DE3609804A1 - Thiazolyl cyano-coumarins and their use for the areal concentration of light - Google Patents

Abstract

The invention relates to coumarin derivatives of the general formula <IMAGE> in which B<1> and B<2> are identical or different aliphatic, cycloaliphatic, aromatic or heterocyclic radicals, X is oxygen or imino, Z<1> is hydrogen, C1- to C4-alkyl, C1- to C4-alkyl which is optionally substituted by hydroxyl, cyano, C1- to C4-alkoxy, chlorine, bromine, carboxyl, carbo-C1- to -C4-alkoxy, carboxamido or acetoxy, or is cyclohexyl, benzyl, phenylethyl, phenyl or p-tolyl, Z<2> is hydrogen, C1- to C4-alkyl or C1- to C4-alkyl which is optionally substituted by cyano, C1- to C4-alkoxy, chlorine, bromine, carboxyl, carbo-C1- to -C4-alkoxy, carboxamido or acetoxy, Z<1> and Z<2>, together with the nitrogen, are the radical of a 5- or 6-membered saturated heterocyclic ring, and Z<1> and/or Z<2> may each form a ring with the ortho position (with respect to the N atom). The compounds according to the invention are suitable as fluorescent compounds in plastics, light-collecting systems and as laser dyes.

Description

Devices in which visible light is incorporated into plastic Fluorescent dyes can be concentrated, for. B. from the German Publications 30 01 857, 26 20 115 and 25 54 226 known.

The fluorescent compounds are required for the conversion of light energy have high lightfastness in electrical or thermal energy, so that usually consist of transparent plastics Devices have a service life sufficient for the application.

It is also used to convert light into electrical energy particularly advantageous if the compounds used have good separation of absorption and emission bands in that used in the application Have medium. It is also advantageous if they are individually or in combination with other fluorescent dyes if possible absorb a large part of the visible sunlight and as fluorescent light submit.

It is also crucial for the efficiency of the light concentration the fluorescence quantum yield and the solubility of the fluorescent dye in the application medium, e.g. B. in the polymer matrix. Each scattering particles leads to a disruption of the light conduction by deflection of light in unwanted directions.

The object of the present invention was for the known devices to provide suitable compounds for light concentration, the one high fluorescence, good solubility in the application medium at the same time have high light fastness and a wide absorption range.

It has now been found that the concentration of Light in plastic sheets or foils achieves excellent results, if new coumarin derivatives of the general formula I

used in the
B ¹ and B ^{2 are the} same or different aliphatic, cycloaliphatic, aromatic or heterocyclic radicals,
X oxygen or imino,
Z ^{1 is} hydrogen, C ₁ - to C ₄ -alkyl, optionally substituted by hydroxy, cyano, C ₁ - to C ₄ -alkoxy, chlorine, bromine, carboxyl, carb-C ₁ - to C ₄ -alkoxy, carbonamide or acetoxy ₁ - to C ₄ -alkyl, cyclohexyl, benzyl, phenylethyl, phenyl or p-tolyl,
Z ² is hydrogen, C ₁ - to C ₄ -alkyl or optionally substituted by cyano, C ₁ - to C ₄ -alkoxy, chlorine, bromine, carboxyl, carb-C ₁ - to C ₄ -alkoxy, carboxamide or acetoxy-substituted C ₁ - to C ₄ alkyl and
Z ¹ and Z ² together with the nitrogen represent the residue of a 5- or 6-membered saturated heterocyclic ring and Z ¹ and / or Z ^{2 can} each form a ring with the ortho position (to the N atom).

The compounds of the formula I are notable for very good solubility in the substrate. They also have fluorescence quantum yields that are above Φ = 0.9.

Aliphatic radicals B ¹ and B ² are e.g. B. C ₁ - to C ₁₈ alkyl radicals, which may be linear or branched and optionally interrupted by -O-, -S- or N- and also substituted.

As substituents are z. B. C ₁ - to C ₁₈ alkoxy, C ₁ - to C ₁₈ alkylthio, hydroxy, alkanoyloxy, cycloaliphatic groups, heterocyclic groups, phenyl, phenoxy and / or phenylthio. If there is more than one substituent, these may be the same or different. The number of substituents on the alkyl is preferably 0 or 1.

Suitable cycloaliphatic radicals for B ¹ and B ^{2 are} preferably those having 5 to 6 carbocyclic ring members, these radicals generally having 4 to 30 C atoms. The cycloaliphatic radicals can e.g. B. be substituted by one or more of the following groups: hydroxy, C ₁ - to C ₅ alkyl, methoxy, ethoxy, C ₁ or C ₂ alkylthio; C ₁ - to C ₁₈ -alkanoyloxy and / or carbo-C ₁ - to C ₈ -alkoxy. The cycloaliphatic radicals are derived, for. B. from cyclohexane, from Diels-Alder adduction of cyclopentadiene or cyclohexadiene as diene and C ₂ - to C ₁₈ -alkenes, cyclopentene, cyclohexene, optionally substituted enol ethers, cyclopentenes, cyclohexenes and unsaturated carboxylic acids as the dienophile component.

Aromatic radicals which do not contain any water-solubilizing groups are for B ¹ and B ^2, optionally through chlorine, bromine, hydroxyl, methoxy, ethoxy, methyl, C ₁ -C ₄ -alkyl mercapto, C ₁ -C ₄ -alkanoylamino or C ₁ to C ₄ alkylamino substituted phenyl.

Individual radicals B ¹ and B ² are in addition to the z. B .:
Methyl, ethyl, n- or i-propyl, n-butyl, sec.-butyl, i-butyl, pentyl, hexyl, 2,3-dimethylbutyl, neopentyl, heptyl, 2-methylhexyl, 3-methylhexyl, n- or i -Octyl, 2-ethylhexyl, 6-methylheptyl- (2), 1- or 2-nonyl, 1- or 2-decyl, 2-methylnonyl- (1), 2-methylnonyl- (2), undecyl, dodecyl, tridecyl , Tetradecyl, hexadecyl or octadecyl;
Benzyl, 2-phenylethyl, 2- or 3-phenylpropyl, 3- or 4-phenylbutyl, phenylthioethyl, 2- or 3-phenylthiopropyl, 2-phenoxyethyl or 2- or 3-phenoxypropyl;
- (CH ₂ CH ₂ O) _p -OR ¹ or - (CH ₂ ) ₃ - (OCH ₂ -CH ₂ -) _{p -} -OR ¹ with R ¹ = H, -CH ₃ , -C ₂ H ₅ , - CH (CH ₃ ) ₂ , -C ₄ H ₉ (n) and
p = 1, 2, 3, 4, or 5;
- (CH ₂ ) ₃ ) -OR ² with R ² = C ₁ - to C ₁₃ -alkyl, such as methyl, ethyl, n- or i-propyl, n- or i-butyl, pentyl, n-hexyl, n- Octyl, 2-ethylhexyl, dodecyl, tridecyl, decyl, 2-ethylbutyl or 2-dodecylthioethyl; 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxy-2,2-dimethylpropyl- (1), 8-hydroxy-8-methyl-nonyl- (2) or 4-hydroxybutyl- (2);
2,3-dimethyl-4-stearoyloxy-butyl- (1) or - (2), 3-stearoyloxy-2,2-dimethylpropyl- (1), 2- (3'-heptanoyloxy) -2-methyl-nonyl- (8), 2-stearoyloxy-2-methyl- (8), 4- (3'-heptanoyloxy) butyl- (2), 4-stearoyloxylbutyl (1), 4-butanoyloxy-butyl- (2), 4- (2'-Butanoyloxy) butyl- (2), 8-butanoyloxy-8-methyl-nonyl- (2), 8- (2'-butanoyloxy) -8-methylnonyl- (2), 4-acryloyloxybutyl- (1 ), 4-methacryloyloxy-butyl- (1), 2,3-dimethyl-4-acryloyloxy-butyl- (1) or 2,3-dimethyl-4-methacryloyloxy-butyl- (1);
3-cyanopropyl- (2), 3-cyano-2-methyl-propyl- (1); 1-cyanocyclohexyl or 3-cyano-2-methyl-propyl- (2);
2-cyclohexylethyl, cyclohexylmethyl, bicyclooctylmethyl, adamantylmethyl, adamantylethyl or norbornylmethyl;
2-furanylmethyl, 2-thiopentylmethyl, 2'-pyridylethyl- (2) or 2-pyridylmethyl;
Cyclohexyl, 4-t-butylcyclohexyl, 2,6-dimethylcyclohexyl, 3,3,5- and 2,4,6-trimethylcyclohexyl, 4-isopropylcyclohexyl or 4-methylcylcohexyl;
Bicyclo- [2,2,2] octyl, dicyclopentadienyl, tricyclo- [ ^0.2.10 ] decyl, adamantyl, pinanyl, norbornyl, bornyl or decahydroanthryl- (10);
Phenyl, 2-, 3- or 4-fluorophenyl, 2-, 3- or 4-chlorophenyl, 2-, 3- or 4-bromophenyl, 2-, 3- or 4-tert-butylphenyl, 2-phenylphenyl, 2 -Isopropyl-4-methylphenyl, 2,3-, 2,4-, 2,5- or 2,6-dichlorophenyl, 2,4,5- or 2,4,6-trichlorophenyl, 2-, 3- or 4 -Methylphenyl, 2,3-, 2,4-, 2,5-, 2,6- or 3,5-dimethylphenyl, 2,5,6-trimethylphenyl, 2-methyl-4-chlorophenyl, 3-methyl-5 -chlorophenyl, 2-methyl-6-chlorophenyl, 2-ethylphenyl, 2,6-diethylphenyl, 2,6-diethyl-4-methylphenyl, 2-isopropylphenyl, 4-n-dodecylphenyl, 4-chloro-2-nitrophenyl, 4 -Cyanophenyl-o-nitrophenyl, 2-chloro-5-nitrophenyl, 3-methyl-4-chlorophenyl, 2-methyl-4-nitrophenyl, 3-methyl-4-nitrophenyl, 4-methyl-2-nitrophenyl, 2-cyclohexyl -4-methylphenyl, 2-cyclohexylphenyl, 4-cyclohexylphenyl, 2-, 3- and 4-benzylphenyl, 2-benzyl-4-chlorophenyl, 4-n-propylphenyl or 4-n-butylphenyl.

In the substituted amino radicals of the formula

In addition to the radicals already mentioned, the following may be mentioned as substituents, for example:
For Z ¹ and Z ² : methyl, ethyl, n- or i-propyl, n- or i-butyl, β-methoxyethyl, β-ethoxyethyl, β-acetoxyethyl, β-chloroethyl, β-carbomethoxyethyl, β-carboethoxyethyl, β -Carbobutoxyethyl, β-methoxypropyl, β-ethoxypropyl, β-methoxy-γ-chloropropyl, β-acetoxypropyl, β-cyanoethyl or β-hydroxyethyl.

Together with the nitrogen Z ¹ and Z ² mean z. B. the rest of pyrrolidine, piperidine, 3-methylpiperidine, 4-methylpiperidine, 2-methyl-4-phenylpiperidine, morpholine, piperazine or N-methylpiperazine.

To prepare the compounds of the formula I, it is first possible to use compounds of formula II

with compounds of formula III

to compounds of the formula IV

implement, Y is cyan, C ₁ - to C ₄ -alkoxycarbonyl or carbamoyl and preferably cyan or carbamoyl. The cyano group is then introduced by the method described in DE-OS 28 44 299. One can also use compounds of the formula

with compounds of the formula

implement (Hal is chlorine or bromine) and the cyano group as indicated introduce.

The preparation of compounds of formula V is e.g. B. from the DL-PS 1 09 017 known.

The compounds of the formula III are prepared analogously to that of Hantzsch (Ann. 250, 257) specified method.

The reactions to the compounds of formula IV can be carried out analogously to known ones Methods are made, it is convenient to work in one organic solvents, such as alcohols, glycols, glycol ethers, hydrocarbons, Halogenated hydrocarbons, amides, ethers, ketones or Dimethyl sulfoxide, optionally in a mixture with water.  

Preferred solvents are, for example, methanol, ethanol, n- or i-propanol, n- or i-butanol, glycol monomethyl or ethyl ether or Toluene.

The condensation reaction is preferably carried out in the presence of an acidic or basic catalyst made, are suitable as catalysts such. B. acetic acid, tertiary amines such as triethylamine, piperidine or pyrrolidine.

Compounds of the formula V are also obtained if compounds of the Formula VI

in which Z ¹ , Z ² and X have the meaning given above, reacted with H ₂ S in an organic solvent in the presence of a basic catalyst such as triethylamine at temperatures between 50 and 120 ° C. As organic solvents such. B. alcohols, glycols, glycol ethers, hydrocarbons, pyridine or amines can be used. Details of the reaction procedure can be found in the examples, in which information on parts and percentages, unless stated otherwise, relate to the weight.

The process products are still cleaned if necessary and optionally separated into their components, e.g. B. by recrystallization or by boiling with solvents under grinding conditions. The Purification can also be done using atmospheric chromatographic separation processes Pressure or overpressure.

If necessary, the cleaning process is one or more times repeated. Different cleaning methods can also be combined in order to obtain very pure compounds I.

The compounds according to the invention are generally used in Suitable plastics incorporated for the application. For this, the Plastic powdered as granules with the required amount of I and the Granules are then extruded into sheets. Incorporation into the Plastic can also be made by diffusing the required amount of I or by adding the required amount of I to the monomer of the plastic subsequent polymerization to plastic.  

As plastics (medium) come e.g. B. for use for light concentration for solar cells, preferably polymethyl methacrylate, polymethyl acrylate, Polystyrene or polydiethylene glycol diallyl biscarbonate, further suitable polyamides and polycarbonates.

Because of the good solubility of the compounds I in organic solvents, can be used even if the Plastic plates are produced using the casting process.

The light collection systems can e.g. B. in connection with solar cells for utilization solar energy and in scintillators of a known type [s. e.g. B. J. B. Birks: The Theory and Practice of Scintillation Counting, Pergamon Press, London 1964; J. Opt. Am. 39, 912 (1949); J. Appl. Phys. 40, 3544 (1969), Nuclear Instruments a. Methods 87: 111-123 (1970); Research Disclosure, p. 43 (1977); DE-OS 26 29 641)] find use. About that they are also suitable in connection with electronic controls Display device with very low energy consumption. Also suitable they themselves without electronic components for various display, information and Marking purposes, e.g. B. in passive display elements, signs and traffic signs like traffic lights and in drawing devices.

The compounds of the invention can also be used as laser dyes be used.

Compounds of the formula Ia are of particular importance

in the
T ¹ and T ² C ₁ to C ₄ alkyl,
T ³ C ₁ to C ₄ alkyl or phenyl optionally substituted by chlorine, methyl or ethyl and
T ^{4 are} optionally substituted C ₄ to C ₁₈ alkyl.

The invention is illustrated by the following examples.

example 1

In a solution of 72.6 g of 4-t-butylcyclohexyl benzoylchloroacetic acid 25.6 g of thiocarbamoylacetamide are introduced into 300 ml of DMF and then heated to 40 ° C and then 5 hours to 80 ° C. The reaction mixture is stirred into ice, with 50 percent. Sodium hydroxide solution to pH 7-8 provided, extracted with ethyl acetate and the solvent evaporated. Man receives 110 g of the compounds with the formula

as a yellow syrup.

If you use the appropriate starting materials and otherwise proceed like given in Example 1, the thiazoles given in Table 1 are obtained of formula III.

Table 1

Example 7

54.5 g of p-diethylaminosalicylaldehyde and 110 g of the product from Example 1 are refluxed in 250 ml isobutanol with 27.9 ml piperidine for 1 hour heated. The mixture is allowed to cool to room temperature, filtered off with suction, washed with petroleum ether and dries at 60 ° C. 52 g of coumarin are produced with the formula

Schump .: 226-228 ° C  

The procedure is as in Example 7 and the starting materials are used the Salicylaldehyde S given in Table 2 with the Thiazoles T from Examples 2 to 6 µm, the Coumarins given in Table 2.

Table 2

Example 17

1.16 g of sodium cyanide are added to 11.16 g of the coumarin from Example 7 in 200 ml of DMF dissolved in 3 ml of water added dropwise. It will be 2 hours at room temperature touched. Then 10.63 g of lead tetraacetate are added in portions and stirred overnight at room temperature. The reaction mixture is precipitated on ice, suction filtered, washed with water and methanol and at 60 ° C dried in vacuo. 11.6 g of coumarin with the formula are obtained

The crude product is purified by column chromatography on silica gel (Eluent: methylene chloride).

Mp: 236-239 ° C
Absorbance: λ max in CHCl ₃ : 541 nm
λ max in PMMA: 532 nm extinction: λ max in CHCl ₃ : 597 nm
λ max in PMMA: 590 nm Φ : 0.96

The procedure is as given in Example 17 and the starting materials are Coumarins listed in Table 2, the table 3 is obtained Cyancumarins.  

Table 3

Application example 1

In molten polymethyl methacrylate, 0.01% of the dye is removed Example 17 dissolved, homogeneously distributed and processed into fluorescent plates.

Example of use 2

1000 parts of polymethyl methacrylate (granules) with 0.01 parts of Powder from Example 22 evenly powdered. The mixture is then extruded into sheets.

Application example 3 to 25

According to the application examples 1 or 2, fluorescent plates or films produced:

Claims (5)

1. Coumarin derivatives of the general formula in the
B ¹ and B ^{2 are the} same or different aliphatic, cycloaliphatic, aromatic or heterocyclic radicals,
X oxygen or imino,
Z ^{1 is} hydrogen, C ₁ - to C ₄ -alkyl, optionally substituted by hydroxy, cyano, C ₁ - to C ₄ -alkoxy, chlorine, bromine, carboxyl, carb-C ₁ - to C ₄ -alkoxy, carbonamide or acetoxy ₁ - to C ₄ -alkyl, cyclohexyl, benzyl, phenylethyl, phenyl or p-tolyl,
Z ² is hydrogen, C ₁ - to C ₄ -alkyl or optionally substituted by cyano, C ₁ - to C ₄ -alkoxy, chlorine, bromine, carboxyl, carb-C ₁ - to C ₄ -alkoxy, carboxamide or acetoxy-substituted C ₁ - to C ₄ alkyl,
Z ¹ and Z ² together with the nitrogen represent the remainder of a 5- or 6-membered saturated heterocyclic ring and Z ¹ and / or Z ^{2 can} each form a ring with the O position (to the N atom). 2. Compounds according to claim 1 of the formula in the
T ¹ and T ² C ₁ to C ₄ alkyl,
T ³ C ₁ to C ₄ alkyl or phenyl optionally substituted by chlorine, methyl or ethyl and
T ^{4 are} optionally substituted C ₄ to C ₁₈ alkyl. 3. Use of the compounds according to claim 1 as fluorescent dyes in organic material. 4. Use of the compounds according to claim 1 in light collection systems. 5. Use of the compounds according to claim 1 as laser dyes.