EP1817805A1

EP1817805A1 - Use of phenothiazine-s-oxides and phenothiazine -s,s-dioxides in the form of matrix materials for organic light-emitting diodes

Info

Publication number: EP1817805A1
Application number: EP05808298A
Authority: EP
Inventors: Thomas Gessner; Wolfgang Kowalsky; Christian Schildknecht
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2004-11-25
Filing date: 2005-11-23
Publication date: 2007-08-15
Also published as: DE102004057073A1; WO2006056416A1; KR20070090214A; JP2008522389A; US20080018238A1; CN101065857A

Abstract

The invention relates to the use of phenothiazine-S-oxides and phenothiazine-S,S dioxides in the form of matrix materials for organic light-emitting diodes, in particular in the form of matrix materials in the light-emitting layer of the organic light-emitting diodes. The organic light-emitting diodes comprising the organic layer which contains at least one type of phenothiazine-S-oxide or phenothiazine-S,S dioxide in the form of matrix materials and at least one another substance distributed therein in the form of an emitter, the light-emitting layers consisting of one or several types of phenothiazine-S-oxides or phenothiazine-S,S dioxides in the form of the matrix material and at least another substance distributed therein in the form of the emitter, the organic light-emitting diodes comprising corresponding light-emitting layers and devices provided with corresponding organic light emitting diodes are also disclosed.

Description

Use of phenothiazine S-oxides and -S, S-dioxides as matrix materials for organic light-emitting diodes

description

The present invention relates to the use of phenothiazine S-oxides and -S, S-dioxides as matrix materials for organic light-emitting diodes, in particular as matrix materials in the light-emitting layer of organic light-emitting diodes, organic light emitting diodes comprising a light-emitting layer, which at least at least one phenothiazine S-oxide or -S, S-dioxide as a matrix material and at least one further substance distributed therein as an emitter, light-emitting Schich¬ th which at least one phenothiazine S-oxide or -S, S-dioxide as Matrix material and at least one further substance distributed therein as an emitter, Licht¬ emitting layers, which consist of one or more phenothiazine S-oxides or - S, S-dioxides as matrix material and at least one further distributed therein substance as emitter emitter, organic Light-emitting diodes containing corresponding Licht¬ emitting layers, and devices which corresponding org Ani¬ cal LEDs included.

In organic light emitting diodes (OLEDs), the property of materials is used to emit light when excited by electric current. OLEDs are of particular interest as an alternative to cathode ray tubes and liquid crystal displays for the production of flat screens. Due to the very compact design and the intrinsically low power consumption, devices containing OLEDs are particularly suitable for mobile applications, for example for applications in mobile phones, laptops, etc.

Numerous materials have been proposed which emit light upon excitation by electric current. These materials can act as light emitters per se or consist of a matrix material which contains the actual light emitter in distributed form.

Phenoxazine and phenothiazine derivatives are generally used in the art as charge transport materials.

Thus, EP-A 0 517 542 relates to aromatic amino compounds which are distinguished by good heat stability and may, inter alia, comprise a phenothiazine unit. These aromatic amino compounds are used as hole transport materials in OLEDs. EP-A 0 562 883 also relates to hole transport materials which are used in OLEDs and which have high heat stability. As hole transport materials wer¬ the tris-phenothiazinyl-triphenylamine derivatives or tris-phenoxazinyl-triphenylamine derivatives used.

DE-A 101 43 249 relates to a process for the preparation of conjugated oligo- and polyphenothiazines and their use as hole conductors in organic light emitting diodes and field effect transistors. The oligo- and Polyphenothiazine be prepared by Kreuz¬ coupling of functionalized phenothiazine derivatives.

EP-A 0 535 672 discloses an electrophotographic photoreceptor which contains an organic conductive material in its photosensitive layer. Suitable organic conductive materials include compounds having phenothiazine structural units.

US 5,942,615 and JP-A 11-158165 relate to phenothiazine and phenoxazine derivatives, a charge transport material containing these derivatives, and an electrophotographic photoreceptor containing the disclosed charge transport material. The phenothiazine or phenoxazine derivatives are derivatives of the following formula:

wherein Ar ¹ and Ar ^{2 are} aryl groups, R ¹ and R ^{2 are} H, lower alkyl or aryl, R ^{3 is} lower alkyl, an alicyclic hydrocarbon radical having 5 to 7 carbon atoms, aryl or aralkyl, XS or O and m and n is 0 or 1. With regard to a luminescence, in particular an electroluminescence, of the abovementioned compounds, both US Pat. No. 5,942,615 and JP-A 11-158165 contain no information.

Furthermore, some very special phenothiazine and phenoxazine derivatives are known from the prior art which are used as luminescent materials in the light-emitting layer of an OLED.

For example, JP-A 2003-007466 relates to an OLED which has a long lifetime and high luminance which contains as the luminescent material a polymer which has repeating units based on phenothiazine or phenoxazine derivatives. In JP-07-109449, inter alia, the phentazine S, S-dioxide derivative

described as material in OLEDs.

JP-A 2000-328052 relates to luminescent material which emits light in the yellow to red region of the electromagnetic spectrum and is composed of a monocyclic or condensed polycyclic compound having two specific substituents. These particular substituents are substituents of the following formula:

Mean in it

Bs or O,

R ^{1 is} H, alkyl or aryl and

R ² , R ^{3 are} independently selected from H, CN, halogen, alkylcarbonyl and alkoxycarbonyl, preferably R ² and R ^{3 are} CN.

As condensed polycyclic compounds phenothiazine and phenoxazine derivatives are mentioned.

KR 2003-0029394 relates to red phosphors which are suitable for organic electroluminescence. These phosphors have a phenocyanidine group, has good hole transport properties and an anthracenyl, the ^* nentransportvermögen a good electrical features. Depending on the substitution pattern of the phosphors can These not only show luminescence in the yellow and red, but also in the green region of the electromagnetic spectrum. These particular phosphors have one of the following formulas

The radicals R ¹ and R ² may be H, aryl, heteroaryl, halogen or saturated or unge¬ saturated hydrocarbons. A special feature of these compounds is that they not only have light emission properties but also hole transport properties and electron transport properties due to their particular substitution pattern.

JP-A 2004-075750 relates to phenoxazine derivatives of the formula

wherein R _{1 is} an aromatic or aliphatic linking group and R _{2 is} an alkyl, alkenyl, alkyl ether, alkoxy, amino, aryl or aryloxy group. The phenoxazine derivatives are used in the light-emitting layer of an OLED as fluorescent substances.

The object of the present application is to provide matrix materials for use in O-LEDs, in particular in the light-emitting layers of the OLEDs, which are easily accessible and in combination with the actual emitter (s) good luminance and quantum yields OLEDs effect.

This object is achieved by the use of compounds of the formula I.

in which mean:

X is a group SO or SO ₂ ,

R ^{1 is} hydrogen, alkyl, cyclic alkyl, heterocyclic alkyl, aryl, heteroaryl, a grouping of formula II

a grouping of formula III

or

a grouping of formula IV

X ¹ , X ² , X ^{3 are} independently of one another and independently of X a group SO or SO ₂ ,

R, FT, R 1, R ⁷ , R ⁸ , R ¹¹ , R ^12, independently of one another, are alkyl, aryl or heteroaryl,

m, n, q, r, t, u, x, y are independently 0, 1, 2 or 3, R ⁶ , R ⁹ , R ¹⁰ independently of one another alkyl, aryl, alkoxy or aryloxy,

s. v. w independently 0, 1 or 2,

B is an alkylene bridge -CH ₂ -C _k H _2K -. wherein one or more non-adjacent CH ₂ groups of the unit -Cι _< H _2k - may be replaced by oxygen or NR,

R is hydrogen or alkyl,

k 0, 1, 2, 3, 4, 5, 6, 7 or 8,

j 0 or 1

and

z 1 or 2.

as matrix materials in organic light-emitting diodes.

The matrix materials of the formula I used according to the invention are readily accessible and, in combination with the actual emitter (s), have good luminous densities and quantum yields when used in OLEDs.

The alkyl radicals and the alkyl radicals of the alkoxy groups according to the present application can be straight-chain as well as branched and / or optionally substituted with substituents selected from the group consisting of aryl, alkoxy and halo. The alkyl radicals are preferably unsubstituted. Suitable aryl substituents are mentioned below.

The cyclic alkyl radicals and the cyclic alkyl radicals of the alkoxy groups according to the present application may optionally be substituted by substituents selected from the group consisting of aryl, alkoxy and halogen. The cyclic alkyl radicals are preferably unsubstituted. Suitable aryl substituents are mentioned below.

Suitable halogen substituents are fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine, more preferably fluorine and chlorine.

Examples of suitable alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl. Both the n-isomers of these radicals and also branched isomers such as isopropyl, isobutyl, isopentyl, sec-butyl, tert-butyl, neopentyl, 3,3-dimethylbutyl, 2-ethylhexyl, etc. included. Preferred alkyl groups are methyl and ethyl.

Examples of suitable cyclic alkyl radicals are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl. If appropriate, these may also be polycyclic ring systems, such as decalinyl, norbomanyl, boranonyl or adamantyl. The cyclic alkyl radicals may be unsubstituted or, if appropriate, substituted by one or more further radicals, as has been mentioned by way of example above for the alkyl radicals.

Suitable alkoxy groups are derived according to the alkyl radicals as defined above. For example, OCH ₃ , OC ₂ H ₅ , OC ₃ H ₇ , OC ₄ H ₉ and OC ₈ Hi _{7 may be mentioned here} . C ₃ H ₇ , C ₄ H ₉ and OC ₈ Hi ₇ include both the n-isomers and branched isomers such as isopropyl, isobutyl, sec-butyl, tert-butyl and 2-ethylhexyl. Particularly preferred are methoxy, ethoxy, n-octoxy and 2-ethyl-hexoxy.

Aryl in the present invention refers to radicals which are derived from monocyclic or bicyclic aromatics which contain no ring heteroatoms. Unless they are monocyclic systems, the term aryl for the second ring also denotes the saturated form (Perhydroform) or the partially unsaturated form (for example, the dihydroform or tetrahydroform), if the respective forms are known and stable, possible. That is, in the present invention, the term aryl includes, for example, bicyclic groups in which both both of the groups are aromatic and bicyclic groups in which only one of the rings is aromatic. Examples of aryl are: phenyl, naphthyl, indanyl, 1, 2-dihydronaphthenyl, 1, 4-dihydronaphthenyl, indenyl or 1, 2,3,4-tetrahydronaphthyl. Aryl is particularly preferably phenyl or naphthyl, very particularly preferably phenyl.

The aryl radicals may be unsubstituted or substituted by one or more further radicals. Suitable further radicals are selected from the group consisting of alkyl, aryl, alkoxy, aryloxy, arylcarbonyloxy, heteroaryl, hydroxy and halogen. Preferred alkyl, aryl, alkoxy and halogen radicals have already been mentioned above. The aryl radicals are preferably unsubstituted or substituted by one or more alkoxy groups. More preferably, aryl is unsubstituted phenyl, 4-alkylphenyl, 4-alkoxyphenyl, 2,4,6-trialkylphenyl or

2,4,6-trialkoxyphenyl, where as 4-alkylphenyl, 4-alkoxyphenyl, 2,4,6-trialkylphenyl and 2,4,6-trialkoxyphenyl, in particular 4-methylphenyl, 4-methoxyphenyl, 2,4,6-tri- methyl-phenyl and 2,4,6-trimethoxyphenyl come into consideration. Suitable aryloxy and arylcarbonyloxy groups are derived respectively from the aryl radicals as defined above. Particularly preferred is phenoxy and phenylcarbonyloxy.

Heteroaryl is to be understood as meaning monocyclic or bicyclic heteroaromatics which can be derived in part from the abovementioned aryl by replacing at least one carbon atom in the aryl skeleton by a heteroatom. Preferred heteroatoms are N, O and S. Particularly preferred is the optionally fused backbone selected from systems such as pyridine and five-membered heteroaromatics such as thiophene, pyrrole, imidazole or furan. The backbone may be substituted at one, several or all substitutable positions, suitable substituents being the same as those already mentioned under the definition of aryl. Preferably, however, the heteroaryl radicals are unsubstituted. Particular mention may be made of pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, thiophen-2-yl, thiophen-3-yl, pyrrol-2-yl, pyrrol-3-yl, furan-2 -yl, furan-3-yl and imidazol-2-yl and the corresponding benza- nellierten radicals.

Heterocyclic alkyl is to be understood as meaning radicals which differ from the above-mentioned cyclic alkyl in that at least one carbon atom in the cyclic alkyl backbone is replaced by a heteroatom. Preferred heteroatoms are N, O and S. The backbone may be substituted at one, several or all substitutable positions, suitable substituents being those already mentioned under the definition of aryl. Particular mention should be made here of the nitrogen-containing radicals pyrrolidin-2-yl, pyrrolidin-3-yl, piperidin-2-yl, piperidin-3-yl, piperidin-4-yl.

The moiety -C _k H _2k - of the alkylene bridge B is especially the linear alkylene chains -CH ₂ -, - (CH ₂ Jr, - (CH _Z ) ₃ -, - (CH ₂ ) ₄ -, - (CH ₂ ) ₅ -, - (CH ₂ ) ₆ -, - (CH ₂ ) ₇ - and - (CH ₂ ) ₈ - but these may also be branched such that, for example, chains -CH (CH ₃ ) -, -C (CH ₃ ) ₂ -, -CH ₂ -CH (CH ₃ ) -, -CH (CH ₃ ) -CH (CH ₃ ) -, ^ (CH 1 -C 4 H 1 -), -CH (CHG ) -CH ₂ -CH (CH ₃ ) -, -CH (CH ₃ HCH ₂ ) ₂ -CH (CH ₃ ) -, -CH (CH ₃ ) - (CH ₂ ) ₃ -CH (CH ₃ ) -, - CH (CH ₃ HCH _Z ) ₄ -CH (CH ₃ ) -, -C (CH ₃ ) _Z -CH ₂ -C (CH ₂ ) ₂ - or -C (CH ₃ ) z - (CH ₂ ) ₂ -C ( CH ₃₎ ₂ - come into question can Furthermore _k in the unit -C H _2k -.. a of the alkylene bridge B or more non-adjacent CH ₂ groups may be replaced by oxygen or NR Examples are in particular -0-C ₂ H ₄ -O-, -O- (C ₂ H ₄ -O-);., -NR-C ₂ H ₄ -NR- or -NR- (C ₂ H ₄ -NR-J ₂ , where R is in particular for Wasser¬ fabric, methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl or tert-butyl.

If R ¹ assumes the meaning of a grouping of the formula II with z equal to 2, the two (R ⁴ ) _q and (R ⁵ ) _{r may} each be different from one another according to type and number. Furthermore, the two X ¹ can be different from each other. The optionally substituted phenothiazine skeletons of the formulas I and II are preferably identical, ie (R ² ) _m and (R ⁵ ) _r , (R ³ ) _n and (R ⁴ ) _q and also X and X ¹ (for z = 1) or (R ² ) _m and the two (R ⁵ ) _r , (R ³ ) _n and the two (R ⁴ ) _q and X and the two X ¹ (for z = 2) each have the same meaning.

If R ¹ assumes the meaning of a group of the formula III, the optionally substituted phenothiazine skeletons of the formulas I and III are preferably identical, ie (R ² ) _m and (R ⁸ ) _u , (R ³ ) _n and (R ⁷ ) _t and X and X ² each have the same meaning.

If R ¹ assumes the meaning of a group of the formula IV, the optionally substituted phenothiazine skeletons of the formulas I and IV are preferably identical, ie (R ² ) _m and (R ¹¹ ) _x , (R ³ ) _n and (R ¹² ) _y and X and X ³ each have the same meaning.

In a preferred embodiment, the present invention relates to the use of compounds of the formula I in which the variables have the following meanings:

X is a group SO or SO ₂ ,

R ^{1 is} hydrogen, methyl, ethyl, cyclohexyl, pyrrolidin-2-yl, pyrrolidin-3-yl, piperidin-2-yl, piperidin-3-yl, piperidin-4-yl, phenyl, 4-alkylphenyl, 4-alkoxy phenyl, 2,4,6-trialkylphenyl, 2,4,6-trialkoxyphenyl, furan-2-yl, furan-3-yl, pyrrol-2-yl, pyrrol-3-yl, thiophen-2-yl, thiophene 3-yl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyrimidine

2-yl, pyrimidin-4-yl, pyrimidin-5-yl, sym-triazinyl, phenyl, 4-alkoxyphenyl,

a grouping of formula II

a grouping of formula III

or

a grouping of formula IV

X ¹ , X ² , X ^{3 are} independent of one another and independently of X.

Group SO or SO2,

R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ¹¹ , R ^{12 are} independently aryl,

m, n, q, r, t, u, x, y are independently 0 or 1,

R ⁶ , R ⁹ , R ¹⁰ independently of one another are alkyl or alkoxy,

s, v, w are independently 0 or 1,

B is an alkylene bridge -CH ₂ -C _k H _2K -,

k is 0, 1, 2, 3, 4, 5, 6, 7 or 8

j 0 or 1

and

z 1 or 2. Aryl is preferably in the radicals R ^2, R ^3, R \ R ^5, R ^7, R ^8, R ¹¹ and R ¹² independently of one another, phenyl, naphth-1-yl or naphth-2-yl.

If R ¹ assumes the meaning of a grouping of the formula II with z equal to 2, the two (R ⁴ ) _q and (R ⁵ ) _{r may} each be different from one another according to type and number. Furthermore, the two X ¹ can be different from each other.

The optionally substituted phenothiazine skeletons of the formulas I and II are preferably identical, ie (R ² ) _m and (R ⁵ ) _r , (R ³ ) "and (R ⁴ ) _q and also X and X ¹ (for z = 1) or (R ² ) _m and the two (R ⁵ ) _r , (R ³ ) _n and the two (R ⁴ ) _q and X and the two X ¹ (for z = 2) each have the same meaning.

When R ¹ assumes the meaning of a moiety of formula III, which if appropriate substituted phenothiazine skeletons of the formulas I and III are preferably the same, ie (R ²⁾ _m and (R ⁸⁾ _U1 (R ³⁾ _n and (R ⁷ ) _t and X and X ² each have the same meaning.

Examples of compounds of the formula I ₁ in which R ^{1 is} hydrogen, alkyl, cyclic alkyl, heterocyclic alkyl, aryl or heteroaryl are listed below:

wherein R ^{1 is} one of the following groups

means.

Examples of compounds of the formula I in which R ^{1 has} the meaning of a grouping of the formula II are listed below:

for z = 1:

for z = 2:

Examples of compounds of the formula I in which R ^{1 has} the meaning of a grouping of the formula III are listed below:

Examples of compounds of formula I ₁ where R ¹ is a Gruppie¬ tion of the formula IV belongs, are listed below:

where k in the formulas I / IV a and I / IV c can each assume the values O or 1 to 8 and for the formulas I / IV b and I / IV d the value of j in the bridge unit - (B) _j - CH ₂ - is equal to O, respectively.

The listed phenothiazine S-oxide or phenothiazine S, S-dioxide derivatives of the formula I used according to the invention can be prepared by processes known to the person skilled in the art.

The preparation of the compounds of the formula I is preferably carried out by appropriate substitution of the commercially available phenothiazine skeleton (ie m and n are both equal to O). The radicals R ² and / or R ³ are thereby introduced by electrophilic aromatic substitution. Suitable reaction conditions are known to the person skilled in the art. The radical R ¹ is - if it is not hydrogen - introduced by electrophilic substitution on the nitrogen, for example by reaction with a suitable alkyl or aryl halide. The oxidation of the sulfur in the phenothiazine skeleton to the SO or SO ₂ group usually takes place in the last synthesis step.

Alternatively, however, the preparation of the compounds of the formula I can also be carried out starting from already functionalized building blocks which are suitable for the preparation of the phenothiazine S-oxide or phenothiazine SS-dioxide derivatives. For example, the phenothiazine derivatives used according to the invention can be prepared starting from sulfurized with the radicals R ² and / or R ³ functionalized diphenylamine derivatives by heating. The preparation of the functionalized diphenylamine derivatives is known to the person skilled in the art. Here, too, the oxidation of the sulfur in the phenothiazine skeleton to the SO or SO ₂ group usually takes place in the last synthesis step.

Suitable processes for the oxidation of the phenothiazines to the phenothiazine S-oxides and phenothiazine S, S-dioxides used according to the invention are known to the person skilled in the art and are described, for example, in M. Tosa et al. Heterocyclic Communications, Vol. 7, no. 3, 2001, pp. 277-282.

The oxidation to phenothiazine S-oxide derivatives is carried out for example by means of H ₂ O ₂ in ethanol, ethanol-acetone mixtures or oxalic acid, by means of ammonium persulfate, nitric acid, nitrous acid, inorganic nitrogen oxides, optionally together with (air) oxygen, NO ⁺ BF ₄ VO ₂ , CrO ₃ in pyridine, ozone, tetramethyloxirane, perfluoroalkyloxaziridines or by electrochemical methods. Furthermore, the oxidation of the correspondingly functionalized phenothiazines of the formula I to the corresponding phenoxazine S-oxide derivatives of the formula I by means of m-chloroperbenzoic acid in CH ₂ Cl ₂ at temperatures of 0 to 5 ⁰ C or by means of a mixture of fuming Nitric acid and glacial acetic acid in CCI ₄ (see, for example, M. Tosa et al., Heterocyclic Communications, Vol. 7, No. 3, 2001, pp. 277-282).

The oxidation to phenothiazine S, S-dioxide derivatives is carried out, for example, by means of peracids, such as peracetic acid, which is accessible for example from H ₂ O ₂ and AcOH, or m-chloroperbenzoic acid, sodium perborate, NaOCl or heavy metal systems such as KMnO ₄ ZH ₂ O, Et ₃ PhN ⁺ MnO ₄ ^' in organic media, OsO ₄ / N-methylmorpholine N-oxide. Thus, the oxidation of the correspondingly functionalized phenothiazines of the formula I to the corresponding phenothiazine-S, S-dioxide derivatives of the formula I by means of an aqueous solution of KMnO ₄ and C ₁₆ H ₃₅ N (CH ₃ ) ₃ ⁺ Cl ^" in CHCl ₃ at Room temperature or by means of m-chloroperbenzoic acid in CH ₂ Cl ₂ at room temperature (see, for example, M. Tosa et al., Heterocyclic Communications, Vol. 7, No. 3, 2001, pp. 277-282). To prepare the phenothiazine S, S-dioxide derivatives, the phenothiazine derivative and the oxidizing agent, preferably m-chloroperbenzoic acid, in a molar Ver¬ ratio of generally 1: 1, 8 to 1: 4, preferably 1: 1, 9 to 1: 3.5, more preferably 1: 1, 9 to 1: 3 used.

For the preparation of phenothiazine S-oxide derivatives, the phenothiazine derivative and the oxidizing agent are used in a molar ratio of generally 1: 0.8 to 1: 1, 5, preferably 1: 1 to 1: 1, 3. Oxidizing agents with which no further oxidation to the corresponding S, S-dioxide derivatives takes place, for example H ₂ O ₂ , can be used in a greater excess than the above-mentioned with respect to the Phe¬ nothiazin derivative.

The oxidation is generally carried out in a solvent, preferably in a solvent selected from the group consisting of halogenated hydrocarbons and dipolar aprotic solvents. Examples of the former or the latter are methylene chloride or acetonitrile and sulfolane.

Depending on the oxidizing agent, the oxidation to the phenothiazine-S-oxide derivatives usually takes place at atmospheric pressure in a temperature range from -10 ⁰ C to + 50 ⁰ C and the oxidation to the phenothiazine-SS-dioxide derivatives usually at atmospheric pressure in a temperature range of 0 to + 100 ^° C. The reaction time of the oxidation is generally 0.25 to 24 hours.

The suitable conditions for the oxidation of the respective phenothiazine derivatives to give the corresponding phenothiazine S-oxide or phenothiazine S, S-dioxide derivatives, however, can be determined in any case by a person skilled in the art without any problems in preliminary experiments. For example, the progress of the oxidation can be monitored by analytical methods, such as IR spectroscopy.

In a preferred variant, the phenothiazine S-oxide derivatives are prepared by oxidation of the corresponding I phenothiazine derivatives of the formula I with m-chloro-perbenzoic acid as the oxidizing agent in CH ₂ Cl ₂ at 0 to 20 ⁰ C of the formula.

The phenothiazine S, S-dioxide derivatives of the formula I are preferably prepared by oxidation of the corresponding phenothiazine derivatives of the formula I with m-chloroperbenzoic acid as the oxidant in CH ₂ Cl ₂ at 0 to 40 ^° C.

The isolation and work-up of the resulting phenothiazine S-oxides and phenothiazine S, S-dioxides is carried out by methods known to those skilled in the art.

The preparation of the compounds of the formula I used according to the invention is illustrated by way of example below. As a result, as well as with knowledge of the state of the Technically the person skilled in the art will be able to prepare the further compounds used according to the invention.

The preparation of the compounds of the formula I in which R ^{1 is} hydrogen, alkyl, cyclic alkyl, heterocyclic alkyl, aryl or heteroaryl is advantageously carried out starting from a skeleton of the formula 1

by

aa) N-alkylation or N-arylation of the skeleton of the formula 1, ab) halogenation, ac) coupling reaction with the precursor compounds corresponding to the desired radicals R ² and R ³ , ad) oxidation of the S to SO or SO ₂ ,

wherein step aa) is carried out only when R ^{1 is} different from hydrogen (in the following statements for the preparation of the compounds of formula I under N-alkylation or N-arylation and N-alkylated or N-arylated with respect to Definition of the radical R ¹ not only the N-substitution with alkyl radicals but also the N-substitution with cyclic alkyl radicals and heterocyclic alkyl radicals or not only the N-substitution with aryl radicals but also the N-substitution with heteroaryl radicals are understood; The meaning of the corresponding alkyl or aryl reagents for N-alkylation or N-arylation is also cycloalkyl and heterocycloalkyl or heteroaryl reagents).

Suitable reaction conditions for carrying out steps aa), ab), ac) and ad) are known to the person skilled in the art. In the following, preferred variants of steps aa), ab), ac) and ad) are mentioned.

Step aa)

The N-alkylation or N-arylation is preferably carried out by reacting the basic skeleton of the formula 1 with an alkyl halide or aryl halide of the formula R ¹ -Hal, where R ^{1 has} already been defined above and Hal is Cl, Br or I, preferably I , meaning. In this case, work is carried out in the presence of bases, these being known to the person skilled in the art. These are preferably alkali metal or alkaline earth metal hydroxides, such as NaOH, KOH, Ca (OH) ₂ , alkali metal hydrides, such as NaH ₁ KH, alkali metal amides, such as NaNH ₂ , alkali or alkaline earth metal carbonates, such as K ₂ CO ₃ , or alkali metal alkoxides, such as NaOMe, NaO. Furthermore, mixtures of the abovementioned bases are suitable. Particular preference is given to NaOH, KOH or NaH.

The N-alkylation (described, for example, in M. Tosa et al., Heterocycl Communications, Vol. 7, No. 3, 2001, pp. 277-282) or N-arylation (for example in H. Gilman and DA Shira). ley, J. Am. Chem. Soc., 66 (1944) 888; D. Li et al., Dyes and Pigments 49 (2001) 181-186) is preferably carried out in a solvent. Suitable solvents are e.g. polar aprotic solvents, such as dimethyl sulfoxide, dimethylformamide or alcohols. It is likewise possible to use an excess of the alkyl or aryl halide used as solvent, the use of an excess of LJ on alkyl or aryl iodides being preferred. The reaction may further be carried out in a nonpolar aprotic solvent, e.g. Toluene, when a phase transfer catalyst, e.g. tetra-n-butylammonium hydrogensulfate, an¬ is essential (as disclosed, for example, in I. Gozlan et al., J. Heterocycl Chem 21 (1984) 613-614).

However, the N-arylation can also be carried out by copper-catalyzed coupling of the compound of formula 1 with an aryl halide, preferably an aryl iodide (Ullmann reaction). A suitable method for N-arylation of phenothiazine in the presence of copper bronze is described, for example, in H. Gilman et al., J. Am. Chem. Soc. 66 (1944) 888-893.

The molar ratio of the compound of the formula 1 to the alkyl halide or aryl halide of the formula R ¹ -Hal is generally 1: 1 to 1: 2, preferably 1: 1 to 1: 1.5.

The N-alkylation or N-arylation is typically conducted at atmospheric pressure and in a temperature range from 0 to 220 ⁰ C or to the boiling point of the solu- used sungsmittels. The reaction time is usually 0.5 to 48 hours.

The suitable conditions for the N-alkylation or N-arylation of the compound of the formula 1 can be determined in any case by a person skilled in the art without any problems in preliminary experiments. For example, the progress of N-alkylation or N-arylation can be monitored by analytical methods, such as IR spectroscopy.

The crude product obtained is processed in accordance with methods known to those skilled in the art. Step down)

The halogenation can be carried out according to methods known to the person skilled in the art. Preferably, bromination or iodination takes place in the 3- and 7-position of the optionally N-alkylated or N-arylated skeleton of the formula 1.

A bromination of the optionally in step aa) N-alkylated or N-arylated backbone of formula 1 in the 3- and 7-position of the backbone can, for. B. according to M. Jovanovich et al. J. Org. Chem. 1984, 49, 1905 - 1908 by reaction with bromine in acetic acid. Furthermore, bromination can be carried out according to the method described in C. Bodea et al. Acad. Rep. Rome. 13 (1962) 81-87.

An iodination of the optionally in step aa) N-alkylated or N-arylated Grund¬ backbone of the formula 1 in the 3- and 7-position of the backbone can, for example, according to the in M. Sailer et al. J. Org. Chem. 2003, 68, 7509-7512. Initially, a lithiation of the corresponding, optionally N-alkylated or N-arylated, 3,7-dibromo-substituted backbone of the formula 1 is carried out, followed by iodination of the lithiated product.

The lithiation with a lithium base such as n-butyllithium or lithium diisopropylamide, is generally conducted at temperatures from -78 to +25 ° C, preferably -78 to 0 ⁰ C, particularly preferably -78 ° C according to known in the art Method durch¬ led. Subsequently, the reaction mixture is warmed to room temperature and worked up in accordance with methods known in the art.

Step ac)

The (non-oxidized) phenothiazine derivatives on which the phenothiazine S-oxide and -SS-dioxide derivatives of the formula I are used are preferably prepared by coupling reaction with precursor compounds which correspond to the desired radicals R ² and R ³ , produced. Suitable coupling reactions are, for example, the Suzuki coupling or the Yamamoto coupling, the Suzuki coupling being preferred.

Suzuki coupling can be used to prepare compounds which are substituted by the desired radicals R ² and R ³ at positions 3 and 7 of the (optionally N-alkylated or N-arylated) phenothiazine skeleton of the formula 1, by the corresponding 3,7-halogenated, in particular 3,7-brominated, phenothiazines under Pd (0) catalysis and in the presence of a base with boronic acids or boronic acid esters which correspond to the desired radicals R ² and R ³ reacted ¬ the. Instead of the boronic acids or boronic esters corresponding to the desired radicals R ² and R ³ , it is also possible to use other boron-containing compounds which carry the desired radicals R ² and R ³ in the reaction with the halogenated phenothiazine derivatives. Such boron-containing compounds correspond for example to the general formulas R ² -B (O- [C (R ^' ) ₂ ] _n -O) and R ³ -B (O- [C (R ^' ) ₂ ] _n -O), wherein R ² and R ^{3 have} the meanings given above and R ^'are identical or different radicals hydrogen or C ₁ -C ₂₀ -AikyI, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec Butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n Heptyl, isoheptyl, n-octyl, n-decyl, n-dodecyl or n-octadecyl; preferably C _r C ₁₂ alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl , neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl or n-decyl, more preferably dC ₄ -alkyl, such as methyl, ethyl, n-propyl, iso-propyl , n-butyl, isobutyl, sec-butyl and tert-butyl, very particularly preferably methyl, and n is an integer from 2 to 10, preferably 2 to 5.

The boronic acids, boronic esters and boron-containing compounds corresponding to the desired radicals R ² and R ³ can be prepared by processes known in the art or are commercially available. For example, it is possible to prepare the boronic acids and boronic esters by reacting Grignard or lithium reagents with boranes, diboranes or borates.

As Pd (0) catalysts, all conventional Pd (0) catalysts are suitable. For example, tris (dibenzylideneacetone) dipalladium (0) or tetrakis (triphenylphosphine) palladium (0) can be used. Furthermore, a Pd (II) salt can be used in admixture with a ligand, for example Pd (ac) ₂ or PdCl ₂ and PPh ₃ , where Pd (O) is formed in situ. To carry out the coupling, an excess of PPh _{3 can be} added. The catalysts are generally used in an amount of 0.001 to 15 mol%, preferably 0.01 to 10 mol%, particularly preferably 0.1 to 5 mol%, based on the halogenated phenothiazine derivative used.

In the case of the Suzuki coupling, all bases customarily used for this purpose can be used. Preference is given to alkali metal carbonates, such as sodium or potassium carbonate. The base is generally used in 2 to 200 times, preferably 2 to 100 times, more preferably 2 to 80 times the molar excess, based on the halogenated phenothiazine derivative used.

The component corresponding to the desired radicals R ² and R ³ (boronic acid, the corresponding boronic acid ester or the other suitable boron-containing compounds) is present in a ratio of 100 to 400 mol%, preferably 100 to 300 mol%, particularly preferably 100 to 150 mol% to the halogenated phenothiazine derivative ein¬ set. The reaction is usually carried out under atmospheric pressure at a temperature of 40 to 140 ⁰ C, preferably 60 to 120 ° C, particularly preferably 70 to 100 ⁰ C.

The reaction generally takes place in the absence of oxygen. The reaction is usually carried out in a solvent such as benzene, toluene, tetrahydrofuran, 1,4-dioxane, dimethoxyethane, dimethylformamide, ethanol or petroleum ether. It is also possible to use a mixture of tetrahydrofuran, dimethoxyethane or ethanol and water as solvent.

In a particularly advantageous variant of the process, a halogenated phenothiazine derivative is introduced in solution under protective gas and is present with the base, which is preferably dissolved (for example in a dimethoxyethane / water mixture) and which desired Residues R ² and R ^{3 are added} to corresponding boronic acids. Subsequently, the Pd (0) catalyst is added under protective gas. It is stirred for a period of generally from 2 to 120 hours, preferably from 4 to 72 hours, more preferably from 6 to 48 hours, at the abovementioned temperatures and pressures. Following this, the reaction mixture is worked up by the methods known to the person skilled in the art.

In addition, it is possible to prepare compounds which are substituted by the desired radicals R ² and R ³ at positions 3 and 7 of the (optionally N-alkylated or N-arylated) phenothiazine skeleton of the formula 1, in that the corresponding 3,7 halogenated, in particular 3,7-brominated, phenothiazines with Ni (0) catalysis with halogen compounds, in particular bromine compounds which correspond to the desired radicals R ² and R ³ are reacted (Yamamoto coupling).

Preferably, in the Yamamoto coupling with the exclusion of oxygen, a solution, preferably a DMF solution, of the catalyst prepared from a Ni (0) compound, preferably Ni (COD) ₂ , and bipyridyl in equimolar amounts are used. With exclusion of oxygen, the halogenated, preferably brominated, phenothiazine derivative and the halogen compounds corresponding to the desired radicals R ² and R ³ , in particular bromine compounds, in a solvent, preferably toluene, are added to this solution, with exclusion of oxygen. added.

The reaction conditions in the preparation of the phenothiazine derivatives by Ya¬ mamoto coupling, such as temperature, pressure, solvent and ratio of haloge- nated, preferably brominated, phenothiazine derivative to the R ² and R ³ corresponding components corresponding to those of Suzuki coupling.

As Ni (0) compounds for the preparation of the catalyst, all customary Ni (O) compounds are suitable. For example, Ni (C ₂ H ₄ J ₃ , Ni (1,5-cyclooctadiene) ₂ Are (,, Ni (COD) ₂ "). Ni (1,6-cyclodecadiene) ₂ or Ni (1, 5,9-all-trans-Cyclododeratrien) ₂ sets einge¬ The catalysts are. Generally in an amount of 1 to 100 mol%, preferably 5 to 80 mol%, particularly preferably 10 to 70 mol%, based on the halogenated phenothiazine derivative used.

Suitable process conditions and catalysts, in particular for the Suzuki coupling, are, for example, in Suzuki-Miyaura cross-coupling: A. Suzuki, J. Organomet. Chem. 576 (1999) 147-168; B-alkyl Suzuki-Miyaura cross-coupling: S.R. Chemler et al., Angew. Chem. 2001, 113, 4676-4701 and the literature cited therein.

Step ad)

Preferred oxidizing agents and process conditions for the oxidation of the phenothiazines to the corresponding phenothiazine S, S-dioxide derivatives have been mentioned above and are described, for example, in M. Tosa et al., Heterocyclic Commun. 7 (2001) 277-282.

The preparation of the compounds of the formula I in which R ^{1 is} a grouping of the formula II or III is advantageously carried out starting from a skeleton of the formula 1

by

ba) halogenation, bb) respective coupling reaction with the precursor compounds corresponding to the desired radicals R ² and R ³ or R ⁴ and R ⁵ or R ⁷ and R ⁸ , bc) N-arylation of the radicals R ² and R ³ desired or R ⁴ and R ⁵ or R ⁷ and R ⁸ substituted phenothiazines with the groups corresponding compounds, bd) oxidation of the S to SO or SO ₂ .

Suitable reaction conditions for carrying out steps ba), bb) and bd) have already been described in detail for the corresponding reaction steps ab), ac) and ad).

Step bc) is advantageously carried out in analogy to step aa). The connection of the unit

with the unit (s)

respectively.

via the corresponding phenylene or biphenylyl unit takes place here

by copper-catalyzed coupling of the compounds of formulas 1a and 1b

with the corresponding aryl halide, preferably the aryl iodide, of formula 2

HaI = Cl, Br, I or

by copper-catalyzed coupling of the compounds of the formulas 1a and 1c

(1a) (1c) with the corresponding aryl dihalide, preferably the aryl diiodide, of formula 3

Hal = Cl, Br, I

Shall the symmetrical connections

or

respectively.

With reference to the N-arylation of phenothiazine in the presence of copper bronze according to H. Gilman et al., J. Am., it is possible to prepare, taking into account the stoichiometry of the reactants. Chem. Soc. 66 (1944) 888-893.

In the case of various phenothiazine derivatives of the formulas 1a and 1b, for example for z = 1, this procedure leads to product mixtures PT ¹ -phen-PT ¹ , PT ¹ -phen-PT ² , PT ² -phen-PT ² , where PT ¹ and PT ² each for a different phe- nothiazine unit, which is derived from the corresponding compounds of formulas 1a and 1b, or phen for an optionally substituted, phenylene unit which is derived from the corresponding compound of formulas derives stands. If, in addition, the unit phen is unsymmetrical, then the number of different compounds in the product mixture increases since, in addition to the compound PT ¹ -phen-PT ² , its isomeric compound PT ² -phen-PT ¹ is present.

The same applies in the case of various phenothiazine derivatives of the formulas 1a and 1c, where the compounds PT ¹ -biphen-PT \ PT ¹ -biphen-PT ³ and PT ³ -biphen-PT ³ erhal¬ th, and -for the case In addition, the unbalanced unit biphenal additionally contains the PT ³ -biphen-PT ¹ isomeric compound PT ¹ -biphen-PT ³ . PT ¹ and PT ³ each represents a different phenothiazine unit derived from the corresponding compounds of formulas 1a and 1c, or biphene for an optionally substituted biphenylyl moiety derived from the corresponding compound of formula 3 ,

However, it is possible by means of a suitable experimental procedure to increase the yield of the desired product. For example, the aryl halide or biphenyl dihalogenide, optionally dissolved in an inert solvent, can be initially charged together with the copper powder and the first phenothiazine (PT ¹ -H), if appropriate also dissolved in the same inert solvent, can be added. Thereby formed for the most part, the product PT ¹ -phen-Hal or Hal-biphen PT ^1, which then in the subsequent step with the second phenothiazine derivative (PT ² PT -H or ³ -H) to the product PT ¹ - phen-PT ² (for z = 1) or PT ¹ -biphen-PT ³ reacted. The formation of isomers Products PT ² -phen-PT ¹ or PT ^3- biphen-PT ¹ can be in the normal case! but not influenced by such a procedure.

With regard to the reaction conditions, in the case of the abovementioned method, the preparation of the symmetrical compounds will be oriented. Taking into account the further prior art, the skilled person, if appropriate by carrying out additional preliminary experiments, thus opens up the suitable conditions without much effort.

Alternatively, in step bc), a base-catalyzed reaction of the compounds of formulas 1a and 1b

with the corresponding aryl fluoride of the formula 2 ^'

respectively.

a base-catalyzed reaction of the compounds of formulas 1a and 1c

with the corresponding aryl difluoride of the formula 3 '

(3 ^' )

respectively. Suitable bases in this case are the compounds mentioned under step aa). In particular, NaH is suitable as the base.

The base deprotonated compounds of the formulas 1a and 1b or 1a and 1c then react under nucleophilic aromatic substitution with the compounds of the formulas 2 'and 3', respectively. With regard to the preparation of the symmetrical and unsymmetrical compounds of the formula I in which R ^{1 is a} grouping of the formula II or III, reference is made by analogy to the previous statements.

The preparation of the compounds of the formula I in which R ^{1 is} a group of the formula IV is advantageously carried out starting from a skeleton of the formula 1

by

ca) halogenation, cb) respective coupling reaction with the precursor compounds corresponding to the desired radicals R ² and R ³ or R ⁴ and R ⁵ or R ⁷ and R ^8, respectively, cc) N-alkylation of the radicals R ² and R ³ desired or R ⁴ and R ⁵ or R ⁷ and R ⁸ substituted phenothiazines with the group

- (B) -C

^J H ₂ corresponding compound, cd) oxidation of the S to SO or SO ₂ .

Suitable reaction conditions for carrying out steps ca), cb) and cd) have already been described in detail for the corresponding reaction steps ab), ac) and ad).

Step cc) is carried out analogously to the N-alkylation as described under step aa).

With regard to the preparation of the symmetrical and unsymmetrical compounds of the formula I ₁ in which R ^{1 is} a group of the formula IV, reference is likewise made analogously to the previous statements. The oxidation step last listed in the abovementioned production process, in which the sulfur of the phenothiazine skeleton is converted into the group SO or SO ₂ , can of course also be carried out at an earlier point in time. Accordingly, in a modification of the stated preparation process, for example, compounds of the formula 1 ^{'can also be used.}

are assumed, in which X represents a group SO or SO ₂ .

The compounds of the formula I are outstandingly suitable for use as matrix materials in organic light-emitting diodes (OLEDs). In particular, they are ideally suited as matrix materials in the light-emitting layer of the OLEDs.

Another object of the present invention is therefore the use of the compounds of formula I as matrix materials in the light-emitting layer of the organic light emitting diode.

The use of the compounds of the formula I as matrix materials is not intended to preclude these compounds themselves also emitting light. However, the matrix materials used according to the invention have the effect that, in the case of compounds which are used as emitters in OLEDs, an increase in the luminous density and quantum yield compared to otherwise conventional matrix materials is normally achieved if they are embedded in the former.

Many of these emitter compounds are based on metal complexes, in which case the complexes of the metals Ru ₁ Rh, Ir, Pd and Pt, in particular the complexes of Ir have attained significance. The compounds of the formula I used according to the invention are particularly suitable as matrix materials for emitters based on such metal complexes. In particular, they are suitable for use as matrix materials together with complexes of Ru, Rh, Ir, Pd and Pt, particularly preferably for use together with complexes of Ir.

Suitable metal complexes for use together with the compounds of the formula I as matrix materials in OLEDs are described, for example, in the publications WO 02/60910 A1, WO 02/68453 A1, US 2001/0015432 A1, US 2001/0019782 A1 US 2002/0055014 A1, US 2002/0024293 A1, US 2002/0048689 A1, EP 1 191 612 A2, EP 1 191 613 A2, EP 1 211 257 A2, US 2002/0094453 A1, WO 02/02714 A2, WO 00/70655 A2, WO 01/41512 A1 and WO 02/15645 A1.

Suitable metal complexes for use with the compounds of formula I as matrix materials in OLEDs are e.g. also carbene complexes, as described in the earlier international application PCT / EP / 04/09269. The disclosure of this application is hereby explicitly referred to and this disclosure is to be considered incorporated into the content of the present application. In particular, suitable metal complexes for use together with the compounds of formula I as matrix materials in OLEDs carbene ligands of nach¬ following, in the earlier international application PCT / EP / 04/09269 disclosed structures (the designation of the variables was from the application PCT / EP / 04/09269, with a view to a more precise definition of the variables, reference is expressly made to this application):

in which mean: * the attachment sites of the ligand to the metal center;

z, z are the same or different, CH or N;

R ¹² , R ^{12 are} identical or different, an alkyl, aryl, heteroaryl or alkenyl radical, be¬ preferably an alkyl or aryl radical or in each case 2 radicals R ¹² or R ¹² together form a fused ring, optionally at least one He Preferably, each of 2 radicals R ¹² or R ¹² together form a fused aromatic C ₆ ring, wherein one of these, preferably six-membered, aromatic ring optionally one or more further aromatic rings may be fused where any conceivable annulation is possible, and the fused radicals may in turn be substituted; or R ¹² or R ¹² is a radical having donor or acceptor activity, preferably selected from the group consisting of halo genresten, preferably F, Cl, Br, particularly preferably F; Alkoxy, aryloxy, carbonyl, ester, amino, amide, CHF ₂ , CH ₂ F, CF ₃ , CN, thio groups and SCN;

t and t 'are identical or different, preferably equal to 0 to 3, where, when t or t'> 1, the radicals R ¹² and R ^{12 may be} identical or different, preferably t or t 'is 0 or 1, the radical R ¹² or R ¹² is, when t or t 'is 1, in the ortho, meta or para position to the point of attachment to the nitrogen atom adjacent to the carbene carbon atom;

R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ^{11 are} hydrogen, alkyl, aryl, heteroaryl, alkenyl or a substituent with donor or acceptor action, preferably selected from halogen radicals, preferably F, Cl, Br, particularly preferably F, alkoxy radicals, aryloxy radicals, carbonyl radicals, ester radicals, amine radicals, amide radicals, CH ₂ F groups, CHF ₂ groups, CF ₃ groups, CN groups, thio groups and SCN groups, preferably hydrogen, alkyl, heteroaryl or aryl,

R ^{10 is} alkyl, aryl, heteroaryl or alkenyl, preferably alkyl, heteroaryl or aryl, or in each case 2 radicals R ¹⁰ together form a fused ring which may optionally contain at least one heteroatom, preferably nitrogen, preferably 2 radicals R ^{10 in} each case together form a fused aromatic C ₆ ring, wherein one or more further aromatic rings may optionally be fused to this, preferably six-membered, aromatic ring, any conceivable annulation being possible, and the fused radicals in turn being able to be substituted; or R ¹⁰ means one NEN remainder with donor or acceptor, preferably selected from the group consisting of halogen radicals, preferably F, Cl, Br, most preferably F; Alkoxy, aryloxy, carbonyl, ester, amino, amide, CHF ₂ , CH ₂ F, CF ₃ , CN, thio groups and SCN

v is 0 to 4, preferably 0, 1 or 2, most preferably 0, wherein when v

0, the four carbon atoms of the aryl radical in formula c, which if appropriate substituted with R ¹⁰ , carry hydrogen atoms.

In particular, suitable metal complexes for use together with the compounds of the formula I as matrix materials in OLEDs contain Ir carbene complexes of the following structures disclosed in the earlier international application PCT / EP / 04/09269:

where the variables have the meanings already mentioned above. Further suitable metal complexes for use together with the compounds of the formula I as matrix materials in OLEDs are in particular also:



where M is Ru (III), Rh (III), Ir (III), Pd (II) or Pt (II), n is Ru (III), Rh (III) and Ir (III) is 3, for Pd (II) and Pt (II) assumes the value 2 and Y ² and Y ³ signify hydrogen, methyl, ethyl, n-propyl, isopropyl or tert-butyl. Preferably, M is Ir (III) with n equal to 3. Y ³ is preferably methyl, ethyl, n-propyl, iso-propyl or tert-butyl.

Further suitable metal complexes for use together with the compounds of the formula I as matrix materials in OLEDs are in particular also:

X = O ₁ S

wherein M is Ru (III), Rh (III), Ir (III) ₁ Pd (II) or Pt (II), n is Ru (III), Rh (III) and Ir (IIl) is 3, for Pd (II) and Pt (II) is 2 and Y ^{3 is} hydrogen, methyl, ethyl, n-propyl, iso-propyl or tert-butyl. Preferably, M is Ir (III) with n equal to 3. Y ³ is preferably methyl, ethyl, n-propyl, iso-propyl or tert-butyl.

wherein M is Ru (III), Rh (III) and especially Ir (III), Pd (II) or Pt (II), n is Ru (III), Rh (III) and Ir (III) is 3 and for Pd (II) and Pt (II) assumes the value 2.

Furthermore, complexes with different carbene ligands and / or with ligands L come into question, the latter being mono- or dianionic and may be both mono- and bidentate.

The following table gives schematically complexes ML ^' (L ^" ) ₂ with trivalent metal centers and two different carbene ligands L ^' and L ^" where M is, for example, Ru (III), Rh (III) or Ir (III), in particular Ir (III), and L ^' and L "are, for example, ligands selected from the group of ligands L ¹ to L ⁷

Y ^{2 is} hydrogen, methyl, ethyl, n-propyl, isopropyl or tert-butyl and Y ³ methyl, ethyl, n-propyl, iso-propyl or tert-butyl. designated. A representative of these complexes with different carbene ligands (L ^' = L ⁴ with Y ² = hydrogen and Y ³ = methyl, L ^" = L ² with Y ² = hydrogen and Y ³ = methyl) is spielsweise:

Of course, in the complexes of trivalent metal centers (for example in the case of Ru (III), Rh (III) or Ir (III)) used as emitters in the matrix materials of the formula I, all three carbene ligands may also be different from one another.

Examples of complexes of trivalent metal centers M with ligands L (here monoanionic, bidentate ligand) as "spectator ligands" are LML ^' L ^" , LM (L ^' ) ₂ and L ₂ ML ^' , where M is approximately Ru (III), Rh (III) or Ir (III), in particular Ir (III), and L ^' and L "have the meaning given above. For the combination of L ^' and L ^" in the complexes LML'L" this yields:

Suitable ligands L are, in particular, the acetylacetonate and its derivatives, the picolinate, Schiff's bases, amino acids and the bidentate monoanionic ligands mentioned in WO 02/15645; In particular, the acetylacetonate and pico linat of interest. In the case of complexes L ₂ ML ^' , the ligands L may be the same or different.

A representative of these complexes with different carbene ligands (L '= L ⁴ with Y ² = hydrogen and Y ³ = methyl, L "= L ² with Y ² = hydrogen and Y ³ = methyl) is spielsweise:

wherein z ¹ and z ² in the symbol

stand for the two teeth of the ligand L. Y ³ denotes hydrogen, methyl, ethyl, n-propyl, isopropyl or tert-butyl, in particular methyl, ethyl, n-propyl or iso-propyl.

The present invention therefore relates to organic light-emitting diodes comprising a light-emitting layer which contains at least one compound of the formula I as matrix material and at least one further substance distributed therein as emitter. Another object of the present invention is also a light-emitting layer containing at least one compound of formula I as a matrix material and at least one further substance distributed therein as an emitter.

In particular, a further subject of the present invention is a light-emitting layer consisting of one or more compounds of the formula I as matrix material and at least one further substance distributed therein as an emitter.

Organic light-emitting diodes (OLEDs) are basically built up of several layers, for example:

1. anode

2. Hole-transporting layer

3. Light-emitting layer 4. Electron-transporting layer 5. Cathode

It is also possible from the above-mentioned structure different layer sequences, which are known in the art. For example, it is possible that the OLED does not have all of the layers mentioned, for example an OLED with the layers (1) (anode), (3) (light-emitting layer) and (5) (cathode) is also suitable , wherein the functions of the layers (2) (hole-transprotating layer) and (4) (electron-transprotective layer) are taken over by the adjacent layers. OLEDs comprising layers (1), (2), (3) and (5) or layers (1), (3), (4) and (5) are also suitable.

The phenothiazine S-oxide and phenothiazine S, S-dioxide derivatives of the formula I can be used as charge-transporting, in particular hole-transporting materials, but they are preferably used as matrix materials in the light-emitting layer.

The phenothiazine S-oxide or phenothiazine S, S-dioxide derivatives of the formula I used according to the invention can be present as the sole matrix material-without further additives-in the light-emitting layer. However, it is likewise possible that in addition to the phenothiazine-S-oxide or phenothiazine-S, S-dioxide derivatives of the formula I used according to the invention, further compounds are present in the light-emitting layer. For example, a fluorescent dye may be present to alter the emission color of the emitter molecule present. Furthermore, a diluent material can be used. This diluent material may be a polymer, for example poly (N-vinylcarbazole) or polysilane. However, the diluent material may also be a small molecule, for example 4,4'-N ₁ N'-dicarbazolebiphenyl (CBP = CDP) or tertiary aromatic amines. If a diluent material is used, the proportion of the invention used Phenothiazine S-oxide or phenothiazine S, S-dioxide derivatives of the formula I in the light-emitting layer generally still at least 40 wt .-%, preferably 50 to 100 wt .-% based on the total weight of phenothiazine -S-oxide or phenothiazine S, S-dioxide derivative and diluent.

The individual of the abovementioned layers of the OLED can in turn be composed of 2 or more layers. For example, the hole-transporting layer may be composed of a layer into which holes are injected from the electrode and a layer that transports the holes away from the hole-injecting layer into the light-emitting layer. The electron-transporting layer may also consist of several layers, for example a layer in which electrons are injected through the electrode and a layer which receives electrons from the electron-injecting layer and transports them into the light-emitting layer. These layers are selected in each case according to factors such as energy level, temperature resistance and charge carrier mobility, as well as the energy difference of said layers with the organic layers or the metal electrodes. The expert is able to structure the

OLEDs to be chosen so that it is optimally adapted to the inventively used as emitter substances organic compounds.

To obtain particularly efficient OLEDs, the HOMO (highest occupied molecular orbital) of the hole-transporting layer should be aligned with the work function of the anode, and the LUMO (lowest unoccupied molecular orbital) of the electron-transporting layer should be aligned with the work function of the cathode ,

Another object of the present application is an OLED containing a light-emitting layer which contains at least one compound of formula I as Mat¬ rixmaterial and at least one further substance distributed therein as an emitter, or which consists of one or more compounds of formula I as a matrix material and at least one further substance distributed therein as an emitter.

The anode (1) is an electrode that provides positive charge carriers. It can be constructed, for example, of materials which contain a metal, a mixture of different metals, a metal alloy, a metal oxide or a mixture of different metal oxides. Alternatively, the anode may be a conductive polymer. Suitable metals include the metals of groups Ib, IVa, Va and VIa of the Periodic Table of the Elements as well as the transition metals of the group Villa. When the anode is to be transparent, mixed metal oxides of groups IIb, IMb and IVb of the Periodic Table of the Elements (old IUPAC version), for example indium tin oxide (ITO), are generally used. It is also possible that the anode (1) contains an organic material, for example polyaniline, as described for example in Nature, Vol. 357, Pages 477 to 479 (June 11, 1992). At least either the anode or the cathode should be at least partially transparent in order to be able to decouple the light formed.

Suitable hole transport materials for the layer (2) of the OLED according to the invention are disclosed, for example, in Kirk-Othmer Encyclopedia of Chemical Technology, 4th Edition, Vol. 18, pages 837 to 860, 1996. Both hole transporting molecules and polymers can be used as hole transport material. Commonly used hole transporting molecules are selected from the group consisting of 4,4'-bis [N- (1-naphthyl) -N-phenyl-amino] biphenyl (α-NPD), N, N'-diphenyl-N , N'-bis (3-methylphenylH1, 1'-biphenyl] -4,4'-diamine (TPD) ₁ 1, 1-bis [(di-4-tolylamino) - phenyl] cyclohexane (TAPC), N, N ^< -Bis (4-methylphenyl) -N, N'-bis (4-ethylphenyl) - [1, 1'- (3,3'-dimethyl) biphenyl] -4,4'-diamine (ETPD), tetrakis ^ -methylphenyO-NNN'.N' ^. δ-phenylenediamine (PDA), α-phenyl-4-N, N-diphenylaminostyrene (TPS), p- (diethylamino) -benzaldehyde diphenylhydrazone (DEH), triphenylamine (TPA), bis [ 4- (N, N -diethylamino) -2-methylphenyl) (4-methylphenyl) ethane (MPMP), 1-phenyl-3- [p- (diethylamino) styryl] -5- [p- (diethylamino) phenyl ] pyrazoline (PPR or DEASP), 1,2-trans-bis (9H-carbazol-9-yl) cyclobutane (DCZB), N, N, N ', N'-tetrakis (4-methylphenyl) - (1, 1 -biphenyl) -4,4'-diamine (TTB), 4,4 ^1, 4 "-tris (N, N-diphenylamino) triphenylamine (TDTA), porphyrin compounds and phthalocyanines such as copper phthalocyanines. Üblicherwei The employed hole-transporting polymers are selected from the group consisting of polyvinylcarbazoles, (phenylmethyl) polysilanes and polyanilines. It is also possible to obtain holes-transporting polymers by doping holes-transporting molecules into polymers such as polystyrene and polycarbonate. Suitable hole transporting molecules are the molecules already mentioned above.

Suitable electron transport materials for the layer (4) of the OLEDs according to the invention include chelated metals with oxinoid compounds, such as tris (8-quinolinolato) aluminum (Alq ₃ ), phenanthroline-based compounds, such as 2,9-dimethyl-4,7-diphenyl-1, 10-phenanthroline (DDPA = BCP) or 4,7-diphenyl-1,10-phenanthroline (DPA) and azole compounds such as 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1, 3,4- oxadiazole (PBD) and 3- (4-biphenylyl) -4-phenyl-5- (4-t-butylphenyl) -1, 2,4-triazole (TAZ). In this case, the layer (4) can serve both to facilitate the electron transport and as a buffer layer or as a barrier layer, in order to avoid quenching of the exciton at the boundary surfaces of the layers of the OLED. Preferably, the layer (4) improves the mobility of the electrons and reduces quenching of the exciton.

Of the materials mentioned above as hole transport materials and electron transport materials, some may serve several functions. For example, some of the electron-conducting materials are simultaneously hole-blocking materials if they have a deep HOMO. The charge transport layers can also be electronically doped in order to improve the transport properties of the materials used, on the one hand to make the layer thicknesses more generous (avoidance of pinholes / short circuits) and, on the other hand, to minimize the operating voltage of the device. For example, the hole transport materials can be doped with electron acceptors, for example phthalocyanines or arylamines such as TPD or TDTA can be doped with tetrafluorotetracyanchinodimethane (F4-TCNQ). For example, the electron transport materials may be doped with alkali metals, for example Alq ₃ with lithium. The electronic doping is known to the person skilled in the art and described, for example, in W. Gao, A. Kahn, J. Appl. Phys., Vol. 94, no. 1, 1 July 2003 (p-doped organic layers); AG Werner, F. Li, K. Harada, M. Pfeiffer, T. Fritz, K. Leo. Appl. Phys. Lett., Vol. 82, no. 25, 23 June 2003 and Pfeiffer et al., Organic Electronics 2003, 4, 89-103.

The cathode (5) is an electrode which serves to introduce electrons or negative charge carriers. Suitable materials for the cathode are selected from the group consisting of alkali metals of group Ia, for example Li, Cs, alkaline earth metals of group IIa, for example calcium, barium or magnesium, metals of group IIb of the Periodic Table of the Elements (old IUPAC). Version) comprising the lanthanides and actinides, for example samarium. Furthermore, it is also possible to use metals such as aluminum or indium, as well as combinations of all the metals mentioned. Furthermore, lithium-containing organometallic compounds or LiF can be applied between the organic layer and the cathode to reduce the operating voltage.

The OLED according to the present invention may additionally contain further layers which are known to the person skilled in the art. For example, a layer can be applied between the layer (2) and the light-emitting layer (3), which facilitates the transport of the positive charge and / or adapts the band gap of the layers to one another. Alternatively, this further layer can serve as a protective layer. In an analogous manner, additional layers may be present between the light-emitting layer (3) and the layer (4) in order to facilitate the transport of the negative charge and / or to adapt the band gap between the layers to one another. Alternatively, this layer can serve as a protective layer.

In a preferred embodiment, in addition to the layers (1) to (5), the OLED according to the invention contains at least one of the further layers mentioned below: a hole injection layer between the anode (1) and the hole-transporting layer (2); a block layer for electrons between the hole-transporting layer (2) and the light-emitting layer (3); a blocking layer for holes between the light-emitting layer (3) and the electron-transporting layer (4); an electron injection layer between the electron-transporting

Layer (4) and the cathode (5).

However, it is also possible that the OLED does not have all of the layers (1) to (5) mentioned, for example an OLED having the layers (1) (anode), (3) (light-emitting layer) and (5 ) (Cathode), wherein the functions of the layers (2) (hole-transporting layer) and (4) (electron-transporting layer) are taken over by the adjacent layers. OLEDs comprising layers (1), (2), (3) and (5) or layers (1), (3), (4) and (5) are also suitable.

The person skilled in the art knows how to select suitable materials (for example based on electrochemical investigations). Suitable materials for the individual layers are known to those skilled in the art and e.g. in WO 00/70655.

Furthermore, each of the mentioned layers of the OLED according to the invention can be developed from two or more layers. Furthermore, it is possible that some or all of the layers (1), (2), (3), (4), and (5) are surface treated to increase the efficiency of charge carrier transport. The selection of materials for each of said layers is preferably determined by obtaining an OLED having a high efficiency and lifetime.

The preparation of the OLEDs according to the invention can be carried out by methods known to the person skilled in the art. In general, the OLED according to the invention is produced by successive vapor deposition (vapor deposition) of the individual layers on a suitable substrate. Suitable substrates are, for example, glass or polymer films. For vapor deposition, conventional techniques can be used such as thermal evaporation, chemical vapor deposition and others. In an alternative process, the organic layers can be coated from solutions or dispersions in suitable solvents, using coating techniques known to those skilled in the art.

In general, the various layers have the following thicknesses: anode (1) 500 to 5000 A, preferably 1000 to 2000 A; Hole-transporting layer (2) 50 to 1000 A, preferably 200 to 800 A, light-emitting layer (3) 10 to 1000 A, preferably 100 to 800 A ₁ electron-transporting layer (4) 50 to 1000 A, preferably 200 to 800 A, cathode (5) 200 to 10,000 A _1, preferably 300 to 5000 A. The location of the recombination zone of holes and electrons in the inventive OLED and thus the emission spectrum of the OLED can be affected by the relative thickness of each layer. That is, the thickness of the electron transport layer should preferably be selected so that the electron / holes recombination zone is in the light-emitting layer. The ratio of the layer thicknesses of the individual layers in the OLED depends on the materials used. The layer thicknesses of optionally used additional layers are known to the person skilled in the art.

By using the phenothiazine S-oxide or phenothiazine S, S-dioxide derivatives of the formula I according to the invention as matrix materials in the light-emitting layer of the OLEDs according to the invention, OLEDs can be obtained with high efficiency. The efficiency of the OLEDs according to the invention can be further improved by optimizing the other layers. For example, highly effi¬ cient cathodes such as Ca or Ba, optionally in combination with an intermediate layer of LiF, can be used. Shaped substrates and new hole-transporting materials which bring about a reduction in the operating voltage or an increase in the quantum efficiency can likewise be used in the OLEDs according to the invention. Furthermore, additional layers may be present in the OLEDs to adjust the energy levels of the various layers and to facilitate electroluminescence.

The OLEDs according to the invention can be used in all devices where electroluminescence is useful. Suitable devices are preferably selected from stationary and mobile screens. Stationary screens are e.g. Screens of computers, televisions, screens in printers, kitchen appliances, billboards, lighting and signboards. Mobile screens are e.g. Screens in mobile phones, laptops, digital cameras, vehicles and destination displays on buses and trains.

Furthermore, the phenothiazine-S-oxide or phenothiazine-S.S-dioxide derivatives of the formula I used according to the invention can be used in OLEDs with inverse structure. The compounds of the formula I used according to the invention in these inverse OLEDs are preferably used in turn as matrix materials in the light-emitting layer. The structure of inverse OLEDs and the usual materials used therein are known in the art.

The following examples further illustrate the invention. Examples

Example 1 :

3-phenyl-phenothiazine-5,5-dioxide

A suspension of 2.00 g (7.2 mmol) of 3-phenylphenothiazine (synthesized according to J. Cymerman-Craig, WP Rogers and GP Warwick, Aust. J. Chem. 1955, 8, 252-257) in 45 ml of methylene chloride At room temperature, while stirring, 3.40 g (13.8 mmol) of 70% strength m-chloroperbenzoic acid were added in portions. After stirring for 4 hours at room temperature, the precipitate was filtered off, washed with methylene chloride and dried in vacuo. The crude product (0.95 g) was recrystallized twice from acetic acid. After drying, the light gray solid in high vacuum at 100 ⁰ C 0.492 g (22% of theory..) Of analytically pure substance were obtained with a melting point of 269 - obtained 272 ° C, the solution in tetra hydrofuran at λ = 383 nm fluores¬ ed. ,

Example 2:

a) 10-methyl-3,7-diphenylphenothiazine

2.70 g (6.7 mmol) of 3,7-dibromo-IO-methylphenothiazine (synthesized according to C. Bodea and M. Terdic, Acad. Rep. Rome, 1962, 13, 81-87), 1.85 g ( 14.9 mmol) of 98% phenyl boronic acid, 0.11 g (0.14 mmol) of palladium bis (triphenylphosphine) dichloride and 1.03 g (7.4 mmol) of potassium carbonate were dissolved in 55 ml dimethoxyethane and 28 ml Water under nitrogen at reflux (75 ⁰ C) heated for five hours. The reaction mixture was cooled to room temperature and stirred overnight. The precipitate was filtered off, washed successively with 125 ml of ethanol and hot water and dried at 70 ⁰ C in vacuo. The crude product (2.30 g) was refluxed in cyclohexane for two hours. According to After drying the suspension, the residue was dried, dissolved in 40 ml of methylene chloride and filtered through a glass frit filled with silica gel. After removal of the solvent, 1.05 g (43% n. Th.) Of pale yellow analytically pure solid having a mp. Of 239 - 241 ⁰ C were obtained, whose solution in chloroform at λ = 464 nm fluoresced.

b) 10-Methyl-3,7-diphenylphenothiazine-5,5-dioxide

A solution of 1.95 g (5.3 mmol) of 10-methyl-3,7-diphenylphenothiazine in 65 ml of methylene chloride was charged with 2.67 g (10.7 mmol) of 70% strength m-chloroperbenzoic acid Room temperature and stirred for two hours at 20 - 25 ⁰ C stirred. The reaction solution was shaken successively twice each with 10 ml of 10% potassium hydroxide solution, 10 ml of 5% hydrochloric acid and 10 ml of saturated sodium bicarbonate solution. The organic phase was separated and purified by column chromatography (eluent: ethyl acetate). The crude product obtained (1.80 g) was recrystallized from toluene and then sublimed under high vacuum. There was added 0.65 g (31% of theory..) Of light beige, analytically pure solid, m.p. 242 -. Obtain 245 ⁰ C, the solution in chloroform at λ = 386 nm fluoresced.

Example 3:

a) 10-Methyl-3,7-bis (1-naphthyl) phenothiazine

9.30 g (25.1 mmol) of 3,7-dibromo-10-methylphenothiazine, 9.50 g (55.2 mmol) of 1-naphthylboronic acid, 0.407 g (0.50 mmol) of palladium bis (triphenylphosphine) dichloride and 3.80 g (27.5 mmol) of potassium carbonate were dissolved in 204 ml of dimethoxyethane and 101 ml

Refluxed under nitrogen for five hours under nitrogen. The re- The reaction mixture was cooled to room temperature, stirred overnight and then filtered. The residue was washed with 470 ml of ethanol and hot water and dried at 70 ⁰ C in vacuo. The solid was dissolved in 100 ml of methylene chloride and filtered through silica gel. After removal of the solvent in vacuo, a sticky mass was obtained, which crystallized after addition of 200 ml of methanol with stirring over night. The crystals were filtered off, washed with 300 ml of methanol ge and dried at 40 ⁰ C in vacuo. There were 10.33 g of light yellow Mikrokris- metals having a melting point of 185 -. Received 190 ⁰ C. The crude product was recrystallized twice from ethyl acetate. 5.71 g (49% of theory..) Of analytically pure, almost colorless microcrystals, m.p. 191 -. Obtain 194 ⁰ C, the solution fluoresced in Chloro¬ form at λ = 468 nm.

b) 10-Methyl-3,7-bis (1-naphthyl) -phenothiazine-5-oxide

To an ice-cooled suspension of 2.50 g (5.37 mmol) of 10-methyl-3,7-bis (1-naphthyl) phenothiazine in 60 ml of methylene chloride was added a solution of 1.20 g

(5.35 mmol) of 77% m-chloroperbenzoic acid in 20 ml of methylene chloride within

Dripped for 30 min. The reaction solution was stirred at 0 - 5 ⁰ C for 2 hours. Subsequently, a further 0.60 g (2.70 mmol) of m-chloroperbenzoic acid, dissolved in 10 ml of methylene chloride, were added dropwise. The solution was stirred for 2 hours at 0-5 ⁰ C and then warmed to room temperature. After shaking out the reaction solution with in each case twice 15 ml of 10% KOH, 15 ml of 5% HCl and 25 ml of saturated sodium bicarbonate solution, the organic phase was purified by column chromatography on silica gel (mobile phase: methylene chloride). The first fraction contained the sulfone (see Example 3c) from which 0.38 g (14% of theory) of analytically pure colorless solid with a melting point of 221-225 ° C. were isolated, the solution of which in chloroform fluoresced at λ = 385 nm. After separation of the sulfone, the eluent was changed to ethyl acetate, whereupon a second fraction was obtained. After removal of the solvent, a sticky paste was obtained which crystallized upon addition of water. There were 1, 53 g (59% d. Th.) Of analytically pure light brown Fest¬ material having a decomposition point> 150 ⁰ C, of which the solution fluoresced 388 nm in chloroform at λ =.

c) 10-methyl-3,7-bis (1-naphthyl) phenothiazine-5,5-dioxide

For preparation as a by-product in the synthesis of 10-methyl-3,7-bis (1-naphthyl) -phenothiazine-5-oxide, see b). For a targeted production of the sulfone, the use of at least two molar equivalents of m-chloroperbenzoic acid is recommended. Colorless microcrystals were having an mp of 221 - 225 obtained ⁰ C, the solution fluoresced nm in chloroform at λ = 385th.

Example 4:

a) 10-methyl-3,7-bis (2-naphthyl) phenothiazine

9.30 g (25.1 mmol) of 3,7-dibromo-10-methylphenothiazine, 9.50 g (55.2 mmol) of 2-naphthylboronic acid, 0.407 g (0.50 mmol) of palladium bis (triphenylphosphine) dichloride and 3.80 g (27.5 mmol) of potassium carbonate were refluxed in 204 ml of dimethoxyethane and 101 ml of water under nitrogen for five hours. The reaction mixture was cooled to room temperature, stirred overnight and then filtered. The residue was washed with 470 ml of ethanol and hot water and dried at 70 ⁰ C in vacuo. The solid was dissolved in 200 ml of methylene chloride and filtered through silica gel. After removal of the solvent in vacuo, 9.6 g of greenish yellow solid were obtained (mp 276-281 ⁰ C), which was recrystallized from 500 ml of toluene. There were 7.10 g (61% of theory..) Of analytically pure gelbglän- collapsing micro-crystals with an MP of 285 -. Obtain 289 ⁰ C, the solution in chloroform at λ = 402 nm fluoresced.

b) 10-Methyl-3,7-bis (2-naphthyl) -phenothiazine-5-oxide

To a iced suspension of 2.50 g (5.37 mmol) of 10-methyl-3,7-bis (2-naphthylphenothiazine in 60 ml of methylene chloride was added a solution of 1.20 g (5.35 mmol) 77%. . solution of m-chloroperbenzoic acid in 20 ml of methylene chloride dropwise over 30 minutes The reaction solution was stirred at 0 2 hours -. 5 ⁰ C stirred on closing were further 0.60 g (2.70 mmol) of m-chloroperbenzoic acid dissolved in 10 . ml of methylene chloride is added dropwise the solution was for 2 hours at 0 - stirred nachge¬ 5 ⁰ C and then warmed to room temperature After shaking the Reaktions¬ solution each twice 15 ml of 10% KOH, 15 ml of 5% HCl and 25 ml. saturated sodium bicarbonate solution, the organic phase was purified by column chromatography on silica gel (eluent: methylene chloride) The first fraction Ent¬ held 0.62 g sulfone (see under c)), which was recrystallized from 36 ml o-dichlorobenzene de. There were 0.44 g (16% of theory..) Of yellowish solid, m.p. 328 -. 332 ⁰ C obtained. After separation of the sulfone, the mobile phase was switched to ethyl acetate. After removal of the solvent, 1.30 g of solid were obtained, which was recrystallized from 134 ml of acetic acid. There was added 0.54 g (21% of theory..) Analysenrei¬ ner beige solid having a melting point of 275 - 280 ⁰ C obtained whose Lö¬ solution in chloroform at λ = 402 nm fluoresced..

c) 10-Methyl-3,7-bis (2-naphthyl) phenothiazine-5,5-dioxide

For preparation as a by-product in the synthesis of 10-methyl-3,7-bis (2-naphthyl) -phenothiazine-5-oxide, see under b). For a targeted production of the sulfone, the use of at least two molar equivalents of m-chloroperbenzoic acid is recommended. Yellowish microcrystals were having a melting point of 328 - 332 ⁰ C receive..

Example 5: a) 1, 3-phenylene-10,10 ^'-bis (phenothiazine)

The preparation was carried out according to K. Okada et al., J. Am. Chem. Soc. 1996, 118, 3047-3048.

18.5 g (91.9 mmol) of phenothiazine, 15.6 g (46.3 mmol) of 98% 1, 3-diiodobenzene, 19.4 g (140 mmol) of potassium carbonate and 1.16 g (18.3 mmol ) Activated copper powder were heated to 200 ⁰ C and stirred for 24 h at this temperature. The reaction mixture was cooled to 140 ⁰ C and then treated with 200 ml of ethyl acetate. The suspension was heated to boiling for one hour under reflux and then hot filtered. The filtrate was diluted with 300 ml of methanol to precipitate, which was filtered off, washed with methanol and dried at 80 ⁰ C in vacuo. There were obtained 8.91 g of a pink solid having a mp of 186-188 ⁰ C.

b) 1,3-phenylene-10,10'-bis (phenothiazine) -5,5'-dioxide

6.28 g (13.3 mmol) of 1,3-phenylene-10,10 ^'-bis (phenothiazine) was dissolved in 220 ml Methy¬ lenchlorid. After stirring for 15 min at room temperature, 17.9 g (79.9 mmol) of 77% strength m-chloroperbenzoic acid were added in portions. The reaction solution was stirred for 24 hours at room temperature, during which a precipitate precipitated. The solution was filtered, and the residue was washed with methylene chloride and sucked dry. The solid was suspended in hot water. The aqueous suspension was adjusted to pH 11 with 5% strength potassium hydroxide solution and then filtered hot. The residue was washed with hot water at 80 ⁰ C in vacuo getrock¬ net. The solid (5.07 g) was recrystallized from dimethylformamide. There were Obtain 3.72 g of colorless microcrystals analytically pure mp. 412 ⁰ C, fluoresced de¬ ren solution in toluene at λ = 375 nm (S).

Example 6:

a) 1,4-phenylene-10,10'-bis (phenothiazine)

19.9 g (98.9 mmol) of phenothiazine, 16.6 g (49.8 mmol) of 99% 1, 4-diiodobenzene, 20.9 g (151 mmol) of potassium carbonate and 1.25 g (19.7 mmol ) Activated copper powder were heated to 196 ⁰ C and stirred for 17 h at this temperature. After cooling the reaction mixture to room temperature, 200 ml of hot water were added. The suspension was stirred for one hour and then filtered. The residue was washed with hot water and dried at 80 ⁰ C in vacuo. The crude product (21.6 g) was refluxed in 200 ml of methylene chloride for one hour under reflux. After the solution had cooled to room temperature, it was filtered through silica gel. Three fractions were obtained, the first two of which were combined (11.7 g) and recrystallised from ethyl acetate. The third fraction contained the desired product of value (5.0 g). A total of 13.47 g of beige solid with a mp. Of 254 - 263 ⁰ C were obtained.

b) 1,4-phenylene-10,10'-bis (phenothiazine) -5,5'-dioxide

4.98 g (10.5 mmol) of 1,4-phenylene-10,10 ^'-bis (phenothiazine) were dissolved in 175 ml methylene chloride. After stirring for 1 h at room temperature, 10.41 g (46.5 mmol) of 77% strength m-chloroperbenzoic acid were added in portions. The reaction solution was stirred at room temperature for 24 hours, during which a precipitate precipitated. The solution was filtered, and the residue was washed with methylene chloride and sucked dry. The solid was suspended in 200 ml of hot water. The aqueous suspension was adjusted to pH 11.3 with 5 ml of 10% potassium hydroxide solution, stirred for 1 h and then filtered hot. The residue was washed with hot water and dried at 80 ⁰ C in vacuo. The solid (5.37 g) was recrystallized twice from sulfolane. There were 2.87 g (51%) of pale pink microcrystals analytically pure with mp.> 360 ⁰ C, the solution fluoresced nm in methylene chloride at λ = 480.

Example 7:

10-methylphenothiazine-5,5-dioxide

The preparation was carried out according to M. Tosa et al., Heterocyclic Commun. 7 (2001) 277-282.

A solution of 10.0 g (45.9 mmol) of 98% strength 10-methylphenothiazine in 350 ml of methylene chloride was admixed at room temperature with 22.65 g (91.9 mmol) of 70% strength m-chloroperbenzoic acid and 5 Stirred at 20 - 25 ⁰ C h. After filtration of the solution, the filtrate was shaken out successively twice with 100 ml of 10% potassium hydroxide solution, 100 ml of 5% hydrochloric acid and 70 ml of saturated sodium bicarbonate. The organic phase was concentrated to 150 ml and then filtered through silica gel. From the second fraction was 4.89 g (43% of theory..) Beige micro crystals with an MP of 226 -. 235 ⁰ C (Lit. 225-226 ⁰ C) analytically pure. Recrystallization in acetic acid afforded colorless crystals, which melted at 226 - 233 ⁰ C. A solution of the substance in chloroform fluoresced at λ = 351, 376 (S) nm. Example 8:

a) 10-phenylphenothiazine

The preparation was carried out according to D. Li et al., Dyes and Pigments 49 (2001) 181-186.

96.0 g (482 mmol) of phenothiazine, 298.5 g (1434 mmol) of 98% iodobenzene, 80.0 g (579 mmol) of potassium carbonate and 2.00 g (31 5 mmol) of copper powder were applied to 190-200 ⁰ C heated and stirred for 6 h at this temperature. Subsequently, the excess iodobenzene was distilled off. The reaction mixture was diluted with 480 mL of ethanol and heated to reflux for 1 h. The solution was filtered hot. After cooling, the precipitate was filtered off, washed with ethanol and dried in vacuo. There were 77.7 g (58.5% of theory..) Gray microcrystals having an mp of 95 - (- 97 ⁰ C Lit. 95) was obtained, b) 0-phenylphenothiazine-5,5-dioxide. 96 ⁰ C

The preparation of the compound known from the literature (H. Gilman and R. O. Ranck, J. Org. Chem. 1958, 23, 1903-1906) was carried out in analogy to that of M. Tosa et al., Heterocyclic Commun. 7 (2001) 277-282.

A solution of 5.50 g (20.0 mmol) of 10-phenylphenothiazine in 220 ml of methylene chloride was admixed at room temperature with 11.84 g (48.0 mmol) of 70% strength m-chloroperbenzoic acid and 8 h at 20-25 ⁰ C. touched. The solution was concentrated to dryness. The residue was suspended in hot water and heated to 80 - 85 ⁰ C heated. At this temperature, the pH was adjusted to 7-8 with 32 ml of 10% potassium hydroxide solution. The solution was stirred for 30 minutes, then filtered, washed with hot water. see and dried in vacuo at 80 ⁰ C. The crude product (5.77 g) was dissolved in 30 ml of methylene chloride and filtered through silica gel. From the second fraction 2.92 g (.. 47% of theory) of beige microcrystals were obtained with a mp of 212 -. 217 ⁰ C (Lit. 212-213 ⁰ C) analytically pure. Recrystallization from acetic acid afforded colorless crystals, melting at 212 - 217 ⁰ C melted. A solution of the substance in chloroform fluoresced at λ = 348, 386 (S), 452 (S) nm.

Example 9:

a) 0- (4-methoxyphenyl) phenothiazine

18.77 g (94.2 mmol) of phenothiazine, 66.5 g (284 mmol) of 98% 4-iodoanisole, 15.7 g (114 mmol) of potassium carbonate and 0.392 g (6.17 mmol) of copper powder were added

Heated 190 - 200 ⁰ C and stirred for 48 h at this temperature. Subsequently, the excess iodobenzene was distilled off. The reaction mixture was added with 200 ml hei¬ SSEM water and heated for 1 h at 90 ⁰ C. The solution was filtered hot. After cooling, the precipitate was filtered off, washed with ethanol and dried in vacuo. The crude product (29.0 g) was recrystallized from 345 ml of acetic acid. There were 22.54 g (78.4% of theory..) Beige micro crystals with an MP of 173 -. 176 ⁰ C (Lit. 172-174 ⁰ C).

b) 0- (4-Methoxyphenyl) phenothiazine-5,5-dioxide

A solution of 5.00 g (16.4 mmol) of 10- (methoxyphenyl) phenothiazine in 175 ml of methylene chloride was admixed at room temperature with 9.76 g (39.6 mmol) of 70% strength m-chloroperbenzoic acid and Stirred at 20 - 25 ⁰ C for 4 h. The solution was concentrated to dryness. The residue was taken up with 200 ml of hot water and heated to 80-85 ⁰ C. At this temperature, the pH was adjusted to 7-8 with 25 ml of 10% potassium hydroxide solution. The solution was stirred for 30 min, then riert filt¬, washed with hot water and dried in vacuo at 80 ⁰ C. The crude product (5.25 g) was dissolved in 70 ml of methylene chloride and filtered through silica gel. . After removal of the solvent 4.41 g (.. 80% of theory) of colorless microcrystals, m.p. 265 were - 266 ^C C analytically pure. Recrystallization from acetic acid afforded colorless crystals, melting at 264 - 270 ⁰ C melted. A solution of the substance in chloroform fluoresced at λ = 474 nm.

Example 10:

a) O-mesitylphenothiazine

9.92 g (49.8 mmol) of phenothiazine, 25.0 g (99.6 mmol) of 98% 2,4,6-trimethyliodobenzene, 8.30 g (60.0 mmol) of potassium carbonate and 0.207 g ( 3.26 mmol) copper powder were heated to 180 ⁰ C and stirred for 24 h at this temperature. Subsequently, the excess 2,4,6-trimethyliodobenzene was distilled off. The reaction mixture was admixed with 300 ml of water and stirred overnight. The suspension was filtered, washed neutral with hot water and dried in vacuo at 80 ⁰ C. The crude product (16.6 g) was refluxed in 500 ml of ethanol for 2 hours and then diluted with 200 ml of water. The precipitate was filtered off, dried in vacuo at 80 ⁰ C (10.5 g) and dissolved in 150 ml of toluene. The solution was filtered through silica gel. After concentrating the filtrate, 7.22 g light brown Mikrokris- were metals having a melting point of 192 -. 200 ⁰ C obtained.

b) 0-mesitylphenothiazine-5,5-dioxide

A solution of 1.50 g (4.73 mmol) of 10-Mesitylphenothiazin in 55 ml of methylene chloride was added at room temperature with 2.80 g (11, 4 mmol) of 70% m-chloroperbenzoic acid and 8 h at 20-25 ⁰ C. touched. The solution was extracted by shaking twice in succession each time with 20 ml of 10% strength potassium hydroxide solution, 20 ml of 5% strength hydrochloric acid and 15 ml of saturated sodium bicarbonate solution. The solution was filtered through silica gel. . After concentration of the filtrate, 1.43 g (.. 86% of theory) of beige microcrystals having an mp of 242 were - isolated in analytically pure 246 ⁰ C. Recrystallization from acetic acid afforded colorless crystals, melting at 240 - 246 ⁰ C melted. A solution of the substance in chloroform fluoresced at λ = 349, 370 (S) nm.

Example 11:

a) 1, 3,5-phenylene-10,10 ^' , 10 ^" -tris (phenothiazine)

To a suspension of 6.00 g (150 mmol) of sodium hydride (60% dispersion in parafin oil) in 150 ml of anhydrous dimethylformamide were added 30.19 g (150 mmol) of phenothiazine at room temperature with stirring and nitrogen. temperature to 40 ⁰ C increase. After the evolution of hydrogen had ceased (about 20 minutes), a solution of 6.20 g (46.0 mmol) of 98% strength 1,3,5-trifluorobenzene in 10 ml of dimethylformamide was added dropwise to the reaction solution over a period of 15 minutes. Subsequently, the reaction solution was first heated at 80 ^° C. for two hours, then at 100 ^° C. for 16 hours. After cooling to room temperature, the reaction solution was precipitated in 500 ml of ice water. The precipitate was filtered off with suction, washed neutral with hot water and then dispersed in 500 ml of methanol. The suspension was heated to reflux for one hour. After cooling to Raum¬ temperature the solid was filtered off, washed with methanol and dried at 50 ⁰ C in vacuo. 24.80 g of solid were obtained, which were refluxed in ethyl acetate for one hour under reflux. After cooling to room temperature, the solid was filtered off with suction, washed with ethyl acetate and heated again in ethyl acetate for one hour under reflux to boiling. After Abküh¬ len to room temperature the solid was filtered off with suction, washed with Essigester and dried at 80 ⁰ C in vacuo. 23.34 g (76% of theory) of light gray solid having a melting point of 264-268 ° C. were obtained. b) 1, 3,5-phenylene-10,10M0 ^" -tris (phenothiazine-5,5-dioxide)

A solution of 6.70 g (10.0 mmol) of 1, 3,5-phenylene-10,10 ', 10 ^" -tris (phenothiazine) in 180 mL of methylene chloride was added portionwise at room temperature with 22.19 g (90.0 mmol) of 70% strength m-chloroperbenzoic acid and stirred for 24 h at 20-25 ^° C. The reaction mixture was concentrated to dryness, then treated with 150 ml of hot water and 46 ml of 10% potassium hydroxide solution The solid was filtered off with suction, with hot Washed water until neutral and dried in vacuo at 80 ⁰ C. 7.63 g beige colored microcrystals having a melting point of> 360 ⁰ C were obtained.

Example 12: Benzoic acid 4- (5,5-dioxo-phenothiazin-10-yl) -phenyl ester

a) 10- (2-hydroxyphenyl) phenothiazine

35.9 g (180 mmol) of phenothiazine, 44.5 g (198 mmol) of 98% 4-iodophenol (2-iodophenol can also be used), 29.9 g (216 mmol) of potassium carbonate and 0.75 g ( 12 mmol) copper powder were heated to 198 ° C and stirred at this temperature for 3.5 h. The reaction melt was cooled to 140 ⁰ C and then treated with 150 ml of water within 3 min, the reaction mixture solidified. After cooling with dry ice, the solid was isolated, crushed in a mortar and mixed with 150 ml of water. The suspension was subjected to steam distillation in order to remove excess iodophenol. Subsequently was the solid was filtered off with suction and washed with water. The moist solid wur¬ de in 400 ml of ethanol, stirred overnight at room temperature, then filtered off with suction, washed with ethanol and dried in vacuo at 80 ^C C. The crude product (16.6 g) was refluxed in 500 ml of ethanol for 2 hours and then diluted with 200 ml of water. The precipitate was filtered off, dried in vacuo at 80 ⁰ C (10.5 g) and dissolved in 150 ml of toluene. The solution was filtered through silica gel. After concentrating the filtrate, 7.22 g of light brown microcrystals were obtained with a melting point of 192 - 200 obtained ^0C.

b) Benzoic acid 2- (phenothiazin-10-yl) phenyl ester

To a solution of 4.00 g (13.7 mmol) of 10- (2-hydroxyphenyl) phenothiazine in 24 ml of pyridine 16.0 g (114 mmol) of benzoyl chloride were added dropwise with stirring at 0-5 ° C within 30 min , After stirring for 2 h at room temperature, the reaction solution was heated to 60-65 ° C and stirred for 15 min at this temperature. After cooling to room temperature, the suspension was stirred overnight. After addition of 300 ml of ice water, the suspension was slowly concentrated with 19 ml. Acetic acid (pH 0.9) and stirred for 1 h. The suspension was filtered through a glass frit. The residue was washed neutral with 2 l of water and dried at 60 ⁰ C in vacuo. There were 2.87 g (53% of theory..) Of colorless microcrystals having a melting point of 144 - 148 obtained ^0C.

c) Benzoic acid 2- (5,5-dioxo-phenothiazin-10-yl) -phenyl ester

A solution of 1.32 g (3.33 mmol) of benzoic acid 2- (phenothiazin-10-yl) -phenyl ester in 50 ml of methylene chloride was added at room temperature with 1.81 g (7.33 mmol) 70% Added m-chloroperbenzoic acid and stirred at 20 ⁰ C for 24 h. The solution was concentrated to dryness in vacuo. The residue was taken up in 50 ml of water. The suspension was heated to 80 ⁰ C and stirred for 20 min after addition of 4.5 ml of 10% potassium hydroxide solution. The beige solid was filtered hot with suction, washed with water and hei¬ SSEM at 7O ⁰ C dried (1.285 g). A solution of the solid in 22 ml of methylene chloride was filtered through silica gel MN 60, washing with a mixture of 100 parts of methylene chloride and 1 part of methanol. After concentration of the filtrate, the residue was recrystallized from acetic acid. There were 0.93 g (65% of theory..) Of colorless microcrystals obtained at 228 - 232 ⁰ C melted.

Example 13: 10- (2-Hydroxyphenyl) phenothiazine-5,5-dioxide

A solution of 1.50 g (5.14 mmol) of 10- (2-hydroxyphenyl) phenothiazine in 50 ml of methylene chloride was reacted at room temperature with 2.79 g (11.31 mmol) of 70% strength m-chloroperbenzoic acid added and stirred for 5.5 h at room temperature. The solution was concentrated in vacuo to dryness. The residue was taken up in 100 ml of water. The suspension was heated to 8O ⁰ C and stirred for 20 min after addition of 7.5 ml of 10% potassium hydroxide solution. The solid was filtered off with suction while hot, washed with hot water and dried at 70 ^° C. (1.45 g). The beige solid was recrystallised twice from 42 ml of acetic acid each time. There were 0.92 g (55% of theory) of colorless microcrystals at 282 - 287 ⁰ C melted.

Example 14: Benzoic acid 4- (5,5-dioxo-phenothiazin-10-yl) -phenyl ester

a) (4-iodophenyl) benzyl ether

A reaction mixture of 21, 40 g (95.3 mmol) of 98% 4-iodophenol, 12.19 g (95.3 mmol) of 99% benzyl chloride, 20.73 g (150 mmol) of potassium carbonate and 250 ml of acetone were added Heated to reflux and heated to boiling for 30 hours. After cooling to room temperature, the reaction mixture was filtered. The filtrate was concentrated and then cooled in an ice bath, whereupon a precipitate precipitated out. This was separated via a blue band filter and then dried. The crude product (23.22 g) was recrystallized from 70 ml of ethanol. 17.20 g (58% of theory) of colorless microcrystals having a melting point of 61.degree.-62.degree. C. (Lit 62 ⁰ C) were obtained.

b) 10- (4-benzyloxyphenyl) phenothiazine

5.56 g (27.9 mmol) of phenothiazine, 8.65 g (27.9 mmol) of (4-iodophenyl) benzyl ether, 4.64 g (33.5 mmol) of potassium carbonate, and 0.116 g (1.82 mmol). Copper powder was heated to 19O ⁰ C and stirred for 24 h at this temperature. The reaction melt was cooled to 110 ° C, then diluted with 200 ml of toluene and stirred at 112 ⁰ C for one hour. The solution was filtered hot. The cooled to room temperature filtrate was purified on silica gel in toluene. The beige crude product (6.52 g) was recrystallized from 125 ml of ethanol. 4.79 g (45% of theory) of beige-colored microcrystals having a melting point of 144 ° -146 ° C. were obtained.

c) 10- (4-Benzyloxyphenyl) phenothiazine-5,5-dioxide

A solution of 4.60 g (12.1 mmol) of 10- (4-benzyloxyphenyl) phenothiazine in 130 ml of methylene chloride was admixed at room temperature with 6.53 g (26.5 mmol) of 70% strength m-chloroperbenzoic acid and Stirred for 3 h at room temperature. The solution was concentrated in vacuo to dryness. The residue was taken up in 150 ml of water. The suspension was heated to 80 ^° C. and, after addition of 14 ml of 10% potassium hydroxide solution, stirred for 20 minutes. The solid was filtered off hot, washed with hot ser Was¬ and dried at 100 ⁰ C. There were beigefarbe¬ ner solid with a mp of 203 4.78 g (96% of theory) -. Obtain 208 ⁰ C. To methylene chloride to remove residues, 0.96 g of solid was sublimated under high vacuum at 200 ⁰ C. There were obtained 0.78 g of analytically pure colorless microcrystals, which melted at 204 -208 ⁰ C.

d) 10- (4-hydroxyphenyl) phenothiazine-5,5-dioxide

3.10 g (7.50 mmol) of 10- (4-benzyloxyphenyl) phenothiazine-5,5-dioxide, 2.30 g

(35.7 mmol) of 98% ammonium formate and 7.5 g of 10% palladium on charcoal were refluxed in 225 ml of acetone for one hour. After cooling to room temperature, the solution was filtered. The filtrate was einge¬ concentrated and stirred after addition of 10 ml of methanol overnight. The solid was filtered off, washed with methanol and overall at 11O ⁰ C in a vacuum oven dries. There were 1, 47 g (61% of theory) of analytically pure light gray microcrystals having ei¬ nem mp of 308 - 311 obtained ^0C..

e) Benzoic acid 4- (5,5-dioxo-phenothiazin-10-yl) -phenyl ester

To a solution of 0.72 g (2.22 mmol) of 10- (4-hydroxyphenyl) phenothiazine-5,5-dioxide in 120 mL of acetonitrile was added 0.68 g (6.68 mmol) of triethylamine and 0.34 g (2.44 mmol) of benzoyl chloride. After 45 min. Stirring at room temperature, the solvent was distilled off. The residue was taken up in 100 ml of hot water and stirred at 75 ^° C. for 30 min. The solid was filtered off with suction while hot, washed with hot water and dried at 12O ⁰ C in a convection oven. There were 0.87 g (92 of theory%) of colorless microcrystals, m.p. 233 - 235 ⁰ C th conservation..

Example 15: 10- (3,5-Difluorophenyl) phenothiazine-5,5-dioxide

a) 10- (3,5-difluorophenyl) phenothiazine

To a suspension of 2.00 g (50.0 mmol) of sodium hydride (60% dispersion in paraffin oil) in 100 ml of anhydrous dimethylformamide was added 10.07 g with stirring and nitrogen (50.0 mmol) phenothiazine was added over 10 min at room temperature, the reaction temperature rose to 32 ° C. After the evolution of hydrogen had ceased (about 20 minutes), a solution of 7.41 g (55.0 mmol) of 98% strength 1,3,5-trifluorobenzene in 50 ml of dimethylformamide was added in the course of 15 minutes to the reaction solution heated to 85 ° C. dripped. Subsequently, the reaction solution was stirred for 24 hours at this Tempe¬ temperature. After cooling to room temperature, the reaction solution was slowly precipitated in 500 ml of ice water. The aqueous suspension was stirred for 2 h after addition of 18 g of sodium chloride and then filtered. The residue was washed with water and dried. The solid was suspended in 200 ml of hexane and heated at reflux for 1 h. After cooling to room temperature, the suspension was filtered. The filtrate was concentrated in vacuo to dryness. The residue (7.00 g) was stirred up in 230 ml of a mixture of 40 parts of hexane and 1 part of ethyl acetate and filtered. The filtrate was chromatographed on silica gel with an eluent of 40 parts hexane and 1 part ethyl acetate. After removal of the solvent-means of the residue at 8O ⁰ C and 1.8 X NG ^{"was 5} mbar, with a portion of the substance sublimed. The residual in the original solid was recrystallized from 40 ml of ethanol. There was added 1.18 g (7.6% of theory) of analytically pure colorless microcrystals having a melting point of 111-115 ° C.

b) 10- (3,5-Difluorophenyl) -phenothiazine-5,5-dioxide

A solution of 1.40 g (4.50 mmol) of 10- (3,5-difluorophenyl) phenothiazine in 40 ml of methylene chloride was treated at room temperature with 2.46 g (10.0 mmol) of 70% strength m-chloro - Perbenzoic acid added and stirred for 2 h at room temperature. The solution was concentrated in vacuo to dryness. The residue was stirred in 100 ml of 50 ⁰ C warm water for 30 min. The suspension was treated with 7.5 ml of 10% potassium hydroxide solution, stirred for 30 minutes and then filtered. The solid was filtered off with suction while hot, washed with hot water and dried at 80.degree. The tan solid (1.54 g) was recrystallized twice from acetic acid. After drying at 13O ⁰ C in a high vacuum, 0.73 g (47% of theory) of analytically pure colorless microcrystals were obtained which melted at 255 ° -258 ° C. Example 16: 10- (2-pyridyl) -phenothiazine-5,5-dioxide

a) 10- (2-pyridyl) phenothiazine

4.46 g (22.4 mmol) of phenothiazine, 9.36 g (47.6 mmol) of 98% 2-iodopyridine, 3.72 g (26.9 mmol) of potassium carbonate and 0.093 g (1.5 mmol) of copper powder were heated to 192 ° C and stirred for 24 h at this temperature. The reaction melt was cooled to 100 ⁰ C, then slowly diluted with 200 ml of ethanol and heated to reflux for one hour under reflux. After cooling to room temperature, the reaction mixture was filtered to leave a sticky paste which was dissolved in 100 ml of methylene chloride. The methylene chloride solution was purified on silica gel to give two fractions. The second fraction was concentrated to dryness. There were 2.55 g (41% of theory) of beige microcrystals having a melting point of 107 - receive - 109 ⁰ C (110 ⁰ C Lit .: 109).

b) 10- (2-pyridyl) -phenothiazine-5,5-dioxide

A solution of 2.20 g (7.96 mmol) of 10- (2-pyridyl) phenothiazine in 80 ml of methylene chloride was added at room temperature while cooling with 4.32 g (17.5 mmol) of 70% strength m-chloroperbenzoic acid added and stirred for 2 h at room temperature. The solution was concentrated in vacuo to dryness. The residue was taken up in 200 ml of 70 ° C hot water and treated with 10 ml of 10% KOH. After stirring for 30 minutes, the suspension was filtered. The residue was washed with hot water and dried at 50 ° C in vacuo. The colorless solid (1.87 g) was dissolved in 20 ml of a mixture of 99 parts of methylene chloride and one part of methanol and purified on silica gel. The purified solution was concentrated to dryness. After this Drying of the residue at 70 ° C in vacuo, this was recrystallized from 10 ml of acetic acid. There were 1.09 g

(44% of theory) of analytically pure colorless microcrystals, which melted at 186 - 19O ⁰ C. After prolonged standing of the acetic acid filtrate at room temperature, 0.32 g of colorless microcrystals having a melting point of 184.degree.-188.degree. C. precipitated (total yield: 57%).

Example 17: 10- [4- (N-phenyl-2-benzimidazolyl) -phenyl] -phenothiazine-5,5-dioxide

a) N-phenyl-2 ~ (4-iodophenyl) benzimidazole

37.47 g (136 mmol) of 97% pure 4-iodobenzoyl chloride and 12.82 g (68.2 mmol) of 98% o-aminodiphenylamine were heated to 100 ⁰ C, wherein from 85 to 9O ⁰ C, a stirrable melt was formed. After completion of the evolution of gas (5 min), the melt solidified. The reaction mass was kept at 100 ^° C. for a further 3 hours. After cooling, this was mixed with 100 ml of ethanol with stirring. The precipitate was filtered off, washed with ethanol and stirred again in 400 ml of ethanol. The suspension was heated to 75 ^° C. to give a solution which was adjusted to pH 8 with 29 ml of 25% ammonia. After cooling to 5 - 10 ⁰ C the Nie¬ Derschlag was aspirated, washed with cold ethanol and dried cabinet at 75 ° C in a vacuum. There were 18.37 g (68% of theory) of light gray microcrystals having an mp of 178 - 181 obtained ^0C..

b) 10- [4- (N-phenyl-2-benzimidazolyl) -phenyl] -phenothiazine

7.77 g (39.0 mmol) of phenothiazine, 17.00 g (42.9 mmol) of N-phenyl-2- (4-iodophenyl) benzimidazole, 6.47 g (46.8 mmol) of potassium carbonate and 0.162 g (2.54 mmol) Kupferpul¬ ver were heated to 195 - 200 ⁰ C and stirred for 19 h at this temperature. The Reakti¬ onsschmelze was cooled to 130 ⁰ C and then diluted with 100 ml of ethanol. After 30 min. Heating under reflux, the solution became hot, filtered. The suspension was concentrated to dryness and then treated with 150 ml of methylene chloride. After Filtrati¬ on the filtrate was filtered through silica gel. 11.03 g of beige microcrystals were obtained.

c) 10- [4- (N-phenyl-2-benzimidazolyl) -phenyl] -phenothiazine-5,5-dioxide

A solution of 6.14 g of 10- [4- (N-phenyl-2-benzimidazolyl) -phenyl] -phenothiazine in 180 ml of methylene chloride was added at room temperature while cooling with 7.17 g (28.9 mmol) of 70% m Added perchloroperbenzoic acid and stirred for 1 h at room temperature. The solution was treated with 60 ml of 10% KOH. After removal of the methylene chloride the suspension was diluted with 100 ml of hot water. The precipitate was filtered off, washed with hot water and dried at 8O ⁰ C in a vacuum. The crude product (4.82 g) was recrystallized from 48 ml of acetic acid. 3.02 g (46% of theory) of beige-colored microcrystals having a melting point of 286-288 ° C. were obtained.

Example 18: 10- (2-thiophenyl) phenothiazine-5,5 ^'dioxide

a) 10- (2-thiophenyl) -phenothiazine

8.4 g (42 mmol) of phenothiazine, 9.1 g (42 mmol) of 98% 2-iodothiophene, 7.0 g (51 mmol) of potassium carbonate and 0.18 g (2.8 mmol) of copper powder were ⁰ to 140 C heated and stirred for 7 hours at this temperature. The reaction melt was cooled, treated with 200 ml of ethanol, heated to reflux and filtered hot. The residue was washed twice with ethanol. The ethanol solution was concentrated and, after column chromatography (mobile phase ethyl acetate / cyclohexane 2: 5), 3.13 g of desired product were obtained, which was used in the same way for the subsequent reaction step b).

b) 10- (2-thiophenyl) phenothiazine-5,5 ^'dioxide

3.13 g (11.1 mmol) of 10- (2-thiophenyl) -phenothiazine from reaction step a) were dissolved in 100 ml of methylene chloride. At 0-5 ⁰ C, 5.52 g (22.4 mmol) of 77% m-chloroperbenzoic acid were added in portions. The reaction solution was stirred at room temperature for 2 hours. The reaction mixture was concentrated and the residue was dissolved in 250 ml of methylene chloride. The organic phase was washed three times with 20 ml of 10% potassium hydroxide solution and five times with 50 ml of demineralized water. After column chromatography (eluent methylene chloride) the desired product was obtained, which was further purified by crystallization from acetic acid and then sublimation. There were 0.34 g (10% of theory..) Of colorless microcrystals having a melting point of 230 - 234 obtained ^0C.

Example 19: 2,5- (1,4-Dimethoxyphenylen) -10,10 ^'-bis (phenothiazine) ^-5,5' dioxide

a) 2,5- (1, 4-Dimethoxyphenylen) -10,10 ^'-bis (phenothiazine)

0.8 g (4.0 mmol) of phenothiazine, 0.88 g (2.2 mmol) of 97% 1,4-diiodo-2,5-dimethoxybenzene, 0.66 g (4.8 mmol) of potassium carbonate and 0.016 g (0.25 mmol) of activated copper powder were heated to 14O ⁰ C in DMSO (10 ml) and stirred at this temperature for 15 hours. After the reaction mixture had cooled to room temperature, 30 ml of methylene chloride were added and the suspension was filtered. The methylene chloride solution was washed three times with 25 ml each of 0.1 molar hydrochloric acid, dried and concentrated. There was obtained 0.99 g of the title compound as a colorless solid.

b) 2,5- (1, 4-Dimethoxyphenylen) -10,10 ^'-bis (phenothiazine) ^-5,5' -clioxid

0.43 g (0.81 mmol) 2,5- (1,4-Dimethoxyphenylen) -10,10 ^'-bis (phenothiazine) from Reakti¬ ons step a) were dissolved in 15 ml of methylene chloride. After stirring for 1 hour at room temperature, 0.56 g (3.2 mmol) of 77% strength m-chloroperbenzoic acid were added in portions. The reaction solution was stirred at room temperature for 24 hours to precipitate. The suspension was concentrated and the residue in demineralized water with 10 ml of 10% sodium hydroxide ge¬ adjusted to pH 12, stirred for 1 hour at 70 ⁰ C and then filtered. The residue was washed with hot water and dried at 80 ⁰ C in vacuo. There was obtained 0.20 g (41%) of desired product.

Example 20: Preparation of an OLED

The ITO substrate used as the anode is first with commercial Reinigungsmit¬ stuffs for the LCD production (Deconex 20NS ^® and neutralizing agent 25ORGAN- ACID ^®) and subsequently cleaned in an acetone / isopropanol mixture in an ultrasonic bath. To remove possible organic residues, the substrate is exposed to a continuous flow of ozone for another 25 minutes in an ozone furnace. This treatment also improves hole injection of the ITO.

Thereafter, the organic materials specified below are ^{"evaporated 7} mbar on the cleaned substrate. As Lochlei¬ is ter first 1-TNATA (4,4 ', 4" at a rate of about 2 nm / min at about 10 -tris (N - (Naphth-1-yl) -N-phenyl-amino) -triphenylamine) in a layer thickness of 17.5 nm applied to the substrate. This is followed by the deposition of a 9.5 nm thick exciton blocker layer of the compound

(For preparation see Ir complex (7) in the application PCT / EP / 04/09269).

Subsequently, a mixture of 34 wt .-% of the compound

and 66% by weight of the compound

(see Example 5b)) in a thickness of 20 nm, with the former compound acting as emitter, the latter as matrix material. Thereafter, a BCP Lochblocker- and electron conductor layer in a thickness of 47.5 nm, a 0.75 nm thick lithium fluoride layer and finally a 110 nm thick Al electrode is evaporated.

To characterize the OLED, electroluminescence spectra are recorded at different currents or voltages. Furthermore, the current voltage voltage characteristic in combination with the radiated light output. The light output can be converted into photometric variables by calibration with a luminance meter.

For the OLED described above, the following electro-optical data result:

Claims

claims

1. Use of compounds of the formula I.

in which mean:

X is a group SO or SO ₂ ,

R ^{1 is} hydrogen, alkyl, cyclic alkyl, heterocyclic alkyl, aryl, heteroaryl,

a grouping of formula II

a grouping of the formula

or a grouping of formula IV

X ¹ , X ² , X ^{3 are} independent and independent of each other

X is a group SO or SO ₂ ,

R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ¹¹ , R ¹² independently of one another alkyl, aryl or heteroaryl,

m, n, q, r, t, u, x, y independently of one another are O, 1, 2 or 3,

R ⁶ , R ⁹ , R ^{10 are} independently alkyl, aryl, alkoxy or

aryloxy,

s, v, w are independently 0, 1 or 2,

B is an alkylene bridge -CH ₂ -C _k H _2I c, wherein one or more non-adjacent CH ₂ groups of the moiety -C _k H _2k - may be replaced by oxygen or NR,

R is hydrogen or alkyl,

k 0, 1, 2, 3, 4, 5, 6, 7 or 8,

j 0 or 1

and

z 1 or 2.

as matrix materials in organic light-emitting diodes. 2. Use according to claim 1, characterized in that compounds of the formula I are used, wherein the variables have the following meanings auf¬:

X is a group SO or SO ₂ ,

R ^{1 is} hydrogen, methyl, ethyl, cyclohexyl, pyrrolidin-2-yl, pyrrolidin-3-yl, piperidin-2-yl, piperidin-3-yl, piperidin-4-yl, phenyl, 4-alkylphenyl, 4- Alkoxyphenyl, 2,4,6-trialkylphenyl, 2,4,6-trialkoxyphenyl, furan-2-yl, furan-3-yl, pyrrol-2-yl, pyrrol-3-yl, thiophen-2-yl, Thiophen-3-yl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, sym-triazinyl, phenyl, 4- alkoxyphenyl,

a grouping of formula II

a grouping of the formula

or a grouping of formula IV

m, n, q, r, t, u, x, y are independently 0 or 1,

R ⁶ , R ⁹ , R ¹⁰ independently of one another are alkyl or alkoxy,

s, v, w are independently 0 or 1,

B is an alkylene bridge -CH ₂ -C _k H _2k -,

k 0, 1,

2, 3, 4, 5, 6, 7 or 8,

j 0 or 1

and

z 1 or 2.

3. Use according to claim 1 or 2, characterized in that the compounds of the formula I according to claim 1 or 2 are used as matrix materials in the Licht¬ emitting layer of the organic light emitting diode.

4. Organic light-emitting diode comprising a light-emitting layer, characterized in that the light-emitting layer contains at least one compound of the formula I according to claim 1 or 2 as a matrix material and at least one further substance distributed therein as an emitter.

5. Light-emitting layer comprising at least one compound of the formula I according to claim 1 or 2 as matrix material and at least one further substance distributed therein as emitter.

6. Light-emitting layer consisting of one or more compounds of the formula I according to claim 1 or 2 as matrix material and at least one further substance distributed therein as an emitter.

7. Organic light-emitting diode containing a light-emitting layer according to An¬ claim 5 or 6.

8. Device selected from the group consisting of fixed screens, such as computer screens, televisions, printer screens, kitchen appliances and billboards, lighting, signage and mobile displays

Screens such as screens in mobile phones, laptops, digital cameras, vehicles and destination displays on buses and trains containing an organic Leucht¬ diode according to claim 4 or 7.