DE2952228A1 - Light collecting system contg. amino or alkoxy cyano coumarin cpd. - with carboxylic or heterocyclic substit. giving high quantum yield - Google Patents

Abstract

Light-collecting system contains a coumarin deriv. of the formula (I) (in which T is O or NR4; R4 is H or opt. substd. ar(alk)yl or cycloalkyl; R1 is a C-bound 5- or 6-membered carbo- or heterocycle or an N-bound 5- or 6-membered heterocycle which is rotationally asymmetrical about the coumarin-N-heterocycle bond, these 5- and 6-membered rings have nonionic substits. and can be condensed with an opt. substd. benzene or naphthalene ring; X is -NR2R3 or -OR'2; R2 is H or opt. substd. (cyclo)alkyl or ar(alk)yl; R3 is R2, R6-(Y)n-CO- or R7-(Y)n-SO2-; R6 and R7 are opt. substd. (cyclo)alkyl or ar(alk)yl; Y is NH or O; n is O or 1; R2 and R3, when R3 is R2, together with the N atom can form a 5- or 6-membered heterocycle opt. contg. other heteroatoms and opt. with nonionic substits. and a condensed, opt. substd. benzene or naphthalene ring, or R2 and R3 together are a CHR8- gp.; R8 is opt. substd. (cyclo)alkyl or ar(alk)yl; and R'2 is opt. substd. (cyclo) alkyl, ar(alk)yl or alkenyl)..

Description

Light barrier systems using coumarin

vaten as energy converters devices for collecting diffuse electromagnetic Radiation by utilizing fluorescence are known.

The core of the collector is a visually denser one compared to the surroundings Medium containing centers capable of fluorescence (DE-OS 2 620 115).

The economic usefulness of a light collection system becomes in high Measure determined by the usefulness of the dye used in it as a light converter.

Extreme demands are placed on the optical quality of this dye (Solid body problems XIX, 427 (1979)).

The invention relates to new light collection systems which are characterized in that they use a coumarin derivative of the formula as an energy converter contain.

In formula (I): T 0 or NR4, where R4 is hydrogen, if appropriate substituted alkyl or optionally substituted aryl; R1 one over a carbon atom bonded carbo- or heterocyclic 5- or 6-membered ring or a 5- or 6-membered heterocyclic ring bonded via an N atom, which leads to an axis passing through the coumarin-N-heterocycle is rotationally asymmetrical, wherein said 5- or 6-membered rings carry non-ionic substituents can and on them an optionally substituted benzene or an optionally substituted naphthalene ring can be fused on; R2 optionally substituted Alkyl, alkenyl, optionally substituted cycloalkyl, optionally substituted Aryl, optionally substituted aralkyl.

R1 preferably represents a 5- or 6-membered heterocyclic Ring which contains 1, 2 or 3 heteroatoms from the series N, O, S and to which a benzene ring may be fused, both the heterocyclic ring and the fused Benzene ring by, for example, alkyl, aryl, aralkyl, cycloalkyl, halogen, alkoxy, Cyan and acyl can be substituted.

As examples of R1 meaning a 5- or 6-membered heterocyclic Ring to which a benzene ring can be fused may be mentioned: pyrazole, imidazole, Thiazole, oxazole, 1.2.4-triazole, 1.3.4-oxdiazole, 1.3.4-thiadiazole, benzimidazole, Benzthiazole, benzoxazole, pyridine.

R1 particularly preferably represents a heterocyclic radical of the formula denotes in the YO, NR5 or S, where R5 stands for hydrogen, alkyl, aryl, cycloalkyl or aralkyl and the ring A has preferably 1 to 2 substituents from the series C1-C4-alkyl, C1-C4-alkoxy, bromine, chlorine , Phenyl, cyclohexyl, C1-C4-alkylsulfonyl, sulfamoyl or C1-C4-alkoxycarbonyl can be substituted.

Alkyl (R4, R5, R2 and as a non-ionic substituent of the 5- or 6-membered Rings R1) preferably represents C1-C6-alkyl. g alkenyl (R2) preferably represents C2-C7-alkenyl, especially allyl.

Aryl (R4, R5, R2 and as a non-ionic substituent of the 5- or 6-membered Rings R1) preferably represents phenyl.

Cycloalkyl (R2, R5 and, as a non-ionic substituent, the 5- or 6-membered rings R1) preferably represents C3-C7-cycloalkyl, particularly preferred for cyclohexyl.

Aralkyl (R2, R5 and as a non-ionic substituent of the 5- or 6-membered Rings R1) preferably represents benzyl and phenethyl.

Acyl (R1) preferably represents (C1-C6-alkyl) carbonyl, benzoyl, C1-C6-alkylsulfonyl and phenylsulfonyl.

Halogen as a non-ionic substituent on the 5- or 6-membered rings R1 preferably represents chlorine, bromine and fluorine.

Alkoxy as a non-ionic substituent on the 5- or 6-membered rings R1 preferably represents C1-C6-alkoxy.

Substituted alkyl (R2, R4) represents alkyl, for example by Halogen such as chlorine and bromine, hydroxyl, cyano, trifluoromethyl, cl -C6-alkoxy, C1-C6-alkylsulfonyl, Phenylsulfonyl, carbamoyl mono- and disubstituted by C1-C6-alkyl and phenyl, Carbamoyl, sulfamoyl, sulfamoyl mono- and disubstituted by C1-C6-alkyl and phenyl and amino mono- or disubstituted by C1-C6-alkyl and phenyl can be.

Substituted aryl (R2, R4), substituted cycloalkyl (R2) and substituted Aralkyl (R2) stands for aryl, cycloalkyl or aralkyl, (R2) stands for aryl, cycloalkyl or aralkyl, in addition to the substituents mentioned above for alkyl, for example can also be substituted by C1-C6-alkyl.

R2 preferably denotes optionally by acetoxy, C1-C4-alkoxy, Phenoxy, cyclohexyloxy, phenyl-C1-C2-alkoxy, bromine or chlorine-substituted C1-C5-alkyl, Allyl, cyclohexyl or phenyl-C1-C2-alkyl.

Dyes of the formula can preferably be used as light converters in R2 C1-C4-alkyl, in particular methyl and ethyl, YX O, NR; or S denote, where R51 denotes C1-C4-alkyl, in particular methyl or phenyl, and the ring A 'denotes C1-C4-alkyl, in particular methyl, C1-C4-alkoxy, in particular methoxy, halogen, in particular chlorine, alkylsulfonyl, in particular methylsulfonyl and sulfamoyl may be substituted.

A process for the preparation of dyes of the formula (I) is characterized in that compounds of the formula in which R1, R2 and Z have the meaning given above, are reacted with cyanide salts in a polar organic solvent in a manner known per se (cf. DE-OS 2 844 299) and treated simultaneously or subsequently with oxidizing agents.

Suitable polar organic solvents are alcohols such as methanol, Ethanol, isopropanol, 2-methoxyethanol, 2-ethoxyethanol, ethylene glycol, 2-cyanoethanol, but especially dipolar aprotic organic solvents such as dimethylformamide, as well as pyridine and picolines An intermediate isolation of the cyanide addition product not necessary.

Suitable oxidizing agents are, for example, atmospheric oxygen, hydrogen peroxide, Persulfates, perborates, nitric acid, bromine, sulfuryl chloride, lead tetraacetate and Chloranil.

Water-soluble cyanides are advantageously used as cyanide salts especially alkali cyanides.

The implementation of cyanide salts is in the temperature range from 0 to 1200C, preferably at 10 to 600C, and the oxidation in the range from -5 to 30 ° C, preferably carried out at 0 to 150C.

The starting dyes of the formula (IV) are known or known Process to manufacture.

Relevant patent publications are, for example, US 3,014,041, 3,288,801, 3,496,188, 3,816,413, 3,839,333, 3,669,621, 3,704,302, 3,839,351, 3,776 905, 3 968 119, 4 055 568 and GB 1 269 004, 1 313 253 and 1 318 975.

The new light collection systems, which are molded bodies more suitable Geometry, i.e. optical systems in which the ratio of emission to absorption area 1:50 to 1: 2000, are suitable, incident diffuse to absorb electromagnetic radiation and put it in an opposite direction to the environment optically denser medium to emit almost lossless, making the main part of the emission light remains totally reflected in the medium.

Only the portion of emitted light, the emission band of which is largely is free from absorption is useful for the purpose of the invention.

It is therefore advisable to use the dyes of the formula (I) before use in the light collecting systems especially to clean. In particular, they must be largely be free of long-wave absorbing impurities.

The invention therefore preferably relates to light collection systems that thereby are characterized in that they contain a dye of the formula (I) in a 0.05% solution, for example in chloroform, measured in a layer thickness of 10 cm, an increase in transmission from 0% to> 90% with a change the wavelength of 25 to 100 nm, preferably 25 to 45 nm.

The cleaning of the dyes can in favorable cases by multiple careful crystallization take place.

It is usually separated by column chromatography on solid supports like Al203 or SiO2 required. A high degree of purity is obtained particularly gently by distribution chromatography, e.g. by Steady-Ståte (O'Keefe) or countercurrent distribution after Craig.

The new light collection systems can e.g. in connection with solar cells for harnessing solar energy and in scintillators of a known type (see e.g. 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 2 629 641) find use. In addition, they are suitable in conjunction with electronic controls as display devices with very low energy consumption, and they are also suitable for all kinds of display, Information and marking purposes, e.g. in passive display elements, information and Traffic signs like traffic lights.

The light harvesting systems of the invention contain the dye in a liquid or a solid dissolved, depending on the area of application of the Light collection system, a wide variety of geometric shapes come into question. Suitable solid media such as those used for collecting light in connection with solar cells and Are used in passive display elements are e.g. translucent, optical Usable plastics such as homo- and copolymers of acrylic acid (derivatives) or Polycarbonates. Furthermore, the light harvesting systems can also use the dye in a liquid - e.g.

Contains alcohol, reton, halogenated hydrocarbons, ethers in solution. Suitable solvents are e.g. ethanol, propanol, methyl ethyl ketone, acetone, Cyclohexanone, chloroform, perchlorethylene, glycol monomethyl ether.

The use of the dyes of the formula (I) in solids is preferred.

The use according to the invention of the dyes of the formula (I) is to a high degree. advantageous, as they have a good quantum yield and a high Gain factor have excellent lightfastness and thus an economic one Ensure usability of the new light collection systems. The special feature of this class of substances is the very large Stokes shift, even with long-wave absorption with very good lightfastness at the same time.

It must be described as surprising that the dyes of Formula (I) are suitable for advantageous use in light harvesting systems, as numerous s-ark fluorescent dyes such as

Rhodamine G are not useful. They are also very far-reaching Requirements placed on the optical quality of laser dyes in many cases insufficient to make use of these dyes in light harvesting systems to recommend.

Example 1 19.2 g of @ 6-methoxy - @ - (benzthiazolyl-2-) 4-cyano-7-ethoxycoumarin are dissolved in 1200 ml of dichlorobenzene and mixed with 0.5 g of Tonsil. It's getting hot filtered and, after cooling, 15.1 g of crystals are obtained. This crystallization will repeated twice, omitting the tonsil in the last. The yellow ones Crystals have a melting point of 3020C.

488 mg of the compound obtained in this way are dissolved in 1 l of chloroform and the transmission T is measured in a layer thickness of 10 cm. The transmission is 0% at 550 nm and 92% at 580 nm. The fluorescence quantum yield i is 1.00, the Stokes shift 135 nm and the proportion of usable fluorescence is 88%. The "proportion of usable fluorescence" means the percentage of the originally determined fluorescent light that is not lost through reabsorption. z - 45 ~ z ffi es n tr ur vo> CD m R2 r N Stokes oo au co Y, rn m XONN cs fluoresce. N it df N cn 'Q) 0.48 X 95 67 215 3 O ko rz N rn o cO NO \ O ao 'u, rz aD Decomp \ O rr) ON 100 65 CH3-O- 90 212 5 X g NOO t Oo arro QiOr UPC rCI dP 0.71 m CD 87 230 8 @ s D 00 0 rs 9 X OOOOO ~ O I ~ n $ QN g ZR . ^ Zsr ° S t IO OIOO) OO | U) IIIII n :: X nnn P; UUUUQC) C) w z ffi as o N continuation R2 R1 t% 2 Stokes T usable. Fp. Example no. Cm cr t cr \ au U 0.75 119 t 85 244 o Ero cu cu N m dP N I. Pk n cu m NO nN Õ SN n 1> w «c 3rl Ztu Ez DO 08 CH-0- X g ffi OO t O a ~ OO » > Un oP>>«> C3 9 o OOO U R. ZOZOZO YYY N ll 4 OO @ llll U} O Un U) O WI 2 = R n II ON X «UUC) U

Claims (6)

Claims 1. Light collection system, characterized in that it is a coumarin derivative of the formula contains, in which T 0 or NR4, where R4 is hydrogen, optionally substituted alkyl or optionally substituted aryl; R1 is a carbo- or heterocyclic 5- or 6-membered ring bonded via a carbon atom or a 5- or 6-membered heterocyclic ring bonded via an N atom, which is rotationally asymmetrical about an axis passed through the coumarin-N-heterocycle , wherein said 5- or 6-membered rings can carry non-ionic substituents and an optionally substituted benzene or an optionally substituted naphthalene ring can be fused to them; R2 represents optionally substituted alkyl, alkenyl, optionally substituted cycloalkyl, optionally substituted aryl and optionally substituted aralkyl. 2. light collection systems according to claim 1, characterized in that R2 for optionally by acetoxy, Ct-C4-alkoxy, phenoxy, cyclohexyloxy, phenyl-C1-C2-alkoxy, Bromine or chlorine-substituted C1-C5-alkyl, allyl, cyclohexyl or phenyl-C1-C2-alkyl stands. 3. Light collection system according to claims 1 and 2, characterized in that that it contains a coumarin derivative of the formula (I) in which R1 is a pyrazolyl, Itidazolyl, thiazolyl, oxazolyl, 1.2.4-thiazolyl, 1.3.4-oxdiazolyl, 1.3.4-thiadiazolyl, Benzimidazolyl, benzthiazolyl, benzoxazolyl or pyridinyl radical, where the mentioned heterocyclic radicals can be substituted. 4. light collection system, characterized in that it is a coumarin derivative of the formula contains, in which R21 denotes C1-C4-alkyl, in particular methyl and ethyl, Y 'denotes O, NR6 or S, where R6 denotes C1-C4-alkyl, in particular methyl, or phenyl and where the ring A' denotes C1-C4- Alkyl, in particular methyl, C1-C4-alkoxy, in particular methoxy, alkylsulfonyl, in particular methylsulfonyl, sulfamoyl and halogen, in particular chlorine, can be substituted 5. light collection system, characterized in that it contains a coumarin derivative according to claims 1 to 4, in a 0.05% own solution, measured in a layer thickness of 10 cm Increase in transmission from 0 F to 90% with a change in wavelength of 25 to 100 nm, preferably 25 to 45 nm. 6. Use of coumarin derivatives according to claims 1 to 4 as Energy converters in light collection systems.