Method of manufacturing materials for use in electronic devices

Abstract

The present invention relates to a process for the manufacture of indolo [3, 2, 1-jk] carbazoles and derivatives thereof by reaction of a compound of formula (1) with at least one source of nitrosyl cations.

Description

[0001] The present invention relates to a method for producing materials for use in electronic devices, in particular organic electroluminescent devices.

[0002] Electronic devices containing organic, organometallic and / or polymer semiconductors are becoming increasingly important and are being used in many commercial products for reasons of cost and their performance. Examples here include organic-based charge transport materials (e.g. triarylamine-based hole transport materials) in copiers, organic or polymer light emitting diodes (OLED or PLED) in readout and display devices, or organic photoreceptors in copiers. Organic solar cells (O-SCs), organic field effect transistors (O-FETs), organic thin film transistors (O-TFTs), organic integrated circuits (O-ICs), organic photoamplifiers and organic laser diodes (O-lasers) are at an advanced stage of development and may have great future significance.

[0003] An electronic device in the context of the present invention is understood to mean an organic electronic device which contains an organic semiconductor material as functional material. In particular, the electronic device represents an electroluminescent device such as an OLED.

[0004] The construction of OLEDs using organic compounds as functional materials is known to the person skilled in the art from the prior art. In general, an OLED is understood to mean an electronic device which has one or more layers comprising organic compounds and which emits light when a voltage is applied.

[0005] In electronic devices, especially OLEDs, there is a great need for improved performance data, especially with regard to lifetime, efficiency and operating voltage. No satisfactory solutions have been found so far for these aspects.

[0006] Electronic devices generally comprise a cathode, an anode and at least one functional layer, which is preferably a light-emitting layer. In addition to these layers, they may also comprise further layers, for example in each case one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, electron blocking layers and / or charge generation layers.

[0007] The performance data of electronic devices are mainly affected by the hole transport layer and the electron transport layer.

[0008] Indolo[3,2,1-jk]carbazole is a very important structural unit in this type of materials, especially in e- and h-TMMs (electron-conducting or hole-conducting triplet matrix materials), narrow-band SEBs (blue singlet emitters), HTMs (hole-transporting materials) and EBMs (electron-blocking materials).

[0009] In the known method, the second ring is closed starting from the N-arylated carbazole. Since the ring can be closed with either of the two six-membered rings of the carbazole, the regioisomerism cannot be controlled.

[0010]

[0011] According to the ring-closing reaction, X' here can be H or a corresponding reactive group.

[0012] Known ring-closing reactions include thermal decomposition (Wharton et al., Chem. Eur. J. 15 (2009) 5482), oxidative cyclization (Jones et al., Adv. Synth. Catal. 357 (2015) 945), transition metal catalysis (Lv et al., Tetrahedron Letters 53 (2012) 5248) and diazotization (Hiraga et al., Tetrahedron 94 (2021) 132317; Hiraga et al., Tetrahedron 86 (2021) 132049).

[0013] However, yields are often low and reaction conditions are often not permissive for other groups.

[0014] Pyrolysis is complex in terms of equipment and requires extreme conditions. Moreover, it is only applicable to volatile groups.

[0015] Transition metal catalysis usually requires high temperatures and long reaction times, and requires the use of transition metals. In addition, only low to zero regioselectivities are observed. And this is often the case with large amounts of catalyst.

[0016] In the diazotization, only low yields were achieved and zero or only low regioselectivities were observed.

[0017] Chatterjee et al., Org. Lett. 19 (2017) 1906 reported the preparation of carbazole from diphenylamine by photocatalytic intramolecular ring closure reaction in the presence of t-BuONO in an oxygen atmosphere. The reaction requires an oxygen atmosphere and strong light irradiation. The yields obtained were also very low, and higher reaction temperatures did not lead to better yields.

[0018] The object of the present invention is to provide a method for preparing indolo[3,2,1-jk]carbazole and its derivatives.

[0019] Therefore, the present invention provides a method for preparing indolo[3,2,1-jk]carbazole and its derivatives, the method comprising the following steps:

[0020]

[0021] a) providing a composition comprising a compound of formula (1) and at least one source of nitrosyl cations;

[0022] b) converting the composition in a) into a diazonium salt;

[0023] c) optionally isolating the diazonium salt of formula (2);

[0024] d) converting into a compound of formula (3);

[0025] And the symbols used therein are as follows:

[0026] Ar 1 ,Ar 2 ,Ar 3 are identical or different in each case and are an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and which may be substituted by one or more R groups, where two or more R groups may together form an aromatic or heteroaromatic ring system;

[0027] Y 1 , Y 2 are identical or different in each case and are a single bond, S, CO, O, NR, BR, C═CR2, CR2, SO2, SiR2, GeR2, P(O)R, Se or Te;

[0028] R is identical or different at each occurrence and is: H, D, F, Cl, Br, I, OAr', N(R 1 )2,N(Ar')2,SAr',B(OR 1 )2,CHO,C(=O)R 1 , CR 1 =C(R 1 )2,CN,C(=O)OR 1 ,C(=O)NR 1 ,Si(R 1 )3, NO2, P(=O)(R 1 )2, OSO2R 1 , OR 1 ,S(=O)R 1 ,S(=O)2R 1 , SR 1 , a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl or alkynyl group may in each case be replaced by one or more R 1 group, wherein one or more non-adjacent CH2 groups may be replaced by -R 1 C=CR 1 -、-C≡C-、Si(R1 2. CONR 1 NR 1 ,C=O,C=S,-C(=O)O-,P(=O)(R 1 ), -O-, -S-, SO or SO2, or has 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms and in each case may be replaced by one or more R 1 Aromatic or heteroaromatic ring systems substituted with groups, wherein two or more R groups, preferably bonded to the same ring, can together form a substituted group which can be substituted with one or more R groups. 1 aliphatic, heteroaliphatic, aromatic or heteroaromatic ring systems substituted with radicals;

[0029] Ar' is identical or different in each case and is a ring having 5 to 40 aromatic ring atoms and may be replaced by one or more R 1 Aromatic or heteroaromatic ring system substituted with a radical, wherein two or more R 1 The groups may together form an aromatic or heteroaromatic ring system;

[0030] R 1 are the same or different in each case and are: H, D, F, I, B (OR 2 )2,CHO,C(=O)R 2 , CR 2 =C(R 2 )2,CN,C(=O)OR 2 ,Si(R 2 )3, NO2, P(=O)(R 2 )2, OSO2R 2 , SR 2 , OR 2 ,N(R 2 )2,S(=O)R 2 ,S(=O)2R 2 , a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl or alkynyl group may in each case be replaced by one or more R 2 group and one or more CH2 groups in the above groups may be replaced by -R 2 C=CR 2 -、-C≡C-、Si(R 2 )2. C=O, C=S, -C(=O)O-, NR 2 ,CONR 2 、P(=O)(R 2), -O-, -S-, SO or SO2, and wherein one or more hydrogen atoms in the above groups may be replaced by D, F, Cl, Br, I, CN or NO2, or have 5 to 30 aromatic ring atoms and in each case may be replaced by one or more R 2 Aromatic or heteroaromatic ring system substituted with a radical, wherein two or more R 1 The groups may together form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system;

[0031] R 2 are in each case identical or different and are H, D, F, CN or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by D or F; at the same time, two or more R 2 The substituents may be linked to each other and form a ring;

[0032] is an anion, preferably an anion derived from a nitrosyl cation source.

[0033] In a preferred embodiment, Ar 1 ,Ar 2 and Ar 3 are identical or different in each case and are an aryl or heteroaryl group or a fluorene group having 6 to 13 aromatic ring atoms, wherein the aryl or heteroaryl group and the fluorene group may each be substituted by one or more R groups. More preferably, Ar 1 ,Ar 2 and Ar 3 are identical or different in each case and are an aryl group having 6 to 10 aromatic ring atoms or a heteroaryl group having 6 to 13 aromatic ring atoms or a fluorene group, wherein the aryl or heteroaryl group and the fluorene group may each be substituted by one or more R groups. Most preferably, Ar 1 ,Ar 2 and Ar 3 are identical or different in each case and are phenyl, naphthyl, fluorene, dibenzofuran, dibenzothiophene, carbazole, azadibenzofuran or diazadibenzofuran. Particularly preferably, Ar 1 ,Ar 2 and Ar 3 are in each case identical or different and are phenyl, dibenzofuran or carbazole, wherein Ar 1 ,Ar 2 and Ar 3 At least two of the groups are phenyl groups.

[0034] In a preferred embodiment of the present invention, the compounds of formula (1), (2) and (3) are compounds of formula (1-1), (2-1) and (3-1):

[0035]

[0036] Among them, in addition:

[0037] X is identical or different at each occurrence and is CR or N, with the proviso that not more than two X groups per ring are N.

[0038] It is also possible that the compound of formula (1) or (1-1) has more than one structural unit for carrying out the reaction of the present invention. This enables more complex structures to be prepared in one step by multiple ring closures. Preferred are compounds having one, two or three, preferably one or two structural units for carrying out the reaction of the present invention. Examples of such structures having two structural units are, for example, the structures of the following formulae (1a), (2a) and (3a):

[0039]

[0040] The symbols used correspond to those of formulae (1), (2) and (3), and the preferred embodiments also correspond to those of formulae (1), (2) and (3).

[0041] Contains N and Y 1 The two six-membered rings of Ar 3 The bond can be cis or trans, as shown in the following formula (3a):

[0042] .

[0043] The preferred options applicable to formulas (1a), (2a) and (3a) are the same as those described above for Ar 1 ,Ar 2 ,Ar 3 , Y 1 and Y 2 The same.

[0044] Preferred compounds having two structural units are compounds of formula (1-1a), (2-1a) and (3-1a):

[0045]

[0046] The symbols used correspond to those in formulas (1-1), (2-1) and (3-1).

[0047] Similarly, compounds of formula (1-1b) to (1-1h) can be converted to compounds of the following formula (3-1b) to (3-1h):

[0048]

[0049]

[0050] The symbols used herein have the definitions given above.

[0051] In the context of the present invention, an aryl group contains 6 to 40 carbon atoms; in the context of the present invention, a heteroaryl group contains 5 to 40 carbon atoms and at least one heteroatom, provided that the sum of carbon atoms and heteroatoms is at least 5. The heteroatoms are preferably selected from N, O and / or S. Here, an aryl group or a heteroaryl group is understood to mean: a simple aromatic ring, i.e. benzene; or a simple heteroaromatic ring, such as pyridine, pyrimidine, thiophene, etc.; or a fused (annulated) aryl or heteroaryl group, such as naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc. In contrast, aromatic compounds which are linked to one another by single bonds, such as biphenyl, are not referred to as aryl or heteroaryl groups, but as aromatic ring systems.

[0052] In the context of the present invention, the aromatic ring system contains 6 to 60 carbon atoms, preferably 6 to 40 carbon atoms in the ring system. In the context of the present invention, the heteroaromatic ring system contains 1 to 60 carbon atoms, preferably 1 to 40 carbon atoms and at least one heteroatom in the ring system, provided that the sum of carbon atoms and heteroatoms is at least 5. Heteroatoms are preferably selected from N, O and / or S. In the context of the present invention, an aromatic or heteroaromatic ring system is understood to refer to the following system: it does not necessarily only contain an aryl or heteroaryl group, but wherein two or more aryl or heteroaryl groups can also be connected by non-aromatic units (preferably less than 10% of non-H atoms) such as carbon, nitrogen or oxygen atoms or carbonyl groups. These are also understood to refer to systems such as biphenyl, terphenyl, bipyridine or phenylpyridine in which two or more aryl or heteroaryl groups are directly connected to each other. For example, in the context of the present invention, systems such as fluorene, 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, stilbene etc. are also to be regarded as aromatic ring systems, and likewise systems in which two or more aryl groups are linked, for example, via linear or cyclic alkyl groups or via silyl groups. Preferred aromatic or heteroaromatic ring systems are: simple aryl or heteroaryl groups, and groups in which two or more aryl or heteroaryl groups are directly linked to one another, such as biphenyl, terphenyl, quaterphenyl or bipyridine, and further fluorene or spirobifluorene.

[0053] The electron-rich heteroaromatic ring system is characterized in that it is a heteroaromatic ring system that does not contain an electron-deficient heteroaryl group. An electron-deficient heteroaryl group is: a six-membered heteroaryl group having at least one nitrogen atom; or a five-membered heteroaryl group having at least two heteroatoms, one of which is a nitrogen atom and the other is an oxygen, sulfur or substituted nitrogen atom, wherein other aryl or heteroaryl groups may also be fused to these groups in various cases. In contrast, an electron-rich heteroaryl group is a five-membered heteroaryl group having exactly one heteroatom selected from oxygen, sulfur and substituted nitrogen, to which other aryl groups and / or other electron-rich five-membered heteroaryl groups may be fused. Thus, examples of electron-rich heteroaryl groups are pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, carbazole, dibenzofuran, dibenzothiophene or indenocarbazole. Electron-rich heteroaryl groups are also referred to as electron-rich heteroaromatic groups.

[0054] An electron-deficient heteroaromatic ring system is characterized in that it comprises at least one electron-deficient heteroaryl group and particularly preferably comprises no electron-rich heteroaryl groups.

[0055] In the context of the present invention, the term "alkyl group" is used as a general term for straight-chain and branched alkyl groups and cyclic alkyl groups. Similarly, the terms "alkenyl group" and "alkynyl group" are used as a general term for straight-chain or branched alkenyl or alkynyl groups and cyclic alkenyl or alkynyl groups.

[0056] In the context of the present invention, a cyclic alkyl, alkoxy or thioalkoxy group is understood to mean a monocyclic, bicyclic, tricyclic or polycyclic group.

[0057] In the context of the present invention, aliphatic hydrocarbon radicals or alkyl radicals or alkenyl or alkynyl radicals which contain 1 to 40 carbon atoms and in which individual hydrogen atoms or CH2 groups can be replaced by the abovementioned radicals preferably mean methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, tert-pentyl, 2-pentyl, neopentyl, cyclopentyl, n-hexyl, sec-hexyl, tert-hexyl, 2-hexyl, 3-hexyl, neohexyl, cyclohexyl, 1-methylcyclopentyl, 2-methylpentyl, n-heptyl, cyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, 2 ... , 2-heptyl, 3-heptyl, 4-heptyl, cycloheptyl, 1-methylcyclohexyl, n-octyl, cyclooctyl, 2-ethylhexyl, 1-bicyclo[2.2.2]octyl, 2-bicyclo[2.2.2]octyl, 2-(2,6-dimethyl)octyl, 3-(3,7-dimethyl)octyl, adamantyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, 1,1-dimethyl-n-hexan-1-yl, 1,1-dimethyl-n-heptan-1-yl, 1,1-dimethyl-n-octan-1-yl, 1,1-dimethyl-n- 1,1-dimethyl-n-dodecane-1-yl, 1,1-dimethyl-n-tetradecane-1-yl, 1,1-dimethyl-n-hexadecane-1-yl, 1,1-dimethyl-n-octadecane-1-yl, 1,1-diethyl-n-hexane-1-yl, 1,1-diethyl-n-heptane-1-yl, 1,1-diethyl-n-octane-1-yl, 1,1-diethyl-n-decane-1-yl, 1,1-diethyl-n-dodecane-1-yl, 1,1-diethyl-n-tetradecane-1-yl, 1,1-diethyl-n-decane-1-yl, hexadecane-1-yl, 1,1-diethyl-n-octadecane-1-yl, 1-(n-propyl)-cyclohex-1-yl, 1-(n-butyl)cyclohex-1-yl, 1-(n-hexyl)cyclohex-1-yl, 1-(n-octyl)cyclohex-1-yl and 1-(n-decyl)cyclohex-1-yl, vinyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, cyclooctadienyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl radicals. Alkoxy radicals having 1 to 40 carbon atoms OR 1 Preferably, these are understood to mean methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, 2-methylbutoxy, n-hexyloxy, cyclohexyloxy, n-heptyloxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy and 2,2,2-trifluoroethoxy. Thioalkyl radicals SR having 1 to 40 carbon atoms 1In particular, it is to be understood as meaning methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, n-pentylthio, sec-pentylthio, n-hexylthio, cyclohexylthio, n-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio, vinylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio or octynylthio. Generally, the alkyl, alkoxy or thioalkyl group according to the present invention can be linear, branched or cyclic, wherein one or more non-adjacent CH2 groups can be replaced by the above groups; in addition, one or more hydrogen atoms can also be replaced by D, F, Cl, Br, I, CN or NO2, preferably by F, Cl or CN, more preferably by F or CN.

[0058] Aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, which in each case may also be substituted by the abovementioned radicals or hydrocarbyl radicals and which can be attached to the aromatic or heteroaromatic system via any desired position are understood to mean in particular radicals derived from benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene, letrozole, perylene, fluoranthene, tetracene, pentacene, benzopyrene, biphenyl, biphenylylidene, terphenyl, biphenylene, pyridine ... triphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, cis- or trans-indenocarbazole, cis- or trans-indolocarbazole, cis- or trans-monobenzoindenofluorene, cis- or trans-dibenzoindenofluorene, trimerized indene, isotrimerized indene, spirotrimerized indene, spiroisotrimerized indene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline quinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenoximidazole, pyridinimidazole, pyrazinimidazole, quinoxalineimidazole, oxadiazole, benzoxadiazole, naphthimidazole, anthraquinone, phenoxadiazole, isoxadiazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, hexaazaterphenylene, benzopyridazine, pyrimidine, benzopyrimidine pyridine, quinoxaline, 1,5-diazaanthracene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenazine, phenothiazine, fluorescein ring, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5- oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole.

[0059] In the context of this specification, the expression that two or more groups together can form a ring system is to be understood in particular as meaning that the two groups are connected to one another by a chemical bond under the formal elimination of two hydrogen atoms. This is illustrated by the following scheme:

[0060] .

[0061] However, in addition, the above wording should also be understood to mean that if one of the two groups is hydrogen, the second group is bound to the position of the hydrogen atom, thereby forming a ring. This will be illustrated by the following scheme:

[0062] .

[0063] In a first step, a composition comprising a compound of formula (1) and at least one source of nitrosyl cations is provided.

[0064] A nitrosyl cation source is a compound or a combination of compounds which release nitrosyl cations under reaction conditions. The nitrosyl cations may already be present in the source, as in the case of nitrosyl salts, or may be generated in situ, as in the case of nitrites or esters with acids.

[0065] The source of nitrosyl cations used is preferably soluble in the composition.

[0066] In a preferred embodiment, the source of nitrosyl cations is selected from at least one nitrosyl salt, and / or a combination of a nitrite or ester compound and an acid; preferably at least one nitrosyl salt, and / or a combination of an organic nitrite ester compound and an acid. The acid is preferably a protic acid compound. In this way, nitrosyl cations can be formed by the elimination of water and / or alcohol.

[0067] Examples of nitrosyl salts are nitrosyl fluoride, nitrosyl chloride, nitrosyl bromide, nitrosyl cyanide, nitrosyl azide, nitrosyl perchlorate, nitrosyl perfluoroborate and nitrosyl hexafluorophosphate. The use of nitrosyl salts avoids the use of acids, which allows the presence of acid-labile groups in the compound of formula (1).

[0068] Examples of nitrite compounds are inorganic nitrites, such as sodium nitrite, potassium nitrite or ammonium nitrite.

[0069] Preference is given to organic nitrite compounds, in particular alkyl nitrites (nitrites), preferably selected from ethyl nitrite, propyl nitrite, isopropyl nitrite, 1-butyl nitrite, tert-butyl nitrite, amyl nitrite or isoamyl nitrite.

[0070] The nitrite or ester compound releases the nitrosyl cation in the presence of an acid. The acid is preferably a protic acid compound, such as nitric acid, sulfuric acid, hydrochloric acid, glacial acetic acid, trifluoroacetic acid, toluenesulfonic acid (especially in anhydrous form or monohydrate), trifluoromethanesulfonic acid, tetrafluoroboric acid or an ammonium salt such as ammonium tetrafluoroborate. For example, protonated complexes of these acids with ether can also be used. Examples of suitable compounds are also oxygen Ion HOR'2 +, wherein R' is identical or different and is H, an alkyl group as defined above or an aryl group. Preferably, R' is identical or different at each occurrence and is H or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms.

[0071] The composition preferably comprises at least one organic solvent, preferably a polar solvent, particularly preferably acetonitrile, dichloromethane, tetrahydrofuran, 1,4-dioxane, dimethylformamide, dimethyl sulfoxide, dimethylacetamide, methanol, ethanol, n-propanol, isopropanol, diethyl ether, tert-butyl methyl ether or tert-butyl ethyl ether, more preferably dichloromethane.

[0072] The composition is preferably a solution of a compound of formula (1).

[0073] The concentration can be adjusted according to the reactants and the solvent. The concentration of the compound of formula (1) is preferably up to 10 mmol / L, more preferably up to 5 mmol / L.

[0074] In a preferred embodiment of the present invention, at least one source of nitrosyl cations is added to the compound of formula (1).

[0075] In a preferred embodiment, the nitrosyl cation source is added at a temperature below 10°C, in particular below 8°C, more preferably below 5°C. The temperature is selected so that the composition can still be stirred. The preferred temperature is -10°C to 5°C, more preferably 0°C.

[0076] In the case of a combination of an acid and a nitrite or ester compound, it is preferred to first add the acid and then the nitrite or ester compound. It is preferred to add at least the nitrite or ester compound at the above temperature; it is particularly preferred to add the acid and the nitrite or ester compound at the above temperature.

[0077] The nitrosyl cation source is preferably added while stirring the composition. In the case of adding a solution, it is added dropwise. In the case of adding a solid, such as a nitrosyl salt, it is preferably added in two or more portions.

[0078] After each addition, the composition is advantageously stirred for 5 minutes to 2 hours, preferably at the same temperature as at the time of the addition.

[0079] In a preferred embodiment, the nitrosyl cation source is added to the compound of formula (1) in an equimolar amount or in excess, based on the nitrosyl cation, preferably at least 1 equivalent, more preferably at least 1.01 equivalents, in particular at least 1.02 equivalents. Particularly preferred are 1.02 to 1.1 equivalents. If the compound of formula (1) has two or more amino groups for diazotization, the equivalents are based on the number of amino groups for diazotization present in the compound of formula (1).

[0080] In the case of nitrite or ester compounds, the equivalents are based on the nitrite or ester compound. The acid is preferably added in at least an equimolar amount, especially at least 1.02 equivalents, more preferably at least 1.5 equivalents, and most preferably at least 2 equivalents, based on the amino groups in the compound of formula (1) used for diazotization. The amount of acid may need to be adjusted so that after the compound of formula (1) is protonated, at least 1 equivalent of protons is still available for the protonation of the nitrite or ester compound.

[0081] The reaction in step a) is preferably carried out under protective gas, preferably under nitrogen or argon. A low-oxygen to oxygen-free atmosphere is preferred. This means that the oxygen content is preferably less than 10% by volume, in particular less than 5% by volume, more preferably less than 1% by volume.

[0082] In the case of nitrosyl salt as nitrosyl cation source, the reaction is preferably carried out using dry reactants and solvents. In the case of nitrite or ester compounds, especially inorganic nitrites, the reaction can also be carried out in the presence of water. For example, hydrates of acid or aqueous solutions of acid can be used, such as using HBF4 as a 30% aqueous solution. Then, aqueous phase and organic phase can also be used to react.

[0083] The method is preferably carried out under no illumination, meaning that the reaction vessel has no special lighting. Thus, the reaction can also be converted in an opaque vessel. The diazonium salt is decomposed by heating.

[0084] The reaction is preferably carried out under standard pressure.

[0085] Optionally, the diazonium salt of formula (2) formed can be isolated. Depending on the source of the nitrosyl cation, the anion It is the anion of the nitrosyl salt or the anion of the acid used.

[0086] In the case of isolating the diazonium salt, it is also possible to change the solvent of the composition in step c). The solvent is preferably selected from the solvent in step a).

[0087] For the ring closure reaction, a composition comprising a compound of formula (2) is provided. This can be achieved by dissolving the compound of formula (2), or can be obtained by the reaction in step a).

[0088] In a preferred embodiment, the composition is added at a temperature below 10°C, especially below 8°C, more preferably below 5°C. The temperature selected here is such that the composition can still be stirred. Preferably the temperature is between -10°C and 5°C, more preferably 0°C.

[0089] The composition is then converted into a compound of formula (3). This releases nitrogen. This is preferably achieved by heating the composition relative to the temperature in step a). The heating can be controlled according to the release of nitrogen. The temperature difference from step a) is preferably at least 10°C.

[0090] Preference is given to heating to at least 20° C., preferably to at least 30° C. Particular preference is given to heating to at most 200° C., preferably at most 150° C., more preferably at most 100° C.

[0091] Particular preference is given to heating to 20°C to 200°C, in particular 20°C to 150°C, very particularly 20°C to 100°C and in particular 20°C to 60°C.

[0092] The degree of conversion can be determined by measuring the amount of nitrogen released. The reaction is preferably carried out until the molar amount of nitrogen released corresponds to at least 80%, in particular at least 90%, most preferably at least 95%, based on the molar amount of the reactants.

[0093] The reaction is preferably continued until the release of nitrogen has ended.

[0094] The release of nitrogen can be regulated by varying the temperature.

[0095] The reaction in step c) is preferably carried out under protective gas, preferably under nitrogen or argon. An oxygen-free atmosphere is preferred. A low-oxygen to oxygen-free atmosphere is preferred. This means that the oxygen content is preferably less than 10% by volume, in particular less than 5% by volume, more preferably less than 1% by volume.

[0096] The reaction is preferably carried out using dry reactants and solvents.

[0097] The reaction is preferably carried out at a pressure equal to that of the ambient environment.

[0098] The obtained product of formula (3) is preferably isolated. This can be achieved by precipitation, extraction and / or removal of the solvent. The obtained solid can still be washed and dried. In addition, the product can be further purified by standard methods of organic chemistry such as recrystallization, chromatography and / or sublimation.

[0099] The conversion of the compound of formula (1) into the compound of formula (3) is preferably carried out to an extent of at least 60% up to quantitative yield on a molar basis.

[0100] The method of the present invention enables the preparation of indolo[3,2,1-jk]carbazole skeletons with high regioselectivity and high yield under mild conditions.

[0101] In a preferred embodiment, Y 1 and Y 2 Select from the following combinations:

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108] In a preferred embodiment, no more than two of the X groups are N, and all the remaining X groups are CR, more preferably in combination with the embodiments in the above table. More preferably, no more than one of the X groups is N, and most preferably, all X groups are CR, more preferably in combination with the embodiments in the above table.

[0109] In a preferred embodiment of the present invention, Y 1 It is a single bond, BR, CR2, CO, N or O, and more preferably a single bond, BR, N or O.

[0110] In another preferred embodiment of the present invention, Y 2 It is a single bond, BR, CR2, CO, N or O, more preferably a single bond, BR, N or O, and most preferably a single bond.

[0111] In a particularly preferred embodiment, Y 1 and Y 2 Select from the following combinations:

[0112]

[0113]

[0114] In a preferred embodiment, no more than two of the X groups are N, and all the remaining X groups are CR, more preferably in combination with the embodiments in the above table. More preferably, no more than one of the X groups is N, and most preferably, all X groups are CR, more preferably in combination with the embodiments in the above table.

[0115] Y 1 and Y 2 Very particularly preferred combinations are the combinations listed in the following table:

[0116]

[0117] In a preferred embodiment, no more than two of the X groups are N, and all the remaining X groups are CR, more preferably in combination with the embodiments in the above table. More preferably, no more than one of the X groups is N, and most preferably, all X groups are CR, more preferably in combination with the embodiments in the above table.

[0118] Preferred substituents R, Ar', R 1 and R 2 In a particularly preferred embodiment of the present invention, the following descriptions of R, Ar', R 1 and R 2 The preferences specified are simultaneous and apply to the structure of formula (1) and all preferred embodiments detailed above.

[0119] In a preferred embodiment of the invention, R is identical or different at each occurrence and is selected from: H, D, F, CN, OR 1 , a linear alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, wherein the alkyl or alkenyl group may be substituted by one or more R 1 substituted with, but preferably unsubstituted with, groups and in which one or more non-adjacent CH2 groups may be replaced by O, or having 6 to 30 aromatic ring atoms and in each case by one or more R 1 At the same time, the two R groups can also form an aliphatic, aromatic or heteroaromatic ring system together. More preferably, R is identical or different in each case and is selected from: H, F, CN, a linear alkyl group having 1 to 6 carbon atoms, in particular having 1, 2, 3 or 4 carbon atoms, or a branched or cyclic alkyl group having 3 to 6 carbon atoms, wherein the alkyl group can be replaced by one or more R in each case. 1 substituted, but preferably unsubstituted, or having 6 to 24 aromatic ring atoms and in each case being replaceable by one or more R 1 Group, preferably non-aromatic R 1 Most preferably, R is identical or different in each case and is selected from: H, or has 6 to 24 aromatic ring atoms and can be replaced by one or more R in each case. 2 Group, preferably non-aromatic R 2 Aromatic or heteroaromatic ring systems substituted with radicals.

[0120] Suitable aromatic or heteroaromatic ring systems R are selected from the group consisting of phenyl; biphenyl, in particular o-, m- or p-biphenyl; terphenyl, in particular o-, m- or p-terphenyl or branched terphenyl; quaterphenyl, in particular o-, m- or p-quaterphenyl or branched quaterphenyl; fluorene which can be attached via the 1, 2, 3 or 4 position; spirobifluorene which can be attached via the 1, 2, 3 or 4 position; naphthalene which can be attached via the 1 or 2 position; indole; benzofuran; benzothiophene which can be attached via the 1, 2, 3 or 4 position; dibenzofuran; carbazole which can be attached via the 1, 2, 3 or 4 position; dibenzothiophene which can be attached via the 1, 2, 3 or 4 position; indenocarbazole; indolocarbazole; pyridine; pyrimidine; pyrazine; pyridazine; triazine; quinoline; quinazoline; benzimidazole; phenanthrene; terphenylidene; or a combination of two or three of these radicals, each of which can be substituted by one or more R 1 When R is a heteroaryl group, especially triazine, pyrimidine or quinazoline, aromatic or heteroaromatic R 1 Group.

[0121] The R group here, when it is an aromatic or heteroaromatic ring system, is preferably selected from the following groups of formulae R-1 to R-166:

[0122]

[0123]

[0124]

[0125]

[0126]

[0127]

[0128]

[0129]

[0130]

[0131]

[0132]

[0133]

[0134]

[0135]

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153]

[0154]

[0155]

[0156]

[0157]

[0158]

[0159]

[0160]

[0161]

[0162]

[0163]

[0164]

[0165]

[0166]

[0167]

[0168]

[0169]

[0170]

[0171]

[0172]

[0173] Where R 1 With the definitions given above, the dashed bonds represent bonds to formula (1), and the following definitions also apply:

[0174] Ar 3 are identical or different in each case and are aromatic rings having 6 to 18 atoms and may be replaced by one or more R 1 a divalent aromatic or heteroaromatic ring system substituted with a radical;

[0175] A 1 The same or different in each case and is BR 1 , C(R 1 )2. NR 1 , O or S, preferably C(R 1 )2. O or S;

[0176] A 2 are identical or different in each case and are C(R 1 )2. NR 1 , O or S;

[0177] p is 0 or 1, where p=0 means Ar 3 The group is absent and the corresponding aromatic or heteroaromatic group is directly bonded to the relevant atom, such as a carbon atom or a heteroatom such as nitrogen;

[0178] r is 0 or 1, where r=0 means there is no A 1 The group is bonded at this position, but R1 The groups are bonded to the corresponding carbon atoms.

[0179] In a preferred embodiment, Ar 3 A divalent aromatic or heteroaromatic ring system comprising a group based on R-1 to R-166, wherein p=0 and the dotted bond and R 1 represents a bond to the aromatic or heteroaromatic group according to R-1 to R-166.

[0180] When the above R-1 to R-166 groups with respect to R have two or more A 1 When the group is a viable choice of these groups, the possible choices include A 1 In this case, the preferred embodiment is one in which A 1 The group is C(R 1 )2. NR 1 , O or S, and the other A 1 The group is C(R 1 )2 or two A 1 The group is S or O or two of them are A 1 The group is O or S.

[0181] When A 1 NR 1 When the substituent R bonded to the nitrogen atom 1 Preferably, the aromatic ring has 5 to 24 atoms and may be replaced by one or more R 2 In a particularly preferred embodiment, the R 1 The substituents are identical or different in each case and are an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably 6 to 12 aromatic ring atoms, and without any fused aryl or heteroaryl groups in which two or more aromatic or heteroaromatic 6-membered ring groups are fused directly to one another, and the aromatic or heteroaromatic ring system may in each case also be substituted by one or more R 2 Particularly preferred are phenyl, biphenyl, terphenyl and quaterphenyl having the bonding modes listed above for R-1 to R-35, wherein these structures may be substituted by one or more R 1 The group is substituted, but preferably is unsubstituted.

[0182] When A 1 C(R 1 )2, the substituent R bonded to the carbon atom 1are preferably identical or different in each case and are a straight-chain alkyl radical having 1 to 10 carbon atoms or a branched or cyclic alkyl radical having 3 to 10 carbon atoms or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may also be replaced by one or more R 2 Most preferably, R 1 is a methyl group or a phenyl group. In this case, R 1 The groups can also form together a ring system, resulting in a spiro ring system.

[0183] In another preferred embodiment of the present invention, R 1 are identical or different in each case and are selected from: H, D, F, CN, OR 2 , a straight-chain alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, wherein the alkyl or alkenyl group may be replaced by one or more R 2 or having 6 to 30 aromatic ring atoms and in each case being replaced by one or more R 2 Aromatic or heteroaromatic ring system substituted with a group; at the same time, two or more R 1 The groups together can form an aliphatic ring system. In a particularly preferred embodiment of the present invention, R 1 are identical or different in each case and are selected from: H; a straight-chain alkyl group having 1 to 6 carbon atoms, in particular having 1, 2, 3 or 4 carbon atoms, or a branched or cyclic alkyl group having 3 to 6 carbon atoms, wherein the alkyl group may be replaced by one or more R 2 or having 6 to 24 aromatic ring atoms and in each case may be replaced by one or more R 2 The aromatic or heteroaromatic ring system may be substituted, but preferably unsubstituted.

[0184] In another preferred embodiment of the present invention, R 2 are in each case identical or different and are: H, F, an alkyl radical having 1 to 4 carbon atoms, or an aryl radical having 6 to 10 carbon atoms, which may be substituted by an alkyl radical having 1 to 4 carbon atoms, but is preferably unsubstituted.

[0185] In another preferred embodiment of the present invention, all R 1 groups, if they are aromatic or heteroaromatic ring systems, or R 2 The radicals, if they are aromatic or heteroaromatic, are selected from the radicals R-1 to R-166, however, in this case these radicals are replaced by R 2 Replace or target R2 The mentioned groups are substituted.

[0186] In a preferred embodiment of the present invention, R, R 1 or R 2 All aromatic or heteroaromatic groups in the group are selected from the corresponding R-1 to R-166 groups, preferably selected from the group wherein A 1 C(R 1 )2 or the corresponding C(R 2 )2 or C(R 3 )2 group, or O or S R-1 to R-166 groups.

[0187] In a preferred embodiment, the R groups do not form any further aromatic or heteroaromatic groups which are fused to the basic skeleton of formula (1).

[0188] The above-mentioned preferred embodiments can be combined with each other as required within the limits defined in claim 1. In a particularly preferred embodiment of the present invention, the above-mentioned preferences occur simultaneously.

[0189] The compound of formula (1) used in the method of the present invention can be prepared by synthetic procedures known to those skilled in the art such as bromination, Suzuki coupling, Ullmann coupling, Heck reaction, Hartwig-Buchwald coupling and the like.

[0190] The 1-(2-aminoaryl)carbazole (3) required for the preparation of indolocarbazole (4) can be prepared, for example, from 1-functionalized carbazoles (1) known from the literature and 2-functionalized anilines (2) in a Suzuki coupling, which in each case involves the reaction of Cl, Br, I or OTf with a boronic acid or boric ester function B(OR)2 (step 1 in Scheme 1). In addition to 2-functionalized anilines (2), 2-functionalized nitroaromatic compounds can also be used. The 1-(2-nitroaryl)carbazole thus obtained can then be reduced to 1-(2-aminoaryl)carbazole (3) by methods familiar to those skilled in the art, for example under transition metal catalysis (homogeneous or heterogeneous) with hydrogen as reducing agent or in an acidic medium containing Sn or Zn. In addition, it is known to synthesize 1-(2-aminoaryl)carbazole (3) from 2,3'-biindole and ketone; see WE Noland et al., Tetrahedron, 2018, 74, 2391; P. Huang et al., Org. & Biomol. Chem., 2017, 15(45), 9622.

[0191] The 1-(2-aminoaryl)carbazole thus obtained is diazotized, preferably under anhydrous conditions in an inert solvent such as tetrahydrofuran, dioxane, dichloromethane (DCM) or acetonitrile (MeCN) under acidic catalysis, preferably using tetrafluoroboric acid etherate and alkyl nitrite as diazotizing agents, preferably using tert-butyl nitrite, amyl nitrite or isoamyl nitrite. After adding the diazotizing agent and briefly stirring the mixture, it is gradually warmed to room temperature, under release of nitrogen and cyclization to form the product (4). The exothermic reaction can be moderated by appropriate temperature control; if necessary, the reaction is completed by gentle heating.

[0192] For the sake of clarity, the description of the substituents on (1), (2), (3) and (4) is omitted below. Reactant (1) may be part of a larger fused system such as indenocarbazole, indolecarbazole, benzofurancarbazole, benzothiophenecarbazole, etc.; reactant (2) may be part of a naphthyl, anthracenyl, phenanthrenyl, terphenylidene, fluorenyl, spirobifluorenyl, dibenzofuranyl, dibenzothiophene, carbazolyl, etc.

[0193] Scenario 1:

[0194]

[0195]

[0196] Similarly, we can use Y 2 The group-bridged amine (5) is converted to (6) to give Y 2 Bridged carbazole (7) (Scheme 2). Scheme 3 shows the use of Y 1 and Y 2 Analogous reaction of the group-bridged amine (8) affords the doubly bridged compound (9).

[0197] Scenario 2:

[0198]

[0199] Scenario 3:

[0200]

[0201] The present invention is illustrated in detail by the following examples, but it is not intended to limit the present invention by this. Those skilled in the art will be able to use the information provided to implement the present invention within the entire scope disclosed, and can apply the method of the present invention to more compounds that can be used in electronic devices without paying creative work. Example

[0202] Unless otherwise stated, the following synthesis is carried out in a dry solvent under a protective gas atmosphere. The metal complex also needs to be handled under light protection or yellow light. Solvents and reagents can be purchased from, for example, Sigma-ALDRICH or ABCR. The corresponding numbers in square brackets or the numbers quoted for individual compounds are related to the CAS numbers of compounds known in the literature. In the case of compounds that can have multiple enantiomers, diastereomers or tautomeric forms, one form is shown in a representative manner.

[0203] From the literature, we know that the synthon LS:

[0204]

[0205]

[0206] A) Synthesis of Synthon S:

[0207] Embodiment B1:

[0208] Stage 1: Synthesis of LS1

[0209]

[0210] Variant 1: Suzuki coupling in the presence of water

[0211] Prepared according to the method of M. Moustakim et al. in Bioorganic & Medicinal Chemistry (2018), 26 (11), 2965. Starting materials: 24.6 g (100 mmol) of 1-bromo-9H-carbazole [16807-11-7], 15.1 g (110 mmol) of 2-aminophenylboronic acid [5570-18-3], 31.8 g (300 mmol) of sodium carbonate, 1.16 g (1 mmol) of tetrakis(triphenylphosphine)palladium (0) [14221-01-3], 200 ml of dioxane, 100 ml of EtOH, 100 ml of water, 90°C, 16 hours. Workup: Add 500 ml of ethyl acetate (EA) and 500 ml of water, separate the organic phase, and extract the aqueous phase twice with 200 ml of EA each time. The combined organic phases were washed twice with 300 ml of water each time, twice with 200 ml of saturated saline solution each time, dried over magnesium sulfate, and EA was removed under reduced pressure. Purification: Silica gel chromatography, n-heptane: dichloromethane (DCM), Torrent automatic column system from A. Semrau. Yield: 21.7 g (83 mmol) 83%; Purity: by 1 HNMR confirmed about 99%.

[0212] Variant 2: Suzuki coupling under anhydrous conditions

[0213] Starting materials: 24.6 g (100 mmol) of 1-bromo-9H-carbazole [16807-11-7], 15.1 g (110 mmol) of 2-aminophenylboronic acid [5570-18-3], 63.7 g (300 mmol) of tripotassium phosphate, 817 mg (1 mmol) of 1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II), complexed with dichloromethane [95464-05-4], 400 ml of dioxane, reflux, 16 hours. Workup: Filter while hot (70°C) through a celite bed as a dioxane slurry, rinse, and concentrate the filtrate under reduced pressure. Add 500 ml of DCM and 500 ml of water, separate the organic phase, and extract the aqueous phase twice with 200 ml of DCM each time. The combined organic phases were washed twice with 300 ml of water each time, twice with 200 ml of saturated saline solution each time, dried over magnesium sulfate, and the DCM was removed under reduced pressure. Purification: Silica gel chromatography, n-heptane: dichloromethane (DCM), Torrent automatic column system from A. Semrau. Yield: 25.0 g (96 mmol) 96%; Purity: by 1 H NMR confirmed about 99%.

[0214] Stage 2: Diazotization and cyclization

[0215] Variant 1: Diazotization with alkyl nitrite

[0216]

[0217] To a well-stirred solution of 25.8 g (100 mmol) LS1 in 1500 ml dichloromethane (DCM) cooled to 0°C was added dropwise 27.2 ml (200 mmol) of HBF4 x Et2O, ~54% [67969-82-8] over about 15 minutes, and the mixture was stirred for 10 minutes. Subsequently, a mixture of 15.9 ml (120 mmol) tert-butyl nitrite [540-80-7] (90%) and 100 ml DCM was added dropwise over 1 hour to the viscous, well-stirred reaction mixture, which was stirred at 0°C for another hour, then gradually warmed to about 20°C over the course of about 5 hours, and stirred at about 20-25°C for another 10 hours to complete the reaction (caution: nitrogen evolved! - the exothermic reaction can be moderated by temperature control). After the nitrogen release is complete, 200 ml of saturated sodium bicarbonate solution are gradually added (caution: foaming!), the mixture is stirred for another 30 minutes, the organic phase is separated and dried over magnesium sulfate, the desiccant is filtered off and the filtrate is concentrated at about 40°C, the distilled DCM is replaced by continuous addition of about 200 ml of ethanol. The precipitated product is filtered off, washed twice with 50 ml of ethanol each time and dried under reduced pressure. Yield: 16.5 g (68 mmol), 68%; purity: 1 H NMR determined about 98%. Further purification can be carried out by chromatography (silica gel, n-heptane / DCM 2:1>1:1, or other eluents), recrystallization or hot extractive crystallization (common organic solvents, such as DCM / acetonitrile mixtures) and fractional sublimation under vacuum or high vacuum.

[0218] In addition to the use of tert-butyl nitrite [540-80-7], it is also possible to use, for example, isoamyl nitrite [110-46-3] instead.

[0219] Variant 2: Diazotization with nitrosyl salts

[0220] The method is similar to variant 1, replacing tert-butyl nitrite with 12.3 g (105 mmol) nitrosyl tetrafluoroborate [14635-75-7], which is introduced in portions as a solid over the course of 5 to 10 minutes. Yield: 15.3 g (63 mmol), 63%; purity: 1 H NMR confirmed about 98%.

[0221] When di-, tri-, tetra-, etc., amino (-NH2) or bromine (-Br) units are used, the stoichiometry in stage 1 and stage 2 is adjusted accordingly.

[0222] Similarly, the following compounds can be prepared by two stages of Suzuki coupling and cyclization, with yields typically ranging from 40 to 90% in the case of monocyclization and 20 to 60% in the case of dicyclization.

[0223]

[0224]

[0225]

[0226]

[0227]

[0228]

[0229]

[0230]

[0231]

[0232]

[0233]

[0234]

[0235]

[0236]

[0237]

[0238]

[0239]

[0240]

[0241]

Claims

1. A method for preparing indolo[3,2,1-jk]carbazole and its derivatives, the method comprising the following steps: or Among them, in formula (1a), (2a) and (3a), the compound containing Y 1 The two rings of N and Ar 3 The bonding can be cis or trans, a) providing a composition comprising a compound of formula (1) or (1a) and at least one source of nitrosyl cations; b) converting the composition in a) into a diazonium salt; c) optionally isolating the diazonium salt of formula (2) or (2a); d) converting into a compound of formula (3) or (3a); And the symbols used therein are as follows: Ar 1 ,Ar 2 ,Ar 3 are identical or different in each case and are an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms and which may be substituted by one or more R groups, where two or more R groups may together form an aromatic or heteroaromatic ring system; Y 1 , Y 2 are identical or different in each case and are a single bond, S, CO, O, NR, BR, C═CR2, CR2, SO2, SiR2, GeR2, P(O)R, Se or Te; R is identical or different at each occurrence and is: H, D, F, Cl, Br, I, OAr', N(R 1 )2,N(Ar')2,SAr',B(OR 1 )2,CHO,C(=O)R 1 , CR 1 =C(R 1 )2,CN,C(=O)OR 1 ,C(=O)NR 1 ,Si(R 1 )3, NO2, P(=O)(R 1 )2, OSO2R 1 , OR 1 ,S(=O)R 1 ,S(=O)2R 1 , SR 1 , a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl or alkynyl group may in each case be replaced by one or more R 1 group, wherein one or more non-adjacent CH2 groups may be replaced by -R 1 C=CR 1 -、-C≡C-、Si(R 1 2. CONR 1 NR 1 ,C=O,C=S,-C(=O)O-,P(=O)(R 1 ), -O-, -S-, SO or SO2, or has 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms and in each case may be replaced by one or more R 1 An aromatic or heteroaromatic ring system substituted with one or more R groups, wherein two or more R groups, preferably bonded to the same ring, can together form a 1 aliphatic, heteroaliphatic, aromatic or heteroaromatic ring systems substituted with radicals; Ar' is identical or different in each case and is a ring having 5 to 40 aromatic ring atoms and may be replaced by one or more R 1 Aromatic or heteroaromatic ring system substituted with a radical, wherein two or more R 1 The groups may together form an aromatic or heteroaromatic ring system; R 1 are the same or different in each case and are: H, D, F, I, B (OR 2 )2,CHO,C(=O)R 2 , CR 2 =C(R 2 )2,CN,C(=O)OR 2 ,Si(R 2 )3, NO2, P(=O)(R 2 )2, OSO2R 2 , SR 2 , OR 2 ,N(R 2 )2,S(=O)R 2 ,S(=O)2R 2 , a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl or alkynyl group may in each case be replaced by one or more R 2 group and one or more CH2 groups in the above groups may be replaced by -R 2 C=CR 2 -、-C≡C-、Si(R 2 )2. C=O, C=S, -C(=O)O-, NR 2 ,CONR 2 、P(=O)(R 2 ), -O-, -S-, SO or SO2, and wherein one or more hydrogen atoms in the above groups may be replaced by D, F, Cl, Br, I, CN or NO2, or have 5 to 30 aromatic ring atoms and in each case may be replaced by one or more R 2 Aromatic or heteroaromatic ring system substituted with a radical, wherein two or more R 1 The groups may together form an aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system; R 2 are in each case identical or different and are H, D, F, CN or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 carbon atoms, in which one or more hydrogen atoms may also be replaced by D or F; at the same time, two or more R 2 The substituents may be linked to each other and form a ring; is an anion, preferably an anion derived from a nitrosyl cation source.

2. The method according to claim 1, wherein the method comprises compounds of formula (1-1), (2-1) and (3-1): The symbols used herein have the definitions given in claim 1, and in addition: X is identical or different at each occurrence and is CR or N, with the proviso that not more than two X groups per ring are N.

3. The method according to claim 1, wherein the compounds of formula (1-1a) to (1-1h) are converted into compounds of formula (3-1a) to (3-1h), respectively, The symbols used herein have the definitions given in claim 1, and in addition: X is identical or different at each occurrence and is CR or N, provided that not more than two X groups per ring are N; W is BR, CR2, NR or O.

4. The method according to one or more of claims 1 to 3, wherein the source of nitrosyl cations is soluble in the composition.

5. The method according to one or more of claims 1 to 4, wherein the source of nitrosyl cations is selected from at least one nitrosyl salt, and / or a combination of a nitrite compound and an acid.

6. The method according to one or more of claims 1 to 5, wherein the composition comprises at least one organic solvent.

Images