DE4401911A1 - Use of aryl or heteroarylazoanilines in non-linear optics - Google Patents

Abstract

The invention relates to the use in non-linear optics of azo dyes of formula I and the use of polymers containing azo dyes which include as characteristic monomer units bivalent groups derived from an azo dye of formula (I) wherein: D represents the residue of a diazo component derived from an aniline or from a five-membered aromatic heterocyclic amine whose heterocyclic ring includes one to three heteroatoms chosen from the group nitrogen, oxygen and sulphur and which can be anellated by a benzene, thiophene, pyridine or pyrimidine ring; R<1> and R<2> represent, independently of each other, hydrogen, C1-C6-alkyl or C5-C7-cycloalkyl; and R<3> and R<4> represent, independently of each other, hydrogen or C1-C6 alkyl which can be substituted by hydroxyl, acryloyloxyl or methacryloyloxyl, at least one of the two groups R<1> and R<2> not being hydrogen.

Description

The present invention relates to the use of azo color substances with a diazo component that differs from aniline or from a five-membered aromatic heterocyclic amine conducts one to three heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, in hetero cyclic ring and by a benzene, thiophene, Pyridine or pyrimidine ring can be fused, and one Coupling component from the aniline series in the non-linear optics, Polymers that differ from the azo dyes mentioned direct, and their use in nonlinear optics.

The nonlinear optical properties of organic compounds are used in many areas of optoelectronics. Examples of this are applications in frequency doubling, in Phase modulators, optical amplifiers, interferometers, optical switches or in telecommunications.

It is well known that organic materials, in particular other polymers with special chromophores nonlinear optical Can have properties that are sometimes greater than the comparable inorganic materials.

The currently most commonly used materials are on organic crystals, e.g. B. from potassium dihydrogen phosphate or Lithium niobate. These crystals are complex and high Manufacturing costs as well, due to their rigid structure only difficult to use in optical devices. Another disadvantage are their low nonlinear effects.

A particular advantage of suitable organic chromophores and their application in polymeric materials lies in their simple Manufacturing and processing.

The chromophores used in nonlinear optics are in usually in either crystalline or polymer-bound form used.

From Angew. Chem., Vol. 96, pages 637 to 651, 1984, is the An use of stilbene derivatives or special azo dyes for known this purpose.

The object of the present invention was to find suitable ones organic chromophores based on aryl or heteroarylazo Provide anilines that are beneficial for use suitable in nonlinear optical systems. In particular, should such azo compounds have high hyperpolarizability values point.

It has now been found that azo dyes of the formula I

in the

D for the remainder of a diazo component which is derived from an aniline or from a five-membered aromatic heterocyclic amine which has one to three heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur in the heterocyclic ring and by a benzene, Thiophene, pyridine or pyrimidine ring can be fused,
R¹ and R² are each independently hydrogen, C₁-C₆-alkyl or C₅-C₇-cycloalkyl and
R³ and R⁴ independently of one another each represent hydrogen or C₁-C₆-alkyl, which can be substituted by acryloyloxy or methacryloyloxy,

with the proviso that at least one of the two radicals R¹ and R² is different from hydrogen,
advantageous for use in nonlinear optics.

The use of azo dyes according to the invention is preferred of the formula I in which D represents the remainder of a diazo component, which differs from an aniline or from a heterocyclic amine from the pyrrole, furan, thiophene, pyrazole, imidazole, oxazole, Isoxazole, thiazole, isothiazole, triazole, oxadiazole, thiadi azole, benzofuran, benzthiophene, benzimidazole, benzoxazole, Benzothiazole, benzisothiazole, pyridothiophene, pyrimidothiophene or thienothiazole series.  

The use of azo according to the invention is particularly preferred dyes of formula I, the D for the rest of a diazo component nente, which differs from an aniline or from a hetero cyclic amine from the pyrrole, thiophene, pyrazole, thiazole, Isothiazole, triazole, thiadiazole, benzthiophene, benzothiazole, Benzisothiazole, pyridothiophene, pyrimidothiophene or thieno thiazole series.

The use of such azo color is of particular importance substances of the formula I in the nonlinear optics, in the

D for a residue of the formula

stands in what

L¹ nitro, cyano, C₁-C₆-alkanoyl, benzoyl, C₁-C₆-alkylsulfonyl, optionally substituted phenylsulfonyl or a radical of the formula -CH = T, where T is hydroxyimino, C₁-C₄-alkoxyimino or a radical of a CH- has an acidic compound,
L² is hydrogen, C₁-C₆-alkyl, halogen, hydroxy, mercapto, optionally substituted by phenyl or C₁-C₄-alkoxy, C₁-C₆-alkoxy, optionally substituted phenoxy, optionally substituted by phenyl, C₁-C₆-alkylthio, optionally substituted phenylthio , C₁-C₆ alkylsulfonyl or optionally substituted phenylsulfonyl,
L³ cyano, C₁-C₄ alkoxycarbonyl or nitro,
L⁴ hydrogen, C₁-C₆ alkyl or phenyl,
L⁵ C₁-C₆ alkyl or phenyl,
L⁶ hydrogen, cyano, C₁-C₄ alkoxycarbonyl, C₁-C₆ alkanoyl, thiocyanato or halogen,
L⁷ phenyl, nitro, cyano, C₁-C₆ alkanoyl, benzoyl, C₁-C₄ alkoxy carbonyl, C₁-C₆ alkylsulfonyl, optionally substituted phenylsulfonyl or a radical of the formula -CH = T, in which T has the abovementioned meaning,
L⁸ hydrogen, C₁-C₆-alkyl, cyano, halogen, optionally substituted by phenyl or C₁-C₄-alkoxy C₁-C₆-alkoxy, optionally substituted by phenyl, C₁-C₆-alkylthio, optionally substituted phenylthio, C₁-C₆-alkylsulfonyl , optionally substituted phenylsulfonyl or C₁-C₄-alkoxycar bonyl,
L⁹ cyano, optionally substituted by phenyl C₁-C₆-alkyl, optionally substituted by phenyl C₁-C₆-alkylthio, optionally substituted phenyl, thienyl, C₁-C₄-alkyl thienyl, pyridyl or C₁-C₄-alkylpyridyl,
L¹⁰ phenyl or pyridyl,
L¹¹ trifluoromethyl, nitro, C₁-C₆-alkyl, phenyl, optionally substituted by phenyl C₁-C₆-alkylthio or C₁-C₆-dialkylamino,
L¹² C₁-C₆-alkyl, phenyl, 2-cyanoethylthio or 2- (C₁-C₄-alkoxy carbonyl) ethylthio,
L¹³ hydrogen, nitro or halogen,
L¹⁴ hydrogen, cyano, C₁-C₄ alkoxycarbonyl, nitro or halogen and
L¹⁵, L¹⁶ and L¹⁷ are the same or different and are each independently hydrogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, halo gene, nitro, formyl, cyano, C₁-C₄-alkoxycarbonyl, C₁-C₆-alkyl sulfonyl or optionally substituted phenylsulfonyl or L¹⁶ also optionally substituted by nitro-substituted phenylazo.

All alkyl occurring in the above formulas I and II groups can be straight or branched.

If substituted phenyl in the above formulas I and II Unless otherwise noted, groups can occur as sub stituents z. B. C₁-C₄ alkyl, chlorine, bromine, nitro or C₁-C₄ alkoxy be considered. The phenyl radicals usually have 1 up to 3 substituents.

Radicals L², L⁴, L⁵, L⁸, L⁹, L¹¹, L¹², L¹⁵, L¹⁶, L¹⁷, R¹, R², R³ and R⁴ are z. B. methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl or 2-methylpentyl.

R¹ and R² are z. B. cyclopentyl, cyclohexyl or Cycloheptyl.

R³ and R⁴ are still z. B. 2-hydroxyethyl, 2-hydroxy propyl, 3-hydroxypropyl, 2-hydroxybutyl, 4-hydroxybutyl, 5-hydroxypentyl, 6-hydroxyhexyl, 2-aminoethyl, 2-aminopropyl, 3-aminopropyl, 2-aminobutyl, 4-aminobutyl, 5-aminopentyl, 6-aminohexyl, 2-acryloyloxyethyl, 2-methacryloyloxyethyl, 2- or 3-acryloyloxypropyl, 2- or 3-methacryloyloxypropyl, 2- or 4-acryloyloxybutyl, 2- or 4-methacryloyloxybutyl, 5-acryloyl oxypentyl, 5-methacryloyloxypentyl, 6-acryloyloxyhexyl or 6-methacryloyloxyhexyl.

L⁹ are still z. B. benzyl or 1- or 2-phenylethyl.  

L², L⁸, L⁹ and L¹¹ are z. B. Methylthio, ethyl thio, propylthio, isopropylthio, butylthio, isobutylthio, pen tylthio, hexylthio, benzylthio or 1- or 2-phenylethylthio.

L² and L⁸ are still z. B. phenylthio, 2-methylphenyl thio, 2-methoxyphenylthio or 2-chlorophenylthio.

L², L⁸, L¹⁵, L¹⁶ and L¹⁷ are also z. B. methoxy, ethoxy, Propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, pentyloxy, Isopentyloxy, neopentyloxy, tert-pentyloxy, hexyloxy or 2-methylpentyloxy.

Residues L⁶ are, like also residues L², L⁸, L¹³, L¹⁴, L¹⁵, L¹⁶ and L¹⁷, e.g. B. fluorine, chlorine or bromine.

Residues L⁷ are, like also residues L¹, L², L⁸, L¹⁵, L¹⁶ and L¹⁷, e.g. B. methylsulfonyl, ethylsulfonyl, propylsulfonyl, iso propylsulfonyl, butylsulfonyl, isobutylsulfonyl sec-butyl sulfonyl, pentylsulfonyl, isopentylsulfonyl, neopentylsulfonyl, Hexylsulfonyl, phenylsulfonyl, 2-methylphenylsulfonyl, 2-methoxy phenylsulfonyl or 2-chlorophenylsulfonyl.

L³ residues are, like also residues L⁶, L⁷, L⁸, L¹⁴, L¹⁵, L¹⁶ and L¹⁷, e.g. B. methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, Isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl or sec-butoxycarbonyl.

L² and L⁸ are still z. B. 2-methoxyethoxy, 2-ethoxy ethoxy, 2- or 3-methoxypropoxy, 2- or 3-ethoxypropoxy, 2- or 4-methoxybutoxy, 2- or 4-ethoxybutoxy, 5-methoxypentyl oxy, 5-ethoxypentyloxy, 6-methoxyhexyloxy, 6-ethoxyhexyloxy, Benzyloxy or 1- or 2-phenylethoxy.

Residues L¹¹ are still z. B. Dimethylamino, Diethylamino, Di propylamino, diisopropylamino, dibutylamino, dipentylamino, di hexylamino or N-methyl-N-ethylamino.

Residues L¹² are still z. B. 2-methoxycarbonylethylthio or 2-ethoxycarbonylethylthio.

L⁹ are still z. B. phenyl, 2-, 3- or 4-methylphenyl, 2,4-dimethylphenyl, 2-, 3- or 4-methoxyphenyl, 2-, 3- or 4-chlorophenyl, 2-, 3- or 4-methoxyphenyl, 2- or 3-methyl thienyl or 2-, 3- or 4-methylpyridyl.  

L¹, L⁶ and L⁷ are still z. B. formyl, acetyl, propionyl, Butyryl, pentanoyl or hexanoyl.

When L¹ or L⁷ are -CH = T, where T is from a CH-acidic compound H₂T derives, can be as CH-acidic Connections H₂T z. B. Compounds of formula

come into consideration, whereby

Z¹ cyano, nitro, C₁-C₄-alkanoyl, optionally substituted benzoyl, C₁-C₄-alkylsulfonyl, optionally substituted phenylsulfonyl, carboxyl, C₁-C₄-alkoxycarbonyl, C₃-C₄-alkenyl oxycarbonyl, phenoxycarbonyl, carbamoyl, C₁-C₄-mono- or di alkylcarbamoyl, optionally substituted phenylcarbamoyl, optionally substituted phenyl, benzthiazol-2-yl, benzimidazol-2-yl, 5-phenyl-1,3,4-thiadiazol-2-yl or 2-hydroxyquinoxalin-3-yl,
Z² C₁-C₄-alkyl, C₁-C₄-alkoxy or C₃-C₄-alkenyloxy,
Z³ C₁-C₄-alkoxycarbonyl, C₃-C₄-alkenyloxycarbonyl, phenylcarbamoyl or benzimidazol-2-yl,
Z⁴ cyano, C₁-C₄ alkoxycarbonyl or C₃-C₄ alkenyloxycarbonyl,
Z⁵ hydrogen, C₁-C₆-alkyl, C₁-C₄-alkanoylamino or benzoyl amino,
Z⁶ is hydrogen, C₁-C₄ alkyl or phenyl,
Z⁷ oxygen or sulfur and
Z⁸ C₁-C₄ alkyl mean.

The rest of the compounds of formula IIIa, IIIb or IIIc, where Z¹ is cyano, C₁-C₄ alkanoyl, C₁-C₄-alkoxycarbonyl or C₃-C₄-alkenyloxycarbonyl, Z² C₁-C₄-alkyl, C₁-C₄-alkoxy or C₃-C₄-alkenyloxy, Z³ C₁-C₄-alkoxycarbonyl or C₃-C₄-alkenyloxycarbonyl and Z⁴ cyano mean to emphasize.

Of particular note is the rest of Verbin of the formulas IIIa, IIIb or IIIc, in which Z¹ is cyano, C₁-C₄-alkoxycarbonyl or C₃-C₄-alkenyloxycarbonyl, Z² C₁-C₄-alkoxy or C₂-C₄-alkenyloxy, Z³ C₁-C₄-alkoxycarbonyl or C₃-C₄-alkenyl oxycarbonyl and Z⁴ mean cyano.

The use of azo color according to the invention should be emphasized substances of formula I, in the D for the rest of a diazo component stands, which is from an aniline, aminothiazole or aminothiophene derives, with residues of the formula IIb, IId or IIp particularly to are called.

The use of Azo dyes of the formula I in which R¹ is hydrogen and R² is C₁-C₄ alkyl.

The use of Azo dyes of the formula I in which R³ and R⁴ independently of one another which each represent C₁-C₄-alkyl.

The use of Azo dyes of the formula I in which R¹ is hydrogen and R² is C₃-C₄-alkyl, in particular for isopropyl, sec-butyl and tert Butyl, stand.

Also to be particularly emphasized is the Ver Use of azo dyes of the formula I in which D represents a radical of the formula IIb, IId or IIp, in which

L¹ nitro, cyano or formyl,
L² C₁-C₄ alkyl or halogen,
L³ cyano, C₁-C₄ alkoxycarbonyl or nitro,
L⁷ phenyl, cyano or formyl,
L⁸ C₁-C₄ alkyl or halogen,
L¹⁵ hydrogen,
L¹⁶ nitro, cyano or C₁-C₄ alkoxycarbonyl and
L¹⁷ is hydrogen or nitro.

The azo dyes of the formula I are known per se and, for. B. in EP-201 896, DE-A-31 08 077, US-A-4 843 153 or GB-A-1 546 803 or can be according to those mentioned there Methods can be obtained.

The azo dyes of the formula I have particularly large molecular ones Hyperpolarizability values (β).

The present invention further relates to azo dyes polymers that hold as characteristic monomer units a bivalent radical, which differs from an azo dye of Formula I derives, as well as residues of formulas IV, V and VI

have wherein

Q¹ is hydroxy, C₁-C₆ alkoxy, oxiranylmethoxy, phenoxy, amino or C₁-C₄ mono- or dialkylamino,
Q² is hydrogen or methyl and
W is C₂-C₁₀ alkylene,

where the proportion of the monomer units of the bivalent radicals which derived from formula I, 1 to 100 mol%, that of formula IV 0 to 99 mol%, that of the formula V 0 to 99 mol% and that  Formula VI 0 to 75 mol%, in each case based on the polymer, and the average molecular weight of the polymer 1000 to 500,000.

Preferably a bivalent residue obeys which differs from one Azo dye of the formula I is derived, the formula VII

wherein Y is C₂-C₆ alkylene and D, R¹, R², R⁴ and Q² each have the above meaning.

The production of the new polymers can be per se knew methods such as z. B. in J. Polymer Sci., Part A, Poly mer Chem., volume 28, pages 1 to 13, 1990, he consequences.

It is advisable to use an appropriate azo dye Formula I with an acrylic compound of formula VIII

in which Q¹ and Q² each have the meaning given above, Styrene and a cinnamic acid ester of formula IX

in which Q² and W each have the meaning given above, in the above molar ratio in an inert solvent (e.g. Toluene or xylene) in the presence of a radical initiator (e.g. azo bis-isobutyronitrile).

Polymers containing the azo dyes of the formula I, too are advantageous for use in nonlinear optics.

The polymers according to the invention are thermally stable and ver add particularly large molecular hyperpolarizability values (β).  

The determination of the molecular hyperpolarizability can e.g. B. according to the solvatochromism measurement method (see for example Z. Natur Research, Volume 20a, pages 1441 to 1471, 1965, or J. Org. Chem., Volume 54, pages 3775 to 3778, 1989). One determines the position of the absorption band of a compound in different those solvents. The shift of the absorption band is then directly proportional to the β value, i.e. H. Connections with large solvatochromic shift exhibit a large molecular hyper polarizability and are therefore well suited for use in nonlinear optical systems (see for example Chemistry and Industry, October 1, 1990, pages 600 to 608).

In particular, the suitability of the dyes in the Telecommunications, in electro-optical modulators (e.g. mach Zehnder inferometer), in optical switches, at frequency mix or highlight in waveguides.

The following examples are intended to explain the invention in more detail.

Manufacture of dyes Dye 1

9.15 g (0.05 mol) of 2,4-dinitroaniline were dissolved in 30 ml of sulfuric acid (85 wt .-%) submitted and at 0 to 5 ° C with 17 g nitrosyl sulfuric acid added. The mixture was stirred at 0 to 5 ° C for 2 h. On the suspension obtained was then added to a solution of 14.3 g (0.05 mol) of N, N-dibutyl-2-isopropylaniline in 100 ml of ice vinegar. The mixture was stirred at 0 to 5 ° C for 1 h and then with vinegar ester extracted. A column filtration over silica gel with toluene 4.2 g of dye of the formula gave as solvent

Dye 2

6.9 g (0.05 mol) of 4-nitroaniline were dissolved in 30 ml of sulfuric acid dissolves and diazotized at 0 to 5 ° C with 17 g of nitrosylsulfuric acid. The mixture was stirred at 0 to 5 ° C for 2 h and then the solution was added to one Suspension of 14.34 g (0.05 mol) of N, N-dibutyl-2-isopropylaniline in 100 ml of water, 50 ml of hydrochloric acid and 50 ml of glacial acetic acid. After that was stirred for 1 h at 20 ° C and then extracted with ethyl acetate. The solvent was removed under reduced pressure and the  Residue by column filtration over silica gel with toluene as Solvent cleaned. 3.95 g of the dye were obtained formula

Dye 3

1.05 g (0.005 mol) of 2-amino-4-chloro-5-phenylthiazole was added in 8 ml Glacial acetic acid / propionic acid (17: 3 v / v) and suspended at 0 to 5 ° C 2 ml of 85% by weight sulfuric acid are added. At this temperature 1 ml of nitrosylsulfuric acid was added. This solution was given to a suspension of 1.45 g (0.005 mol) of N, N-dibutyl-2-iso propylaniline in 20 g ice water, 0.2 g amidosulfonic acid and 2.5 ml conc. Hydrochloric acid. The mixture was stirred for a further 15 h at 20 ° C. and extra then with glacial acetic acid. After evaporation of the solution the product was purified by means of reduced pressure Column chromatography on silica gel with ethyl acetate / toluene (1: 2 v / v) as eluent. 1.48 g of the dye were obtained formula

C₂₆H₃₃N₄SCl (469.10)
Calcd: C 66.57; H 7.03; N 11.94.
Found: C 66.20; H 6.98; N 12.03.

Dye 4

3.5 g (0.02 mol) of 3,5-dicyano-4-methyl-1-aminothiophene were added to 60 ml glacial acetic acid / propionic acid (17: 3 v / v) suspended and at 20 ° C. mixed with 20 ml of 85 wt .-% sulfuric acid. Then was added dropwise at 0 ° C 4 ml nitrosylsulfuric acid. The resulting one light brown suspension was stirred at 0 to 5 ° C for 2 h and then towards a solution of N, N-dibutyl-2-isopropylaniline in 50 ml Ice water, 1 g amidosulfonic acid and 6 ml conc. Given hydrochloric acid. The pH was adjusted to 4 with sodium acetate and the mixture was left Stir at 20 ° C for 1 h. Then you sucked off the dye, washed with water and dried under reduced pressure. The dye  was by column chromatography on silica gel with the Laufmit toluene / ethyl acetate (2: 1 v / v) system. You got 4.1 g of the dye of the formula

C₂₄H₃₁N₅S (421.61)
Calcd: C 68.37; H 7.93; N 16.61; S 7.59.
Found: C 68.54; H 7.88; N 15.98; S 7.19.

According to the in Z. Naturforschung, volume 20a, pages 1441 to 1471, 1965, the method described was the absorption maximum individual dyes in dioxane and dimethyl sulfoxide (DMSO) and then the solvatochromic shift Δ  [cm^-1] certainly.

The respective measurement results are shown in the following table leads.

table

Claims (8)

1. Use of azo dyes of the formula I. in derD for the remainder of a diazo component which is derived from an aniline or from a five-membered aromatic heterocyclic amine which has one to three heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur in the heterocyclic ring and by one Benzene, thiophene, pyridine or pyrimidine ring can be fused,
R¹ and R² are each independently hydrogen, C₁-C₆-alkyl or C₅-C₇-cycloalkyl and
R³ and R⁴ each independently represent hydrogen or C₁-C₆-alkyl, which may be substituted by acryloyloxy or methacryloyloxy, with the proviso that at least one of the two radicals R¹ and R² is different from hydrogen,
in nonlinear optics. 2. Use of azo dyes according to claim 1, characterized ge indicates that D represents the remainder of a diazo component, which differs from an aniline or from a heterocyclic Amine from the pyrrole, furan, thiophene, pyrazole, imidazole, Oxazole, isoxazole, thiazole, isothiazole, triazole, Oxadiazole, thiadiazole, benzofuran, benzthiophene, benz imidazole, benzoxazole, benzthiazole, benzisothiazole, Pyridothiophene, pyrimidothiophene or thienothiazole series derives.   3. Use of azo dyes according to claim 1, characterized ge indicates that D represents the remainder of a diazo component, which differs from an aniline or from a heterocyclic Amine from the pyrrole, thiophene, pyrazole, thiazole, iso thiazole, triazole, thiadiazole, benzthiophene, benzthiazole, Benzisothiazole, pyridothiophene, pyrimidothiophene or Thienothiazole series. 4. Use of azo dyes according to claim 1, characterized characterized in that R¹ is hydrogen and R² is C₁-C₄ alkyl stand. 5. Use of azo dyes according to claim 1, characterized ge indicates that R³ and R⁴ are each independently for C₁-C₄ alkyl. 6. Use of azo dyes according to claim 1, characterized ge indicates that R¹ for hydrogen and R² for C₃-C₄-alkyl stands. 7. Azo-containing polymers which, as characteristic monomeric units, have a bivalent radical which is derived from an azo dye of the formula I according to claim 1, and also residues of the formulas IV, V and VI in whichQ¹ is hydroxy, C₁-C₆alkoxy, oxiranylmethoxy, phenoxy, amino or C₁-C₄mono- or dialkylamino,
Q² is hydrogen or methyl and
W is C₂-C₁₀ alkylene, the proportion of the monomer units of the bivalent radicals derived from formula I being 1 to 100 mol%, those of the formula IV 0 to 99 mol% and those of the formula V 0 to 99 mol -% and that of the formula VI 0 to 75 mol%, in each case based on the polymer, and the average molecular weight of the polymer are 1000 to 500,000. 8. Use of the azo-containing polymers according to Claim 7 in nonlinear optics.