CN118251380A

CN118251380A - Spiro- (indan-fluorene) compounds and their use in organic electronic devices

Info

Publication number: CN118251380A
Application number: CN202280073125.XA
Authority: CN
Inventors: Y·埃斯基; T·贝克; U·伯伦斯
Original assignee: Duotecan Exclusive Synthetic Holding Co
Current assignee: Duotecan Exclusive Synthetic Holding Co
Priority date: 2021-11-04
Filing date: 2022-10-31
Publication date: 2024-06-25

Abstract

The present invention relates to spiro- (indan-fluorene) type (I) compounds, especially those bearing primary amino groups, and the corresponding diarylamino compounds. The invention further relates to a method for the production of said compounds and to the use thereof in organic electronic components, in particular as Hole Transport Materials (HTM) or Electron Blocking Materials (EBM).

Description

Spiro- (indan-fluorene) compounds and their use in organic electronic devices

Technical Field

The present invention relates to spiro- (indan (indane) -fluorene) type compounds, especially those bearing a primary amino group and the corresponding diarylamino compounds, and to processes for their preparation. The invention further relates to the use of diarylaminospira- (indan-fluorene) derivatives in organic electronic devices, in particular as Hole Transport Materials (HTM) or Electron Blocking Materials (EBM). The invention further relates to the use of the diarylaminospiro- (indan-fluorene) compounds bearing a primary amino group as intermediates for the synthesis of the corresponding diarylamino compounds, and as valuable components for chemical synthesis.

Background

"Organic electronic devices" mainly relate to the development, characterization and application of new materials and manufacturing processes for the production of electronic components based on small organic molecules or polymers with desired electronic properties. These include in particular Organic Field Effect Transistors (OFETs), such as Organic Thin Film Transistors (OTFTs); organic electroluminescent devices such as Organic Light Emitting Diodes (OLEDs); organic Solar Cells (OSCs), such as excitonic solar cells, dye Sensitized Solar Cells (DSSCs) or perovskite solar cells; photoconductive materials in electrophotography, especially Organic Photoconductors (OPC); an organic optical detector, an organic photoreceptor, an Organic Field Quench Device (OFQDs), a light-emitting electrochemical cell (LECs), and an organic laser diode. Such organic semiconducting materials may be formed from compounds with good electron donor properties (p-conductors) or from compounds with good electron acceptor properties (n-conductors). Organic semiconductors have very low intrinsic charge carrier concentrations relative to inorganic semiconductors. The organic semiconductor matrix material is therefore typically doped to give good semiconductor properties.

By "organic photovoltaic device" is meant the use of organic elements to directly convert radiant energy (mainly solar energy) into electrical energy. In contrast to inorganic solar cells, light does not directly generate free charge carriers in organic solar cells, but rather forms excitons first, i.e. electrically neutral excited states in the form of electron-hole pairs. These excitons may be separated at an appropriate photoactive interface (organic donor-acceptor interface or interface with an inorganic semiconductor). For this purpose, it is necessary that excitons which have been generated in the volume of the organic material can diffuse to the photosensitive interface. Excitons diffuse to the photoactive interface and thus play an important role in organic solar cells. There is a great demand for developing materials which have the greatest transport width and high mobility (high exciton diffusion length) in the photoinduced excited state and are therefore advantageously suitable for use as active materials in so-called excitonic solar cells.

Certain triarylamines are widely known for use in organic electronics applications.

WO 2018/206769 describes 1, 3-trimethyl-3-phenylindane derivatives substituted with at least two diarylamino moieties, and their use in organic electronic devices.

WO 2020/094847 describes di-, tri-and tetraphenylindane derivatives and their use in organic electronic devices, in particular as Hole Transporting Materials (HTM) or Electron Blocking Materials (EBM).

WO 2012/034627 describes compounds of formula (a):

Wherein the method comprises the steps of

Ar is an aromatic ring system, and the aromatic ring system,

Ar ¹ and Ar ² are aromatic or heteroaromatic ring systems having 6 to 60C atoms,

R is in each case selected from H, D, F, cl, br, I, CN, si (R ²)₃, straight-chain alkyl, alkoxy or thioalkyl having from 1 to 40C atoms, or branched or cyclic alkyl, alkoxy or thioalkyl having from 3 to 40C atoms, or an aromatic or heteroaromatic ring system having from 6 to 60C atoms, or aralkyl having from 5 to 60 aromatic ring atoms,

M is 0, 1, 2 or 3,

N is, identically or differently, 0, 1,2, 3 or 4,

P is 0,1 or 2.

These compounds are useful in electronic devices, preferably selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field effect transistors, organic thin film transistors, organic light emitting transistors, organic solar cells, organic dye sensitized solar cells, organic optical detectors, organic photoreceptors, organic field quench devices, light emitting electrochemical cells, organic laser diodes and organic plasmonic light emitting devices, especially organic electroluminescent devices.

EP 1624500 A1 describes, for example, the use of spirobifluorene compounds of the formula (a) in organic matrix materials having a glass transition temperature of at least 120 ℃ and an energy level of the Highest Occupied Molecular Orbital (HOMO) of the matrix material of at most 5.4eV:

Wherein the substituent R may be in particular NH ₂ or NPh ₂.

EP 3018119 A1 describes aromatic amine compounds of the formula (B):

Wherein the method comprises the steps of

Ar ^a represents an aryl group having 6 to 50 ring carbon atoms, a hetero ring having 5 to 50 ring atoms

Aryl or a group in which 2 to 4 groups are selected from aryl and heteroaryl groups are attached, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a group having 6

Aryl of up to 12 ring carbon atoms, wherein R ¹ and R ² may also be bonded to each other to form a hydrocarbon ring.

Preferably, R ¹ and R ² do not form hydrocarbon rings. There is no disclosure that R ¹ and R ² form a group of the formula:

wherein # denotes a bond to the rest of the molecule.

These arylamine compounds can be used as materials for organic electroluminescent devices, for example, as hole transport materials.

WO 2014/072017 A1 describes a spiro- (thia/xanthene-fluorene) type compound which is suitable for use as a functional material in an electronic device.

EP 1623970 A1 describes arylamine compounds of the formula (C):

Wherein the method comprises the steps of

X is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 40 carbon atoms or a substituted or unsubstituted heterocyclic group having 5 to 40 carbon atoms,

Ar ¹、Ar²、Ar³ and Ar ⁴ are each independently a substituted or unsubstituted aryl group having 6 to 40 carbon atoms or a substituted or unsubstituted heterocyclic group having 5 to 40 carbon atoms; provided that at least one of Ar ¹、Ar²、Ar³ and Ar ⁴ is a group of formula (C-1):

Wherein the method comprises the steps of

R ¹ and R ² are each independently a hydrogen atom, a substituted or unsubstituted amino group, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms or a substituted or unsubstituted heterocyclic group having 5 to 40 carbon atoms,

R ³ represents an aromatic group forming a cyclic structure,

Ar ⁵ is a single bond or a divalent aromatic or heterocyclic bridging group,

L is a single bond, -O-, -S-, -NR ⁴ -or-CR ⁵R⁶ -, wherein R ⁴、R⁵ and R ⁶ are each independently of the other a substituted or unsubstituted alkyl group having from 1 to 50 carbon atoms or a substituted or unsubstituted aryl group having from 6 to 40 carbon atoms,

S, q and r are each integers from 0 to 2; and

R ¹ and R ² may be combined with each other to form a ring.

In particular X is a monovalent, divalent or trivalent residue of benzene, biphenyl, terphenyl, naphthalene, fluorene, pyrene, spirobifluorene, 1, 2-stilbene, carbazole, dibenzofuran, dibenzothiophene, fluorenone, oxazole, oxadiazole, thiadiazole or benzimidazole.

Suitable (C-1) radicals are in particular:

these spiro rings do not bear any substituents, in particular no C ₁-C₄ alkyl groups such as methyl.

These arylamine compounds are useful as materials for organic electroluminescent devices, for example, as hole transport materials.

There is still a continuing need for new organic compounds for organic electronic applications. They should be available from efficient and economical synthetic routes. In particular, they should have a lower molecular weight than the compounds known from the prior art, be capable of sublimation and/or possess good electronic application properties. Furthermore, they should be characterized by good thermal stability and high glass transition temperatures. In a specific embodiment, they should be suitable for use in electronically doped semiconductor materials.

It has now surprisingly been found that the spiro- (indan-fluorene) type compounds of the invention are advantageously suitable as hole conductors (p-semiconductor, electron donor) in organic photovoltaic devices. It is particularly suitable as a Hole Transport Material (HTM) or an Electron Blocking Material (EBM).

Disclosure of Invention

The first object of the present invention is a compound of formula (I):

And mixtures thereof, wherein

R ^A is hydrogen or C ₁-C₆ alkyl,

R ^B is hydrogen or C ₁-C₆ alkyl,

R ^C is hydrogen or C ₁-C₆ alkyl,

R ^D is hydrogen or C ₁-C₆ alkyl,

W is a chemical bond or CH ₂,

R ^I、R^II、R^III and R ^IV are independently selected from hydrogen, C ₁-C₄ alkyl, C ₁-C₄ alkoxy, phenyl, NO ₂ and NH ₂,

X is selected from NH₂、NHAr、NAr₂、Cl、Br、I、CH₃SO₃、CF₃SO₃、CH₃-C₆H₄-SO₃、C₆H₅-SO₃、NHCOC(CH₃)₃、NHCOCH₃、NO₂、B(OR^B1)(OR^B2),

Biaryl comprising at least 4 aromatic rings, and

An unsubstituted or substituted pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl or triazinyl group in each case, where the pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl or triazinyl group may be part of a fused ring system comprising 2,3 or more than 3 unsubstituted or substituted rings,

Ar is independently selected for each occurrence from an unsubstituted or substituted aryl group in which 2 Ar groups bonded to a nitrogen atom may also form, together with the nitrogen atom, a fused ring system having 3 or more than 3 unsubstituted or substituted rings,

R ^B1 and R ^B2 are independently of each other hydrogen or C ₁-C₄ alkyl, or R ^B1 together with R ^B2 form a C ₂-C₆ alkanediyl moiety;

Y is independently selected from the group consisting of C ₁-C₆ alkyl, phenyl and CF ₃ at each occurrence, wherein phenyl is unsubstituted or substituted with 1, 2 or 3 substituents selected from the group consisting of C ₁-C₆ alkyl,

Q is 0, 1, 2,3 or 4,

R is 0, 1, 2 or 3,

Z is O, S, NAr or a bond.

In a specific embodiment, X is selected from NH₂、NHAr、NAr₂、Cl、Br、I、CH₃SO₃、CF₃SO₃、CH₃-C₆H₄-SO₃、C₆H₅-SO₃、NHCOC(CH₃)₃、NHCOCH₃ or NO ₂.

A specific embodiment is a primary amine compound represented by the above formula (I), wherein X is a group of the formula-NH ₂.

Yet another embodiment is an amine compound represented by formula (I) above, wherein X is a group of formula-NHAr.

Yet another embodiment is a diarylamine compound represented by formula (I) above, wherein X is selected from the group of formula-NAr ₂.

Yet another embodiment is a diarylamine compound represented by formula (I) above, wherein X is selected from unsubstituted or substituted triazinyl, more preferably substituted triazinyl, especially substituted 1,3, 5-triazinyl.

Yet another specific embodiment is a diarylamine compound represented by formula (I) above, wherein X is selected from biaryl groups comprising at least 4 aromatic rings.

Yet another embodiment is a diarylamine compound represented by formula (I) above, wherein R ^A and R ^B are both C ₁-C₄ alkyl. In a particularly preferred embodiment, R ^A and R ^B are both methyl.

The following compounds (i.x1) to (i.x6) are specifically excluded from the compounds of formula (I):

a further object of the present invention is the use of at least one compound of formula (I) as defined above and below:

as Hole Transport Materials (HTM) in organic electronics,

As Electron Blocking Material (EBM) in an organic electronic device,

Use in Organic Solar Cells (OSCs), solid-state dye-sensitized solar cells (DSSCs) or perovskite solar cells, in particular as hole transport material in organic solar cells, as a substitute for liquid electrolytes in dye-sensitized solar cells, as hole transport material in perovskite solar cells,

Use in Organic Light Emitting Diodes (OLEDs), in particular for displays and illumination of electronic devices.

Yet another object of the present invention is an electroluminescent device comprising an upper electrode, a lower electrode, wherein at least one of the electrodes is transparent, an electroluminescent layer, and optionally an auxiliary layer, wherein the electroluminescent device comprises at least one compound of formula (I) as defined above or below.

Preferably, the electroluminescent device comprises at least one compound of formula (I) in a hole transport layer or in an electron blocking layer.

In a preferred embodiment, the electroluminescent device is an Organic Light Emitting Diode (OLED).

Yet another object of the present invention is an organic solar cell comprising:

A cathode which is arranged to be electrically connected to the anode,

The anode is a metal-oxide-semiconductor anode,

One or more photosensitive regions comprising at least one donor material and at least one acceptor material in separate layers or in the form of a bulk heterojunction layer,

Optionally, at least one further layer selected from exciton blocking layers, electron conducting layers and hole transporting layers,

Wherein the organic solar cell comprises at least one compound of formula (I) as defined above or below.

Yet another object of the present invention is a process for the preparation of a compound of formula (I) called (i.a1) (hereinafter "pathway 1"):

Wherein the method comprises the steps of

R ^A is hydrogen or methyl, and the hydrogen is methyl,

R ^B is hydrogen or methyl, and the hydrogen is methyl,

R ^C is hydrogen, and the hydrogen atom,

R ^D is hydrogen, and the hydrogen atom,

W is a chemical bond or CH ₂,

R ^I、R^II、R^III and R ^IV are independently selected from hydrogen, C ₁-C₄ alkyl, C ₁-C₄ alkoxy and phenyl,

Q is 0 or 1 and the number of the groups,

R is 0 or 1, and the number of the groups is 1,

Z is O, S, NAr or a chemical bond,

The method comprises the following steps:

a1 Providing a compound of formula (V.a):

Wherein X is H, cl or Br,

A2 Reaction of a compound of formula (V.a) with a compound of formula (vi.a1) or (vi.a2):

Wherein the method comprises the steps of

Z ^a is Cl, br, I, CH ₃SO₃、CF₃SO₃、CH₃-C₆H₄-SO₃ or C ₆H₅-SO₃,

To give compounds of the formula (vii.a1) or (vii.a2):

a3 Cyclizing a compound of formula (VII.a1) or (VII.a2) wherein in the case where X is Br or Cl, compound (I.a1) is obtained,

A4 In the case where X is H, brominating or nitrifying the cyclized product in step a 3) to obtain the compound (I.a1).

In a specific embodiment, providing a compound of formula (V.a) in step a 1) comprises the following sub-steps a 11) to a 12):

a11 Providing a ketone of formula (ii.a):

wherein X is H or Br,

A12 Reacting a ketone of formula (ii.a) with a compound of formula (iii.a):

Wherein the method comprises the steps of

Met is Li or a group Mg-Hal, wherein Hal is Cl, br or I,

Alcohol (iv.a) is obtained:

Subsequent reduction gives the compound of formula (V.a):

Thus, a preferred embodiment of pathway 1 relates to a process for preparing a compound of formula (i.a1) comprising steps a 11), a 12), a 3), and optionally a 4) (in case substituent X in compound (ii.a) provided in step a 11) is H).

Preferably, in step a 1) of the above process, the ketone of formula (ii.a) wherein X is H is subjected to bromination to give a ketone of formula (ii.a) wherein X is Br, and optionally the brominated product is subjected to one or more treatment steps.

Yet another object of the present invention is a process for the preparation of a compound of formula (I) called (i.b1) (hereinafter "pathway 2"):

Wherein the method comprises the steps of

R ^A is hydrogen or methyl, and the hydrogen is methyl,

R ^B is hydrogen or methyl, and the hydrogen is methyl,

R ^C is hydrogen, and the hydrogen atom,

R ^D is hydrogen, and the hydrogen atom,

W is a chemical bond or CH ₂,

R ^I、R^II、R^III and R ^IV are selected from the definitions shown in one row of the table below,

R^I	R^II	R^III	R^IV
				Methyl group	Hydrogen gas	Hydrogen gas	Methyl group
Methyl group	Methyl group	Hydrogen gas	Methyl group
				Methyl group	Methoxy group	Methyl group	Hydrogen gas
Hydrogen gas	Hydrogen gas	Hydrogen gas	Hydrogen gas
				Hydrogen gas	Methyl group	Hydrogen gas	Hydrogen gas
Hydrogen gas	Hydrogen gas	Hydrogen gas	Methyl group
				Methyl group	Methyl group	Methyl group	Methyl group
Methyl group	Methoxy group	Methyl group	Methyl group
				Hydrogen gas	Methyl group	Hydrogen gas	Methyl group
Hydrogen gas	Hydrogen gas	Methoxy group	Hydrogen gas
				Methoxy group	Hydrogen gas	Hydrogen gas	Hydrogen gas
Hydrogen gas	Methoxy group	Phenyl group	Hydrogen gas
				Phenyl group	Methoxy group	Hydrogen gas	Hydrogen gas

X is Cl, br, I or NO ₂,

Q is 0 or 1 and the number of the groups,

R is 0 or 1, and the number of the groups is 1,

Z is O, S, NAr or a chemical bond,

The method comprises the following steps:

b1 Providing a compound of formula (ii.b):

Wherein X is H, cl, br, I or NO ₂,

B2 Reacting a compound of formula (ii.b) with an aromatic compound of formula (iii.b):

/>

Compound (iv.b) is obtained:

b3 Reacting a compound of formula (iv.b) with a compound of formula (vi.a1) or (vi.a2):

Wherein the method comprises the steps of

Z ^a is Cl, br, I, CH ₃SO₃、CF₃SO₃、CH₃-C₆H₄-SO₃ or C ₆H₅-SO₃, giving a compound of formula (VII. B1) or (VII. B2):

b4 Cyclizing a compound of formula (VII.b1) or (VII.b2), wherein in the case where X is Cl, br, I or NO ₂, compound (I.b1) is obtained,

B5 In the case where X is H, brominating or nitrifying the cyclized product in step b 4) to obtain the compound (I.b1).

Yet another object of the present invention is a process for the preparation of a compound of formula (I) called (i.c1) (hereinafter "pathway 3"):

Wherein the method comprises the steps of

R ^A is a methyl group, and the amino group is a methyl group,

R ^B is a methyl group, and the amino group is a methyl group,

R ^C is hydrogen or methyl, and the hydrogen is methyl,

R ^D is hydrogen or methyl, and the hydrogen is methyl,

X is Cl or Br,

Q is 0 or 1 and the number of the groups,

R is 0 or 1, and the number of the groups is 1,

Z is O, S, NAr or a chemical bond,

The method comprises the following steps:

c1 Providing a compound of formula (iv.c):

c2 Reacting compound (iv.c) with an olefin (viii.c) in the presence of a lewis acid (e.g., BF ₃ ether complex):

Compound (I.c1) is obtained.

Yet another object of the present invention is a process for the preparation of a compound of formula (I) called (i.d1) (hereinafter "pathway 4"):

Wherein the method comprises the steps of

R ^A is hydrogen or methyl, and the hydrogen is methyl,

R ^B is hydrogen or methyl, and the hydrogen is methyl,

R ^C is hydrogen, and the hydrogen atom,

R ^D is hydrogen, and the hydrogen atom,

W is a chemical bond or CH ₂,

R ^I、R^II、R^III and R ^IV are hydrogen,

Q is 0 or 1 and the number of the groups,

R is 0 or 1, and the number of the groups is 1,

Z is O, S, NAr or a chemical bond,

The method comprises the following steps:

d1 Providing a ketone of formula (ii.d):

d2 Reacting a ketone of formula (ii.d) with a compound of formula (iii.d):

Wherein the method comprises the steps of

Met is Li or a group Mg-Hal, wherein Hal is Cl, br or I,

Alcohol (iv.d) is obtained:

subsequent removal of water gives compounds of formula (v.d1) or (v.d2):

d3 Cyclizing the compound of formula (v.d1) or (v.d2), wherein compound (i.d1) is obtained.

Yet another object of the present invention is a process for the preparation of a compound of formula (I) called (i.e1) (hereinafter "pathway 5"):

Wherein the method comprises the steps of

R ^A is hydrogen or methyl, and the hydrogen is methyl,

R ^B is hydrogen or methyl, and the hydrogen is methyl,

R ^C is hydrogen, and the hydrogen atom,

R ^D is hydrogen, and the hydrogen atom,

W is a chemical bond or CH ₂,

Y ¹ is H, C ₁-C₆ alkyl, phenyl or CF ₃, wherein phenyl is unsubstituted or substituted by 1, 2 or 3 substituents selected from C ₁-C₆ alkyl,

Y ² is H or Cl,

R is 0 or 1, and the number of the groups is 1,

Z is O, S or NAr, and the total number of the components is,

The method comprises the following steps:

e1 Providing a compound of formula (ii.e):

wherein Z, Y ¹、Y² and Y ³ are selected from the definitions set forth in one row of the table below,

Z	Y¹	Y²	Y³
				O	H	H	H
O	H	Cl	H
				O	C ₁-C₆ alkyl, unsubstituted or substituted benzene, CF ₃	H	H
S	H	Cl	Br
				S	C ₁-C₆ alkyl, unsubstituted or substituted benzene, CF ₃	Cl	Br
NBoc	H	Cl	Br
				NBoc	C ₁-C₆ alkyl, unsubstituted or substituted benzene, CF ₃	Cl	Br

E2 Metallization of the compound of formula (ii.e) to give the compound of formula (iii.e):

Wherein the method comprises the steps of

Met is Li or a group Mg-Br,

Z is O, S or NBoc,

E3 Reacting a compound of formula (iii.e) with a compound of formula (iv.e):

wherein, in the case where Z is O or S, the compound (V.e1) is obtained:

and in the case where Z is NBoc, the compound (V.e2) is obtained:

e4 Cyclizing the compound of formula (v.e1) to give the compound of formula (i.e1):

wherein Z is O or S,

Or cyclizing the compound of formula (v.e2) to give the compound of formula (vi.e2):

e5 Reacting a compound of formula (vi.e2) with an aromatic compound of formula (IX):

Ar-Z^b(IX)

Wherein the method comprises the steps of

Z ^b is selected from Cl, br, I, CH ₃SO₃、CF₃SO₃、CH₃-C₆H₄-SO₃,

C ₆H₅-SO₃ or CF ₃(CF₂)₃SO₃,

To give a compound of formula (I.e1) wherein Z is NAr.

The invention further relates to a process for the preparation of a compound of formula (I) wherein X is NAr ₂, NHAr or NH ₂.

Still another object of the present invention is a process for the preparation of a compound of formula (I) called (i.f1) or (i.f2):

Wherein the method comprises the steps of

R ^A is hydrogen or C ₁-C₆ alkyl,

R ^B is hydrogen or C ₁-C₆ alkyl,

R ^C is hydrogen or C ₁-C₆ alkyl,

R ^D is hydrogen or C ₁-C₆ alkyl,

W is a chemical bond or CH ₂,

Ar is independently selected in each occurrence in the NHAr group from the group consisting of unsubstituted or substituted aryl groups in each occurrence,

The 2 Ar groups in the NAr ₂ groups have identical or different meanings and are independently selected from the group consisting of unsubstituted or substituted aryl groups in each case, wherein the 2 Ar groups bound to a nitrogen atom may also form together with the nitrogen atom a fused ring system having 3 or more than 3 unsubstituted or substituted rings,

Q is 0 or 1 and the number of the groups,

R is 0 or 1, and the number of the groups is 1,

Z is O, S, NAr or a chemical bond,

The method comprises the following steps:

f11 Providing a compound of formula (i.f11):

Wherein the method comprises the steps of

X is selected from Cl, br, I and CF ₃SO₃,

F12 Amination of the compound of formula (i.f11) from step f 11) with an aromatic amine of formula (x.f1) or (x.f2) in the presence of a palladium complex catalyst and a base:

to give compounds of the formula (I.f1) or (I.f2),

Or (b)

F21 Providing a secondary amine compound of formula (i.f1) or a primary amine compound of formula (i.f2):

f22 Reacting a compound of formula (I.f1) with an aromatic compound of formula (X.f) in the presence of a palladium complex catalyst and a base

The compound is subjected to an arylation reaction:

Ar-Z^b (X.f)

Wherein the method comprises the steps of

Z ^b is selected from Cl、Br、I、CH₃SO₃、CF₃SO₃、CH₃-C₆H₄-SO₃、C₆H₅-SO₃ or CF ₃(CF₂)₃SO₃,

Ar group in NHAr group of the compound of formula (I.f1) and Ar group in aromatic compound of formula (X.f) may have the same or different meanings,

To give compounds of the formula (I.f2) in which 2 Ar groups in the NAr ₂ groups have identical or different meanings,

Or (b)

An arylation reaction of a compound of formula (i.f21) with an aromatic compound of formula (X.f) in the presence of a palladium complex catalyst and a base, followed by a second arylation reaction with the same aromatic compound of formula (X.f) or an aromatic compound of formula (X.f) in which the Ar groups have different meanings:

Ar-Z^b (X.f)

to give compounds of the formula (I.f2) in which 2 Ar groups in the NAr ₂ groups are identical or have different meanings.

Preferably, in the above process, the compound of formula (i.f11) provided in step f 11) is selected from:

Compounds of formula (I.a1) obtainable by a process as defined above and below comprising steps a 1), a 2), a 3), and if desired a 4),

Compounds of the formula (I.b1) obtainable by a process as defined above and below comprising steps b 1), b 2), b 3), b 4), b 5) and, if desired, b 6),

Compounds of formula (I.c1), obtainable by a process comprising steps c 1) and c 2) as defined above and below,

Compounds of formula (i.d1), obtainable by a process as defined above and below comprising steps d 1), d 2) and a 3), or

Compounds of formula (i.e1), obtainable by a process as defined above and below comprising steps e 1), e 2), e 3) and e 4) or e 5).

Yet another object of the present invention is a process for the preparation of a compound of formula (I), designated (I.g):

Wherein the method comprises the steps of

X ^Ar is selected from biaryl groups comprising at least 4 aromatic rings, and in each case unsubstituted or substituted pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl or triazinyl, where pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl or triazinyl may be part of a fused ring system comprising 2, 3 or more than 3 unsubstituted or substituted rings,

R ^A is hydrogen or C ₁-C₆ alkyl,

R ^B is hydrogen or C ₁-C₆ alkyl,

R ^C is hydrogen or C ₁-C₆ alkyl,

R ^D is hydrogen or C ₁-C₆ alkyl,

W is a chemical bond or CH ₂,

Q is 0 or 1 and the number of the groups,

R is 0 or 1, and the number of the groups is 1,

Z is O, S, NAr or a chemical bond,

The method comprises the following steps:

g1 Providing a compound of formula (i.g1):

Wherein R ^B1 and R ^B2 are each independently of the other hydrogen or C ₁-C₄ alkyl, or R ^B1 together with R ^B2 form a C ₂-C₆ alkanediyl moiety,

G2 Coupling a compound of formula (i.g1) with a heteroaromatic compound of formula (X.g) in the presence of a palladium catalyst:

X^Ar-Z^c (X.g)

Wherein the method comprises the steps of

Z ^c is selected from Cl, br, I or CF ₃SO₃,

To give a compound of formula (I.g).

A preferred embodiment is a process for the preparation of a compound of formula (I) designated (I.g11):

Wherein the method comprises the steps of

E ¹ is N or CR ^g1,

E ² is N or CR ^g2,

E ³ is N or CR ^g3,

E ⁴ is N or CR ^g4,

E ⁵ is N or CR ^g5,

Provided that 1, 2 or 3 of the ring members E ¹ to E ⁵ are N,

R ^g1 to R ^g5 are independently selected from hydrogen, C ₁-C₄ alkyl and unsubstituted or substituted aryl, wherein 2 or more groups selected from CR ^g1、CR^g2、CR^g3、CR^g4 and CR ^g5 may form together with the N-heterocycle to which they are bonded a fused ring system comprising 2,3 or more than 3 unsubstituted or substituted rings,

R ^A is hydrogen or C ₁-C₆ alkyl,

R ^B is hydrogen or C ₁-C₆ alkyl,

R ^C is hydrogen or C ₁-C₆ alkyl,

R ^D is hydrogen or C ₁-C₆ alkyl,

W is a chemical bond or CH ₂,

Q is 0 or 1 and the number of the groups,

R is 0 or 1, and the number of the groups is 1,

Z is O, S, NAr or a chemical bond,

The method comprises the following steps:

g1 Providing a compound of formula (i.g1):

G2 Coupling the compound of formula (i.g1) with a heteroaromatic compound of formula (x.ga) in the presence of a palladium catalyst:

Wherein the method comprises the steps of

Z ^c is selected from Cl, br, I or CF ₃SO₃,

To give a compound of formula (I.g).

Detailed Description

The compounds of formula (I) and their preparation have at least one of the following advantages:

the compounds of formula (I) are distinguished by good thermal and environmental stability.

In general, the compounds (I) have a high glass transition temperature. They are generally sublimable and allow fabrication of devices by physical vapor deposition.

The compounds of the formula (I) are particularly suitable as organic semiconductors. They generally act as p-semiconductors. Preferred applications of the compounds (I) are Hole Transport Materials (HTM) or Electron Blocking Materials (EBM).

The compounds of formula (I) further have good properties in OPV (organic photovoltaic device) applications. They allow the excited states (excitons) generated by the absorbed photons to pass very long distances, i.e. they have good exciton diffusion lengths. The present invention further allows to provide such compounds of formula (I) wherein the size of the semiconductor band gap can be tuned to make very efficient use of sunlight.

The process of the invention allows a very efficient and economical synthesis of many kinds of compounds of formula (I). Thus, it can easily provide the compound (I) having the properties optimized for the intended use.

The compounds of formula (I) have 1 or 2 chiral centers in their spiro cores, so that they may exist as mixtures of enantiomers or diastereomers, either as pure enantiomers or as pure diastereomers. The present invention provides racemic mixtures of compounds of formula (I) or diastereomers (e.g., example 6), as well as pure enantiomers or racemic pure diastereomers or enantiomerically pure diastereomers (enantiopure diastereoisomers) of compounds of formula (I). The compounds of formula (I) may be obtained in enantiomerically and diastereomerically enriched forms, respectively, or in pure form by standard methods known in the art, including, for example, chiral separation or by preparation of the compounds of formula (I) using the appropriate chiral compound as starting material. Suitable compounds of formula (I) also include all possible regioisomers and mixtures thereof.

It should be noted that in the formulae described herein, methyl groups may be represented by solid lines. Thus, for example, the following formulae describe 2 schemes for the same compound

It should also be noted that no hydrogen atoms are shown in the formula unless explicitly indicated otherwise in the formula. In other words, the hydrogen atoms are explicitly shown in some of the specific formulas of the present application, but are not shown in most cases as is common in practice. Accordingly, the definition that an aromatic ring (e.g., a benzene ring) may be substituted with 0 to x substituents (e.g., substituent Y) means that the ring atom that can be substituted but is not substituted carries a hydrogen atom.

As used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise.

The definitions of the variables specified in the above formulae use collective terms that are generally representative of the corresponding substituents. The definition of C _n-C_m gives the number of carbon atoms possible in each case in the corresponding substituent or substituent moiety.

The word "halogen" denotes in each case fluorine, bromine, chlorine or iodine, in particular chlorine, bromine or iodine. Similarly, the term "halogen" in each case denotes fluorine, chlorine, bromine or iodine.

The term "unbranched" as used herein also refers to linear or straight chain.

The term "C _n-C_m alkyl" as used herein refers to branched or unbranched saturated hydrocarbon groups having n to m carbon atoms, for example having 1 to 2 carbon atoms ("C ₁-C₂ alkyl"), 1 to 4 carbon atoms ("C ₁-C₄ alkyl"), or 1 to 6 carbon atoms ("C ₁-C₆ alkyl"). C ₁-C₂ alkyl is methyl or ethyl. Examples of C ₁-C₄ alkyl, in addition to those described for C ₁-C₂ alkyl, are propyl, isopropyl, butyl, 1-methylpropyl (sec-butyl), 2-methylpropyl (isobutyl) or 1, 1-dimethylethyl (tert-butyl). In addition to those described for C ₁-C₄ alkyl, examples of C ₁-C₆ alkyl are also pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, 1-ethylpropyl, 1-dimethylpropyl, 1, 2-dimethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-dimethylbutyl 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2-dimethylbutyl, 2, 3-dimethylbutyl, 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 2-trimethylpropyl, 1, 2-trimethylpropyl, 1-ethyl-1-methylpropyl or 1-ethyl-2-methylpropyl.

Similarly, the term "C _n-C_m alkoxy" refers to a straight or branched alkyl group (as described above) having n to m carbon atoms (e.g., 1 to 2 carbon atoms or1 to 4 carbon atoms or1 to 6 carbon atoms) attached to the remainder of the molecule via an oxygen atom at any bond in the alkyl group. C ₁-C₂ alkoxy is methoxy or ethoxy. Examples of C ₁-C₄ alkoxy groups other than those described for C ₁-C₂ alkoxy groups are n-propoxy, 1-methylethoxy (isopropoxy), butoxy, 1-methylpropoxy (sec-butoxy), 2-methylpropoxy (isobutoxy) or1, 1-dimethylethoxy (tert-butoxy). In addition to those described for the C ₁-C₄ alkoxy groups, examples of C ₁-C₆ alkoxy are also pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1-dimethylpropoxy, 1, 2-dimethylpropoxy, 2-dimethylpropoxy, 1-ethylpropoxy, hexyloxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy 1, 1-dimethylbutoxy, 1, 2-dimethylbutoxy, 1, 3-dimethylbutoxy, 2-dimethylbutoxy, 2, 3-dimethylbutoxy, 3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1, 2-trimethylpropoxy, 1, 2-trimethylpropoxy, 1-ethyl-1-methylpropoxy or 1-ethyl-2-methylpropoxy.

The term "C _n-C_m cycloalkyl" as used herein refers to a monocyclic n-to m-membered saturated cycloaliphatic radical having, for example, 3 to 8 carbon atoms. Examples of C ₃-C₈ cycloalkyl are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

Similarly, the term "C _n-C_m cycloalkoxy" refers to a monocyclic n-to m-membered saturated cycloaliphatic group, such as C ₃-C₈ cycloalkyl (as described above), which is attached to the backbone by an O-linkage.

The term "aryl" as used herein refers to monocyclic, bicyclic, tricyclic and tetracyclic aromatic hydrocarbon groups having 6 to 18 ring carbon atoms, wherein said rings are fully condensed (fused), or two aromatic rings may also be bonded via a chemical bond and selected from the group consisting of-CH ₂ -, -O-, divalent radicals of-S-or-N (H) -are linked to one another. Examples include phenyl, naphthyl, anthryl, phenanthryl, fluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, 11H-benzo [ b ] fluorenyl, naphtho [2,3-b ] benzofuranyl, naphtho [2,3-b ] benzothiophenyl, and 5H-benzo [ b ] carbazolyl. aryl groups may be substituted at 1, 2, 3,4, more than 4 or all substitutable positions. Suitable substituents are generally C ₁-C₆ -alkyl, C ₁-C₆ -alkoxy, carbazol-9-yl (N-bonded carbazolyl), which are unsubstituted or substituted by C ₁-C₄ -alkyl, C ₁-C₄ -alkoxy and phenyl, Wherein the phenyl group is substituted on part thereof with 1,2, 3 or 4 different or identical substituents selected from the group consisting of C ₁-C₄ alkyl and C ₁-C₄ alkoxy. Furthermore, suitable substituents attached at the aryl group are also generally diphenylamino, C ₅-C₈ cycloalkyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl and phenanthryl, where the cyclic rings in the 8 last-mentioned groups are each unsubstituted or substituted by 1, 2, 3, 4 or 5 different or identical substituents from the group C ₁-C₄ alkyl, C ₁-C₄ alkoxy and carbazol-9-yl, The carbazol-9-yl is unsubstituted or substituted by C ₁-C₄ alkyl, C ₁-C₄ alkoxy and phenyl, wherein the phenyl is substituted on part thereof by 1,2, 3 or 4 different or identical substituents selected from C ₁-C₄ alkyl and C ₁-C₄ alkoxy. Furthermore, 2 substituents bonded to the same carbon atom of the fluorenyl or 11H-benzo [ b ] fluorenyl group may together form an alkylene group (CH ₂)_r, r is 4,5, 6 or 7, thus forming a 5 to 8 membered saturated carbocyclic ring in which 1 or2 hydrogen atoms in the group may be replaced by a C ₁-C₄ alkyl or C ₁-C₄ alkoxy group, Or 2 substituents bonded to the same carbon atom of a fluorenyl or 11H-benzo [ b ] fluorenyl group may together form an alkylene group (CH ₂)_r, r is 4, 5, 6, or 7, so forming a5 to 8 membered saturated carbocyclic ring which may be benzo-fused with 1 or 2 phenyl groups (benz-annelated), wherein the phenyl ring is optionally substituted with 1, 2,3, or 4 identical or different C ₁-C₄ alkyl or C ₁-C₄ alkoxy groups.

The term "biaryl containing at least 4 aromatic rings" means a structure in which at least two aryl groups (subgroup) are bound by a single bond between 2 aromatic rings. Preferably, the biaryl comprises 4, 5, 6, 7, 8 or more than 8 aromatic rings.

If a moiety is described as "optionally substituted," the moiety may be unsubstituted or substituted.

If a moiety is described as "substituted," then a non-hydrogen group is located at the position of the hydrogen group of any substitutable atom of the moiety. If more than one substitution is present in one moiety, the non-hydrogen groups may be the same or different (unless otherwise indicated).

Preferred compounds according to the invention are compounds of formula (I) wherein R ^A is hydrogen or C ₁-C₄ alkyl. More preferably, R ^A is methyl or ethyl.

Also preferred are compounds of formula (I) wherein R ^B is hydrogen or C ₁-C₄ alkyl. More preferably, R ^B is methyl or ethyl.

In a particularly preferred embodiment, R ^A and R ^B are both methyl. In yet another specific embodiment, R ^A and R ^B are both hydrogen.

Preferred compounds according to the invention are compounds of formula (I) wherein R ^C and R ^D are independently selected from hydrogen and C ₁-C₄ alkyl.

In a preferred embodiment, one of the substituents R ^C and R ^D is C ₁-C₄ alkyl and the other is hydrogen. In particular, one of the substituents R ^C and R ^D is methyl and the other is hydrogen. In a particularly preferred embodiment, R ^C and R ^D are both hydrogen.

In a preferred embodiment, W is a bond. In another preferred embodiment, W is CH ₂.

In a specific embodiment, substituents R ^A、R^B、R^C and R ^D are selected from the definitions set forth in one row of the table below.

R^A	R^B	R^C	R^D
				Methyl group	Methyl group	Hydrogen gas	Hydrogen gas
Methyl group	Methyl group	Methyl group	Hydrogen gas
				Hydrogen gas	Hydrogen gas	Hydrogen gas	Hydrogen gas

Preferably, in the compounds of formula (I), X is-NH ₂ or-NHAr or-NAr ₂ or a biaryl comprising at least 4 aromatic rings, or a substituted pyridinyl, or a substituted pyridazinyl, or a substituted pyrimidinyl, or a substituted pyrazinyl, or a substituted triazinyl, wherein pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, or triazinyl may be part of a fused ring system comprising 2,3, or more than 3 unsubstituted or substituted rings.

In a preferred embodiment, compound (I) comprises an X group which is a biaryl comprising at least 4 aromatic rings and comprises at least one child group (subgroup) comprising 2 or more (e.g., 3, 4,5, 6 or more) fused aromatic rings.

In yet another preferred embodiment, compound (I) comprises an X group that is a biaryl comprising at least 4 aromatic rings and comprises at least two child groups, wherein each child group comprises 2 or more (e.g., 3,4, 5, 6 or more) fused aromatic rings.

In a specific embodiment, all fused rings are benzene rings.

In particular, X is selected from the following groups:

Wherein # denotes the bonding position to the rest of the compound.

In yet another preferred embodiment, compound (I) comprises an X group selected from substituted pyridinyl, or substituted pyridazinyl, or substituted pyrimidinyl, or substituted pyrazinyl, or substituted triazinyl, wherein substituted pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, or triazinyl are substituted with one or more substituents R ^Het1, wherein each R ^Het1 is independently selected from aryl, wherein aryl is unsubstituted or substituted with 1, 2, or 3 substituents selected from C ₅-C₁₂ aryl.

In a preferred embodiment, in the compounds of formula (I) X is a substituted triazinyl group. In a specific embodiment, X is selected from substituted 1,3, 5-triazinyl groups. In particular, in the compounds of formula (I) X is a group selected from HET1 to HET5 groups:

/>

Wherein # represents the bonding position to the remainder of the compound and R ^Het1 is each independently selected from aryl, wherein aryl is unsubstituted or substituted with 1,2, or 3 substituents selected from C ₁-C₄ alkyl, F, CF ₃, and C ₅-C₁₂ aryl. In a specific embodiment, both R ^Het1 are phenyl.

Preferably, in the compounds of formula (I), X is-NH ₂ or-NHAr or-NAr ₂.

Preferably, in the compounds of formula (I), each Y group is independently selected from C ₁-C₆ alkyl, phenyl and CF ₃, wherever it occurs, wherein phenyl is unsubstituted or substituted with 1, 2 or 3 substituents selected from C ₁-C₆ alkyl. More preferably, each Y group is independently selected from methyl, CF ₃, and phenyl, wherever it occurs.

Preferably, in the compounds of formula (I), q is 0 or 1. In one embodiment, q is 0. In yet another embodiment, q is 1.

Preferably, in the compounds of formula (I), r is 0 or 1. In one embodiment, r is 0.

Preferably, substituents R ^I、R^II、R^III and R ^IV are selected from the definitions set out in one row of the table below.

The compounds of formula (I) encompass structural isomers (regioisomers) with respect to the positions of substituents R ^I、R^II、R^III and R ^IV. Depending on the route and starting materials used for the synthesis of compound (I), a single compound or a mixture of two or more regioisomers (I) may be obtained. The regioisomer mixture can be separated to give the isomer in enriched or pure form. Mixtures of two or more regioisomers (I) may also be used for applications in organic electronic devices, as described below. Accordingly, a particular embodiment of the invention relates to a mixture of compounds of formula (I) wherein the substituents R ^I、R^II、R^III and R ^IV of each compound are selected from the definitions set out in one row of the table below.

R^I	R^II	R^III	R^IV
				Hydrogen gas	Hydrogen gas	Methoxy group	Hydrogen gas
Methoxy group	Hydrogen gas	Hydrogen gas	Hydrogen gas

The above-mentioned compounds can be prepared, for example, by synthetic route 2 as defined above and below, wherein 2-phenyl anisole is used as aromatic compound (iii.b).

Another particular embodiment of the invention relates to mixtures of compounds of formula (I) wherein the substituents R ^I、R^II、R^III and R ^IV of each compound are selected from the definitions set out in one row of the table below.

R^I	R^II	R^III	R^IV
				Hydrogen gas	Methoxy group	Phenyl group	Hydrogen gas
Phenyl group	Methoxy group	Hydrogen gas	Hydrogen gas

The above-mentioned compounds can be prepared, for example, by the synthetic route 1 as defined above and below, wherein a Grignard compound of 3-bromoanisole is used as compound (iii.a).

Preferably, in the compounds of formula (I), Z is O, S, NAr or a bond.

Preferably, the compound of formula (I) is selected from the group consisting of compounds (i.a), (I.B), (i.c), (i.d), (I.E), (I.F), (I.G) and (I.H):

Wherein the method comprises the steps of

R ^A is hydrogen or C ₁-C₄ alkyl,

R ^B is hydrogen or C ₁-C₄ alkyl,

R ^C is hydrogen or C ₁-C₄ alkyl,

R ^D is hydrogen or C ₁-C₄ alkyl,

R ^V is hydrogen, C ₁-C₄ alkyl or CF ₃,

Biaryl comprising at least 4 aromatic rings, and

R ^B1 and R ^B2 are each independently of the other hydrogen or C ₁-C₄ alkyl, or R ^B1 together with R ^B2 form a C ₂-C₆ alkanediyl moiety.

Preferred are compounds of formula (i.a), (I.B), (ic), (i.d), (I.E), (I.F), (I.G) and (I.H) wherein R ^A is hydrogen or methyl or ethyl.

Also preferred are compounds of formula (i.a), (I.B), (ic), (i.d), (I.E), (I.F), (I.G) and (I.H) wherein R ^B is hydrogen or methyl or ethyl.

More preferred among the compounds of formulae (i.a), (I.B), (i.c), (i.d), (I.E), (I.F), (I.G) and (I.H) are compounds wherein R ^A is methyl and R ^B is methyl.

Preferably, in the compounds of formulae (i.a), (I.B), (i.c), (i.d), (I.E), (I.F), (I.G) and (I.H), X is selected from-NH ₂ and-NAr ₂. Preferred are compounds of formula (i.a), (I.B), (i.c), (id), (I.E), (I.F), (I.G) and (I.H) wherein R ^I、R^II、R^III and R ^IV are independently selected from hydrogen, methyl, phenyl and methoxy. Preferably, 0, 1,2 or 3 of the groups R ^I、R^II、R^III and R ^IV are not hydrogen.

Preferred are compounds of formula (i.a), (I.B), (ic), (i.d), (I.E), (I.F), (I.G) and (I.H) wherein R ^V is hydrogen, methyl or CF ₃. Preferably, the compound of formula (I) is selected from compounds (i.a), (I.B), (i.c), (i.d), (I.E), (I.F), (I.G) and (I.H):

/>

Wherein the method comprises the steps of

R ^A is hydrogen or C ₁-C₄ alkyl,

R ^B is hydrogen or C ₁-C₄ alkyl,

R ^C is hydrogen or C ₁-C₄ alkyl,

R ^D is hydrogen or C ₁-C₄ alkyl,

X is selected from NH₂、NHAr、NAr₂、Cl、Br、I、CH₃SO₃、CF₃SO₃、CH₃-C₆H₄-SO₃、C₆H₅-SO₃、NHCOC(CH₃)₃ or NHCOCH ₃,

R ^I、R^II、R^III and R ^IV are independently selected from hydrogen, C ₁-C₄ alkyl, C ₁-C₄ alkoxy, NO ₂ and NH ₂,

Ar is independently selected for each occurrence from an unsubstituted or substituted aryl group in which 2 Ar groups bonded to a nitrogen atom may also form, together with the nitrogen atom, a fused ring system having 3 or more than 3 unsubstituted or substituted rings.

Preferred are compounds of formula (i.a), (I.B), (i.c), (i.d), (I.E), (I.F), (I.G) and (I.H) wherein R ^A is hydrogen or methyl or ethyl.

Also preferred are compounds of formula (i.a), (I.B), (i.c), (i.d), (I.E), (I.F), (I.G) and (I.H) wherein R ^B is hydrogen or methyl or ethyl.

Preferably, in the compounds of formulae (I.A), (I.B), (I.C), (I.D), (I.E), (I.F), (I.G) and (I.H), X is selected from-NH ₂ and-NAr ₂. Preferred are compounds of formula (i.a), (I.B), (i.c), (i.d), (I.E), (I.F), (I.G) and (I.H) wherein R ^I、R^II、R^III and R ^IV are independently selected from hydrogen, methyl, phenyl and methoxy.

Preferably, 0, 1,2 or 3 of the groups R ^I、R^II、R^III and R ^IV are not hydrogen. More preferably, 0, 1 or 2 of the groups R ^I、R^II、R^III and R ^IV are not hydrogen.

Preferably, the compound of formula (I) is selected from compounds (i.1) to (i.33):

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wherein Ar is independently selected for each occurrence from an unsubstituted or substituted aryl group in which 2 Ar groups bonded to a nitrogen atom may also form, together with the nitrogen atom, a fused ring system having 3 or more than 3 unsubstituted or substituted rings.

Preferably, the compound of formula (I) is selected from compounds (i.34) to (i.72):

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In the compounds (I) and (i.a), (I.B), (i.c), (i.d), (I.E), (I.F), (I.G) and (I.H) in which X is NAr ₂, and in the compounds (i.a), (I.B), (i.c), (i.d), (I.E), (I.F), (I.G) and (I.H) in which X is NAr ₂, and in the compounds of the formulae (i.3), (i.6), (I.9), (i.12), (i.15), (i.18), (i.21), (i.24), (i.27), (i.30) and (i.33), and in the compounds of the formulae (i.36), (i.39), (i.42), (i.45), (i.48), (i.51), (i.54), (i.57), (i.60), (i.63), (i.66), (i.69) and (i.72), the nitrogen atom of which the nitrogen atom of the bond 2 has the same meaning or different Ar.

Preferred are compounds of formulae (I)、(I.A*)、(I.B*)、(I.C*)、(I.D*)、(I.E*)、(I.F*)、(I.G*)、(I.H*)、(I.A)、(I.B)、(I.C)、(I.D)、(I.E)、(I.F)、(I.G) and (I.H) wherein X is selected from-NAr ₂ and-NHAr, and compounds of formulae (I.2)、(I.3)、(I.5)、(I.6)、(I.8)、(I.9)、(I.11)、(I.12)、(I.14)、(I.15)、(I.17)、(I.18)、(I.20)、(I.21)、(I.23)、(I.24)、(I.26)、(I.27)、(I.29)、(I.30)、(I.32) and (i.33), and compounds of formulae (I.35)、(I.36)、(I.38)、(I.39)、(I.41)、(I.42)、(I.44)、(I.45)、(I.47)、(I.48)、(I.50)、(I.51)、(I.53)、(I.54)、(I.56)、(I.57)、(I.59)、(I.60)、(I.62)、(I.63)、(I.65)、(I.66)、(I.68)、(I.69)、(I.71) and (i.72) wherein Ar groups are independently selected from unsubstituted or substituted phenyl, unsubstituted or substituted naphthyl, unsubstituted or substituted phenanthryl, unsubstituted or substituted anthracenyl, unsubstituted or substituted fluorenyl, unsubstituted or substituted C-bonded carbazolyl, unsubstituted or substituted dibenzofuranyl, unsubstituted or substituted dibenzothiophenyl, or 2 Ar groups, together with the nitrogen atom to which they are attached, form an unsubstituted or substituted N-bonded carbazolyl.

More preferably, each Ar, wherever it occurs, is selected from:

phenyl, biphenyl, terphenyl, tetrabiphenyl, wherein phenyl, biphenyl, terphenyl, and tetrabiphenyl are unsubstituted or substituted with one or more substituents R ^Ar1;

Naphthyl, anthryl, phenanthryl, fluorenyl, spirobifluorenyl, C-bonded carbazolyl, dibenzofuranyl, dibenzothiophenyl, xanthenyl, thioxanthenyl and 9, 10-dihydroacridinyl, wherein naphthyl, phenanthryl, fluorenyl, spirobifluorenyl, C-bonded carbazolyl, dibenzofuranyl, dibenzothiophenyl, xanthenyl, thioxanthenyl and 9, 10-dihydroacridinyl are unsubstituted or substituted with one or more substituents R ^Ar2;

Or 2 Ar groups together with the nitrogen atom to which they are attached may form an N-bonded carbazolyl group which is unsubstituted or substituted with one or more substituents R ^Ar3;

Wherein the method comprises the steps of

Each R ^Ar1 is independently selected from:

C ₁-C₆ alkyl group, C ₁-C₆ alkoxy group,

Carbazol-9-yl, wherein the carbazol-9-yl may be substituted with 1, 2, 3 or 4 substituents selected from C ₁-C₄ alkyl, C ₁-C₄ alkoxy and phenyl, wherein phenyl may be substituted with 1, 2, 3 or 4 different or identical substituents selected from C ₁-C₄ alkyl and C ₁-C₄ alkoxy,

Diphenylamino, C ₅-C₈ -cycloalkyl, naphthyl and m-terphenyl-5' -group, wherein the cyclic rings in the last-mentioned 4 groups are each unsubstituted or substituted by 1,2,3 or 4 different or identical substituents from the group consisting of C ₁-C₄ -alkyl, C ₁-C₄ -alkoxy and carbazol-9-yl, wherein carbazol-9-yl can be substituted by 1,2,3 or 4 different or identical substituents from the group consisting of C ₁-C₄ -alkyl, C ₁-C₄ -alkoxy and phenyl, wherein phenyl can be substituted by 1,2,3 or 4 different or identical substituents from the group consisting of C ₁-C₄ -alkyl and C ₁-C₄ -alkoxy,

The 2R ^Ar1 groups bound to adjacent carbon atoms together with the carbon atoms to which they are bound may form a saturated 5-membered heterocyclic ring having 1 oxygen atom or 2 non-adjacent oxygen atoms as a ring member, which is unsubstituted or substituted with 1 or 2 groups selected from C ₁-C₄ alkyl;

Each R ^Ar2 is independently selected from:

c ₁-C₆ alkyl, C ₁-C₆ -alkoxy,

Diphenylamino, C ₅-C₈ cycloalkyl and phenyl, where the cyclic rings in the last-mentioned 3 radicals are each unsubstituted or substituted by 1,2, 3 or 4 different or identical substituents from the group consisting of C ₁-C₄ alkyl, C ₁-C₄ alkoxy and carbazol-9-yl, where carbazol-9-yl can be substituted by 1,2, 3 or 4 different or identical substituents from the group consisting of C ₁-C₄ alkyl, C ₁-C₄ alkoxy and phenyl, where phenyl can be substituted by 1,2, 3 or 4 different or identical substituents from the group consisting of C ₁-C₄ alkyl and C ₁-C₄ alkoxy,

The 2R ^Ar2 groups bound to adjacent carbon atoms together with the carbon atoms to which they are bound may form a saturated 5-membered heterocyclic ring having 1 oxygen atom or 2 non-adjacent oxygen atoms as a ring member, which is unsubstituted or substituted with 1 or 2 groups selected from C ₁-C₄ alkyl, and

Wherein in the case where Ar is fluorenyl, xanthenyl, thioxanthenyl or 9, 10-dihydroacridinyl, 2 geminal R ^Ar2 groups may form an alkylene group (CH ₂)_r, R is 4, 5 or 6; and

Each R ^Ar3 is independently selected from C ₁-C₆ alkyl, C ₁-C₆ -alkoxy, diphenylamino and phenyl, wherein the cyclic rings in the last-mentioned 2 groups are each unsubstituted or substituted with 1,2,3 or 4 different or identical substituents selected from C ₁-C₄ alkyl and C ₁-C₄ alkoxy.

Specific examples of Ar groups include the following groups of formulae (AR-I) to (AR-LIX):

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Wherein the method comprises the steps of

# In each case represents a bonding site to a nitrogen atom;

in formulas AR-I、AR-II、AR-III、AR-IV、AR-V、AR-VI、AR-VII、AR-VIII、AR-IX、AR-X、AR-XI、AR-XII、AR-XIII、AR-XIV、AR-XV、AR-XVI、AR-XVII、AR-XVIII、AR-XIX、AR-XX、AR-XXI、AR-XXII and AR-XXIII:

R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷、R¹⁸ And R ¹⁹, if present, is independently selected from hydrogen, linear or branched C ₁-C₄ alkyl, linear or branched C ₁-C₄ alkoxy and carbazol-9-yl, wherein the carbazol-9-yl may be substituted with 1, 2,3 or 4 different or the same substituents selected from C ₁-C₄ alkyl, C ₁-C₄ alkoxy, phenyl, tolyl, xylyl, 2,4, 6-trimethylphenyl and anisoyl;

In formulas AR-XXV、AR-XXVI、AR-XXVII、AR-XXVIII、AR-XXIX、AR-XXX、AR-XXXI、AR-XXXII、AR-XXXIII、AR-XXXIV、AR-XXXV、AR-XXXVI、AR-XXXVII、AR-XXXVIII、AR-XXXIX、AR-XL、AR-XLI、AR-XLII、AR-XLIII、AR-XLIV、AR-XLV、AR-LIII、AR-LIV、AR-LV、AR-LVI、AR-LVIII and AR-LIX:

R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R^9a、R^9b、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵ And R ¹⁶, if present, are independently of one another selected from hydrogen, linear or branched C ₁-C₄ alkyl, linear or branched C ₁-C₄ alkoxy, carbazol-9-yl and phenyl, where carbazol-9-yl and phenyl are unsubstituted or substituted by 1,2 or 3 different or identical substituents selected from C ₁-C₄ alkyl, C ₁-C₄ alkoxy, phenyl, tolyl, xylyl and 2,4, 6-trimethylphenyl, and

Furthermore, R ^9a and R ^9b in the formulae AR-XXV, AR-XXVI, AR-XXVII and AR-LIII may together form an alkylene group (CH ₂)_r, R is 4, 5 or 6, where 1 or 2 hydrogen atoms in the group may be replaced by methyl or methoxy;

In formulae AR-XLVI, AR-XLVI and AR-XLVIII:

R ¹、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R^9a、R^9b and R ^9c, if present, are independently of one another selected from hydrogen, straight-chain or branched C ₁-C₄ alkyl, straight-chain or branched C ₁-C₄ alkoxy, phenyl, 1-naphthyl, 2-naphthyl, 9-fluorenyl and carbazol-9-yl, where phenyl, 1-naphthyl, 2-naphthyl, 9-fluorenyl or carbazol-9-yl are unsubstituted or substituted by 1,2 or 3 different or identical substituents selected from C ₁-C₄ alkyl and C ₁-C₄ alkoxy,

Furthermore, R ^9a and R ^9b in the formulae AR-XLVI, AR-XLVI and AR-XLIII may together form an alkylene radical (CH ₂)_r, R is 4, 5 or 6, in which 1 or 2 hydrogen atoms in the radical may be replaced by methyl or methoxy;

in formulae AR-XXIV, AR-XLIX, AR-L, AR-LI and AR-LII:

R ³、R⁴、R⁵ and R ⁶, if present, are independently of one another selected from hydrogen, straight-chain or branched C ₁-C₄ alkyl, straight-chain or branched C ₁-C₄ alkoxy, phenyl, 1-naphthyl, 2-naphthyl, 9-fluorenyl and carbazol-9-yl, where phenyl, 1-naphthyl, 2-naphthyl, 9-fluorenyl or carbazol-9-yl are unsubstituted or substituted by 1,2 or 3 different or identical substituents selected from C ₁-C₄ alkyl and C ₁-C₄ alkoxy,

R ^e is hydrogen, C ₁-C₆ alkyl or C ₃-C₈ cycloalkyl, and

R ^f is hydrogen, C ₁-C₆ alkyl or C ₃-C₈ cycloalkyl.

In formulae AR-I、AR-II、AR-III、AR-IV、AR-V、AR-VI、AR-VII、AR-VIII、AR-IX、AR-X、AR-XI、AR-XII、AR-XIII、AR-XIV、AR-XV、AR-XVI、AR-XVII、AR-XVIII、AR-XIX、AR-XX、AR-XXI、AR-XXII and AR-XXIII, each of the radicals R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷、R¹⁸ and R ¹⁹, if present, is preferably selected from hydrogen, C ₁-C₂ alkyl, C ₁-C₂ alkoxy and carbazol-9-yl, which carbazol-9-yl can be substituted with 1 or 2 substituents selected from C ₁-C₂ alkyl, C ₁-C₂ alkoxy, phenyl, tolyl, xylyl, 2,4, 6-trimethylphenyl and anisoyl. In particular, each of groups R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷、R¹⁸ and R ¹⁹, if present, is selected from hydrogen, methyl, methoxy and carbazol-9-yl, which carbazol-9-yl is unsubstituted or substituted with 1 or 2 different or identical substituents selected from methyl, methoxy, phenyl, tolyl, xylyl, 2,4, 6-trimethylphenyl and anisoyl.

In formulas AR-XXV、AR-XXVI、AR-XXVII、AR-XXVIII、AR-XXIX、AR-XXX、AR-XXXI、AR-XXXII、AR-XXXIII、AR-XXXIV、AR-XXXV、AR-XXXVI、AR-XXXVII、AR-XXXVIII、AR-XXXIX、AR-XL、AR-XLI、AR-XLII、AR-XLIII、AR-XLIV、Ar-XLV、AR-LIII、AR-LIV、AR-LV、AR-LVI、AR-LVIII and AR-LIX, each of the groups R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵ and R ¹⁶, if present, is typically selected from hydrogen, C ₁-C₂ alkyl, C ₁-C₂ alkoxy and carbazol-9-yl, which carbazol-9-yl may be substituted with 1 or 2 substituents selected from the group consisting of C ₁-C₂ alkyl, C ₁-C₂ alkoxy, phenyl, tolyl, xylyl, 2,4, 6-trimethylphenyl and anisyl; R ^9a and R ^9b, if present, are each independently of the others typically hydrogen, C ₁-C₂ alkyl, phenyl or together form a group- (CH ₂)₄ -or- (CH ₂)₅ -). In particular, each of groups R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵ and R ¹⁶, if present, is selected from hydrogen, methyl, methoxy and carbazol-9-yl, which carbazol-9-yl may be substituted with 1 or 2 substituents selected from methyl, methoxy, phenyl, tolyl, xylyl, 2,4, 6-trimethylphenyl and anisoyl. In particular, R ^9a and R ^9b, if present, are each independently of the other hydrogen, methyl, phenyl or together form- (CH ₂)₄ -or- (CH ₂)₅ -group).

In the formulae AR-XLVI, AR-XLVI and AR-XLVI, the radicals R ¹、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R^9a、R^9b and R ^9c, if present, are selected from the group consisting of hydrogen, C ₁-C₂ alkyl, C ₁-C₂ alkoxy, phenyl, 1-naphthyl, 2-naphthyl, 9-fluorenyl and carbazol-9-yl, where phenyl, 1-naphthyl, 2-naphthyl, 9-fluorenyl or carbazol-9-yl are unsubstituted or substituted by 1 or 2 different or identical substituents selected from the group consisting of C ₁-C₂ alkyl and C ₁-C₂ alkoxy; furthermore, R ^9a and R ^9b in the formulae AR-XLVI, AR-XLVI and AR-XLIII may together form an alkylene radical (CH ₂)_r, R is 4, 5 or 6, in which 1 or 2 hydrogen atoms in the radical may be replaced by methyl or methoxy.

In the formulae AR-XXIV, AR-XLIX, AR-L, AR-LI and AR-LII, each R ³、R⁴、R⁵ and R ⁶, if present, is selected from the group consisting of hydrogen, C ₁-C₂ alkyl, C ₁-C₂ alkoxy, phenyl, 1-naphthyl, 2-naphthyl, 9-fluorenyl and 9-carbazolyl, wherein phenyl, 1-naphthyl, 2-naphthyl, 9-fluorenyl or 9-carbazolyl is unsubstituted or substituted by 1, 2 or 3 different or identical substituents selected from the group consisting of C ₁-C₂ alkyl and C ₁-C₂ alkoxy,

R ^e is hydrogen or methyl, and

R ^f is hydrogen or methyl.

Ar groups bonded to nitrogen atoms in the above formulae (AR-I) to (AR-XLVI) may be combined with each other as required.

Preferably, in the compounds (I), (i.a), (I.B), (i.c), (i.d), (I.E), (I.F), (I.G) and (I.H) wherein X is NAr ₂, and in the compounds of formula (i.3), (i.6), (I.9), (i.12), (i.15), (i.18), (i.21), (i.24), (i.25), (i.27), (i.30) and (i.33), one of the Ar groups bonded to the nitrogen atom is selected from Ar-XXIV, ar-XXV, ar-XXX, ar-XLVI, ar-XLVIII, ar-XLIX and Ar-L groups as defined above, and the other Ar group bonded to the nitrogen atom is selected from AR-I、AR-II、AR-IV、AR-XIX、AR-XXV、AR-XXIX、AR-XXX、AR-XXXI、AR-XXVIII、AR-XXXIV、AR-XLVI、AR-XLVII、AR-XLVIII、AR-XLIX、AR-LI、AR-LII、AR-LIII、AR-LVII、AR-LVIII、AR-LV and Ar-XXXIII groups as defined above.

More preferably, in compounds (I) and (I.A), (I.B), (I.C), (I.D), (I.E), (I.F), (I.G) and (I.H) wherein X is NAr ₂, and in compounds (I.A), (I.B), (I.C), (I.D), (I.E), (I.F), (I.G) and (I.H) wherein X is NAr ₂, and in compounds of formulae (I.3), (I.6), (I.9), (I.12), (I.15), (I.18), (I.21), (I.24), (I.25), (I.27), (I.30) and (I.33), and in compounds of formulae (I.36), (I.39), (I.42), (I.45), (I.48), (I.51), (I.54), (I.57), (I.60), (I.63), (I.66), (I.69) and (I.72),

One of the Ar groups is selected from the group AR-XIX as defined above and the other Ar group is selected from the group AR-XXV as defined above, or

One of the Ar groups is selected from the group AR-XXV as defined above and the other Ar group is selected from the group AR-XXIX as defined above, or

One of the Ar groups is selected from the group AR-XXV as defined above and the other Ar group is selected from the group AR-XXXI as defined above, or

One of the Ar groups is selected from the group AR-XXV as defined above, and the other Ar group is selected from the group AR-XLVI as defined above, or

One of the Ar groups is selected from the group AR-XXV as defined above and the other Ar group is selected from the group AR-XLVIII as defined above, or

One of the Ar groups is selected from the group AR-XXV as defined above, and the other Ar group is selected from the group AR-XLLVIII as defined above, or

One of the Ar groups is selected from the group AR-XXV as defined above, and the other Ar group is selected from the group AR-XLIX as defined above, or

One of the Ar groups is selected from the group AR-XXV as defined above and the other Ar group is selected from the group AR-L as defined above, or

One of the Ar groups is selected from the group AR-XXV as defined above, and the other Ar group is selected from the group AR-LI as defined above, or

One of the Ar groups is selected from the group of AR-XXV as defined above, and the other Ar group is selected from the group of AR-LII as defined above, or

One of the Ar groups is selected from the group AR-XXV as defined above, and the other Ar group is selected from the group AR-LIII as defined above, or

One of the Ar groups is selected from the group AR-XXV as defined above and the other Ar group is selected from the group AR-XXXIII as defined above, or

One of the Ar groups is selected from the group AR-XXV as defined above and the other Ar group is selected from the group AR-LVII as defined above, or

One of the Ar groups is selected from the group AR-XXV as defined above and the other Ar group is selected from the group AR-LVIII as defined above, or

2 Ar groups are each selected from the group consisting of AR-XXX as defined herein.

Specific examples of Ar groups include phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2, 4-dimethylphenyl, 2, 6-dimethylphenyl, 3, 5-dimethylphenyl, 2,4, 6-trimethylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 3, 4-dimethoxyphenyl, 2-phenylphenyl, 3-phenylphenyl, 4- (o-tolyl) phenyl, 4- (m-tolyl) phenyl, 4- (p-tolyl) phenyl, 4- (2, 6-dimethylphenyl) phenyl 1-methyl-4-phenyl, 2-methyl-4-phenyl, 3-methyl-4-phenyl, 2, 6-dimethyl-4-phenyl, 3-methyl-4- (o-tolyl) phenyl, 3-methyl-4- (m-tolyl) phenyl, 3-methyl-4- (o-tolyl) phenyl, 3-methyl-4- (2, 4, 6-trimethylphenyl) phenyl, 3-methyl-4- (2, 4-dimethylphenyl) phenyl, 3-methyl-4- (2, 6-dimethylphenyl) phenyl, 4- (4-methoxyphenyl) phenyl, 4-methoxy-3-phenyl, 3-methoxy-4-phenyl, 2-methoxy-5-phenyl, 2-methoxy-4, 5-diphenyl-phenyl, 3, 4-diphenyl-phenyl, 3, 5-diphenyl-phenyl, 3- (4-phenyl) phenyl, 4- (4-phenyl) phenyl 1, 3-Benzodioxol-5-yl, 3- (3, 5-diphenylphenyl) phenyl, 4-diphenylaminophenyl, 1-naphthyl, 2-naphthyl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-dimethylfluoren-2-yl 9-methyl-9-phenyl-fluoren-2-yl, 9-diphenylfluoren-2-yl, 9-dimethylfluoren-3-yl, 9-methyl-9-phenyl-fluoren-3-yl, 9-diphenylfluoren-3-yl, 9-dimethylfluoren-4-yl, 9-methyl-9-phenyl-fluoren-4-yl 9, 9-diphenylfluoren-4-yl, dibenzofuran-2-yl, dibenzofuran-3-yl, 9-methylcarbazol-2-yl, 9-phenylcarbazol-2-yl, 9-methylcarbazol-3-yl, 9-phenylcarbazol-3-yl, 4- (1-naphthyl) phenyl, 4- (2-naphthyl) phenyl, 4- (carbazol-9-yl) -phenyl, 4- (3, 6-dimethoxycarbazol-9-yl) phenyl, 4- (3, 6-dimethylcarbazol-9-yl) phenyl, 9' -spirobis (fluoren) -2-yl

Wherein # represents a bonding site to a nitrogen atom.

Also preferred, 2 Ar groups together with the nitrogen atom to which they are attached form an N-bonded carbazolyl group, 9H-acridin-10-yl group, 10H-phenazin-5-yl group, 10H-phenothiazin-10-yl group, indol-1-yl group, 10H-phenoxazin-10-yl group, benzotriazol-1-yl group, benzimidazol-1-yl group, indazol-1-yl group, which is unsubstituted or substituted with one or more, e.g., 1, 2, 3, 4 or more than 4 substituents R ^Ar3, wherein R ^Ar3 is as defined above. In particular, wherever it occurs, R ^Ar3 is phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl. Specific examples include carbazol-9-yl, 3, 6-di-tert-butylcarbazol-9-yl, 3-phenylcarbazol-9-yl, 3- (o-tolyl) carbazol-9-yl, 3- (m-tolyl) carbazol-9-yl, 3- (p-tolyl) carbazol-9-yl, 3- (m-anisoyl) carbazol-9-yl, 3- (p-anisoyl) carbazol-9-yl, 3, 6-diphenylcarbazol-9-yl, 3, 6-di (o-tolyl) carbazol-9-yl, 3, 6-di (m-tolyl) carbazol-9-yl, 3, 6-di (o-tolyl) carbazol-9-yl, 3, 6-di (m-anisoyl) carbazol-9-yl, 3, 6-di (p-anisoyl) carbazol-9-yl, 3, 6-dimethyl carbazol-9-yl and 3, 6-dimethoxy-carbazol-9-yl.

Specifically, regardless of where it occurs, -NAr ₂ is selected from formulas (A-1) to (A-112) set forth in Table A below. Table a:

/>

# denotes the bonding position to the rest of the molecule,

Ar is selected from the groups of formulae A-98 to A-112 in Table A, the groups of formulae (AR-I) to (AR-LVI) described above.

In particular, the NAr ₂ group, wherever it occurs, is selected from the groups of formulae (1) to (58):

/>

Wherein the method comprises the steps of

# Represents the bonding position to the rest of the compound.

In a specific embodiment, the compound of formula (I) is selected from the compounds indicated in the examples.

The compounds of formula (I) of the present invention and the starting materials for their preparation can be prepared in analogy to known organic chemical processes described in the literature. Substituents, variables and indices are as defined above for formula (I), unless otherwise indicated.

Pathway 1

One aspect of the present invention relates to a process for preparing a compound of formula (i.a1), as defined in the "summary of the invention" above, comprising steps a 1), a 2), a 3), and optionally a 4) (in the case of a compound (V.a) in which the substituent X is H provided in step a 1). In a specific embodiment, step a 1) comprises sub-steps a 11) and a 12).

Step a 1)

A compound of formula (V.a):

Wherein X is H or Br, can be prepared by one skilled in the art by conventional procedures. For example, 2-bromo-9-phenyl-9H-fluorene can be prepared by brominating 9-phenyl-9H-fluorene with elemental bromine. The educt 9-phenyl-9H-fluorene is commercially available from, for example, sigma-Aldrich/Merck. Alternatively 2-bromo-9-phenyl-9H-fluorene can be prepared as described in US2021/50523A1 by adding phenylmagnesium bromide to 2-bromofluorenone and reducing the resulting alcohol to a hydrocarbon, for example using triethylsilane and trifluoroacetic acid in dichloromethane.

In a specific embodiment of pathway 1, compound (V.a) is prepared in sub-steps a 11) and a 12) as outlined in the summary of the invention. First, a ketone of formula (ii.a) is provided. The compounds of the formula (ii.a) used as educts in step a 11) are commercially available or can be prepared by the person skilled in the art by routine procedures. In particular, 9-fluorenone, 2-bromo-9-fluorenone, xanthone (xanthone), 2-bromoxanthone, thioxanthone, N-phenylacridone, and numerous derivatives thereof are commercially available from, for example, sigma-Aldrich/Merck.

A compound of formula (iv.a):

Can be prepared by Grignard reaction of ketone (II.a) with aryl magnesium halide of formula (III) to give the corresponding alcohol of formula (IV.a) as intermediate. In an alternative embodiment, an aryl lithium compound may be used as nucleophile to react with the carbonyl group of ketone (ii.a) to give alcohol (iv.a). The reduction of the alcohol of formula (iv.a) to the corresponding compound of formula (V) can be carried out by treatment with a hydrosilane in the presence of a strong lewis acid, for example using triethylsilane in the presence of boron trifluoride THF-complex.

Step a 2)

Substitution of compound (V.a) with methallyl or isopentenyl can be carried out by reaction with compounds (vi.a1) and (vi.a2), respectively, wherein Z ^a is a leaving group such as halogen, mesylate, triflate, p-tosylate or besylate. Thus, a suitable compound (vi.a1) is the chloride 3-chloro-2-methyl-1-propene (methallyl chloride, isobutenyl chloride) and a suitable compound (vi.a2) is the chloride 1-chloro-3-methyl-but-2-ene (isopentenyl chloride). The substitution may also be carried out with other olefinic compounds to give structurally different compounds (I), for example with crotyl (but-2-en-1-yl: Z ^a-CH₂＝CHCH₃. The reaction is generally carried out in the presence of a base, such as an alkali metal hydroxide, optionally in the presence of a phase transfer catalyst, an alkali metal alkoxide or an alkali metal amide.

Step a 3)

In step a 3), the compound (vii.a1) or (vii.a2) is subjected to a cyclization reaction to produce a spiro compound. The cyclization is typically carried out in the presence of an acidic catalyst. Suitable catalysts are, for example, trifluoromethanesulfonic acid, trifluoroacetic acid, p-toluenesulfonic acid, methanesulfonic acid, sulfuric acid, hydrochloric acid, polyphosphoric acid, acidic ion exchangers and the like. As shown in the following scheme (but not bound by any theory), compound (vii.a1) results in the formation of a five-membered ring, while compound (vii.a2) results in the formation of a six-membered ring.

In the case where the substituent X in the cyclized product is Br or Cl, cyclizing directly gives the objective compound (I.a1).

Step a 4)

In the case where the substituent X is H in the cyclized product obtained in step a 3), the cyclized product may be subjected to bromination to obtain the objective compound (I.a1) wherein X is Br. The reaction may be carried out by direct bromination with elemental bromine. In a preferred embodiment, bromination is performed using N-bromosuccinimide (NBS). Preferably, a solvent containing or consisting of acetonitrile is used, and NBS is generally used in an amount of about 1 equivalent relative to the cyclized product. It was found that good site selectivity to the benzene ring position, as well as good chemical selectivity to the monobrominated product, was obtained using NBS bromination. Alternatively the cyclisation product from step a 3) wherein X is H may be nitrated to give compound (i.a1) wherein X is NO ₂. The reaction can be carried out by direct nitration with a nitrating acid, i.e. a mixture of concentrated nitric acid and concentrated sulfuric acid. Direct nitration yields the target compound with at least useful selectivity. The treatment of the brominated or nitrated product may be carried out by standard methods such as crystallization or column chromatography. The compound of formula (i.a1) wherein X is NO ₂ can be subjected to nitro reduction to give the corresponding primary amine (x=nh ₂).

Pathway 2

Step b 1)

Fluorenol, xanthenol (xanthol), thioxanthol (thioxanthol) and acridinium compounds of formula (ii.b) are commercially available or can be prepared by a person skilled in the art by conventional methods. Thus, a wide variety of fluorenol compounds (ii.b) can be prepared by reduction of the corresponding fluorenones with, for example, complex metal hydrides (e.g., sodium borohydride, potassium borohydride, lithium aluminum hydride, etc.), or hydrogenation in the presence of, for example, a diphosphine alkane/diamine Ru catalyst. As described in step a 11) above, a number of fluorenones, such as 2-bromo-9-fluorenone, are commercially available from, for example, sigma-Aldrich/Merck.

Step b 2)

The hydroxyl group of intermediate (ii.b) may be substituted with aromatic compound (iii.b) in the presence of an acidic catalyst to give compound (iv.b). Preferably, the compound (III.b) is selected from electron-rich aromatic compounds, in particular para-xylene, meta-trimethylbenzene (1, 2, 4-trimethylbenzene), 2, 6-dimethyl anisole, 2,3, 6-trimethyl anisole, 2,5, 6-trimethyl anisole or 2-phenyl anisole.

Compound (iii.b) may simultaneously act as a solvent. Suitable solvents are, in principle, those which do not participate in the reaction, generally halogenated hydrocarbons, ethers or deactivated aromatic hydrocarbons. Preferably the halogenated hydrocarbon is dichloromethane or 1, 2-dichloroethane. Preferably, the hydrocarbon is a commercially available heterogeneous hydrocarbon fraction, such as a hexane fraction, white spirit or light petroleum oil.

Suitable catalysts are protic acids, lewis acids, aluminum silicates, ion exchange resins, zeolites, naturally occurring sheet silicates or modified sheet silicates. Preferably, the catalyst is selected from p-toluene sulfonic acid. Further preferred as catalysts are zinc chloride and BF ₃ etherate. Also preferred are Zeolith from NortonNaturally occurring sheet silicates, in particular from Laporte Adsorbents co ]A shape; and modified sheet silicates, e.g., envirocat/>, from Contract ChemicalsEnvirocat/>Or Envirocat/>In particular, alCl ₃、PCl₅、P₄O₁₀ and HClO ₄ in nitromethane are not used as catalysts in step b 2).

Steps b 3), b 4) and b 5)

With respect to reaction steps b 3), b 4) and b 5), the above-described reaction steps a 2), a 3) and a 4) are cited.

Pathway 3

Step c 1)

The compounds of formula (iv.c) can be prepared analogously to compound (iv.a) by the reaction steps a 11) and a 12) described above.

Step c 2)

Olefins (VIII. C), such as 2-methyl-2-butene, are commercially available. The reaction of the compound (iv.c) with the olefin (viii.c) is carried out in the presence of a lewis acid, for example a BF ₃ ether complex, such as BF ₃ THF complex. Suitable solvents are halogenated hydrocarbons, such as dichloromethane or1, 2-dichloroethane.

Pathway 4

Step d 1)

The compound of formula (ii.d) applies to compound (ii.a) of step a 11) of pathway 1 above. Suitable starting materials for the illite reaction are, for example, phenethyl bromide, cinnamyl bromide or neophenyl chloride.

Step d 2)

Compound (iii.d) is commercially available or can be prepared by a person skilled in the art by conventional methods. For example, new phenyl chloride (1-chloro-2-methyl-2-phenylpropane) and the corresponding grignard compound 2-methyl-2-phenylpropyl magnesium chloride are commercially available from, for example, sigma-Aldrich/Merck. The grignard addition reaction is generally carried out at a temperature in the range of 0 to 90 ℃, preferably 10 to 80 ℃. The dehydration is generally carried out at the same temperature as the grignard reaction. Suitable acids for dehydration are hydrochloric acid, trifluoroacetic acid, p-toluenesulfonic acid, polyphosphoric acid and sulfuric acid. The reaction may advantageously be carried out as a one-pot reaction.

Step d 3)

The cyclization is typically carried out in the presence of an acidic catalyst. Suitable catalysts are, for example, trifluoromethanesulfonic acid, trifluoroacetic acid, p-toluenesulfonic acid, methanesulfonic acid, alCl ₃, sulfuric acid, hydrochloric acid, polyphosphoric acid, acidic ion exchangers, etc.

Pathway 5

Step e 1)

The compounds of formula (ii.e) are commercially available or can be prepared by a person skilled in the art by conventional methods. For example, diphenyl ether, 4-chlorodiphenyl ether, diphenyl sulfide, diphenyl amine, 4-chlorodiphenyl amine are commercially available.

Step e2

The metallization of the compound (ii.e) to give the compound (iii.3) can be carried out by reaction with an organolithium compound, such as n-butyllithium. In the alternative, if Y ³ is halogen, the reaction with magnesium results in the corresponding grignard compound. Alternatively, the Grignard reagent may be obtained by reacting an aryl halide with magnesium isopropylchloride in the presence of lithium chloride ("Turbo Grignard").

Step e3

Suitable 1-indanone compounds (iv.e) are commercially available or can be prepared by a person skilled in the art by conventional methods. For example, 1-indanone, 3-methyl-1-indanone, 3-dimethyl-1-indanone, alpha-tetralone (1, 2,3, 4-tetrahydro-1-naphthalenone), and the like are commercially available from, for example, sigma-Aldrich/Merck. 3, 3-dimethylindan-1-one may be prepared from 3-methyl-3-phenylbutyric acid by the methods described in the examples.

Preparation of arylamines (I.f1) and (I.f2)

The compound of formula (I) wherein X is a group of formula NHAr or NAr ₂ can be obtained in a process comprising steps f 11) and f 12) according to the Buchwald-Hartwig reaction by arylation reaction between a compound (I.f11) wherein X is selected from Cl, br, I and CF ₃SO₃ and a primary aromatic amine of formula (X.f1) or a secondary aromatic amine of formula (X.f2) in the presence of a palladium catalyst. In the alternative, the compound of formula (I) wherein X is a group of formula NHAr or NAr ₂ may be obtained in a process comprising steps f 21) and f 22) by arylation reaction between a primary aromatic amine of formula (x.f1) or a secondary aromatic amine of formula (x.f21) and an aromatic compound (X.f).

Suitable palladium catalysts or catalyst precursors are, for example, bis (dibenzylideneacetone) palladium (0) (Pd (dba) ₂), tris (dibenzylideneacetone) dipalladium (0) (Pd ₂(dba)₃), [1, 1-bis (diphenylphosphino) -ferrocene ] dichloropalladium (II) (PdCl ₂ (dppf)), palladium chloride (PdCl ₂), bis (acetonitrile) palladium chloride (Pd (ACN) ₂Cl₂), [1, 3-bis (2, 6-diisopropylphenyl) imidazol-2-ylidene ] (3-chloropyridyl) dichloropalladium (pep-iPr), [1, 3-bis (2, 6-bis-3-pentylphenyl) imidazol-2-ylidene ] (3-chloropyridyl) dichloropalladium (pep-iPent) or palladium acetate (Pd (OAc) ₂). Preferably, the catalyst is palladium acetate, pd (dba) ₂ or Pd ₂(dba)₃.

The reaction is generally carried out in the presence of a ligand. The ligand is any molecule that coordinates the palladium precursor and facilitates the Buchwald-Hartwig reaction, preferably a dialkylbiaryl phosphine or tri-t-butylphosphine. Examples of dialkylbiaryl phosphine ligands include 2-dicyclohexylphosphino-2 ' - (N, N-dimethylamino) biphenyl (DavePhos), 2-dicyclohexylphosphino-2 ',4',6' -triisopropylbiphenyl (Xphos), 2-dicyclohexylphosphino-2 ',6' -dimethoxybiphenyl (Sphos), 2-di-tert-butylphosphino-2 ',4',6' -triisopropylbiphenyl (tBuXPhos), (2-biphenylyl) dicyclohexylphosphine, 2- (dicyclohexylphosphino) biphenyl (CyJohnPhos), (2-biphenylyl) di-tert-butylphosphine (JohnPhos), 2-dicyclohexylphosphino-2 ',6' -diisopropylbiphenyl (RuPhos), 2-di-tert-butylphosphino-2 ' -methylbiphenyl (tBuMePhos), 2-di-tert-butylphosphino-3, 4,5, 6-tetramethyl-2 ',4',6' -triisopropyl-1, 1' -biphenyl, 2-di-tert-butylphosphino-2 ' -methylbiphenyl (tBuMePhos), 2-di-tert-butylphosphino-3, 4',6' -triisobutylphosphino-2, 6' -dimethylbiphenyl (tBuMePhos), and 2-di-tert-butylphosphino-2 ',6' -trimethylphosphine (4, 6' -triisopropylphosphine). 6 '-triisopropyl-1, 1' -biphenyl (BrettPhos) or Amphos. The palladium catalyst and phosphine ligand are preferably used in a molar ratio of ligand in the range of about 0.5 to about 5 moles per mole of palladium catalyst.

Typically the reaction is carried out in the presence of a base, such as an alkali metal alkoxide, alkaline earth metal alkoxide, alkali metal carbonate or alkaline earth metal carbonate, alkali metal amide or trialkylamine. Preferably, the base is sodium tert-butoxide, cesium carbonate, lithium bis (trimethylsilyl) amide, sodium bis (trimethylsilyl) amide, potassium bis (trimethylsilyl) amide, lithium diisopropylamide or lithium dicyclohexylamide. More preferably, the base is sodium t-butoxide.

The reaction is usually carried out in a solvent. Suitable solvents are, for example, aliphatic hydrocarbons, such as pentane, hexane, cyclohexane and petroleum ether; aromatic hydrocarbons such as toluene, ortho, meta, and para-xylene; ethers such as diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran and dimethoxyethane; amides, such as dimethylformamide or N-methylpyrrolidone. The reaction temperature is generally in the range between 50 and 130 ℃. The reaction is typically operated under an inert atmosphere (e.g., under dry nitrogen or argon).

Suitable secondary amines and processes for their preparation are described in the literature, for example, in WO 2018/206769 A1, WO 2012/015265 A1, CN 111675687A, CN 111848642A, WO 2021/141356 A1.

Preparation of heteroaryl substituted spiro compounds g 1)

The compounds of formula (I) wherein X is a substituted pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl or triazinyl group can be obtained in a process comprising steps g 1) and g 2) according to the Suzuki reaction in the presence of a palladium catalyst by a coupling reaction between a compound (i.g1) wherein X is a boronic acid or boronic ester group and a heteroaromatic compound (X.g).

Preferably, in group B (OR ^B1)(OR^B2), R ^B1 and R ^B2 are each independently of the other hydrogen OR C ₁-C₆ alkyl, OR R ^B1 together with R ^B2 form a C ₂-C₆ -alkanediyl moiety, for example ethane-1, 2-diyl, propane-1, 3-diyl OR 1, 2-tetramethylethane-1, 2-diyl.

The boronated compound (i.g1) may be prepared via a Miyaura boronation reaction, for example by treating the corresponding compound in which X is selected from bromo, chloro or trifluoromethanesulfonate groups with diboronic acid, or by metallizing and reacting the metallized product with a borate when X is halogen.

The compounds of the invention are particularly suitable for use in electronic devices. An electronic device here refers to a device comprising at least one layer comprising at least one organic compound.

The invention thus further relates to the use of a compound of formula (I) or a mixture of at least two different compounds of formula (I):

as Hole Transport Materials (HTM) in organic electronics,

As Electron Blocking Material (EBM) in an organic electronic device,

Use in Organic Light Emitting Diodes (OLEDs), in particular for displays and illumination of electronic devices,

For electrophotography, in particular as photoconductive material in Organic Photoconductors (OPC),

-For organic optical detectors, organic photoreceptors, organic field quench devices (O-FQDs), light-emitting electrochemical cells (LECs) and organic laser diodes.

The compounds of the invention are particularly suitable as Hole Transport Materials (HTM) in organic electronic devices. HTM is used in a wide range of electronic devices and applications, such as organic Electroluminescent (EL) devices and solar cells.

The compounds of the invention may be used as HTM alone or in combination with at least one other HTM. Suitable other hole transport materials are known in the art. Preferred hole transporting materials for the combination are spiro-OMeTAD, 2', 7' -tetrakis (N, N '-di-4-methoxy-3, 5-dimethylphenylamine) -9,9' -spirofluorene, tris (P-anisoyl) amine, N, N, N ', N' -tetrakis (4-methoxyphenyl) -1,1 '-biphenyl-4, 4' -diamine, 2, 7-bis [ N, N-di (4-methoxyphenyl) amino ] -9, 9-spirobifluorene, poly (3-hexylthiophene) (P3 HT), poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonate) (PEDOT: PSS), poly [ di (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] (PTAA), niO and V ₂O₅.

Furthermore, the compounds of the invention as HTM may be combined with at least one further additive. Suitable additives are pyridine compounds, such as tert-butylpyridine; imidazoles as disclosed in WO2013/026563 claims 1 to 15, and pages 15 to 17; or polymer additives such as poly (4-vinylpyridine), or copolymers thereof with, for example, vinyl styrene or alkyl methacrylates. The preferred pyridine compound is t-butylpyridine.

The compounds of the invention as HTM may be combined with lithium salts as described in Phys.Chem., chem.Phys,2013,15,1572-2579.

The usefulness of pyridine compounds is described in Sol.

In addition, the compounds of the invention that can be used as HTM can be combined with p-dopants such as N(C₆H₅Br)₃、SbCl₆、V₂O₅、MoO₃、WO₃、Re₂O₃、F₄-TCNQ( tetrafluorotetracyanoquinodimethane), HAT-CN (1,4,5,8,9,11-hexa-terphenyl hexacarbonitrile), F6-TCNNQ (1, 3,4,5,7, 8-hexafluorotetracyanoquinodimethane, from Novaled), NDP-9 (a p-dopant from Novaled) or Co complex salts. Suitable dopants are described in chem. Suitable [3] -decenes (radialenes) as described in EP 2,180,029 A1 can also be used.

The invention further relates to an electroluminescent device comprising an upper electrode, a lower electrode, wherein at least one of the electrodes is transparent, an electroluminescent layer, and optionally an auxiliary layer, wherein the electroluminescent device comprises at least one compound of formula (I). The same preferences apply to the substrate as previously described. In particular, at least one compound of formula (I) or (i.a) is used in the hole transport layer or the electron blocking layer.

The invention further relates to an electroluminescent device in the form of an Organic Light Emitting Diode (OLED). In the organic light emitting device, an electron blocking layer is disposed adjacent to an emission layer. The blocking layer may be used to reduce the number of charge carriers (electrons or holes) and/or excitons that leave the emissive layer. An electron blocking layer may be disposed between the emissive layer and the hole transport layer to block electrons from exiting the emissive layer in a direction from the hole transport layer. Similarly, a hole blocking layer may be disposed between the emissive layer and the electron transport layer to block holes from exiting the emissive layer in the direction of the electron transport layer.

OLEDs can be used in a variety of applications, such as single or multi-color displays, lighting applications, or pharmaceutical and/or cosmetic applications, such as phototherapy.

An organic electroluminescent device, in particular in the form of an OLED, comprises a cathode, an anode and at least one emissive layer. In addition to these layers, further layers, for example in each case one or more hole-injecting layers, hole-transporting layers, hole-blocking layers, electron-transporting layers, electron-injecting layers, exciton-blocking layers, electron-blocking layers and/or charge-generating layers, may also be included. An intermediate layer having, for example, an exciton blocking function can likewise be introduced between the two emission layers. It should be noted, however, that each of these layers need not be present.

Here, the organic electroluminescent device may include one emission layer or a plurality of emission layers. If a plurality of emission layers are present, they preferably have a total of a plurality of emission maxima between 380 nm and 750 nm, an overall white light is achieved, i.e. various luminescent compounds capable of fluorescing or phosphorescing are used in the emission layers. Particularly preferred is a system with three emissive layers, wherein the three layers exhibit blue, green and orange or red emission (see e.g. WO 2005/01013 for basic structure). Here, all of the emissive layers may be fluorescent, or all of the emissive layers may be phosphorescent, or one or more of the emissive layers may be fluorescent and one or more of the other layers may be phosphorescent.

Depending on the exact structure, the compounds according to the invention according to the embodiments described above can be used here in different layers. Preferably the organic electroluminescent device comprises a compound of formula (I) or a preferred embodiment as a hole transporting material in a hole transporting or hole injecting or electron blocking layer, or as a host material for fluorescent or phosphorescent emitters, in particular phosphorescent emitters. The preferred embodiments described above are also applicable to the use of materials in organic electronic devices.

In a preferred embodiment of the present invention, the compound of formula (I) or a preferred embodiment is used as a hole transporting or hole injecting material in a hole transporting or hole injecting layer. The emissive layer may be fluorescent or phosphorescent in this case.

The hole injection layer is typically a layer that aids in the injection of electrons from the anode into the organic layer. The hole injection layer may be located immediately adjacent to the anode.

The hole transport layer transports holes from the anode to the emissive layer and is located between the hole injection layer and the emissive layer.

To enhance the hole transport characteristics, a doped hole transport layer may be used. The architecture of practical OLEDs often improves quantum efficiency by using graded heterojunctions. In a graded heterojunction architecture, the composition of the hole and electron transporting materials is continuously changed within the emissive layer with the dopant emitter. The graded heterojunction architecture combines the benefits of both conventional architectures by improving charge injection while balancing charge transport within the emission region.

In a further preferred embodiment of the present invention, the compounds of formula (I) or preferred embodiments thereof are used in an electron blocking layer. The electron blocking layer may be used to reduce the number of charge carriers (electrons) that leave the emissive layer. The electron blocking layer is typically a layer immediately adjacent to the emissive layer on the anode. An electron blocking layer may be disposed between the emissive layer and the hole transport layer to block electrons from exiting the emissive layer in a direction from the hole transport layer.

The compounds of the formula (I) or preferred embodiments thereof are particularly preferably used for hole transport layers or electron blocking layers.

In a further preferred embodiment of the present invention, the compounds of the formula (I) or preferred embodiments thereof are used as matrix materials for fluorescent or phosphorescent compounds, in particular phosphorescent compounds, in the emissive layer. Here, the organic electroluminescent device may comprise one emission layer or a plurality of emission layers, wherein at least one emission layer comprises at least one compound of the present invention as a host material.

If a compound of formula (I) or a preferred embodiment thereof is used as matrix material for the emissive compound in the emissive layer, it is preferably used in combination with one or more phosphorescent materials (triplet emitters). For the purposes of the present application, phosphorescence refers to luminescence from an excited state, in particular from an excited triplet state, of spin multiplex > 1. For the purposes of the present application, all luminescent complexes containing overmetallics or lanthanides, in particular all luminescent iridium, platinum and copper complexes, are regarded as phosphorescent compounds.

The mixture comprising the compound of formula (I) or a preferred embodiment and the luminescent compound comprises between 99.9 and 1 wt. -%, preferably between 99 and 10 wt. -%, more preferably between 97 and 60 wt. -%, in particular between 95 and 80 wt. -% of the compound of formula (I) or a preferred embodiment, based on the total mixture comprising the emitter and the compound of formula (I). Correspondingly, the mixture comprises between 0.1 and 99% by weight, preferably between 1 and 90% by weight, more preferably between 3 and 40% by weight, in particular between 5 and 20% by weight, of emitters, based on the overall mixture comprising emitters and the compound of formula (I).

A further object of the present invention is the use of at least one compound of formula (I) as defined above in Organic Solar Cells (OSCs). The compounds of the general formula (I) are used in particular as hole transport materials or electron blocking materials in organic solar cells.

Organic solar cells generally have a layer structure and generally comprise at least the following layers: an anode, a photoactive layer, and a cathode. These layers are generally suitable for substrates suitable for this purpose. The structure of organic solar cells is described, for example, in US 2005/0098726 and US 2005/0224905.

The present invention provides an organic solar cell comprising a substrate having at least one cathode and at least one anode, and a material comprising at least one compound of formula (I) as defined above as at least one layer. The organic solar cell of the present invention comprises at least one photoactive region. The photoactive region may comprise two layers, each having a uniform composition and forming a planar donor-acceptor heterojunction. The photoactive region may also comprise a mixed layer and form a donor-acceptor heterojunction in the form of a donor-acceptor bulk heterojunction.

Accordingly, the present invention also relates to an organic solar cell comprising:

A cathode which is arranged to be electrically connected to the anode,

The anode is a metal-oxide-semiconductor anode,

One or more photoactive regions comprising at least one donor material and at least one acceptor material in separate layers or in the form of a bulk heterojunction layer,

Wherein the organic solar cell comprises at least one compound of formula (I) as defined above or a composition comprising at least two different compounds of formula (I) as defined above.

In a first embodiment, the heterojunction may have a planar configuration (see Two layer organic photovoltaic cell, C.W.Tang, appl.Phys.Lett.,48 (2), 183-185 (1986), or n.karl, a.bauer, J.J.Marktanner,M./>F./>Mol. Cryst. Liq. Cryst.,252,243-258 (1994)).

In a second embodiment, the heterojunction may be a bulk heterojunction, also known as an interpenetrating donor-acceptor network. Organic photovoltaic cells with bulk heterojunction are described, for example, in c.j.brabec, n.s.sariciftci, adv.funct.mate of j.c. hummelen, 11 (1), 15 (2001), or j.xue, b.p.rand, s.uchida, and s.r.forrest, j.appl.Phys.98,124903 (2005).

The compounds of formula (I) can be used in batteries having a MiM, pin, pn, mip or Min structure (m=metal, p=p-doped organic or inorganic semiconductor, n=n-doped organic or inorganic semiconductor, i=intrinsically conductive system of the organic layer; see for example org.electron, 5 (4), 175 (2004), or Maennig et al appl.Phys.a 79,1-14 (2004)).

The compounds of formula (I) may also be used in tandem cells. Tandem cells are described, for example, in J.appl.Phys,93 (7), 3693-3723 (2003) of P.Peumans, A.Yakimov, S.R.Forrest. The tandem cell is composed of two or more sub-cells. Individual subcells, some subcells, or all subcells may have a photoactive donor-acceptor heterojunction. Each donor-acceptor heterojunction may be in the form of a planar heterojunction or in the form of a bulk heterojunction. The subcells forming the tandem cell may be connected in parallel or in series. Preferably, there is an additional recombination layer between the individual subcells in each case. The individual sub-cells have the same polarity, i.e., typically, cells having only a forward structure are combined with each other or cells having only a reverse structure are combined with each other.

Suitable substrates for organic solar cells are, for example, oxide materials, polymers, and combinations thereof. Preferred oxide materials are selected from glass, ceramic, siO ₂, quartz, and the like. Preferred polymers are selected from the group consisting of polyethylene terephthalate, polyolefins (such as polyethylene and polypropylene), polyesters, fluoropolymers, polyamides, polyurethanes, polyalkyl (meth) acrylates, polystyrene, polyvinylchloride and mixtures and composites.

Suitable electrodes (cathode, anode) are in principle semiconductors, metal alloys, semiconductor alloys, and combinations thereof. Preferred metals are those of groups 2, 8, 9, 10, 11 or 13 of the periodic table, for example Pt, au, ag, cu, al, in, mg or Ca. Preferred semiconductors are, for example, doped Si, doped Ge, indium Tin Oxide (ITO), fluorinated Tin Oxide (FTO), gallium Indium Tin Oxide (GITO), zinc Indium Tin Oxide (ZITO), and the like. Preferred metal alloys are, for example, pt, au, ag, cu et al based alloys.

The material for the light-facing electrode (anode in the forward configuration and cathode in the reverse configuration) is preferably a material that is at least partially transparent to the incident light. It preferably comprises an electrode with glass and/or a transparent polymer as carrier material. Electrical contact connections are typically made through metal layers and/or Transparent Conductive Oxides (TCOs). It preferably includes ITO, doped ITO, FTO (fluorine doped tin oxide), AZO (aluminum doped tin oxide), znO, tiO ₂, ag, au, pt. In a specific embodiment, the material of the electrode for facing away from the light (cathode in the forward configuration and anode in the reverse configuration) is a material that at least partially reflects the incident light. Including metal films, preferably Ag, au, al, ca, mg, in, and mixtures thereof.

In a first embodiment, the organic solar cell according to the invention is a single cell with a flat heterojunction and forward structure. In one embodiment, the battery has the following structure:

An at least partially transparent conductive layer (upper electrode, anode),

A hole conducting layer (hole transport layer, HTL),

A layer comprising a donor material and a layer comprising a donor material,

A layer comprising a material of the receptor,

Exciton blocking and/or electron conducting layers,

A second conductive layer (back electrode, cathode).

In a second embodiment, the organic solar cell according to the invention is a single cell with a flat heterojunction and inverted structure. In one embodiment, the battery has the following structure:

an at least partially transparent conductive layer (cathode),

Exciton blocking and/or electron conducting layers,

A layer comprising a material of the receptor,

A layer comprising a donor material and a layer comprising a donor material,

A hole conducting layer (hole transport layer, HTL),

A second conductive layer (back electrode, anode).

In a third embodiment, the organic solar cell according to the invention is a single cell with a forward structure and a bulk heterojunction. In one embodiment, the battery has the following structure:

an at least partially transparent conductive layer (anode),

A hole conducting layer (hole transport layer, HTL),

A mixed layer comprising a donor material and an acceptor material forming a donor-acceptor heterojunction in the form of a bulk heterojunction,

An electron-conducting layer,

Exciton blocking and/or electron conducting layers,

A second conductive layer (back electrode, cathode).

In a fourth embodiment, the organic solar cell according to the invention is a single cell with a reverse structure and with a bulk heterojunction.

Examples of different kinds of donor-acceptor heterojunctions are donor-acceptor bilayers with flat heterojunctions, or heterojunctions designed as hybrid planar hybrid heterojunctions or gradient bulk heterojunctions or annealed bulk heterojunctions. Fabrication of hybrid planar hybrid heterojunctions is described in adv. In this structure, there is a mixed heterojunction layer formed by simultaneous evaporation of the acceptor and donor materials between the uniform donor and acceptor materials. In yet another specific embodiment, the donor-acceptor-heterojunction is in the form of a gradient bulk heterojunction. In a mixed layer composed of donor and acceptor materials, the donor-acceptor ratio gradient changes. In yet another embodiment, the donor-acceptor-heterojunction is designed as an annealed bulk heterojunction; see, for example, nature 425,158-162,2003. Methods of fabricating such solar cells include an annealing step before or after metal deposition. As a result of annealing, the donor and acceptor materials can separate, resulting in more extended percolation paths.

A further object of the present invention is the use of at least one compound of formula (I) or (i.a) as defined above in solid state Dye Sensitized Solar Cells (DSSCs) or perovskite solar cells. These compounds are used in particular as substitutes for liquid electrolytes in dye-sensitized solar cells and as hole transport materials in perovskite solar cells.

The compounds of formula (I) or (i.a) can be advantageously used as HTMs in perovskite solar cells. It can also be used to provide solid-state DSSC devices instead of the liquid electrolyte of conventional DSSCs.

The compounds of the invention are therefore preferably used for photosensitizing nanoparticle layers which comprise a sensitizing dye or perovskite and at least one compound of the general formula (I) according to the invention.

In a first embodiment, the compounds of the invention are used for the neutralization of DSSCs. DSSC configurations are typically based on a transparent substrate coated with a transparent conductive layer, the working electrode. The n-conductive metal oxide is typically applied to the electrode or its vicinity, for example a nanoporous TiO ₂ layer about 2 to 20 microns thick. On its surface, in turn, typically adsorbs a monolayer of photosensitizing dye, which can be converted to an excited state by light absorption. This layer carrying the photosensitizing dye is commonly referred to as the light absorbing layer of DSSC. The counter electrode may optionally have a metal catalytic layer, such as a platinum catalytic layer, that is several microns thick.

In principle, all sensitizing dyes are suitable as long as the LUMO energy state is slightly higher than the conducting band edge of the photoelectrode to be sensitized. Examples of dyes are disclosed in Nanoenergy, de so za, flavio Leandro, leite, edson Roberto (eds.), springer, ISBN 978-3-642-31736-1, pages 58 to 74, or black dyes as described in US 8,383,553. Preferred dyes are described in WO 2015049031 A1, which is incorporated herein by reference.

In a second embodiment, the compounds of the invention are used in perovskite solar cells. Perovskite suitable for Perovskite Solar Cells (PSCs) are known in the art. In principle, the perovskite material comprised by the device according to the invention may be part of the charge transport layer, but may also be part of another layer or be a frame within the device.

Suitable perovskite materials may comprise two halides corresponding to formula Xa _p-X Xb (x), where Xa and Xb are each independently selected from CI, br or I, and x is greater than 0 and less than 3. Suitable perovskite materials are also disclosed in WO 2013/171517, claims 52 to 71 and claims 72 to 79, which are incorporated herein by reference in their entirety. Suitable perovskite materials are CsSnI₃、CH₃NH₃PbI₂Cl、CH₃NH₃PbI₃、CH₃NH₃Pb(I_1-xBr_x)₃、CH₃NH₃SnI₂Cl、CH₃NH₃SnI₃ or CH ₃NH₃Sn(I_1-xBr_x)₃, and 0< x <1.

Preferred perovskite materials are disclosed on page 18, lines 5 to 17 of WO 2013/171517. As stated, the perovskite is generally selected from CH₃NH₃PbBrI₂、CH₃NH₃PbBrCl₂、CH₃NH₃PbIBr₂、CH₃NH₃PbICl₂、CH₃NH₃SnF₂Br、CH₃NH₃SnF₂I and (H ₂N＝CH-NH₂)PbI_3zBr_3(1-z), where z is greater than 0 and less than 1.

The charge transport layer of the present invention as described above or the device of the present invention as described above or below may further comprise an insulator, such as alumina, as described in Science,338,643,2012 of Michael M.Lee et al.

The charge transport layer of the present invention or the device of the present invention as described above or below may further comprise semiconducting oxide nanoparticles. The charge transport layer of the invention or the device of the invention preferably comprises semiconducting oxide nanoparticles.

According to a preferred embodiment of the invention, the semiconductor is based on a material selected from Si、TiO₂、SnO₂、Fe₂O₃、WO₃、ZnO、Nb₂O₅、CdS、ZnS、PbS、Bi₂S₃、CdSe、GaP、InP、GaAs、CdTe、CuInS₂ and/or CuInSe ₂.

Preferably, the charge transport layer of the invention as described above is present on a glass support or plastic or metal foil, optionally together with a dense layer of TiO ₂. Preferably, the carrier is electrically conductive.

The invention further relates to an electronic or optoelectronic device comprising a charge transport layer as described or preferably as described above. Preferably, the invention further relates to a solid state dye sensitized solar cell comprising a charge transport layer as described or preferably as described above. Suitable inventive device structures further comprising mixed perovskite halides are described in claims 52 to 71 and claims 72 to 79 of WO 2013/171517, which are incorporated herein by reference in their entirety.

Suitable inventive device structures further comprising a dielectric framework in conjunction with perovskite material are described in claims 1 to 90 of WO 2013/171518 or claims 1 to 94 of WO 2013/171520, which are incorporated herein by reference in their entirety.

Suitable inventive device structures further comprising semiconductor and perovskite materials are described in WO 2014/020499 claims 1 and 3 to 14, which are incorporated herein by reference in their entirety. The surface-increasing framework structures described therein comprise nanoparticles, which are applied to and/or immobilized on a support layer, such as porous TiO ₂.

Suitable inventive device structures comprising planar heterojunctions are described in WO 2014/045021 claims 1 to 39, which are incorporated herein by reference in their entirety. Such devices feature a thin film with a light absorbing or emitting perovskite disposed between n-type (electron conducting) and p-type (hole conducting) layers. Preferably, the film is a compact film. Furthermore, the present invention relates to a method of preparing an electrochemical device and/or an optoelectronic device as described above or preferably as described above, the method comprising the steps of:

-providing a first and a second electrode;

Providing a charge transport layer of the invention as described above. The choice of the first and second electrodes is itself unlimited. The substrate may be rigid or flexible.

The abbreviations used in the following examples are as follows:

Al: aluminum;

DCM: dichloromethane;

HPLC: high performance liquid chromatography;

HSQC: heteronuclear single quantum coherence

ITO: indium tin oxide;

NDP-9, NHT-18: type Novaled n dopants are commercially available from Germany Novaled AG, germany;

and (3) NMR: nuclear magnetic resonance;

Pd (dba) ₂: bis (dibenzylideneacetone) palladium (0);

Pd ₂(dba)₃: tris (dibenzylideneacetone) dipalladium (0);

RuPhos: 2-dicyclohexylphosphino-2 ',6' -diisopropyloxybiphenyl;

SPhos: 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl;

TBME: t-butyl methyl ether;

THF: tetrahydrofuran;

v/v: volume/volume.

Other definitions: room temperature means a temperature range of about 20 to 25 ℃. Overnight represents a period in the range of 14 to 20 hours.

Examples

I) Preparation of intermediates

I.a) aryl bromide and aryl chloride precursors

Example 1:

2-bromo-2 ',3' -dihydrospiro- [ fluorene-9, 1' -indene ]

Step 1 a):

(E) -2-bromo-9- (2-phenylethylene) -9H-fluorene

A three-necked flask equipped with a reflux condenser and a dropping funnel was charged with magnesium shavings (5.49 g, 226 mmol, 1.5 eq.) and THF (20 ml) under an inert atmosphere. The resulting mixture was heated to 50 ℃. Initially, about 5% of the total 2-bromoethylbenzene was added to the flask via a dropping funnel containing 41.8 g (226 moles) of 2-bromoethylbenzene. After the start of the grignard reaction, additional THF (150 ml, 1.5 eq) was added followed by the slow addition of the remaining 2-bromoethylbenzene while maintaining the temperature in the temperature range between 40 and 50 ℃. A solution of 2-bromo-9-fluorenone (38.9 g, 150 mmol, 1.0 eq.) in THF (150 ml) at 60℃was then added to the flask at reflux over 15 minutes. After the end of the addition, the reaction mixture was kept stirring for 3 hours while being cooled to room temperature. The reaction mixture was then carefully poured into ice-cold 2M aqueous monoammonium citrate (250 ml). Heptane (200 ml) was added and the organic layer separated. The solvent was removed by rotary evaporation and the crude product was dissolved in glacial acetic acid (75 ml). This solution was added to a solution of 96% sulfuric acid (21.6 g, 116 mmol) in glacial acetic acid (150 ml) at 60 to 75 ℃. The resulting mixture was stirred at 60 ℃ for an additional 15 minutes and then poured into water (450 ml). The product was extracted with heptane (200 ml). The organic layer was separated and washed with 20% aqueous sodium hydroxide (150 ml). The organic layer was dried over MgSO ₄, evaporated and purified by column chromatography (silica gel, cyclohexane) to give the product as a mixture of E-and Z-isomers in a yield of 20.9 g (40%) based on 2-bromofluorenone.

¹³C NMR：(101MHz,CS₂ : Acetone (acetone) -d₆ 5:1)：δ＝141.34(q),140.20(q),140.01(q),139.44(q),139.36(q),139.19(q),139.14(q),137.88(q),137.65(q),137.16(q),135.35(q),135.32(q),131.02(p),130.63(p),130.63(p),130.42(p),129.03(p),129.01(p),128.77(p),128.75(p),128.50(p),128.12(p),128.03(p),127.65(p),127.65(p),126.84(p),126.80(p),125.12(p),123.52(p),121.48(q),121.35(q),121.29(p),121.02(p),120.21(p),120.19(p),119.80(p),36.05(s),36.03(s).

Step 1 b):

2-bromo-2 ',3' -dihydrospiro- [ fluorene-9, 1' -indene ]

A solution of the product from step 1 a) (20.9 g, 57.5 mmol) in o-dichlorobenzene was added dropwise over 1 hour at a temperature of 60 to 75 ℃ to a solution of trifluoromethanesulfonic acid (4.36 g, 28.8 mol) in o-dichlorobenzene (200 ml). The reaction mixture was stirred at this temperature for another 30 minutes, then cooled to room temperature and quenched by the addition of triethylamine (8.7 g, 86 mmol). The solvent was removed by rotary evaporation and the crude product was partitioned between heptane (200 ml) and water (50 ml). The organic layer was separated and filtered through a pad of silica gel, which was subsequently washed with heptane (1.0 l). The product was then further purified by repeated column chromatography (silica gel, heptane) and crystallization from 94% ethanol (10 ml/g) to yield the title compound as a colorless solid (6.3 g, 38%).

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC),CS₂: acetone (acetone) -d₆ 5:1)：δ/δ＝(32.41/3.42,CH₂),(40.09/2.63,CH₂),(63.25,C-q),(120.13/7.73,CH),(121.42/7.65,CH),(121.79,C-q),(123.70/6.39,CH),(124.03/7.15,CH),(125.17/7.39,CH),(127.22/7.00,CH),(127.31/7.28,CH),(127.68/7.19,CH),(127.76/7.34,CH),(128.31/7.25,CH),(130.57/7.45,CH),(138.95,C-q),(138.97,C-q),(144.19,C-q),(146.77,C-q),(152.28,C-q),(154.76,C-q).

Example 2:

2-bromo-3 ',3' -dimethyl-2 ',3' -dihydro-spiro- [ fluorene-9, 1' -indene ]

Step 2 a):

Bromination of 2-bromo-9-phenyl-9H-fluorene via 9-phenyl-9H-fluorene

9-Phenyl-9H-fluorene (153 g, 0.63 mol) was dissolved in o-dichlorobenzene (550 ml) at 60 ℃. The solution was cooled to 45 ℃ and about 20% of the total (101 g, 0.63 mole) bromine was added. The solution was stirred for 20 minutes, followed by the addition of the next 20% bromine. After cooling to 25 ℃, the next 20% bromine was added. When the vigorous HBr release ceased, 20% of the total of the remaining two portions of bromine was added. The reaction mixture was then stirred at 20 ℃ for 16 hours. The reaction mixture was cooled to 5 ℃ and additional bromine (15 g, 94 mmol) was added at 5-10 ℃. The mixture was stirred overnight then brought to room temperature and quenched by the addition of 20% aqueous NaOH (200 ml). The organic layer was separated and methanol (1650 ml) was slowly added with stirring at 20 ℃. The product was crystallized over a period of 1 hour. It was filtered, washed with a 1:3v/v mixture of o-dichlorobenzene and methanol (50 ml), followed by methanol (50 ml) to give 33.3 g of product. A second portion was obtained from the filtrate after adding water (18 ml), followed by stirring for 16 hours. The crystals were filtered and washed with a 1:3v/v mixture of o-dichlorobenzene and methanol (50 ml), followed by methanol (50 ml) to give a total of 41.3 g (32%) of product.

¹³C NMR:(101MHz,CDCl₃):δ＝149.92(q),147.63(q),140.70(q),140.02(2C,q),130.55(p),128.89(2C,p),128.62(p),128.35(2C,p),127.79(p),127.58(p),127.18(p),125.44(p),121.24(p),121.09(q),119.99(p),54.39(p). The spectroscopic data are consistent with those shown in J.org.chem.2017,82,18,9675-9681.

Alternatively 2-bromo-9-phenyl-9H-fluorene can be prepared as described in US2021/50523A1, comprising adding phenylmagnesium bromide to 2-bromofluoren-9-one and reducing the resulting alcohol to hydrocarbons with triethylsilane and trifluoroacetic acid in dichloromethane. The NMR data of the product were identical to those obtained by the above steps.

Step 2 b):

2-bromo-9- (2-methylallyl) -9-phenyl-9H-fluorene

To a solution of the material from step 2 a) (74.7 g, 232 mmol) in THF (200 ml) at a temperature between 25 and 35 ℃ under an inert atmosphere was added sodium tert-butoxide (27.6 g, 279 mmol) in small portions. The mixture was stirred at 30 ℃ for 30 minutes, then methallyl chloride (27.3 g, 302 mmol) was added over 15 minutes. After stirring for a further 15 minutes, the reaction mixture was filtered through a pad of silica gel. The filter pad was then rinsed with TBME (100 ml). The solvent was removed from the combined filtrates using a rotary evaporator. The residue was crystallized from a mixture of ethyl acetate (100 ml) and isopropanol (100 ml). The product was filtered and washed with a mixture of the same solvents (30 ml). After drying 71.7 g (90%) of the product are obtained as a white solid.

¹³C NMR:(101MHz,CDCl₃):δ＝153.50(q),151.05(q),144.44(q),141.06(q),139.91(q),139.84(q),130.45(p),128.56(p),128.34(p),127.71(p),127.51(p),126.77(p),126.50(p),125.21(p),121.31(p),120.99(q),120.03(p),115.51(s),58.93(q),45.48(s),24.08(t).

Step 2 c):

2-bromo-3 ',3' -dimethyl-2 ',3' -dihydro-spiro- [ fluorene-9, 1' -indene ]

A solution of the material from step 2 b) (71 g, 0.19 mol) in DCM (200 ml) was added to a solution of trifluoromethanesulfonic acid (9.4 g, 60 mmol, 0.31 eq.) in DCM (400 ml) at-10 ℃ over 140 min. The mixture was then warmed for 10 minutes to 5 ℃ and then cooled again to-10 ℃. Excess triethylamine (5.4 g) was added to quench the acid. The solvent was evaporated and the crude product was dissolved in a mixture of toluene (50 ml) and 94% ethanol (200 ml). The first quantity of product crystallizes. It was filtered to give 15.6 g of a colourless solid. The mother liquor was evaporated and purified by repeated column chromatography (silica gel, heptane/toluene 20:1 or heptane/DCM 7:3) followed by fractional crystallization from heptane/isopropanol 10:1 or acetone to give further product (15.4 g). Total yield: 31.0 g, 44%.

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC),CS₂: acetone (acetone) -d₆ 5:1)：δ/δ＝(32.68/1.71,CH₃),(32.79/1.71,CH₃),(44.26,C-q),(54.10/2.71,CH₂),(62.81,C-q),(119.80/7.80,CH),(121.12/7.69,CH),(121.54,C-q),(122.98/7.41,CH),(124.41/6.44,CH),(124.49/7.26,CH),(127.39/7.43,CH),(127.54/7.09,CH),(127.80/7.39,CH),(127.91/7.35,CH),(128.36/7.34,CH),(130.40/7.55,CH),(138.82,C-q),(139.04,C-q),(145.14,C-q),(153.21,C-q),(154.68,C-q),(156.92,C-q).

Example 3:

Alternative route to 2-bromo-3 ',3' -dimethyl-2 ',3' -dihydrospiro- [ fluorene-9, 1' -indene ] step 3 a):

2-bromo-9- (2-methyl-2-phenylpropyl) -9H-fluoren-9-ol

A three-necked flask equipped with a reflux condenser and a dropping funnel was charged with magnesium shavings (6.1 g, 0.25 mol) and THF (30 ml) under an inert atmosphere. After the addition of bromine (0.3 ml), the mixture was heated to reflux. About 10% of the total chloride was added to the flask from a dropping funnel containing fresh phenyl chloride (34.0 g, 0.2 ml) and heating was continued until the reaction mixture became cloudy. Additional THF (120 ml) was then added to the flask and the remaining fresh phenyl chloride was added under reflux over 45 minutes. After the end of the addition, heating was continued under reflux for a further 4 hours. A warm solution of 2-bromo-9-fluorenone (39 g, 0.15 mol) in THF (150 ml) was then added at 60℃over 10 minutes. The mixture was kept under reflux for another 10 minutes, then quenched by the addition of 2M aqueous monoammonium citrate (200 ml). After cooling to room temperature, the organic layer was separated and evaporated. The crude product was dissolved in cyclohexane and chromatographed on a column of silica gel (heptane/DCM gradient 9:1. Fwdarw.3:7 followed by a heptane/ethyl acetate gradient 9:1. Fwdarw.4:1) to give 45.2 g (76%) of the product as an orange viscous oil.

¹³C NMR：(101MHz,CS₂ : Acetone (acetone) -d₆ 5:1)：δ＝151.05(q),149.30(q),148.24(q),138.50(q),138.23(q),131.06(p),128.52(p),128.49(p),127.72(p),127.65(p),125.63(p),125.50(p),124.74(p),121.56(q),120.62(p),119.60(p),81.17(q),52.96(s),36.41(q),31.52(t),29.15(t).

Step 3 b):

2-bromo-3 ',3' -dimethyl-2 ',3' -dihydro-spiro- [ fluorene-9, 1' -indene ]

Anhydrous aluminum chloride (28 g, 0.21 mol, 5 eq) and DCM (300 ml) were placed under an inert atmosphere in a three-necked 1 liter flask equipped with an internal thermometer and a dropping funnel. The dropping funnel was filled with a solution of the product from step 3 a) (16.6 g, 0.042 mol) in dichloromethane (50 ml). The flask was immersed in a cooling bath and the slurry contained was cooled to-50 ℃ with stirring. The solution in the dropping funnel was then slowly added to the reaction flask while maintaining the temperature in the range between-50 ℃ and-40 ℃. The time required for the addition was about 2 hours. After the end of the addition, the mixture was stirred continuously for a further 30 minutes while maintaining the temperature between-40 ℃ and-30 ℃. Then 10% aqueous hydrochloric acid (300 ml) was carefully added while maintaining the temperature below-10 ℃ and the reaction quenched. The organic layer was separated, dried over sodium sulfate, and then the solvent was removed with a rotary evaporator. The crude product was then redissolved in dichloromethane and coated on silica (40 g). Plug filtration over a silica plug (50 ml) with cyclohexane (0.75 l) as eluent gave a yellow filtrate. After removal of the solvent, a solid was obtained, which was slurried in ethanol (80 ml), filtered and dried to give 7.93 g (50%) of a yellowish solid. After recrystallisation from cyclohexane (80 ml) 6.06 g (38%) of pure product are obtained.

Example 4:

2-bromo-3 ',3',4',7' -tetramethyl-2 ',3' -dihydro-spiro- [ fluorene-9, 1' -indene ]

Step 4 a):

2-bromo-9- (2, 5-dimethylphenyl) -9H-fluoren-9-ol

The grignard reaction mixture was prepared from magnesium shavings (29 g, 1.2 mol) and THF (200 ml) under argon in a 2.5 l apparatus with an overhead stirrer followed by the addition of several iodines. About 1/20 of the total amount of 2-bromo-para-xylene (205 g, 1.1 mole) was added to the reaction mixture. Once the reaction started THF (500 ml) was added followed by dropwise addition of the remaining 2-bromo-p-xylene over 40 minutes. The reaction mixture was stirred for an additional 1 hour and cooled to 30 ℃. A solution of 2-bromo-9-fluorenone (259 g, 1.0 mol) in 800 ml THF was then added at 60℃at a rate such that the reaction continued at reflux. After the addition was completed, the mixture was stirred for another 30 minutes, and then a solution of sulfuric acid (100 g, 1.0 mol) in 400 ml of water was added under reflux. The organic layer was separated and THF was removed by rotary evaporation. The remaining crude product was dissolved in methanol (700 ml) at 60 ℃. After addition of several seeds, the product crystallized and was filtered at 40 ℃. The product was washed with ethanol (50 ml) followed by methanol (3×100 ml). 292 g (80%) of product are obtained as a colorless solid after drying.

¹³ C NMR: (101 MHz, acetone -d₆)：δ＝152.43(q),149.99(q),139.97(q),139.40(q),134.69(q),131.70(p),131.65(q),131.51(p),128.83(p),128.64(p),128.26(p),128.08(p),127.87(p),124.75(p),122.20(q),121.36(p),120.11(p), is about 82.0 (q, wide, found by HMBC) 21.61 (t), 19.29 (t.) an acrylic quaternary carbon resonance is lost, probably due to slow exchange on the NMR time scale.

Step 4 b):

2-bromo-9- (2, 5-dimethylphenyl) -9H-fluorene

The material from step 4 a) (43 g, 118 mmol) was dissolved in DCM (200 ml) under an inert atmosphere. The solution was cooled to 0 ℃ and triethylsilane (34.2 g, 294 mmol) was then added. Boron trifluoride-THF complex (41.2 g, 294 mmol) was added dropwise over 15 minutes. The reaction mixture was stirred at 0 ℃ for another 1 hour and then carefully added to ice-cold water (200 ml) with vigorous stirring. The organic layer was separated and the aqueous layer was extracted with DCM (100 ml). The combined organic layers were evaporated and the residue recrystallized from isopropanol (200 ml) to give 33.0 g (80%) of the product as a white solid.

¹³C NMR：(101MHz,CS₂ : Acetone (acetone) -d₆ 5:1)：δ＝150.65(q),149.10(q),148.25(q),146.75(q),140.24(q),140.17(q),139.88(q),139.83(q),138.77(q),137.19(q),135.83(q),135.18(q),133.86(q),133.63(p),132.89(q),131.98(p),130.71(p),130.42(p),130.35(p),128.52(p),128.48(p),128.09(p),128.05(p),128.01(p),127.94(p),127.89(p),127.57(p),127.50(p),125.33(p),124.81(p),121.58(q),121.53(q),121.44(p),121.39(p),120.26(p),120.23(p),56.31(p),50.00(p),21.27(t),20.99(t),20.12(t),17.96(t).

Alternatively, the product of step 4 b) may be prepared as follows: 2-bromo-9H-fluoren-9-ol (5.2 g, 20 mmol) was dissolved in p-xylene (100 ml) at 110 ℃. P-toluenesulfonic acid monohydrate (1.9 g, 10 mmol) was added followed by stirring at 110℃for 2 hours. After cooling to 20 ℃ water (40 ml) was added, the organic layer was separated and the solvent removed by rotary evaporation. The residue was dissolved in isopropanol at 60 ℃ and crystallized at 20 ℃ after addition of several seeds. This gave 5.2 g (74%) of a colorless solid. The GC residence time and NMR-spectroscopy data of the product were identical to those obtained from example 2, step 4 b) above.

Step 4 c):

2-bromo-9- (2, 5-dimethylphenyl) -9- (2-methallyl) -9H-fluorene

To a solution of the material from step 4 b) (6.99 g, 20.0 mmol) in THF (50 ml) was added sodium tert-butoxide (2.31 g, 24 mmol). After stirring for 15 minutes, methallyl chloride (2.72 g, 20 mmol) was added at a temperature between 20 and 30 ℃. After stirring for 15 minutes, water (10 ml) and heptane (25 ml) were added. The organic layer was separated, dried over MgSO ₄ and filtered. After removal of the solvent from the filtrate, the product was obtained by crystallization of the residue from isopropanol (50 ml). 6.53 g (81%) of a colourless solid are obtained.

¹³C NMR：(101MHz,CS₂ : Acetone (acetone) -d₆)：δ＝150.65(q),149.10(q),148.25(q),146.75(q),140.24(q),140.17(q),139.88(q),139.83(q),138.77(q),137.19(q),135.83(q),135.18(q),133.86(q),133.63(p),132.89(q),131.98(p),130.71(p),130.42(p),130.35(p),128.52(p),128.48(p),128.09(p),128.05(p),128.01(p),127.94(p),127.89(p),127.57(p),127.50(p),125.33(p),124.81(p),121.58(q),121.53(q),121.44(p),121.39(p),120.26(p),120.23(p),56.31(p),50.00(p),21.27(t),20.99(t),20.12(t),17.96(t).

Step 4 d):

The product from step 4 c) (5.0 g, 12 mmol) was dissolved in DCM (20 ml). Boron trifluoride-THF-complex (10 ml) was added and the resulting mixture was stirred for 3 days. The reaction was then quenched by the addition of water (50 ml). The organic layer was separated and the aqueous layer was extracted with DCM (20 ml). The combined organic layers were washed with saturated potassium bicarbonate solution, dried over MgSO ₄, filtered, and evaporated. The product was crystallized from isopropanol (20 ml) and filtered to give 3.40 g (70%) of a colourless solid.

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC),CS₂: acetone (acetone) -d₆ 5:1)：δ/δ＝(17.01/1.09,CH₃),(19.39/2.55,CH₃),(30.42/1.69,CH₃),(30.45/1.70,CH₃),(44.77,C-q),(57.23/2.51,CH₂),(62.45,C-q),(119.99/7.70,CH),(121.22/7.62,CH),(121.93,C-q),(124.17/7.12,CH),(127.32/7.32,CH),(127.45/7.24,CH),(128.38/7.27,CH),(130.04/6.69,CH),(130.16/7.44,CH),(131.29,C-q),(131.73/6.93,CH),(132.78,C-q),(139.04,C-q),(139.21,C-q),(142.64,C-q),(150.34,C-q),(153.26,C-q),(155.75,C-q).

Example 5:

4, 5-tetramethyl-2- (3 ',3',4',7' -tetramethyl-2 ',3' -dihydrospiro- [ fluoren-9, 1' -inden ] -2-yl) -1,3, 2-dioxaborolan

Sodium acetate (12.3 g, 150 mmol, 3.0 eq), bis (pinacolato) diboron (bis (pinacolato) diboron) (14.0 g, 58 mmol, 1.1 eq) and the product from example 4, step 4 d) (20.17 g, 50 mmol, 1.0 eq) were placed in a flask. 2-methyltetrahydrofuran (200 ml) was then added. The reaction mixture was placed under an inert atmosphere by 3 vacuum/nitrogen backfill cycles. Pd (dppf) Cl ₂*CH₂Cl₂ (0.81 g, 1mmol, 2 mol%) was added under nitrogen reverse flow. The mixture was stirred under reflux for 24 hours. After cooling to room temperature, water (100 ml) was added. The organic layer was separated and evaporated to dryness. The crude product was purified by column chromatography (heptane/EtOAc 10:1→5:1). The purified fractions were combined and the solvent was evaporated. The residue was crystallized from 20ml of heptane to give 4.1 g of a colorless solid. The mother liquor was evaporated to give another batch (4.1 g) of product. The total yield was 8.2 g (36% based on the theoretical value of aryl bromide).

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC),CS₂: acetone -d₆5:1)δ/δ(17.04/1.03,CH₃),(19.52/2.56,CH₃),(24.98/1.34,2*CH₃),(25.02/1.33,2*CH₃),(30.45/1.73,CH₃),(30.53/1.70,CH₃),(44.74,C-q),(57.25/2.48,2.53,CH₂),(62.19,C-q),(83.32,2×C-q),(119.02/7.69,C-H),(120.21/7.73,C-H),(124.25/7.13,C-H),(127.08/7.32,C-H),(128.36/7.25,C-H),(129.91/6.67,C-H),(130.35/7.48,C-H),(131.1,C-q),(131.43/6.92,C-H),(132.85,C-q),(134.05/7.74,C-H),(140,C-q),(142.91,C-q),(143.41,C-q),(150.26,C-q),(152.59,C-q),(154.07,C-q). in ¹³ C spectrum did not observe quaternary carbon adjacent to the boron ester, most likely because it was too broad.

Example 6:

The product from example 5 (4.50 g, 10 mmol, 1.0 eq), potassium carbonate (4.5 g, 33 mmol, 3.3 eq) and 2-chloro-4, 6-diphenyl-1, 3, 5-triazine (2.91 g, 10.5 mmol, 1.1 eq) were placed in a flask. Water (11 g) and THF (60 ml) were added. The apparatus was placed under an inert atmosphere by 3 vacuum/nitrogen backfill cycles. Bis (triphenylphosphine) palladium dichloride (95 mg, 0.135 mmol, 1.35 mol%) and triphenylphosphine (72 mg, 0.275 mmol, 2.75 mol%) were added under a reverse flow of nitrogen. The mixture was heated at reflux for 12 hours. Sodium diethyldithiocarbamate trihydrate (3.0 g, 13 mmol) is then added and the mixture is maintained at reflux for another 30 minutes. Toluene (60 ml) was added and the organic layer was separated and dried over MgSO ₄. After filtration the organic solvent was removed and the residue was crystallized from acetone (50 ml). The crystals were filtered, washed with acetone (20 ml) and dried to give the product (4.50 g, 81% based on the product from example 5) as a colourless, blue fluorescent solid.

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC),CS₂: acetone (acetone) -d₆5:1)δ/δ(17.14/1.14,CH₃),(19.55/2.62,CH₃),(30.37/1.90,CH₃),(30.58/1.77,CH₃),(44.89,C-q),(57.23/2.68,2.62,CH₂),(62.46,C-q),(119.86/7.94,C-H),(120.67/7.85,C-H),(124.39/7.20,C-H),(124.92/8.59,C-H),(127.37/7.39,C-H),(128.64/7.55,4*C-H),(128.66/8.82,C-H),(129/7.34,C-H),(129.12/8.72,4*C-H),(130.13/6.70,C-H),(131.32,C-q),(131.72/6.96,C-H),(132.51/7.59,2*C-H),(132.89,C-q),(135.67,C-q),(136.25 2*C-q),(139.42,C-q),(143.04,C-q),(144.66,C-q),(150.42,C-q),(153.62,C-q),(154.82,C-q),(171.2/,2*C-q),(171.43,C-q).

Example 7:

2-bromo-3 ',3',5',7' -tetramethyl-2 ',3' -dihydro-spiro- [ fluorene-9, 1' -indene ]

Step 7 a):

2-bromo-9- (2, 4-dimethylphenyl) -9- (2-methallyl) -9H-fluorene

A solution of 2-bromofluoren-9-one (25.9 g, 100 mmol, 1 eq.) in m-xylene (100 ml) and methanol (40 ml) was prepared at 55deg.C. To this solution was added a solution of sodium borohydride (1.89 g, 50 mmol, 0.5 eq.) in 20% NaOH aqueous solution (16 g, 80 mmol, 0.8 eq.) over 60 minutes. The resulting mixture was stirred and held at reflux for another 30 minutes. Water (100 ml) was then added and stirring was stopped after 5 minutes. After separating the layers, the lower aqueous layer was discarded. Meta-xylene (100 ml) was added to the remaining organic layer. The remaining water was removed via azeotropic distillation with a Dean-Stark trap (trap). Phosphoric acid (85%, 2.5 g, 22 mmol, 0.22 eq) was then added and the reaction mixture was kept at reflux for 2 hours.

After cooling to 20 ℃, the mixture was washed with water (100 ml). The organic layer was separated and the aqueous layer extracted with meta-xylene (50 ml). The combined organic layers were evaporated to dryness and the remaining crude product was dissolved in THF (200 ml). Sodium tert-butoxide (9.8 g, 0.10 mol,1 eq) was added followed by methallyl chloride (15 g, 0.17 mol, 1.6 eq) which resulted in a slightly exothermic reaction. The mixture was stirred for another 2 hours, then quenched by the addition of saturated ammonium chloride solution (100 ml). Heptane (100 ml) was added and the aqueous layer was removed after separation of the layers. The organic layer was again washed with water (200 ml). After removal of the solvent from the organic layer, the residue was crystallized from a 4:1 methanol/toluene mixture (150 ml). The crystallized product was filtered and washed with cold methanol (50 ml) and after drying 19.1 g of a yellowish solid was obtained. The second batch was obtained by evaporating the mother liquor and crystallizing the residue from acetone/MeOH 1:1 (100 ml). The solid was filtered to give 5.1 g of a brown solid. The combined yield was 24.2 g (60%).

¹³C NMR：(101MHz,CS₂ : Acetone (acetone) -d₆ 5:1)：δ＝153.00(q),150.48(q),140.77(q),140.69(q),139.52(q),137.84(q),137.41(q),136.37(q),133.51(p),130.15(p),127.79(p),127.41(p),127.38(p),127.17(p),126.60(p),124.16(p),121.42(q),121.19(p),120.07(p),116.35(s),58.20(q),48.27(s),24.45(t),20.95(t),19.87(t).

Step 7 b):

The product from step 7 a) (20.2 g, 50.2 mmol) and Amberlyst in dry hydrogen form were reacted with(6.3 G) a suspension in chlorobenzene (150 ml) was heated to 90℃for 48 hours. After cooling to 20 ℃, amberlyst was filtered through a pad of silica gel and washed with toluene (100 ml). The filtrate was evaporated to dryness and the remaining crude product was crystallized from a 1:1v:v mixture of isopropanol/heptane (80 ml, 60 ℃ C. To 20 ℃ C.). The crystals were filtered and washed 2 times with a 1:1v:v isopropanol/heptane mixture (10 ml) to give 11.3 g of a colorless solid. The mother liquor was evaporated and the residue was crystallized from a 5:1v:v isopropanol/heptane mixture (60 ml, 60 ℃ to 20 ℃) to give another batch which was filtered and washed with 5:1v:v isopropanol/heptane (10 ml) followed by isopropanol (10 ml) to give 4.0 g of product. Total yield: 15.3 g (76%).

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC),CS₂; acetone (acetone) D65:1)δ/δ(17.07/1.11,CH₃),(21.5/2.36,CH₃),(32.65/1.58,CH3),(32.76/1.58,CH3),(43.37,C-q),(55.66/2.51,CH2),(62.54,C-q),(119.93/7.7,C-H),(121.16/7.62,C-H),(121.27/6.95,C-H),(121.98,C-q),(124.18/7.11,C-H),(127.32/7.32,C-H),(127.48/7.23,C-H),(128.38/7.25,C-H),(130.17/7.44,C-H),(130.66/6.61,C-H),(134.67,C-q),(137.88,C-q),(139.01,C-q),(139.06,C-q),(139.17,C-q),(153.16,C-q),(154.17,C-q),(155.66,C-q).

Example 8:

2-bromo-3 ',3',4',5',7 '-pentamethyl-2', 3 '-dihydrospiro- [ fluorene-9, 1' -indene ]

Step 8 a):

2-bromo-9- (2, 4, 5-trimethylphenyl) -9H-fluoren-9-ol

Magnesium shavings (14.7 g, 605 mmol, 1.2 eq) and THF (100 ml) were placed under an inert atmosphere. A spatula tip of iodine was added to the reaction mixture followed by 3 ml of a solution of 1-bromo-2, 4, 5-trimethylbenzene (109.6 g, 550.5 mmol, 1.1 eq.) in THF (80 ml). Once the grignard reaction has begun, the reaction mixture is diluted with THF (170 ml) and the remaining portion of the aryl bromide solution is added dropwise. When the addition was complete, the mixture was stirred at 60 ℃ for another 45 minutes. Separately, a THF (450 ml) warm (60 ℃) solution of 2-bromo-9-fluorenone (130.1 g, 502.6 mmol, 1.0 eq.) was prepared. This solution was added to the grignard reaction mixture maintained under reflux.

When about 200 ml of 2-bromofluorenone solution has been added to the grignard reaction mixture, an insoluble material is formed which can no longer be stirred. The addition was thus stopped and the reaction mixture was cooled to ambient temperature. It was then quenched by the addition of an ice-cold mixture of sulfuric acid (66 g) and water (220 ml), which resulted in the formation of a clear binary mixture. The organic layer was separated and the solvent removed with a rotary evaporator. The residue was crystallized from methanol (100 ml). The crystals were filtered, washed with methanol (100 ml) and dried to give 71.3 g (37%) of the desired product.

¹³C NMR：(101MHz,CS₂ Acetone -d₆ 5:1)δ152.61(q),150.17(q),139.35(q),139.31(q),137.34(q),135.21(q),133.37(p),133.22(q),131.97(q),131.56(p),128.88(p),128.71(p),128.57(p),128.22(p),124.84(p),122.35(q),121.35(p),120.13(p),82.14(q),19.88(t),19.40(t),19.29(t).

Step 8 b):

2-bromo-9- (2, 4, 5-trimethylphenyl) -9H-fluorene

To a cold solution (1 ℃) of the product from step 8 a) (69.8 g, 184 mmol, 1.0 eq.) in DCM (200 ml) was added triethylsilane (28.1 g, 242 mmol, 1.3 eq.) in one portion. Boron trifluoride tetrahydrofuran complex (33.6 g, 240 mmol, 1.3 eq.) was then added dropwise over 30 minutes while maintaining the temperature in the range between 0 and 15 ℃. After the addition of boron trifluoride is completed, the mixture is warmed to ambient temperature. Solid separation started to occur during reduction, so some DCM (50 ml) was added. Methanol (200 ml) was added after brief stirring with a glass rod, and DCM was distilled off from the mixture followed by isopropanol (500 ml). After heating to reflux, the mixture was cooled to 20 ℃. The crystals formed were filtered and washed with isopropanol (100 ml). After drying 62.9 g (94%) of the product were obtained as a colourless solid.

¹ The H-NMR spectrum showed a ratio of 1.7:1.0 (ρ and ρ') and the signals of the slow 2 rotamers were exchanged on the NMR time scale.

¹ H NMR: (400 MHz, CS2: acetone-d ₆ 5:1) delta 7.76 (m, 1H Ar p and 1HAr p '), 7.67 (m, 1H Ar p and 1H Ar p '), 7.54-7.42 (m, 1H Ar p and 1H Ar p '), 7.40-7.21 (m, 3H Ar p and 4H Ar p '), 7.18 (m, 1H Ar p and 4H Ar p ') 1H Arρ'),7.02(s,1H Arρ),6.70(s,1H Arρ'),6.03(s,1H Arρ),5.29(s,1H,C-Hρ),4.91(s,1H,C-Hρ'),2.71(s,3H,CH₃ρ),2.38(s,3H,CH₃ρ'),2.25(s,3H,CH₃ρ'),2.21(s,3H,CH₃ρ),1.96(s,3H,CH₃ρ),1.08(s,3H,CH₃ρ').

Step 8 c):

2-bromo-9- (2-methylallyl) -9- (2, 4, 5-trimethylphenyl) -9H-fluorene

The product from step 8 b) (61.7 g, 170 mmol, 1.0 eq.) was suspended in THF (200 ml) followed by the addition of sodium tert-butoxide (18.0 g, 187 mmol, 1.1 eq.). The resulting suspension was stirred in an ice bath. Methallyl chloride (19.5 g, 215 mmol, 1.3 eq.) was added over 20 minutes at 0 ℃. The reaction mixture was stirred at 20 ℃ for 2 hours, then water (100 ml) and heptane (200 ml) were added followed by tert-butyl methyl ether (100 ml). The organic layer was washed with water (100 ml), separated and dried over MgSO ₄. During filtration, a portion of the product crystallized. It was redissolved with toluene (150 ml). The filtrate was concentrated using a rotary evaporator, which resulted in crystallization of the majority of the product. The crystals were filtered and washed with isopropanol. The mother liquor was evaporated to give 29.3 g of an orange oil which was crystallized from isopropanol (reflux → 20 ℃). The crystals were filtered and washed with isopropanol (10 ml). Total yield: 52.6 g (75%) of a colourless solid.

¹³C NMR：(101MHz,CS₂ Acetone -d₆ 5:1)δ153.13(q),150.61(q),140.76(q),140.70(q),139.60(q),138.07(q),134.77(q),134.75(q),134.23(p),133.15(q),130.09(p),128.73(p),127.76(p),127.47(p),127.32(p),124.20(p),121.42(q),121.13(p),120.03(p),116.33(s),58.21(q),48.30(s),24.50(t),19.95(t),19.39(t),19.20(t).

Step 8 d):

The product from step 8 c) (38.4 g, 92.0 mmol) and Amberlyst in dry hydrogen form were combinedA suspension of (7.04 g) in chlorobenzene (180 ml) was heated to 90℃for 90 minutes. After cooling to 20 ℃, the catalyst was filtered and washed with toluene (30 ml). The solvent was removed from the filtrate by rotary evaporation. The residue was crystallized from a 10:1v:v mixture of toluene and isopropanol (55 ml, reflux → 20 ℃). The crystals were filtered, washed with toluene and dried. After evaporation of the mother liquor and crystallization from a 5:3v:v mixture of toluene and isopropanol (20 ml, reflux → 20 ℃), followed by washing with heptane, a second portion is obtained. Total yield: 33.3 g (87%) of a colourless solid.

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC),CS₂: acetone (acetone) -d₆ 5:1)δ/δ(15.52/2.43,CH₃),(17.02/1.07,CH₃),(20.33/2.26,CH₃),(31.03/1.72,CH₃),(31.08/1.71,CH₃),(44.8,C-q),(57.96/2.51,CH₂),(61.97,C-q),(119.93/7.69,C-H),(121.13/7.60,C-H),(121.98,C-q),(124.18/7.14,C-H),(127.25/7.31,C-H),(127.51/7.26,C-H),(128.34/7.25,C-H),(129.86,C-q),(130.08/7.43,C-H),(132.14,C-q),(132.22/6.62,C-H),(137.38,C-q),(139,C-q),(139.13,C-q),(140.5,C-q),(150.46,C-q),(153.52,C-q),(156,C-q).

Example 9:

mixtures of 2-bromo-6 '-methoxy-3', 3 '-dimethyl-2', 3 '-dihydrospiro- [ fluorene-9, 1' -indene ] with 2-bromo-4 '-methoxy-3', 3 '-dimethyl-2', 3 '-dihydrospiro- [ fluorene-9, 1' -indene ]

Step 9 a):

2-bromo-9- (3-methoxyphenyl) -9H-fluorene

Grignard reagents were prepared from magnesium shavings (5.35 g, 220 mmol) and 3-bromoanisole (41.1 g, 220 mmol) in THF (220 ml). A warm solution of 2-bromo-9-fluorenone (51.8 g, 200 mmol) in THF (300 ml) was then added to the grignard solution. The temperature of the grignard solution was 50 c at the beginning and the reflux temperature was reached during the addition. The reaction mixture was stirred for 1 hour and then cooled to 30 ℃. The reaction mixture was poured onto a mixture of ice (100 g), 32% hcl (100 ml) and saturated sodium chloride solution (100 ml). Cyclohexane (200 ml) was added and the organic layer was separated and dried over MgSO ₄. After filtration and removal of the solvent, a crude compound oil was obtained, which was dissolved in DCM (250 ml). The solution was cooled to-10 ℃ under inert gas and triethylsilane (34.9 g, 300 mmol) was added followed by slow addition of BF ₃ -THF complex (42.0 g, 300 mmol). After the exothermic reaction ceased, the mixture was stirred at 20 ℃ for 30 minutes. It was then cooled to 0 ℃, water (200 ml) was added followed by heptane (200 ml). The organic layer was separated, neutralized with saturated potassium bicarbonate solution (50 ml), and dried over MgSO ₄. After filtration and removal of the solvent with a rotary evaporator, the crude compound was purified by column chromatography (silica gel, heptane/ethyl acetate gradient, 1:20→1:10) to give 65.3 g of the product as a colourless oil.

¹³C NMR：(101MHz,CS₂ : Acetone (acetone) -d₆)：δ＝160.02(q),149.81(q),147.34(q),141.78(q),140.05(q),139.99(q),130.60(p),129.91(p),128.75(p),127.93(p),127.78(p),125.55(p),121.59(q),121.37(p),120.76(p),120.18(p),114.16(p),112.57(p),54.75(p),54.57(p).

Step 9 b):

2-bromo-9- (3-methoxyphenyl) -9- (2-methallyl) -9H-fluorene

The product from step 9 a) (32.6 g, 92.8 mmol) was placed in a flask followed by THF (180 ml). Sodium tert-butoxide (10.7 g, 111 mmol) was added to the resulting solution at a temperature between 0 and 15 ℃. The solution immediately turned red. Methallyl chloride (14.6 g, 139 mmol) was added over about 5 minutes at a temperature in the range of between 5 and 25 ℃. After stirring at room temperature for 1 hour, 75ml of n-heptane were added to the reaction mixture followed by a 1:1 mixture of 75ml of saturated ammonium chloride solution and water. After separation of the layers, the aqueous layer was discarded and the organic layer was dried (MgSO ₄). After filtration, the solvent was removed from the filtrate by rotary evaporation and the remaining crude product was crystallized from 150 ml of methanol. The crystals were filtered at room temperature, washed with 50 ml of methanol and dried to give 20.8 g (55%) of a colorless solid.

¹³C NMR：(101MHz,CS₂ : Acetone (acetone) -d₆ 5:1)：δ＝159.69(q),153.37(q),150.74(q),145.73(q),140.80(q),139.83(q),139.81(q),130.40(p),129.46(p),128.37(p),127.73(p),127.63(p),125.28(p),121.43(p),121.27(q),120.18(p),118.97(p),115.83(s),113.27(p),111.39(p),58.81(q),54.72(t),45.27(s),24.16(t).

Step 9 c):

The product from step 9 b) (16.5 g, 41 mmol) was dissolved in 80 ml of DCM. This solution was then added dropwise over 15 minutes to a solution of trifluoromethanesulfonic acid (2.4 g, 16 mmol, 0.4 eq.) in 100 ml DCM at room temperature. The mixture was then stirred at room temperature for another 30 minutes, followed by the addition of water (50 ml) and a saturated solution of potassium bicarbonate (50 ml). The organic layer was separated and the aqueous layer was extracted with TBME (20 ml). The combined organic layers were evaporated and the remaining crude product was dissolved in cyclohexane. The solution was filtered through a silica gel column (diameter=7 cm, height=2 cm, eluent=650 ml of 20:1 heptane/ethyl acetate). The solvent was evaporated from the filtrate and the crude product was purified by flash chromatography (silica gel, heptane/ethyl acetate 92:8). Isomer a from the column fraction was crystallized from heptane (6.7 g, 41%) and isomer B from heptane/ethyl acetate 95:5 (2.8 g, 17%).

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC)CS₂ of isomer a: acetone (acetone) -d₆ 5:1)：δ/δ＝(32.76/1.64,CH₃),(32.81/1.63,CH₃),(43.27,C-q),(54.67/2.62,CH₂),(54.75/3.51,O-CH₃),(62.66,C-q),(108.04/5.76,CH),(115.43/6.79,CH),(120.01/7.71,CH),(121.30/7.63,CH),(122.01,C-q),(123.64/7.19,CH),(124.51/7.16,CH),(127.60/7.33,CH),(127.82/7.27,CH),(128.50/7.27,CH),(130.45/7.46,CH),(138.83,C-q),(139.02,C-q),(145.12,C-q),(145.91,C-q),(154.24,C-q),(156.70,C-q),(159.58,C-q).

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC)CS₂ of isomer B: acetone (acetone) -d₆ 5:1)：δ/δ＝(30.06/1,74,1.75,2×CH₃),(44.90,C-q),(54.87/2.59,CH₂),(54.91/3.92,O-CH₃),(62.98,C-q),(109.56/6.71,CH),(116.79/5.84,CH),(119.93/7.70,CH),(121.22/7.62,CH),(121.90,C-q),(124.54/7.16,CH),(127.49/7.31,CH),(127.84/7.27,CH),(128.41/7.25,CH),(129.11/6.93,CH),(130.33/7.44,CH),(138.78,C-q),(138.98,C-q),(139.22,C-q),(146.81,C-q),(154.30,C-q),(156.70,C-q),(156.78,C-q).

Example 10:

2-bromo-5 '-methoxy-3', 3',4',6 '-tetramethyl-2', 3 '-dihydro-spiro- [ fluorene-9, 1' -indene ]

Step 10 a):

2-bromo-9-methoxy-9- (4-methoxy-3, 5-dimethylphenyl) -9H-fluorene

Magnesium shavings (12.8 g, 525 mmol, 1.2 eq) and THF (85 ml) were placed under an inert atmosphere. A spatula tip of iodine was added to the reaction mixture followed by 3 ml of a solution of 5-bromo-2-methoxy-1, 3-dimethylbenzene (98.8 g, 459 mmol, 1.1 eq.) in THF (210 ml). After the start of the grignard reaction, the remaining portion of the aryl bromide solution was added at reflux temperature over 45 minutes. The mixture was then kept under reflux for another 45 minutes and then stirred at 60 ℃ for another 45 minutes. A warm solution (60 ℃) of 2-bromo-9-fluorenone (109 g, 421 mmol, 1.0 eq.) in THF (340 ml) was prepared. This solution was added to the grignard mixture while remaining under vigorous reflux. The mixture was kept under reflux for another 45 minutes after the end of the addition. The reaction was then quenched by careful addition of a mixture of sulfuric acid (43.5 g) and water (170 ml) at reflux temperature. The organic layer was separated after layer separation and the solvent was removed therefrom. The remaining oily crude product was crystallized from methanol (300 ml), filtered and washed with cold methanol (100 ml) to give 126 g (73%) of the desired product as a colourless solid. NMR analysis showed that solvolysis of methanol to methyl ether occurred during recrystallization, most likely caused by the presence of trace amounts of sulfuric acid.

¹³C NMR：(101MHz,CS₂ Acetone -d₆ 5:1)δ156.27(q),149.75(q),146.88(q),139.92(q),139.76(q),137.52(q),132.04(p),130.22(q),129.33(p),128.61(p),128.56(p),126.12(2*p),125.51(p),122.42(q),121.54(p),120.26(p),88.59(q),59.08(t),51.10(t),16.31(2*t).

Step 10 b):

2-bromo-9- (4-methoxy-3, 5-dimethylphenyl) -9H-fluorene

To a solution of the product from step 10 a) (60.0 g, 147 mmol, 1.0 eq.) in DCM (200 ml) was added triethylsilane (44.6 g, 380 mmol, 2.6 eq.) at 0 ℃. Boron trifluoride tetrahydrofuran complex (52.9 g, 380 mmol, 2.6 eq.) was added at 0℃over 10 minutes between 0 and 30 ℃. The mixture was stirred at 20℃for 1 hour. The mixture was then poured into water, the organic layer was separated and washed with 5% sodium hydroxide solution (100 ml). The organic layer was separated and the solvent was removed therefrom by rotary evaporation. The crude product was suspended in isopropanol (150 ml) and then filtered and washed with cold isopropanol (50 ml) to give 50.5 g (91%) of a colourless solid.

¹³C NMR：(101MHz,CS₂ Acetone -d₆)d 156.19(q),150.35(q),147.83(q),139.96(q),139.95(q),135.51(q),131.06(2*q),130.46(p),128.75(3*p),127.89(p),127.66(p),125.58(p),121.45(q),121.38(p),120.14(p),59.14(t),54.01(p),16.20(2*t).

Step 10 c):

2-bromo-9- (4-methoxy-3, 5-dimethylphenyl) -9- (2-methylallyl) -9H-fluorene

In a 500ml flask, the material from step 10 b) (25.6 g, 67.5 mmol, 1.0 eq.) and sodium tert-butoxide (7.64 g, 79.5 mmol, 1.18 eq.) were dissolved in THF (170 ml). Methallyl chloride (9.5 g, 0.10 moles, 1.6 equivalents) was added to the resulting mixture at a temperature between 0-20 ℃ over 10 minutes. Stirring was continued for another 2 hours at 20 ℃ before heptane (100 ml) and water (50 ml) were added. The organic layer was separated and dried over magnesium sulfate. After filtration, the solvent was removed from the filtrate to give the crude product. The product was purified by crystallization from isopropanol (170 ml, 60 ℃ C. Fwdarw.20 ℃ C.). The crystals were filtered and washed with cold isopropanol (50 ml) to give 23.6 g (81%) of the product as a colourless solid.

¹³C NMR：(101MHz,CS₂ Acetone -d₆ 5:1)d 155.83(q),153.82(q),151.18(q),140.84(q),139.80(q),139.19(q),130.48(q),130.30(p),128.35(p),127.74(p),127.53(p),126.98(2*p),125.27(p),121.38(p),121.32(q),120.13(p),115.76(s),59.11(t),58.35(q),45.40(s),24.20(p),16.36(2*p). a quaternary carbon signal.

Step 10 d):

The material from step 10 c) (19.2 g, 44.3 mmol, 1.0 eq.) was suspended in chlorobenzene (68 ml). The slurry was heated to 60℃and then boron trifluoride tetrahydrofuran complex (12.3 g, 87.0 mmol, 2.0 eq.) was added. The mixture was stirred at 60℃for 16 hours. After cooling to 20 ℃, the reaction was quenched with water (35 ml). The organic layer was separated, washed with 5% aqueous NaOH (35 ml) followed by water (35 ml). The organic layer was separated and dried over MgSO ₄. After filtration the solvent was removed from the filtrate to give the crude product. It was crystallized from heptane (120 ml, 60 ℃ C. To 20 ℃ C.). The solid was filtered and washed with heptane (20 ml) to give a colourless solid (12.5 g, 65%).

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC)CS₂: acetone (acetone) -d₆ 5:1)δ/δ＝(11.85/2.45,CH₃),(16.27/2.02,CH₃),(30.55/1.74,CH₃),(30.59/1.75,CH₃),(45.36,C-q),(56.35/2.62,CH₂),(59.12/3.68,CH₃),(61.69,C-q),(119.91/7.71,C-H),(121.23/7.63,C-H),(121.82,C-q),(124.26/5.89,C-H),(124.54/7.15,C-H),(126.83,C-q),(127.42/7.31,C-H),(127.81/7.26,C-H),(128.37/7.25,C-H),(130.24/7.44,C-H),(130.26,C-q),(138.73,C-q),(138.97,C-q),(140.63,C-q),(148.57,C-q),(154.62,C-q),(157.16,C-q),(157.26,C-q).

Example 11:

2-bromo-2 ',3',3',4',7 '-pentamethyl-2', 3 '-dihydro-spiro- [ fluorene-9, 1' -indene ]

The product of example 4, step 4 a) (18.3 g, 50.0 mmol) was added to a mixture of dichloromethane (25 ml) and 2-methyl-2-butene (13 g, 0.19 mol). The resulting mixture was vigorously stirred at 0 ℃. BF ₃ -THF complex (22.8 g, 163 mmol) was then added followed by stirring at room temperature for 16 hours. The resulting precipitate was filtered and washed 2 times with TBME (20 ml). The product was obtained as a colourless solid (8.2 g, 39%) as a 1:1.4 ratio mixture of diastereomers.

¹³C NMR(101MHz,CS₂ Of the major isomer a (2 ' r, 9S) -2-bromo-2 ',3',3',4',7' -pentamethyl-2 ',3' -dihydrospiro- [ fluorene-9, 1' -indene ]: acetone (acetone) -d₆ 5:1)：δ＝156.10(q),150.83(q),147.71(q),142.11(q),140.28(q),139.50(q),132.67(q),131.50(Ar-CH),131.30(q),130.14(Ar-CH),129.62(Ar-CH),129.24(Ar-CH),127.39(Ar-CH),127.13(Ar-CH),126.15(Ar-CH),121.80(q),121.00(Ar-CH),120.03(Ar-CH),66.89(q),57.47(CH),46.62(q),29.65(CH₃),23.44(CH₃),19.64(CH₃),17.39(CH₃),8.76(CH₃).

Minor isomer B (2 'R, 9R) -2-bromo-2', 3',3',7 '-tetramethyl-2', 3 '-dihydrospiro- [ fluorene-9, 1' -indene ] ¹³C NMR(101MHz,CS₂: acetone (acetone) -d₆ 5:1)：δ＝153.52(q),150.77(q),150.33(q),142.00(q),140.43(q),139.40(q),132.64(q),131.56(Ar-CH),131.39(q),130.22(Ar-CH),129.65(Ar-CH),128.19(Ar-CH),127.35(Ar-CH),127.22(Ar-CH),123.80(Ar-CH),121.09(q),121.16(Ar-CH),119.81(Ar-CH),66.96(q),57.63(CH),46.47(q),29.72(CH₃),23.52(CH₃),19.63(CH₃),17.44(CH₃),8.61(CH₃).

Example 12:

2-bromo-4 ',4' -dimethyl-3 ',4' -dihydro-2 'H-spiro- [ fluorene-9, 1' -naphthalene ]

Step 12 a):

2-bromo-9- (3-methylbut-2-en-1-yl) -9-phenyl-9H-fluorene

The product from example 2, step 2 a) (34.6 g, 108 mmol) was placed in a flask under an inert atmosphere, followed by THF (150 ml). Sodium tert-butoxide (15.5 g, 162 mmol) was added to the resulting solution at a temperature between 0 and 15 ℃. The solution immediately turned red. Isopentenyl chloride (purity about 85 mass%, 20g, 160 mmol) was added over about 5 minutes while maintaining the temperature between 25 and 35 ℃. The mixture was stirred at room temperature for 20 minutes and then concentrated to about half its volume by rotary evaporation. The resulting suspension was dissolved in a mixture of toluene (100 ml) and water (100 ml). The organic layer was separated, filtered through a pad of silica gel and rinsed with toluene (100 ml). The combined filtrates were evaporated and the residue was dissolved in a mixture of isopropanol (60 ml) and ethyl acetate (3 ml). The product crystallized spontaneously, yielding 21.2 g of material. After evaporation of the mother liquor, a second quantity (8.0 g) of product is obtained after crystallization from isopropanol (25 ml). Total yield: 70%. The compound crystallizes into the isopropanol solvate.

¹³C NMR：(101MHz,CS₂ : Acetone (acetone) -d₆ 5:1)：δ＝154.93(q,1C),152.30(q 1C),144.69(q 1C),140.72(q 1C),140.35(q 1C),134.49(q 1C),131.13(p 1C),129.31(p,2C),128.74(p,1C),128.66(p,1C),128.32(p,1C),127.56(p,2C),127.48(p,1C),125.51(p,1C),122.45(p,1C),121.41(q,1C),120.96(p,1C),120.07(p,1C),59.89(q,1C),36.71(s,1C),18.13(t,2C).

Step 12 b):

The material from step 12 a) was placed in a flask and melted in vacuo to remove residual 2-propanol, yielding 26.5 g (68.1 mmol) of solvent-free material. This material was dissolved in 200 ml of DCM. In another flask, a solution of trifluoromethanesulfonic acid (1.6 ml, 17 mmol) in 200 ml DCM was prepared. The solution of starting material was slowly dropped into the acid solution over 30 minutes while maintaining the reaction temperature in the range between 0 and 10 ℃. After the end of the addition, the mixture was stirred at 0 to 10 ℃ for a further 1 hour. Triethylamine (3 ml, 22 mmol) was then added and the reaction quenched. The reaction mixture was concentrated to a total volume of about 100 ml, isopropanol (150 ml) was added and more solvent was removed by rotary evaporation at a bath temperature of 70 ℃ and a final pressure of 350 mbar until a volume of 100 ml was reached. When the product started to crystallize, the flask was removed from the heating bath and cooled to room temperature. The product was filtered and washed with isopropanol (100 ml). The crude product was then recrystallized from a mixture of isopropanol (150 ml) and toluene (50 ml) to give 11.7 g (44%) of a colorless solid.

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC)CS₂: acetone (acetone) -d₆ 5:1)：δ/δ＝(32.37/1.63,CH₃),(32.42/1.62,CH₃),(33.27/2.14,CH₂),(33.77,C-q),(36.11/2.14,CH₂),(55.55,C-q),(120.29/7.75,CH),(121.51/7.66,CH),(121.88,C-q),(125.08/7.20,CH),(126.21/6.82,CH),(126.72/7.48,CH),(127.28/7.15,CH),(127.60/7.35,CH),(128.12/7.26,CH),(128.28/7.36,CH),(129.02/6.24,CH),(130.46/7.49,CH),(136.54,C-q),(138.80,C-q),(139.00,C-q),(146.00,C-q),(154.79,C-q),(157.17,C-q).

Example 13:

Mixture of 2-bromo-7 '-methoxy-4', 4 '-dimethyl-3', 4 '-dihydro-2' h-spiro- [ fluorene-9, 1 '-naphthalene ] (a) with 2-bromo-5' -methoxy-4 ',4' -dimethyl-3 ',4' -dihydro-2 'h-spiro- [ fluorene-9, 1' -naphthalene ] (B) step 13 a):

2-bromo-9- (3-methoxyphenyl) -9- (3-methylbut-2-en-1-yl) -9H-fluorene

The flask was charged with the product from step 9a of example 9 (32.6 g, 92.8 mmol) followed by THF (180 ml). Sodium tert-butoxide (10.7 g, 111 mmol) was added to the resulting solution at a temperature between 0 and 15 ℃. The solution turned red immediately. Isopentenyl chloride (purity about 85 mass%, 14.6 g, 119 mmol) was added over about 5 minutes at a temperature between 5 and 25 ℃. After stirring at room temperature for 1 hour, 75 ml of n-heptane was added to the reaction mixture followed by a 1:1 mixture of 75 ml of saturated ammonium chloride solution and water. The organic layer was separated and dried over MgSO ₄. After filtration the solvent was removed from the filtrate by rotary evaporation and the crude product was purified by column chromatography (silica gel, n-heptane: ethyl acetate 95:5) to give 29.6 g (76%) of the product as a colourless oil.

¹³C NMR：(101MHz,CS₂ : Acetone (acetone) -d₆ 5:1)：δ＝159.76(q),153.73(q),151.21(q),144.83(q),139.55(q),139.48(q),133.76(q),130.32(p),129.49(p),127.99(p),127.87(p),127.56(p),124.77(p),121.40(q),121.39(p),120.13(p),119.71(p),119.28(p),113.59(p),111.35(p),58.87(q),54.71(t),36.45(s),25.78(t),17.98(t).

Step 13 b):

mixtures of 2-bromo-7 '-methoxy-4', 4 '-dimethyl-3', 4 '-dihydro-2' H-spiro- [ fluorene-9, 1 '-naphthalene ] (A) with 2-bromo-5' -methoxy-4 ',4' -dimethyl-3 ',4' -dihydro-2 'H-spiro- [ fluorene-9, 1' -naphthalene ] (B)

The product from step 13 a) (23.6 g, 56.3 mmol) was dissolved in 80 ml of dichloromethane in a flask. This solution was added dropwise over 20 minutes to a 20 ℃ solution of trifluoromethanesulfonic acid (2.0 ml, 22.4 mmol, 0.4 eq.) in DCM (100 ml). The resulting dark reaction mixture was stirred at room temperature for 30 minutes, then quenched by the addition of 5ml of triethylamine. The dark color immediately disappeared. The solvent was stripped and the crude product was partitioned between cyclohexane (150 ml) and water (50 ml). The aqueous layer was separated and extracted with a mixture of cyclohexane (20 ml) and TBME (5 ml). The combined organic layers were evaporated. Repeated recrystallization from isopropanol (about 4 ml/g) gave product a in 7.79 g yield. The combined mother liquors were evaporated and subjected to column chromatography, followed by crystallization of the product fraction from isopropanol to give isomer B (4.95 g) and an additional amount of isomer a (2.96 g). Total yield of a: 46% of B was found to be present in a total yield of 21%.

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC)CS₂ of isomer a: acetone (acetone) -d₆ 5:1)：δ/δ＝(32.34/1.57,CH₃),(32.40/1.56,CH₃),(33.21,C-q),(33.37/2.09,CH₂),(36.07/2.08,CH₂),(54.48/3.45,CH₃),(55.75,C-q),(113.13/5.67,CH),(113.47/6.72,CH),(120.32/7.77,CH),(121.62/7.69,CH),(121.62,C-q),(124.93/7.19,CH),(127.60/7.35,CH),(127.79/7.37,CH),(128.08/7.26,CH),(128.12/7.33,CH),(130.44/7.42,CH),(137.67,C-q),(138.32,C-q),(138.70,C-q),(138.95,C-q),(154.60,C-q),(156.98,C-q),(157.44,C-q).

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC)CS₂ of isomer B: acetone (acetone) -d₆ 5:1)δ/δ＝(28.92/1.68,2×CH₃),(33.21,C-q),(33.84/2.07,CH₂),(38.88/2.07,CH₂),(54.94/3.90,CH₃),(56.07,C-q),(109.95/6.67,CH),(120.24/7.73,CH),(121.46/7.64,CH),(121.69,C-q),(121.95/5.81,CH),(125.15/7.17,CH),(126.73/6.76,CH),(127.48/7.33,CH),(127.98/7.23,CH),(128.32/7.30,CH),(130.31/7.46,CH),(134.50,C-q),(138.74,C-q),(138.87,C-q),(138.95,C-q),(154.77,C-q),(157.21,C-q),(158.84,C-q).

Example 14:

2-bromo-4 ',4',5',8' -tetramethyl-3 ',4' -dihydro-2 'H-spiro- [ fluorene-9, 1' -naphthalene ]

Step 14a:

2-bromo-9- (4-methylpent-3-en-1-yl) -9-phenyl-9H-fluorene

Isopentenyl chloride was prepared from 2-methyl-3-buten-2-ol and 32% HCl as described in Synthesis,1990 (11), 1027-1031. The resulting product contained 84% of isopentenyl chloride and 16% of 3-chloro-3-methylbut-1-ene, which was used in the resulting state.

1 Liter was bottled to give the product from example 4, step 4 b) (110.74 g, 0.317 mol) and THF (300 ml). To the resulting solution was added sodium t-butoxide (34.4 g, 0.348 mol) and a dark red suspension formed. The mixture was cooled (ice bath) and then isopentenyl chloride (39.8 g, 0.380 mol) was added.

A yellow suspension was formed to which water (200 ml) and heptane (200 ml) were added. After brief stirring and separation of the layers, the organic layer was separated and dried over MgSO ₄. The crude product (138.9 g, 92% purity) was obtained after removal of the solvent as a yellow-orange resin and was used directly in the next step.

Step 14b:

The material from step 14 a) of example 14 (137.4 g, 0.329 mol) was dissolved in Wen Lvben (500 ml) and added 15 (Hydrogen form) (26.4 g). The mixture was heated at reflux overnight and then cooled to ambient temperature. To remove Amberlyst, the mixture was filtered through a pad of silica. The silica pad was washed with toluene and the solvent was removed from the combined filtrates using a rotary evaporator. The residue was redissolved in heptane (300 ml) at 80 ℃ and the solution was then cooled slowly. The small sample in the flask was scraped to give a seed crystal, which was added to the heptane solution at 30 ℃. The product began to crystallize slowly and after stirring at ambient temperature for 3 hours the crystals were filtered and washed with heptane (150 ml) and methanol (50 ml). After drying 43.1 g of a product with a purity of 94.4% are obtained. Recrystallisation from heptane gave 39.2 g (31.8% yield) of the product with 99% purity.

¹H NMR：(400MHz,CS₂ : Acetone -d₆ 5:1)δ7.75(d,J＝7.4Hz,Ar-H,1H),7.66(d,J＝8.0Hz,Ar-H,1H),7.46(br,Ar-H,1H),7.33(br,Ar-H,1H),7.24(td,J＝7.4,1.1Hz,Ar-H,1H), was about 7.20 (br, ar-H,1H, overlap ),7.14-6.94(br,Ar-H,1H),6.92(d,J＝7.6Hz,Ar-H,1H),6.63(d,J＝7.6Hz,Ar-H,1H),2.66(s,CH₃,3H),2.43(br,CH₂,1H),2.26(br,CH₂,1H),1.68(s,CH₃,3H),1.66(s,CH₃,3H),1.63(br,CH₂,1H, recognized by HSQC as being due to overlap with CH ₃ -signal), 1.22 (br, CH ₂,1H),1.01(s,CH₃, 3H). Chemical shifts of broad aromatic multiple peaks due to the functional group structure of the compound cannot be accurately determined due to overlap with other signal moieties.

Example 15:

3, 3-dimethylindan-1-one

Step 15 a):

3-methyl-3-phenylbutyric acid

The starting material 3-methyl-3-phenylbutyric acid was prepared by the procedure described in J.E.Leffer and J.T.Barbas, J.am.chem.Soc.1981,103 (26), 7768-7773. 105 g (58.5%) of 3-methyl-3-phenylbutyric acid were obtained from 168 g (1.0 mol) of fresh phenylchloride. The solvent was removed from the mother liquor to give a residue (55 g) containing 70% of the acid. Thus, about 20% of additional product was obtained.

¹H NMR:(400MHz,CDCl₃):δ＝7.42('d',2H),7.37('tr',2H),7.25('tr',1H),2.70(s,2H),1.52(s,6H).¹³C NMR:(101MHz,CDCl₃)δ178.13(CO),148.02(q),128.27(2Ar-CH),126.09(Ar-CH),125.43(2Ar-CH),48.07(CH₂),37.03(q),28.85(2CH₃).

Step 15 b):

3, 3-dimethylindan-1-one

The flask was filled with sulfuric acid 96% (200 ml) and heated to 50 ℃. 102 g (0.572 mol) of solid 3-methyl-3-phenylbutyric acid from step 15 a) were then added. The temperature of the mixture was increased to 95 ℃ during the addition, and the mixture was then kept at 80 ℃ with stirring until the conversion was over (20 minutes). The mixture was cooled to 50 ℃ and poured onto crushed ice (500 g). Heptane (30 ml) was added to the resulting micro-temperature mixture and the organic layer was separated. The aqueous layer was extracted with additional heptane (30 ml) and TBME (50 ml). The combined organic layers were neutralized with saturated potassium hydrogencarbonate solution and dried over sodium sulfate. After removal of the solvent from the filtrate, 3-dimethylindan-1-one is obtained as a colorless oil (66.4 g, 72%, purity > 99%).

¹H NMR:(400MHz,CDCl₃):δ＝7.49,("d",1H),7.40("tr",1H),7.32("d",1H),7.15("tr",1H),2.38(s,2H),1.21(s,6H).

¹³C NMR:(101MHz,CDCl₃):δ＝205.19(CO),163.55(q),135.15(q),134.79(CH),127.24(CH),123.43(CH),123.04(CH),52.72(CH₂),38.29(q),29.82(CH₃).

Example 16:

2-chloro-3 ',3' -dimethyl-10-phenyl-2 ',3' -dihydro-10H-spiro- [ acridine-9, 1' -indene ]

Step 16 a):

6-chloro-3 ',3' -dimethyl-1-phenyl-2 ',3' -dihydrospiro- [ benzo [ d ] [1,3] oxazin-4, 1' -indene ] -2 (1H) -one

To a solution of tert-butyl-N- (2-bromo-4-chloro-phenyl) -N-phenylcarbamate (27.0 g 70.6 mmol) in THF (250 ml) cooled to-70 ℃ was added N-butyllithium (30 ml, 74.1 mmol) under an inert atmosphere while maintaining the temperature between-70 and-50 ℃. The mixture was stirred at-75 ℃ for 1 hour, then a solution of 3, 3-dimethylindan-1-one (12.4 g, 77.6 mmol) from step 9 b) of example 9 in THF (30 ml) was added while maintaining the temperature between-70 and-40 ℃. The mixture was stirred continuously in the cold bath for a further 15 minutes, and then the mixture was warmed to 20 ℃. The solvent was removed by rotary evaporator and the residue was dissolved in toluene (200 ml) and then filtered through a pad of silica gel. The silica pad was washed with additional toluene (100 ml) and the solvent was removed from the filtrate. After silica gel chromatography (heptane/ethyl acetate gradient 9:1→4:1) and precipitation from heptane (50 ml), the product was obtained as an off-white solid (6.3 g, 25%).

¹³C NMR：(101MHz,CS₂ : Acetone (acetone) -d₆ 5:1)：δ＝153.67(q),149.01(q),139.37(q),138.35(q),137.54(q),130.91(p),129.89(p),129.18(p),129.14(q),128.59(p),128.57(p),128.43(q),127.91(p),125.42(p),124.82(p),123.08(p),116.94(p),90.17(q),55.14(s),42.86(q),30.89(t),29.42(t).

Step 16 b):

2-chloro-3 ',3' -dimethyl-2 ',3' -dihydro-10H-spiro- [ acridine-9, 1' -indene ]

To a solution of the product of step 16 a) (5.90 g, 15.1 mmol) in glacial acetic acid (80 ml) was added sulfuric acid 96% (0.83 g, 8.3 mmol). The mixture was refluxed for 1 hour, cooled to 40 ℃, and then quenched by the addition of triethylamine (5.0 ml). The solvent was removed by rotary evaporation and the residue was partitioned between DCM (50 ml) and 20% aqueous sodium hydroxide (50 ml). TBME (20 ml) was added to facilitate phase separation. The organic layer was separated and evaporated in the presence of 20 g of silica gel. The crude compound adsorbed onto the silica gel was placed on a column containing 40 g of silica gel. Eluting with 4:1 heptane/ethyl acetate to give the desired compound. The product (4.14 g, 79%) was obtained as a yellowish solid after removal of the solvent from the eluate.

¹³C NMR：(101MHz,CS₂ : Acetone (acetone) -d₆ 5:1)：δ＝153.78(q),145.03(q),139.11(q),138.32(q),131.48(q),129.11(q),128.35(p),127.90(p),127.35(p),126.96(p),126.93(p),126.88(p),126.53(p),124.93(q),122.62(p),120.78(p),114.89(p),113.77(p),61.99(s),53.86(q),42.91(q),31.65(t),31.63(t).

Step 16 c):

To a solution of the product from step 11 b) (2.41 g, 6.97 mmol) in bromobenzene (25 g, 0.16 mol, 23 eq.) was added tris (dibenzylideneacetone) dipalladium (0) (33 mg, 35 μmol, 0.5 mol%), 4- (di-tert-butylphosphine) -N, N-dimethylaniline (38 mg, 0.14 mmol, 2 mol%) and sodium tert-butoxide (0.837 g, 8.71 mmol, 1.25 eq.) under an inert atmosphere. The resulting solution was stirred at 90℃for 16 hours. Silica gel (10 g) was then added and the mixture was stirred briefly and filtered through silica gel (10 g). The solvent was removed from the filtrate using a rotary evaporator. After methanol (20 ml) was added to the residue, the product crystallized and was filtered. The product (2.83 g, 96%) was obtained as a yellowish solid after washing with methanol (15 ml) and drying.

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC)CS₂: acetone (acetone) -d₆ 5:1)：δ/δ＝(31.59/1.32,CH₃),(31.61/1.36,CH₃),(43.02,C-q),(53.94,C-q),(62.27/2.35,CH₂),(114.29/6.35,CH),(115.42/6.33,CH),(121.31/6.75,CH),(122.86/7.40,CH),(125.81,C-q),(126.31/6.88,CH),(126.68/6.92,CH),(126.74/6.65l,CH),(127.11/7.23,CH),(127.17/6.64,CH),(128.03/7.43,CH),(128.60/7.47,CH),(128.63/7.58,CH),(130.59,C-q),(131.08/7.70,2×CH),(131.17/7.41,2×CH),(132.94,C-q),(140.18,C-q),(140.77,C-q),(141.02,C-q),(144.48,C-q),(154.02,C-q).

Example 17:

2 '-chloro-3, 3-dimethyl-2, 3-dihydro-spiro- [ indene-1, 9' -xanthene ]

The flask was charged under an inert atmosphere with 4-chlorodiphenyl ether (17.0 g, 83.1 mmol) and diethyl ether (80 ml). After cooling to-10 ℃, a 2.5M solution of n-butyllithium in hexane (40 ml, 91 mmol) was added dropwise to the resulting solution while maintaining the temperature in the range between-10 and-5 ℃. The reaction mixture was stirred for 20 hours. THF (50 ml) was then added and the mixture was cooled to-40 ℃. A solution of the product from step 9 b) of example 9 (16.1 g, 99.7 mmol) in THF was added dropwise while maintaining the temperature between-40 and-30 ℃. After the addition was complete, the cooling bath was removed and the mixture was warmed to ambient temperature. After addition of a mixture of saturated NH ₄ Cl solution (50 ml) and water (50 ml) followed by layer separation, the organic layer was separated and the solvent was removed with a rotary evaporator. The residue was dissolved in glacial acetic acid (150 ml). Sulfuric acid (15 ml, 96%) was added and the reaction was heated to 100 ℃ for 1 hour. After cooling to 20 ℃, the mixture was poured into water (400 ml) and extracted 2 times with cyclohexane (100 ml, then 50 ml). The combined organic layers were washed with 20% aqueous sodium hydroxide (100 ml). The organic layer was separated, filtered through a pad of silica gel, and then washed with cyclohexane (300 ml). The filtrate was evaporated and the residue was dissolved in isopropanol (60 ml) from which the first product was obtained as a white solid (3.70 g). The second fraction was obtained by removing the solvent from the mother liquor at a temperature up to 190 ℃ under vacuum (15 mbar). Crystallization from the subsequent residue of acetonitrile (50 ml) gives a further 3.65 g of the desired product. Total yield: 7.35 g, 26%.

¹³C NMR：(101MHz,CS₂ : Acetone (acetone) -d₆ 5:1)：δ＝153.52(q),151.50(q),149.43(q),145.86(q),132.32(q),131.70(q),131.30(q),128.34(p),128.12(p),128.08(p,2C),127.98(p),127.39(p),126.70(p),123.26(p),122.50(p),116.33(p),116.24(p),62.94(s),51.41(q),43.17(q),31.88(t),31.78(t).

Example 18:

2 '-bromo-3, 3-dimethyl-2, 3-dihydrospiro- [ indene-1, 9' -xanthene ]

Step 18 a):

3, 3-dimethyl-2, 3-dihydro-spiro- [ indene-1, 9' -xanthene ]

The flask was charged under an inert atmosphere with diphenyl ether (34.0 g, 200 mmol) and THF (120 ml). After cooling to-30 ℃, 88 ml (220 mmol) of a 2.5M solution of n-butyllithium in hexane was added dropwise to the resulting solution while maintaining the temperature in the range between-30 and-20 ℃. The reaction mixture was warmed to 20 ℃ over 1 hour to complete the lithiation reaction, and then cooled again to 0 ℃. A solution of 3, 3-dimethylindan-1-one (28.9 g, 180 mmol) from step 9 b) of example 9 is added dropwise while maintaining the temperature between 0 and 10 ℃ followed by stirring at 5 ℃ for 30 minutes. The reaction was quenched by the addition of a mixture of 32% HCl (50 ml) and water (25 ml) at 15 to 25 ℃. The organic layer was separated and the solvent removed with a rotary evaporator. The residue was dissolved in glacial acetic acid (250 ml), sulfuric acid 96% (25 ml) was added and the mixture was heated to 110 ℃ for 3 hours. The reaction mixture was then cooled to room temperature and extracted 2 times with cyclohexane (300 ml for the first time, then 100 ml). The combined cyclohexane layers were neutralized with saturated potassium bicarbonate solution (500 ml). The organic layer was separated and the solvent removed by rotary evaporation. The residue was crystallized from acetonitrile (100 ml), filtered, washed with acetonitrile (50 ml) and dried to give 17.5 g of a colorless solid. Another portion was obtained by concentrating the mother liquor and adding methanol (100 ml) followed by washing with methanol (50 ml). The overall yield of the product was 20.3 g (36.1%).

¹³C NMR：(101MHz,CS₂ : Acetone (acetone) -d₆ 5:1)：δ＝153.54(q),151.38(q),145.78(q),131.65(q),128.38(p),128.11(p),127.94(p,2C),127.47(p,2C),126.67(p),123.50(p,2C),122.50(p),116.39(p,2C),62.93(s),51.37(q),43.17(q),31.83(t).

Step 18 b):

2 '-bromo-3, 3-dimethyl-2, 3-dihydrospiro- [ indene-1, 9' -xanthene ]

The material from step 18 a) (27.0 g, 86.4 mmol) was dissolved in a mixture of acetonitrile (150 ml) and chlorobenzene (15 ml) at 70 ℃. N-bromosuccinimide (15.4 g, 86.4 mmol) was added in small portions over 30 minutes. The reaction was refluxed for 24 hours, then methanol (35 ml) was added to prevent the succinimide from precipitating on cooling. The mixture was cooled to 40 ℃ and seed crystals were added. After cooling to room temperature, the solid formed was filtered and washed with acetonitrile (50 ml) followed by methanol (50 ml). The compound was dried and recrystallized from a mixture of toluene (30 ml) and isopropanol (30 ml) to give 10.3 g (31%) of the title compound as a colorless solid.

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC)CS₂: acetone (acetone) -d₆ 5:1)：δ/δ＝(31.82/1.40,CH₃),(31.86/1.43,CH₃),(43.29,C-q),(51.50,C-q),(62.85/2.36,CH₂),(116.20,C-q),(116.45/7.11,CH),(118.28/7.04,CH),(122.73/7.36,CH),(123.87/6.94,CH),(126.51/6.98,CH),(127.74/7.18,CH),(127.95/6.69,CH),(128.41/7.33,CH),(128.81/7.43,CH),(130.45/7.29,CH),(130.46/6.83,CH),(131.07,C-q),(134.00,C-q),(144.81,C-q),(150.61,C-q),(151.10,C-q),(153.60,C-q).

Example 19:

2' -bromo-3,3,7 ' -trimethyl-2, 3-dihydrospiro- [ indene-1, 9' -xanthene ]

Step 19 a):

The flask was charged with THF (200 ml) and 4-methyldiphenyl ether (36.8 g, 200 mmol, 1 eq.) under an inert atmosphere. After cooling to-70 ℃, a 2.5M solution of n-butyllithium in hexane (80 ml, 200 mmol, 1 eq.) was added while maintaining the temperature in the range between-75 and-50 ℃. The reaction was then warmed to ambient temperature overnight. After cooling again to-75 ℃, a solution of the product from example 9 (35.2 g, 220 mmol, 1.1 eq.) in THF (80 ml) was added dropwise while maintaining the temperature in the range of-75 to-70 ℃. The time required for this addition was 60 minutes.

The mixture was stirred in the cooling bath for another 45 minutes and then warmed to-20 ℃. The reaction was then quenched by addition of a mixture of saturated ammonium chloride solution (60 ml) and water (40 ml). After cyclohexane (100 ml) was added and stirred for several minutes, the layers were separated. The solvent was distilled from the organic layer and the unreacted starting material was distilled in vacuo at a pressure of 20 mbar and an external temperature of 200 ℃.

The residue was dissolved in glacial acetic acid (300 ml) at 40 ℃. Sulfuric acid (96%, 30 ml, 54 g, 0.53 mol) was added and the reaction was stirred at 80 ℃ for 1 hour. After cooling to 30 ℃, the reaction mixture was poured into water (700 ml) and extracted 3 times with cyclohexane (200 ml, then 50ml 2 times). The combined organic extracts were washed with water (200 ml) and then the solvent was removed with a rotary evaporator. The residue was crystallized from isopropanol (100 ml, 60 ℃ C. To 20 ℃ C.). The crystals were filtered and dried to give 16.9 g of the desired compound as colorless crystals. After column chromatography (silica gel, heptane) and crystallization from methanol (50 ml), a second batch of 4.6 g was obtained from the mother liquor. Total yield: 21.5 g (33%).

¹³C NMR：(101MHz,CS₂ Acetone -d₆ 5:1)δ153.51(Cq),151.49(Cq),149.42(Cq),145.85(Cq),132.31(Cq),131.69(Cq),131.28(Cq),128.33(Cp),128.11(Cp),128.08(2*Cp),127.98(Cp),127.38(Cp),126.70(Cp),123.26(Cp),122.49(Cp),116.32(Cp),116.24(Cp),62.94(Cs),51.40(Cq),43.16(Cq),31.89(Ct),31.79(Ct),21.07(Ct).

Step 19 b):

2' -bromo-3,3,7 ' -trimethyl-2, 3-dihydrospiro- [ indene-1, 9' -xanthene ]

The product from step 19 a) (21.0 g, 64.3 mmol, 1.0 eq.) was suspended in acetonitrile (120 ml). The mixture was heated to 70 ℃ to dissolve the starting material, then N-bromosuccinimide (11.5 g, 64.3 mmol, 1.0 eq) was added and the mixture heated at reflux for 1 hour. GC analysis of the mixture at this time showed unreacted starting material. More N-bromosuccinimide (1.2 g, 6.7 mmol, 0.1 eq) was added and the mixture was kept at reflux for a further 2 hours. Methanol (12 ml) was then added and after cooling to 5 ℃ the product crystallized. The crystals were filtered and washed with a mixture of acetonitrile (15 ml) and methanol (15 ml). The product was recrystallized from isopropanol (200 ml, reflux to-10 ℃), filtered, washed with isopropanol (50 ml, 0 ℃), and dried to give 17.6 g (68%) of the desired compound as a colourless powder.

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC)CS₂: acetone (acetone) -d₆ 5:1)δ,δ(21.06/2.21,CH₃),(31.77/1.40,CH₃),(31.82/1.40,CH₃),(43.25,C-q),(51.5,C-q),(62.83/2.32,CH₂),(115.89,C-q),(116.27/6.97,C-H),(118.2/6.99,C-H),(122.7/7.35,C-H),(126.51/6.95,C-H),(128.04/6.46,C-H),(128.36/7.32,6.97,2C-H),(128.74/7.425,C-H),(130.32/7.25,C-H),(130.46/6.74,C-H),(130.67,C-q),(132.77,C-q),(134.01,C-q),(144.86,C-q),(149.11,C-q),(150.69,C-q),(153.55,C-q).

Example 20:

2' -bromo-3, 3-dimethyl-7 ' - (trifluoromethyl) -2, 3-dihydro-spiro- [ indene-1, 9' -xanthene ]

Step 20 a):

3, 3-dimethyl-2 '- (trifluoromethyl) -2, 3-dihydro-spiro- [ indene-1, 9' -xanthene ]

The flask was charged with THF (200 ml) and 4-trifluoromethyl diphenyl ether (23.8 g, 100 mmol,1 eq) under an inert atmosphere. The solution was cooled to-75 ℃ and 2.3M n-hexyllithium (44 ml, 100 mmol,1 eq.) was added to hexane while maintaining the temperature below-50 ℃.

The mixture was then warmed to ambient temperature overnight. After cooling the mixture back to-75 ℃, a solution of the product of example 9 (17.6 g, 110 mmol, 1.1 eq.) in THF (40 ml) was added over 30 minutes while maintaining the temperature below-60 ℃. After the addition was complete, stirring was continued for another 30 minutes at about-60 ℃, and the mixture was then warmed to-15 ℃.

A mixture of saturated ammonium chloride solution (60 ml) and water (40 ml) was added to quench the reaction. Cyclohexane (100 ml) was then added to the reaction mixture, and after delamination the organic layer was separated and the solvent was removed from it with a rotary evaporator. Unreacted starting material was distilled off from the residue in vacuo (14 mbar) at an oil bath temperature of 200 ℃. The remaining residue was dissolved in glacial acetic acid (150 ml) and sulfuric acid (96%, 15 ml, 27 g, 0.27 mol) was added. The mixture was stirred at 80℃for 19 hours. After cooling to 30 ℃, the mixture was poured into water (750 ml) and the product was extracted with cyclohexane/TBME 9:1 (200 ml, then 50ml 2 times). The combined organic extracts were washed with water (100 ml) and the solvent was removed using a rotary evaporator. The residue was purified by chromatography (silica gel, heptane > heptane/DCM 9:1). Solvent was removed from the product containing fractions to give a colourless oil (20.9 g, 50% based on 4-trifluoromethyl diphenyl ether).

¹³C NMR：(101MHz,CS₂ Acetone -d₆)δ153.76(q,q,J＝1.4Hz),153.60(q),150.76(q),144.70(q),132.38(q),130.99(q),128.91(p),128.47(p),127.98(p),127.87(p),126.34(p),125.46(q,q,J＝32.6Hz),125.26(p,q,J＝3.8Hz),124.65(p,q,J＝3.7Hz),124.27(p),123.99(q,J＝272.0Hz),122.77(p),116.98(p),116.45(p),62.97(s),51.38(q),43.28(q),31.74(t),31.66(t).

Step 20 b):

To a solution of the product from step 20 a) (16.4 g, 43.1 mmol, 1.0 eq.) in chlorobenzene (20 ml) was added iodine (0.1 g, 0.4 mmol, 0.9 mol%). The mixture was cooled to-30 ℃ and then bromine (7.0 g, 43.8 mmol, 1.02 eq.) was added over 2 minutes. The mixture was warmed to 20 ℃ after the exothermic reaction ceased. The reaction was checked after 60 minutes for conversion of starting material by GC. Additional bromine (0.70 g, 4.4 mmol, 0.10 eq.) was added at 20 ℃ and the mixture stirred at 20 ℃ for a further 3 hours. Finally, 20% aqueous sodium hydroxide (20 ml) was added to quench the reaction. The organic layer was separated and the aqueous layer was extracted with TBME (10 ml). The combined organic extracts were washed with water (100 ml), filtered with a cotton plug and evaporated to dryness at a temperature of up to 120 ℃ at 25 mbar to remove more volatile material. The residue was pure product and obtained as colorless glassy solid.

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC)CS₂: acetone (acetone) -d₆ 5:1)δ/δ(31.61/1.40,CH₃),(31.73/1.44,CH₃),(43.39,C-q),(51.47,C-q),(62.88/2.37,2.36,CH₂),(117.02,C-q),(117.05/7.26,C-H),(118.32/7.09,C-H),(122.98/7.41,C-H),(123.88/,C-q,q,J＝272.1Hz),(124.91/7.49,C-H,q,J＝3.7Hz),(125.27/7.09,C-H,q,J＝3.8Hz),(125.86/,C-q,q,J＝32.6Hz),(126.16/6.98,C-H),(128.75/7.39,C-H),(129.31/7.49,C-H),(130.52/6.84,C-H),(130.86/7.34,C-H),(131.82,C-q),(133.28,C-q),(143.76,C-q),(149.95,C-q),(153.41/,C-q,q,J＝1.3Hz),(153.65,C-q).

Example 21:

3, 4-dihydro-2H-spiro- [ naphthalen-1, 9 '-xanthene ] -2' -amine

Step 21 a):

A solution of diphenyl ether (51.0 g, 0.30 mol, 1.0 eq.) in THF (100 ml) was cooled to-75deg.C. Then added dropwise to a 2.5M solution of n-butyllithium in hexane (120 ml, 0.30 mol, 1.0 eq.) under an inert atmosphere while maintaining the temperature in the range between-78 and-50 ℃. The mixture was then warmed to ambient temperature overnight. It is then cooled back to-75 ℃ and added dropwise to a solution of alpha-tetralone (45.3 g, 310 mmol, 1.03 eq.) in tert-butyl methyl ether (30 ml) while maintaining the temperature in the range between-75 and-60 ℃. When the addition was complete, stirring was continued in the cooling bath for 30 minutes. The reaction was then warmed to-10 ℃ and quenched by the addition of saturated ammonium chloride solution (100 ml). The organic layer was separated and the aqueous layer was extracted with toluene (50 ml). The solvent was removed from the combined organic layers using a rotary evaporator.

Unreacted material was then removed from the residue by vacuum distillation (20 mbar) at a temperature of up to 190 ℃. After cooling, the residue was dissolved in glacial acetic acid (400 ml), sulfuric acid (96%; 27 ml, 39 g, 0.48 mol) was added, and the mixture was heated to 110 ℃ over 60 minutes. After cooling to 20 ℃, the reaction mixture was poured into water (1.2 l). The product was extracted with toluene (100 ml3 times). The solvent was removed from the combined extracts using a rotary evaporator. The crude product obtained was dissolved in cyclohexane (100 ml) at 60 ℃ and purified by column chromatography (d=12.5 cm, h=5 cm, eluting with 4 liters of heptane). After evaporation of the solvent 45 g of a colourless oil are obtained, which is crystallised from 94% ethanol (denaturation with 1% toluene, 450 ml, reflux → 0 ℃). The crystals were filtered and washed 2 times with 94% ethanol (30 ml each) to give 38.5 g (43%) of the desired product.

¹³C NMR：(101MHz,CS₂ Acetone -d₆ 5:1)δ151.25(q),140.57(q),138.94(q),132.18(p),131.71(q),129.54(p),128.82(p),127.42(p),126.71(p),126.60(p),123.02(p),116.22(p),44.22(q),43.17(s),30.58(s),19.14(s).

Step 21 b):

2 '-Nitro-3, 4-dihydro-2H-spiro- [ naphthalene-1, 9' -xanthene ]

The product from step 21 a) (38.0 g, 127 mmol, 1.0 eq.) was dissolved in a mixture of chlorobenzene (100 ml) and glacial acetic acid (50 ml). A mixture of sulfuric acid (96%; 23.5 g, 0.24 mol, 1.9 eq.) and nitric acid (99%, 8.9 g; 0.14 mol, 1.1 eq.) was prepared in an Erlenmeyer flask. The nitrating acid was transferred to a dropping funnel, and the residual acid in the conical flask was dissolved in glacial acetic acid (20 ml) and added directly to the reaction mixture at 10 ℃. The nitrating acid was added dropwise to the reaction mixture at a temperature of 10℃over 30 minutes. Stirring was continued for 1 hour at 10 ℃ and then quenched with water (250 ml). The organic layer was separated and the aqueous layer was extracted with chlorobenzene (50 ml). The solvent was removed from the combined organic layers using a rotary evaporator, and the remaining crude product was then dissolved in a mixture of isopropanol (200 ml) and toluene (10 ml) at 70 ℃. The product crystallized upon cooling to 30 ℃. The crystals were filtered and washed 2 times with isopropanol (20 ml each). After drying, 29.5 g (68%) of the product are obtained as a colourless solid.

¹³C NMR：(101MHz,CS₂ Acetone -d₆ 5:1)δ155.60(q),150.16(q),143.48(q),139.18(q),139.11(q),132.78(q),131.69(p),130.53(q),129.72(p),129.28(p),128.06(p),127.45(p),127.12(p),125.35(p),124.29(p),123.34(p),117.03(p),116.41(p),44.46(q),43.35(s),30.26(s),18.84(s).

Step 21 c):

3, 4-dihydro-2H-spiro- [ naphthalen-1, 9 '-xanthene ] -2' -amine

The product from step 21 b) (29.0 g, 84.4 mmol, 1.0 eq) was dissolved in THF (100 ml) and methanol (100 ml) was added in a flask. The atmosphere in the flask was changed from air to nitrogen by one cycle of suction and nitrogen. The catalyst (4.2 g of 5% Pd on charcoal, water content 50%,1.0 mmol, 1.2 mol%) was added under nitrogen, followed by suction and hydrogen. The reaction was stirred starting from a temperature of 20 ℃. The temperature rose over 45 minutes to a maximum temperature of 45 c, indicating that hydrogenation was proceeding.

After a total reaction time of 2.5 hours, the starting materials were completely converted and the reaction was cooled to room temperature. The catalyst was filtered under an inert atmosphere with a 25 μm pad of silica gel (d=5 cm, h=2 cm). The pad was washed with a 1:1 mixture of THF and MeOH (200 ml). After evaporation of the solvent, the product was purified by column chromatography (silica gel, heptane: etOAc 9:1.fwdarw.4:1). The product fractions were evaporated to give 24.9 g (94%) of the product as a reddish amorphous solid.

NMR：¹³C/¹H(101MHz,400MHz(HSQC),CD₂Cl₂)δ/δ(18.69/1.80,CH₂),(30.03/2.98,CH₂),(42.67/2.02,CH₂),(44.41,C-q),(114.41/6.58,C-H),(115.24/6.06,C-H),(115.75/7.13,C-H),(116.37/6.98,C-H),(122.19/6.94,C-H),(126.15/7.13,C-H),(126.36/7.25,C-H),(127.12/7.21,C-H),(128.58/7.28,C-H),(129.49/6.70,C-H),(131.81,C-q),(132.03/6.95,C-H),(132.71,C-q),(139.46,C-q),(140.78,C-q),(141.93,C-q),(144.39,C-q),(151.74,C-q).

Example 22:

2 '-chloro-3, 3-dimethyl-2, 3-dihydro-spiro- [ indene-1, 9' -thioxanthene ]

Step 22 a):

(4-chloro-2- (1, 1-dimethyl-1H-inden-3-yl) phenyl) (phenyl) sulfane

(2-Bromo-4-chlorophenyl) (phenyl) sulfane (700 mg, 2.33 mmol) was dissolved in THF (5 ml) under an inert atmosphere. After cooling to-60 ℃, N-BuLi (0.69 g of 2.5N hexane solution, 2.5 mmol) was carefully added via syringe. The mixture was stirred for 5 minutes while the temperature was reduced to-70 ℃. Thereafter 3, 3-dimethylindan-1-one (0.80 g,5 mmol) from step 9 b) of example 9 is added at a temperature below-50 ℃. The mixture was stirred for another 30 minutes and then warmed to ambient temperature. A mixture of water (20 ml) and saturated ammonium chloride solution (20 ml) was added to quench it. The solvent was extracted with TBME (40 ml) and removed from the organic layer to give a residue which was redissolved in acetic acid (25 ml) and sulfuric acid (2 ml). The mixture was heated to 100℃over 45 minutes to effect cyclization. After cooling to 30 ℃ water (100 ml) was added and the mixture was extracted with TBME (20 ml). The extract was chromatographed on silica (Biotage, 100 g) with heptane. After elution with 10 volumes of heptane, the fractions obtained were all free of product and only (4-chlorophenyl) phenyl sulfide was eluted. Thus, chromatography was continued with a column volume of 2 times the heptane/ethyl acetate mixture (4:1, v:v). Here, one fraction contains the product and 3, 3-dimethylindan-1-one in a ratio of about 1:1. Indanone is removed in vacuo (180 ℃,50 mbar) to leave the product (170 mg). The structure of the product was shown by NMR spectrum to be (4-chloro-2- (1, 1-dimethyl-1H-inden-3-yl) phenyl) - (phenyl) sulfane.

Step 22 b):

2 '-chloro-3, 3-dimethyl-2, 3-dihydro-spiro- [ indene-1, 9' -thioxanthene ]

The material from step 12 a) (170 mg, 0.47 mmol, 1.0 eq.) was dissolved in a mixture of boron trifluoride-THF complex (3.0 ml) and dichloromethane (5.0 ml) at 20 ℃. 0.34 g (2.3 mmol) of trifluoromethanesulfonic acid was added, the reaction mixture was stirred for 2 minutes, and then quenched by the addition of water (20 ml). The resulting mixture was extracted with a mixture of heptane (10 ml) and TBME (10 ml). The organic layer was separated and the solvent removed with a rotary evaporator. Cyclohexane (30 ml) was added to the residue and the solution was chromatographed on silica gel using heptane to give 60 mg (35%) of the desired compound as a colourless oil.

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC)CS₂: acetone (acetone) -d₆ 5:1)：δ/δ＝(30.90/1.23,CH₃),(30.93/1.18,CH₃),(42.87,C-q),(54.91/2.39,CH₂),(58.65,C-q),(123.59/7.41,CH),(126.34/7.14,CH),(126.49/7.06,CH),(126.54/7.16,CH),(127.06/7.43,CH),(127.12/6.85,CH),(127.36/6.81,CH),(127.47/7.47,CH),(128.02/7.23,CH),(128.19/7.41,CH),(128.98/7.51,CH),(131.61,C-q),(132.39,C-q),(132.41,C-q),(141.74,C-q),(143.00,C-q),(145.74,C-q),(154.26,C-q).

Example 23:

2' -bromo-3,3,7 ' -trimethyl-2, 3-dihydrospiro- [ indene-1, 9' -thioxanthene ]

Step 23 a):

2', 3-trimethyl-2, 3-dihydrospiro- [ indene-1, 9' -thioxanthene ]

A three-necked flask equipped with a reflux condenser and a dropping funnel was charged with magnesium shavings (1.45 g, 59.7 mmol, 1.26 eq.) and 3 ml of 1-bromo-2- (p-tolylthio) benzene (13.3 g, 47.5 mmol, 1.0 eq.) in THF (40 ml) under an inert atmosphere. A drop of bromine was added to start the reaction. After the start of the grignard reaction, the remaining aryl bromide was added over 15 minutes while maintaining a gentle reflux. After the addition was complete, the reaction mixture was stirred for a further 20 minutes and then cooled to room temperature. The product from example 15b (8.2 g, 51 mmol, 1.1 eq.) was added dropwise over 5 minutes. The mixture was stirred for another 10 minutes after the exothermic reaction ceased. The reaction was then quenched by the addition of 2M aqueous monoammonium citrate (50 ml). The organic layer was separated and the solvent was removed by rotary evaporation. The remaining crude product was dissolved in glacial acetic acid (25 ml) and sulfuric acid (96%, 1.0ml, 18 mmol, 0.39 eq.) was added. The reaction was stirred at 20℃for 30 minutes. It was then poured into water (150 ml) and the product extracted with cyclohexane (40 ml). The organic layer was separated, filtered through a pad of silica gel (d=6cm, h=2cm) and then eluted with cyclohexane (400 ml). The filtrate was evaporated to give 21.6 g of crude (2- (1, 1-dimethyl-1H-inden-3-yl) phenyl) (p-tolyl) sulfane.

It was dissolved in DCM (20 ml) and the solution was added dropwise to a solution of trifluoromethanesulfonic acid (1.0 ml, 11 mmol, 0.24 eq.) in DCM (20 ml) at 20 ℃ over 15 min. The mixture was stirred for another 10 minutes and then quenched with 20% NaOH (40 ml). The product was extracted with TBME (40 ml). The organic layer was dried over magnesium sulfate, filtered, and the solvent was removed from the filtrate using a rotary evaporator. The residue was suspended in isopropanol at 60 ℃ and the suspension cooled back to 20 ℃. The crystals were filtered and washed with cold isopropanol (10 ml) and methanol (20 ml) to give after drying 5.2 g (32%) of a colourless solid.

¹³C NMR：(101MHz,CS₂ : Acetone (acetone) -d₆ 5:1)δ154.27(q),143.77(q),143.65(q),142.63(q),135.52(q),133.22(q),l29.51(q),128.57(p),128.32(p),127.72(p),127.23(p),127.12(p),127.05(p),127.04(p),127.01(p),126.19(p),126.01(p),58.55(q),55.07(s),42.77(q),30.97(t),30.93(t),21.43(t).

Step 23 b):

2' -bromo-3,3,7 ' -trimethyl-2, 3-dihydrospiro- [ indene-1, 9' -thioxanthene ]

The product from step 23 a) (4.8 g, 14 mmol, 1.0 eq.) was suspended in DCM (40 ml). Iodine (0.3 g, 1 mmol, 0.08 eq) was added followed by bromine (2.3 g, 14 mmol, 1.0 eq). The mixture was stirred at 40℃for 30 minutes. The solvent was then removed with a rotary evaporator and the residue was crystallized from acetonitrile (50 ml) at 20 ℃. The crystals were filtered and washed 2 times with acetonitrile (20 ml each). After drying 4.6 g (78%) of the product are obtained as a colourless solid.

NMR：¹³C/¹H(101MHz,400MHz(HSQC),CDCl₃)δ/δ(21.32/2.21,CH₃),(30.88/1.18,2*CH₃),(43.03,C-q),(54.65/2.41,CH₂),(58.66,C-q),(119.87,C-q),(123.39/7.41,C-H),(126.83/7.38,C-H),(127.08/7.01,C-H),(127.18/7.49,C-H),(127.88/6.68,C-H),(128.13/7.28,C-H),(128.35/7.32,C-H),(128.65/7.53,C-H),(128.71,C-q),(129.00/7.29,C-H),(129.91/7.00,C-H),(132.42,C-q),(136.15,C-q),(141.72,C-q),(143.25,C-q),(146.34,C-q),(154.52,C-q).

I.b) preparation of secondary amines

Example 24:

N- (9, 9-dimethyl-9H-fluoren-2-yl) -dibenzo [ b, d ] furan-2-amine

This material is synthesized via coupling of 2-bromo-dibenzo [ b, d ] furan with 9, 9-dimethyl-9H-fluoren-2-amine as described in WO 2018/206769 A1.

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC),CS₂: acetone (acetone) -d₆ 5:1)：δ/δ＝(27.22/1.49,2×CH₃),(46.44,C-q),(110.34/7.76,CH),(110.87/7.17,CH),(111.73/7.52,CH),(112.13/7.46,CH),(115.48/7.05,CH),(118.97/7.56,CH),(119.97/7.28,CH),(120.84/7.90,CH),(120.98/7.54,CH),(122.45/7.36,CH),(122.68/7.31,CH),(124.46,C-q),(124.96,C-q),(125.91/7.17,CH),(127.12/7.24,CH),(127.23/7.44,CH),(131.37,C-q),(139.23,C-q),(139.69,C-q),(144.64,C-q),(151.50,C-q),(152.73,C-q),(155.07,C-q),(156.75,C-q),(7.13,NH).

Example 25:

N1- (9, 9-dimethyl-9H-fluoren-2-yl) -N4, N4-diphenylbenzene-1, 4-diamine

This material is synthesized via coupling of 4-aminotriphenylamine with 9, 9-dimethyl-9H-fluoren-2-amine as described in WO 2012/015265 A1.

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC),CS₂: acetone (acetone) -d₆ 5:1)：δ/δ＝(27.24/1.48,2×CH₃),(46.44,C-q),(111.42/7.15,CH),(116.17/7.02,CH),(118.74/7.08,2×CH),(119.04/7.54,CH),(120.94/7.51,CH),(122.04/6.92,2×CH),(122.45/7.34,CH),(123.12/7.04,4×CH),(126.00/7.16,CH),(126.86/7.00,2×CH),(127.13/7.23,CH),(129.26/7.20,4×CH),(131.68,C-q),(139.60,C-q),(139.75,C-q),(140.29,C-q),(143.43,C-q),(148.03,2×C-q),(152.74,C-q),(154.98,C-q).

Example 26:

n- (4- (9, 9-dimethylacrid-10 (9H) -yl) phenyl) -9, 9-dimethyl-9H-fluoren-2-amine

This material was synthesized via coupling of 9, 9-dimethyl-10- (4' -bromophenyl) -9, 10-dihydro-acridine with 9, 9-dimethyl-9H-fluoren-2-amine as described in CN 111675687A.

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC),CS₂: acetone (acetone) -d₆ 5:1)：δ/δ＝(27.30/1.52,2×CH₃),(31.51/1.68,2×CH₃),(35.74,C-q),(46.55,C-q),(112.89/7.28,CH),(114.46/6.37,2×CH),(117.56/7.15,CH),(118.33/7.34,2×CH),(119.31/7.57,CH),(120.73/6.84,2×CH),(121.04/7.58,CH),(122.53/7.36,CH),(125.21/7.37,2×CH),(126.37/7.19,CH),(126.56/6.92,2×CH),(127.24/7.25,CH),(129.61,C-q),(131.95/7.13,2×CH),(132.55,C-q),(132.84,C-q),(139.40,C-q),(141.22,C-q),(142.31,C-q),(143.75,C-q),(152.86,C-q),(155.03,C-q),(2.32,NH).

Example 27:

n- (9, 9-dimethyl-9H-fluoren-2-yl) -9, 9-dimethyl-10-phenyl-9, 10-dihydro-acridin-2-amine

This material was synthesized via coupling of 9, 9-dimethyl-9H-fluoren-2-amine with 2-bromo-9, 9-dimethyl-10-phenyl-9, 10-dihydro-acridine.

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC),CS₂: acetone (acetone) -d₆ 5:1)：δ/δ＝(27.37/1.43,2×CH₃),(31.63/1.68,2×CH₃),(35.99,C-q),(46.34,C-q),(109.63/6.99,CH),(114.13/6.18,CH),(115.00/6.80,CH),(115.12/6.15,CH),(117.77/7.25,CH),(118.78/6.71,CH),(118.86/7.47,CH),(120.60/6.82,CH),(121.04/7.42,CH),(122.38/7.29,CH),(125.43/7.36,CH),(125.73/7.12,CH),(126.60/6.87,CH),(127.11/7.19,CH),(128.13/7.53,CH),(129.00,C-q),(130.59,C-q),(130.64,C-q),(130.95/7.65,2×CH),(131.49/7.33,2×CH),(136.06,C-q),(136.17,C-q),(139.79,C-q),(140.89,C-q),(141.56,C-q),(144.99,C-q),(152.54,C-q),(154.93,C-q),(6.33,NH).

Example 28:

Bis (dibenzo [ b, d ] furan-2-yl) amine

Step 28 a):

n, N-bis (dibenzo [ b, d ] furan-2-yl) acetamides

This material was synthesized as described in EP2239259 via the coupling of 2-bromodibenzo [ b, d ] furan with acetamide using 1, 4-dioxane as solvent.

Step 28 b):

Bis (dibenzo [ b, d ] furan-2-yl) amine

This amine was synthesized by amide cleavage in ethanol/THF using potassium hydroxide as described in EP 2239259.

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC),CS₂: acetone (acetone) -d₆ 5:1)δ/δ(109.80/7.66,2×CH),(111.74/7.60,2×CH),(112.29/7.53,2×CH),(119.27/7.22,2×CH),(120.74/7.89,2×CH),(122.51/7.34,2×CH),(124.27,2×C-q),(125.11,2×C-q),(127.21/7.48,2×CH),(140.07,2×C-q),(151.74,2×C-q),(156.86,2×C-q),(5.74,NH).

Example 29:

N- (9, 9-dimethyl-9H-fluoren-2-yl) -9, 9-dimethyl-9H-xanthen-2-amine

This material was synthesized as described in WO 2021/141356 A1, using Amphos (di-tert-butyl- (4-dimethylaminophenyl) -phosphine) instead of P (t-Bu) ₃ as catalyst via coupling of 9, 9-dimethyl-9H-fluoren-2-amine with 2-bromo-9, 9-dimethyl-9H-xanthene.

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC),CS₂: acetone (acetone) -d₆ 5:1)：δ/δ＝(27.36/1.50,2×CH₃),(32.59/1.69,2×CH₃),(34.06,C-q),(46.46,C-q),(110.48/7.07,CH),(115.65/6.91,CH),(116.54/7.00,CH),(117.05/7.23,CH),(117.28/6.97,CH),(119.07/7.55,CH),(119.19/6.97,CH),(121.15/7.52,CH),(122.53/7.35,CH),(123.17/7.07,CH),(126.06/7.20,CH),(126.42/7.41,CH),(127.24/7.26,CH),(127.60/7.19,CH),(129.22,C-q),(130.33,C-q),(131.38,C-q),(138.43,C-q),(139.62,C-q),(144.30,C-q),(145.05,C-q),(150.44,C-q),(152.68,C-q),(155.06,C-q),(6.17,NH).

Example 30:

N- (9, 9-dimethyl-9H-fluoren-2-yl) -9, 9-dimethyl-9H-thioxanth-2-amine

This material is similar to WO 2021/141356 A1, synthesized via the coupling of 9, 9-dimethyl-9H-fluoren-2-amine with 2-bromo-9, 9-dimethyl-9H-thioxanthene using Amphos instead of P (t-Bu) ₃ as catalyst.

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC),CS₂: acetone (acetone) -d₆ 5:1)：δ/δ＝(25.22/1.67,2×CH₃),(27.30/1.48,2×CH₃),(40.40,C-q),(46.46,C-q),(111.64/7.18,CH),(114.60/7.37,CH),(115.88/6.97,CH),(116.69/6.99,CH),(119.13/7.55,CH),(121.05/7.52,CH),(122.49/7.35,CH),(123.46,C-q),(124.75/7.49,CH),(126.13/7.15,CH),(126.13/7.19,CH),(126.48/7.23,CH),(127.19/7.25,CH),(127.34/7.39,CH),(128.07/7.26,CH),(132.00,C-q),(133.86,C-q),(139.55,C-q),(142.03,C-q),(142.56,C-q),(143.21,C-q),(143.27,C-q),(152.75,C-q),(154.96,C-q),(6.93,NH).

Example 31:

N- (9, 9-dimethyl-9H-fluoren-2-yl) -9-phenyl-9H-carbazol-3-amine

This material was synthesized following the general procedure of Buchwald-Hartwig amination via coupling of 9- (4-bromophenyl) -9H-carbazole with 9, 9-dimethyl-9H-fluoren-2-amine (see further below).

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC),CS₂: acetone (acetone) -d₆ 5:1)δ/δ(27.36/1.48,2×CH₃),(46.42,C-q),(109.87/7.39,CH),(110.01/7.10,CH),(110.46/7.35,CH),(111.80/7.89,CH),(114.81/6.98,CH),(118.89/7.52,CH),(120.14/7.21,CH),(120.58/8.00,CH),(120.64/7.25,CH),(121.04/7.49,CH),(122.43/7.33,CH),(123.38,C-q),(124.36,C-q),(125.76/7.15,CH),(126.27/7.38,CH),(126.83/7.59,2×CH),(127.14/7.23,CH),(127.30/7.46,CH),(130.08/7.63,2×CH),(130.78,C-q),(136.35,C-q),(136.80,C-q),(138.00,C-q),(139.85,C-q),(141.16,C-q),(145.57,C-q),(152.64,C-q),(155.07,C-q),(6.71,NH).

Example 32:

N- (4- (9H-carbazol-9-yl) phenyl) -9, 9-dimethyl-9H-fluoren-2-amine

This material was synthesized as described in KR2016/12500,2016A via coupling of 9- (4-bromophenyl) -9H-carbazole with 9, 9-dimethyl-9H-fluoren-2-amine.

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC),CS₂: acetone (acetone) -d₆ 5:1)δ/δ(27.29,2×CH3),(46.54,C-q),(109.92/7.36,2×CH),(112.75/7.28,CH),(117.44/7.15,CH),(117.70/7.33,2×CH),(119.30/7.57,CH),(119.95/7.21,2×CH),(120.40/8.05,2×CH),(121.05/7.58,CH),(122.53/7.36,CH),(123.21,2×C-q),(126.04/7.37,2×CH),(126.36/7.19,CH),(127.24/7.25,CH),(128.19/7.39,2×CH),(129.21,C-q),(132.80,C-q),(139.41,C-q),(141.26,C-q),(142.42,C-q),(143.43,2×C-q),(152.84,C-q),(155.05,C-q),(7.25,NH).

Example 33:

N- (9, 9-dimethyl-9H-fluoren-2-yl) -3, 3-dimethyl-2, 3-dihydrobenzofuran-5-amine

The material is synthesized by coupling 9, 9-dimethyl-9H-fluorene-2-amine and 5-bromo-3, 3-dimethyl-2, 3-dihydro-benzofuran.

And (3) NMR: ¹³C/¹H(101MHz/400MHz,CS₂: acetone-d ₆), delta/delta= (27.31/1.44,

2×CH₃),(27.41/1.37,2×CH₃),(41.97,C-q),(46.32,C-q),(84.40/4.20,CH₂),(109.60/6.95,CH),(110.04/6.62,CH),(114.53/6.81,CH),(115.59/6.93,CH),(118.80/7.48,CH),(120.74/6.87,CH),(120.95/7.43,CH),(122.38/7.31,CH),(125.67/7.13,CH),(127.09/7.21,CH),(130.43,C-q),(136.26,C-q),(137.18,C-q),(139.83,C-q),(145.63,C-q),(152.54,C-q),(154.77,C-q),(154.94,C-q),(6.46NH).

Example 34:

n- (9, 9-dimethyl-9H-fluoren-2-yl) benzo [ c ] [1,2,5] thiadiazol-5-amine

The starting material 5-bromobenzo [ c ] [1,2,5] thiadiazole was synthesized as described in RSC adv, 2016,6,66978 via reaction of 4-bromobenzene-1, 2-diamine with thionyl chloride. ¹³C(101MHz,CDCl₃ ) Delta 155.27,153.33,133.20,124.52,123.82,122.17.

As described in the general procedure for Buchwald-Hartwig coupling (see further below), aryl bromo 5-bromobenzo [ c ] [1,2,5] thiadiazole (31.7 g, 147 mmol, 1.0 eq) was coupled with bis (9, 9-dimethyl-9H-fluoren-2-yl) amine (32.4 g, 155 mmol, 1.05 eq) in toluene (250 ml) using sodium tert-butyrate (20% solution in THF; 77.9 g, 162 mmol, 1.1 eq), tri-tert-butylphosphonium tetrafluoroborate (0.54 g, 1.84 mmol, 1.25 mol%) and Pd ₂(dba)₃ (0.68 g, 0.74 mmol, 0.5 mol%).

After cooling, functionalized silica gel (1.5 g, 3-mercaptoethyl sulfide silica, SPM32, phosphonicS.com) was added to the reaction mixture. The suspension was stirred until it appeared homogeneous. It was then filtered through a pad of silica gel (about 25 g) and then washed with toluene having a volume about the same as the column volume. After removal of solvent from the combined filtrates, the product was further purified by column chromatography (heptane/EtOAc) followed by crystallization from cyclohexane. The product was obtained as an orange solid (35.2 g, 70%) with a purity better than 98.3% (according to hplc @340 nm).

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC),CS₂: acetone (acetone) -d₆ 5:1)δ/δ(27.17/1.51,2×CH₃),(46.62,C-q),(99.04/7.45,CH),(114.50/7.34,CH),(119.15/7.22,CH),(119.57/7.59,CH),(121.04/7.63,CH),(121.61/7.74,CH),(122.59/7.37,CH),(125.96/7.42,CH),(126.73/7.21,CH),(127.28/7.26,CH),(134.14,C-q),(139.12,C-q),(140.98,C-q),(145.38,C-q),(151.01,C-q),(153.03,C-q),(155.02,C-q),(156.70,C-q),(7.75,NH).

Example 35:

n- (9, 9-dimethyl-9H-fluoren-2-yl) -3,3,7-trimethyl-2, 3-dihydrobenzofuran-5-amine step 35 a):

5-bromo-3,3,7-trimethyl-2H-benzofuran

To a solution of 4-bromo-2-methylphenol (100 g, 0.53 mol) in DCM (150 ml) was added concentrated sulfuric acid (96%; 28g, 0.28 mol). Methallyl chloride (97 g, 1.1 mole) was added dropwise over 2 hours at a temperature of 30 to 40 ℃. When the addition was complete, the mixture was stirred at a temperature between 20 and 30 ℃ for a further 1 hour. The resulting mixture was then carefully added over 30 minutes to a vigorously stirred aqueous (180 ml) solution of sodium hydroxide (80 g, 2.0 mol). The solvent is partially distilled off due to the heat of neutralization. The remaining dichloromethane was also distilled off, and the remaining mixture was extracted 2 times with cyclohexane (100 ml for the first time, then 50 ml). The combined extracts were dried over sodium sulfate, filtered and concentrated by rotary evaporation. 87 g of the crude product are obtained, which is distilled (bp. =135 to 141 ℃ at 15 mbar). The product was then further purified by column chromatography (silica gel, n-heptane) to yield 19.0 g (15%) of a colorless oil.

¹³C NMR:(101MHz,CDCl₃),δ＝156.68(q),138.04(q),131.72(p),122.85(p),121.89(q),112.13(q),84.52(s),42.42(q),27.49(2*Ct),15.00(t).

Step 35 b):

N- (3,3,7-trimethyl-2, 3-dihydrobenzofuran-5-yl) acetamide

Cuprous iodide (1.42 g, 7.42 mmol), potassium phosphate (22.0 g, 103 mmol) and acetamide (8.82 g, 149 mmol) were placed under an inert atmosphere. 1, 4-dioxane (60 ml), 5-bromo-3,3,7-trimethyl-2H-benzofuran (15.0 g, 62.2 mmol) and N, N' -dimethylethylenediamine (1.32 g, 14.9 mmol) were added. The reaction mixture was then refluxed for 17 hours. After cooling to 20 ℃, the reaction mixture was diluted with ethyl acetate (200 ml) and washed with a mixture of saturated ammonium chloride solution (50 ml) and 25% aqueous ammonia (50 ml). The organic layer was separated, dried over magnesium sulfate and evaporated by rotary evaporation. The residue was recrystallized from a mixture of cyclohexane (50 ml) and ethyl acetate (50 ml), filtered, and washed with a mixture of ethyl acetate (20 ml) and cyclohexane (40 ml) to give 12.8 g (78%) of a colorless solid.

¹³C NMR:(101MHz,DMSO),δ＝167.96(q),153.24(q),136.19(q),133.02(q),120.85(p),118.75(q),112.18(p),83.89(s),42.32(q),27.63(2*Ct),24.23(t),15.48(t).

Step 35 c):

N- (9, 9-dimethylfluoren-2-yl) -N- (3,3,7-trimethyl-2H-benzofuran-5-yl) acetamide

The product from step 35 b) (9.27 g, 42.3 mmol), 2-bromo-9, 9-dimethylfluorene (12.7 g, 46.5 mmol), potassium phosphate (10.9 g, 50.7 mmol) and cuprous iodide (0.80 g, 4.2 mmol) were placed under argon atmosphere. 1, 4-Dioxane (80 mL) was added followed by N, N' -dimethylethylenediamine (0.75 g, 8.5 mmol). The mixture was stirred under reflux for 5 hours, then additional cuprous iodide (0.80 g, 4.2 mmol) was added. The mixture was kept under reflux for 15 hours, then cooled to room temperature and diluted with toluene (100 ml). The organic layer was washed 2 times with saturated ammonium chloride solution (2×50 ml). The aqueous layers were combined and extracted with 20ml of toluene. The combined organic layers were dried over magnesium sulfate, then filtered over a pad of silica gel (d=5 cm, h=1 cm), which was then washed with ethyl acetate (150 ml). The filtrate was evaporated to dryness and the residue was refluxed with isopropanol (50 ml) until solids began to appear. After cooling to room temperature, the solid was filtered and washed with isopropanol (20 ml) to give 14.0 g of N- (9, 9-dimethylfluoren-2-yl) -N- (3,3,7-trimethyl-2H-benzofuran-5-yl) acetamide.

Step 35 d):

Subjecting the material from step 35 c) to hydrolysis to obtain the final product

The solid obtained in step 35 c) was placed in a flask under an inert atmosphere together with potassium hydroxide (purity 85%,9.3 g, 0.14 mol). A mixture of THF (45 ml) and ethanol (45 ml) was added and the resulting suspension was refluxed for 21 hours. The solvent was removed by rotary evaporation and the solid residue was partitioned between water (40 ml) and t-butyl methyl ether (60 ml). The organic layer was washed with water (40 ml), dried over magnesium sulfate, filtered and concentrated by rotary evaporation. The crude compound was purified by column chromatography (silica gel, toluene/n-heptane 1:1) to afford 11.3 g (72%) of the desired compound.

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC),CS₂: acetone (acetone) -d₆ 5:1)：δ/δ＝(15.51/2.19,CH₃),(27.34/1.45,2×CH₃),(27.50/1.36,2×CH₃),(42.23,C-q),(46.31,C-q),(84.13/4.21,CH₂),(109.68/6.94,CH),(113.12/6.78,CH),(114.50/6.81,CH),(118.80/7.49,CH),(119.94,C-q),(120.93/7.43,CH),(122.32/6.71,CH),(122.38/7.31,CH),(125.65/7.13,CH),(127.10/7.21,CH),(130.34,C-q),(136.14,C-q),(136.28,C-q),(139.87,C-q),(145.78,C-q),(152.54,C-q),(153.24,C-q),(154.93,C-q),(6.30,NH).

Example 36:

N- (9, 9-dimethyl-9H-fluoren-2-yl) -3, 5-trimethyl-2, 3-dihydrobenzofuran-7-amine step 36 a):

7-bromo-3, 5-trimethyl-2H-benzofuran

To a solution of 2-bromo-4-methylphenol (100 g, 0.53 mmol) in DCM (100 ml) was added trifluoromethanesulfonic acid (8.0 g, 53 mmol). Methallyl chloride (53 g, 0.58 mol) was added dropwise over 30 minutes at a temperature of 5 ℃. The mixture was stirred at 20 ℃ for 22 hours after the end of the addition. The reaction mixture was then carefully added to a vigorously stirred solution of sodium hydroxide (32 g, 0.79 mol) in water (120 ml) over 30 minutes. The reaction reaches reflux due to the heat of neutralization. The organic layer was separated and the aqueous layer was extracted with toluene (100 ml). The combined organic extracts were washed with 2M sodium hydroxide solution (50 ml), dried over magnesium sulfate, filtered and concentrated by rotary evaporation. 116 g of the crude product are obtained, which are distilled at 143 to 145℃under 15 mbar, giving 81.2 g (62%) of a colourless oil.

¹³C NMR:(101MHz,CDCl₃):δ＝153.64(q),137.26(q),130.90(q),130.39(p),121.44(p),101.34(q),83.77(s),42.29(q),26.74(2*Ct),19.89(t).

Step 36 b):

N- (3, 5-trimethyl-2, 3-dihydrobenzofuran-7-yl) acetamide

Cuprous iodide (4.74 g, 24.9 mmol), potassium phosphate (81.7 g, 373 mmol) and acetamide (44.1 g, 747 mmol) were placed under an inert atmosphere. 1, 4-dioxane (240 ml), 7-bromo-3, 5-trimethyl-2H-benzofuran (60.0 g, 249 mmol) and N, N' -dimethylethylenediamine (4.39 g, 49.8 mmol) were added and the reaction mixture was refluxed for 21 hours. After cooling to 20 ℃, the reaction mixture was washed with a mixture of saturated sodium chloride solution (60 ml), 32% hydrochloric acid (60 ml) and water (60 ml). The organic layer was separated, dried over magnesium sulfate and evaporated by rotary evaporation to give 50.1 g (90%) of a brown solid.

¹³C NMR:(101MHz,DMSO):δ＝168.76(q),147.47(q),137.21(q),129.67(q),122.13(p),122.03(q),118.62(p),84.36(s),42.44(q),27.52(2*Ct),23.94(t),21.28(t).

Step 36 c):

n- (9, 9-dimethyl-9H-fluoren-2-yl) -N- (3, 5-trimethyl-2, 3-dihydrobenzofuran-7-yl) acetamide

The product from step 36 b) (13.4 g, 61.0 mmol) was placed under argon together with 2-bromo-9, 9-dimethylfluorene (18.3 g, 67.1 mmol), potassium phosphate (15.5 g, 73.2 mmol) and cuprous iodide (1.16 g, 6.10 mmol). 1, 4-Dioxane (50 mL) was added followed by N, N' -dimethylethylenediamine (1.08 g, 12.2 mmol). The mixture was kept under reflux for 16 hours, then cooled to room temperature, diluted with toluene (60 ml) and washed with saturated ammonium chloride solution (50 ml). The aqueous layer was extracted again with toluene (50 ml). The combined organic layers were washed with saturated ammonium chloride solution (50 ml), dried over magnesium sulfate, then filtered over a pad of silica gel (d=5 cm, h=1 cm), then washed with ethyl acetate (100 ml). The filtrate was evaporated to dryness and the residue was purified by fractional crystallization from cyclohexane/isopropanol 9:1 (1.5-3.0 ml/g) or N-heptane/isopropanol 19:1 (1.0-3.0 ml/g) to give 20.0 g of solid N- (9, 9-dimethylfluoren-2-yl) -N- (3, 5-trimethyl-2H-benzofuran-7-yl) acetamide.

Step 36 d):

Subjecting the product from step 36 c) to hydrolysis to obtain the final product

The product from step 36 c) was placed in a flask under an inert atmosphere along with potassium hydroxide (85% pure, 8.2 g, 0.12 mole, 4.0 eq.). A mixture of THF (45 ml) and ethanol (45 ml) was added and the resulting suspension was refluxed for 17 hours. The solvent was removed by rotary evaporation and the solid residue was partitioned between water (40 ml) and t-butyl methyl ether (60 ml). The organic layer was washed with water (40 ml), dried over magnesium sulfate, filtered and concentrated by rotary evaporation. The crude compound was purified by column chromatography (silica gel, toluene/n-heptane 1:1) to afford 9.78 g (43%) of the desired compound.

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC),CS₂: acetone (acetone) -d₆ 5:1)：δ/δ＝(21.61/2.31,CH₃),(27.30/1.48,2×CH₃),(27.42/1.39,2×CH₃),(42.57,C-q),(46.43,C-q),(84.58/4.23,CH₂),(111.84/7.10,CH),(114.92/6.49,CH),(116.24/6.92,CH),(116.34/7.01,CH),(119.11/7.54,CH),(120.81/7.51,CH),(122.46/7.34,CH),(126.05/7.17,CH),(127.03,C-q),(127.14/7.24,CH),(130.36,C-q),(131.85,C-q),(136.36,C-q),(139.63,C-q),(142.86,C-q),(146.50,C-q),(152.76,C-q),(154.84,C-q),(6.07,NH).

Example 37:

n- (9, 9-dimethyl-9H-fluoren-2-yl) dibenzo [ b, d ] thiophen-2-amine

The amine was synthesized as described in KR2016149879 a using Amphos instead of P (t-Bu) ₃ as catalyst via coupling of 2-bromodibenzo [ b, d ] thiophene with 9, 9-dimethyl-9H-fluoren-2-amine.

And (3) NMR: ¹³C/¹H(101MHz/400MHz,CS₂ Acetone-d ₆): delta/delta= (27.32/1.51,

2×CH₃),(46.51,C-q),(110.11/7.92,CH),(111.88/7.23,CH),(116.58/7.09,CH),(119.18/7.56,CH),(119.27/7.27,CH),(121.10/7.56,CH),(121.69/8.00,CH),(122.52/7.35,CH),(123.01/7.79,CH),(123.43/7.67,CH),(124.35/7.39,CH),(126.19/7.19,CH),(126.85/7.41,CH),(127.23/7.25,CH),(131.43,C-q),(132.16,C-q),(135.49,C-q),(136.71,C-q),(139.56,C-q),(140.65,C-q),(141.14,C-q),(143.51,C-q),(152.79,C-q),(155.08,C-q),(6.97,NH).

Example 38:

N- (9, 9-dimethyl-9H-fluoren-2-yl) benzo [ d ] [1,3] dioxol-5-amine

Following the general procedure for Buchwald-Hartwig coupling (see below), 5-bromobenzo [ d ] [1,3] dioxole (40.0 g, 199 mmol, 1.0 eq.) was coupled with bis (9, 9-dimethyl-9H-fluoren-2-yl) amine (42.5 g, 203 mmol, 1.02 eq.) in toluene (300 ml) using sodium tert-butyrate (20% solution in THF; 105 g, 219 mmol, 1.1 eq.), tri-tert-butylphosphonium tetrafluoroborate (0.87 g, 2.98 mmol, 1.5 mol%) and Pd ₂(dba)₃ (1.09 g, 1.19 mmol, 0.6 mol%).

After complete conversion and cooling to ambient temperature, functionalized silica gel (1.5 g, 3-mercaptopropyl ethyl sulfide silica, SPM32, phosphonics.com) was added to the reaction mixture. The suspension was stirred until it appeared homogeneous. It was then filtered through a pad of silica gel (20-30 g). The filter cake was further washed with toluene having a volume about the same as the column volume. The solvent was removed from the combined filtrates, leaving the crude product.

It was purified by column chromatography (heptane/EtOAc) followed by crystallization from isopropanol to provide the product as a yellowish solid (37.3 g, 57%) of 99.1% purity (according to hplc @340 nm).

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC),CS₂: acetone (acetone) -d₆ 5:1)δ/δ(27.30/1.45,2×CH₃),(46.39,C-q),(100.96/5.90,CH₂),(101.84/6.66*,CH),(108.65/6.66*,CH),(110.55/6.99,CH),(112.04/6.55,CH),(115.40/6.87,CH),(118.97/7.49,CH),(120.96/7.45,CH),(122.41/7.31,CH),(125.90/7.14,CH),(127.13/7.21,CH),(131.22,C-q),(137.88,C-q),(139.66,C-q),(142.30,C-q),(144.45,C-q),(148.26,C-q),(152.63,C-q),(154.97,C-q).

II preparation of the Compounds of formula (I)

General procedure for Buchwald-Hartwig amination:

the aryl halide, mono-or di-aryl amine and sodium t-butyrate were suspended in toluene (about 15 ml/mmol aryl halide) under an inert atmosphere. To the resulting suspension, under an inert atmosphere, the catalyst Pd ₂(dba)₃ or Pd (OAc) ₂ and the appropriate ligand (RuPhos or SPhos) are added. The resulting mixture was heated at reflux for 16 hours. The post-processing is performed according to one of the following general processing procedures.

Processing program a:

After cooling, an aqueous ammonium chloride solution (about 20%,10 ml/mmol of product) was added to the reaction mixture. The resulting emulsion was filtered through a filter layer made of celite, which had been slurried in ethyl acetate. The celite pad was then washed with ethyl acetate (about 15 ml/mmol). After delamination, the organic layer from the filtrate was successively washed with water (10 ml/mmol), saturated sodium chloride solution (10 ml/mmol), and then dried over anhydrous sodium sulfate. The solvent was filtered and removed from the filtrate to give the crude product, which was further purified as described in the corresponding examples.

Processing procedure B:

After cooling, an aqueous solution of ascorbic acid (5%, about 10 ml/mmol) was added to the reaction mixture. The resulting emulsion was filtered through a pad of celite, which was prepared as described in operation 1, followed by washing with ethyl acetate (about 15 ml/mmol). After delamination, the organic layer from the filtrate was successively washed with water (10 ml/mmol), saturated sodium chloride solution (10 ml/mmol), and then dried over anhydrous sodium sulfate. Filtration and removal of solvent from the filtrate gave the crude product, which was further purified as described in the corresponding examples.

Processing procedure C:

After cooling, silica gel (about 2 g/mmol) was added to the reaction mixture. The suspension was stirred until it appeared homogeneous. Then filtered through a pad of silica gel (20-30 g) and then washed with toluene having a volume approximately equal to the column volume. After removal of the solvent from the combined filtrates, the product was further purified as described in the corresponding examples.

Processing procedure D:

after cooling, 1.5 g of functionalized silica gel (3-mercaptopropyl ethyl sulfide silica, phosphonicS SPM, 32) was added to the reaction mixture. The suspension was stirred until it appeared homogeneous. Then filtered through a pad of silica gel (20-30 g) and then washed with toluene having a volume approximately equal to the column volume. After removal of the solvent from the combined filtrates, the product was further purified as described in the corresponding examples.

Example 39:

N, N-bis (9, 9-dimethyl-9H-fluoren-2-yl) -2',3' -dihydro-spiro- [ fluoren-9, 1' -indene ] -2-amine

The aryl bromide (5.90 g, 17.0 mmol) from step 1b of example 1 was coupled with bis (9, 9-dimethyl-9H-fluoren-2-yl) amine (6.96 g, 17.3 mmol) in 120 ml of toluene using sodium tert-butyrate (1.71 g, 17.8 mmol), amphos (0.092 g, 0.34 mmol) and Pd ₂(dba)₃ (0.079 g, 0.09 mmol) as described in the general procedure for Buchwald-Hartwig amination. The post-processing is performed according to procedure D. Crystallization of the crude product from acetone/isopropanol afforded the product as a yellowish solid (11.1 g, 98%) with a purity of 95.9% according to hplc @340 nm. Further purification by crystallization from t-butyl methyl ether/isopropanol afforded the product as a yellowish solid (10.0 g, 88%) with a purity of 96.6% (according to hplc @340 nm).

The title compound was further purified by sublimation in vacuo (10 ^-6-10^-7 mbar, 150-240 ℃) to give a purity of up to 99.4% according to hplc @340 nm.

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC),CS₂: acetone (acetone) -d₆ 5:1)：δ/δ＝(27.05/1.43,2×CH₃),(27.08/1.37,2×CH₃),(32.35/3.20,CH₂),(40.50/2.57,CH₂),(46.56,2q-C),(63.15,q-C),(118.57/7.24,2×CH),(119.45/7.65,CH),(119.60/7.04,CH),(119.66/7.58,2×CH),(120.76/7.63,CH),(120.91/7.53,2×CH),(122.59/7.35,2×CH),(123.22/7.07,2×CH),(123.45/7.15,CH),(123.66/6.51,CH),(123.89/7.10,CH),(125.03/7.24,CH),(126.74/7.21,2×CH),(127.06/7.15,CH),(127.07/6.99,CH),(127.27/7.26,2×CH),(127.34/7.09,CH),(127.59/7.29,CH),(134.23,2×C-q),(134.87,C-q),(139.04,2×C-q),(139.70,C-q),(144.10,C-q),(147.31,2×C-q),(147.44,C-q),(147.76,C-q),(152.56,C-q),(153.23,2×C-q),(154.09,C-q),(154.78,2×C-q).

Example 40:

n, N-bis (9, 9-dimethyl-9H-fluoren-2-yl) -3',3' -dimethyl-2 ',3' -dihydro-spiro- [ fluoren-9, 1' -indene ] -2-amine

The aryl bromide (4.50 g, 12.0 mmol) from step 2c of example 2 was coupled with bis (9, 9-dimethyl-9H-fluoren-2-yl) amine (5.01 g, 12.5 mmol) in 100ml of toluene using sodium tert-butyrate (1.23 g, 12.8 mmol), amphos (0.065 g, 0.24 mmol) and Pd ₂(dba)₃ (0.055 g, 0.06 mmol) as described in the general procedure for Buchwald-Hartwig amination. The post-processing is performed according to procedure B. The crude product was purified by crystallization from acetone/isopropanol to provide an off-white solid product (6.0 g, 72%) with a purity of 96.6% (using a UV-VIS detector according to HPLC, 340 nm wavelength, hplc@340 nm). After concentrating the mother liquor an additional product (1.36 g, purity 90.0% (hplc@340 nm)) was obtained. The overall yield of the product was 87%.

The title compound was further purified by sublimation in vacuo (10 ^-6-10^-7 mbar, 150-240 ℃) to give a product with a purity of up to 99.5% according to hplc @340 nm.

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC),CS₂: acetone (acetone) -d₆ 5:1)：δ/δ＝(27.04/1.35,2×CH₃),(27.08/1.42,2×CH₃),(32.37/1.34,CH₃),(32.52/1.58,CH₃),(43.74,C-q),(46.55,2×C-q),(54.47/2.58,CH₂),(62.52,C-q),(118.52/7.23,2×CH),(119.28/7.64,CH),(119.65/7.58,2×CH),(119.94/6.98,CH),(120.60/7.62,CH),(120.87/7.54,2×CH),(122.58/7.35,2×CH),(122.85/7.15,CH),(123.18/7.13,CH),(123.26/7.05,2×CH),(124.35/6.39,CH),(124.41/7.07,CH),(126.73/7.22,2×CH),(127.17/7.16,CH),(127.25/7.26,2×CH),(127.37/7.28,CH),(127.51/7.00,CH),(127.75/7.15,CH),(134.21,2×C-q),(134.73,C-q),(139.03,2×C-q),(139.73,C-q),(145.60,C-q),(147.27,2×C-q),(147.84,C-q),(152.66,C-q),(153.23,2×C-q),(154.62,C-q),(154.79,2×C-q),(156.21,C-q).

Example 41:

N- (3 ',3' -dimethyl-2 ',3' -dihydrospiro- [ fluoren-9, 1' -inden ] -2-yl) -N- (9, 9-dimethyl-9H-fluoren-2-yl) -9, 9-dimethyl-9H-xanthen-2-amine

The aryl bromide (5.21 g, 13.9 mmol, 1.0 eq.) from step 2c of example 2 and the product (6.02 g, 14.4 mmol) from example 29 were coupled in 100 ml toluene using sodium tert-butyrate (1.43 g, 14.8 mmol), amphos (0.075 g, 0.28 mmol) and Pd ₂(dba)₃ (0.062 g, 0.07 mmol) as described in the general method of Buchwald-Hartwig amination. The post-treatment was performed according to procedure C.

The crude product was purified by crystallization from acetone/isopropanol to afford the product as a yellowish solid (7.7 g, 77%) with a purity of 92.0% (340 nm according to hplc). Additional product (1.36 g, 90.0% purity by hplc@340 nm) was obtained after reduction of the mother liquor. The crude product (6.3 g) was further purified by column chromatography (heptane/dichloromethane) and crystallization (heptane/isopropanol) to give the title compound as an off-white solid (4.6 g, 73%) with purity of 98.4% (according to hplc @340 nm).

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC),CS₂: acetone (acetone) -d₆ 5:1)：δ/δ＝(27.02/1.33,CH₃),(27.06/1.41,CH₃),(32.36/1.36,CH₃),(32.38/1.56,CH₃),(32.46/1.58,CH₃),(32.67/1.48,CH₃),(33.97,C-q),(43.75,C-q),(46.51,C-q),(54.44/2.57,CH₂),(62.50,C-q),(116.44/6.99,CH),(117.40/6.95,CH),(117.61/7.18,CH),(119.03/6.94,CH),(119.20/7.64,CH),(119.55/7.58,CH),(120.57/7.61,CH),(120.81/7.52,CH),(122.36/7.06,CH),(122.42/6.99,CH),(122.55/7.36,CH),(122.86/7.17,CH),(123.07/7.23,CH),(123.30/7.06,CH),(124.32/6.38,CH),(124.36/7.07,CH),(124.71/6.94,CH),(126.43/7.38,CH),(126.61/7.21,CH),(127.06/7.15,CH),(127.21/7.26,CH),(127.34/7.27,CH),(127.48/6.99,CH),(127.59/7.18,CH),(127.73/7.16,CH),(129.18,C-q),(130.63,C-q),(133.75,C-q),(134.26,C-q),(139.06,C-q),(139.78,C-q),(142.83,C-q),(145.71,C-q),(146.33,C-q),(147.27,C-q),(147.90,C-q),(150.17,C-q),(152.67,C-q),(153.19,C-q),(154.58,C-q),(154.76,C-q),(156.17,C-q).

Example 42:

n- (3 ',3' -dimethyl-2 ',3' -dihydrospiro- [ fluoren-9, 1' -inden ] -2-yl) -N- (9, 9-dimethyl-9H-fluoren-2-yl) dibenzo [ b, d ] furan-2-amine

The aryl bromide (5.50 g, 14.7 mmol, 1.0 eq.) from step 2c of example 2 and the product (5.72 g, 15.2 mmol) from example 24 were coupled in 100ml of toluene using sodium tert-butyrate (1.51 g, 15.7 mmol, 1.07 eq.), amphos (0.079 g, 0.29 mmol) and Pd ₂(dba)₃ (0.067 g, 0.07 mmol) as described in the general method of Buchwald-Hartwig amination. The post-processing is performed according to procedure D. Purification of the crude product from crystallization in acetone/toluene afforded the product as a yellowish solid (5.5 g, 56%) with a purity of 99.7% (340 nm according to hplc).

After mother liquor reduction and crystallization of the residue from isopropanol, additional product (3.6 g, 37%, 95.5% purity according to hplc @340 nm) was obtained. The total yield was 93%.

The title compound was further purified by sublimation in vacuo (10 ^-6-10^-7 mbar, 150-240 ℃) to give a product with a purity of up to 99.8% according to hplc @340 nm.

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC),CS₂: acetone (acetone) -d₆ 5:1)：δ/δ＝(27.12/1.32,CH₃),(27.15/1.42,CH₃),(32.31/1.32,CH₃),(32.57/1.57,CH₃),(43.72,C-q),(46.55,C-q),(54.60/2.57,CH₂),(62.54,C-q),(111.85/7.53,CH),(112.53/7.47,CH),(117.71/7.24,CH),(117.84/7.77,CH),(119.02/7.02,CH),(119.23/7.63,CH),(119.60/7.57,CH),(120.64/7.60,CH),(120.92/7.51,CH),(121.01/7.79,CH),(122.32/7.06,CH),(122.56/7.35,CH),(122.66/7.01,CH),(122.86/7.14,CH),(122.96/7.28,CH),(124.40/7.08,CH),(124.40/6.41,CH),(125.54/7.35,CH),(126.67/7.22,CH),(127.11/7.16,CH),(127.25/7.25,CH),(127.38/7.29,CH),(127.51/7.44,CH),(127.51/7.01,CH),(127.77/7.16,CH),(124.20,C-q),(125.39,C-q),(133.86,C-q),(134.24,C-q),(139.06,C-q),(139.82,C-q),(143.30,C-q),(145.63,C-q),(147.59,C-q),(148.31,C-q),(152.68,C-q),(152.80,C-q),(153.20,C-q),(154.55,C-q),(154.80,C-q),(156.22,C-q),(156.84,C-q).

Example 43:

N- (3 ',3' -dimethyl-2 ',3' -dihydrospiro- [ fluoren-9, 1' -inden ] -2-yl) -N- (9, 9-dimethyl-9H-fluoren-2-yl) dibenzo [ b, d ] thiophen-2-amine

As described in the general procedure for Buchwald-Hartwig amination, aryl bromide (5.50 g, 14.7 mmol, 1.0 eq.) from step 2c of example 2 and diarylamine (5.91 g, 15.1 mmol, 1.03 eq.) from example 37 were coupled in toluene (100 ml) using sodium tert-butyrate (1.51 g, 15.7 mmol, 1.07 eq.), amphos (0.079 g, 0.29 mmol, 2 mol%) and Pd ₂(dba)₃ (0.067 g, 0.07 mmol, 0.5 mol%). The post-processing is performed according to procedure D. Purification of the crude product from crystallization in acetone/toluene afforded the product as a yellowish solid (6.8 g, 68%) with a purity of 98.7% (340 nm according to hplc).

The title compound (5.54 g) was further purified by sublimation in vacuo (10 ^-6-10^-7 mbar, 150-255 ℃) to give the title compound as a yellowish solid (3.61 g, purity up to 99.7% according to hplc @340 nm).

And (3) NMR: ¹³C/¹H(101MHz/400MHz,CS₂ Acetone -d₆)：δ/δ＝(27.10/1.32,CH₃),(27.14/1.42,CH₃),(32.30/1.30,CH₃),(32.57/1.57,CH₃),(43.72,C-q),(46.57,C-q),(54.59/2.57,CH₂),(62.54,C-q),(117.59/7.93,CH),(118.24/7.24,CH),(119.29/7.63,CH),(119.59/7.01,CH),(119.67/7.56,CH),(120.70/7.60,CH),(120.97/7.52,CH),(121.87/7.88,CH),(122.58/7.34,CH),(122.81/7.09,CH),(122.87/7.12,CH),(122.97/7.80,CH),(123.06/7.04,CH),(123.58/7.69,CH),(124.36/6.41,CH),(124.43/1.07,CH),(124.57/7.36,CH),(124.85/7.27,CH),(126.77/7.20,CH),(127.03/7.42,CH),(127.20/7.17,CH),(127.27/7.27,CH),(127.39/7.29,CH),(127.52/6.99,CH),(127.79/7.13,CH),(134.13,C-q),(134.23,C-q),(134.65,C-q),(135.28,C-q),(136.86,C-q),(139.00,C-q),(139.73,C-q),(140.50,C-q),(145.11,C-q),(145.54,C-q),(147.24,C-q),(147.92,C-q),(152.68,C-q),(153.22,C-q),(154.57,C-q),(154.87,C-q),(156.28,C-q).

Example 44:

N, N-bis (9, 9-dimethyl-9H-fluoren-2-yl) -6 '-methoxy-3', 3 '-dimethyl-2', 3 '-dihydro-spiro- [ fluoren-9, 1' -indene ] -2-amine

The aryl bromide major isomer a (5.50 g, 13.6 mmol) from step 9c of example 9 and bis (9, 9-dimethyl-9H-fluoren-2-yl) amine (5.56 g, 13.8 mmol) were coupled in 100ml of toluene using sodium tert-butyrate (1.37 g, 14.2 mmol), amphos (0.074 g, 0.27 mmol) and Pd ₂(dba)₃ (0.062 g, 0.07 mmol) as described in the general method of Buchwald-Hartwig amination. The post-processing is performed according to procedure D. Crystallization of the crude product from t-butyl methyl ether/isopropanol afforded the product as a yellowish solid (8.0 g, 81%) with a purity of 98.0% according to hplc @340 nm. Additional product (1.0 g, 98.1% purity according to hplc @340 nm) was obtained after reduction of the mother liquor. The total yield was 91%.

The product was further purified by sublimation in a vacuum zone (10 ^-6-10^-7 mbar, 150-245 ℃) to give a product with a purity of up to 98.6% according to hplc @340 nm.

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC),CS₂: acetone (acetone) -d₆ 5:1)：δ/δ＝(27.05/1.37,2×CH₃),(27.11/1.44,2×CH₃),(32.60/1.32,CH₃),(32.79/1.55,CH₃),(43.05,C-q),(46.57,2×C-q),(54.76/3.58,CH₃),(55.12/2.58,CH₂),(62.53,C-q),(108.25/5.89,CH),(114.89/6.70,CH),(118.57/7.26,2×CH),(119.31/7.64,CH),(119.67/7.59,2×CH),(119.94/7.02,CH),(120.64/7.62,CH),(120.89/7.55,2×CH),(122.60/7.36,2×CH),(123.18/7.14,CH),(123.31/7.08,2×CH),(123.41/7.03,CH),(124.43/7.10,CH),(126.76/7.22,2×CH),(127.23/7.18,CH),(127.27/7.27,2×CH),(127.43/7.29,CH),(134.25,2×C-q),(134.69,C-q),(139.05,2×C-q),(139.74,C-q),(144.97,C-q),(146.72,C-q),(147.28,2×C-q),(147.88,C-q),(153.26,2×C-q),(154.49,C-q),(154.82,2×C-q),(156.10,C-q),(159.47,C-q).

Example 45:

N, N-bis (9, 9-dimethyl-9H-fluoren-2-yl) -2',3',3',4',7 '-pentamethyl-2', 3 '-dihydrospiro- [ fluoren-9, 1' -indene ] -2-amine

As described in the general procedure for Buchwald-Hartwig amination, a mixture of aryl bromide (5.00 g, 12.0 mmol) from example 11 and bis (9, 9-dimethyl-9H-fluoren-2-yl) amine (4.91 g, 12.2 mmol) was coupled in 100ml of toluene using sodium tert-butyrate (1.21 g, 12.6 mmol), amphos (0.065 g, 0.24 mmol) and Pd ₂(dba)₃ (0.055 g, 0.06 mmol). The post-processing is performed according to procedure D. Crystallization of the crude product from t-butyl methyl ether/isopropanol afforded the product as a yellowish solid (7.5 g, 84%) with a purity of 96.5% according to hplc @340 nm.

The title compound was further purified by sublimation in vacuo (10 ^-6-10^-7 mbar, 150-240 ℃) to give a purity of up to 99.7% according to hplc @340 nm.

¹³C NMR：(101MHz,CS₂ : Acetone (acetone) -d₆ 5:1)：δ＝8.82,9.18,17.54,17.74,19.58,19.65,23.31,23.45,27.03,27.10,27.11,27.17,29.61,29.74,46.28,46.44,46.54,46.56,57.53,57.55,66.69,66.82,118.03,118.29,119.25,119.39,119.61,119.66,119.92,120.54,120.67,120.80,120.90,122.58,122.73,123.01,123.36,123.76,123.77,124.09,126.08,126.11,126.68,126.71,127.19,127.22,127.27,129.49,129.54,131.19,131.23,131.28,132.37,132.60,133.87,134.11,135.73,136.79,139.08,139.10,140.27,141.18,142.70,142.77,146.78,147.45,147.52,147.66,147.81,149.53,150.60,150.66,153.18,153.18,153.75,154.75,155.46.

Example 46:

n, N-bis (9, 9-dimethyl-9H-fluoren-2-yl) -3',3',4',7' -tetramethyl-2 ',3' -dihydrospiro- [ fluoren-9, 1' -inden ] -2-amine

The product from example 4 step 4 d) (3.20 g, 7.9 mmol) was coupled with bis (9, 9-dimethyl-9H-fluoren-2-yl) amine (3.25 g, 8.1 mmol) in 80 ml toluene using sodium tert-butyrate (0.80 g, 8.3 mmol), amphos (0.043 g, 0.16 mmol) and Pd ₂(dba)₃ (0.036 g, 0.04 mmol) as described in the general procedure for Buchwald-Hartwig amination. The post-processing is performed according to procedure D. Crystallization of the crude material from THF/isopropanol afforded the product as 94.8% pure according to hplc @340 nm as a yellowish solid (4.4 g, 76%).

The title compound was further purified by sublimation in vacuo (10 ^-6-10^-7 mbar, 150-240 ℃) to give a purity of up to 99.5% according to hplc @340 nm.

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC),CS₂: acetone (acetone) -d₆ 5:1)：δ/δ＝(17.29/1.27,CH₃),(19.39/2.42,CH₃),(27.03/1.39,2×CH₃),(27.16/1.43,2×CH₃),(30.29/1.65,CH₃),(30.52/1.45,CH₃),(44.61,C-q),(46.56,2×C-q),(57.70/2.50,CH₂),(62.34,C-q),(118.31/7.21,2×CH),(119.32/7.65,CH),(119.65/7.58,2×CH),(120.21/7.00,CH),(120.69/7.64,CH),(120.86/7.53,2×CH),(122.58/7.36,2×CH),(123.02/7.07,2×CH),(123.68/7.16,CH),(124.17/7.08,CH),(126.71/7.22,2×CH),(127.18/7.18,CH),(127.18/7.30,CH),(127.26/7.27,2×CH),(129.90/6.67,CH),(131.17,C-q),(131.43/6.83,CH),(132.59,C-q),(134.10,2×C-q),(135.30,C-q),(139.07,2×C-q),(139.89,C-q),(143.30,C-q),(147.40,2×C-q),(147.82,C-q),(150.11,C-q),(153.20,2×C-q),(153.32,C-q),(154.77,2×C-q),(155.28,C-q).

Example 47:

9- (3 ',3',4',7' -tetramethyl-2 ',3' -dihydro-spiro- [ fluoren-9, 1' -inden ] -2-yl) -9H-carbazole

As described in the general procedure for Buchwald-Hartwig amination, aryl bromide (8.50 g, 21.1 mmol, 1.0 eq.) from step 4c of example 4 was coupled with 9H-carbazole (3.70 g, 22.1 mmol, 1.05 eq.) in toluene (150 ml) using sodium tert-butyrate (2.23 g, 23.2 mmol, 1.1 eq.), amphos (0.114 g, 0.42 mmol, 2 mol%) and Pd ₂(dba)₃ (0.097 g, 0.11 mmol, 0.5 mol%). The work-up is carried out according to general procedure D.

The crude product was crystallized from acetone/toluene to give a colorless solid (8.6 g, 83%) with a purity of 100% (340 nm according to hplc).

The compound (5.56 g) was further purified by sublimation in a vacuum zone (10 ^-6-10^-7 mbar, 100-200 ℃) to give the product as a colourless solid (5.02 g, up to 100% pure according to hplc @340 nm). The melting point of the product was 233 ℃.

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC),CS₂: acetone (acetone) -d₆ 5:1)δ/δ(17.16/1.23,CH₃),(19.39/2.48,CH₃),(30.39/1.71,CH₃),(30.42/1.63,CH₃),(44.75,C-q),(57.59/2.62,CH₂),(62.56,C-q),(109.79/7.29,2×CH),(120.10/7.81,CH),(120.26/7.20,2×CH),(120.43/8.02,2×CH),(121.04/7.98,CH),(122.70/7.31,CH),(123.46,C-q),(124.31/7.19,CH),(125.73/7.54,CH),(126.13/7.31,2×CH),(127.37/7.38,CH),(128.27/7.30,CH),(129.98/6.71,CH),(131.32,C-q),(131.70/6.89,CH),(132.68,C-q),(137.00,C-q),(139.32,C-q),(139.36,C-q),(140.73,C-q),(142.86,C-q),(150.33,C-q),(153.86,C-q),(155.58,C-q).

Example 48:

3, 6-diphenyl-9- (3 ',3',4',7' -tetramethyl-2 ',3' -dihydro-spiro- [ fluoren-9, 1' -inden ] -2-yl) -9H-carbazole

As described in the general procedure for Buchwald-Hartwig amination, aryl bromide (7.00 g, 17.4 mmol, 1.0 eq.) from step 4c of example 4 was coupled with amine 3, 6-diphenyl-9H-carbazole (5.65 g, 17.7 mmol, 1.02 eq.) in toluene (100 ml) using sodium tert-butyrate (1.75 g, 18.2 mmol, 1.05 eq.), amphos (0.094 g, 0.35 mmol, 2 mol%) and Pd ₂(dba)₃ (0.079 g, 0.09 mmol, 0.5 mol%). Because the conversion was incomplete, additional tri-tert-butylphosphonium tetrafluoroborate (0.201 g, 0.69 mmol, 4 mol%) and Pd ₂(dba)₃ (0.159 g, 0.17 mmol, 1.0 mol%) were added and the reaction was complete. The work-up is carried out according to general procedure D.

The crude product was purified by column chromatography (heptane/DCM) to give the product as a colorless solid (10.4 g, 93%) with a purity of 99.9% (according to hplc @340 nm).

The title compound (11.0 g) was further purified by sublimation in vacuo (10 ^-6-10^-7 mbar, 150-230 ℃) to give the title compound as a colorless solid (9.73 g) with a purity of up to 100% according to hplc @340 nm. The purified product had a T _g of 150.9 ℃.

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC),CS₂: acetone (acetone) -d₆ 5:1)δ/δ(17.20/1.25,CH₃),(19.41/2.49,CH₃),(30.43/1.66,CH₃),(30.43/1.72,CH₃),(44.78,C-q),(57.61/2.64,CH₂),(62.60,C-q),(110.27/7.39,2×CH),(119.12/8.34,2×CH),(120.15/7.83,CH),(121.12/8.01,CH),(122.52/7.37,CH),(124.27,2×C-q),(124.33/7.19,CH),(125.55/7.61,CH),(125.80/7.60,2×CH),(126.69/7.29,2×CH),(127.31/7.66,4×CH),(127.40/7.39,CH),(128.33/7.31,CH),(128.94/7.43,4×CH),(130.01/6.73,CH),(131.37,C-q),(131.75/6.90,CH),(132.69,C-q),(133.65,2×C-q),(136.90,C-q),(139.27,C-q),(139.47,C-q),(140.66,2×C-q),(141.80,2×C-q),(142.84,C-q),(150.37,C-q),(153.87,C-q),(155.68,C-q).

Example 49:

N- (9, 9-dimethyl-9H-fluoren-2-yl) -N- (3 ',3',4',7' -tetramethyl-2 ',3' -dihydrospiro- [ fluoren-9, 1' -inden ] -2-yl) dibenzo [ b, d ] furan-2-amine

As described in the general procedure for Buchwald-Hartwig amination, aryl bromide (6.50 g, 16.1 mmol, 1.0 eq.) from step 4c of example 4 was coupled with diarylamine (6.17 g, 16.4 mmol, 1.02 eq.) from example 24 in toluene (100 ml) using sodium tert-butyrate (1.63 g, 16.9 mmol, 1.05 eq.), amphos (0.087 g, 0.32 mmol, 2 mol%) and Pd ₂(dba)₃ (0.074 g, 0.08 mmol, 0.5 mol%). The work-up is carried out according to general procedure D.

The crude product was purified by column chromatography (heptane/dichloromethane) to provide the product as a pale yellow solid (12.1 g) with a purity of 99.7% (according to hplc @340 nm).

The title compound (5.53 g) was further purified by sublimation in vacuo (10 ^-6-10^-7 mbar, 150-240 ℃) to give the title compound as a yellowish solid (5.10 g) with a purity of up to 99.7% according to hplc @340 nm. The purified product had a T _g of 134.2 ℃.

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC),CS₂: acetone (acetone) -d₆ 5:1)δ/δ(17.28/1.26,CH₃),(19.35/2.39,CH₃),(27.06/1.35,CH₃),(27.18/1.41,CH₃),(30.30/1.62,CH₃),(30.36/1.39,CH₃),(44.55,C-q),(46.53,C-q),(57.78/2.47,CH₂),(62.31,C-q),(111.84/7.52,CH),(112.47/7.45,CH),(117.46/7.73,CH),(117.58/7.18,CH),(119.23/6.98,CH),(119.23/7.62,CH),(119.58/7.56,CH),(120.67/7.60,CH),(120.89/7.51,CH),(120.93/7.78,CH),(122.48/7.01,CH),(122.54/7.34,CH),(122.66/7.07,CH),(122.92/7.28,CH),(124.10/7.06,CH),(124.20,C-q),(125.33,C-q),(125.45/7.27,CH),(126.64/7.20,CH),(127.07/7.16,CH),(127.14/7.28,CH),(127.23/7.25,CH),(127.47/7.44,CH),(129.85/6.66,CH),(131.13,C-q),(131.41/6.81,CH),(132.60,C-q),(133.78,C-q),(134.75,C-q),(139.07,C-q),(139.92,C-q),(143.28,C-q),(143.47,C-q),(147.70,C-q),(148.27,C-q),(150.10,C-q),(152.66,C-q),(153.15,C-q),(153.28,C-q),(154.78,C-q),(155.18,C-q),(156.82,C-q).

Example 50:

n- (dibenzo [ b, d ] furan-2-yl) -N- (3 ',3',4',7' -tetramethyl-2 ',3' -dihydrospiro- [ fluoren-9, 1' -inden ] -2-yl) dibenzo [ b, d ] furan-2-amine

As described in the general procedure for Buchwald-Hartwig amination, aryl bromide (6.25 g, 15.5 mmol, 1.0 eq.) from example 4 step 4 c) was coupled with diarylamine (5.52 g, 15.8 mmol, 1.02 eq.) from example 28 b) in toluene (100 ml) using sodium tert-butyrate (1.56 g, 16.3 mmol, 1.05 eq.), tri-tert-butylphosphonium tetrafluoroborate (0.180 g, 0.62 mmol, 4 mol%) and Pd ₂(dba)₃ (0.142 g, 0.15 mmol, 1 mol%). The work-up is carried out according to general procedure D.

The crude product was purified by crystallization from acetone to afford the product as a colorless solid (9.8 g, 94%) with a purity of 99.9% (according to hplc @340 nm).

The title compound (5.0 g) was further purified by sublimation in vacuo (10 ^-6-10^-7 mbar, 150-245 ℃) to give the title compound as a yellowish solid (4.5 g, purity up to 99.9% according to hplc @340 nm). The purified product had a T _g of 131.5 ℃.

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC),CS₂: acetone (acetone) -d₆ 5:1)δ/δ(17.28/1.26,CH₃),(19.29/2.35,CH₃),(30.02/1.32,CH₃),(30.38/1.60,CH₃),(44.48,C-q),(57.98/2.46,CH₂),(62.29,C-q),(111.82/7.51,2×CH),(112.46/7.44,2×CH),(116.93/7.72,2×CH),(118.04/6.95,CH),(119.17/7.61,CH),(120.63/7.58,CH),(120.95/7.76,2×CH),(121.32/7.01,CH),(122.89/7.27,2×CH),(123.99/7.05,CH),(124.19,2×C-q),(125.00/7.27,2×CH),(125.33,2×C-q),(126.96/7.16,CH),(127.12/7.27,CH),(127.46/7.44,2×CH),(129.75/6.65,CH),(131.12,C-q),(131.41/6.79,CH),(132.65,C-q),(134.09,C-q),(139.98,C-q),(143.22,C-q),(143.78,2×C-q),(148.74,C-q),(150.13,C-q),(152.48,2×C-q),(153.33,C-q),(155.08,C-q),(156.82,2×C-q).

Example 51:

N- (9, 9-dimethyl-9H-fluoren-2-yl) -N- (3 ',3',4',7' -tetramethyl-2 ',3' -dihydrospiro- [ fluoren-9, 1' -inden ] -2-yl) dibenzo [ b, d ] thiophen-2-amine

As described in the general procedure for Buchwald-Hartwig amination, aryl bromide (7.00 g, 17.4 mmol, 1.0 eq.) from step 4c of example 4 was coupled with diarylamine (6.93 g, 17.7 mmol, 1.02 eq.) from example 37 in toluene (100 ml) using sodium tert-butyrate (1.75 g, 18.2 mmol, 1.05 eq.), amphos (0.094 g, 0.35 mmol, 2 mol%) and Pd ₂(dba)₃ (0.079 g, 0.09 mmol, 0.5 mol%). The work-up is carried out according to general procedure D.

The crude product was purified by column chromatography (heptane/dichloromethane) to afford the product as a pale yellow solid (10.8 g, 87%) (purity up to 99.9% according to hplc @340 nm).

The title compound (10.5 g) was further purified by sublimation in vacuo (10 ^-6-10^-7 mbar, 150-260 ℃) to give the title compound as a yellowish solid (10.2 g, purity up to 99.9% according to hplc @340 nm). The T _g of the purified product was 143.2 ℃.

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC),CS₂: acetone (acetone) -d₆ 5:1)δ/δ(17.29/1.28,CH₃),(19.34/2.39,CH₃),(27.02/1.37,CH₃),(27.17/1.42,CH₃),(30.28/1.62,CH₃),(30.36/1.39,CH₃),(44.57,C-q),(46.57,C-q),(57.76/2.49,CH₂),(62.34,C-q),(117.28/7.92,CH),(118.08/7.23,CH),(119.33/7.65,CH),(119.66/7.58,CH),(119.79/7.02,CH),(120.77/7.64,CH),(120.96/7.54,CH),(121.80/7.88,CH),(122.57/7.35,CH),(122.86/7.07,CH),(122.98/7.80,CH),(123.22/7.12,CH),(123.55/7.70,CH),(124.13/7.08,CH),(124.53/7.36,CH),(124.62/7.27,C-q),(126.74/7.22,C-q),(127.03/7.42,CH),(127.17/7.29,CH),(127.17/7.18,CH),(127.26/7.26,CH),(129.86/6.66,CH),(131.18,C-q),(131.43/6.81,CH),(132.55,C-q),(133.94,C-q),(134.16,C-q),(135.19,C-q),(135.28,C-q),(136.83,C-q),(139.02,C-q),(139.86,C-q),(140.51,C-q),(143.24,C-q),(145.29,C-q),(147.37,C-q),(147.91,C-q),(150.12,C-q),(153.21,C-q),(153.33,C-q),(154.87,C-q),(155.29,C-q).

Example 52:

3, 6-di-tert-butyl-9- (3 ',3',4',7' -tetramethyl-2 ',3' -dihydrospiro- [ fluorene-9, 1' -indene ] -2-yl) -9H-carbazole

As described in the general procedure for Buchwald-Hartwig amination, aryl bromide (8.00 g, 19.8 mmol, 1.0 eq.) from step 4c of example 4 was coupled with amine 3, 6-di-tert-butyl-9H-carbazole (5.65 g, 20.2 mmol, 1.02 eq.) in toluene (100 ml) using sodium tert-butyrate (2.00 g, 20.8 mmol, 1.05 eq.), amphos (0.107 g, 0.40 mmol, 2.0 mol%) and Pd ₂(dba)₃ (0.091 g, 0.10 mmol, 0.5 mol%). The work-up is carried out according to general procedure D.

The crude product was purified by crystallization from acetone to afford the product as a colorless solid (11.1 g, 91%) with a purity of 99.3% (340 nm according to hplc).

The title compound (11.0 g) was further purified by sublimation in vacuo (10 ^-6-10^-7 mbar, 150-230 ℃) to give the title compound as a colourless solid (9.73 g, up to 100% pure according to hplc @340 nm). The melting point of the purified product was 260.0 ℃.

¹³C/¹H(101MHz,400MHz(HSQC),CS₂ : Acetone (acetone) -d₆ 5:1)：δ/δ＝(17.18/1.24,CH₃),(19.43/2.50,CH₃),(30.42/1.72,CH₃),(30.48/1.66,CH₃),(32.14/1.49,6×CH₃),(34.49,C-q),(44.77,C-q),(57.63/2.63,CH₂),(62.55,C-q),(109.37/7.23,2×CH),(116.57/8.04,2×CH),(120.01/7.80,CH),(120.94/7.95,CH),(122.22/7.30,CH),(123.55,2×C-q),(123.75/7.38,2×CH),(124.29/7.18,CH),(125.30/7.53,CH),(127.34/7.38,CH),(128.12/7.29,CH),(129.97/6.73,CH),(131.31,C-q),(131.69/6.90,CH),(132.71,C-q),(137.58,C-q),(138.85,C-q),(139.15,2×C-q),(139.43,C-q),(142.36,2×C-q),(142.95,C-q),(150.34,C-q),(153.82,C-q),(155.49,C-q).

Example 53:

N, N-bis (9, 9-dimethyl-9H-fluoren-2-yl) -5 '-methoxy-3', 3',4',6 '-tetramethyl-2', 3 '-dihydro-spiro- [ fluoren-9, 1' -inden ] -2-amine

As described in the general procedure for Buchwald-Hartwig amination, aryl bromide (6.00 g, 13.8 mmol, 1.0 eq.) from step 10d of example 10 was coupled with diarylaminedi (9, 9-dimethyl-9H-fluoren-2-yl) amine (5.67 g, 14.1 mmol, 1.02 eq.) using sodium tert-butyrate (1.40 g, 14.5 mmol, 1.05 eq.), amphos (0.075 g, 0.28 mmol, 2 mol%) and Pd ₂(dba)₃ (0.063 g, 0.07 mmol, 0.5 mol%) in toluene (100 ml). The work-up is carried out according to general procedure D.

The crude product was purified by crystallization from heptane to afford the product as a yellowish solid (9.8 g, 93%) with a purity of 98.5% (according to hplc @340 nm).

The title compound (5.48 g) was further purified by sublimation in vacuo (10 ^-6-10^-7 mbar, 150-255 ℃) to give the title compound as a yellowish solid (4.89 g, purity up to 99.4% according to hplc @340 nm). The purified product had a T _g of 153.4 ℃.

And (3) NMR: ¹³C/¹H(101MHz/400MHz,CS₂: acetone (acetone) -d₆ 5:1)δ/δ(11.85/2.30,CH₃),(16.53/2.07,CH₃),(27.00/1.36,2×CH₃),(27.09/1.42,2×CH₃),(30.54/1.42,CH₃),(30.56/1.66,CH₃),(45.14,C-q),(46.54,2×C-q),(56.87/2.54,CH₂),(59.04/3.62,OCH₃),(61.57,C-q),(118.53/7.24,2×CH),(119.19/7.60,CH),(119.64/7.57,2×CH),(119.92/7.01,CH),(120.50/7.58,CH),(120.86/7.53,2×CH),(122.58/7.35,2×CH),(123.00/7.10,CH),(123.32/7.06,2×CH),(124.31/6.02,CH),(124.48/7.07,CH),(126.59,C-q),(126.73/7.21,2×CH),(127.10/7.15,CH),(127.26/7.26,3×CH),(129.97,C-q),(134.19,2×C-q),(134.65,C-q),(139.05,2×C-q),(139.62,C-q),(141.38,C-q),(147.28,2×C-q),(147.72,C-q),(148.35,C-q),(153.22,2×C-q),(154.77,2×C-q),(154.90,C-q),(156.44,C-q),(157.02,C-q).

Example 54:

n, N-bis (9, 9-dimethyl-9H-fluoren-2-yl) -3',3',5',7' -tetramethyl-2 ',3' -dihydrospiro- [ fluoren-9, 1' -inden ] -2-amine

As described in the general procedure for Buchwald-Hartwig amination, aryl bromide (6.50 g, 16.1 mmol, 1.0 eq.) from step 7b of example 7 was coupled with bis (9, 9-dimethyl-9H-fluoren-2-yl) amine (6.60 g, 16.4 mmol, 1.02 eq.) in toluene (100 ml) using sodium tert-butyrate (1.63 g, 16.9 mmol, 1.05 eq.), amphos (0.087 g, 0.32 mmol, 2 mol%) and Pd ₂(dba)₃ (0.074 g, 0.08 mmol, 0.5 mol%). The work-up is carried out according to general procedure D. The crude product was purified by crystallization from acetone to afford the product as a colorless solid (10.8 g, 93%) with a purity of 98.4% (340 nm according to hplc).

The title compound (5.07 g) was further purified by sublimation in vacuo (10 ^-6-10^-7 mbar, 150-245 ℃) to give the title compound as a yellowish solid (4.69 g, purity up to 99.8% according to hplc @340 nm). The purified product had a T _g of 142.9 ℃.

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC),CS₂: acetone (acetone) -d₆ 5:1)δ/δ(17.23/1.27,CH₃),(21.41/2.27,CH₃),(26.95/1.37,2×CH₃),(27.09/1.41,2×CH₃),(32.54/1.31,CH₃),(32.63/1.52,CH₃),(43.19,C-q),(46.53,2×C-q),(56.06/2.48,CH₂),(62.41,C-q),(118.28/7.19,2×CH),(119.27/7.64,CH),(119.62/7.57,2×CH),(120.12/6.97,CH),(120.63/7.63,CH),(120.83/7.52,2×CH),(121.13/6.81,CH),(122.56/7.35,2×CH),(123.02/7.04,2×CH),(123.59/7.13,CH),(124.13/7.07,CH),(126.70/7.21,2×CH),(127.16/7.17,CH),(127.16/7.29,CH),(127.24/7.26,2×CH),(130.51/6.58,CH),(134.07,2×C-q),(134.40,C-q),(135.23,C-q),(137.44,C-q),(139.04,2×C-q),(139.72,C-q),(139.86,C-q),(147.36,2×C-q),(147.78,C-q),(153.19,2×C-q),(153.25,C-q),(153.94,C-q),(154.74,2×C-q),(155.11,C-q).

Example 55:

N, N-bis (9, 9-dimethyl-9H-fluoren-2-yl) -3',3',4',5',7 '-pentamethyl-2', 3 '-dihydrospiro- [ fluoren-9, 1' -indene ] -2-amine

As described in the general procedure for Buchwald-Hartwig amination, aryl bromide (7.00 g, 16.8 mmol, 1.0 eq.) from step 8c of example 8 was coupled with diarylaminedi (9, 9-dimethyl-9H-fluoren-2-yl) amine (6.87 g, 17.1 mmol, 1.02 eq.) using sodium tert-butyrate (1.69 g, 17.6 mmol, 1.05 eq.), amphos (0.091 g, 0.34 mmol), and Pd ₂(dba)₃ (0.077 g, 0.08 mmol, 0.5 mol%) in toluene (100 ml). The work-up is carried out according to general procedure D.

The crude product was purified by crystallization from acetone to afford the product as a colorless solid (11.2 g, 91%) with a purity of 99.4% (340 nm according to hplc).

The title compound (5.43 g) was further purified by sublimation in vacuo (10 ^-6-10^-7 mbar, 150-245 ℃) to give the title compound as a yellowish solid (5.07 g, purity up to 99.7% according to hplc @340 nm). The purified product had a T _g of 148.0 ℃.

And (3) NMR: ¹H/¹³C(400MHz,101MHz(HSQC),CS₂: acetone (acetone) -d₆)δ/δ(15.41/2.28,CH₃),(17.18/1.21,CH₃),(20.25/2.18,CH₃),(26.97/1.38,2×CH₃),(27.14/1.42,2×CH₃),(30.83/1.65,CH₃),(31.06/1.45,CH₃),(44.60,C-q),(46.52,2×C-q),(58.38/2.48,CH₂),(61.79,C-q),(118.26/7.19,2×CH),(119.26/7.62,CH),(119.62/7.56,2×CH),(120.20/6.98,CH),(120.62/7.61,CH),(120.83/7.51,2×CH),(122.55/7.34,2×CH),(123.00/7.04,2×CH),(123.61/7.12,CH),(124.13/7.07,CH),(126.68/7.21,2×CH),(127.07/7.28,CH),(127.12/7.16,CH),(127.24/7.25,2×CH),(129.72,C-q),(131.87,C-q),(132.05/6.57,CH),(134.03,2×C-q),(135.25,C-q),(136.93,C-q),(139.06,2×C-q),(139.81,C-q),(141.13,C-q),(147.39,2×C-q),(147.72,C-q),(150.23,C-q),(153.17,2×C-q),(153.53,C-q),(154.71,2×C-q),(155.49,C-q).

Example 56:

N, N-bis (9, 9-dimethyl-9H-fluoren-2-yl) -4',4' -dimethyl-3 ',4' -dihydro-2 'H-spiro- [ fluoren-9, 1' -naphthalen ] -2-amine

As described in the general procedure for Buchwald-Hartwig amination, aryl bromide (5.25 g, 13.5 mmol) from step 12c of example 12 was coupled with bis (9, 9-dimethyl-9H-fluoren-2-yl) amine (5.63 g, 14.0 mmol) in 100ml of toluene using sodium tert-butyrate (1.39 g, 14.4 mmol), amphos (0.073 g, 0.27 mmol) and Pd ₂(dba)₃ (0.062 g, 0.07 mmol). The post-treatment was performed according to procedure C. Crystallization of the crude product from acetone/isopropanol afforded the product as a yellowish solid (9.0 g, 98%) with a purity of 96.6% according to hplc @340 nm.

The title compound (6.15 g) was further purified by sublimation in vacuo (10 ^-6-10^-7 mbar, 150-245 ℃) to give the title compound (5.26 g, purity according to hplc @340 nm as high as 99.9%). The melting point of the purified product was 263.0 ℃.

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC),CS₂: acetone (acetone) -d₆ 5:1)：δ/δ＝(27.04/1.44,2×CH₃),(27.06/1.38,2×CH₃),(32.04/1.22,CH₃),(32.40/1.49,CH₃),(33.49/2.07,CH₂),(33.56,C-q),(36.03/1.96,CH₂),(46.58,2×C-q),(55.37,C-q),(118.60/7.27,2×CH),(119.59/7.69,CH),(119.66/7.60,2×CH),(120.56/6.99,CH),(120.85/7.56,CH),(120.91/7.66,2×CH),(122.59/7.37,2×CH),(122.88/7.16,CH),(123.41/7.07,2×CH),(124.88/7.13,CH),(125.94/6.84,CH),(126.67/7.31,CH),(126.74/7.24,2×CH),(126.80/7.16,CH),(126.92/7.07,CH),(127.25/7.26,2×CH),(127.40/7.32,CH),(128.70/6.35,CH),(134.27,2×C-q),(134.50,C-q),(137.41,C-q),(139.03,2×C-q),(139.76,C-q),(145.78,C-q),(147.30,2×C-q),(147.41,C-q),(153.27,2×C-q),(154.65,C-q),(154.83,2×C-q),(156.11,C-q).

Example 57:

N- (4 ',4' -dimethyl-3 ',4' -dihydro-2 'H-spiro- [ fluoren-9, 1' -naphthalen ] -2-yl) -N- (9, 9-dimethyl-9H-fluoren-2-yl) dibenzo [ b, d ] furan-2-amine

As described in the general procedure for Buchwald-Hartwig amination, aryl bromide (5.70 g, 14.6 mmol) from step 12c of example 12 was coupled with the product from example 24 (5.61 g, 14.9 mmol) in 100 ml toluene using sodium tert-butyrate (1.48 g, 15.4 mmol), amphos (0.079 g, 0.29 mmol) and Pd ₂(dba)₃ (0.067 g, 0.07 mmol). The post-processing is performed according to procedure D. Crystallization of the crude product from acetone/isopropanol afforded the product as a yellowish solid (9.0 g, 90%) with a purity of 98.1% according to hplc @340 nm.

The title compound (5.21 g) was sublimated through a vacuum area (10 ^-6-10^-7 mbar, further purified at 150-250 ℃) to give the title compound (4.95 g, purity up to 99.8% according to hplc @340 nm). The glass temperature T _g of the purified product was 139.3 ℃.

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC),CS₂: acetone (acetone) -d₆ 5:1)：δ/δ＝(27.11/1.42,CH₃),(27.17/1.34,CH₃),(31.98/1.17,CH₃),(32.47/1.47,CH₃),(33.55,C-q),(33.56/2.07,CH₂),(35.95/1.94,CH₂),(46.56,C-q),(55.38,C-q),(111.85/7.53,CH),(112.54/7.48,CH),(117.80/7.25,CH),(117.91/7.78,CH),(119.52/7.66,CH),(119.61/7.57,CH),(119.66/6.99,CH),(120.88/7.61,CH),(120.94/7.53,CH),(121.02/7.79,CH),(122.01/7.08,CH),(122.56/7.35,CH),(122.85/7.01,CH),(122.96/7.28,CH),(124.21,C-q),(124.86/7.12,CH),(125.40,C-q),(125.80/7.30,CH),(125.93/6.83,CH),(126.66/7.29,CH),(126.69/7.27,CH),(126.74/7.15,CH),(126.93/7.05,CH),(127.25/7.26,CH),(127.40/7.29,CH),(127.51/7.45,CH),(128.74/6.35,CH),(133.92,C-q),(133.99,C-q),(137.42,C-q),(139.04,C-q),(139.82,C-q),(143.31,C-q),(145.75,C-q),(147.57,C-q),(147.86,C-q),(152.82,C-q),(153.22,C-q),(154.56,C-q),(154.81,C-q),(156.04,C-q),(156.84,C-q).

Example 58:

N, N-bis (9, 9-dimethyl-9H-fluoren-2-yl) -4',4',5',8' -tetramethyl-3 ',4' -dihydro-2 'H-spiro- [ fluoren-9, 1' -naphthalen ] -2-amine

As described in the general procedure for Buchwald-Hartwig amination, aryl bromide (7.00 g, 16.8 mmol, 1.0 eq.) from step 14b of example 14 was coupled with diarylaminedi (9, 9-dimethyl-9H-fluoren-2-yl) amine (6.87 g, 17.1 mmol, 1.02 eq.) using sodium tert-butyrate (1.69 g, 17.6 mmol, 1.05 eq.), amphos (0.091 g, 0.34 mmol), and Pd ₂(dba)₃ (0.077 g, 0.08 mmol, 0.5 mol%) in toluene (100 ml). The post-processing is performed according to procedure D.

The crude product was purified by column chromatography (heptane/DCM) to give the product as a colorless solid (10.2 g, 82%) with a purity of 99.4% (according to hplc @340 nm).

The title compound (10.0 g) was further purified by sublimation in vacuo (10 ^-6-10^-7 mbar, 150-250 ℃) to give the title compound (9.7 g, purity up to 99.4% according to hplc @340 nm). The glass temperature T _g of the purified product was 143.1 ℃.

¹³C-NMR：(101MHz,CS₂ : Acetone (acetone) -d₆ 5:1)δ(20.67,CH₃),(24.38,CH₃),(27.03,2×CH₃),(27.12,2×CH₃),(27.97,CH₃),(31.70,CH₃),(35.20,C-q),(37.65,CH₂),(40.31,CH₂),(46.55,2×C-q),(57.09,C-q),(118.34,2×CH),(118.66,CH),(119.64,2×CH),(119.99,CH),(120.85,2×CH),(121.34,CH),(122.57,2×CH),(122.86,CH),(123.11,2×CH),(124.73,CH),(126.14,CH),(126.70,2×CH),(127.07,CH),(127.25,2×CH),(130.04,CH),(132.15,CH),(134.11,2×C-q),(134.44,C-q),(134.50,C-q),(134.68,C-q),(135.87,C-q),(136.15,C-q),(139.06,2×C-q),(139.45,C-q),(145.81,C-q),(147.40,2×C-q),(147.71,C-q),(153.20,2×C-q),(154.75,2×C-q),(157.81,C-q).

Example 59:

N, N-bis (9, 9-dimethyl-9H-fluoren-2-yl) -7' -methoxy-4 ',4' -dimethyl-3 ',4' -dihydro-2 ' H-spiro- [ fluoren-9, 1' -naphthalen ] -2-amine

The main isomer a (6.00 g, 14.3 mmol, 1.0 eq.) of aryl bromide from step 13b of example 13 was coupled with bis (9, 9-dimethyl-9H-fluoren-2-yl) amine (5.86 g, 14.6 mmol) in 100 ml of toluene using sodium tert-butyrate (1.44 g, 15.0 mmol), amphos (0.077 g, 0.29 mmol) and Pd ₂(dba)₃ (0.066 g, 0.07 mmol) as described in the general procedure for Buchwald-Hartwig amination. The post-processing is performed according to procedure D.

Crystallization of the crude product from t-butyl methyl ether/isopropanol afforded the product as a yellowish solid (8.7 g, 82%) with a purity of 96.7% according to hplc @340 nm. Additional product (1.2 g, 96.2% purity according to hplc @340 nm) was obtained after mother liquor was reduced. The total yield was 93%.

The title compound (5.9 g) was further purified by sublimation in vacuo (10 ^-6-10^-7 mbar, 150-245 ℃) to give the title compound (4.49 g, purity up to 98.5% according to hplc @340 nm). The glass temperature T _g of the purified product was 147.6 ℃.

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC),CS₂: acetone (acetone) -d₆ 5:1)：δ/δ＝(27.15/1.42,2×CH₃),(27.15/1.48,2×CH₃),(32.33/1.22,CH₃),(32.76/1.49,CH₃),(33.11,C-q),(33.78/2.08,CH₂),(36.16/1.97,CH₂),(46.63,2×C-q),(54.55/3.54,OCH₃),(55.71,C-q),(113.00/5.89,CH),(113.36/6.67,CH),(118.66/7.73,2×CH),(119.67/7.70,CH),(119.72/7.62,2×CH),(120.68/7.06,CH),(120.93/7.67,CH),(120.97/7.58,2×CH),(122.64/7.39,2×CH),(123.01/7.22,CH),(123.47/7.13,2×CH),(124.92/7.20,CH),(126.81/7.25,2×CH),(126.86/7.20,CH),(127.33/7.29,2×CH),(127.50/7.33,CH),(127.76/7.24,CH),(134.33,2×C-q),(134.50,C-q),(138.11,C-q),(138.57,C-q),(139.09,2×C-q),(139.74,C-q),(147.35,2×C-q),(147.41,C-q),(153.31,2×C-q),(154.51,C-q),(154.88,2×C-q),(155.98,C-q),(157.36,C-q).

Example 60:

N, N-bis (9, 9-dimethyl-9H-fluoren-2-yl) -3',3' -dimethyl-10-phenyl-2 ',3' -dihydro-10H-spiro- [ acridin-9, 1' -inden ] -2-amine

The aryl chloride (2.63 g, 6.2 mmol, 1.0 eq.) from step 16c of example 16 was coupled with bis (9, 9-dimethyl-9H-fluoren-2-yl) amine (2.55 g, 6.4 mmol) in 50 ml toluene using sodium tert-butyrate (0.63 g, 6.5 mmol), amphos (0.034 g, 0.16 mmol) and Pd ₂(dba)₃ (0.029 g, 0.03 mmol) as described in the general method of Buchwald-Hartwig amination. The post-processing is performed according to procedure D. The crude product was purified by column chromatography (heptane/dichloromethane) to afford the product as a yellowish solid (3.7 g, 75%) with a purity of 99.0% (340 nm according to hplc).

The title compound (3.28 g) was further purified by sublimation in vacuo (10 ^-6-10^-7 mbar, 150-260 ℃) to give the title compound (2.93 g, purity up to 99.8% according to hplc @340 nm). The glass temperature T _g of the purified product was 148.9 ℃.

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC),CS₂: acetone (acetone) -d₆ 5:1)：δ/δ＝(27.09/1.39,2×CH₃),(27.16/1.40,2×CH₃),(31.50/1.28,CH₃),(31.77/1.21,CH₃),(42.87,C-q),(46.45,2C-q),(54.00,C-q),(62.51,AB,2.38,2.41,2J＝13Hz,CH₂),(114.13/6.35,CH),(115.23/6.35,CH),(117.07/7.07,2×CH),(119.43/7.53,2×CH),(120.65/7.43,2×CH),(120.93/6.70,CH),(122.03/6.88,2×CH),(122.52/7.32,2×CH),(122.59/7.18,CH),(124.47/6.80,CH),(125.26/6.60,CH),(126.44/7.18,2×CH),(126.61/6.91,CH),(126.91/7.12,CH),(127.20/7.23,2×CH),(127.38/6.57,CH),(127.74/7.15,CH),(128.21/7.22,CH),(128.41/7.56,CH),(130.69,C-q),(130.96/7.70,2×CH),(131.36/6.45,2×CH),(132.45,C-q),(133.12,2×C-q),(138.16,C-q),(139.24,2×C-q),(140.83,C-q),(141.11,C-q),(141.26,C-q),(145.00,C-q),(147.69,2×C-q),(153.10,2×C-q),(153.57,C-q),(154.54,2×C-q).

Example 61:

n, N-bis (9, 9-dimethyl-9H-fluoren-2-yl) -3, 3-dimethyl-2, 3-dihydro-spiro- [ inden-1, 9 '-xanthen ] -2' -amine

As described in the general procedure for Buchwald-Hartwig amination, aryl bromide (5.50 g, 14.1 mmol) from step 18b of example 18 was coupled with bis (9, 9-dimethyl-9H-fluoren-2-yl) amine (5.87 g, 14.6 mmol) in 100 ml of toluene using sodium tert-butyrate (1.45 g, 15.0 mmol), amphos (0.076 g, 0.28 mmol) and Pd ₂(dba)₃ (0.064 g, 0.07 mmol). The post-processing is performed according to procedure D.

Crystallization of the crude product from acetone/isopropanol afforded 89.3% pure product according to hplc @340 nm as a yellowish solid (7.0 g, 70%). Additional product (1.4 g, 14%, 95.3% purity according to hplc @340 nm) was obtained after reduction of the mother liquor. The total yield was 84%.

The title compound (5.62 g) was further purified by sublimation in vacuo (10 ^-6-10^-7 mbar, 150-240 ℃) to give the title compound (4.97 g, purity up to 99.8% according to hplc @340 nm). The glass temperature T _g of the purified product was 131.0 ℃.

And (3) NMR: ¹³C/¹H(101MHz,400MHz(HSQC),CS₂: acetone (acetone) -d₆ 5:1)：δ/δ＝(26.97/1.40,2×CH₃),(27.04/1.41,2×CH₃),(31.53/1.34,CH₃),(31.66/1.19,CH₃),(43.08,C-q),(46.51,2×C-q),(51.58,C-q),(62.99/2.38,CH₂),(116.31/7.12,CH),(117.38/7.11,CH),(117.46/7.12,2×CH),(119.50/7.59,2×CH),(120.76/7.51,2×CH),(122.24/6.94,2×CH),(122.50/7.18,CH),(122.56/7.37,2×CH),(123.45/6.94,CH),(125.02/7.08,CH),(125.21/6.61,CH),(126.24/6.94,CH),(126.57/7.22,2×CH),(127.20/7.26,2×CH),(127.56/7.19,CH),(128.05/7.16,CH),(128.15/6.64,CH),(128.34/7.22,CH),(131.26,C-q),(132.72,C-q),(133.56,2×C-q),(139.12,2×C-q),(143.23,C-q),(145.62,C-q),(147.55,2×C-q),(147.78,C-q),(151.38,C-q),(153.13,C-q),(153.18,2×C-q),(154.73,2×C-q).

Example 62:

n, N-bis (9, 9-dimethyl-9H-fluoren-2-yl) -3,3,7' -trimethyl-2, 3-dihydrospiro- [ inden-1, 9' -xanthen ] -2' -amine

As described in the general procedure for Buchwald-Hartwig amination, aryl bromide (6.00 g, 14.8 mmol, 1.0 eq.) from step 19b of example 19 was coupled with diarylaminedi (9, 9-dimethyl-9H-fluoren-2-yl) amine (6.06 g, 15.1 mmol, 1.02 eq.) using sodium tert-butyrate (1.49 g, 15.5 mmol, 1.05 eq.), amphos (0.080 g, 0.30 mmol, 2 mol%) and Pd ₂(dba)₃ (0.069 g, 0.07 mmol, 0.5 mol%) in toluene (100 ml). The post-processing is performed according to procedure D.

The crude product was purified by crystallization from acetone/toluene to afford the product as a colorless solid (7.8 g, 73%) with a purity of 99.6% (according to hplc @340 nm).

The title compound (5.1 g) was further purified by sublimation in vacuo (10 ^-6-10^-7 mbar, 150-240 ℃) to give the title compound as a yellowish solid (4.5 g, purity up to 99.9% according to hplc @340 nm). The glass temperature T _g of the purified product was 131.7 ℃.

And (3) NMR: ¹H/¹³C(400MHz,101MHz(HSQC),CS₂: acetone (acetone) -d₆)δ/δ(21.01/2.20,CH₃),(27.03/1.39,2×CH₃),(27.10/1.40,2×CH₃),(31.70/1.34,CH₃),(31.70/1.16,CH₃),(43.07,C-q),(46.49,2×C-q),(51.59,C-q),(63.01/2.35,CH₂),(116.20/6.98,CH),(117.34/7.06,CH),(117.42/7.08,2×CH),(119.50/7.55,2×CH),(120.73/7.47,2×CH),(122.21/6.91,2×CH),(122.47/7.15,CH),(122.54/7.34,2×CH),(125.00/7.04,CH),(125.36/6.53,CH),(126.29/6.91,CH),(126.56/7.20,2×CH),(127.22/7.25,2×CH),(128.05/7.14,CH),(128.19/6.98,CH),(128.30/7.22,CH),(128.30/6.43,CH),(130.84,C-q),(132.29,C-q),(132.73,C-q),(133.49,2×C-q),(139.12,2×C-q),(142.94,C-q),(145.71,C-q),(147.54,2×C-q),(147.91,C-q),(149.39,C-q),(153.04,C-q),(153.13,2×C-q),(154.66,2×C-q).

Example 63:

N, N-bis (9, 9-dimethyl-9H-fluoren-2-yl) -3, 3-dimethyl-7 ' - (trifluoromethyl) -2, 3-dihydro-spiro- [ inden-1, 9' -xanthen ] -2' -amine

As described in the general procedure for Buchwald-Hartwig amination, aryl bromide (6.00 g, 13.1 mmol, 1.0 eq.) from step 20b of example 20 was coupled with diarylaminedi (9, 9-dimethyl-9H-fluoren-2-yl) amine (5.35 g, 13.3 mmol, 1.02 eq.) using sodium tert-butyrate (1.32 g, 13.7 mmol, 1.05 eq.), amphos (0.071 g, 0.26 mmol, 2 mol%) and Pd ₂(dba)₃ (0.060 g, 0.07 mmol, 0.5 mol%) in toluene (100 ml). The post-processing is performed according to procedure D.

The crude product was purified by crystallization from acetone to afford the product as a pale yellow solid (8.6 g, 83%) with a purity of 99.7% (340 nm according to hplc).

The title compound (5.0 g) was further purified by sublimation in vacuo (10 ^-6-10^-7 mbar, 150-230 ℃) to give the title compound as a yellowish solid (4.6 g, purity up to 99.9% according to hplc @340 nm). The glass temperature T _g of the purified product was 125.1 ℃.

And (3) NMR: ¹H/¹³C(400MHz,101MHz(HSQC),CS₂: acetone (acetone) -d₆)δ/δ(27.03/1.40,2×CH₃),(27.10/1.41,2×CH₃),(31.50/1.34,CH₃),(31.68/1.20,CH₃),(43.18,C-q),(46.53,2×C-q),(51.58,C-q),(63.03/2.39,CH₂),(117.00/7.27,CH),(117.46/7.14,CH),(117.71/7.11,2×CH),(119.57/7.57,2×CH),(120.81/7.50,2×CH),(122.44/6.95,2×CH),(122.58/7.36,2×CH),(122.73/7.20,CH),(123.33,CF₃(q,¹J_C,F＝272.0Hz)),(124.70/7.48,CH(q,J＝3.7Hz)),(124.76/6.59,CH),(124.94/7.10,CH),(125.29,C-q(q,J_C,F＝32.5Hz)),(125.50/6.91,CH(q,J_C,F＝3.9Hz)),(125.97/6.94,CH),(126.70/7.22,2×CH),(127.26/7.27,2×CH),(128.43/7.20,CH),(128.85/7.27,CH),(131.96,C-q(q,J_C,F＝1.0Hz)),(133.84,2×C-q),(139.03,2×C-q),(144.04,C-q),(144.65,C-q),(146.85,C-q),(147.35,2×C-q),(153.12,C-q),(153.15,2×C-q),(153.77,C-q(q,J_C,F＝1.1Hz)),(154.78,2×C-q).

Example 64:

N, N-bis (9, 9-dimethyl-9H-fluoren-2-yl) -3,3,7' -trimethyl-2, 3-dihydrospiro- [ indene-1, 9' -thioxanthen ] -2' -amine

As described in the general procedure for Buchwald-Hartwig amination, aryl bromide (4.92 g, 11.7 mmol, 1.0 eq.) from step 23b of example 23 was coupled with diarylaminedi (9, 9-dimethyl-9H-fluoren-2-yl) amine (4.78 g, 11.9 mmol, 1.02 eq.) using sodium tert-butyrate (1.18 g, 12.3 mmol, 1.05 eq.), amphos (0.063 g, 0.23 mmol), and Pd ₂(dba)₃ (0.054 g, 0.06 mmol, 0.5 mol%) in toluene (100 ml). The post-processing is performed according to procedure D.

The crude product was purified by crystallization from acetone to afford the product as a colorless solid (7.5 g, 87%) with a purity of 99.5% (340 nm according to hplc).

The title compound (5.3 g) was further purified by sublimation in vacuo (10 ^-6-10^-7 mbar, 150-245 ℃) to give the title compound as a yellowish solid (4.8 g, purity up to 99.8% according to hplc @340 nm). The glass temperature T _g of the purified product was 143.1 ℃.

And (3) NMR: ¹H/¹³C(400MHz,101MHz(HSQC),CS₂: acetone (acetone) -d₆)δ/δ(21.41/2.20,CH₃),(27.04/1.41,2×CH₃),(27.06/1.40,2×CH₃),(30.88/1.14,CH₃),(30.96/1.21,CH₃),(42.71,C-q),(46.53,2×C-q),(54.81/2.44,CH₂),(58.79,C-q),(118.08/7.10,2×CH),(119.59/7.59,2×CH),(120.79/7.50,2×CH),(122.41/7.02,CH),(122.58/7.36,2×CH),(122.96/6.93,2×CH),(123.18/7.19,CH),(123.99/6.64,CH),(126.70/7.22,2×CH),(126.77/6.97,CH),(127.01,C-q),(127.07/6.97,CH),(127.16/7.34,CH),(127.27/7.27,2×CH),(127.91/6.57,CH),(127.91/7.36,CH),(127.96/6.96,CH),(128.36/7.14,CH),(130.04,C-q),(133.98,2×C-q),(135.43,C-q),(139.07,2×C-q),(142.00,C-q),(143.50,C-q),(145.06,C-q),(146.17,C-q),(147.20,2×C-q),(153.20,2×C-q),(153.90,C-q),(154.72,2×C-q).

Example 65:

N- (9, 9-dimethyl-9H-fluoren-2-yl) -N- (3 ',3',4',7' -tetramethyl-2 ',3' -dihydrospiro- [ fluoren-9, 1' -inden ] -2-yl) benzo [ d ] [1,3] dioxol-5-amine

The aryl bromide (8.00 g, 19.8 mmol, 1.0 eq.) from step 4d of example 4 was coupled with the diarylamine (6.66 g, 20.2 mmol, 1.02 eq.) from example 38 in toluene (100 ml) using sodium tert-butyrate (20% solution in THF; 10.5 g, 21.8 mmol, 1.1 eq.), tri-tert-butylphosphonium tetrafluoroborate (0.014 g,0.05mmol, 0.25 mol%) and Pd ₂(dba)₃ (0.018 g, 0.02 mmol, 0.1 mol%) as described in the general procedure for Buchwald-Hartwig coupling. After cooling, cyanuric acid (0.035 g,10 equivalents relative to Pd ₂dba₃) and diatomaceous earth (about 1.5 g) were added to the reaction mixture. The suspension was stirred for a further 15 minutes. The mixture was then filtered through a pad of celite (about 1.8 g) followed by flushing with toluene (about 10 ml). The solvent was evaporated to give the crude product (15 g) as a brown foam.

The crude product was purified by column chromatography (heptane/DCM) followed by crystallization from acetone/isopropanol to provide the product as a colorless solid (10.9 g, 84%) with a purity of 99.4% (according to hplc @340 nm).

The title compound (9.7 g) was further purified by sublimation in vacuo (10 ^-6-10^-7 mbar, 150-240 ℃) to give the title compound as a yellowish solid (7.7 g, purity up to 99.8% according to hplc @340 nm).

And (3) NMR: ¹H/¹³C(400MHz,101MHz(HSQC),CS₂: acetone (acetone) -d₆)δ/δ(17.20/1.21,CH₃),(19.37/2.43,CH₃),(27.04/1.33,CH₃),(27.18/1.39,CH₃),(30.29/1.63,CH₃),(30.38/1.44,CH₃),(44.56,C-q),(46.48,C-q),(57.73/2.45,CH₂),(62.27,C-q),(101.36/5.94,CH₂),(107.26/6.61,CH),(108.70/6.68,CH),(117.21/7.09,CH),(118.76/6.57,CH),(119.08/6.89,CH),(119.19/7.61,CH),(119.52/7.54,CH),(120.53/7.58,CH),(120.74/7.48,CH),(122.19/6.93,CH),(122.50/7.33,CH),(122.52/7.00,CH),(124.07/7.05,CH),(126.55/7.19,CH),(127.00/7.15,CH),(127.10/7.27,CH),(127.18/7.24,CH),(129.85/6.66,CH),(131.10,C-q),(131.39/6.83,CH),(132.65,C-q),(133.54,C-q),(134.60,C-q),(139.10,C-q),(139.94,C-q),(142.19,C-q),(143.32,C-q),(144.02,C-q),(147.41,C-q),(148.00,C-q),(148.41,C-q),(150.11,C-q),(153.11,C-q),(153.25,C-q),(154.64,C-q),(155.03,C-q).

Example 66:

N- ([ 1,1 '-biphenyl ] -2-yl) -N- (9, 9-dimethyl-9H-fluoren-2-yl) -3',3',4',7 '-tetramethyl-2', 3 '-dihydro-spiro- [ fluoren-9, 1' -inden ] -2-amine

The aryl bromide (8.00 g, 19.8 mmol, 1.0 eq.) from example 4 step 4d was coupled with diarylamine N- ([ 1,1' -biphenyl ] -2-yl) -9, 9-dimethyl-9H-fluoren-2-amine (7.31 g, 20.2 mmol, 1.02 eq.) in toluene (100 ml) using sodium tert-butyrate (20% solution in THF; 10.5 g, 21.8 mmol, 1.1 eq.), tri-tert-butylphosphonium tetrafluoroborate (0.014 g,0.05 mmol, 0.25 mmol) and Pd ₂(dba)₃ (0.018 g, 0.02 mmol, 0.1 mol%) as described in the general procedure for Buchwald-Hartwig coupling. After cooling, cyanuric acid (0.075 g, 20 equivalents relative to Pd ₂dba₃) was added to the mixture and stirred for 15 minutes. The mixture was then filtered through a pad of celite (about 5 g) and the solvent was removed from the filtrate to give the crude product (18 g) as a brown foam.

The crude product was purified by crystallization from acetone to afford the product as a pale yellow solid (12.5 g, 92%) with a purity of 99.6% (340 nm according to hplc).

The crude product (12.1 g) was further purified by sublimation in a vacuum zone (10 ^-6-10^-7 mbar, 150-230 ℃) to give the title compound as a yellowish solid (10.8 g, purity up to 99.9% according to hplc @340 nm). The glass temperature T _g of the purified product was 119.9 ℃.

And (3) NMR: ¹H/¹³C(400MHz,101MHz(HSQC),CS₂: acetone (acetone) -d₆)δ/δ(17.25/1.10,CH₃),(19.35/2.41,CH₃),(27.09/1.20,CH₃),(27.15/1.31,CH₃),(30.36/1.61,CH₃),(30.48/1.41,CH₃),(44.54,C-q),(46.36,C-q),(57.40/2.33,CH₂),(62.13,C-q),(115.92/6.90,CH),(117.91/6.67,CH),(119.01/7.54,CH),(119.38/7.48,CH),(120.14/7.43,CH),(120.49/7.35,CH),(121.16/6.79,CH),(121.45/6.81,CH),(122.43/7.29,CH),(123.98/7.00,CH),(126.04/7.28,CH),(126.35/7.16,CH),(126.79/7.11,CH),(127.01/7.01,CH),(127.03/7.23,CH),(127.10/7.21,CH),(127.93/7.02,2×CH),(128.47/7.17,2×CH),(128.96/7.35,CH),(129.55/7.30,CH),(129.75/6.66,CH),(130.95,C-q),(131.27/6.82,CH),(132.09/7.31,CH),(132.68,C-q),(132.77,C-q),(133.84,C-q),(139.16,C-q),(139.57,C-q),(140.05,C-q),(140.21,C-q),(143.40,C-q),(144.90,C-q),(147.27,C-q),(147.33,C-q),(149.99,C-q),(153.04,C-q),(153.14,C-q),(154.16,C-q),(154.41,C-q).

Example 67:

N- (9, 9-dimethyl-9H-fluoren-2-yl) -9-phenyl-N- (3 ',3',4',7' -tetramethyl-2 ',3' -dihydrospiro- [ fluoren-9, 1' -indene ] -2-yl) -9H-carbazol-3-amine

The aryl bromide (8.00 g, 19.8 mmol, 1.0 eq.) from step 4d of example 4 was coupled with the diarylamine (7.31 g, 20.2 mmol, 1.02 eq.) from example 31 in toluene (100 ml) using sodium tert-butyrate (20% solution in THF; 10.5 g, 21.8 mmol, 1.1 eq.), tri-tert-butylphosphonium tetrafluoroborate (0.014 g, 0.05mmol, 0.25 mol%) and Pd ₂(dba)₃ (0.018 g,0.02mmol, 0.1 mol%) as described in the general procedure for Buchwald-Hartwig coupling. After cooling, cyanuric acid (0.055 g, 10 equivalents relative to Pd ₂dba₃) was added to the mixture and stirred for 15 minutes. The mixture was then filtered through a pad of celite (4.7 g). The pad was washed with more toluene (100 ml) and then the solvent was removed from the combined filtrates to give the crude product (17.9 g). The crude product (17.6 g) was purified by column chromatography (heptane/DCM) followed by crystallization from heptane to provide the product as a yellowish solid (10.9 g, 61.9%) of 99.7% purity (according to hplc @340 nm).

And (3) NMR: ¹H/¹³C(400MHz,101MHz(HSQC),CS₂: acetone (acetone) -d₆)δ/δ(17.25/1.26,CH₃),(19.34/2.39,CH₃),(27.08/1.32,CH₃),(27.18/1.39,CH₃),(30.26/1.61,CH₃),(30.40/1.40,CH₃),(44.55,C-q),(46.48,C-q),(57.78/2.47,CH₂),(62.29,C-q),(109.92/7.36,CH),(110.68/7.32,CH),(117.04/7.18,CH),(117.88/7.88,CH),(118.80/7.01,CH),(119.12/7.60,CH),(119.46/7.53,CH),(120.36/7.17,CH),(120.57/7.57,CH),(120.64/7.89,CH),(120.76/7.47,CH),(122.08/6.99,CH),(122.47/7.04,CH),(122.49/7.32,CH),(123.25,C-q),(124.08/7.04,CH),(124.53,C-q),(125.20/7.21,CH),(126.42/7.18,CH),(126.44/7.36,CH),(126.88/7.59,2×CH),(126.88/7.14,CH),(127.09/7.26,CH),(127.16/7.23,CH),(127.53/7.49,CH),(129.83/6.65,CH),(130.13/7.65,2×CH),(131.08,C-q),(131.34/6.80,CH),(132.63,C-q),(133.24,C-q),(134.30,C-q),(137.68,C-q),(137.73,C-q),(139.20,C-q),(140.05,C-q),(140.86,C-q),(141.24,C-q),(143.39,C-q),(148.00,C-q),(148.55,C-q),(150.08,C-q),(153.12,C-q),(153.23,C-q),(154.63,C-q),(155.03,C-q).

Example 68:

n1- (9, 9-dimethyl-9H-fluoren-2-yl) -N4, N4-diphenyl-N1- (3 ',3',4',7' -tetramethyl-2 ',3' -dihydro-spiro- [ fluoren-9, 1' -inden ] -2-yl) benzene-1, 4-diamine

The aryl bromide (8.00 g, 19.8 mmol, 1.0 eq.) from step 4d of example 4 was coupled with diarylamine (9.16 g, 20.2 mmol, 1.02 eq.) from example 25 in toluene (100 ml) using sodium tert-butyrate (20% solution in THF; 10.5 g, 21.8 mmol, 1.1 eq.), tri-tert-butylphosphonium tetrafluoroborate (0.014 g, 0.05 mmol, 0.25 mol%) and Pd ₂(dba)₃ (0.018 g, 0.02 mmol, 0.1 mol%) as described in the general procedure for Buchwald-Hartwig coupling. After cooling, cyanuric acid (10 equivalents relative to Pd ₂dba₃) and diatomaceous earth (4.7 g) were added to the reaction mixture. The suspension was stirred for a further 15 minutes. It was then filtered and the celite pad was washed with toluene (100 ml). After removal of the solvent from the combined filtrates, the crude product (17.4 g, purity 71.3%) was further purified via chromatography.

The crude product (17.4 g) was purified by column chromatography (heptane/DCM) and the product-containing fractions evaporated to yield 9.6 g of a foam. Crystallization from isopropanol provides the product as a pale yellow solid.

And (3) NMR: ¹H/¹³C(400MHz,101MHz(HSQC),CS₂: acetone (acetone) -d₆)δ/δ(17.20/1.20,CH₃),(19.38/2.45,CH₃),(27.03/1.35,CH₃),(27.17/1.40,CH₃),(30.34/1.63,CH₃),(30.36/1.45,CH₃),(44.56,C-q),(46.50,C-q),(57.70/2.44,CH₂),(62.26,C-q),(117.72/7.14,CH),(119.25/7.61,CH),(119.57/7.54,CH),(119.69/6.89,CH),(120.57/7.60,CH),(120.81/7.50,CH),(122.52/7.33,CH),(122.61/7.00,CH),(122.68/6.97,2×CH),(122.90/7.09,CH),(123.84/7.05,4×CH),(124.06/7.05,CH),(125.41/6.95,2×CH),(125.51/7.01,2×CH),(126.61/7.19,CH),(127.08/7.16,CH),(127.12/7.27,CH),(127.20/7.25,CH),(129.38/7.22,4×CH),(129.86/6.65,CH),(131.07,C-q),(131.40/6.85,CH),(132.68,C-q),(133.84,C-q),(134.87,C-q),(139.06,C-q),(139.93,C-q),(142.73,C-q),(142.93,C-q),(143.32,C-q),(147.12,C-q),(147.68,2×C-q),(147.81,C-q),(150.11,C-q),(153.13,C-q),(153.29,C-q),(154.71,C-q),(155.10,C-q).

Example 69:

3',3',4',7' -tetramethyl-2- (10- (naphthalen-1-yl) anthracen-9-yl) -2',3' -dihydro-spiro- [ fluorene-9, 1' -indene ]

The product from example 5 (9.30 g, 20.6 mmol, 1.03 eq), 9-bromo-10- (1-naphthyl) -4a, 10-didehydroanthracene (7.67 g, 20.0 mmol, 1.00 eq), potassium carbonate (9.5 g, 69 mmol, 3.4 eq), water (30 ml) and THF (75 ml) were bottled under an inert atmosphere. To the stirred reaction mixture were added bis (triphenylphosphine) palladium dichloride (21 mg, 0.030 mmol, 1.5 mol%) and triphenylphosphine (22 mg, 0.084 mmol, 4.2 mol%). The mixture was heated under reflux for 13 hours. After cooling to room temperature, the reaction mixture was partitioned between toluene (400 ml) and water (30 ml). The aqueous layer was discarded and the organic layer was washed 2 times with water (50 ml each). The organic layer was evaporated to dryness and the resulting crude compound was crystallized from cyclohexane (80 ml, 50 ℃ C. To 20 ℃ C.). The filter cake was washed with cyclohexane (40 ml) and isopropanol (40 ml) and after drying gave 11.7 g (91%) of the product as a pale yellowish solid. An analytical sample was obtained from recrystallization from THF.

The NMR spectrum of the product was too complex to specify a signal, since the 2 rotamers were present in a ratio of almost 1:1. The melting point was 216 ℃.

Application examples

III.1 HOMO and LUMO energy levels of hole transport materials

HOMO was determined by cyclic voltammetry:

The method (Onset method) at the beginning is mainly used for analysis of samples that do not show a definite redox event or only one of 2 events. To evaluate HOMO, E _ons was determined via tangent to the slope of the oxidation event using straight-line extrapolation (using IVIUM Soft). HOMO is further calculated using the intersection between the tangent line and the starting slope.

Ferrocene was used as a reference system from which the fermi level (4.4 ev) was measured on the day of each measurement to avoid bias within the measurement series. HOMO is determined by formula [1] with reference to the reference system:

[1] E _Homo＝-|E_ons +4.4 electron volts

E _1/2 method:

Or evaluating HOMO using the E _1/2 method on fully reversible redox events. The basic parameters of the cyclic voltammogram were first determined (IVIUM Soft) and from this E _1/2 was calculated. The HOMO in the formula [1] was measured using the obtained value (instead of E _on).

HOMO-LUMO-GAP was determined by UV/VIS spectrometry:

To determine the optical bandgap λ _ons, a tangent (with a slope measured at the inflection point) is drawn at the inflection point of the falling edge of the longest wavelength absorption band (measured by Origin 2020 or primary differential using Excel). The abscissa crossing is called the optical head (lambda _ons) and corresponds to the energy between HOMO and LUMO. E _gopt[eV]＝1240/λ_Ons [ nm ] was followed by e=h×c/λ. LUMO is calculated from the HOMO energy level added to the band gap.

HOMO and LUMO energy level tables for Compounds

Compounds of formula (I)	HOMO[eV]	LUMO[eV]
			Example 39	-5.04	-1.97
Example 40	-5.04	-2.03
			Example 41	-5.03	-1.96
Example 42	-5.07	-2.01
			Example 43	-5.07	-2.01
Example 44	-5.04	-1.98
			Example 45	-5.03	-1.96
Example 46	-5.03	-1.97
			Example 47	-5.33	-1.82
Example 48	-5.52	-2.05
			Example 49	-5.07	-2.01
Example 50	-5.13	-1.89
			Example 51	-5.08	-2.01
Example 52	-5.47	-2.03
			Example 53	-5.03	-1.96
Example 54	-5.06	-2.00
			Example 55	-5.02	-1.96
Example 56	-5.03	-1.97
			Example 57	-5.06	-2.00
Example 58	-5.03	-1.97
			Example 59	-5.03	-1.96
Example 60	-4.81	-1.80
			Example 61	-5.03	-1.94
Example 62	-5.03	-1.94
			Example 63	-5.08	-1.97
Example 64	-5.05	-1.95

III.2 conductivity of hole transport materials

Conductivity was measured using NDP-9 as p-dopant. The glass substrate (35 mm x 50 mm) was completely cleaned and then coated with a 155 nm thick layer of Indium Tin Oxide (ITO) having grooves 20 microns wide, i.e. the ITO was divided into 2 segments of grooves. The trench is filled with the compound of formula (I) and NDP-9 as the p-dopant material by co-evaporating the compound of formula (I) and the p-dopant material. The thickness of each doped layer was 50 nm. Conductivity was measured after applying a voltage from 10 volts between 2 pieces of ITO.

The conductivities of 2 different sample geometries (channel length of sample geometry a of 188 mm; channel length of sample geometry B of 146 mm) were determined at the respective doping ratios (1 vol%, 3 vol% and 5 vol%) and the samples to be tested contained these 2 geometries.

A table of compound (I) and its glass temperature T _g or melting temperature T _m, and its conductivity at each ratio of dopant NDP-9. Some compounds currently only measure glass temperature.

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Claims

1.A compound of formula (I):

And mixtures thereof, wherein

R ^A is hydrogen or C ₁-C₆ alkyl,

R ^B is hydrogen or C ₁-C₆ alkyl,

R ^C is hydrogen or C ₁-C₆ alkyl,

R ^D is hydrogen or C ₁-C₆ alkyl,

W is a chemical bond or CH ₂,

Biaryl comprising at least 4 aromatic rings, and

Y is independently selected from the group consisting of C ₁-C₆ alkyl, phenyl and CF ₃ at each occurrence, wherein phenyl is unsubstituted or substituted with 1,2 or 3 substituents selected from the group consisting of C ₁-C₆ alkyl,

Q is 0, 1,2, 3 or 4,

R is 0, 1, 2 or 3,

Z is O, S, NAr or a bond.

2. A compound of formula (I):

And mixtures thereof, wherein

R ^A is hydrogen or C ₁-C₆ alkyl,

R ^B is hydrogen or C ₁-C₆ alkyl,

R ^C is hydrogen or C ₁-C₆ alkyl,

R ^D is hydrogen or C ₁-C₆ alkyl,

W is a chemical bond or CH ₂,

X is selected from NH₂、NHAr、NAr₂、Cl、Br、I、CH₃SO₃、CF₃SO₃、CH₃-C₆H₄-SO₃、C₆H₅-SO₃、NHCOC(CH₃)₃、NHCOCH₃ or NO ₂, wherein

Q is 0, 1,2, 3 or 4,

R is 0, 1, 2 or 3,

Z is O, S, NAr or a bond.

3. A compound of formula (I) according to claim 1 or 2, selected from the group consisting of compounds (i.a), (I.B), (i.c), (id), (I.E), (I.F), (I.G) and (I.H):

Wherein the method comprises the steps of

R ^A is hydrogen or C ₁-C₄ alkyl,

R ^B is hydrogen or C ₁-C₄ alkyl,

R ^C is hydrogen or C ₁-C₄ alkyl,

R ^D is hydrogen or C ₁-C₄ alkyl,

R ^V is hydrogen, C ₁-C₄ alkyl or CF ₃,

Biaryl comprising at least 4 aromatic rings, and

An unsubstituted or substituted pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl or triazinyl group in each case, where the pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl or triazinyl group may be part of a fused ring system comprising 2, 3 or more than 3 unsubstituted or substituted rings, where

4. A compound of formula (I) according to claim 1 or 2, selected from compounds (i.a), (I.B), (i.c), (i.d), (I.E), (I.F), (I.G) and (I.H):

Wherein the method comprises the steps of

R ^A is hydrogen or C ₁-C₄ alkyl,

R ^B is hydrogen or C ₁-C₄ alkyl,

R ^C is hydrogen or C ₁-C₄ alkyl,

R ^D is hydrogen or C ₁-C₄ alkyl,

Ar is independently selected at each occurrence from the group consisting of unsubstituted or substituted aryl groups in each occurrence, wherein

The 2 Ar groups bound to a nitrogen atom may also form together with the nitrogen atom a fused ring system having 3 or more than 3 unsubstituted or substituted rings.

5. A compound of formula (I) according to claim 1 or 2, selected from compounds (i.1) to (i.33):

6. A compound of formula (I) according to claim 1 or 2, selected from compounds (i.34) to (i.72):

7. A compound according to any one of the preceding claims wherein Ar groups are independently selected for each occurrence from:

Wherein the method comprises the steps of

Each R ^Ar1 is independently selected from:

C ₁-C₆ alkyl group, C ₁-C₆ alkoxy group,

The two R ^Ar1 groups bound to adjacent carbon atoms together with the carbon atoms to which they are bound may form a saturated 5-membered heterocyclic ring having 1 oxygen atom or 2 non-adjacent oxygen atoms as a ring member, which is unsubstituted or substituted with 1 or 2 groups selected from C ₁-C₄ alkyl;

Each R ^Ar2 is independently selected from:

c ₁-C₆ alkyl, C ₁-C₆ -alkoxy,

8. A compound according to any one of the preceding claims, wherein Ar groups are independently selected for each occurrence from groups of formulae (Ar-I) to (Ar-LIX):

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Wherein the method comprises the steps of

# In each case represents a bonding site to a nitrogen atom;

Furthermore, R ^9a in the formulae AR-XXV, AR-XXVI, AR-XXVII, AR-LIII and AR-LIX together with R ^9b may form an alkylene group (CH ₂)_r, R is 4, 5 or 6,

Wherein 1 or 2 hydrogen atoms in the group may be replaced by methyl or methoxy;

In formulae AR-XLVI, AR-XLVI and AR-XLVIII:

in formulae AR-XXIV, AR-XLIX, AR-L, AR-LI and AR-LII:

R ³、R⁴、R⁵ and R ⁶, if present, are independently of one another selected from the group consisting of hydrogen, linear or branched C ₁-C₄ alkyl, linear or branched C ₁-C₄ alkoxy, phenyl, 1-naphthyl, 2-naphthyl, 9-fluorenyl and 9-carbazolyl, wherein phenyl, 1-naphthyl, 2-naphthyl, 9-fluorenyl or 9-carbazolyl are unsubstituted or substituted by 1,2 or 3 different or identical substituents selected from the group consisting of C ₁-C₄ alkyl and C ₁-C₄ alkoxy,

R ^e is hydrogen, C ₁-C₆ alkyl or C ₃-C₈ cycloalkyl, and

R ^f is hydrogen, C ₁-C₆ alkyl or C ₃-C₈ cycloalkyl.

9. A compound according to any one of the preceding claims, wherein X is (NAr ₂) and one of the Ar groups bonded to the nitrogen atom is selected from the groups AR-XXIV, AR-XXV, AR-XXXI, AR-XLVI, AR-XLIII, AR-XLIX and AR-L as defined in claim 8, and the other Ar group bonded to the nitrogen atom is selected from the groups AR-I、AR-II、AR-IV、AR-XIX、AR-XXV、AR-XXIX、AR-XXXI、AR-XXVIII、AR-XXXIV、AR-XLVI、AR-XLVII、AR-XLVIII、AR-XLIX、AR-LI、AR-LII、AR-LIII、AR-LIV、AR-LVII、AR-LVIII、AR-LV and AR-XXXIII as defined in claim 8,

Preferably, the method comprises the steps of,

One of the Ar groups is selected from the group of AR-XIX as defined in claim 8, and the other Ar group is selected from the group of AR-XXV as defined in claim 8, or

One of the Ar groups is selected from the group consisting of AR-XXV as defined in claim 8, and the other Ar group is selected from the group consisting of AR-XXIX as defined in claim 8, or

One of the Ar groups is selected from the group consisting of AR-XXV as defined in claim 8, and the other Ar group is selected from the group consisting of AR-XXXI as defined in claim 8, or

One of the Ar groups is selected from the group consisting of AR-XXV as defined in claim 8, and the other Ar group is selected from the group consisting of AR-XLVI as defined in claim 8, or

One of the Ar groups is selected from the group consisting of AR-XXV as defined in claim 8, and the other Ar group is selected from the group consisting of AR-XLVIII as defined in claim 8, or

One of the Ar groups is selected from the group consisting of AR-XXV as defined in claim 8, and the other Ar group is selected from the group consisting of AR-XLLVIII as defined in claim 8, or

One of the Ar groups is selected from the group consisting of AR-XXV as defined in claim 8, and the other Ar group is selected from the group consisting of AR-XLIX as defined in claim 8, or

One of the Ar groups is selected from the group consisting of an AR-XXV group as defined in claim 8, and the other Ar group is selected from the group consisting of an AR-L group as defined in claim 8, or

One of the Ar groups is selected from the group consisting of AR-XXV as defined in claim 8, and the other Ar group is selected from the group consisting of AR-LI as defined in claim 8, or

One of the Ar groups is selected from the group consisting of an AR-XXV group as defined in claim 8, and the other Ar group is selected from the group consisting of an AR-LII group as defined in claim 8, or

One of the Ar groups is selected from the group consisting of an AR-XXV group as defined in claim 8, and the other Ar group is selected from the group consisting of an AR-LIII group as defined in claim 8, or

One of the Ar groups is selected from the group consisting of AR-XXV as defined in claim 8, and the other Ar group is selected from the group consisting of AR-XXXIII as defined in claim 8, or

One of the Ar groups is selected from the group consisting of AR-XXV as defined in claim 8, and the other Ar group is selected from the group consisting of AR-LVII as defined in claim 8, or

One of the Ar groups is selected from the group consisting of AR-XXV as defined in claim 8, and the other Ar group is selected from the group consisting of AR-LVIII as defined in claim 8, or

2 Ar groups are selected from the group consisting of AR-XXXI as defined in claim 8.

10. A compound according to any one of the preceding claims wherein the (NAr ₂) groups are independently selected at each occurrence from groups of formulae (1) to (58):

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Wherein the method comprises the steps of

# Represents the bonding position to the rest of the compound.

11. Use of at least one compound of the general formula (I) as defined in any one of claims 1 to 10, as follows:

as Hole Transport Materials (HTM) in organic electronics,

As Electron Blocking Material (EBM) in an organic electronic device,

12. An electroluminescent device comprising an upper electrode, a lower electrode, an electroluminescent layer and optionally an auxiliary layer, wherein at least one of the electrodes is transparent, which electroluminescent device comprises at least one compound of formula (I) as defined in any one of claims 1 to 10, and which is preferably in a hole transporting layer or in an electron blocking layer.

13. The electroluminescent device of claim 12 in the form of an Organic Light Emitting Diode (OLED).

14. An organic solar cell, comprising:

A cathode which is arranged to be electrically connected to the anode,

The anode is a metal-oxide-semiconductor anode,

Optionally, at least one further layer selected from exciton blocking layers, electron conducting layers, hole transport layers,

Wherein the organic solar cell comprises at least one compound of formula (I) as defined in any one of claims 1 to 10.

15. A process for the preparation of a compound of formula (I) designated (i.a1):

Wherein the method comprises the steps of

R ^A is hydrogen or methyl, and the hydrogen is methyl,

R ^B is hydrogen or methyl, and the hydrogen is methyl,

R ^C is hydrogen, and the hydrogen atom,

R ^D is hydrogen, and the hydrogen atom,

W is a chemical bond or CH ₂,

Q is 0 or 1 and the number of the groups,

R is 0 or 1, and the number of the groups is 1,

Z is O, S, NAr or a chemical bond,

The method comprises the following steps:

a1 Providing a compound of formula (V.a):

Wherein X is H, cl or Br,

Wherein the method comprises the steps of

To give compounds of the formula (vii.a1) or (vii.a2):

A4 In the case where X is H, brominating or nitrifying the cyclized product in step a 3),

Compound (I.a1) was obtained.

16. The method of claim 15, wherein providing a compound of formula (V.a) comprises the steps of: a11 Providing a ketone of formula (ii.a):

Wherein X is H, cl or Br,

A12 Reacting a ketone of formula (ii.a) with a compound of formula (iii.a):

Wherein the method comprises the steps of

Met is Li or a group Mg-Hal, wherein Hal is Cl, br or I,

Alcohol (iv.a) is obtained:

Subsequent reduction affords the compound of formula (V.a).

17. The process according to claim 16, wherein in step a 11) the ketone of formula (ii.a) wherein X is H is subjected to bromination to obtain a ketone of formula (ii.a) wherein X is Br, and optionally the brominated product is subjected to one or more treatment steps.

18. A process for the preparation of a compound of formula (I) designated (i.b1):

Wherein the method comprises the steps of

R ^A is hydrogen or methyl, and the hydrogen is methyl,

R ^B is hydrogen or methyl, and the hydrogen is methyl,

R ^C is hydrogen, and the hydrogen atom,

R ^D is hydrogen, and the hydrogen atom,

W is a chemical bond or CH ₂,

X is Cl, br, I or NO ₂,

Q is 0 or 1 and the number of the groups,

R is 0 or 1, and the number of the groups is 1,

Z is O, S, NAr or a chemical bond,

The method comprises the following steps:

b1 Providing a compound of formula (ii.b):

Wherein X is H, cl, br, I or NO ₂,

Compound (iv.b) is obtained:

Wherein the method comprises the steps of

Obtaining a compound of formula (vii.b1) or (vii.b2):

B5 In the case where X is H, brominating or nitrifying the cyclized product in step b 4),

Compound (I.b1) is obtained.

19. A process for the preparation of a compound of formula (I) designated (i.c1):

Wherein the method comprises the steps of

R ^A is a methyl group, and the amino group is a methyl group,

R ^B is a methyl group, and the amino group is a methyl group,

R ^C is hydrogen or methyl, and the hydrogen is methyl,

R ^D is hydrogen or methyl, and the hydrogen is methyl,

X is Cl or Br,

Q is 0 or 1 and the number of the groups,

R is 0 or 1, and the number of the groups is 1,

Z is O, S, NAr or a chemical bond,

The method comprises the following steps:

c1 Providing a compound of formula (iv.c):

c2 Reacting compound (iv.c) with an olefin (viii.c) in the presence of a lewis acid, such as BF ₃ ether complex:

Compound (I.c1) is obtained.

20. A process for the preparation of a compound of formula (I) designated (i.d1):

Wherein the method comprises the steps of

R ^A is hydrogen or methyl, and the hydrogen is methyl,

R ^B is hydrogen or methyl, and the hydrogen is methyl,

R ^C is hydrogen, and the hydrogen atom,

R ^D is hydrogen, and the hydrogen atom,

W is a chemical bond or CH ₂,

R ^I、R^II、R^III and R ^IV are hydrogen,

Q is 0 or 1 and the number of the groups,

R is 0 or 1, and the number of the groups is 1,

Z is O, S, NAr or a chemical bond,

The method comprises the following steps:

d1 Providing a ketone of formula (ii.d):

d2 Reacting a ketone of formula (ii.d) with a compound of formula (iii.d):

Wherein the method comprises the steps of

Met is Li or a group Mg-Hal, wherein Hal is Cl, br or I,

Alcohol (iv.d) is obtained:

Water is subsequently removed to obtain compounds of formula (v.d1) or (v.d2):

d3 Cyclizing the compound of formula (V.d1) or (V.d2) to give compound (I.d1).

21. A process for the preparation of a compound of formula (I) designated (i.e1):

Wherein the method comprises the steps of

R ^A is hydrogen or methyl, and the hydrogen is methyl,

R ^B is hydrogen or methyl, and the hydrogen is methyl,

R ^C is hydrogen, and the hydrogen atom,

R ^D is hydrogen, and the hydrogen atom,

W is a chemical bond or CH ₂,

R ^I、R^II、R^III and R ^IV are independently selected from hydrogen, C ₁-C₄ alkyl and C ₁-C₄ alkoxy,

Y ¹ is H, C ₁-C₆ alkyl, phenyl or CF ₃, wherein phenyl is unsubstituted or substituted by 1,2 or 3 substituents selected from C ₁-C₆ alkyl,

Y ² is H or Cl,

R is 0 or 1, and the number of the groups is 1,

Z is O, S or NAr, and the total number of the components is,

The method comprises the following steps:

e1 Providing a compound of formula (ii.e):

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Wherein the method comprises the steps of

Met is Li or a group Mg-Br,

Z is O, S or NBoc, e 3) reacting a compound of formula (III.e) with a compound of formula (IV.e):

wherein in the case where Z is O or S, a compound (V.e1) is obtained:

and in the case where Z is NBoc, the compound (V.e2) is obtained:

wherein Z is O or S,

Ar-Z^b(IX)

Wherein the method comprises the steps of

To give a compound of formula (I.e1) wherein Z is NAr.

22. A process for the preparation of a compound of formula (I) designated (i.f1) or (i.f2):

Wherein the method comprises the steps of

R ^A is hydrogen or C ₁-C₆ alkyl,

R ^B is hydrogen or C ₁-C₆ alkyl,

R ^C is hydrogen or C ₁-C₆ alkyl,

R ^D is hydrogen or C ₁-C₆ alkyl,

W is a chemical bond or CH ₂,

Q is 0 or 1 and the number of the groups,

R is 0 or 1, and the number of the groups is 1,

Z is O, S, NAr or a chemical bond,

The method comprises the steps of

F11 Providing a compound of formula (i.f11):

Wherein the method comprises the steps of

X is selected from Cl, br, I and CF ₃SO₃,

ArNH₂ Ar₂NH

(X.f1) (X.f2)

to give compounds of the formula (I.f1) or (I.f2),

Or (b)

F21 Providing a secondary amine compound of formula (i.f1) or a primary amine compound of formula (i.f21):

f22 In the presence of a palladium complex catalyst and a base, subjecting a compound of formula (i.f1) to an arylation reaction with an aromatic compound of formula (X.f):

Ar-Z^b (X.f)

Wherein the method comprises the steps of

Or (b)

Ar-Z^b (X.f)

To give compounds of the formula (I.f2) in which 2 Ar groups in the NAr ₂ groups have identical or different meanings.

23. The process according to claim 22, wherein the compound of formula (i.f11) provided in step f 11) is selected from:

A compound of formula (I.a1) obtainable by a process as claimed in any of claims 15 to 17,

A compound of formula (I.b1), obtainable by a process as claimed in claim 18,

A compound of formula (I.c1), obtainable by a process as claimed in claim 19,

A compound of formula (I.d1), obtainable by a process as claimed in claim 20, or

-A compound of formula (i.e1), obtainable by the process according to claim 21.

24. A process for preparing a compound of formula (I) designated (I.g):

/>

Wherein the method comprises the steps of

R ^A is hydrogen or C ₁-C₆ alkyl,

R ^B is hydrogen or C ₁-C₆ alkyl,

R ^C is hydrogen or C ₁-C₆ alkyl,

R ^D is hydrogen or C ₁-C₆ alkyl,

W is a chemical bond or CH ₂,

Q is 0 or 1 and the number of the groups,

R is 0 or 1, and the number of the groups is 1,

Z is O, S, NAr or a chemical bond,

The method comprises the following steps:

g1 Providing a compound of formula (i.g1):

X^Ar-Z^c (X.g)

Wherein the method comprises the steps of

Z ^c is selected from Cl, br, I or CF ₃SO₃,

To give a compound of formula (I.g).

25. A process for the preparation of a compound of formula (I) designated (i.g11):

Wherein the method comprises the steps of

E ¹ is N or CR ^g1,

E ² is N or CR ^g2,

E ³ is N or CR ^g3,

E ⁴ is N or CR ^g4,

E ⁵ is N or CR ^g5,

Provided that 1,2 or 3 of the ring members E ¹ to E ⁵ are N, R ^g1 to R ^g5 are independently selected from hydrogen, C ₁-C₄ alkyl and unsubstituted or substituted aryl, wherein 2 or more groups selected from CR ^g1、CR^g2、CR^g3、CR^g4 and CR ^g5 may form, together with the N-heterocycle to which they are bonded, a fused ring system comprising 2,3 or more than 3 unsubstituted or substituted rings,

R ^A is hydrogen or C ₁-C₆ alkyl,

R ^B is hydrogen or C ₁-C₆ alkyl,

R ^C is hydrogen or C ₁-C₆ alkyl,

R ^D is hydrogen or C ₁-C₆ alkyl,

W is a chemical bond or CH ₂,

Q is 0 or 1 and the number of the groups,

R is 0 or 1, and the number of the groups is 1,

Z is O, S, NAr or a chemical bond,

The method comprises the following steps:

g1 Providing a compound of formula (i.g1):

Wherein the method comprises the steps of

Z ^c is selected from Cl, br, I or CF ₃SO₃,

To give a compound of formula (I.g).