Method for producing aryl oligoamines

Details Method for producing aryl oligoamines Method for producing aryl oligoamines

2000-05-10

2002-11-05

Barts, Samuel (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Amino nitrogen containing

C564S308000, C564S404000, C564S405000, C564S406000, C564S407000

Reexamination Certificate

active

06476265

ABSTRACT:

Aryl and heteroaryl derivatives containing a plurality of amine units (hereinafter referred to as aryl oligoamines) have been used in various applications for some time. Thus, they can be employed, for example, as hole conductors in xerography (see, for example, P. M. Borsenberger, D. S. Weiss, Organic Photoreceptors for Imaging Systems, Marcel Dekker, Inc.), in organic electroluminescence devices (see, for example, J. Kido, Bull, Electrochem. 1994, 10, 1-13; DE-A-197 11 714) and dye-sensitized photovoltaic cells (see, for example, DE-A 197 11 714).
Compounds of this type which have attracted particular interest are, inter alia, derivatives of spirobifluorene (see, for example, DE-A 197 11714).
Aryl oligoamines are generally synthesized using variants of the Ullmann reaction (J. March. Adv. Org. Chem. 4th Ed., p. 665, John Wiley & Sons, New York 1992). Thus, the preparation of, for example, 4,4′,4″-tris(N,N-diphenylamino)triphenylamine (Shirota et al., Chem. Lett. 1989, 1145-1148) and tris(4-phenoxazin-10-ylphenyl)amine (Higuchi et al., Mol. Cryst. Liq. Cryst. 1994, 242, 127-134) by this route has been described. This reaction has also been described for producing hole conductors based on spiro compounds such as N,N,N′,N′,N″,N″,N′″,N′″-octaphenylspiro-9,9′-bifluorene-2,2′,7,7′-tetramine (Salbeck et al., Book of Abstracts, 213
th
ACS National Meeting, San Francisco 1997, 199).
It is generally the case that the preparation of aryl oligoamines is associated with increased difficulties compared to that of aryl monoamines. Thus, for example, it is known that Ullmann reactions can be carried out at a yield of about 80% under optimum conditions. If this is then assumed for each step of a tri-coupling or tetra-coupling reaction, the calculated yield is then only 51 or 41%, which firstly has an adverse effect on the economy and secondly makes it more difficult to purify the products.
It has surprisingly been found that aryl oligoamines can be prepared simply and in good yields by direct coupling of a primary or secondary amine with an activated aromatic in the presence of a base, a palladium component and a phosphine ligand.
Although a similar process is known from U.S. Pat. No. 5,576,460, that document describes only the preparation of aryl monoamines. In addition, a yield of merely 75% is obtained in the sole example, from which a person skilled in the art would conclude that such a method is less suitable than the Ullmann reaction for building up aryl oligoamines.
The invention accordingly provides a process for preparing aryl oligoamines, which comprises reacting an amine with an activated aromatic and a base in a temperature range from 0 to 150° C. in the presence of a palladium component and a phosphine ligand.
For the purposes of the present invention, an aryl oligoamine is a compound which contains at least two amine units bound to aromatic groups.
Preferred starting compounds are activated aromatics of the formula (I),
(R)
n
—A—(X)
m
  (I)
where the symbols and indices have the following meanings:
A is an aromatic and/or heteroaromatic radical which has from 2 to 200 carbon atoms and can contain a plurality of aromatic and/or heteroaromatic groups, where such groups are then fused (for example anthracene, triphenylene) or unfused (for example biphenyl, terphenyl, 1,3,5-triphenylbenzene);
R are identical or different and are each NO
2
, CN, F, an unbranched or branched alkyl group having from 1 to 22 carbon atoms, where one or more CH
2
groups may be replaced by —O—, —S—, —CO—, —O—CO—, —CO—O—, —O—CO—O—, —CR
1
═CR
2
, —C≡C—, SiR
3
R
4
, C
4
-C
10
-aryldiyl, C
4
-C
10
-heteroaryldiyl, cyclohexylene, —NR
5
—, where heteroatoms must not be directly bonded to one another, and where one or more H atoms may be replaced by F, Cl, Br;
R
1
, R
2
are identical or different and are H, CN, C
1
-C
12
-alkyl , C
4
-C
10
-aryl;
R
3
, R
4
are identical or different and are C
1
-C
12
-alkyl, C
4
-C
10
-aryl;
R
5
is C
1
-C
12
-alkyl, C
4
-C
10
-aryl;
X is Cl, Br, I, mesylate, tosylate or C
1
-C
12
-perfluoroalkylsulfonate;
m is a natural number and 2≦m≦y;
n is a natural number and 0≦n≦y−m;
y is the number of free valences on the parent unit A.
The symbols and indices in the formula (I) preferably have the following meanings:
R are identical or different and are each NO
2
, CN, F, an unbranched or branched alkyl group having from 1 to 22 carbon atoms;
X is Cl, Br, I, tosylate;
m is such that 3≦m≦y.
The symbols and indices in the formula (I) particularly preferably have the following meanings:
A is benzene, naphthalene, anthracene, pyrene, triphenylene, biphenyl, fluorene, terphenyl, 1,3,5-triphenylbenzene, spiro-9,9′-bifluorene, 2,2′,7,7′-tetraphenylspiro-9,9′-bifluorene, 2,2′,7,7′-tetra(4′-biphenylyl)spiro-9,9′-biphenyl, 2,4,7,2′,4′,7′-hexaphenylspiro-9,9′-bifluorene or 2,4,7,2′,4′,7′-hexa(4′-biphenylyl)spiro-9,9′-bifluorene or another oligophenylene-substituted derivative of spiro-9,9′-bifluorene;
R are identical or different and are each NO
2
, CN, F, an unbranched or branched alkyl group having from 1 to 22 carbon atoms;
X is Br, I;
m is4, 5 or 6 and
n is 0, 1, 2, 3, 4, 5, 6.
Very particularly preferred activated aromatics of the formula (I) are those of the formula (la)
where
X are identical or different and are each Br, I or H and k,l,p,q,r,s are 0, 1, 2, 3, 4,
with the proviso that at least two, preferably at least four, of the radicals X are Br or I.
Preferred amine components are those of the formula (II),
H—NR
7
R
8
  (II)
where the symbols have the following meanings:
R
7
, R
8
are identical or different and are each
a) H;
b) a straight-chain, branched or cyclic alkyl group having from 1 to 22 carbon atoms, where one or more CH
2
groups may be replaced by —O—, —S—, —CO—, —OCO—, —CO—O—, —O—CO—O—, —CR
1
═CR
2
, —C≡C—, SiR
3
R
4
, C
4
-C
10
-aryldiyl, C
4
-C
10
-heteroaryldiyl, cyclohexylene, —NR
5
—, where heteroatoms must not be directly bonded to one another, and where one or more H atoms may be replaced by F, Cl, Br; where R
1
to R
5
are as defined in the formula (I);
c) a C
4
-C
12
-aryl or heteroaryl group which may be substituted by one or more radicals R, where R are identical or different and are as defined in the formula (I).
End products of the process of the invention and their preferences may be derived from the starting materials and their preferences.
The starting materials for the process are known in principle and are either commercially available or can be prepared by known methods with which those skilled in the art are familiar, for example as described in Houben-Weyl, Methoden der Organischen Chemie, Georg Thieme Verlag, Stuttgart.
The ratio of the starting materials is not critical and can therefore be varied within a wide range; preference is given to a ratio of activated group to amine of 1:0.8-2, particularly preferably 1:1-1.5.
According to the invention, the starting compounds, viz. amine and activated aromatic, are reacted in a coupling reaction to form an aryl oligoamine. To carry out the reaction, the amine, the activated aromatic, a base and catalytic amounts of a palladium catalyst containing phosphine ligands or a palladium salt and a phosphine are taken up in a solvent and reacted at a temperature of from 0° C. to 150° C., preferably from 30° C. to 140° C., particularly preferably from 50° C. to 120° C., very particularly preferably from 80° C. to 120° C., for a time of from 1 hour to 200 hours, preferably from 5 hours to 100 hours, particularly preferably from 10 hours to 80 hours. The work-up is carried out by methods which are known per se and with which those skilled in the art are familiar, for example by hydrolysis, stirring with a solvent, phase separation and removal of the solvent. Preferably, the palladium component is also removed by stirring with a complexing agent. Complexing agents wh

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