EP0757707A1 - Colorants au methine de thiazole - Google Patents

Colorants au methine de thiazole

Info

Publication number
EP0757707A1
EP0757707A1 EP95915868A EP95915868A EP0757707A1 EP 0757707 A1 EP0757707 A1 EP 0757707A1 EP 95915868 A EP95915868 A EP 95915868A EP 95915868 A EP95915868 A EP 95915868A EP 0757707 A1 EP0757707 A1 EP 0757707A1
Authority
EP
European Patent Office
Prior art keywords
formula
alkyl
methine dyes
hydrogen
residue
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.)
Ceased
Application number
EP95915868A
Other languages
German (de)
English (en)
Inventor
Stefan Beckmann
Karl-Heinz Etzbach
Rüdiger Sens
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.)
BASF SE
Original Assignee
BASF SE
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
Priority claimed from DE19944414882 external-priority patent/DE4414882A1/de
Priority claimed from DE19944434990 external-priority patent/DE4434990A1/de
Priority claimed from DE1995102702 external-priority patent/DE19502702A1/de
Application filed by BASF SE filed Critical BASF SE
Publication of EP0757707A1 publication Critical patent/EP0757707A1/fr
Ceased legal-status Critical Current

Links

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
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/06—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups three >CH- groups, e.g. carbocyanines
    • 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
    • C09B23/0091—Methine or polymethine dyes, e.g. cyanine dyes having only one heterocyclic ring at one end of the methine chain, e.g. hemicyamines, hemioxonol

Definitions

  • the present invention relates to new methine dyes of the formula I.
  • R is hydrogen, optionally substituted -CC-alkyl or optionally substituted phenyl
  • Q 1 is hydrogen, C 1 -C 6 -alkyl, chlorine or bromine and Q 2 is hydrogen or C 1 -C 4 -alkyl, and
  • Y is a residue from the aniline, aminonaphthalene, indole,
  • the object of the present invention was to provide new methine dyes which are advantageously suitable for use in polymeric nonlinear optical systems.
  • dyes should such dyes have high hyperpolarizability values, good thermal stability, good compatibility with the polymers used in non-linear optical systems and good film-forming properties with copolymers.
  • Suitable radicals Y are e.g. those of the formulas Ha to Ili
  • n for 0 or 1
  • Z 3 and Z 4 are identical or different and, independently of one another, each represent hydrogen, Ci-Cio-alkyl, which is optionally substituted and can be interrupted by 1 or 2 oxygen atoms in ether function, C 3 -C 4 alkenyl, C 5 -C 7 cycloalkyl, phenyl or tolyl or together with the nitrogen atom connecting them for a 5- or 6-membered saturated heterocyclic radical which optionally contains further heteroatoms,
  • Z 6 represents hydrogen, halogen, C 1 -C 1 -alkyl, optionally substituted phenyl, optionally substituted benzyl, cyclohexyl, thienyl, hydroxy or C 1 -C 1 -monoalkylamino.
  • Alkenyl groups can be straight or branched.
  • substituents can be, for example, cyano, phenyl, tolyl, hydroxy, C 1 -C 6 -alkanoyloxy.
  • Suitable radicals Q 1 , Q 2 , R, Z 1 , Z 2 , Z 3 , Z 4 , Z 6 and Z 7 are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl.
  • R, Z 1 , Z 3 , Z, Z 6 and Z 7 are further, for example, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl , Decyl or isodecyl (the names isooctyl, isononyl and isodecyl are trivial names and come from the alcohols obtained after oxosynthesis - cf. üllmann's Encyclopedia of
  • Z 1 , Z 3 , Z 4 and Z 7 are, for example, 2-methoxethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 2- or 3-methoxypropyl, 2- or 3-ethoxypropyl, 2- or 3-propoxypropyl, 2- or 3-butoxypropyl, 2- or 4-methoxybutyl, 2- or 4-ethoxybutyl, 2- or 4-butoxybutyl, 3,6-dioxaheptyl, 3, 6-dioxaoctyl, 4, 8 -Dioxanonyl, 3,7-dioxaoctyl, 3,7-dioxanonyl, 4,7-dioxaoctyl, 4,7-dioxanonyl, or 4,8-dioxadecyl.
  • R, Z 3 and Z 4 are, for example, benzyl, 2-methylbenzyl or 1- or 2-phenylethyl.
  • Residues R and Z 6 are, like residues Z 5 , for example phenyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4-ethylphenyl, 2-, 3- or 4-propylphenyl, 2-, 3-or 4-isopropylphenyl, 2-, 3- or 4-butylphenyl, 2,4-dimethylphenyl, 2-, 3- or 4-cyclopropylphenyl, 2-, 3- or 4-cyclobutylphenyl, 2-, 3- or 4-cyclopentylphenyl, 2-, 3- or 4-cyclohexylphenyl, 2-, 3- or 4-cycloheptylphenyl, 2-, 3- or 4-hydroxyphenyl, 2-, 3- or 4-methoxyphenyl , 2-, 3- or 4-ethoxyphenyl, 2-, 3- or 4-isobutoxyphenyl, 2,4-dimethoxyphenyl, 2-, 3- or 4-chlorophenyl, 2,4-dichlorophenyl, 2-, 3- or
  • R, Z 3 and Z 4 are furthermore, for example, 2-cyanoethyl, 2- or 3-cyanopropyl, 2-acetyloxyethyl, 2- or 3-acetyloxypropyl, 2-isobutyryloxyethyl, 2- or 3-isobutyryloxypropyl, 2-methoxycarbonylethyl, 2- or 3-methoxycarbonylpropyl, 2-ethoxcarbonyl-ethyl, 2- or 3-ethoxycarbonylpropyl, 2-dimethylaminocarbonyl-oxyethyl, 2-diethyla inocarbonyloxyethyl, 2- or 3-Di_r.eth.yl-aminocarbonyloxypropyl, 2- or 3- Diethylaminocarbonyloxypropyl, 2-methoxycarbonyloxyethyl, 2- or 3-methoxycarbonyloxypropyl, 2-ethoxycarbonyloxyethyl, 2- or 3-ethoxycarbonyl
  • Residues Z 1 and Z 2 are furthermore, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy or sec-butoxy.
  • Z 1 radicals are, for example, methylsulfonylamino, ethylsulfonylamino,
  • Propylsulfonylamino isopropylsulfonylamino, butylsulfonylamino, mono- or dimethylaminosulfonylamino, mono- or diethylaminosulfonylamino, mono- or dipropylaminosulfonylamino, mono- or diisopropylaminosulfonylamino, mono- or dibutylamino-sulfonylamino-sulfonylamino-sulfonylamino-sulfonylamino-sulfonylamino-sulfonylamino-sulfonylamino
  • Z 5 and Z 6 are, for example, fluorine, chlorine or bromine.
  • Z 6 radicals are also, for example, benzyl, 2-methylbenzyl, 2,4-dimethylbenzyl, 2-methoxybenzyl, 2,4-dimethoxybenzyl, methylamino, ethylamino, propylamino, isopropylamino, butylamino, pentylamino, hexylamino, heptylamino, octylamino or 2-ethylhexyla ino.
  • Z 3 and Z 4 together with the nitrogen atom connecting them represent a 5- or 6-membered saturated heterocyclic radical which may have further heteroatoms, for example pyrrolidinyl, piperidinyl, morpholinyl, piperazinyl or N- (-C-C 4 Alkyl) piperazinyl come into consideration.
  • dyes of the formula I in which Y is derived from a component from the aniline series, in particular residues of the formula Ha.
  • Dyes of the formula I which have at least one polymerizable group, in particular an acryloyloxy or methacryloyloxy radical, are also of particular importance.
  • Another object of the present invention are thiazole derivatives of the formula IVa
  • W is hydrogen, Ci-C ⁇ alkanoyl, acryloyl or methacryloyl.
  • the methine dyes of the formula I can be prepared by methods known per se.
  • the compounds according to the invention are thermally stable and have particularly large molecular hyperpolarizability values ( ⁇ o).
  • the dyes have good compatibility with the polymers used in nonlinear optical systems and good film-forming properties in copolymers.
  • the determination of the molecular hyperpolarizability can e.g. according to the solvatochromism measurement method (see, for example, Z. Naturaba, volume 20a, pages 1441 to 1471, 1965, or J. Org. Chem., volume 54, pages 3775 to 3778, 1989).
  • the position of the absorption band of a compound in various solvents e.g. in dioxane and dimethyl sulfoxide.
  • the shift in the absorption band is then directly proportional to the ßo value, i.e.
  • Compounds with a large solvatochromic shift have a large molecular hyperpolarizability and are therefore well suited for use in nonlinear optical systems (see, for example, Chemistry and Industry, 1990, pages 600 to 608).
  • Mach-Zehnder interferometer e.g. Mach-Zehnder interferometer
  • optical switches in frequency mixing or in waveguides.
  • the new methine dyes of the formula I are also advantageous, for example for dyeing or printing textile materials. These are, for example, fibers or fabrics, in particular made of polyesters, in addition also of cellulose esters or polyamides, or mixed fabrics made of polyesters and cellulose fibers or wool.
  • the new methine dyes of the formula I are advantageously suitable for dyeing bulk polymers, for use in electrophotography as dyes for electrostatic toners or as dyes for thermal transfer.
  • Example 2 was carried out analogously to Example 1, but 4-diethylaminocinnamaldehyde was used instead of the dimethylamino compound. 3.30 g of the compound of the formula were obtained
  • Phenothiazine added. The mixture was then heated to 50 ° C. for 4 h. After this time, the mixture was cooled to 20 ° C., the residue formed was suction filtered and washed with water. The product was dried at 50 ° C under reduced pressure. 0.81 g of the compound of the formula was obtained c) 0.76 g (2.9 mmol) of the compound obtained under b) were stirred in 10 ml of ethanol and with 20 mg of phenothiazine and
  • the compound was heated with 3.5 g (0.02 mol) of 4-dimethylaminocinnamaldehyde in 20 ml of acetic anhydride at 100 ° C. for 1 h. After cooling, the precipitate formed was suction filtered, washed with 20 ml of xylene and 10 ml of methanol. After drying at 50 ° C. under reduced pressure, 2.4 g of the dye of the formula were obtained
  • the suitability of the dyes according to the invention in nonlinear optics is furthermore determined by the determination of the hyperpolar
  • the relevant size ⁇ g ßo in the methine dye 35 according to the invention is 5 times as large as in the compound known from the literature and thus impressively underlines the suitability of the new dyes in non-linear optics.

Landscapes

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

Abstract

L'invention concerne des colorants au méthine de la formule (I) dans laquelle R désigne hydrogène, alkyle C1-C10 substitué ou phényle éventuellement substitué, X désigne azote ou un reste de la formule CQ?1, CH=CQ1¿-CH, CH=CH-CH=CH-CH, (i) ou (ii) où Q1 désigne hydrogène, alkyle C¿1?-C4, chlore ou brome et Q?2¿ désigne hydrogène ou alkyle C¿1?-C4, et Y désigne un reste issu de la série aniline, aminophtaline, indole, aminoquinoléine, aminothiazole ou aminothiophène. L'invention concerne également leur utilisation en optique non linéaire, ainsi que de nouveaux dérivés du thiazole.
EP95915868A 1994-04-28 1995-04-12 Colorants au methine de thiazole Ceased EP0757707A1 (fr)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
DE19944414882 DE4414882A1 (de) 1994-04-28 1994-04-28 Thiazolmethinfarbstoffe
DE4414882 1994-04-28
DE4434990 1994-09-30
DE19944434990 DE4434990A1 (de) 1994-09-30 1994-09-30 Thiazolmethinfarbstoffe
DE19502702 1995-01-28
DE1995102702 DE19502702A1 (de) 1995-01-28 1995-01-28 Thiazolmethinfarbstoffe
PCT/EP1995/001348 WO1995029958A1 (fr) 1994-04-28 1995-04-12 Colorants au methine de thiazole

Publications (1)

Publication Number Publication Date
EP0757707A1 true EP0757707A1 (fr) 1997-02-12

Family

ID=27206322

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95915868A Ceased EP0757707A1 (fr) 1994-04-28 1995-04-12 Colorants au methine de thiazole

Country Status (5)

Country Link
US (1) US5714616A (fr)
EP (1) EP0757707A1 (fr)
JP (1) JPH09512572A (fr)
KR (1) KR970702901A (fr)
WO (1) WO1995029958A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4922301B2 (ja) 2005-09-05 2012-04-25 オスラム オプト セミコンダクターズ ゲゼルシャフト ミット ベシュレンクテル ハフツング 有機電子素子における正孔注入の改善のための新規材料並びに前記材料の使用
CN111548322A (zh) * 2020-06-10 2020-08-18 杭州福莱蒽特股份有限公司 一种甲川类新型染料及合成

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2732221A1 (de) * 1977-07-16 1979-02-01 Basf Ag Organische verbindungen
US4808332A (en) * 1987-10-09 1989-02-28 Hoechst Celanese Corp. Acrylic copolymers exhibiting nonlinear optical response
DE3904797A1 (de) * 1989-02-17 1990-08-30 Merck Patent Gmbh Nichtlinear optische materialien mit vicinalen donor- und akzeptorgruppen
DE4218359A1 (de) * 1992-06-04 1993-12-09 Basf Ag Polymerisate, die Methin- oder Azamethinfarbstoffe enthalten

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9529958A1 *

Also Published As

Publication number Publication date
WO1995029958A1 (fr) 1995-11-09
KR970702901A (ko) 1997-06-10
JPH09512572A (ja) 1997-12-16
US5714616A (en) 1998-02-03

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