellungsmittels Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung eines optischen Aufhel- lungsmittels durch Zusatz einer fluoreszierenden Ver bindung zu einem Träger, dadurch gekennzeichnet, dass als fluoreszierende Verbindung ein farbloses oder nahezu farbloses Arylpyrazolin der Formel
EMI0001.0008
verwendet wird, in der Ar einen Arylrest, wie z. B.
Phenyl oder Naphthyl, X Wasserstoff oder einen Arylrest und Y eine freie oder funktionell abgewan delte Carboxylgruppe bedeuten, wobei der am Stick stoff gebundene Benzolkern und der am Kohlenstoff gebundene Arylrest auch weiter substituiert sein kön nen, z.
B. durch eine bzw. eine weitere Carboxyl- gruppe, durch Halogen, durch niedere Alkylgruppen, durch Hydroxyl-, Alkoxy-, Amino- oder Acylamino- gruppen; als funktionelle abgewandelte Carboxylgrup- pen kommen zum Beispiel deren Salze, Ester oder Amide in Betracht.
Die carboxylgruppenhaltigen Arylpyrazolinverbin- dungen können in mannigfacher Weise hergestellt worden sein, z. B. durch Einwirkung von carboxyl- gruppenhaltigen Arylhydrazinen auf co-Dialkylamino- arylketone, auf Vinylarylketone, wie z.
B. Benzalaceto- phenon, oder auf die Salze von Aminoäthylarylketo- nen. Die erfindungsgemäss hergestellten Aufhellungs- mittel können zur Aufhellung der verschiedenartigsten Materialien dienen, z. B. zum Aufhellen von Textil materialien, wie Cellulosefasern, Wolle oder synthe tischen Fasern, ferner zum Aufhellen von Papier und anderen mehr.
Sie eignen sich auch gut zum Aufhel len von Fasern, Folien oder anderen Gebilden aus Acrylnitrilpolymerisaten. Die Arylpyrazolinderivate können auch mit gutem Erfolg bei der Herstellung von fluoreszierenden Gebilden aus synthetischen Poly kondensaten gemäss dem Verfahren des schweiz. Patentes Nr. 354250 verwendet werden.
Die in den nachfolgenden Beispielen angegebenen Teile sind Gewichtsteile.
<I>Beispiel 1</I> In<B>10000</B> Teile einer für Seifenflocken geeigne ten Grundseife werden 1-3 Teile 1-p-CaTboxyphe- nyl-3-phenylpyrazolin in einer Mischvorrichtung vor dem Aufbringen auf dem Walzenstuhl eingearbeitet. Die bei der üblichen Weiterverarbeitung erhaltenen Seifenflocken vermögen Wäsche, die mit diesen Sei fenflocken gewaschen wird, hervorragend aufzuhellen.
Anstelle von 1-p-Carboxyphenyl-3-phenylpyrazo- lin kann man auch das Natriumsalz oder den Äthyl- ester verwenden.
Das Salz, die freie Säure bzw. ihr Äthylester kön nen in folgender Weise hergestellt werden: 120 Teile Acetophenon werden mit 55 Teilen Ammoniumehlorid .und 155 Teilen 30 o/oigem Form aldehyd im siedenden Wasserbad unter Rühren und Rückfluss 1 Stunde erhitzt. Die untere Schicht wird abgetrennt und mit einer Lösung von 152 Teilen p-Hydrazinobenzoesäurehydrochlorid und 204 Teilen wasserfreier Soda in 1400 Teilen Wasser unter Rüh ren 3 Stunden zum
Sieden erhitzt. Es fällt dann das Natriumsalz des 1-p-Carboxyphenyl-3-phenylpyrazo- lins aus. Durch Zugabe von Salzsäure zu der Suspen sion des Natriumsalzes in Wasser lässt sich die freie Säure vom Schmelzpunkt 244 gewinnen.
Zur Herstellung des Äthylesters werden 125 Teile des so erhaltenen Salzes bzw. der Säure in 750 Teilen Alkohol suspendiert und bei 30-40 langsam mit 75 Teilen Thionylchlorid versetzt. Nach etwa 7stün- digem Kochen unter Rückfluss wird die Reaktions lösung heiss filtriert. Aus dem Filtrat kristallisiert dann der Ester aus, der nach nochmaliger Umkristallisation aus Alkohol einen Schmelzpunkt von 112 zeigt.
<I>Beispiel 2</I> Einer etwa 80 % Fettsäure enthaltenden Grund- seife werden in der Mischapparatur vor der Polier maschine pro 100 Teile unter Rühren 0,01-0,03 Teile 1-p-Carboxyphenyl-3-p-chlorphenylpyrazolin zu- gesetzt. Textilmaterialien, die mit einer solchen Seife gewaschen sind, zeigen ein brillantes Weiss.
Das verwendete 1-p-Carboxyphenyl 3-p-chlorphe- nylpyrazolin kann in folgender Weise hergestellt wer den: 54 Teile ss-Chlorpropionsäure werden mit 77,5 Teilen Thionylchlorid 11/2 Stunden auf dem Wasser bad unter Wasserausschluss erhitzt; dann lässt man das Reaktionsgemisch zu einem Gemisch von 81 Teilen Aluminiumchlorid und<B>170</B> Teilen trockenem Chlor benzol zufliessen.
Nach 24stündigem Stehen wird die Mischung auf Eis-Salzsäure ausgetragen; die Chlor benzoischicht wird abgetrennt und mit 95 Teilen p- Hydrazinobenzoesäurehydrochlorid, 80 Teilen Pyridin und 750 Teilen Methanol 2 Stunden unter Rückfluss zum Sieden erhitzt. Das so gebildete 1-p-Carboxy- phenyl-3-p-chlorphenylpyrazolin zeigt einen Schmelz punkt von 270-272 .
Process for producing an optical brightening agent The present invention relates to a process for producing an optical brightening agent by adding a fluorescent compound to a carrier, characterized in that the fluorescent compound is a colorless or almost colorless arylpyrazoline of the formula
EMI0001.0008
is used in which Ar is an aryl radical, such as e.g. B.
Phenyl or naphthyl, X is hydrogen or an aryl radical and Y is a free or functionally altered carboxyl group, the benzene nucleus bonded to the stick material and the aryl radical bonded to the carbon can also be further substituted, e.g.
B. by one or a further carboxyl group, by halogen, by lower alkyl groups, by hydroxyl, alkoxy, amino or acylamino groups; as functionally modified carboxyl groups, for example, their salts, esters or amides come into consideration.
The carboxyl group-containing arylpyrazoline compounds can have been prepared in many ways, eg. B. by the action of aryl hydrazines containing carboxyl groups on co-dialkylamino aryl ketones, on vinyl aryl ketones, such as.
B. Benzalacetophenon, or on the salts of Aminoäthylarylketonen. The lightening agents prepared according to the invention can be used to lighten a wide variety of materials, eg. B. to lighten textile materials such as cellulose fibers, wool or synthetic fibers, also to lighten paper and other more.
They are also well suited for Aufhel len fibers, films or other structures made of acrylonitrile polymers. The arylpyrazoline derivatives can also be used with good success in the production of fluorescent structures from synthetic polycondensates according to the Swiss method. Patent No. 354250 can be used.
The parts given in the following examples are parts by weight.
<I> Example 1 </I> In <B> 10000 </B> parts of a base soap suitable for soap flakes, 1-3 parts of 1-p-CaTboxyphenyl-3-phenylpyrazoline are mixed in a mixing device before application on the roller frame incorporated. The soap flakes obtained in the usual further processing are able to lighten laundry that is washed with these soap flakes outstandingly.
Instead of 1-p-carboxyphenyl-3-phenylpyrazoline, the sodium salt or the ethyl ester can also be used.
The salt, the free acid or its ethyl ester can be prepared in the following way: 120 parts of acetophenone are heated with 55 parts of ammonium chloride and 155 parts of 30% formaldehyde in a boiling water bath with stirring and reflux for 1 hour. The lower layer is separated and treated with a solution of 152 parts of p-hydrazinobenzoic acid hydrochloride and 204 parts of anhydrous soda in 1400 parts of water with stirring for 3 hours
Boiling heated. The sodium salt of 1-p-carboxyphenyl-3-phenylpyrazoline then precipitates out. The free acid with a melting point of 244 can be obtained by adding hydrochloric acid to the suspension of the sodium salt in water.
To prepare the ethyl ester, 125 parts of the salt or acid thus obtained are suspended in 750 parts of alcohol and, at 30-40, 75 parts of thionyl chloride are slowly added. After refluxing for about 7 hours, the reaction solution is filtered hot. The ester then crystallizes out of the filtrate and, after further recrystallization from alcohol, has a melting point of 112.
<I> Example 2 </I> A basic soap containing about 80% fatty acid is mixed with 0.01-0.03 parts of 1-p-carboxyphenyl-3-p-chlorophenylpyrazoline per 100 parts in the mixing apparatus in front of the polishing machine added. Textile materials that have been washed with such a soap show a brilliant white.
The 1-p-carboxyphenyl 3-p-chlorophenylpyrazoline used can be prepared in the following manner: 54 parts of β-chloropropionic acid are heated with 77.5 parts of thionyl chloride for 11/2 hours on a water bath with exclusion of water; then the reaction mixture is allowed to flow into a mixture of 81 parts of aluminum chloride and 170 parts of dry chlorobenzene.
After standing for 24 hours, the mixture is poured onto ice-hydrochloric acid; the chlorobenzoic layer is separated off and heated to boiling under reflux for 2 hours with 95 parts of p-hydrazinobenzoic acid hydrochloride, 80 parts of pyridine and 750 parts of methanol. The 1-p-carboxy-phenyl-3-p-chlorophenylpyrazoline thus formed has a melting point of 270-272.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE356435X | 1955-10-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH356435A true CH356435A (en) | 1961-08-31 |
Family
ID=6290276
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH356435D CH356435A (en) | 1955-10-10 | 1956-09-27 | Process for the preparation of an optical brightening agent |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH356435A (en) |
-
1956
- 1956-09-27 CH CH356435D patent/CH356435A/en unknown
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