DE824818C - Process for the production of cyanine dyes - Google Patents

Process for the production of cyanine dyes

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Publication number
DE824818C
DE824818C DEP12020A DEP0012020A DE824818C DE 824818 C DE824818 C DE 824818C DE P12020 A DEP12020 A DE P12020A DE P0012020 A DEP0012020 A DE P0012020A DE 824818 C DE824818 C DE 824818C
Authority
DE
Germany
Prior art keywords
methylene
weight
parts
cyanine dyes
production
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
Application number
DEP12020A
Other languages
German (de)
Inventor
Dr Max Coenen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Priority to DEP12020A priority Critical patent/DE824818C/en
Application granted granted Critical
Publication of DE824818C publication Critical patent/DE824818C/en
Expired legal-status Critical Current

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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
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/0008—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain
    • C09B23/0025—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain the substituent being bound through an oxygen atom
    • 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
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/0008—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain
    • C09B23/005—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain the substituent being a COOH and/or a functional derivative thereof
    • C09B23/0058—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain the substituent being a COOH and/or a functional derivative thereof the substituent being CN
    • 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
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/14—Styryl dyes
    • C09B23/143—Styryl dyes the ethylene chain carrying a COOH or a functionally modified derivative, e.g.-CN, -COR, -COOR, -CON=, C6H5-CH=C-CN

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Coloring (AREA)

Description

Verfahren zur Herstellung von Cyaninfarbstoffen Es wurde gefunden, daß man neuartige Cyaninfarbstoffe von großer Klarheit der Nuance erhält, wenn man die durch Umsetzung von co-Chloracetylderivaten heterocyclischer Basen mit Salzen der Cyanwasserstoffsäure zugänglichen co-Cyanacetylderivate heterocyclischer Methylenbasen der allgemeinen Formel in der R1 = Äthylen, Vinylen oder Arylen, wie z. B. Phenylen und Naphthylen, R2 = Alkyl, Aralkyl oder Aryl, X,= Stickstoff, Schwefel, Sauerstoff, Vinylen oder Methylen, bedeuten, mit aromatischen oder heterocyclischen Aldehyden umsetzt. Dabei greift die Aldehydgruppe in die der Cyangru.ppe der Methylen,base benachbarte Methylengruppe unter Wasserabspaltung und Verknüpfung der beiden Molekülreste durch eine Doppelbindung ein.Process for the preparation of cyanine dyes It has been found that novel cyanine dyes of great clarity of shade are obtained if the co-cyanoacetyl derivatives of heterocyclic methylene bases of the general formula obtainable by reacting co-chloroacetyl derivatives of heterocyclic bases with salts of hydrocyanic acid in which R1 = ethylene, vinylene or arylene, such as. B. phenylene and naphthylene, R2 = alkyl, aralkyl or aryl, X = nitrogen, sulfur, oxygen, vinylene or methylene, is reacted with aromatic or heterocyclic aldehydes. The aldehyde group intervenes in the methylene group adjacent to the cyangru.ppe of the methylene base, splitting off water and linking the two molecular residues through a double bond.

Als co-Cyanacetylverbindungen heterocycli.scher Methylenbasen können z. B. Verwendung finden: 1, 3, 3-Trimethyl-2-methylen-o)-cyanacetyl-indolin, 5-Methoxy-1, 3, 3-trimethyl-2-methylen-co-cyanacetyl-indolin, r-Methyl-2-methylen-ü)-cyanacetyl-i, 2-dihydrobenzthiazol und i-Methyl-2-rnethylen-cocyanacetyl-i, 2-dihydrochinolin.As co-cyanoacetyl compounds, heterocyclic methylene bases can z. B. Use: 1, 3, 3-trimethyl-2-methylene-o) -cyanacetyl-indoline, 5-methoxy-1, 3, 3-trimethyl-2-methylen-co-cyanoacetyl-indoline, r-methyl-2-methylen-ü) -cyanacetyl-i, 2-dihydrobenzthiazole and i-methyl-2-methylene-cocyanacetyl-1,2-dihydroquinoline.

Als aromatische oder heterocyclische Aldehyde eignen sich für das vorliegende Verfahren z. B.: Benzaldehyd, o-, m- und p-Chlorbenzaldehyd, Salicylaldehyd, p-Oxybenzaldehyd, p-Nitrobenzaldehyd, p-Dimethylaminobenzaldehyd, Pyrrol-2-aldehyd, Indbl-3-al,dehyd, i-Methyl-2-phenyl-indol-3-aldehyd, 1, 3, 3-Trimethyl-2-methylen-irndolin-ü)-aldehyd, i-Methyl-2-methylen-thiazolin-co-aldehyd und i-Methyl-2-methylen-1, 2-dihydrobenzthiazol-(»-aldehyd. In der Regel empfiehlt es sich, die Umsetzung der Komponenten. durch Erhitzen in einem Lösungsmittel in Gegenwart saurer oder alkalischer Kondensatiornsmittel vorzunehmen.As aromatic or heterocyclic aldehydes are suitable for the present proceedings z. E.g .: benzaldehyde, o-, m- and p-chlorobenzaldehyde, salicylaldehyde, p-oxybenzaldehyde, p-nitrobenzaldehyde, p-dimethylaminobenzaldehyde, pyrrole-2-aldehyde, Indbl-3-al, dehyd, i-methyl-2-phenyl-indole-3-aldehyde, 1, 3, 3-trimethyl-2-methylene-indoline-ü) -aldehyde, i-methyl-2-methylene-thiazoline-co-aldehyde and i-methyl-2-methylene-1,2-dihydrobenzthiazole - (»- aldehyde. In It is usually best to implement the components. by heating in one Carry out solvents in the presence of acidic or alkaline condensing agents.

Als Kondensationsmittel eignen sich z. B. Piperidnn, Piperidinacertat, Natriummethylat, Natriumäthylat, Essigsäurearnhydrid, Phosphoroxychlorid, Sulfondtiamid und Cyclohexylsulfondiamid.Suitable condensing agents are, for. B. Piperidnn, Piperidinacertat, Sodium methylate, sodium ethylate, acetic acid anhydride, phosphorus oxychloride, sulfondiamide and cyclohexyl sulfone diamide.

Als Lösungsmittel können z. B. verwendet werden Methanol, Äthanol, Propanol, Butanol, Aceton oder Chloroform.As a solvent, for. B. are used methanol, ethanol, Propanol, butanol, acetone or chloroform.

Die neuen. Cyaninfarbstoffe eignen sich z. B. zum Färben von Gebilden aus Cel.luloseesterrn Beispiel i 24 Gewichtsteile 1, 3, 3-Trimethyl-2-methylen-cocyanacetyl-indolin werden zusammen mit i2 Gewichtsteeilen 4-Oxybenzaldehydi in 5oo Gewichtsteilen Methanol unter Zusatz von 2 Gewichtsteilen Piperidin 3 Stunden, unter Rühren und RückfluB gekocht. Das Reaktionsgemisch färbt sich intensiv dunkelgelb. Man trägt es nach dem Erkalten in 5oo Gewichtsteile Wasser ein und säuert die wässerige Suspension des ausgeschiedenen Farbstoffes mit Essigsäure an. Der in intensiv gelben Flocken abgeschiedene Farbstoff wird aus Methanol umkristallisiert. Man erhält etwa 28 Gewichtsteile eines gelbroten Pulvers, das Acetatseide in klaren goldgelben Tönen färbt. Beispiel e 25 Gewichtssteile 1, 3, 3, 5-Tetramethyl-2-methylen-co-cyanacetyl-indol.in werden in der in; Beispiel i beschriebenen Weise mit. 15 Gewichtsteilen, p-Dimethylaminobenzaldehyd kondensiert. Man erhält 3oGewichtstei,le einfies rotenFarbstoffes, derAcetatseide in orangegelben Tönen färbt.The new. Cyanine dyes are suitable, for. B. for dyeing structures from cellulose ester Example i 24 parts by weight of 1, 3, 3-trimethyl-2-methylenecocyanacetylindoline are together with i2 parts by weight of 4-Oxybenzaldehydi in 500 parts by weight of methanol with the addition of 2 parts by weight of piperidine for 3 hours, with stirring and reflux cooked. The reaction mixture turns an intense dark yellow. One carries it after cooling in 500 parts by weight of water and acidifies the aqueous suspension of the precipitated dye with acetic acid. The one in intense yellow flakes deposited dye is recrystallized from methanol. About 28 parts by weight are obtained a yellow-red powder that dyes acetate silk in clear golden-yellow tones. example e 25 parts by weight of 1, 3, 3, 5- tetramethyl-2-methylen-co-cyanacetyl-indol.in become in the in; Example i described using. 15 parts by weight, p-dimethylaminobenzaldehyde condensed. 30 parts by weight of a red dye, the acetate silk, are obtained colors in orange-yellow tones.

Beispiel 3 27 Gewichtsteile 5-Methoxy-1, 3, 3-trimethyl-2-methylen-w-cyanacetyl-indolin werden zusammen mit 2o Gewichtsteilen 1, 3, 3-Trimethyl-2-methylenindolin-co-aldehyd in 5oo Gewichtsteilen Äthanol unter Zugabe von 2 Gewichtsteilen Natriumäthylat unter RückfluB zum Sieden erhitzt. Aus dem orange gefärbten Reaktionsgemisch wird der Alkohol abdestilliert, wobei der Farbstoff als rotgelbe Kristallmasse von bläulichem Oberflächenglanz hinterbleibt. Die Ausbeute beträgt etwa 3o Gewichtsteile. Der Farbstoff färbt Acetatseide klar orange.Example 3 27 parts by weight of 5-methoxy-1, 3, 3-trimethyl-2-methylene-w-cyanoacetyl-indoline are together with 2o parts by weight 1, 3, 3-trimethyl-2-methyleneindoline-co-aldehyde in 500 parts by weight of ethanol with the addition of 2 parts by weight of sodium ethylate Heated to boiling reflux. The orange colored reaction mixture becomes the Alcohol distilled off, the dye as a red-yellow crystal mass of bluish Surface gloss remains. The yield is about 30 parts by weight. The dye dyes acetate silk clear orange.

Claims (1)

PATENTANSPRUCH: Verfa!hreru zur Herstellung von Cyaninfarbstoffen, dadurch gekennzeichnet, daB man co-Cyanacetylderivate heterocyclischer Methylenbasen der allgemeinen Formel in der R1 = Äthylen, Vinylen oder Arylen, wie z. B. Phenylen und! Naphthylen, R2 = Alkyl, Aralkyl oder Aryl, X = Stickstoff, Schwefel, Sauerstoff, Vinylen oder Methylen bedeuten, mit aromatischen oder heterocyclischen Aldehyden umsetzt. PATENT CLAIM: Process for the production of cyanine dyes, characterized in that co-cyanoacetyl derivatives of heterocyclic methylene bases of the general formula are used in which R1 = ethylene, vinylene or arylene, such as. B. Phenylene and! Naphthylene, R2 = alkyl, aralkyl or aryl, X = nitrogen, sulfur, oxygen, vinylene or methylene, is reacted with aromatic or heterocyclic aldehydes.
DEP12020A 1948-10-02 1948-10-02 Process for the production of cyanine dyes Expired DE824818C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DEP12020A DE824818C (en) 1948-10-02 1948-10-02 Process for the production of cyanine dyes

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Application Number Priority Date Filing Date Title
DEP12020A DE824818C (en) 1948-10-02 1948-10-02 Process for the production of cyanine dyes

Publications (1)

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DE824818C true DE824818C (en) 1951-12-13

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2953561A (en) * 1957-09-24 1960-09-20 Gen Aniline & Film Corp Nitrostyryl dye bases and vinylogs thereof derived from 2-cyanomethylazoles
US2957005A (en) * 1960-10-18 W-axdehydes of

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2957005A (en) * 1960-10-18 W-axdehydes of
US2953561A (en) * 1957-09-24 1960-09-20 Gen Aniline & Film Corp Nitrostyryl dye bases and vinylogs thereof derived from 2-cyanomethylazoles

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