Materials for organic electroluminescent devices

Patent metadata

Field	Value
Publication number	US-10454041-B2
Application number	US-201716079151-A
Country	US
Kind code	B2
Filing date	Jan 24, 2017
Priority date	Feb 23, 2016
Publication date	Oct 22, 2019
Grant date	Oct 22, 2019

Abstract

The present invention relates to a process to produce compounds of the formula (1) which are suitable for use in electronic devices, as well as to intermediate compounds of formula (Int-1) and compounds of formula (1-1) and (1-2) obtained via the process. These compounds are particularly suitable for use organic electroluminescent devices. The present invention also relate to electronic devices, which comprise these compounds.

First claim

The invention claimed is:

1. A process for the preparation of a compound according to formula (1),

where the process comprises the following steps:
(a) preparation of a compound of formula (Int-1) by a route (a-1) or by a route (a-2) as follows:
Route (a-1):
(a-1-1) Preparation of a compound of formula (p-3) by first a metalation reaction of a compound of formula (p-1), followed by a cyclization reaction between a fluorenone derivative of formula (p-2) with a compound of formula (p-1i):

(a-1-2) Preparation of a compound of formula (Int-1) by a chemical reaction between a compound of formula (p-3) and a compound of formula (p-4):

Route (a-2):
(a-2-1) preparation of a compound of formula (p-5) by a chemical reaction between a fluorenone derivative of formula (p-2) with a compound of formula (p-4):

(a-2-2) preparation of a compound of formula (Int-1) by first a metalation reaction of a compound of formula (p-1), followed by a cyclization reaction between a fluorenone derivative of formula (p-5) with a compound of formula (p-1i):

(b) preparation of a compound of formula (1) by a chemical reaction, selected from amination reactions, between a compound of formula (Int-1) with a compound of formula (p-6):

where the following applies to the symbols used:
V is CR or N, with the proviso that there are maximum three N per 6-membered-ring, or two adjacent groups V (V—V or V═V) stand for a group of the formula (V-1) or (V-2),

in which the dashed bonds indicate the linking to the spirobifluorene skeleton;
E is a divalent bridge selected from N(R 0 ), B(R 0 ), O, C(R 0 ) 2 ), Si(R 0 ) 2 , C═NR 0 ), C═C(R 0 ) 2 , S, S═O, SO 2 ), P(R 0 ) and P(═O)R 0 ;
Ar L is an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may in each case be substituted by one or more radicals R 1 ;
Ar 1 , Ar 2 are, identically or differently, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case also be substituted by one or more radicals R 2 ; Ar 1 and Ar 2 here may also be connected via a single bond or a divalent bridge selected from —N(R 2 )—, —O—, —S—, —C(R 2 ) 2 —, —C(R 2 ) 2 —C(R 2 ) 2 —, —Si(R 2 ) 2 — and —B(R 2 )—;
R 0 , R, R 2 are selected on each occurrence, identically or differently, from the group consisting of H, D, F, CHO, CN, C(═O)Ar 3 , P(═O)(Ar 3 ) 2 , S(═O)Ar 3 , S(═O) 2 Ar 3 , N(Ar 3 ) 2 , Si(R 3 ) 3 , B(OR 3 ) 2 , OSO 2 R 3 , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R 3 , where in each case one or more non-adjacent CH 2 groups may be replaced by R 3 C═CR 3 , C≡C, Si(R 3 ) 2 , Ge(R 3 ) 2 , Sn(R 3 ) 2 , C═O, C═S, C═Se, P(═O)(R 3 ), SO, SO 2 , O, S or CONR 3 and where one or more H atoms may be replaced by D, F or CN, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R 3 , and an aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 3 , where two adjacent substituents R 0 , two adjacent substituents R or two adjacent substituents R 2 may optionally form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which may be substituted by one or more radicals R 3 ;
R 1 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, CHO, CN, C(═O)Ar 3 , P(═O)(Ar 3 ) 2 , S(═O)Ar 3 , S(═O) 2 Ar 3 , Si(R 3 ) 3 , B(OR 3 ) 2 , OSO 2 R 3 , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R 3 , where in each case one or more non-adjacent CH 2 groups may be replaced by R 3 C═CR 3 , C≡C, Si(R 3 ) 2 , Ge(R 3 ) 2 , Sn(R 3 ) 2 , C═O, C═S, C═Se, P(═O)(R 3 ), SO, SO 2 , O, S or CONR 3 and where one or more H atoms may be replaced by D, F or CN, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R 3 , and an aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 3 , where two adjacent substituents R 1 may optionally form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which may be substituted by one or more radicals R 3 ;
R 3 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, CHO, CN, C(═O)Ar 3 , P(═O)(Ar 3 ) 2 , S(═O)Ar 3 , S(═O) 2 Ar 3 , Si(R 4 ) 3 , B(OR 4 ) 2 , OSO 2 R 4 , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms, each of which may be substituted by one or more radicals R 4 , where in each case one or more non-adjacent CH 2 groups may be replaced by R 4 C═CR 4 , C≡C, Si(R 4 ) 2 , Ge(R 4 ) 2 , Sn(R 4 ) 2 , C═O, C═S, C═Se, P(═O)(R 4 ), SO, SO2, O, S or CONR4 and where one or more H atoms may be replaced by D, F, or CN, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R4, and an aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R4, where two adjacent substituents R3 may optionally form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which may be substituted by one or more radicals R 4 ;
R 4 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, CN, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms, where in each case one or more non-adjacent CH 2 groups may be replaced by SO, SO 2 , O, S and where one or more H atoms may be replaced by D or F, and aromatic or heteroaromatic ring system having 5 to 24 C atoms;
Ar 3 is selected, identically or differently on each occurrence, from the group consisting of an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, more preferably having 5 to 18 aromatic ring atoms, which may in each case also be substituted by one or more radicals R 4 ;
n is 1, 2 or 3;
X 0 is selected from Cl, Br or I;
X 1 is Cl, Br, I, trifluoromethanesulfonate (CF 3 SO 3 —), tosylate (CH 3 C 6 H 4 SO 3 —), mesylate (CH 3 SO 3 —), or —B(OR B ) 2 ;
R B is H, a straight-chain alkyl having 1 to 10 C atoms, where two substituents R B may form a monocyclic aliphatic ring system that may be substituted by an alkyl group having 1 to 3 C atoms;
X 2 is Cl, Br, I, trifluoromethanesulfonate (CF 3 SO 3 —), tosylate (CH 3 C 6 H 4 SO 3 —) or mesylate (CH 3 SO 3 —);
X 3 is Cl, Br, I or

Assignees

• Merck Patent Gmbh

Inventors

• Mujica-Fernaud Teresa
• Montenegro Elvira

Classifications

• C07D411/12

  linked by a chain containing hetero atoms as chain links · CPC title

• C07D307/91

  Dibenzofurans; Hydrogenated dibenzofurans · CPC title

• C07C211/54

  having amino groups bound to two or three six-membered aromatic rings · CPC title

• C07D209/86

  with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system · CPC title

• Y02E10/549

  Organic PV cells · CPC title