Spiro compounds and their use

Details Spiro compounds and their use Spiro compounds and their use

2002-07-26

2004-11-23

Raymond, Richard L. (Department: 1624)

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

Organic compounds

Four or more ring nitrogens in the bicyclo ring system

C546S015000, C548S136000, C548S143000, C548S147000, C548S216000, C548S262200, C548S407000, C548S411000, C564S426000, C585S027000, C514S409000, C514S410000, C514S411000, C514S183000

Reexamination Certificate

active

06822094

ABSTRACT:

Owing to the increasing global demand for electric energy and the limited reserves of coal, oil and gas, which in addition liberate the greenhouse gas CO
2
when they are burnt, the generation of electric power from sunlight has attracted increased interest in recent years.
EP-A 0 333 641 describes a photoelectrochemical cell which comprises a nanoporous metal oxide semiconductor, i.e. a semiconductor which has an extremely roughened surface and thus an increased surface area. The charge transport between semiconductor/chromophore layer and counterelectrode in this cell occurs via an electrolyte solution. Although good results are achieved using such cells, the property profile of such a device is still capable of significant improvement.
EP-A 0 718 858 discloses such a cell having a liquid crystal charge transport material in place of an electrolyte. However, the apparent quantum yields achieved are still in need of improvement.
It has now surprisingly been found that certain derivatives of spirobifluorene are very suitable as charge transport material for photovoltaic cells.
Some structurally different spirobifluorene derivatives are described, for example, in U.S. Pat. No. 5,026,894, J. M. Tour et al. J. Am. Chem. Soc. 112 (1990) 5662 and J. M. Tour et al. Polym. Prepr. (1990) 408 as coupling elements for polymeric, organic semiconductors and are proposed as materials for molecular electronics.
EP-A 0 676 461 describes the use of spiro compounds of the following formula,
where
K
1
and K
2
are, independently of one another, conjugated systems, in electroluminescence devices.
Use in photovoltaic cells cannot be deduced therefrom.
The invention accordingly provides spiro compounds of the formula (I)
where the symbols have the following meanings:
K
1
, L, M, N
1
, R
1
, R
2
, R
3
, R
4
are identical or different and are each
a) hydrogen, —NO
2
, —CN, —F or —Cl,
b) a straight-chain or branched alkyl radical having from 1 to 20 carbon atoms, where
b1) one or more nonadjacent CH
2
groups can be replaced by —O—, —S—, —CO—O—,—O—CO—, —O—CO—O—, NR
5
or —Si(CH
3
)
2
— and/or
b2) one or more CH
2
groups can be replaced by —CH═CH—, —C≡C—, 1,4-phenylene, 1,4-cyclohexylene or 1,3-cyclopentylene and/or
b3) one or more H atoms can be replaced by F and/or Cl, and/or
c) one of the following groups:
d) one of the following groups:
with the proviso that at least one, preferably at least two, of the radicals K
1
, L, M, N
1
, R
1
, R
2
, R
3
, R
4
R is one of the groups listed under c);
X, Y
1
are in each case identical or different and are ═CR
7
— or ═N—;
Z is —O—, —S—, —NR
5
—, —CRR—, —CR═CR— or —CR═N—;
R
5
, R
6
are in each case identical or different and are each
a) hydrogen,
b) a straight-chain or branched alkyl radical having from 1 to 20 carbon atoms, where
b1) one or more nonadjacent CH
2
groups which are not bound to nitrogen can be replaced by —O—, —S—, —CO—O—, —O—CO—, —O—CO—O— or —Si(CH
3
)
2
— and/or
b2) one or more CH
2
groups can be replaced by —CH═CH—, —C≡C—, cyclopropane-1,2-diyl, 1,4-phenylene, 1,4-cyclohexylene or 1,3-cyclopentylene and/or
b3) one or more H atoms can be replaced by F and/or Cl and/or
b4) R
5
and R
6
together can also form a ring;
c) phenyl, biphenyl, 1-naphthyl, 2-naphthyl, 2-thienyl, 2-furanyl;
R
7 , R
8
, R
9
, R
10
, R
11
, R
12
are identical or different and are each
a) hydrogen, —CN, —F, NO
2
or —Cl,
b) a straight-chain or branched alkyl radical having from 1 to 20 carbon atoms, where
b1) one or more nonadjacent CH
2
groups can be replaced by —O—, —S—, —CO—O—, —O—CO—, —O—CO—O—, NR
5
or —Si(CH
3
)
2
— and/or
b2) one or more CH
2
groups can be replaced by —CH═CH—, —C≡C—, cyclopropane-1,2-diyl, 1,4-phenylene, 1,4-cyclohexylene or 1,3-cyclopentylene and/or
b3) one or more H atoms can be replaced by F and/or Cl;
c) phenyl, biphenyl, 1-naphthyl, 2-naphthyl, 2-thienyl, 2-furanyl, —O-phenyl, —O-biphenyl, —O-1-naphthyl, —O-2-naphthyl, —O-2-thienyl, —O-2-furanyl,
m, n, p, q, r are in each case identical or different and are 0, 1, 2, 3, 4, 5 or 6 preferably
0
,
1
,
2
,
3
,
4
, particularly preferably 0, 1, 2, or 3.
The compounds of the formula (II) are preferably amorphous and have high glass transition temperatures.
Preference is given to spirobifluorene derivatives of the formulae (II) a-c
where the symbols have the following meanings:
II.a) K
1
═L═M═N
1
and is selected from the group consisting of:
R are identical or different and are H, alkyl, —O-alkyl, —S-alkyl, each having from 1 to 20 carbon atoms, preferably from 1 to 4 carbon atoms, phenyl, biphenyl, 1-naphthyl, 2-naphthyl, 2-thienyl, 2-furanyl, —O-phenyl, —O-biphenyl, —O-1-naphthyl, —O-2-naphthyl, —O-2-thienyl, —O-2-furanyl, CN, NR
2
, where —O-alkyl/aryl, —S-alkyl/aryl, CN, NO
2
must not be bound to nitrogen;
n=0, 1, 2, 3, 4,
and Q, P
1
are identical or different and are selected from the group consisting of:
where the symbols and indices are as defined above,
II.b) K
1
═N
1
and is selected from the group consisting of:
and L═M and is selected from the group consisting of:
and Q, P
1
are identical or different and are selected from the group consisting of:
where the symbols and indices are as defined above;
IIc) K
1
═M and is selected from the group consisting of:
and M═N
1
and is selected from the group consisting of:
and Q, P
1
are identical or different and are selected from the group consisting of:
where the symbols and indices are as defined above.
Particular preference is given to the following compounds of the formula (II):
IIaa) K
1
═L═M═N
1
and is selected from the group consisting of:
where R
13
is —O—CH
3
, —O—C
2
H
5
, —S—CH
3
, —S—C
2
H
5
, preferably —O—CH
3
, —S—CH
3
, particularly preferably —O—CH
3
;
and Q═P
1
and is selected from the group consisting of:
where R
14
is a straight-chain or branched alkyl group having from 1 to 12, preferably from 1 to 4, carbon atoms;
II.ba) K
1
═M═N
1
═Q═P
1
and is selected from the group consisting of:
where R
13
is as defined above;
II.ca) K
1
═L═M═N
1
and is selected from the group consisting of:
and Q═H and P
1
is selected from the group consisting of:
where R
13
, R
14
are as defined above.
The preparation of the spiro compounds of the invention is carried out by methods known per se from the literature, as are described in standard works on organic synthesis, e.g. Houben-Weyl, Methoden der Organischen Chemie, Georg-Thieme-Verlag, Stuttgart and in the appropriate volumes of the series “The Chemistry of Heterocyclic Compounds” by A. Weissberger and E. C. Taylor (editors).
The preparation is carried out under reaction conditions which are known and suitable for the reactions mentioned. Use can also be made of variants which are known per se and are not mentioned in more detail here.
Compounds of the formula (I) are obtained, for example, starting from 9,9′-spirobifluorene, whose synthesis is described, for example, by R. G. Clarkson, M. Gomberg, J. Am. Chem. Soc. 1030, 52, 2881.
The preparation of compounds of the formula (IIa) can be carried out, for example, starting with a tetrahalogenation in the 2,2′,7,7′ positions of 9,9′-spirobifluorene and a subsequent substitution reaction (see, for example, U.S. Pat. No. 5,026,894) or via a tetraacetylation of the 2,2′,7,7′ positions of 9,9′-spirobifluorene with subsequent C—C coupling after conversion of the acetyl groups into aldehyde groups or heterocycle formation after conversion of the acetyl groups into carboxylic acid groups.
The preparation of compounds of the formula (IIb) can be carried out, for example, by methods analogous to those for the formula (IIa) with the stoichiometric ratios in the reaction being selected so that the 2,2′ or 7,7′ positions are functionalized (see, for example, J. H. Weisburger, E. K. Weisburger, F. E. Ray, J. Am. Chem. Soc. 1959, 72 4253; F. K. Sutcliffe, H. M. Shahidi, D. Paterson, J. Soc. Dyers Colour 1978, 94

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