DE2529434A1 - Fluorescent dyes of coumarin series - contg. thiadiazolyl gps. for use on synthetic fibres - Google Patents
Fluorescent dyes of coumarin series - contg. thiadiazolyl gps. for use on synthetic fibresInfo
- Publication number
- DE2529434A1 DE2529434A1 DE19752529434 DE2529434A DE2529434A1 DE 2529434 A1 DE2529434 A1 DE 2529434A1 DE 19752529434 DE19752529434 DE 19752529434 DE 2529434 A DE2529434 A DE 2529434A DE 2529434 A1 DE2529434 A1 DE 2529434A1
- Authority
- DE
- Germany
- Prior art keywords
- alkyl
- formula
- nitrogen
- alkoxy
- optionally substituted
- 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.)
- Granted
Links
- 125000000332 coumarinyl group Chemical class O1C(=O)C(=CC2=CC=CC=C12)* 0.000 title claims abstract 3
- 229920002994 synthetic fiber Polymers 0.000 title claims 2
- 239000007850 fluorescent dye Substances 0.000 title description 2
- 125000001113 thiadiazolyl group Chemical group 0.000 title 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 22
- 239000000975 dye Substances 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 5
- 238000004043 dyeing Methods 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 3
- 229920003023 plastic Polymers 0.000 claims abstract description 3
- 239000004033 plastic Substances 0.000 claims abstract description 3
- 238000010023 transfer printing Methods 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- -1 cyoloalkyl Chemical group 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 125000005521 carbonamide group Chemical group 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000004040 coloring Methods 0.000 claims description 2
- 125000002541 furyl group Chemical group 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004076 pyridyl group Chemical group 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- 125000001544 thienyl group Chemical group 0.000 claims description 2
- 239000003086 colorant Substances 0.000 claims 1
- 239000000470 constituent Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 239000012209 synthetic fiber Substances 0.000 claims 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 abstract description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 abstract description 6
- XFVZSRRZZNLWBW-UHFFFAOYSA-N 4-(Diethylamino)salicylaldehyde Chemical compound CCN(CC)C1=CC=C(C=O)C(O)=C1 XFVZSRRZZNLWBW-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004952 Polyamide Substances 0.000 abstract description 2
- 229920002678 cellulose Polymers 0.000 abstract description 2
- 229920002239 polyacrylonitrile Polymers 0.000 abstract description 2
- 229920002647 polyamide Polymers 0.000 abstract description 2
- 229920000728 polyester Polymers 0.000 abstract description 2
- 239000004753 textile Substances 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 abstract 2
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 16
- 125000001309 chloro group Chemical group Cl* 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- UCVHPFSVOJEALT-UHFFFAOYSA-N 2-(5-phenyl-3h-thiadiazol-2-yl)acetonitrile Chemical compound S1N(CC#N)NC=C1C1=CC=CC=C1 UCVHPFSVOJEALT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 150000004775 coumarins Chemical class 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- YXHVGMQJXJAUAR-UHFFFAOYSA-N 2-(diethylaminooxy)benzaldehyde Chemical compound CCN(CC)OC1=CC=CC=C1C=O YXHVGMQJXJAUAR-UHFFFAOYSA-N 0.000 description 1
- VQFSROYNMGVXPW-UHFFFAOYSA-N 4-(diethylamino)-2-hydroxybenzaldehyde 4-(dimethylamino)-2-hydroxybenzaldehyde Chemical compound C(C)N(C1=CC(=C(C=O)C=C1)O)CC.CN(C1=CC(=C(C=O)C=C1)O)C VQFSROYNMGVXPW-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 150000002780 morpholines Chemical class 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000004885 piperazines Chemical class 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 150000003235 pyrrolidines Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Classifications
-
- 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
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/02—Coumarine dyes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
- Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
Abstract
Description
Farbstoffe der Cumarinreihe Die Erfindung betrifft Farbstoffe der Formel I in der Z gegebenenfalls substituiertes Alkyl, Cycloalkyl, Aralkyl, Aryl oder Heteroaryl, 21 und Z² Wasserstoff oder gegebenenfalls substituiertes Alkyl, Cycloalkyl, Aralkyl oder Aryl, Z¹ und Z² zusammen mit dem Stickstoff Teil eines heterocyclischen Ringes, Z1 oder z2 usammen mit dem Stickstoff einen in ortho-Stellung zum Stickstoff ankondensierten gesattigten, gegebenenfalls substituierten 5- oder 6-Ring und X Sauerstoff oder Imino bedeuten.Dyes of the Coumarin Series The invention relates to dyes of the formula I in which Z optionally substituted alkyl, cycloalkyl, aralkyl, aryl or heteroaryl, 21 and Z² hydrogen or optionally substituted alkyl, cycloalkyl, aralkyl or aryl, Z¹ and Z² together with the nitrogen part of a heterocyclic ring, Z1 or z2 together with the nitrogen one saturated, unsubstituted or substituted 5- or 6-membered ring condensed ortho to the nitrogen and X is oxygen or imino.
Insbesondere betrifft die Erfindung Farbstoffe der Formel I a in der R C - bis C4-Alkyl, Benzyl, B-Eydroxyäthyl oder -propyl, ß-C1- bis C4-Alkoxyäthyl oder -propyl, ß-Cyanäthyl, ß-Carb-C1- bis C4-alkoxy-4 äthyl, ß-(B'-Äthylmercapto- oder Äthylsulfonyläthoxy)-äthyl, ß-Phenoxyäthyl, Cyclohexyl, gegebenenfalls durch Chlor, Brom, Methyl, Äthyl, Methoxy, Äthoxy oder Cyan substituiertes Phenyl, Naphthyl, Pyridyl, Furyl oder Thienyl, R¹ Wasserstoff, C1 - bis C4-Alkyl, gegebenenfalls durch Cyan, C1- bis C4-Alkoxy, Chlor, Brom, Carboxyl, Carb-C1- bis C4-alkoxy, Carbonamid oder Acetoxy substituiertes C1- bis C4-Alkyl, Cyclohexyl, Benzyl, Phenyläthyl oder Phenyl, R2 Wasserstoff, C1 - bis C4-Alkyl oder gegebenenfalls durch Cyan, Ci bis C4-likoxy, Chlor, Brom, Carboxyl, Carb-C1 - bis C4-alkoxy, Carbonamid oder Acetoxy substituiertes Ci bis C4-likyl, R1 und R2 zusammen mit dem Stickstoff den Rest eines 5- oder 6-gliedrigen gesättigten, heterocyclischen Ringes, R2 zusammen mit dem Stickstoff einen in ortho-Stellung zum Stickstoff ankondensierten Rest der Formel X Sauerstoff oder Imino bedeuten.In particular, the invention relates to dyes of the formula I a in RC - to C4-alkyl, benzyl, B-hydroxyethyl or -propyl, ß-C1- to C4-alkoxyethyl or -propyl, ß-cyanoethyl, ß-carb-C1- to C4-alkoxy-4 ethyl, ß- (B'-ethylmercapto- or ethylsulfonylethoxy) ethyl, ß-phenoxyethyl, cyclohexyl, phenyl, naphthyl, pyridyl, furyl or thienyl, R¹ hydrogen, C1 - bis, optionally substituted by chlorine, bromine, methyl, ethyl, methoxy, ethoxy or cyano C4-alkyl, optionally substituted C1- to C4-alkyl, cyclohexyl, benzyl, phenylethyl or phenyl, R2 Hydrogen, C1 - to C4-alkyl or optionally by cyano, Ci to C4-likoxy, chlorine, bromine, carboxyl, carb-C1 - to C4-alkoxy, carbonamide or acetoxy substituted Ci to C4-likyl, R1 and R2 together with the Nitrogen denotes the remainder of a 5- or 6-membered saturated, heterocyclic ring, R2 together with the nitrogen denotes a remainder of the formula which is condensed ortho to the nitrogen X mean oxygen or imino.
Außer den schon einzeln genannten Resten seien als Substituenten beispielsweise genannt: Für R1 und R2: Methyl, Äthyl, n- oder i-Propyl, n- oder i-Butyl, ß-Methoxyäthyl, ß-Äthoxyäthyl, ß-Acetoxyäthyl, ß-Chloräthyl, ß-Carbomethoxyäthyl, ß-Carboäthoxyäthyl, ß-Carbobutoxyäthyl, ß-Methoxypropyl, ß-Äthoxypropyl, ß-Methoxy-y-chlorpropyl oder ß-Acetoxypropyl.In addition to the radicals already mentioned, examples of substituents are named: For R1 and R2: methyl, ethyl, n- or i-propyl, n- or i-butyl, ß-methoxyethyl, ß-ethoxyethyl, ß-acetoxyethyl, ß-chloroethyl, ß-carbomethoxyethyl, ß-carboethoxyethyl, ß-carbobutoxyethyl, ß-methoxypropyl, ß-ethoxypropyl, ß-methoxy-y-chloropropyl or β-acetoxypropyl.
Zusammen mit dem Stickstoff bedeuten R1 und R2 z. B. den Rest des Pyrrolidins, Piperidins, Morpholins, Piperazins oder N-Xethylpiperazins.Together with the nitrogen, R1 and R2 mean e.g. B. the rest of the Pyrrolidines, piperidines, morpholines, piperazines or N-Xethylpiperazins.
Von besonderer technischer Bedeutung sind Farbstoffe der Formel I b in der R3 Alkyl mit 1 bis 4 C-Atomen, vorzugsweise Methyl oder Äthyl ist und R und X die angegebene Bedeutung haben. Bevorzugt für X ist Sauerstoff und für R gegebenenfalls substituiertes Phenyl.Dyes of the formula I b are of particular industrial importance in which R3 is alkyl with 1 to 4 carbon atoms, preferably methyl or ethyl, and R and X have the meaning given. Oxygen is preferred for X and optionally substituted phenyl for R.
Die neuen fluoreszierenden Farbstoffe sind von hoher Brillanz, die Farbtöne liegen im gelbgrünen Bereich. Sie eignen sich zum Färben von Textilmaterial aus Polyamiden, Celluloseestern, Acrylnitrilpolymerisaten und insbesondere Polyestern sowie zum Färben von Kunststoffen in der Masse. Leicht sublimierende Farbstoffe sind auch für den Transferdruck geeignet.The new fluorescent dyes are of high brilliance that Shades are in the yellow-green area. They are suitable for dyeing textile material from polyamides, cellulose esters, acrylonitrile polymers and especially polyesters as well as for coloring plastics in bulk. Slightly subliming dyes are also suitable for transfer printing.
Die erfindungsgemäßen Farbstoffe sind sehr ausgiebig (farbstark) und ergeben Färbungen mit guter Lichtechtheit und Thermofixierechtheit.The dyes according to the invention are very extensive (color strong) and result in dyeings with good lightfastness and heat-setting fastness.
Zur Herstellung der Verbindungen der Formel I kann man @@ Verbindungen der Formel II mit Verbindungen der Formel III in der Y Cyan oder Carb-C1- bis-C4-alkoxy bedeutet, gemäß DT-PS 1 098 125 oder DT-OS 2 011 500 kondensieren oder b) Verbindungen der Formel IV gemäß DT-PS 1 134 080 cyclisieren oder c> Verbindungen der Formel V in der ein A Schwefel und das andere Sauerstoff ist, gemäß DT-PS 1 249 873 cyclisieren.To prepare the compounds of the formula I, @@ compounds of the formula II with compounds of the formula III in which Y is cyano or carb-C1- to-C4-alkoxy, condense according to DT-PS 1 098 125 or DT-OS 2 011 500 or b) compounds of the formula IV cyclize according to DT-PS 1 134 080 or c> compounds of the formula V in which one A is sulfur and the other is oxygen, cyclize according to DT-PS 1,249,873.
Gegenüber den bekannten Verfahren ergeben sich bei der Herstellung der erfindungsgemäßen Farbstoffe keine Abweichungen, die Reaktionen verlaufen analog.Compared to the known methods, result in the production of the dyes according to the invention no deviations, the reactions proceed analogously.
Verbindungen der Formel IV sind z. B. durch Umsetzung von Verbindungen der Formel II mit Verbindungen der Formel VI NC-CH2COMH-NHCOZ VI zugänglich.Compounds of formula IV are, for. B. by implementing compounds of the formula II with compounds of the formula VI NC-CH2COMH-NHCOZ VI accessible.
In den folgenden Beispielen beziehen sich Angaben über Teile und Prozente, sofern nicht anders vermerkt, auf das Gewicht.In the following examples, parts and percentages relate to unless otherwise noted, by weight.
BeisPiel 1 7 Teile 4-DiäthylPminosalicylaldehyd in 50 Volumenteilen Isopropanol werden mit 9 Teilen 2-[5'-Phenyl-thiadiazolyl-(2')]-essigsäureäthylester und 2 Volumenteilen Pyrrolidin 15 Minuten unter Rückfluß gekocht, dann abgekühlt und abgesaugt.Example 1 7 parts of 4-diethyl-minosalicylaldehyde in 50 parts by volume Isopropanol is mixed with 9 parts of 2- [5'-phenyl-thiadiazolyl- (2 ')] -acetic acid ethyl ester and 2 parts by volume of pyrrolidine refluxed for 15 minutes, then cooled and sucked off.
Man erhält 10 Teile (73 % d. Th.) 3- 5'-Phenyl-thiadiazolyl-(2')]-7-diäthylaminocumarin vom Schmelzpunkt 270 - 272 OC (aus DMF).10 parts (73% of theory) of 3- 5'-phenyl-thiadiazolyl- (2 ')] - 7-diethylaminocoumarin are obtained from melting point 270-272 OC (from DMF).
Beispiel 2 Verwendet man anstelle von 4-Diäthylaminosalicylaldehyd 4-Dimethylaminosalicylaldehyd und verfährt sonst wie im Beispiel 1 angegeso ben, erhält man 3-[5'-Phenylthiadiazolyl-(2')]-7-dimethylaminocumarin in 55 zeiger Ausbeute d. Th. vom Schmelzpunkt 286 - 290 °C.Example 2 Used instead of 4-diethylaminosalicylaldehyde 4-Dimethylaminosalicylaldehyde and otherwise proceed as indicated in Example 1, 3- [5'-Phenylthiadiazolyl- (2 ')] - 7-dimethylaminocoumarin is obtained in 55% yield d. Th. From melting point 286-290 ° C.
Beispiel 3 19,3 Teile Diäthylaminosalicylaldehyd und 20,1 Teile 2-Cyanmethyl-5-phenyl-thiadiazol werden in 100 Volumenteilen Isopropanol mit 5 Volumenteilen Pyrrolidin 15 Minuten unter Rückfluß gekocht.Nach dem Abkühlen saugt man das 3-[5'-Phenylthiadiazolyl-(2')]-7-diäthylamino-2-iminocumarin, vom Schmelzpunkt 228 - 230 OC, in 79 zeiger Ausbeute ab.Example 3 19.3 parts of diethylaminosalicylaldehyde and 20.1 parts of 2-cyanomethyl-5-phenyl-thiadiazole are in 100 parts by volume of isopropanol with 5 parts by volume of pyrrolidine for 15 minutes boiled under reflux.After cooling, the 3- [5'-phenylthiadiazolyl- (2 ')] - 7-diethylamino-2-iminocoumarin, from melting point 228-230 ° C., in 79 yield.
4,6 Teile des lminocumarins werden in 40 Volumenteilen Äthanol mit 10 Volumenteilen Wasser und 10 Volumenteilen konzentrierter Salssäure 1 Stunde gekocht. Nach dem Abkühlen wird abgesaugt, das Filtergut in Wasser suspendiert, mit Ammoniak alkalisch gestellt und erneut abgesaugt. Man erhält 4 Teile (87 % d. Th.) 3-[5'-Phenyl-thiadiazolyl-(2')]-7-diäthylaminocumarin vom Schmelzpunkt 272 - 275 °C.4.6 parts of the lminocoumarin are mixed with 40 parts by volume of ethanol Boiled 10 parts by volume of water and 10 parts by volume of concentrated hydrochloric acid for 1 hour. After cooling, the filter material is suctioned off suspended in water, Made alkaline with ammonia and suctioned off again. 4 parts are obtained (87% of theory). Th.) 3- [5'-Phenyl-thiadiazolyl- (2 ')] - 7-diethylaminocoumarin with a melting point of 272 - 275 ° C.
Analog zu Beispiel 3 werden die in der Tabelle 1 aufgeführten Verbindungen erhalten. The compounds listed in Table 1 are obtained analogously to Example 3.
Beispiel R1 R2 R3 R4 4 -CH3 -CH3 H H 5 C2 5 -C2H5 4-Cl H 6 -C2H5 -C2H5
2-Cl H 7 -CH3 -CH3 4-Cl H 8 -CH3 -CH3 2-Cl H 9 -C2H5 -C2H5 2-Cl 4-Cl 10 -CH3 -CH3
2-Cl 4-Cl 11 -C2H5 -C2R5 2-Cl 6-Cl 12 -CH3 -CH3 2-Cl 6-Cl 13 -CR3 -CH3 4-CH3 H
Beispiel
R¹ R2 R3 R4
In der nachstehenden Tabelle sind weitere Cumarinverbindungen, die
analog hergestellt werden können, Eufgeführt:
Beispiel R1 R2 30 -CH3 Propyl 31 -C2H5 Isopropyl 32 -CH3 Butyl 33 -C2H5 Butyl 34
-CH3 Isobutyl 35 -C 2H5 Isobutyl
Beispiel R¹ R²
Man rührt anschließend 1 Stunde bei 600C und steigert dann die Temperatur allmählich auf 110 00. Man rührt weitere 5 Stunden bei dieser Temperatur, kühlt dann ab, versetzt mit 100 Teilen Äthanol und gießt das Reaktionsgemisch in 2000 Teile Eiswasser. Man rührt 2 Stunden nach und saugt dann den Niederschlag ab. Man erhält 9,3 Teile (82 % d. Th.) 3-5'-(Pyridyl-(4)-thiadiazolyl-(2' )]-7-diäthylamino cumarin vom Schmelzpunkt 280 - 283 0 (aus DMF).The mixture is then stirred for 1 hour at 60 ° C. and the temperature is then increased gradually to 110,000. The mixture is stirred at this temperature for a further 5 hours and then cooled then off, mixed with 100 parts of ethanol and poured the reaction mixture into 2000 Share ice water. The mixture is stirred for a further 2 hours and the precipitate is then filtered off with suction. Man receives 9.3 parts (82% of theory) 3-5 '- (pyridyl- (4) -thiadiazolyl- (2')] - 7-diethylamino coumarin with a melting point of 280-2830 (from DMF).
Analog erhält man die in der Tabelle 3 aufgeführten Verbindungen:
Beispiel R¹ R²
Claims (5)
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19752529434 DE2529434C3 (en) | 1975-07-02 | 1975-07-02 | Colorants of the coumarin series and their uses |
| GB23125/76A GB1543933A (en) | 1975-07-02 | 1976-06-04 | Dyes of the coumarin series |
| US05/693,187 US4055568A (en) | 1975-07-02 | 1976-06-07 | Dyes of the coumarin series |
| CH829776A CH628080A5 (en) | 1975-07-02 | 1976-06-29 | METHOD FOR PRODUCING COLORS OF THE CUMARINE SERIES. |
| JP51076108A JPS604852B2 (en) | 1975-07-02 | 1976-06-29 | Novel coumarin-based dye |
| IT50235/76A IT1062591B (en) | 1975-07-02 | 1976-07-01 | DYES OF THE CUMARINE SERIES |
| FR7620072A FR2316293A1 (en) | 1975-07-02 | 1976-07-01 | COLORING MATERIALS FROM THE COUMARINIC SERIES |
| CH1046178A CH629238A5 (en) | 1975-07-02 | 1978-10-09 | METHOD FOR PRODUCING COLORS OF THE CUMARINE SERIES. |
| CH528281A CH629524A5 (en) | 1975-07-02 | 1981-08-14 | METHOD FOR PRODUCING COLORS OF THE CUMARINE SERIES. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19752529434 DE2529434C3 (en) | 1975-07-02 | 1975-07-02 | Colorants of the coumarin series and their uses |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DE2529434A1 true DE2529434A1 (en) | 1977-01-13 |
| DE2529434B2 DE2529434B2 (en) | 1977-11-03 |
| DE2529434C3 DE2529434C3 (en) | 1978-06-29 |
Family
ID=5950445
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19752529434 Expired DE2529434C3 (en) | 1975-07-02 | 1975-07-02 | Colorants of the coumarin series and their uses |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE2529434C3 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2844299A1 (en) * | 1977-10-13 | 1979-04-19 | Ciba Geigy Ag | NEW COLORS, THEIR PRODUCTION AND USE |
| EP0042090A3 (en) * | 1980-06-12 | 1981-12-30 | Bayer Ag | Dyestuff preparation and its use to obtain warning and signalling colours |
| DE4240168A1 (en) * | 1992-11-30 | 1994-06-01 | Bayer Ag | New 2-tri:fluoro:methyl:thiadiazolyl-coumarin derivs - useful as fluorescent pigments for colouring transparent or translucent plastics |
| CN113149974A (en) * | 2021-03-18 | 2021-07-23 | 温州医科大学 | Small-molecule fluorescent probe, preparation method and application thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2803104A1 (en) * | 1978-01-25 | 1979-07-26 | Bayer Ag | Heterocyclic dyes of benzopyran, benzo-thio-pyran or quinoline type - for use as acid, basic or dispersion dyes |
| DE3031326A1 (en) * | 1980-08-20 | 1982-04-01 | Bayer Ag, 5090 Leverkusen | DYE PREPARATION AND THEIR USE AS A WARNING AND SIGNAL COLOR |
-
1975
- 1975-07-02 DE DE19752529434 patent/DE2529434C3/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2844299A1 (en) * | 1977-10-13 | 1979-04-19 | Ciba Geigy Ag | NEW COLORS, THEIR PRODUCTION AND USE |
| EP0042090A3 (en) * | 1980-06-12 | 1981-12-30 | Bayer Ag | Dyestuff preparation and its use to obtain warning and signalling colours |
| DE4240168A1 (en) * | 1992-11-30 | 1994-06-01 | Bayer Ag | New 2-tri:fluoro:methyl:thiadiazolyl-coumarin derivs - useful as fluorescent pigments for colouring transparent or translucent plastics |
| CN113149974A (en) * | 2021-03-18 | 2021-07-23 | 温州医科大学 | Small-molecule fluorescent probe, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2529434C3 (en) | 1978-06-29 |
| DE2529434B2 (en) | 1977-11-03 |
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| C3 | Grant after two publication steps (3rd publication) | ||
| 8330 | Complete disclaimer |