Cyanated perylene compounds

Abstract

The present invention relates to a cyanated perylene compound of the formula I ##STR00001##
in which
one of the Z substituents and one of the Z* substituents are cyano and the other Z substituent and the other Z* substituent are each independently CO.sub.2R.sup.9, CONR.sup.10R.sup.11, optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl or C.sub.6-C.sub.14-aryl, where R.sup.9, R.sup.10 and R.sup.11 are each as defined in the claims;
and mixtures thereof. The present invention further relates to a composition comprising a cyanated perylene compound of the formula I or mixtures thereof and to a process for preparation thereof; to color converters comprising at least one polymer as matrix material and at least one cyanated perylene compound or mixtures thereof or a composition comprising at least one cyanated perylene compound or mixtures thereof as fluorescent dye; to the use of these color converters and to lighting devices comprising at least one LED and at least one color converter.

Claims

1. A cyanated perylene compound of the formula I ##STR00032## in which one of the Z substituents is cyano and the other Z substituent is CO.sub.2R.sup.9, CONR.sup.10R.sup.11, C.sub.1-C.sub.18-alkyl, C.sub.2-C.sub.18-alkenyl, C.sub.2-C.sub.18-alkynyl, C.sub.3-C.sub.12-cycloalkyl or C.sub.6-C.sub.14-aryl, where C.sub.1-C.sub.18-alkyl, C.sub.2-C.sub.18-alkenyl, C.sub.2-C.sub.18-alkynyl are unsubstituted or bear one or more identical or different Z.sup.a substituents, C.sub.3-C.sub.12-cycloalkyl is unsubstituted or bears one or more identical or different Z.sup.b substituents, and C.sub.6-C.sub.14-aryl is unsubstituted or bears one or more identical or different Z.sup.Ar substituents; one of the Z* substituents is cyano and the other Z* substituent is CO.sub.2R.sup.9, CONR.sup.10R.sup.11, C.sub.1-C.sub.18-alkyl, C.sub.2-C.sub.18-alkenyl, C.sub.2-C.sub.18-alkynyl, C.sub.3-C.sub.12-cycloalkyl or C.sub.6-C.sub.14-aryl, where C.sub.1-C.sub.18-alkyl, C.sub.2-C.sub.18-alkenyl, C.sub.2-C.sub.18-alkynyl are unsubstituted or bear one or more identical or different Z.sup.a substituents, C.sub.3-C.sub.12-cycloalkyl is unsubstituted or bears one or more identical or different Z.sup.b substituents, and C.sub.6-C.sub.14-aryl is unsubstituted or bears one or more identical or different Z.sup.Ar substituents; R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 are each independently selected from hydrogen, cyano, bromine and chlorine, with the proviso that 1, 2, 3, 4, 5, 6, 7 or 8 of the R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 or R.sup.8 substituents are cyano; where R.sup.9 is hydrogen, C.sub.1-C.sub.10-alkyl, C.sub.2-C.sub.10-alkenyl, C.sub.2-C.sub.10-alkynyl, C.sub.3-C.sub.12-cycloalkyl or C.sub.6-C.sub.14-aryl, where C.sub.1-C.sub.10-alkyl, C.sub.2-C.sub.10-alkenyl, C.sub.2-C.sub.10-alkynyl are unsubstituted or bear one or more identical or different R.sup.a substituents, C.sub.3-C.sub.12-cycloalkyl is unsubstituted or bears one or more identical or different R.sup.b substituents and C.sub.6-C.sub.14-aryl is unsubstituted or bears one or more identical or different R.sup.Ar substituents; R.sup.10 and R.sup.11 are each independently hydrogen, C.sub.1-C.sub.10-alkyl, C.sub.2-C.sub.10-alkenyl, C.sub.2-C.sub.10-alkynyl, C.sub.3-C.sub.12-cycloalkyl or C.sub.6-C.sub.14-aryl, where C.sub.1-C.sub.10-alkyl, C.sub.2-C.sub.10-alkenyl, C.sub.2-C.sub.10-alkynyl are unsubstituted or bear one or more identical or different R.sup.a substituents, C.sub.3-C.sub.12-cycloalkyl is unsubstituted or bears one or more identical or different R.sup.b substituents and C.sub.6-C.sub.14-aryl is unsubstituted or bears one or more identical or different R.sup.Ar substituents; each Z.sup.a is independently halogen, hydroxyl, NR.sup.10aR.sup.11a, C.sub.1-C.sub.10-alkoxy, C.sub.1-C.sub.10-haloalkoxy, C.sub.1-C.sub.10-alkylthio, C.sub.3-C.sub.12-cycloalkyl, C.sub.6-C.sub.14-aryl, C(O)R.sup.9a, C(O)OR.sup.9a or C(O)NR.sup.10aR.sup.11a, where C.sub.3-C.sub.12-cycloalkyl is unsubstituted or bears one or more identical or different R.sup.b substituents and C.sub.6-C.sub.14-aryl is unsubstituted or bears one or more identical or different R.sup.Ar substituents; each Z.sup.b and each Z.sup.Ar is independently halogen, hydroxyl, NR.sup.10aR.sup.11a, C.sub.1-C.sub.10-alkyl, C.sub.1-C.sub.10-alkoxy, C.sub.1-C.sub.10-haloalkoxy, C.sub.1-C.sub.10-alkylthio, C(O)R.sup.9a, C(O)OR.sup.9a or C(O)NR.sup.10aR.sup.11a; each R.sup.a is independently halogen, hydroxyl, C.sub.1-C.sub.10-alkoxy, C.sub.3-C.sub.12-cycloalkyl or C.sub.6-C.sub.14-aryl; each R.sup.b is independently halogen, hydroxyl, C.sub.1-C.sub.10-alkyl, C.sub.1-C.sub.10-alkoxy, C.sub.1-C.sub.10-haloalkoxy, C.sub.1-C.sub.10-alkylthio, C.sub.2-C.sub.10-alkenyl, C.sub.2-C.sub.10-alkynyl, C.sub.3-C.sub.12-cycloalkyl or C.sub.6-C.sub.14-aryl; each R.sup.Ar is independently halogen, hydroxyl, C.sub.1-C.sub.10-alkyl, C.sub.1-C.sub.10-alkoxy, C.sub.1-C.sub.10-haloalkoxy, C.sub.1-C.sub.10-alkylthio, C.sub.2-C.sub.10-alkenyl, C.sub.2-C.sub.10-alkynyl, C.sub.3-C.sub.12-cycloalkyl or C.sub.6-C.sub.14-aryl; R.sup.9a is hydrogen, C.sub.1-C.sub.10-alkyl, C.sub.2-C.sub.10-alkenyl, C.sub.2-C.sub.10-alkynyl, C.sub.3-C.sub.12-cycloalkyl or C.sub.6-C.sub.14-aryl; and R.sup.10a, R.sup.11a are each independently hydrogen, C.sub.1-C.sub.10-alkyl, C.sub.2-C.sub.10-alkenyl, C.sub.2-C.sub.10-alkynyl, C.sub.3-C.sub.12-cycloalkyl or C.sub.6-C.sub.14-aryl, and mixtures thereof.

2. A cyanated perylene compound of the formula I according to claim 1, in which 1, 2, 3 or 4 of the R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 or R.sup.8 substituents are cyano.

3. A cyanated perylene compound of the formula I according to claim 1, in which none of the R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 or R.sup.8 substituents are bromine or chlorine.

4. A cyanated perylene compound of the formula I according to claim 1, in which one or two of the R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 or R.sup.8 substituents are cyano and the other R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 or R.sup.8 substituents are hydrogen.

5. A cyanated perylene compound of the formula I according to claim 1, in which one of the Z substituents and one of the Z* substituents are independently selected from C.sub.1-C.sub.10-alkyl, CO.sub.2R.sup.9, phenyl-C.sub.1-C.sub.10-alkyl and phenyl, where phenyl and the phenyl moiety of phenyl-C.sub.1-C.sub.10-alkyl are unsubstituted or bear one or more substituents selected from C.sub.1-C.sub.6-alkyl, and where R.sup.9 is as defined above.

6. A cyanated perylene compound of the formula I according to claim 1, selected from compounds of the formulae (1), (2), (3), (4), (5), (6), (7), (8), (9), (10), (11), (12), (13), (14), (15), (16), (17), (18), (19), and (20) ##STR00033## ##STR00034## ##STR00035## ##STR00036## ##STR00037## in which Z is selected from C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxycarbonyl, phenyl, and phenyl bearing 1, 2 or 3 C.sub.1-C.sub.4-alkyl groups; and Z* is selected from C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxycarbonyl, phenyl, and phenyl bearing 1, 2 or 3 C.sub.1-C.sub.4-alkyl groups; and mixtures thereof.

7. A composition comprising at least one cyanated perylene compound of the formula I according to claim 1.

8. The composition according to claim 7, comprising at least one cyanated perylene compound of the formula I-A ##STR00038## in which one of the Z substituents is cyano and the other Z substituent is C.sub.1-C.sub.18-alkyl, C.sub.2-C.sub.18-alkenyl, C.sub.2-C.sub.18-alkynyl, C.sub.3-C.sub.12-cycloalkyl or C.sub.6-C.sub.14-aryl, where C.sub.1-C.sub.18-alkyl, C.sub.2-C.sub.18-alkenyl, C.sub.2-C.sub.18-alkynyl are unsubstituted or bear one or more identical or different Z.sup.a substituents, where Z.sup.a is as defined above, C.sub.3-C.sub.12-cycloalkyl is unsubstituted or bears one or more identical or different Z.sup.b substituents, where Z.sup.b is as defined above; and C.sub.6-C.sub.14-aryl is unsubstituted or bears one or more identical or different Z.sup.Ar substituents, where Z.sup.Ar is as defined above; one of the Z* substituents is cyano and the other Z* substituent is C.sub.1-C.sub.18-alkyl, C.sub.2-C.sub.18-alkenyl, C.sub.2-C.sub.18-alkynyl, C.sub.3-C.sub.12-cycloalkyl or C.sub.6-C.sub.14-aryl, where C.sub.1-C.sub.18-alkyl, C.sub.2-C.sub.18-alkenyl, C.sub.2-C.sub.18-alkynyl are unsubstituted or bear one or more identical or different Z.sup.a substituents, where Z.sup.a is as defined above, C.sub.3-C.sub.12-cycloalkyl is unsubstituted or bears one or more identical or different Z.sup.b substituents, where Z.sup.b is as defined above; and C.sub.6-C.sub.14-aryl is unsubstituted or bears one or more identical or different Z.sup.Ar substituents, where Z.sup.Ar is as defined above; R.sup.1, R.sup.4, R.sup.5 and R.sup.8 are each hydrogen; two of the R.sup.2, R.sup.3, R.sup.6 or R.sup.7 substituents are hydrogen; and the other R.sup.2, R.sup.3, R.sup.6 or R.sup.7 substituents are cyano; or mixtures thereof, obtainable by a process, comprising: a) halogenating a perylene of the formula II ##STR00039## in which R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 are each hydrogen; to obtain a mixture of 3,9-dihaloperylene of the formula IIIa and 3,10-dihaloperylene of the formula IIIb ##STR00040## in which R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 are each hydrogen; and Hal are each all chlorine or bromine; b) reacting the mixture of compounds of the formulae IIIa and IIIb obtained in a) with an organometallic compound of the formula IV
Z-Met(IV) and optionally with an organometallic compound of the formula V
Z*-Met(V) in which Z is selected from C.sub.1-C.sub.18-alkyl, C.sub.2-C.sub.18-alkenyl, C.sub.2-C.sub.18-alkynyl, C.sub.3-C.sub.12-cycloalkyl and C.sub.6-C.sub.14-aryl, where C.sub.1-C.sub.18-alkyl, C.sub.2-C.sub.18-alkenyl, C.sub.2-C.sub.18-alkynyl are unsubstituted or bear one or more identical or different Z.sup.a substituents, C.sub.3-C.sub.12-cycloalkyl is unsubstituted or bears one or more identical or different Z.sup.b substituents, and C.sub.6-C.sub.14-aryl is unsubstituted or bears one or more identical or different Z.sup.Ar substituents; Z* is selected from C.sub.1-C.sub.18-alkyl, C.sub.2-C.sub.18-alkenyl, C.sub.2-C.sub.18-alkynyl, C.sub.3-C.sub.12-cycloalkyl and C.sub.6-C.sub.14-aryl, where C.sub.1-C.sub.18-alkyl, C.sub.2-C.sub.18-alkenyl, C.sub.2-C.sub.18-alkynyl are unsubstituted or bear one or more identical or different Z.sup.a substituents, C.sub.3-C.sub.12-cycloalkyl is unsubstituted or bears one or more identical or different Z.sup.b substituents, and C.sub.6-C.sub.14-aryl is unsubstituted or bears one or more identical or different Z.sup.Ar substituents; where Z* may also be as defined for Z; Met is B(OH).sub.2, B(OR)(OR), Zn-Hal or Sn(R*).sub.3, in which R and R are each independently hydrogen, C.sub.1-C.sub.30-alkyl, C.sub.5-C.sub.8-cycloalkyl, C.sub.6-C.sub.14-aryl or heteroaryl or R and R together are C.sub.2-C.sub.4-alkylene which optionally bears 1, 2, 3, 4, 5, 6, 7 or 8 substituents selected from C.sub.1-C.sub.4-alkyl, C.sub.5-C.sub.8-cycloalkyl, C.sub.6-C.sub.14-aryl and heteroaryl; Hal is chlorine or bromine; and R* is C.sub.1-C.sub.8-alkyl or phenyl; to obtain a mixture of compounds of the formulae VIa and VIb ##STR00041## in which R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 are each hydrogen; and Z and Z* are each as defined above; c) halogenating the mixture of compounds of the formulae VIa and VIb obtained in b) to obtain a reaction mixture comprising compounds of the formulae VIIa and VIIb ##STR00042## in which Z and Z* are each as defined above, Hal is halogen selected from chlorine and bromine, where the Hal substituents are either all chlorine or all bromine; R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 are each hydrogen or halogen selected from chlorine and bromine, where the R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 substituents that are not hydrogen are either all chlorine or all bromine; d) substituting halogen atoms of the compounds of the formulae VIIa and VIIb present in the reaction mixture obtained in c) for cyano groups, and optionally partly for hydrogen, to obtain at least one compound of the formula I-A or mixtures thereof; and, optionally, e) separating and/or purifying the at least one compound of the formula I-A or mixtures thereof present in the reaction mixture obtained in d).

9. The composition according to claim 8, in which, in formula I-A, one of the Z substituents is cyano and the other Z substituent is C.sub.1-C.sub.6-alkyl, phenyl, or phenyl bearing 1, 2 or 3 C.sub.1-C.sub.4-alkyl groups; one of the Z* substituents is cyano and the other Z* substituent is C.sub.1-C.sub.6-alkyl, phenyl, or phenyl bearing 1, 2 or 3 C.sub.1-C.sub.4-alkyl groups; R.sup.1, R.sup.4, R.sup.5 and R.sup.8 are each hydrogen; two of the R.sup.2, R.sup.3, R.sup.6 or R.sup.7 substituents are cyano and the other R.sup.2, R.sup.3, R.sup.6 or R.sup.7 substituents are hydrogen.

10. The composition according to claim 7, comprising at least one cyanated perylene compound of the formula I-B ##STR00043## in which one of the Z substituents is cyano and the other Z substituent is COOR.sup.9; one of the Z* substituents is cyano and the other Z* substituent is COOR.sup.9; R.sup.1, R.sup.4, R.sup.5 and R.sup.8 are each hydrogen; one of the R.sup.2, R.sup.3, R.sup.6 or R.sup.7 substituents is cyano and the other R.sup.2, R.sup.3, R.sup.6 or R.sup.7 substituents are hydrogen; and R.sup.9 is hydrogen, C.sub.1-C.sub.10-alkyl, C.sub.2-C.sub.10-alkenyl, C.sub.2-C.sub.10-alkynyl, C.sub.3-C.sub.12-cycloalkyl or C.sub.6-C.sub.14-aryl, where C.sub.1-C.sub.10-alkyl, C.sub.2-C.sub.10-alkenyl, C.sub.2-C.sub.10-alkynyl are unsubstituted or bear one or more identical or different R.sup.a substituents, C.sub.3-C.sub.12-cycloalkyl is unsubstituted or bears one or more identical or different R.sup.b substituents and C.sub.6-C.sub.14-aryl is unsubstituted or bears one or more identical or different R.sup.Ar substituents, where R.sup.a, R.sup.b and R.sup.Ar are each as defined above; or mixtures thereof, obtainable by a process comprising: f) a mixture of perylene compounds of the formulae VIIIa and VIIIb ##STR00044## in which R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 are hydrogen; and R.sup.9 is as defined above to obtain a reaction mixture comprising compounds of the formulae IXa and IXb ##STR00045## in which R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 are each hydrogen or halogen selected from chlorine and bromine, where the R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 substituents that are not hydrogen are either all chlorine or all bromine; Hal is halogen selected from chlorine and bromine, where the Hal substituents are either all chlorine or all bromine; and R.sup.9 is as defined above; g) substituting halogen atoms of the compounds of the formulae IXa and IXb present in the reaction mixture obtained in f) for cyano groups, and optionally partly for hydrogen, to obtain at least one compound of the formula I-B or mixtures thereof; and h) separating and/or purifying the at least one compound of the formula I-B or mixtures thereof present in the reaction mixture obtained in g).

11. The composition according to claim 10, in which, in formula I-B, one of the Z substituents is cyano and the other Z substituent is C.sub.1-C.sub.6-alkoxycarbonyl; one of the Z* substituents is cyano and the other Z* substituent is C.sub.1-C.sub.6-alkoxycarbonyl; R.sup.1, R.sup.4, R.sup.5 and R.sup.8 are each hydrogen; one of the R.sup.2, R.sup.3, R.sup.6 or R.sup.7 substituents is cyano and the other R.sup.2, R.sup.3, R.sup.6 or R.sup.7 substituents are each hydrogen.

Description

EXAMPLES

(1) Various fluorescent dyes were synthesized. The fluorescent dyes produced according to the examples were used to produce color converters. For this purpose, these were incorporated as described hereinafter into a matrix composed of a polymer. The polymer used was PMMA (Plexiglas 6N from Evonik), polystyrene (PS168 N from BASF) and PC (Macrolon 2808 from Bayer).

(2) Production of the Color Converters for Testing of the Dyes:

(3) About 2.5 g of polymer and 0.02% by weight of dye were dissolved in about 5 ml of methylene chloride, and 0.5% by weight of TiO.sub.2 was dispersed therein, based in each case on the amount of polymer used. The solution/dispersion obtained was coated onto a glass surface using an applicator frame (wet film thickness 400 m). After the solvent had dried off, the film was detached from the glass and dried in a vacuum drying cabinet at 50 C. overnight. Two circular film pieces having a diameter of 15 mm were punched out of each film of thickness 80 to 85 m, and these served as analysis samples.

(4) Fluorescence quantum yields (FQY) of the analysis samples were measured with the C9920-02 quantum yield measuring system (from Hamamatsu). This was done by illuminating each of the samples with light of 450 to 455 nm in an integration sphere (Ulbricht sphere). By comparison with the reference measurement in the Ulbricht sphere without sample, the unabsorbed fraction of the excitation light and the fluorescent light emitted by the sample are determined by means of a CCD spectrometer. Integration of the intensities over the spectrum of the unabsorbed excitation light or over that of the emitted fluorescent light gives the degree of absorption or fluorescence intensity or fluorescence quantum yield of each sample.

Example 1

Mixture of Compounds of the Formulae (1.a) and (1.b)

(5) ##STR00026##
in which
two of the R.sup.2, R.sup.3, R.sup.6 and R.sup.7 substituents are hydrogen; and
two of the R.sup.2, R.sup.3, R.sup.6 and R.sup.7 substituents are cyano.

1.1 3,9-Dibromoperylene and 3,10-dibromoperylene

(6) A mixture of 14.9 g (59 mmol) of perylene, 400 ml of acetic acid and 18.9 g (236 mmol) of bromine was stirred at 40 C. for four hours. The excess bromine was subsequently destroyed by adding sodium thiosulfate solution. The precipitate was filtered off, washed with water and dried under reduced pressure. This gave 25.46 g (quant.) of the title compounds as a yellowish precipitate.

1.2 3,9-Diphenylperylene and 3,10-diphenylperylene

(7) A mixture of 1.23 g (3 mmol) of 3,9-dibromoperylene and 3,10-dibromoperylene from example 1.1, 30 ml of toluene, 1.46 g (12 mmol) of phenylboronic acid, 2.49 g (18 mmol) of potassium carbonate, 8 ml of water, 0.24 g (0.2 mmol) of tetrakistriphenylphosphinepalladium was heated to 90 C. for 60 hours. After the reaction mixture had been cooled, it was diluted with toluene, the phases were separated and the toluene phase was purified by means of column filtration with silica gel. This gave 1.1 g (92%) of the title compound as a yellow solid. Rf (petroleum ether:toluene 5:1)=0.31.

1.3 Mixture of Compounds of the Formulae (1.3a) and (1.3b)

(8) ##STR00027##
in which
at least two of the R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 substituents are bromine, and the other R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 substituents are hydrogen.

(9) To a mixture of 202 mg (0.5 mmol) of 3,9-diphenylperylene and 3,10-diphenylperylene from example 1.2 and 25 ml of chlorobenzene were added 5 ml of water, 10 ml of chlorobenzene and 800 mg (10 mmol) of bromine, and the mixture was heated at reflux for 22 hours. The reaction mixture was cooled. Thereafter, 200 ml of dilute sodium thiosutfate solution were added at room temperature, the mixture was admixed with ethyl acetate, and the phases were separated and concentrated to obtain the title compounds with an Rf (petroleum ether:toluene 5:1)=0.61.

1.4 Mixture of Compounds of the Formulae (1.a) and (1.b)

(10) 280 mg (0.5 mmol) of the mixture obtained in 1.3, 896 mg (10 mmol) of copper cyanide and 30 ml of NMP (N-methylpyrrolidone) were stirred at 100 C. for 6 h and at 150 C. for a further 16 h. After cooling to room temperature, the mixture was precipitated with dilute HCl, and the precipitate was filtered off with suction, washed with water and dried at 60 C. under reduced pressure. The residue was chromatographed on silica gel (eluent:toluene:ethyl acetate 100:1). This gave 17 mg of the title compounds.

(11) Absorption: .sub.max (CH.sub.2Cl.sub.2): 497 nm;

(12) Emission: .sub.max (CH.sub.2Cl.sub.2): 563 nm

(13) FQY (polystyrene): 92%

(14) T80 half-life (80 mW/cm.sup.2): 59 days in polystyrene

Example 2

Mixture of Compounds of the Formulae (2.a) and (2.b)

(15) ##STR00028##
in which
two of the R.sup.2, R.sup.3, R.sup.6 and R.sup.7 substituents are hydrogen; and
two of the R.sup.2, R.sup.3, R and R.sup.7 substituents are cyano.

2.1 3,9-Bis(o-tolyl)perylene and 3,10-bis(o-tolyl)perylene

(16) A mixture of 4.10 g (10 mmol) of 3,9-dibromoperylene and 3,10-dibromoperylene from example 1.1, 100 ml of toluene, 5.44 g (40 mmol) of 2-methylphenylboronic acid, 8.3 g (60 mmol) of potassium carbonate, 15 ml of water, 2.32 g (2 mmol) of tetrakistriphenylphosphinepalladium was heated to 90 C. for 34 hours. After the reaction mixture had been cooled, it was diluted with toluene, the phases were separated and the toluene phase was purified by means of column filtration with silica gel. This gave 5.54 g of the title compound as a yellow solid, Rf (petroleum ether:toluene 5:1)=0.33, and a by-product with Rf (petroleum ether:toluene 5:1)=0.09.

2.2 Mixture of Compounds of the Formulae (2.2a) and (2.2b)

(17) ##STR00029##
in which
at least two of the R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 substituents are bromine, and the other R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 substituents are hydrogen.

(18) To the mixture of 3,9-bis(o-tolyl)perylene and 3,10-bis(o-tolyl)perylene (1.30 g, 3 mmol) isolated from example 2.1 in 100 ml of chlorobenzene were added, at 40 C., 10 ml of water, 10 ml of chlorobenzene and 4.8 g (60 mmol) of bromine. The mixture was stirred at 70 C. for 16 hours and at 80 C. for 7 hours. The mixture was left to cool to room temperature and diluted with 200 ml of toluene, dilute sodium thiosulfate solution was added, and the phases were separated and concentrated to obtain a residue. The main products formed were tribrominated and tetrabrominated 3,9-bis(o-tolyl)perylene and tribrominated and tetrabrominated 3,10-bis(o-tolyl)perylene, and by-products formed were dibrominated and pentabrominated 3,9-bis(o-tolyl)perylene and 3,10-bis(o-tolyl)perylene. Rf (petroleum ether:toluene 5:1)=0.49, 0.61, 0.38.

2.3 Mixture of Compounds of the Formulae (2.a) and (2.b)

(19) 1.12 g of the residue obtained in example 2.2, 2.69 mg (30 mmol) of copper cyanide and 50 ml of N-methylpyrrolidone were stirred at 100 C. for 3 hours and then at 150 C. for 16 hours. The mixture was left to cool to room temperature and dilute HCl was added. The precipitated solid was filtered off with suction, washed with water and dried under reduced pressure at 60 C. The crude title compound was purified on silica gel (eluent:petroleum ether:THF 10:1).

(20) Rf (petroleum ether:THF 5:1)=0.19.

(21) Absorption: .sub.max (CH.sub.2Cl.sub.2): 489 nm;

(22) Emission: .sub.max (CH.sub.2Cl.sub.2): 547 nm

(23) FQY (polystyrene): 90-91%;

(24) FQY (polycarbonate): 90-91%;

(25) T80 half-life (80 mW/cm.sup.2): 50 days in polystyrene;

(26) T80 half-life (80 mW/cm.sup.2): 61 days in polycarbonate.

Example 3

Mixture of Compounds of the Formulae (3.a) and (3.b)

(27) ##STR00030##
in which
three of the R.sup.2, R.sup.3, R.sup.6 and R.sup.7 substituents are hydrogen; and
one of the R.sup.2, R.sup.3, R.sup.6 and R.sup.7 substituents is cyano.

3.1 Mixture of Compounds of the Formulae (3.1a) and (3.1b)

(28) ##STR00031##
in which
at least one of the R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 substituents is bromine;
and the other R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 substituents are hydrogen.

(29) A mixture of 4.52 g (10 mmol) of diisobutyl perylene-3,9-dicarboxylate and diisobutyl perylene-3,10-dicarboxylate, 150 ml of chlorobenzene, 100 ml of water, 16 g (200 mmol) of bromine and a little iodine was stirred under gentle reflux (about 87 C.) for 3 h. Thereafter, the reaction mixture was cooled and poured onto dilute HCl, and the phases were separated. The organic phase was concentrated. The residue had an Rf (toluene:ethyl acetate 10:1)=0.73.

3.2 Preparation of a Mixture of Compounds of the Formulae (3.a) and (3.b)

(30) A mixture of 6 g (7.8 mmol) of the residue obtained in example 3.1, 6.9 g (6.9 mmol) of Cu(I) cyanide and 150 ml of NMP was stirred at 170 C. for 4 h. The reaction mixture was cooled to room temperature, aqueous ammonia was added and extraction was effected with methylene chloride. The residue of the combined organic phases was purified by a column filtration through silica gel (eluent:toluene).

(31) Absorption: .sub.max (CH.sub.2Cl.sub.2): 481 nm;

(32) Emission: .sub.max (CH.sub.2Cl.sub.2): 511 nm

(33) T80 half-life (80 mW/cm.sup.2): 13 days in polystyrene;

(34) T80 half-life (80 mW/cm.sup.2): 40 days in polycarbonate.

(35) FQY (polystyrene): 93%;

(36) FQY (polycarbonate): 93%.