PL161925B2 - Method of obtaining novel cationic dyes - Google Patents
Method of obtaining novel cationic dyesInfo
- Publication number
- PL161925B2 PL161925B2 PL28773490A PL28773490A PL161925B2 PL 161925 B2 PL161925 B2 PL 161925B2 PL 28773490 A PL28773490 A PL 28773490A PL 28773490 A PL28773490 A PL 28773490A PL 161925 B2 PL161925 B2 PL 161925B2
- Authority
- PL
- Poland
- Prior art keywords
- methyl
- cationic dyes
- methoxy
- toluene
- tetrahydroacridine
- Prior art date
Links
- 239000000975 dye Substances 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims abstract description 8
- 125000002091 cationic group Chemical group 0.000 title claims description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 21
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 claims description 2
- KQGWYBRLAMUHFG-UHFFFAOYSA-N (4-methoxyphenyl)-(10-methyl-2,3,4,4a-tetrahydro-1H-acridin-4-yl)diazene Chemical compound COC1=CC=C(C=C1)N=NC1CCCC2=CC3=CC=CC=C3N(C12)C KQGWYBRLAMUHFG-UHFFFAOYSA-N 0.000 abstract 1
- 150000001768 cations Chemical class 0.000 abstract 1
- 238000010586 diagram Methods 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- -1 10-methyl-1,2,3,4-tetrahydroacridine derivatives Chemical class 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 229920002239 polyacrylonitrile Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- AUPBUDNQIPSXLA-UHFFFAOYSA-N C[N+]1=C2CCCCC2=CC3=CC=CC=C31 Chemical class C[N+]1=C2CCCCC2=CC3=CC=CC=C31 AUPBUDNQIPSXLA-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 125000005597 hydrazone group Chemical group 0.000 description 2
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NDBJTKNWAOXLHS-UHFFFAOYSA-N 4-methoxybenzenediazonium Chemical class COC1=CC=C([N+]#N)C=C1 NDBJTKNWAOXLHS-UHFFFAOYSA-N 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- CIZVQWNPBGYCGK-UHFFFAOYSA-N benzenediazonium Chemical class N#[N+]C1=CC=CC=C1 CIZVQWNPBGYCGK-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 150000005451 methyl sulfates Chemical class 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- RXBYRTSOWREATF-UHFFFAOYSA-N tetrahydroacridine Natural products C1=CC=C2C=C(CCCC3)C3=NC2=C1 RXBYRTSOWREATF-UHFFFAOYSA-N 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
Landscapes
- Coloring (AREA)
Abstract
Description
Przedmiotem wynalazku jest sposób otrzymywania nowych barwników kationowych o ogólnym wzorze przedstawionym na rysunku, w którym R oznacza atom wodoru lub grupę metoksylową. Barwniki te barwią włókna poliakrylonitrylowe na kolor brunatny.The subject of the invention is a process for the preparation of new cationic dyes having the general formula presented in the drawing, in which R represents a hydrogen atom or a methoxy group. These dyes dye polyacrylonitrile fibers brown.
Celem wynalazku jest otrzymanie nowych barwników kationowych pochodnych 10-metylo-l,2,3,4-tetrahydroakrydyny, posiadających utrwaloną formę hydrazonową, uzyskaną w drodze alkilowania grupy azowej, co wpływa korzystnie na własności użytkowe barwników.The aim of the invention is to obtain new cationic dyes of 10-methyl-1,2,3,4-tetrahydroacridine derivatives having a fixed hydrazone form obtained by alkylation of the azo group, which has a positive effect on the usable properties of dyes.
Związki wyjściowe stosowane w sposobie według wynalazku, 4-fenyloazo- i 4-[(4-metoksy)fenylo]azo-10-metylo-l,2,3,4-tetrahydroakrydyna, są związkami nowymi.The starting compounds used in the process according to the invention, 4-phenylazo- and 4 - [(4-methoxy) phenyl] azo-10-methyl-1,2,3,4-tetrahydroacridine, are novel compounds.
Sposobem według wynalazku na 4-fenyloazo- lub 4-[(4-metoksy)fenylo]azo-10-metylo1,2,3,4-tetrahydroakrydynę działa się w toluenie siarczanem dimetylu.In the process of the invention, 4-phenylazo- or 4 - [(4-methoxy) phenyl] azo-10-methyl 1,2,3,4-tetrahydroacridine is treated in toluene with dimethyl sulfate.
Otrzymywane sposobem według wynalazku nowe barwniki kationowe wykazują, dzięki utrwaleniu w ich cząsteczce formy hydrazonowej, bardzo dobre odporności mokre i na światło.The new cationic dyes obtained by the method according to the invention show, due to the hydrazone form in their molecules, very good wet and light fastness.
Wynalazek ilustrują następujące przykłady, w których procenty oznaczają procenty wagowe, a stopnie temperatury podano w stopniach Celsjusza:The invention is illustrated by the following examples in which the percentages are percentages by weight and the degrees of temperatures are in degrees Celsius:
Przykład I. 1,52 g Surowego produktu, wydzielonego po reakcji sprzęgania soli 4-metoksybenzenodiazoniowej z solą 10-metylo-l,2,3,4-tetrahydroakrydyniową, zawierającego 1,0 g (0,003 mola) rozpuszczalnej w toluenie 4-[(4-metoksy)fenylo]azo-10- metylo-l ,2,3,4-tetrahydroakrydyny zadano 150 cm3 bezwodnego toluenu. Uzyskany fioletowy roztwór zatężono pod zmniejszonym ciśnieniem (temperatura łaźni 40 - 45° do około 30 cm3 i dodano 4 cm3 (5,32 g = 0,042 mola) świeżo destylowanego siarczanu dimetylu. Mieszaninę przechowywano w eksykatorze nad tlenkiem wapnia w temperaturze pokojowej lub w temperaturze 60 - 70° przez 30 godzin.Example 1 1.52 g of crude product, isolated after the coupling reaction of 4-methoxybenzenediazonium salt with 10-methyl-1,2,3,4-tetrahydroacridinium salt, containing 1.0 g (0.003 mol) of toluene-soluble 4 - [( 4-methoxy) phenyl] azo-10- methyl-l, 2,3,4-tetrahydroacridine treated with 150 cm 3 of anhydrous toluene. The resulting violet solution was concentrated under reduced pressure (bath temperature 40-45 ° to about 30 cm 3 and 4 cm 3 (5.32 g = 0.042 mol) of freshly distilled dimethyl sulfate was added. The mixture was stored in a desiccator over calcium oxide at room temperature or at room temperature. 60 - 70 ° for 30 hours.
Wydzielony osad odsączono, przemyto toluenem do zaniku zabarwienia rozpuszczalnika, a następnie eterem. Uzyskano 0,65 g (47,4% wydajności) metylosiarczanu 4-[(4-metoksy)fenylo]-azo-1O-metylo-N-metylo-l,2,3,4-tetiaihydroakrydyniowego o temperaturze topnienia 144 147° (z rozkładem), dobrze rozpuszczalnego w wodzie i etanolu. Otrzymany barwnik barwi włókna poliakrylonitrylowe na kolor brunatny.The separated precipitate was filtered off, washed with toluene until the color of the solvent disappeared, and then with ether. The obtained was 0.65 g (47.4% yield) of 4 - [(4-methoxy) phenyl] -azo-1O-methyl-N-methyl-1,2,3,4-tethiaihydroacridinium methyl sulfate with a melting point of 144 147 ° ( with decomposition), easily soluble in water and ethanol. The obtained dye dyes polyacrylonitrile fibers brown.
IR (KBr): 2965,1600, 1500, 1210, 1240 cm4 IR (KBr): 2965, 1600, 1500, 1210, 1240 cm 4
UV-vis (CH3OH): Xm« = 463 nm (ε = 1,66.104) 'HNMR (CDCb): 3,2 - 2,0 (6 H, m); 3,62 (3 H, s);3,70 (3 H,s); 3,8 (3 H, s); 4,68 (3 H, s); 6,84 - 8,3 (9 H, m, C-H aromat.)UV-vis (CH3OH):? M? = 463nm (ε = 1.66.10 4 ); H NMR (CDClb): 3.2-2.0 (6H, m); 3.62 (3H, s) 3.70 (3H, s); 3.8 (3H, s); 4.68 (3H, s); 6.84 - 8.3 (9 H, m, CH aroma)
Przykład Π. 1,0 g Surowego produktu, wydzielonego po reakcji sprzęgania soli benzenodiazoniowej z solą 10-metylo- 1,2,3,4-tetrahydroakrydyniową, zawierającego 0,95 g (0,0032 mola) rozpuszczalnej w toluenie 4-fenyloazo-10-metylo-l,2,3,4-tetrahydroakrydyny zadano 200 cm bezwodnego toluenu i oddzielono 0,05 g nierozpuszczalnych zanieczyszczeń. Czerwonofioletowy roztwór zatężono pod zmniejszonym ciśnieniem (temperatura łaźni 40 - 45°) do objętości około 50 cm3, dodano 4 cm3 (5,32 g = 0,042 mola) świeżo destylowanego siarczanuExample Π. 1.0 g of crude product, isolated after coupling the benzenediazonium salt with 10-methyl-1,2,3,4-tetrahydroacridinium salt, containing 0.95 g (0.0032 mol) of 4-phenylazo-10-methyl soluble in toluene -1,2,3,4-tetrahydroacridine was treated with 200 cm of anhydrous toluene and 0.05 g of insoluble impurities was separated. The reddish-purple solution was concentrated under reduced pressure (bath temperature 40-45 °) to a volume of about 50 cm3, 4 cm3 (5.32 g = 0.042 mol) of freshly distilled sulfate were added
161 925 dimetylu i pozostawiono w eksykatorze nad wodorotlenkiem potasu w temperaturze pokojowej lub w temperaturze 60-70° przez 30 godzin.161 925 dimethyl and left in a desiccator over potassium hydroxide at room temperature or at 60-70 ° for 30 hours.
Postępując dalej sposobem opisanym w przykładzie I wydzielono 0,70 g (71,0% wydajności) metylosiarczanu 4-fenylohydrazono-10-metylo-N-metylo-1,2,3,4-tetrahydroakrydyniowego o temperaturze topnienia 157 - 160° (z rozkładem), dobrze rozpuszczalnego w wodzie i etanolu. Otrzymany barwnik barwi włókna poliakrylonitrylowe na kolor czerwonobrunatny.Following the procedure described in Example 1, 0.70 g (71.0% yield) of 4-phenylhydrazone-10-methyl-N-methyl-1,2,3,4-tetrahydroacridinium methylsulfate, mp 157-160 ° (from decomposition), easily soluble in water and ethanol. The obtained dye dyes polyacrylonitrile fibers red-brown.
IR(KBr): 1970,1600, 1510, 1260,1210 cm1 IR (KBr): 1970, 1600, 1510, 1260, 1210 cm 1
UV-vis (CH3OH): λ™ 454 nm (ε = 1,60 . 104) 'HNMR (CDCb): 2,07 - 2,95 (6 H, m); 3,54 (3 H, s); 3,85 (3 H, s); 4,76 (3 H, s); 7,83 8,70 (10 H, m, C-H aromat).UV-vis (CH 3 OH): λ ™ 454 nm (ε = 1.60. 10 4 ); HNMR (CDCb): 2.07 - 2.95 (6H, m); 3.54 (3H, s); 3.85 (3H, s); 4.76 (3H, s); 7.83 8.70 (10H, m, CH aroma).
Czystość produktów stosowanych w podanych wyżej przykładach kontrolowano za pomocą chromatografii cienkowarstwowej w układzie Ak033aceton. Obecność soli hydrazoniowej stwierdzono przez pojawienie się szybko eluującej fioletowej plamy związku azowego powstałego z soli hydrazoniowej w kontakcie z tlenkiem glinowym. Sól produktu alkilowego pozostawała na starcie.The purity of the products used in the above-mentioned examples was monitored by thin layer chromatography on the Ak033acetone system. The presence of the hydrazonium salt was found by the appearance of a fast-eluting purple spot of the azo compound formed from the hydrazonium salt on contact with the alumina. The salt of the alkyl product remained on startup.
Powstające ewentualnie mieszaniny rozdzielono przez rozpuszczenie ich w ocetonie i podanie na kolumnę wypełnioną możliwie małą ilością obojętnego tlenku glinowego. Eluując acetonem oddzielano fioletową frakcję związku azowego.Any mixtures that may arise were separated by dissolving them in vinegar and feeding them to a column filled with as little inert alumina as possible. By eluting with acetone, the purple azo compound fraction was separated.
Produkty alkilowe pozostające na starcie wymywano etanolem (po osuszeniu kolumny) i stężone roztwory etanolowe dodawano do bezwodnego eteru dietylowego. Następnie wydzielano czyste produkty w postaci metylosiarczanów.The alkyl products remaining on the start were eluted with ethanol (after drying the column) and the concentrated ethanolic solutions were added to anhydrous diethyl ether. The pure products in the form of methylsulfates were then isolated.
Zakład Wydawnictw UP RP. Nakład 90 egz. Cena 10 000 złDepartment of Publishing of the UP RP. Circulation of 90 copies. Price: PLN 10,000
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL28773490A PL161925B2 (en) | 1990-11-12 | 1990-11-12 | Method of obtaining novel cationic dyes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL28773490A PL161925B2 (en) | 1990-11-12 | 1990-11-12 | Method of obtaining novel cationic dyes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| PL287734A2 PL287734A2 (en) | 1991-08-26 |
| PL161925B2 true PL161925B2 (en) | 1993-08-31 |
Family
ID=20052857
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PL28773490A PL161925B2 (en) | 1990-11-12 | 1990-11-12 | Method of obtaining novel cationic dyes |
Country Status (1)
| Country | Link |
|---|---|
| PL (1) | PL161925B2 (en) |
-
1990
- 1990-11-12 PL PL28773490A patent/PL161925B2/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| PL287734A2 (en) | 1991-08-26 |
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