U.S. patent application number 09/530890 was filed with the patent office on 2002-05-30 for substituted poly(arylene vinylenes), method for producing the same, and their use in electroluminescent elements.
Invention is credited to Becker, Heinrich, Kreuder, Willi, Schenk, Hermann, Spreitzer, Hubert, Yu, Nu.
Application Number | 20020064680 09/530890 |
Document ID | / |
Family ID | 7847658 |
Filed Date | 2002-05-30 |
United States Patent
Application |
20020064680 |
Kind Code |
A1 |
Spreitzer, Hubert ; et
al. |
May 30, 2002 |
Substituted poly(arylene vinylenes), method for producing the same,
and their use in electroluminescent elements
Abstract
Poly(arylenevinylenes) comprising at least 20% of recurring
units of the formula (I), 1 where the symbols and indices have the
following meanings: Aryl: is an aryl group having 4 to 14 carbon
atoms; R': is a substituent which is either in the labeled
phenylene position 5 or 6 and is CN, F, Cl, N(R.sup.1R.sup.2) or a
straight-chain, branched or cyclic alkyl, alkoxy or thioalkoxy
group having 1 to 20 carbon atoms, in which, in addition, one or
more H atoms may be replaced by F; R": are identical or different
and are CN, F, Cl or a straight-chain, branched or cyclic alkyl or
alkoxy group having 1 to 20 carbon atoms, where one or more
non-adjacent CH.sub.2 groups may be replaced by --O--, --S--,
--CO--, --COO--, --O--CO--, --NR.sup.1--, --(NR.sup.2R.sup.3).sup.-
+--A.sup.- or --CONR.sup.4--, and where one or more H atoms may be
replaced by F, or an aryl group having 4 to 14 carbon atoms, which
may be substituted by one or more non-aromatic radicals R';
R.sup.1, R.sup.2, R.sup.3, R.sup.4 are identical or different and
are H or an aliphatic or aromatic hydrocarbon radical having 1 to
20 carbon atoms; A.sup.-: is a singly charged anion or an
equivalent thereof; and n: is 0, 1, 2, 3, 4 or 5, are suitable as
electroluminescent materials.
Inventors: |
Spreitzer, Hubert;
(Viernheim, DE) ; Kreuder, Willi; (Mainz, DE)
; Becker, Heinrich; (Glashutten, DE) ; Schenk,
Hermann; (Wiesbaden, DE) ; Yu, Nu; (Knoxville,
TN) |
Correspondence
Address: |
Connolly Bove Lodge And Hutz
1220 Market Street
Wilmington
DE
19899
US
|
Family ID: |
7847658 |
Appl. No.: |
09/530890 |
Filed: |
August 22, 2000 |
PCT Filed: |
October 22, 1998 |
PCT NO: |
PCT/EP98/06722 |
Current U.S.
Class: |
428/690 ;
428/691; 428/917; 528/86 |
Current CPC
Class: |
H05B 33/14 20130101;
H01L 51/0038 20130101; H01L 51/5012 20130101; Y10S 428/917
20130101; C08G 61/02 20130101; H01B 1/128 20130101; C09K 11/06
20130101 |
Class at
Publication: |
428/690 ;
428/691; 428/917; 528/86 |
International
Class: |
B32B 019/04 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 5, 1997 |
DE |
197 48 814.5 |
Claims
1. A poly(arylenevinylene) comprising at least 20% of recurring
units of the formula (I), 96where the symbols and indices have the
following meanings: Aryl: is an aryl group having 4 to 14 carbon
atoms; R': is a substituent which is either in the labeled
phenylene position 5 or 6 and is CN, F, Cl, N(R.sup.1R.sup.2) or a
straight-chain, branched or cyclic alkyl, alkoxy or thioalkoxy
group having 1 to 20 carbon atoms, in which, in addition, one or
more H atoms may be replaced by F; R": are identical or different
and are CN, F, Cl or a straight-chain, branched or cyclic alkyl or
alkoxy group having 1 to 20 carbon atoms, where one or more
non-adjacent CH.sub.2 groups may be replaced by --O--, --S--,
--CO--, --COO--, --O--CO--, --NR.sup.1--,
--(NR.sup.2R.sup.3).sup.30--A.sup.- or --CONR.sup.4--, and where
one or more H atoms may be replaced by F, or an aryl group having 4
to 14 carbon atoms, which may be substituted by one or more
non-aromatic radicals R'; R.sup.1, R.sup.2, R.sup.3, R.sup.4 are
identical or different and are H or an aliphatic or aromatic
hydrocarbon radical having 1 to 20 carbon atoms; A.sup.-: is a
singly charged anion or an equivalent thereof; and n: is 0, 1, 2,
3, 4 or 5.
2. A poly(arylenevinylene) as claimed in claim 1, which has from 10
to 10,000 recurring units.
3. A poly(arylenevinylene) as claimed in claim 1 and/or 2,
essentially consisting of recurring units of the formula (I).
4. A poly(arylenevinylene) as claimed in claim 1 and/or 2, which is
a copolymer.
5. A poly(arylenevinylene) as claimed in claim 4, which comprises
at least two different recurring units of the formula (I).
6. A poly(arylenevinylene) as claimed in claim 5, which, besides
one or more recurring units of the formula (I), comprises one or
more further poly(arylenevinylene) recurring units.
7. A poly(arylenevinylene) as claimed in claim 6, which comprises
one or more 2,5-dialkoxy-1,4-phenylenevinylene recurring units.
8. A poly(arylenevinylene) as claimed in one or more of the
preceding claims, where the symbols and indices in the formula (I)
have the following meanings: Aryl is phenyl, 1- or 2-naphthyl, 1-,
2- or 9-anthracenyl, 2-, 3- or 4-pyridinyl, 2-, 4- or
5-pyrimidinyl, 2-pyrazinyl, 3- or 4-pyridazinyl, 2-, 3-, 4-, 5-,
6-, 7- or 8-quinolinyl, 2- or 3-thiophenyl, 2- or 3-pyrrolyl, 2- or
3-furanyl or 2-(1,3,4-oxadiazol)yl; R' are identical or different
and are CN, F, Cl, CF.sub.3 or a straight-chain or branched alkoxy
group having 1 to 12 carbon atoms; R" are identical or different
and are a straight-chain or branched alkyl or alkoxy group having 1
to 12 carbon atoms; and n is 0, 1, 2 or 3, particularly preferably
0, 1 or 2.
9. A poly(arylenevinylene) as claimed in claim 8, wherein aryl in
the formula (1) is phenyl, 1-naphthyl, 2-naphthyl or
9-anthracenyl.
10. A poly(arylenevinylene) as claimed in claim 9, wherein, in the
recurring unit of the formula (I), the aryl substituent has the
following substitution pattern: 2-, 3- or 4-alkyl(oxy)phenyl, 2,3-,
2,4-, 2,5-, 2,6-, 3,4- or 3,5-dialkyl(oxy)phenyl, 2,3,4,- 2,3,5-,
2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trialkyl(oxy)phenyl, 2-, 3-, 4-,
5-, 6-, 7- or 8-alkyl(oxy)-1-naphthyl, 1-, 3-, 4-, 5-, 6-, 7- or
8-alkyl(oxy)-2-naphthyl or 10-alkyl(oxy)-9-anthracenyl.
11. A process for the preparation of a poly(arylenevinylene) as
claimed in one or more of claims 1 to 10, which comprises
polymerizing one or more monomers comprising one or more
polymerizable biaryls of the formula (II), 97in which Hal and Hal'
are identical or different and are Cl, Br or I, and the other
symbols and indices are as defined in the formula (I), via
base-induced dehydrohalogenation.
12. The use of a poly(arylenevinylene) as claimed in one or more of
claims 1 to 10 as electroluminescent material.
13. An electroluminescent material comprising one or more
poly(arylenevinylene) as claimed in one or more of claims 1 to
10.
14. A process for the production of an electroluminescent material
as claimed in claim 13, which comprises applying one or more
poly(arylenevinylene) comprising recurring units of the formula (I)
as a film to a substrate, which, if desired, contains further
layers.
15. An electroluminescent device containing one or more active
layers, where at least one of these active layers comprises one or
more poly(arylenevinylenes) as claimed in one or more of claims 1
to 10.
16. A poly(arylenevinylene) as claimed in one of claims 1 to 10,
wherein the proportion of TBB defect structures is less than
10%.
17. A polymerizable biaryl derivative of the formula (II) 98in
which Hal and Hal.sup.1 are identical or different and are Cl, Br
or I, and the other symbols and indices are as defined in the
formula (I), with the exception of
2,5-bis(chloromethyl)-4-methoxy-4'-(3,7-dimethyloctyloxy)bip- henyl
and
2,5-bis(chloromethyl)-4-methoxy-3'-(3,7-dimethyloctyloxy)bipheny-
l.
18. A polymerizable biaryl derivative as claimed in claim 17,
wherein the substituent R.sup.1 is a straight-chain or branched
alkoxy group having 1 to 10 carbon atoms, particularly preferably
methoxy.
19. A process for the preparation of a polymerizable biaryl
derivative as claimed in claim 17 or 18, wherein at least one C-C
coupling reaction is carried out in the presence of a catalyst
containing palladium.
20. The use of a poly(arylenevinylene) as claimed in one or more of
claims 1 to 10 as an organic semiconductor, wherein the
poly(arylenevinylene) is processed as a solution in an organic
solvent.
Description
[0001] There is a considerable demand in industry for large-area
solid-state light sources for a number of applications,
predominantly in the area of display elements, display screen
technology and illumination technology. The requirements made of
these light sources can currently not be met entirely
satisfactorily by any of the existing technologies.
[0002] As an alternative to conventional display and illumination
elements, such as incandescent lamps, gas-discharge lamps and
non-self-illuminating liquid-crystal display elements,
electroluminescent (EL) materials and devices, such as
light-emitting diodes (LEDs), have already been in use for some
time.
[0003] Besides inorganic electroluminescent materials and devices,
low-molecular-weight, organic electroluminescent materials and
devices have also been known for about 30 years (see, for example,
U.S. Pat. No. 3,172,862). Until recently, however, the practical
utility of such devices was greatly restricted.
[0004] EP 423 283 and EP 443 861 describe electroluminescent
devices which contain a film of a conjugated polymer as
light-emitting layer (semiconductor layer). Such devices have
numerous advantages, such as the possibility of producing
large-area, flexible displays simply and inexpensively. In contrast
to liquid-crystal displays, electroluminescent displays are
self-illuminating and therefore do not require an additional
back-lighting source.
[0005] A typical device in accordance with EP 423 283 consists of a
light-emitting layer in the form of a thin, dense polymer film
(semiconductor layer) which contains at least one conjugated
polymer. A first contact layer is in contact with a first surface,
and a second contact layer is in contact with a further surface of
the semiconductor layer. The polymer film of the semiconductor
layer has a sufficiently low concentration of extrinsic charge
carriers so that, on application of an electric field between the
two contact layers, charge carriers are introduced into the
semiconductor layer, where one contact layer becomes positive
compared with the other, and the semiconductor layer emits
radiation. The polymers used in devices of this type are referred
to as conjugated. The term "conjugated polymer" is taken to mean a
polymer which has a delocalized electron system along the main
chain. The delocalized electron system gives the polymer
semiconductor properties and enables it to transport positive
and/or negative charge carriers with high mobility.
[0006] EP 423 283 and EP 443 861 describe, as polymeric material
for the light-emitting layer, poly(p-phenylenevinylene), which may
be modified on the aromatic ring by alkyl, alkoxy, halogen or nitro
substituents in order to improve the properties. Polymers of this
type have since then been investigated in a large number of
studies, and bisalkoxy-substituted PPVs in particular have already
been optimized a very long way toward applicational maturity (of.,
for example, J. Salbeck, Ber. Bunsenges. Phys. Chem. 1996, 100,
1667).
[0007] The German patent application 196 52 261.7 with the title
"Aryl-substituted poly(p-arylenevinylenes), process for their
preparation, and their use in electroluminescent components", which
was not published before the priority date of the present
application, proposes aryl-substituted poly(p-arylenevinylenes)
which are also suitable for generating green
electroluminescence.
[0008] However, the development of polymers of this type can in no
way be regarded as complete, and there continues to be plenty of
room for improvement. Thus, inter alia, improvements are still
possible with respect to the service life and stability, in
particular at elevated temperatures.
[0009] The object of the present invention was therefore to provide
electroluminescent materials which, when used in illumination or
display devices, are suitable for improving the property profile of
these devices.
[0010] Surprisingly, it has now been found that
poly(arylphenylenevinylene- s) whose phenylene unit carries a
further substituent in the para- or meta-position to the aryl
radical are particularly suitable as electroluminescent
materials.
[0011] The invention therefore relates to poly(arylenevinylenes)
comprising at least 20% of recurring units of the formula (I),
2
[0012] where the symbols and indices have the following
meanings:
[0013] Aryl: is an aryl group having 4 to 14 carbon atoms;
[0014] R': is a substituent which is either in the labeled
phenylene position 5 or 6 and is CN, F, Cl, N(R.sup.1R.sup.2) or a
straight-chain, branched or cyclic alkyl, alkoxy or thioalkoxy
group having 1 to 20 carbon atoms, in which, in addition, one or
more H atoms may be replaced by F;
[0015] R": are identical or different and are CN, F, Cl or a
straight-chain, branched or cyclic alkyl or alkoxy group having 1
to 20 carbon atoms, where one or more non-adjacent CH.sub.2 groups
may be replaced by --O--, --S--, --CO--, --COO--, --O--CO--,
--NR.sup.1--, --(NR.sup.2R.sup.3).sup.+--A.sup.- or --CONR.sup.4--,
and where one or more H atoms may be replaced by F, or an aryl
group having 4 to 14 carbon atoms, which may be substituted by one
or more non-aromatic radicals R';
[0016] R.sup.1, R.sup.2, R.sup.3, R.sup.4 are identical or
different and are H or an aliphatic or aromatic hydrocarbon radical
having 1 to 20 carbon atoms;
[0017] A.sup.-: is a singly charged anion or an equivalent thereof;
and
[0018] n: is 0, 1, 2, 3, 4 or 5.
[0019] The polymers according to the invention are highly suitable
for use as electroluminescent materials. They have, for example,
the advantage of having constant brightness in long-term operation,
even at elevated temperatures (for example heating for a number of
hours at 85.degree. C).
[0020] It is thus not necessary to adjust the voltage during
long-term operation in order to obtain an initial brightness. This
advantage is particularly evident in the case of battery operation,
since the maximum voltage economically possible is greatly
restricted here.
[0021] Devices containing the polymers according to the invention
also have a long service life.
[0022] Surprisingly, the polymers according to the invention have a
particularly low content of defect structures.
[0023] The polymers generally contain from 10 to 10,000, preferably
from 10 to 5000, particularly preferably from 100 to 500, very
particularly preferably from 250 to 2000, recurring units.
[0024] Polymers according to the invention comprise at least 20%,
preferably at least 30%, particularly preferably at least 40%, of
recurring units of the formula (I).
[0025] Furthermore, preference is also given to copolymers
consisting of recurring units of the formula (I) and recurring
units containing a 2,5-dialkoxy-1,4-phenylenevinylene structure.
Preference is likewise given to copolymers consisting of recurring
units of the formula (I) and recurring units containing a
2-aryl-1,4-arylenevinylene structure which is not further
substituted.
[0026] Preference is furthermore given to copolymers comprising 1,
2 or 3 different recurring units of the formula (I).
[0027] For the purposes of the present invention, the term
"copolymers" covers random, alternating, regular and block-like
structures.
[0028] Preference is also given to polymers comprising recurring
units of the formula (I) in which the symbols and indices have the
following meanings:
[0029] Aryl is phenyl, 1- or 2-naphthyl, 1-, 2- or 9-anthracenyl,
2-, 3- or 4-pyridinyl, 2-, 4- or 5-pyrimidinyl, 2-pyrazinyl, 3- or
4-pyridazinyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-quinolinyl, 2- or
3-thiophenyl, 2- or 3-pyrrolyl, 2- or 3-furanyl or
2-(1,3,4-oxadiazol)yl;
[0030] R' are identical or different and are CN, F, Cl, CF.sub.3 or
a straight-chain or branched alkoxy group having 1 to 12 carbon
atoms;
[0031] R" are identical or different and are a straight-chain or
branched alkyl or alkoxy group having 1 to 12 carbon atoms; and
[0032] n is 0, 1, 2 or 3, particularly preferably 0, 1 or 2.
[0033] Particular preference is given to polymers in which the aryl
substituent in the formula (I) has the following meaning: phenyl,
1-naphthyl, 2-naphthyl or 9-anthracenyl.
[0034] Particular preference is furthermore given to polymers in
which the aryl substituent in the formula (I) has the following
substitution pattern: 2-, 3- or 4-alkyl(oxy)phenyl, 2,3-, 2,4-,
2,5-, 2,6-, 3,4- or 3,5-dialkyl(oxy)phenyl, 2,3,4-, 2,3,5-, 2,3,6-,
2,4,5-, 2,4,6- or 3,4,5-trialkyl(oxy)phenyl, 2-, 3-, 4-, 5-, 6-, 7-
or 8-alkyl(oxy)-1-naphthyl, 1-, 3-, 4-, 5-, 6-, 7- or
8-alkyl(oxy)-2-naphthyl or 10-alkyl(oxy)-9-anthracenyl.
[0035] The polymers according to the invention can be obtained, for
example, by dehydrohalogenation polymerization from starting
materials of the formula (II) in which the symbols and indices are
as defined under the formula (I), and Hal and Hal' are Cl, Br or I;
this is generally carried out by reacting one or more monomers with
a suitable base in a suitable solvent. 3
[0036] These monomers--with the exception of
2,5-bis(chloromethyl)-4-metho- xy-4'-(3,7-dimethyloctyloxy)biphenyl
and 2,5-bis(chloromethyl)-4-methoxy-3-
'-(3,7-dimethyloctyloxy)biphenyl, both of which were disclosed in
WO 98/25874--are novel and are therefore likewise a subject-matter
of this invention.
[0037] To this end, the monomers are dissolved in suitable solvents
in suitable concentrations, brought to the suitable reaction
temperature and mixed with the suitable amount of a suitable base.
After a suitable reaction time has passed, the reaction solution
can be terminated, for example by addition of acid. The polymer is
subsequently purified by suitable methods familiar to the person
skilled in the art, such as, for example, reprecipitation or
extraction.
[0038] Examples of suitable solvents are ethers (for example
diethyl ether, THF, dioxane, dioxolane and tert-butyl methyl
ether), aromatic hydrocarbons (for example toluene, xylenes,
anisole and methylnaphthalene), alcohols (for example ethanol and
tert-butanol), chlorinated compounds (for example chlorobenzene and
dichlorobenzene) and mixtures of these solvents.
[0039] A suitable concentration range is the range from 0.005 to 5
mol/l (monomer/solution volume). Preference is given here to the
range from 0.01 to 2 mol/l, very particularly preferably to the
range from 0.01 to 0.5 mol/l.
[0040] The reaction temperature is generally from -80 to
200.degree. C., preferably from 20 to 140.degree. C.
[0041] Examples of suitable bases are alkali metal hydroxides (NaOH
and KOH), hydrides (NaH and KH) and alkoxides (NaOEt, KOEt, NaOMe,
KOMe and KO Bu), organometallic compounds (nBuLi, sBuLi, tBuLi and
PhLi) and organic amines (LDA, DBU, DMAP and pyridine). A suitable
amount is in the range from 2 to 10 equivalents (based on one
equivalent of monomer), preferably from 3.5 to 8 equivalents,
particularly preferably from 4 to 6 equivalents.
[0042] The reaction time is generally from 5 minutes to 24 hours,
preferably from 0.5 to 6 hours, very particularly preferably from 1
to 4 hours.
[0043] This process is likewise a subject-matter of the
invention.
[0044] The biaryl derivatives indicated in the formula (II) can be
obtained by the route outlined in Scheme 1: 4
[0045] The starting compounds of the formulae (III) and (IV) are
very readily accessible since they can be prepared in a simple
manner and in large amounts from commercially available compounds.
5
[0046] The reactions in Scheme 2 can be explained as follows: the
1,4-dimethyl compound (VI) is generally commercially available (for
example 2,5-dimethylphenol, 2,5-dimethylaniline,
2,5-dimethylbenzonitrile or 2,5-dimethylanisole) or can be prepared
simply from commercially available compounds (for example
alkylation of a corresponding phenol or amine). The compound (VI)
can be halogenated, for example chlorinated or brominated, on the
aromatic ring by standard methods (see, for example, Organikum
[Synthetic Organic Chemistry], VEB Deutscher Verlag der
Wissenschaften, 15.sup.th Edition, pp. 391 ff., Leipzig 1984). The
resultant compounds (VII) are accessible in good yields and in
industrial quantities. Analogously, the compounds of the type (VI')
are also either commercially available or can be prepared easily
(for example 2,5-dibromo-p-xylene). These compounds can then
likewise be converted into compounds of the type (VII) by standard
reactions (for example nucleophilic substitution of a halogen by an
alkoxy radical).
[0047] (VII) can be converted, preferably catalytically (cobalt
catalyst, atmospheric oxygen, see, for example, EP-A 0 121 684)
into the corresponding 1,4-dicarboxylic acids (IIIa). Given a
suitable choice of the reaction conditions, this is possible
irrespective of the substituent. The resultant acids, (IIIa) with
R=H, can, if desired, be converted into the corresponding esters
(R.noteq.H) by standard methods.
[0048] The compounds of the formula (IIIa), which are obtained
virtually quantitatively in this way, can be converted into the
bisalcohols (IIIb) by conventional reduction reactions. These
bisalcohols are also obtainable directly from the compounds of the
formula (VII) by oxidation (see, for example, A. Belli et al.,
Synthesis 1980, 477).
[0049] It may also prove advantageous to delay conversion of the
substituent (P') into the substituent (R') until the stage of the
carboxylic acid or its ester, i.e. to delay carrying out reaction
(1') until this point. This is principally appropriate in the case
of long-chain alkoxy substituents, since these would otherwise
possibly be destroyed by air oxidation.
[0050] The halogen atom can, if desired, be replaced by a boric
acid, borate or trialkyltin group at a suitable stage, as described
below for the compounds the formula (IVa).
[0051] The corresponding perfluoroalkylsulfonates can be prepared,
for example, by esterification of corresponding phenol functions.
6
[0052] Scheme 3 can be explained as follows: the compounds (VIII)
are generally commercially available (for example diverse alkyl-
and dialkylaromatic compounds or alkoxyaromatic compounds) or can
be prepared simply from corresponding precursors (for example
hydroquinone, pyrocatechol, naphthol and the like), for example by
alkylation. The compound (VIII) can then be converted into
compounds of the formula (IVa) by simple halogenation reactions
(Reaction 5), as described above. Many compounds of the formula
(IV) are inexpensive chemicals (for example bromophenol and
bromoaniline) which can be converted simply into compounds of the
formula (IVa) by Reaction 6 (for example alkylation of phenyl
functions). These compounds of the formula (IVa) can then be
metallated by corresponding reagents (for example Mg turnings,
n-BuLi or s-BuLi) and then converted into the corresponding
compounds of the formula (IVb) or (IVc) by corresponding further
reaction, for example with trialkyltin chloride or trialkyl
borate.
[0053] It can thus be seen that the starting compounds (III) and
(IV) are accessible in a simple manner in the requisite range of
variations. The starting compounds (III) and (IV) are converted
into intermediates of the formula (V) by a coupling reaction
(Reaction A in Scheme 1).
[0054] To this end, the compounds of the formulae (III) and (IV)
are reacted in an inert solvent at a temperature in the range from
0.degree. C. to 200.degree. C. in the presence of a palladium
catalyst.
[0055] In each case one of these compounds, preferably the compound
of the formula (III), contains a halogen or perfluoroalkylsulfonate
group and the other contains a boric acid or borate group (IVb) or
a trialkyltin group (IVc).
[0056] In order to carry out the above reaction A with boric acids
or borates of the formula (IVb), Variant Aa, Suzuki coupling, the
aromatic boron compound, the aromatic halogen compound or the
perfluoroalkylsulfonate, a base and catalytic amounts of the
palladium catalyst are added to water or to one or more inert
organic solvents or preferably to a mixture of water and one or
more inert organic solvents and stirred at a temperature of from 0
to 200.degree. C., preferably from 30 to 170.degree. C.,
particularly preferably from 50 to 150.degree. C., especially
preferably from 60 to 120.degree. C., for a period of from 1 hour
to 100 hours, preferably from 5 hours to 70 hours, particularly
preferably from 5 hours to 50 hours. The crude product can be
purified by methods known to the person skilled in the art and
appropriate for the respective product, for example by
recrystallization, distillation, sublimation, zone melting, melt
crystallization or chromatography.
[0057] Examples of organic solvents which are suitable for the
process described are ethers, for example diethyl ether,
dimethoxyethane, diethylene glycol dimethyl ether, tetrahydrofuran,
dioxane, dioxolane, diisopropyl ether and tert-butyl methyl ether,
hydrocarbons, for example hexane, isohexane, heptane, cyclohexane,
toluene and xylene, alcohols, for example methanol, ethanol,
1-propanol, 2-propanol, ethylene glycol, 1-butanol, 2-butanol and
tert-butanol, ketones, for example acetone, ethyl methyl ketone and
isobutyl methyl ketone, amides, for example dimethylformamide,
dimethylacetamide and N-methylpyrrolidone, and nitriles, for
example acetonitrile, propionitrile and butyronitrile, and mixtures
thereof.
[0058] Preferred organic solvents are ethers, such as
dimethoxyethane, diethylene glycol dimethyl ether, tetrahydrofuran,
dioxane and diisopropyl ether, hydrocarbons, such as hexane,
heptane, cyclohexane, toluene and xylene, alcohols, such as
methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol,
tert-butanol and ethylene glycol, ketones, such as ethyl methyl
ketone and isobutyl methyl ketone, amides, such as
dimethylformamide, dimethylacetamide and N-methylpyrrolidone, and
mixtures thereof.
[0059] Particularly preferred solvents are ethers, for example
dimethoxyethane and tetrahydrofuran, hydrocarbons, for example
cyclohexane, toluene and xylene, alcohols, for example ethanol,
1-propanol, 2-propanol, 1-butanol and tert-butanol, and mixtures
thereof.
[0060] In a particularly preferred variant, water and one or more
water-insoluble solvents are employed in the process described.
Examples are mixtures of water and toluene and water, toluene and
tetrahydrofuran.
[0061] Bases which are preferably used in the process described are
alkali and alkaline earth metal hydroxides, alkali and alkaline
earth metal carbonates, alkali metal hydrogencarbonates, alkali and
alkaline earth metal acetates, alkali and alkaline earth metal
alkoxides, and primary, secondary and tertiary amines.
[0062] Particular preference is given to alkali and alkaline earth
metal hydroxides, alkali and alkaline earth metal carbonates and
alkali metal hydrogencarbonates.
[0063] Particular preference is given to alkali metal hydroxides,
such as sodium hydroxide and potassium hydroxide, and alkali metal
carbonates and alkali metal hydrogencarbonates, such as lithium
carbonate, sodium carbonate and potassium carbonate.
[0064] The base is preferably employed in the above process in a
proportion of from 100 to 1000 mol %, particularly preferably from
100 to 500 mol %, very particularly preferably from 150 to 400 mol
%, especially from 180 to 250 mol %, based on the aromatic boron
compound.
[0065] The palladium catalyst contains palladium metal or a
palladium(0) or palladium(II) compound and a complex ligand,
preferably a phosphine ligand.
[0066] The two components can form a compound, for example the
particularly preferred Pd(PPh.sub.3).sub.4, or can be employed
separately.
[0067] Examples of suitable palladium components are palladium
compounds, such as palladium ketonates, palladium acetylacetonates,
nitrilopalladium halides, olefinpalladium halides, palladium
halides, allylpalladium halides and palladium biscarboxylates,
preferably palladium ketonates, palladium acetylacetonates,
bis-.eta..sup.2-olefinpalladium dihalides, palladium(II) halides,
.eta..sup.3-allylpalladium halide dimers and palladium
biscarboxylates, very particularly preferably
bis(dibenzylideneacetone)palladium(0) [Pd(dba).sub.2)],
Pd(dba).sub.2 CHCl.sub.3, palladium bisacetylacetonate,
bis(benzonitrile)palladium dichloride, PdCl.sub.2,
Na.sub.2PdCl.sub.4, dichlorobis(dimethylsulfoxide- )palladium(II),
bis(acetonitrile)palladium dichloride, palladium(II) acetate,
palladium(II) propionate, palladium(II) butanoate and
(1c,5c-cyclooctadiene)palladium dichloride.
[0068] The catalyst can also be palladium in metallic form,
referred to below as simply palladium, preferably palladium in
powdered form or on a support material, for example palladium on
activated carbon, palladium on aluminum oxide, palladium on barium
carbonate, palladium on barium sulfate, palladium on aluminum
silicates, such as montmorillonite, palladium on SiO.sub.2 and
palladium on calcium carbonate, in each case with a palladium
content of from 0.5 to 10% by weight. Particular preference is
given to palladium in powdered form, palladium on activated carbon,
palladium on barium and/or calcium carbonate and palladium on
barium sulfate, in each case with a palladium content of from 0.5
to 10% by weight. Particular preference is given to palladium on
activated carbon with a palladium content of 5 or 10% by
weight.
[0069] The palladium catalyst is employed in the process according
to the invention in a proportion of from 0.01 to 10 mol %,
preferably from 0.05 to 5 mol %, particularly preferably from 0.1
to 3 mol %, especially preferably from 0.1 to 1.5 mol %, based on
the aromatic halogen compound or the perfluoroalkylsulfonate.
[0070] Examples of ligands which are suitable for the process are
phosphines, such as trialkylphosphines, tricycloalkylphosphines and
triarylphosphines, where the three substituents on the phosphorus
may be identical or different, chiral or achiral, and where one or
more of the ligands can link the phosphorus groups from a plurality
of phosphines, and where part of this link may also be one or more
metal atoms.
[0071] Examples of phosphines which can be used in the process
described here are trimethylphosphine, trimethylphosphine,
tricyclohexylphosphine, triphenylphosphine, trisolylphosphine,
tris(o-tolyl)phosphine, tris(4-dimethyl-aminophenyl)phosphine,
bis(diphenylphosphano)methane, 1,2-bis(diphenylphosphano)ethane,
1,3-bis(diphenylphosphano)propane and
1,1'-bis(diphenylphosphano)ferrocene.
[0072] Examples of other suitable ligands are diketones, for
example acetylacetone and octafluoroacetylacetone, and tertiary
amines, for example trimethylamine, triethylamine,
tri-n-propylamine and triisopropylamine.
[0073] Preferred ligands are phosphines and diketones, particularly
preferably phosphines.
[0074] Very particularly preferred ligands are triphenylphosphine,
1,2-bis(diphenylphosphano)ethane, 1,3-bis(diphenylphosphano)propane
and 1,1'-bis(diphenylphosphano)ferrocene, in particular
triphenylphospine.
[0075] Also suitable for the process are water-soluble ligands
containing, for example, sulfonic acid salt and/or sulfonic acid
radicals and/or carboxylic acid salt and/or carboxylic acid
radicals and/or phosphonic acid salt and/or phosphonic acid
radicals and/or phosphonium groups and/or peralkyl-ammonium groups
and/or hydroxyl groups and/or polyether groups of suitable chain
length.
[0076] Preferred classes of water-soluble ligands are phosphines
substituted by the above groups, such as trialkylphosphines,
tricycloalkylphosphines, triarylphosphines, dialkylarylphosphines,
alkyldiarylphosphines and heteroarylphosphines, such as
tripyridylphosphine and trifurylphosphine, where the three
substituents on the phosphorus may be identical or different,
chiral or achiral, and where one or more of the ligands can link
the phosphorus groups from a plurality of phosphines, and where
part of this link may also be one or more metal atoms, phosphites,
phosphinites and phosphonites, phosphols, dibenzophosphols and
cyclic and oligo- and polycyclic compounds containing phosphorus
atoms.
[0077] The ligand is employed in the process in a proportion of
from 0.1 to 20 mol %, preferably from 0.2 to 15 mol %, particularly
preferably from 0.5 to 10 mol %, especially preferably from 1 to 6
mol %, based on the aromatic halogen compound or the
perfluoroalkylsulfonate. It is also possible, if desired, to employ
mixtures of two or more different ligands.
[0078] All or some of the boronic acid derivative employed can be
in the form of the anhydride.
[0079] Advantageous embodiments of the variant Aa process described
are described, for example, in WO 94/101 05, EP-A-679 619, WO-A-694
530 and PCT/EP 96/03154, which are expressly incorporated herein by
way of reference.
[0080] In variant Ab, also known as the Stille coupling, an
aromatic tin compound, preferably of the formula (IVc), is reacted
with an aromatic halogen compound or an aromatic
perfluoroalkylsulfonate, preferably of the formula (III), at a
temperature in the range from 0.degree. C. to 200.degree. C. in an
inert organic solvent in the presence of a palladium catalyst.
[0081] A review of this reaction is given, for example, in J. K.
Stille, Angew. Chemie Int. Ed. Engl. 1986, 25, 508.
[0082] In order to carry out the process, the aromatic tin compound
[lacuna] the aromatic halogen compound or the
perfluoroalkylsulfonate are preferably introduced into one or more
inert organic solvents and stirred at a temperature of from
0.degree. C. to 200.degree. C., preferably from 30.degree. C. to
170.degree. C., particularly preferably from 50.degree. C. to
150.degree. C., especially preferably from 60.degree. C. to
120.degree. C., for a period of from 1 hour to 100 hours,
preferably from 5 hours to 70 hours, particularly preferably from 5
hours to 50 hours. When the reaction is complete, the Pd catalyst
obtained as a solid is separated off, for example by filtration,
and the crude product is freed from solvent or solvents. Further
purification can subsequently be carried out by methods known to
the person skilled in the art and appropriate for the respective
product, for example by recrystallization, distillation,
sublimation, zone melting, melt crystallization or
chromatography.
[0083] Examples of organic solvents which are suitable for the
process described are ethers, for example diethyl ether,
dimethoxyethane, diethylene glycol dimethyl ether, tetrahydrofuran,
dioxane, dioxolane, diisopropyl ether and tert-butyl methyl ether,
hydrocarbon, for example hexane, isohexane, heptane, cyclohexane,
benzene, toluene and xylene, alcohols, for example methanol,
ethanol, 1-propanol, 2-propanol, ethylene glycol, 1-butanol,
2-butanol and tert-butanol, ketones, for example acetone, ethyl
methyl ketone and isobutyl methyl ketones, amides, for example
dimethylformamide (DMF), dimethylacetamide and N-methylpyrrolidone,
and nitrites, for example acetonitrile, propionitrile and
butyronitrile, and mixtures thereof.
[0084] Preferred organic solvents are ethers, such as
dimethoxyethane, diethylene glycol dimethyl ether, tetrahydrofuran,
dioxane and diisopropyl ether, hydrocarbons, such as hexane,
heptane, cyclohexane, benzene, toluene and xylene, alcohols, such
as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol,
tert-butanol and ethylene glycol, ketones, such as ethyl methyl
ketone, or amides, such as DMF.
[0085] Particularly preferred solvents are amides, very
particularly preferably DMF.
[0086] The palladium catalyst contains palladium metal or a
palladium(0) or palladium(II) compound and a complex ligand,
preferably a phosphine ligand.
[0087] The two components can form a compound, for example
Pd(PPh.sub.3).sub.4, or can be employed separately.
[0088] Examples of suitable palladium components are palladium
compounds, such as palladium ketonates, palladium acetylacetonates,
nitrilopalladium halides, olefinpalladium halides, palladium
halides, allylpalladium halides and palladium biscarboxylates,
preferably palladium ketonates, palladium acetylacetonates,
bis-.eta..sup.2-olefinpalladium dihalides, palladium(II) halides,
.eta..sup.3-allylpalladium halide dimers and palladium
biscarboxylates, very particularly preferably
bis(dibenzylideneacetone)palladium(0) [Pd(dba).sub.2)],
Pd(dba).sub.2 CHCl.sub.3, palladium bisacetylacetonate,
bis(benzonitrile)palladium dichloride, PdCl.sub.2,
Na.sub.2PdCl.sub.4, dichlorobis(dimethylsulfoxide- )palladium(II),
bis(acetonitrile)palladium dichloride, palladium(II) acetate,
palladium(II) propionate, palladium(II) butanoate and
(1c,5c-cyclooctadiene)palladium dichloride.
[0089] The palladium catalyst is employed in the process described
in a proportion of from 0.01 to 10 mol %, preferably from 0.05 to 5
mol %, particularly preferably from 0.1 to 3 mol %, especially
preferably from 0.1 to 1.5 mol %, based on the aromatic halogen
compound or the perfluoroalkylsulfonates.
[0090] Examples of ligands which are suitable for the process
described are phosphines, such as trialkylphosphines,
tricycloalkylphosphines and triarylphosphines, where the three
substituents on the phosphorus may be identical or different,
chiral or achiral, and where one or more of the ligands can link
the phosphorus groups from a plurality of phosphines, and where
part of this link may also be one or more metal atoms.
[0091] The ligand is employed in the process described in a
proportion of from 0.1 to 20 mol %, preferably from 0.2 to 15 mol
%, particularly preferably from 0.5 to 10 mol %, especially
preferably from 1 to 6 mol %, based on the aromatic halogen
compound or the perfluoroalkylsulfonate.
[0092] Reaction B
[0093] If the group X' in the intermediate (V) is --COOR, it is
reduced to the bisalcohol, X'.dbd.CH.sub.2OH.
[0094] The reduction can be carried out by known methods familiar
to the person skilled in the art, as described, for example, in
Houben-Weyl, 4.sup.th Edn. Vol. 6, 16, Chapter VIII,
Georg-Thieme-Verlag, Stuttgart 1984.
[0095] Preferred embodiments are the following:
[0096] a) Reaction with LiAIH.sub.4 or diisobutylaluminum hydride
(DIBAL-H) in tetrahydrofuran (THF) or toluene, as described, for
example, in Organikum [Synthetic Organic Chemistry] (see above),
pp. 612 ff.
[0097] b) Reaction with boron hydrides, such as BH.sub.3, as
described, for example, in Houben-Weyl, 4.sup.th Edn. Vol. 6, 16,
Chapter VIII, pp. 211-219, Georg-Thieme-Verlag, Stuttgart 1984.
[0098] c) Reaction with hydrogen in the presence of a catalyst, as
described, for example, in Houben-Weyl, 4.sup.th Edn. Vol. 6, 16,
Chapter VII, pp. 110 ff., Georg-Thieme-Verlag, Stuttgart 1984.
[0099] d) Reaction with sodium or sodium hydride.
[0100] Particular preference is given to reduction using
LiAlH.sub.4 or DIBAL-H.
[0101] Reaction C
[0102] In accordance with the invention, the OH groups in the
bisalcohols of the formula (V) can be replaced by halogen by
nucleophilic substitution.
[0103] In order to prepare chlorides and bromides, it is preferred
to react the corresponding bisalcohol with HCl or HBr, for example
in glacial acetic acid (see, for example, Houben-Weyl, Volume 5/4,
pp. 385 ff., 1960) or with thionyl chloride or bromide, if desired
in the presence of a catalyst (see, for example, Houben-Weyl,
Volume 5/1b, pp. 862 ff., 1962).
[0104] Chlorides can also preferably be prepared by reaction with
phosgene (see, for example, Houben-Weyl, Volume V, 3, pp. 952 ff,
1962) or with BCl.sub.3, and bromides by reaction with
PBr.sub.3.
[0105] Iodides can preferably be prepared by reaction with
phosphorus/iodine by the method of A. I. Vogel (see, for example,
Houben-Weyl, Volume V, 4, pp. 615 ff., 1969).
[0106] Alternatively, the halides can be interchanged in a
comparable manner to the FINKELSTEIN reaction; thus, monomers
containing two different halides, or mixtures thereof, can also
advantageously be employed. The work-up is carried out in all cases
in a simple manner by known methods familiar to a person skilled in
the art.
[0107] The synthetic methods described here enable, for example,
the preparation of the following monomers which can be converted
into polymers according to the invention.
1 7 8 Monomer 1 Monomer 2 9 10 Monomer 3 Monomer 4 11 12 Monomer 5
Monomer 6 13 14 Monomer 7 Monomer 8 15 16 Monomer 9 Monomer 10 17
18 Monomer 11 Monomer 12 19 20 Monomer 13 Monomer 14 21 22 Monomer
15 Monomer 16 23 24 Monomer 17 Monomer 18 25 26 Monomer 19 Monomer
20 27 28 Monomer 21 Monomer 22 29 30 Monomer 23 Monomer 24 31
Monomer 25
[0108] Key: C.sub.4: 2-methylpropyl; C.sub.8: 2-ethylhexyl;
C.sub.10: 3,7-dimethyloctyl.
[0109] Polymers comprising recurring units of the formula (I) can
be prepared from the monomers of the formula (II) accessible in
this way by the polymerization variant indicated above--if desired
with addition of further comonomers. Comonomers of this type are,
for example, the compounds shown below.
2 32 33 Monomer A Monomer B 34 35 Monomer C Monomer D 36 37 Monomer
E Monomer F 38 39 Monomer G Monomer H 40 41 Monomer I Monomer J 42
43 Monomer K Monomer L 44 45 Monomer M Monomer N 46 47 Monomer O
Monomer P 48 49 Monomer Q Monomer R 50 51 Monomer S Monomer T
[0110] Key: C.sub.4: 2-methylpropyl; C.sub.8: 2-ethylhexyl;
C.sub.10: 3,7-dimethyloctyl.
[0111] The homopolymers or copolymers according to the invention
produced in this way are very particularly suitable as
electroluminescent materials. For the purposes of the present
invention, the term "electroluminescent materials" is taken to mean
materials which can be used as an active layer in an
electroluminescent device. The term "active layer" means that the
layer is capable of emitting light (light-emitting layer) on
application of an electric field and/or that it improves the
injection and/or transport of the positive and/or negative charges
(charge injection or charge transport layer).
[0112] The invention therefore also relates to the use of a polymer
comprising at least 20% of recurring units of the formula (I) in an
electroluminescent device, in particular as electroluminescent
material.
[0113] In order to be used as electroluminescent materials, the
polymers comprising structural units of the formula (I) are
generally applied in the form of a film to a substrate by known
methods familiar to the person skilled in the art, such as dipping
or spin coating.
[0114] The invention thus likewise relates to an electroluminescent
device having one or more active layers, where at least one of
these active layers comprises one or more polymers according to the
invention. The active layer can be, for example, a light-emitting
layer and/or a transport layer and/or a charge-injection layer.
[0115] The general construction of electroluminescent devices of
this type is described, for example, in U.S. Pat. Nos. 4,539,507
and 5,151,629. Electroluminescent devices containing polymers are
described, for example, in WO-A 90/13148 and EP-A 0 443 861.
[0116] They usually contain an electroluminescent layer between a
negative electrode and a positive electrode, where at least one of
the electrodes is transparent. In addition, one or more
electron-injection and/or electron-transport layers can be
introduced between the electroluminescent layer and the negative
electrode and/or one or more hole-injection and/or hole-transport
layers can be introduced between the electroluminescent layer and
the positive electrode. Suitable negative electrodes are preferably
metals or metal alloys, for example Ca, Mg, Al, In or Mg/Ag. The
positive electrodes can be metals, for example Au, or other
metallically conducting substances, such as oxides, for example ITO
(indium oxide/tin oxide) on a transparent substrate, for example
made of glass or a transparent polymer.
[0117] In operation, the negative electrode is set to a negative
potential compared with the positive electrode. Electrons are
injected by the negative electrode into the electron-injection
layer/electron-transport layer or directly into the light-emitting
layer. At the same time, holes are injected by the positive
electrode into the hole-injection layer/hole-transport layer or
directly into the light-emitting layer.
[0118] The injected charge carriers move through the active layers
toward one another under the effect of the applied voltage. This
results in electron/hole pairs recombining at the interface between
the charge-transport layer and the light-emitting layer or within
the light-emitting layer with emission of light.
[0119] The color of the emitted light can be varied by means of the
materials used as light-emitting layer.
[0120] Electroluminescent devices are used, for example, as
self-illuminating display elements, such as control lamps,
alphanumeric displays, signs and in opto-electronic couplers.
[0121] The invention is explained in greater detail by the examples
which follow, without this being intended to represent a
limitation.
[0122] Part 1: Synthesis of the Monomers
[0123] A. Synthesis of Compounds of the Formula (III)
EXAMPLE A1
Synthesis of diethyl 2-bromo-5-methoxyterephthalate
a) Synthesis of 4-bromo-2,5-dimethylanisole
[0124] Bromine (291.5 g, 1835 mmol) was added dropwise with
stirring to an initially introduced mixture of 2,5-dimethylanisole
(250 g, 1835 mmol) and Fe powder (3.25 g). The commencement of the
reaction was evident from gas evolution. The remainder of the
bromine was subsequently added dropwise over the course of 3040
minutes at room temperature with water-bath cooling. The reaction
mixture was stirred for about a further 4 hours. The Fe powder was
subsequently separated off, a little chloroform was added to the
solution, and the solution was washed by shaking with water,
resulting in the solution becoming paler. After the solution had
been shaken with 50 ml of saturated aqueous Na.sub.2SO.sub.3
solution, it had become completely colorless. The solution was
shaken again with dilute aqueous NaOH and twice with H.sub.2O and
dried, and the solvent was stripped off. The crude product was
subjected to fractional distillation under reduced pressure.
[0125] The product was obtained as a viscous, colorless oil
(boiling point 68.degree. C., 0.8 mbar): 285 g (72%)
[0126] .sup.1H NMR (CDCl.sub.3): [ppm]=7.25 (s, 1 H, H-aryl), 6.68
(s, 1 H, H-aryl), 3.78 (s, 3 H, O--Me), 2.36, 2.14 (each s, 3+3 H,
CH.sub.3).
b) Synthesis of 2-bromo-5-methoxyterephthalic acid
[0127] A solution of cobalt acetate tetrahydrate (1.25 g, 5 mmol),
manganese acetate tetrahydrate (1.23 g), HBr (0.81 g), sodium
acetate (1.37 g) and 4-bromo-2,5-dimethylanisole (107.5 g, 0.5 mol)
in 380 g of glacial acetic acid was introduced into a 1 l autoclave
(HC-22) fitted with disk agitator, reflux condenser, gas inlet and
gas outlet. The reaction solution was heated to 150.degree. C. with
stirring under a nitrogen atmosphere (17 bar). Air (17 bar) was
passed through the solution (180-200 I/h) at this temperature,
after which the exothermic reaction immediately commenced. The
reaction temperature remained at 150.degree. C. due to external
cooling. The exothermic reaction was complete after about 45
minutes. In order to facilitate a subsequent reaction, an
air/nitrogen mixture (10% of O.sub.2) was passed through the
solution at 150.degree. C. for 30 minutes. The supply of air was
then terminated, and nitrogen was introduced.
[0128] The reactor contents were cooled to 100.degree. C. under a
nitrogen atmosphere, discharged into a flask as a solution and
cooled to 20.degree. C. with stirring, during which the product
crystallized out. The colorless crystal slurry was filtered off
with suction and washed four times with 40 g of glacial acetic acid
each time.
[0129] Drying gave 96.2 g of 2-bromo-5-methoxyterephthalic acid
(70%).
[0130] .sup.1H NMR (DMSO): [ppm]=13.5 (br, 2 H, COOH), 7.87 (s, 1
H, H-aryl), 7.42 (s, 1 H, H-aryl), 3.88 (s, 3 H, O--Me).
c) Synthesis of diethyl 2-bromo-5-methoxyterephthalate
[0131] 2-Bromo-5-methoxyterephthalic acid (202.89 g, 738 mmol) was
initially introduced with 500 ml of EtOH under a protective gas,
and H.sub.2SO.sub.4 was then added at RT with stirring. The mixture
was subsequently refluxed at an internal temperature of 78.degree.
C., and EtOH was distilled off until the internal temperature was
above 100.degree. C. Ethanol was firstly added once more and then
distilled off again. The process was repeated until only the
diester was present according to TLC. Finally, all the ethanol was
stripped off, the resultant crude product was taken up in ethyl
acetate and extracted with aqueous NaHCO.sub.3 solution, and
finally, after phase separation and drying, all the solvent was
again stripped off. The solidified solid obtained was, after
comminution, purified by stirring with hexane, giving 190.4 g (78%)
of pale-yellow crystals.
[0132] Melting point: 61-63.degree. C.
[0133] .sup.1H NMR (CDCl.sub.3): [ppm]=8.00 (s, 1 H, H-aryl), 7.34
(s, 1 H, H-aryl), 4.43+4.37 (each q, 2+2 H, OCH.sub.2, J=7.5 Hz),
3.92 (s, 3 H, O--Me), 1.42+1.38 (each t, 3+3 H, CH.sub.3, J=7.5
Hz).
EXAMPLE A2
Synthesis of diethyl 2-bromo-5-fluoroterephthalate
a) Synthesis of 2-bromo-5-nitro-p-xylene
[0134] 740 g of bromo-p-xylene were initially introduced in acetic
anhydride (ice-bath cooling) and nitrating acid (prepared from 400
ml of fuming nitric acid and 480 ml of concentrated sulfuric acid)
was slowly added dropwise. During the addition, it was ensured that
the internal temperature remained between 22.degree. C.-25.degree.
C. When the addition was complete (duration about 5 hours), the ice
bath was removed, and the mixture was stirred at RT for about a
further 1 hour.
[0135] The entire batch was poured onto 4 l of ice with vigorous
stirring; a viscous oil separated out during this operation. The
aqueous phase was decanted off, water was again added to the oil,
and the mixture was stirred. This procedure (decanting off and
purification) was repeated three times. Finally, methanol was
added, giving a crystalline -solid, which was filtered off with
suction and recrystallized again from a little methanol, finally
giving 230 g (30%) of orange-yellow crystals.
[0136] Melting point: 62-65.degree. C.
[0137] .sup.1H NMR (CDCl.sub.3): [ppm]=7.88 (s, 1 H, H-aryl), 7.53
(s, 1 H, H-aryl), 2.55, 2.44 (each s, 3+3 H, CH.sub.3).
b) Synthesis of 2-amino-5-bromo-p-xylene
[0138] 316 g of 2-bromo-5-nitro-p-xylene were dissolved in 3000 ml
of methanol, freshly produced Raney nickel (about 4 g) was added
under a vigorous stream of N.sub.2, and the mixture was heated to
reflux with vigorous stirring. 275 ml of hydrazine hydrate (80% in
water) were then slowly added dropwise. When the dropwise addition
was complete (duration about 5 hours), the mixture was refluxed for
about a further 6 hours. The catalyst was filtered off, the
methanol was removed in a rotary evaporator, the residue was taken
up in ethyl acetate, and the solution was washed by shaking with
water, dried and re-evaporated in a rotary evaporator. The
resultant crude product was recrystallized from heptane, giving 238
g (87%) of pale-green crystals.
[0139] Melting point: 92-93.degree. C.
[0140] .sup.1H NMR (CDCl.sub.3): [ppm]=7.18 (s, 1 H, H-aryl), 6.56
(s, 1 H, H-aryl), 3,6 (s (br), 2 H, NH.sub.2), 2.27, 2.09 (each s,
3+3 H, CH.sub.3).
c) Synthesis of 2-bromo-5-fluoro-p-xylene
[0141] 373 g of 2-amino-5-bromo-p-xylene were suspended in 1860 ml
of H.sub.2O in a 4 l four-necked flask, the mixture was cooled to
3.degree. C. (internal temperature), and 612 ml of tetrafluoroboric
acid were added. 154 g of NaNO.sub.2 in 300 ml of water were then
added dropwise over the course of 60 minutes. After 60 minutes, the
solid was filtered off with suction and washed with a little cold
5% tetrafluoroboric acid, then with a little cold methanol and
finally with a little cold diethyl ether. The yellow solid (497
g=90%) was dried overnight in an oil-pump vacuum.
[0142] The batch was then halved, and each half was suspended in
about 500 ml of toluene. The suspensions were heated using a hair
drier; each time vigorous evolution of gas commenced, the heating
was stopped until it subsided again. Finally, the mixture was
refluxed until the evolution of gas was complete. The toluene was
removed in a rotary evaporator, and the product was purified by
distillation under reduced pressure (0.1 mbar, 54-57.degree. C.),
giving (in total) 232 g (61%) of colorless oil.
[0143] .sup.1H NMR (CDCl.sub.3): [ppm]=7.32 (d, 1 H, H-aryl,
J.sub.H-F=7 Hz), 6.88 (d, 1 H, H-aryl, J.sub.H-F=10 Hz), 2.33 (s, 3
H, CH.sub.3), 2.21 (d, 3 H, CH.sub.3, J.sub.H-F=2 Hz).
d) Synthesis of 2-bromo-5-fluoroterephthalic acid
[0144] The reaction was carried out analogously to Example A1
(b).
[0145] Drying gave 88% 2-bromo-5-fluoroterephthalic acid.
[0146] .sup.1H NMR (DMSO-d.sub.6): [ppm]=13.8 (br, 2 H, COOH), 8.07
(d, 1 H, H-aryl, J.sub.H-F=7 Hz), 7.68 (d, 1 H, H-aryl,
J.sub.H-F=10.5 Hz).
e) Synthesis of diethyl 2-bromo-5-fluoroterephthalate
[0147] The reaction was carried out analogously to Example A1 (c).
Purification was carried out by stirring with hexane.
[0148] Drying gave 99% of diethyl 2-bromo-5-fluoroterephthalate as
a virtually white powder.
[0149] Melting point: 30.degree. C.
[0150] .sup.1H NMR (CDCl.sub.3): [ppm]=8.19 (d, 1 H, H-aryl,
J.sub.H-F=6.5 Hz), 7.56 (d, 1 H, H-aryl, J.sub.H-F=10.5 Hz),
4.43+4.42 (each q, 2+2 H, OCH.sub.2, J=7.5 Hz), 1.42+1.41 (each t,
3+3 H, CH.sub.3, J=7.5 Hz).
EXAMPLE A3
Synthesis of diethyl 2-bromo-5-chloroterephthalate
a) Synthesis of 2-bromo-5-chloro-p-xylene
[0151] Chloro-p-xylene was brominated analogously to Example A1
(a).
[0152] Recrystallization from methanol gave 72% of
2-bromo-5-chloro-p-xyle- ne as a white powder.
[0153] Melting point: 66-67.degree. C.
[0154] .sup.1H NMR (CDCl.sub.3): [ppm]=7.38 (s, 1 H, H-aryl), 7.19
(s, 1 H, H-aryl), 2.32, 2.30 (each s, 3+3 H, CH.sub.3).
b) Synthesis of 2-bromo-5-chloroterephthalic acid
[0155] The reaction was carried out analogously to Example A1
(b).
[0156] Drying gave 87% of 2-bromo-5-chloroterephthalic acid.
[0157] .sup.1H NMR (DMSO-d.sub.6): [ppm]=13.9 (br, 2 H, COOH), 8.07
(s, 1 H, H-aryl), 7.88 (s, 1 H, H-aryl).
c) Synthesis of diethyl 2-bromo-5-chloroterephthalate
[0158] The reaction was carried out analogously to Example A1 (c).
The purification was carried out by stirring with hexane.
[0159] Drying gave 98% of diethyl 2-bromo-5-chloroterephthalate as
a virtually white powder.
[0160] Melting point: 125.degree. C.
[0161] .sup.1H NMR (CDCl.sub.3): [ppm]=8.08 (s, 1 H, H-aryl), 7.84
(s, 1 H, H-aryl), 4.43+4.41 (each q, 2+2 H, OCH.sub.2, J=7.5 Hz),
1.42+1.38 (each t, 3+3 H, CH.sub.3, J=7.5 Hz).
[0162] B. Synthesis of Compounds of the Formula (IV)
EXAMPLE B1
Synthesis of 3-(3,7-dimethyloctyloxy)benzeneboronic acid
a) Synthesis of 3-(3,7-dimethyloctyloxy)bromobenzene
[0163] 450 ml of ethanol were initially introduced, and Nal (10.5
g; 70 mmol) and KOH (67.3 g; 1.2 mol) were added. A temperature
increase from 25 to 40.degree. C. after addition of the KOH was
observed. After the mixture had been cooled to room temperate,
3-bromophenol (176.5 g; 1 mol) was added, during which the white
suspension became beige.
[0164] 3,7-Dimethyloctyl chloride (186.32 g; 212.94 ml; 1,05 mol)
was added over the course of 3 minutes via a dropping funnel. The
mixture was stirred at RT for a further 2 hours and subsequently
stirred at an internal temperature of 80.degree. C. for 96 hours.
Ethanol was distilled off. The residue was taken up in ethyl
acetate, and the precipitate was separated off by filtration. The
organic phase was extracted three times with 10% strength by weight
aqueous NaOH solution and washed once with H.sub.2O, three times
with H.sub.2O which had been acidified using CO.sub.2 and again
with H.sub.2O. After the mixture had been dried using MgSO.sub.4,
the solvent was stripped off again in a rotary evaporator, and the
crude product was purified by fractional distillation under reduced
pressure.
[0165] Product: high-boiling colorless oil; 180.degree. C. at 2-3
mbar; 262.3 g (84%)
[0166] .sup.1H NMR (400 MHz; CDCl.sub.3): [ppm]=7.12 (pseudo-t; 1
H; J=8 Hz; H-5), 7.05 (m; 2 H; H-2, H-6), 6.81 (ddd; 1 H;
J.sub.1=8, J.sub.2=2, J.sub.3=0.7 Hz; H-4), 3.97 (m; 2 H;
O--CH.sub.2), 1.81 (m; 1 H; O--CH.sub.2--CH.sub.2--CH), 1.70-1.50
(m; 3 H; H-alkyl), 1.35-1.13 (m; 6 H; H-alkyl), 0.93 (d; 3 H; J=7.7
Hz; CH.sub.3), 0.87 (d; 6 H; J=7.7 Hz; CH.sub.3).
b) Synthesis of 3-(3,7-dimethyloctyloxy)benzeneboronic acid
[0167] Mg turnings (24.7 g, 1.02 mol) were initially introduced,
and the apparatus was dried by heating under argon. About 100 ml of
THF were introduced at room temperature via the dropping funnel,
and a few crystals of iodine were added. A few ml of
3-(3,7-dimethyloctyloxy)bromob- enzene were subsequently added
dropwise to the static solution, and the mixture was heated at the
point where the drops entered using a hot-air blower. When the
reaction had commenced, the remainder of the
3-(3,7-dimethyloctyloxy)bromobenzene (total: 313 g, 1 mol, 280 ml)
was continuously added dropwise (70 minutes) with stirring. At the
same time, a further 1100 ml of THF were added. The reaction batch
was refluxed for a further two hours.
[0168] The resultant Grignard reagent was, after cooling to room
temperature, added dropwise under a protective gas and with rapid
stirring to a mixture, cooled to -70.degree. C., of 800 ml of THF
and 123 ml of trimethyl borate (114 g, 1.10 mol) at such a rate
that the internal temperature did not exceed -60.degree. C.
(duration: 3 hours). A pale suspension formed.
[0169] The reaction mixture was stirred into 1200 g of ice water/40
ml of conc. H.sub.2SO.sub.4. The clear phases were separated, and
the water phase was extracted by shaking with ethyl acetate. The
combined organic phases were stirred with water, dried and
evaporated.
[0170] For further purification, the colorless solid obtained in
this way was stirred with about 500 ml of hexane (to which 2 ml of
conc. aqueous HCl had been added), giving 239 g (86%) of a
colorless crystal powder.
[0171] Melting point: 83-89.degree. C.
[0172] .sup.1H NMR (400 MHz; CDCl.sub.3): [ppm]=7.81 (td; 1 H;
J.sub.1=8, J.sub.2=1.3 Hz; H-4), 7.73 (dd; 1 H; J.sub.1=2,
J.sub.2=1.1 Hz; H-2), 7.43 (t; 1 H; J=8 Hz; H-5), 7.13 (ddd; 1 H;
J.sub.1=8, J.sub.2=2, J.sub.3=1.1 Hz; H-6), 4.11 (m; 2 H;
O--CH.sub.2), 1.90 (m; 1 H; O--CH.sub.2--CH.sub.2--CH), 1.75-1.50
(m; 3 H; H-alkyl), 1.44-1.14 (m; 6 H; H-alkyl), 1.00 (d; 3 H; J=7.9
Hz; CH.sub.3), 0.88 (d; 6 H; J=7.8 Hz; CH.sub.3). Contains variable
proportions of anhydrides.
EXAMPLE B2
Synthesis of 4-(3,7-dimethyloctyloxy)benzeneboronic acid
a) Synthesis of 4-(3,7-dimethyloctyloxy)bromobenzene
[0173] Procedure analogous to Example B1, a).
[0174] Yield: 85%
[0175] Boiling point: 180.degree. C. at 2 mbar
[0176] .sup.1H NMR (CDCl.sub.3): [ppm]=7.36, 6.77 (AA'BB', 4 H,
H-aryl), 3.95 (m, 2 H, O--CH.sub.2), 1.82 (m, 1 H, H-3'), 1.6 (m, 3
H, H-2', H-7'), 1.24 (m, 6 H, H-4', H-5', H-6'), 0.94 (d, 3 H, Me,
J=7 Hz), 0.87 (d, 6 H, Me, J=7 Hz).
b) Synthesis of 4-(3,7-dimethyloctyloxy)benzeneboronic acid
[0177] Procedure analogous to Example B1, b).
[0178] Yield: 83%
[0179] Melting point: 57-63.degree. C.
[0180] .sup.1H NMR (CDCl.sub.3): [ppm]=7.67, 6.92 (AA'BB', 4 H,
H-aryl), 4.6 (br, 2 H, B(OH).sub.2), 4.03 (m, 2 H, O--CH.sub.2),
1.87 (m, 1 H, H-3'), 1.65 (m, 3 H, H-2', H-7'), 1.27 (m, 6 H, H-4',
H-5', H-6'), 0.95 (d, 3 H, Me, J=7 Hz), 0.87 (d, 6 H, Me, J=7 Hz).
Contains variable proportions of anhydrides.
EXAMPLE B3
Synthesis of 3,4-bis(2-methylpropoxy)benzeneboronic acid
a) Synthesis of 1,2-bis(2-methylpropoxy)benzene
[0181] Pyrocatechol (220.22 g, 2 mol) and Nal (10.49 g, 0.14 mol)
were initially introduced in 900 ml of ethanol, and the mixture was
heated to reflux. KOH (56.11 g, 1 mol) dissolved in about 300 ml of
ethanol and simultaneously 1-bromo-2-methylpropane (137.03 g, 1
mol, 108.75 ml) were subsequently slowly added dropwise. The
mixture was refluxed further overnight. On the next day, the same
amount of KOH and alkyl bromide were again added. This procedure
was repeated a total of seven times.
[0182] After the reaction mixture had been cooled, the supernatant
was decanted off from the solid. The filter cake was rinsed with
ethanol. The organic phase was evaporated. The filter cake was
dissolved in 1 l of warm water, and the organic phase diluted with
ethyl acetate was added. Phase separation was followed by repeated
stirring with 10% strength aqueous NaOH, washing with water and
drying over Na.sub.2SO.sub.4. The crude product obtained after the
solvent had been stripped off was subjected to fractional
distillation under reduced pressure.
[0183] The product was obtained as a colorless oil (boiling point:
82.degree. C. at 0.18 mbar): 333.4 g (75%).
[0184] .sup.1H NMR (CDCl.sub.3): [ppm]=6.87 (ps-s, 4 H, H-aryl),
3.75 (d, 4 H, O--CH.sub.2, J=8 Hz), 2.13 (ps-non, 2 H, C--H, J=8
Hz), 1.05 (d, 12 H, CH.sub.3, J=8 Hz).
b) Synthesis of 3,4-bis(2-methylpropoxy)bromobenzene
[0185] 1,2-bis(2-methylpropoxy)benzene (359.61 g, 1.62 mol) was
initially introduced with 500 ml of CH.sub.2Cl.sub.2, and a little
iron powder was added. Bromine (266.88 g, 1.78 mol) (mixed with
about 200 ml of CH.sub.2Cl.sub.2) was then slowly added dropwise
with cooling. The batch was stirred at room temperature for about
20 hours. For work-up, the batch was stirred with aqueous
Na.sub.2SO.sub.3 solution, and the iron powder was subsequently
filtered off. The organic phase was then washed by shaking 2.times.
with NaHCO.sub.3 solution, and subsequently washed with water until
neutral. After drying, the organic phase was evaporated.
[0186] Double fractional distillation gave the desired product as a
colorless solid (166.9 g, 34%).
[0187] Melting point: 47.degree. C.
[0188] .sup.1H NMR (CDCl.sub.3): [ppm]=6.98 (m, 2 H, H-2, H-6),
6.73 (m, 1 H, H-5), 3.72, 3.70 (2.times.d, 2.times.2 H,
O--CH.sub.2, J=8 Hz), 2.12 (m, 2 H, CH), 1.04 (m, 12 H,
CH.sub.3).
c) Synthesis of 3,4-bis(2-methylpropoxy)benzeneboronic acid
[0189] Procedure analogous to Example B1, b).
[0190] Yield: 76%
[0191] Melting point: 146.degree. C.
[0192] .sup.1H NMR (CDCl.sub.3): [ppm]=7.81 (dd, 1 H, H-6,
J.sub.1=8 Hz, J.sub.2=1.8 Hz), 7.68 (d, 1 H, H-2, J=1.8 Hz), 6.99
(d, 1 H, H-5, J=8 Hz), 3.89, 3.84 (2.times.d, 2.times.2 H,
O--CH.sub.2, J=8 Hz), 2.13 (m, 2 H, CH), 1.07 (m, 12 H, CH.sub.3).
Contains variable proportions of anhydrides.
EXAMPLE B4
Synthesis of 2,5-dimethoxybenzeneboronic acid
[0193] The synthesis was carried out analogously to Example B1 (b)
(2,5-dimethoxybromobenzene: AVOCADO). The product was obtained as a
white powder in a yield of 90%.
[0194] .sup.1H NMR (CDCl.sub.3): [ppm]=7.38 (d, 1 H, H-6, J=2 Hz),
6.98 (dd, 1 H, H-4, J=2 Hz, J=8 Hz), 6.86 (d, 1 H, H-3, J=8 Hz),
6.10 (s, 2 H, OH), 3.88+3.81 (each s, 3+3 H, OCH.sub.3).
EXAMPLE B5
Synthesis of 2,5-dimethylbenzeneboronic acid
[0195] The synthesis is described in WO98/25874 as Example B3.
EXAMPLE B6
Synthesis of 4-fluorobenzeneboronic acid
[0196] The synthesis was carried out analogously to Example B1 (b)
(4-fluorobromobenzene: Aldrich). The product was obtained as a
white powder in a yield of 86%. (Contains about 25% of
anhydride)
[0197] .sup.1H NMR (DMSO-d.sub.6): [ppm]=7.90 (dd, 2 H, H-3 ,H-5,
J=6 Hz, J=8.2 Hz), 7.84 (dd, 0.5 H, H-3 ,H-5 anhydride, J=6 Hz,
J=8.2 Hz); 7.18 (ps. t, 2 H, H-2, H-6, J=8.4 Hz); ); 7.14 (ps. t,
0.5 H, H-2, H-6-anhydride; J=8.4 Hz).
EXAMPLE B7
Synthesis of 3,5-difluorobenzeneboronic acid
[0198] The synthesis was carried out analogously to Example B1 (b)
(3,5-difluorobromobenzene: Aldrich). The product was obtained
[lacuna] a white powder in a yield of 68%. (Contains about 10% of
anhydride).
[0199] .sup.1H NMR (DMSO-d.sub.6): [ppm]=7.46 (d with shoulder, 2
H, H-2,H-6, J=6 Hz), 7.40 (d with shoulder, 0.2 H, H-2, H-6
anhydride, J=6 Hz); 7.21 (ps. t with shoulder, 1 H, H-4, J=9.2
Hz).
[0200] C. Coupling Reactions in Accordance with Reaction A
EXAMPLE C1
Synthesis of diethyl
2-[4-(3,7-dimethyloctyloxy)phenyl]-5-methoxyterephtha- late
[0201] Diethyl 2-bromo-5-methoxyterephthalate (49.67 g, 150 mmol),
K.sub.2CO.sub.3 (44.23 g, 320 mmol), 140 ml of toluene and 140 ml
of H.sub.2O were initially introduced and flushed with argon for 30
minutes. 4-(3,7-dimethyloctyloxy)boronic acid (44.51 g, 160 mmol)
and Pd(PPh.sub.3).sub.4 (0.7 g, 0.6 mmol) were subsequently added
under a protective gas. The brownish mixture, which was cloudy due
to phase separation, was stirred vigorously at an internal
temperature of 85.degree. C. under a protective-gas blanket. The
reaction was complete after 24 hours (according to TLC). Palladium
residues were removed by stirring with 1% strength aqueous NaCN
solution. After the phases had been separated, the organic phase
was washed (neutral) by shaking firstly with water and subsequently
with dilute HCl/H.sub.2O and subsequently evaporated to dryness in
a rotary evaporator. The product (95% yield) was a colorless
high-viscosity oil (purity>97%).
[0202] .sup.1H NMR (CDCl.sub.3): [ppm]=7.75, 7.35 (2.times.s,
2.times.1 H, H-3, H-6), 7.20, 6.91 (AA'BB', 4 H, H-aryl), 4.37,
4.12 (2.times.q, 2.times.2 H, CO.sub.2CH.sub.2, J=7.6 Hz), 4.02 (m,
2 H, O--CH.sub.2), 3.97 (s, 3 H, O--Me), 1.84 (m, 1 H, H-3"), 1.62
(m, 3 H, H-2", H-7"), 1.37, 1.03 (2.times.t, 2.times.3H,
ester-CH.sub.3, J=7.6 Hz), 1.28 (m, 6 H, H-4", H-5", H-6"), 0.96
(d, 3 H, Me, J=7.5 Hz), 0.87 (d, 6 H, Me, J=7.5 Hz).
EXAMPLE C2
Synthesis of diethyl
2-[3-(3,7-dimethyloctyloxy)phenyl]-5-methoxyterephtha- late
[0203] Synthesis analogous to Example C1. The product (95% yield)
was a colorless high-viscosity oil.
[0204] .sup.1H NMR (CDCl.sub.1): [ppm]=7.78, 7.37 (2.times.s,
2.times.1 H, H-3, H-6), 7.26 (t; 1 H; H-5', J=8 Hz), 6.86 (m; 3 H;
H-2', H-4', H-6'), 4.37, 4.10 (2.times.q, 2.times.2 H,
CO.sub.2CH.sub.2, J=7.6 Hz), 4.00 (m, 2 H, O--CH.sub.2), 3.97 (s, 3
H, O--Me), 1.83 (m, 1 H, H-3"), 1.62 (m, 3 H, H-2", H-7"), 1.37,
1.01 (2.times.t, 2.times.3H, ester-CH.sub.3, J=7.6 Hz), 1.28 (m, 6
H, H-4", H-5", H-6"), 0.95 (d, 3 H, Me, J=7.5 Hz), 0.86 (d, 6 H,
Me, J=7.5 Hz).
EXAMPLE C3
Synthesis of diethyl
2-[3,4-bis(2-methylpropyl)phenyl]-5-methoxyterephthal- ate
[0205] Procedure analogous to Example C1. The product was obtained
as a viscous oil in a yield of 100%.
[0206] .sup.1H NMR (CDCl.sub.3): [ppm]=7.75, 7.32 (2.times.s,
2.times.1 H, H-3, H-6), 6.88 (d, 1 H, H-2, J=2 Hz), 6.80 (m, 2 H,
H-5+H-6), 4.37, 4.12 (2.times.q, 2.times.2 H, CO.sub.2CH.sub.2,
J=7.5 Hz), 3.96 (s, 3 H, O--Me), 3.78, 3.74 (2.times.d, 2.times.2
H, O--CH.sub.2, J=8 Hz), 2.14 (m, 2 H, CH), 1.36, 1.02 (2.times.t,
2.times.3H, ester-CH.sub.3, J=7.5 Hz), 1.04 (m, 12 H,
CH.sub.3).
EXAMPLE C4
Synthesis of diethyl
2-[2,5-dimethoxyphenyl]-5-methoxyterephthalate
[0207] Procedure analogous to Example C1. After stirring in hexane,
the product was obtained as a crystalline solid in a yield of
72%.
[0208] .sup.1H NMR (CDCl.sub.3): [ppm]=7.73, 7.46 (2.times.s,
2.times.1 H, H-3, H-6), 6.82 (m, 3 H, H-3+H-4+H-6), 4.36, 4.11
(2.times.q, 2.times.2 H, CO.sub.2CH.sub.2, J=7.5 Hz), 3.96, 3.81,
3.75 (3.times.s, 3.times.3 H, 3.times.O--Me), 1.36, 1.03
(2.times.t, 2.times.3H, ester-CH.sub.3, J=7.5 Hz).
EXAMPLE C5
Synthesis of diethyl
2-[2,5-dimethylphenyl]-5-methoxyterephthalate
[0209] Procedure analogous to Example C1. The product was obtained
as a viscous oil in a yield of 99%.
[0210] .sup.1H NMR (CDCl.sub.3): [ppm]=7.63, 7.50 (2.times.s,
2.times.1 H, H-3, H-6), 7.10 (d, 1 H, H-3, J=8 Hz), 7.06 (dd, 1 H,
H-4, J=1.3 Hz, J=8 Hz), 6.89 (s (br), 1 H, H-6), 4.35, 4.05
(2.times.q, 2.times.2 H, CO.sub.2CH.sub.2, J=7.5 Hz), 3.99 (s, 3 H,
O--Me), 2.32, 2.02 (2.times.s, 2.times.3 H, CH.sub.3), 1.35, 0.92
(2.times.t, 2.times.3H, ester-CH.sub.3, J=7.5 Hz).
EXAMPLE C6
Synthesis of diethyl
2-[3-(3,7-dimethyloctyloxy)phenyl]-5-fluoroterephthal- ate
[0211] Procedure analogous to Example C1. The product was obtained
as a viscous oil in a yield of 98%.
[0212] .sup.1H NMR (CDCl.sub.3): [ppm]=7.93 (d, 1 H, H-6,
J.sub.H-F=7 Hz), 7.55 (d, 1 H, H-3, J.sub.H-F=11 Hz), 7.26 (t (br);
1 H; H-5', J=8 Hz), 6.87 (m; 3 H; H-2', H-4', H-6'), 4.42, 4.13
(2.times.q, 2.times.2 H, CO.sub.2CH.sub.2, J=7.8 Hz), 3.99 (m, 2 H,
O--CH.sub.2), 1.83 (m, 1 H, H-3"), 1.60 (m, 3 H, H-2", H-7"), 1.40,
1.05 (2.times.t, 2.times.3H, ester-CH.sub.3, J=7.8 Hz), 1.25 (m, 6
H, H-4", H-5", H-6"), 0.94 (d, 3 H, Me, J=7.5 Hz), 0.87 (d, 6 H,
Me, J=7.5 Hz).
EXAMPLE C7
Synthesis of diethyl
2-[3,4-bis(2-methylpropyl)phenyl]-5-fluoroterephthala- te
[0213] Procedure analogous to Example C1. The product was obtained
as a viscous oil in a yield of 100%.
[0214] .sup.1H NMR (CDCl.sub.3): [ppm]=7.91 (d, 1 H, H-6,
J.sub.H-F=7 Hz), 7.50 (d, 1 H, H-3, J.sub.H-F=11 Hz), 6.89 (d; 1 H;
H-5', J=8 Hz), 6.80 (m; 2 H; H-2', H-6'), 4.42, 4.14 (2.times.q,
2.times.2 H, CO.sub.2CH.sub.2, J=7.6 Hz), 3.78, 3.75 (2.times.d,
2.times.2 H, O--CH.sub.2, J=8 Hz), 2.14 (m, 2 H, CH), 1.40, 1.07
(2.times.t, 2.times.3H, ester-CH.sub.3, J=7.5 Hz), 1.05 (m, 12 H,
CH.sub.3).
EXAMPLE C8
Synthesis of diethyl
2-[4-(3,7-dimethyloctyloxy)phenyl]-5-chloroterephthal- ate
[0215] Procedure analogous to Example C1. The product was obtained
as an oil in a yield of 93%.
[0216] .sup.1H NMR (CDCl.sub.3): [ppm]=7.83, 7.78 (2.times.s,
2.times.1 H, H-3, H-6), 7.22, 6.92 (AA'BB', 4 H, H-aryl), 4.41,
4.25 (2.times.q, 2.times.2 H, CO.sub.2CH.sub.2, J=7.6 Hz), 4.03 (m,
2 H, O--CH.sub.2), 1.83 (m, 1 H, H-3"), 1.60 (m, 3 H, H-2", H-7"),
1.41, 1.07 (2.times.t, 2.times.3H, ester-CH.sub.3, J=7.6 Hz), 1.30
(m, 6 H, H-4", H-5", H-6"), 0.96 (d,3 H, Me, J=7.5 Hz), 0.87 (d, 6
H, Me, J=7.5 Hz).
EXAMPLE C9
Synthesis of diethyl 2-chloro-5-phenylterephthalate
[0217] Procedure analogous to Example C1. After distillation under
reduced pressure (0.1 mbar, 170.degree. C.), the product was
obtained as an oil in a yield of 80%.
[0218] .sup.1H NMR (CDCl.sub.3): [ppm]=7.83, 7.80 (2.times.s,
2.times.1 H, H-3, H-6), 7.35 (m (AA'BB'C), 5 H, H-phenyl), 4.42,
4.11 (2.times.q, 2.times.2 H, CO.sub.2CH.sub.2, J=7.5 Hz), 1.40,
1.02 (2.times.t, 2.times.3H, ester-CH.sub.3, J=7.6 Hz).
EXAMPLE C10
Diethyl 2-[3,5-difluorophenyl]-5-methoxyterephthalate
[0219] The procedure was carried out analogously to Example C1.
After crystallization from hexane, the product was obtained as a
colorless solid in a yield of 62%.
[0220] .sup.1H NMR (CDCl.sub.3): [ppm]=7.99, 7.89 (2.times.s,
2.times.1 H, H-3, H-6), 6.88-6.83 (m, 3 H, H-phenyl), 4.44, 4.17
(2.times.q, 2.times.2 H, CO.sub.2CH.sub.2, J=7.0 Hz), 3.97 (s, 3H,
O--CH.sub.3), 1.41, 1.10 (2.times.t, 2.times.3H, ester-CH.sub.3,
J=7.0 Hz).
[0221] D. Reductions in Accordance with Reaction B
EXAMPLE D1
Synthesis of
2,5-bishydroxymethyl-4-methoxyl-4'-(3,7-dimethyloctyloxy)biph-
enyl
[0222] LiAlH.sub.4 (7.9 g, 208 mmol) was initially introduced with
about 250 ml of THF under an argon blanket. Diethyl
2-[4-(3,7-dimethyloctyloxy)- phenyl]-5-methoxyterephthalate (72.2
g, 149 mmol) was diluted with about 60 ml of THF in a dropping
funnel and slowly added dropwise. During this addition, the
reaction mixture was stirred vigorously. The batch, diluted with a
further 100 ml of THF, was then refluxed at 67.degree. C. After 2
hours, it was cooled to RT. When the reduction was complete, 8 ml
of water were carefully added for work-up. 8 ml of aqueous NaOH
solution (15% strength) were subsequently added, and finally 24 ml
of water were added. After each addition, the mixture was stirred
for about a further 15 minutes ("1:1:3 method"). The solid formed
was filtered off with suction and again stirred with THF, and
finally the combined organic phases were evaporated.
Recrystallization from hexane/ethyl acetate (20:1) gave the product
(93% yield) as colorless crystals.
[0223] Melting point: 101.degree. C.
[0224] .sup.1H NMR (CDCl.sub.3): [ppm]=7.21, 6.93 (AA'BB', 4 H,
H-aryl), 7.18, 7.10 (2.times.s, 2.times.1 H, H-3, H-6), 4.70, 4.62
(2.times.s, 2.times.2 H, CH.sub.2O), 4.02 (m, 2 H, O--CH.sub.2),
3.93 (s, 3 H, O--Me), 1.85 (m, 1 H, H-3'), 1.65 (br, 2 H, OH), 1.60
(m, 3 H, H-2', H-7'), 1.28 (m, 6 H, H-4', H-5', H-6'), 0.96 (d, 3
H, Me, J=7.5 Hz), 0.86 (d, 6 H, Me, J=7.5 Hz).
Example D2
Synthesis of
2,5-bishydroxymethyl-4-methoxy-3'-(3,7-dimethyloctyloxy)biphe-
nyl
[0225] Synthesis analogous to Example D1. Stirring with hot hexane.
The product was obtained (99% yield) as a colorless, wax-like
solid.
[0226] Melting point: 55.degree. C.
[0227] .sup.1H NMR (CDCl.sub.3): [ppm]=7.29 (t; 1 H; J=8 Hz; H-5'),
7.21, 7.12 (2.times.s, 2.times.1 H, H-3, H-6), 6.87 (m; 3 H; H-2',
H-4', H-6'), 4.70, 4.64 (2.times.d, 2.times.2 H, CH.sub.2O, J=8
Hz), 4.01 (m, 2 H, O--CH.sub.2), 3.93 (s, 3 H, O--Me), 2.29, 1.63
(2.times.t, 2.times.1 H, OH, J=8 Hz), 1.84 (m, 1 H, H-3'), 1.60 (m,
3 H, H-2', H-7'), 1.25 (m, 6 H, H-4', H-5', H-6'), 0.94 (d, 3 H,
Me, J=7.5 Hz), 0.87 (d, 6 H, Me, J=7.5 Hz).
EXAMPLE D3
Synthesis of
2,5-bishydroxymethyl-4-methoxy-3',4'-bis(2-methylpropyl)biphe-
nyl
[0228] Procedure analogous to Example D1. The product was obtained
as white crystals in a yield of 78% after recrystallization from
ethyl acetate/hexane (1:2).
[0229] Melting point: 110-111.degree. C.
[0230] .sup.1H NMR (CDCl.sub.3): [ppm]=7.19, 7.10 (2.times.s,
2.times.1 H, H-3, H-6), 6.89 (d, 1 H, H-5', J=8 Hz), 6.84 (d, 1 H,
H-2', J=2 Hz), 6.80 (dd, 1 H, H-6', J=8 Hz, J=2 Hz), 4.71, 4.63
(2.times.s, 2.times.2 H, CH.sub.2O), 3.94 (s, 3 H, O--Me), 3.78,
3.75 (2.times.d, 2.times.2 H, O--CH.sub.2, J=8 Hz), 2.15 (m, 2 H,
CH), 1.05 (m, 12 H, CH.sub.3).
EXAMPLE D4
Synthesis of 2,5-bishydroxymethyl-4,2',5'-trimethoxybiphenyl
[0231] Procedure analogous to Example D1. After stirring in hexane,
the product was obtained as a white powder in a yield of 96%.
[0232] Melting point: 91.5-92.5.degree. C.
[0233] .sup.1H NMR (CDCl.sub.3): [ppm]=7.14, 7.10 (2.times.s,
2.times.1 H, H-3, H-6), 6.91 (d, 1 H, H-3', J=8 Hz), 6.87 (dd, 1 H,
H-4', J=8 Hz, J=2 Hz), 6.73 (d, 1 H, H-6', J=2 Hz), 4.71, 4.40
(2.times.d (br), 2.times.2 H, CH.sub.2O), 3.94, 3.78, 3.68
(3.times.s, 3.times.3 H, 3.times.O--Me), 2.1 (s (br), 2 H, OH). The
CH.sub.2OH groups were diastereotopic owing to hindered
rotation.
EXAMPLE D5
Synthesis of
2,5-bishydroxymethyl-4-methoxy-2',5'-dimethylbiphenyl
[0234] Procedure analogous to Example D1. After stirring in hexane,
the product was obtained as a white powder in a yield of 96%.
[0235] Melting point: 147.5-150.degree. C.
[0236] .sup.1H NMR (CDCl.sub.3): [ppm]=7.14 (d, 1 H, H-3', J=8 Hz),
7.11, 7.03 (2.times.s, 2.times.1 H, H-3, H-6), 7.07 (dd, 1 H, H-4',
J=8 Hz, J=1.2 Hz), 6.91 (s (br), 1 H, H-6'), 4.69, 4.40 (2.times.s,
2.times.2 H, CH.sub.2O), 3.93 (s, 3 H, O--Me), 2.31, 2.00
(2.times.s, 2.times.3 H, CH.sub.3).
EXAMPLE D6
Synthesis of
2,5-bishydroxymethyl-4-fluoro-3'-(3,7-dimethyloctyloxy)biphen-
yl
[0237] Procedure analogous to Example D1. However, pure LiAlH.sub.4
was not used but instead, for toning down, one equivalent of
isopropanol was added, i.e. the reduction was carried out using
LiAlH.sub.3(O.sup.iPr). The product was obtained as a
high-viscosity oil in a yield of 94% (purity about 98%).
[0238] .sup.1H NMR (CDCl.sub.3): [ppm]=7.30 (m, 3 H, H-3, H-6,
H-5'), 6.88 (m, 3 H, H-2', H-4', H-6'), 4.78, 4.59 (2.times.d,
2.times.2 H, CH.sub.2O, J=5 Hz), 4.00 (m, 2 H, O--CH.sub.2), 1.85
(m, 2 H, H-3", OH), 1.60 (m, 4 H, H-2", H-7", OH), 1.25 (m, 6 H,
H-4", H-5", H-6"), 0.94 (d, 3 H, Me, J=7.5 Hz), 0.86 (d, 6 H, Me,
J=7.5 Hz).
EXAMPLE D7
Synthesis of
2,5-bishydroxymethyl-4-fluoro-3',4'-bis(2-methylpropyl)biphen-
yl
[0239] Procedure analogous to Example D6. After stirring in hexane,
the product was obtained as a white powder in a yield of 87%.
[0240] Melting point: 78-79.degree. C.
[0241] .sup.1H NMR (CDCl.sub.3): [ppm]=7.31 (d, 1 H, H-6,
J.sub.H-F=7 Hz), 7.27 (d, 1 H, H-3, J.sub.H-F=11 Hz), 6.90 (d; 1 H;
H-5', J=8 Hz), 6.84 (d; 1 H; H-2', J=2 Hz), 6.80 (dd; 1 H; H-6',
J=8 Hz, J=2 Hz), 4.78, 4.60 (2.times.s, 2.times.2 H, CH.sub.2O),
3.80, 3.75 (2.times.d, 2.times.2 H, O--CH.sub.2, J=8 Hz), 2.15 (m,
2 H, CH), 1.05 (m, 12 H, CH.sub.3).
EXAMPLE D8
Synthesis of
2,5-bishydroxymethyl-4-chloro-4'-(3,7-dimethyloctyloxy)biphen-
yl
[0242] Procedure analogous to Example D1. After stirring in
ethylacetate/hexane (1/10), the product was obtained as a white
powder in a yield of 87%.
[0243] Melting point: 90.degree. C.
[0244] .sup.1H NMR (CDCl.sub.3): [ppm]=7.56, 7.37 (2.times.s,
2.times.1 H, H-3, H-6), 7.23, 6.93 (AA'BB', 4 H, H-aryl), 4.79,
4.60 (2.times.s, 2.times.2 H, CH.sub.2O), 4.02 (m, 2 H,
O--CH.sub.2), 1.85 (m, 1 H, H-3"), 1.65 (m, 3 H, H-2", H-7"), 1.35
(m, 6 H, H-4", H-5", H-6"), 0.96 (d, 3 H, Me, J=7.5 Hz), 0.87 (d, 6
H, Me, J=7.5 Hz).
EXAMPLE D9
Synthesis of
2,5-bishydroxymethyl-4-(3,7-dimethyloctyloxy)biphenyl
[0245] 46 g of sodium were added to 1060 ml of 3,7-dimethyloctanol
under a protective gas. The mixture was stirred at 120.degree. C.
for about 3 hours until the sodium salt had fully formed. 223 g of
diethyl 2-chloro-5-phenylteraphthalate were subsequently added
dropwise over the course of 20 minutes at about 100.degree. C. A
cloudy, yellowish mixture formed during this addition. In order to
complete the nucleophilic substitution, the mixture was stirred at
130.degree. C. for a further 5 hours. 500 ml of water were
subsequently added to the cooled batch, the phases were separated,
the mixture was refluxed for a number of hours with ethanol and
finally freed from solvent. The crude product obtained in this way
proved to be (according to NMR) a mixture of various esters.
However, the substitution of the chlorine by the dimethyloctyloxy
group was complete. This crude product was reduced directly
analogously to the description in D1 using LiAlH.sub.4. Finally,
after stirring twice with ethyl acetate/hexane (1/10), the product
(35%) was obtained as white crystals.
[0246] Melting point: 112-115.degree. C.
[0247] .sup.1H NMR (CDCl.sub.3): =[ppm]7.36 (m(AA'BB'C), 5 H,
H-phenyl), 7.19, 7.12 (2.times.s,2.times.1 H, H-3, H-6), 4.72, 4.61
(2.times.d, 2.times.2 H, CH.sub.2O, J=6Hz), 4.13 (m, 2 H,
O--CH.sub.2), 2.35, 1.48 (2.times.t, 2.times.1 H, OH, J=6 Hz), 1.88
(m, 1 H, H-3"), 1.65 (m, 3 H, H-2", H-7"), 1.25 (m, 6 H, H-4",
H-5", H-6"), 0.97 (d, 3 H, Me, J=7.5 Hz), 0.87 (d, 6 H, Me, J=7.5
Hz).
EXAMPLE D10
Synthesis of
2,5-bishydroxymethyl-4-methoxy-3',5'-difluorobiphenyl
[0248] The procedure was carried out analogously to Example D1.
After recrystallization from n-hexane, the product was obtained as
a white powder.
[0249] Melting point: 123.degree. C.
[0250] .sup.1H NMR (CDCl.sub.3): [ppm]=7.60, 7.26 (2.times.s,
2.times.1 H, H-3, H-6); 6.96-6.89 (m, 2H, H-2', H-6'), 6.82 (tt,
1H, H-4', J=8.9, J=2.0); 4.72, 4.58 (2.times.s, 2.times.2 H,
CH.sub.2O), 4.02 (s, 3 H, O--CH.sub.3), 1.84, 1.73 (2 br. s, each
1H, OH).
[0251] E. Halogenations in Accordance with Reaction C
EXAMPLE E1
Synthesis of
2,5-bischloromethyl-4-methoxy-4'-(3,7-dimethyloctyloxy)biphen-
yl
[0252]
2,5-Bishydroxymethyl-4-methoxy-4'-(3,7-dimethyloctyloxy)biphenyl
(54.9 g, 137 mmol) was initially introduced under N.sub.2, and
thionyl chloride (20 ml, 274 mmol) was carefully added. The batch
was stirred at room temperature for 20 hours. The batch was
carefully poured into aqueous NaHCO.sub.3 solution and extracted
with ethyl acetate, and finally the organic phase was washed until
neutral. After the mixture had been dried over MgSO.sub.4, the
ethyl acetate was stripped off, and the product was obtained as a
colorless, high-viscosity oil (40% yield) by distillation in a
short-path distillation apparatus (0.3 mbar, 265.degree. C.).
[0253] .sup.1H NMR (CDCl.sub.3): [ppm]=7.29, 6.95 (AA'BB', 4 H,
H-aryl), 7.27, 7.03 (2.times.s, 2.times.1 H, H-3, H-6), 4.65, 4.53
(2.times.s, 2.times.2 H, CH.sub.2Cl), 4.04 (m, 2 H, O--CH.sub.2),
3.94 (s, 3 H, O--Me), 1.85 (m, 1 H, H-3'), 1.63 (m, 3 H, H-2',
H-7'), 1.28 (m, 6 H, H-4', H-5', H-6'), 0.97 (d, 3 H, Me, J=7.5
Hz), 0.88 (d, 6 H, Me, J=7.5 Hz).
EXAMPLE E2
Synthesis of
2,5-bischloromethyl-4-methoxy-3'-(3,7-dimethyloctyloxy)biphen-
yl
[0254] Procedure analogous to Example E1; the product was obtained
as a colorless, high-viscosity oil (46% yield, purity: 99%) by
distillation in a short-path distillation apparatus (10.sup.-3
mbar, 180.degree. C.).
[0255] .sup.1H NMR (CDCl.sub.3): [ppm]=7.32 (t; 1 H; J=8 Hz; H-5'),
7.30, 7.04 (2.times.s, 2 .times.1 H, H-3, H-6), 6.93 (m; 3 H; H-2',
H-4', H-6'), 4.66, 4.53 (2.times.s, 2.times.2 H, CH.sub.2Cl), 4.04
(m, 2 H, O--CH.sub.2), 3.95 (s, 3 H, O--Me), 1.84 (m, 1 H, H-3'),
1.60 (m, 3 H, H-2, H-7'), 1.25 (m, 6 H, H-4', H-5', H-6'), 0.94 (d,
3 H, Me, J=7.5 Hz), 0.86 (d, 6 H, Me, J=7.5 Hz).
EXAMPLE E3
Synthesis of
2,5-bischloromethyl-4-methoxy-3',4'-bis(2-methylpropyl)biphen-
yl
[0256] Procedure analogous to Example E1; however, hexane was added
as solvent (1 molar solution). The product crystallized out of the
solution. After renewed stirring in hexane, a colorless powder was
obtained in a yield of 60%.
[0257] Melting point: 97.degree. C.
[0258] .sup.1H NMR (CDCl.sub.3): [ppm]=7.28, 7.03 (2.times.s,
2.times.1 H, H-3, H-6), 6.94 (d, 1 H, H-2', J=2 Hz), 6.91 (d, 1 H,
H-5', J=8 Hz), 6.86 (dd, 1 H, H-6', J=8 Hz, J=2 Hz), 4.65, 4.53
(2.times.s, 2.times.2 H, CH.sub.2Cl), 3.94 (s, 3 H, O--Me), 3.80,
3.79 (2.times.d, 2.times.2 H, O--CH.sub.2, J=8 Hz), 2.15 (m, 2 H,
CH), 1.06 (m, 12 H, CH.sub.3).
EXAMPLE E4
Synthesis of 2,5-bischloromethyl-4,2',5'-trimethoxybiphenyl
[0259] Procedure analogous to Example E3. The product crystallized
out of the solution. After renewed stirring in hexane, a colorless
powder was obtained in a yield of 57%.
[0260] Melting point: 71-73.degree. C.
[0261] .sup.1H NMR (CDCl.sub.3): [ppm]=7.23, 7.09 (2.times.s,
2.times.1 H, H-3, H-6), 6.89, 6.81 (m, 2+1 H, H-3', H-4', H-6'),
4.65, 4.45 (2.times.br, 2.times.2 H, CH.sub.2Cl), 3.94, 3.80, 3.70
(3.times.s, 3.times.3 H, 3.times.O--Me). The CH.sub.2Cl groups were
diastereotopic owing to hindered rotation.
Example E5
Synthesis of
2,5-bischloromethyl-4-methoxy-2',5'-dimethylbiphenyl
[0262] Procedure analogous to Example E3. The product was obtained
as a viscous oil in a yield of 67% by distillation in a short-path
evaporator (10.sup.-3 mbar, 115.degree. C.).
[0263] .sup.1H NMR (CDCl.sub.3): [ppm]=7.16 (d, 1 H, H-3', J=8 Hz),
7.15, 7.07 (2.times.s, 2.times.1 H, H-3, H-6), 7.10 (dd, 1 H, H-4',
J=8 Hz, J=1.2 Hz), 6.96 (s (br), 1 H, H-6'), 4.67, 4.63 (AB, 2 H,
CH.sub.2Cl, J=12 Hz), 4.39, 4.30 (AB, 2 H, CH.sub.2Cl, J=12 Hz),
3.95 (s, 3 H, O--Me), 2.33, 2.03 (2.times.s, 2.times.3 H,
CH.sub.3). The CH.sub.2Cl groups were diastereotopic owing to
hindered rotation.
EXAMPLE E6
Synthesis of
2,5-bischloromethyl-4-fluoro-3'-(3,7-dimethyloctyloxy)bipheny-
l
[0264] Procedure analogous to Example E3. The product was obtained
as a viscous oil in a yield of 68% by distillation in a short-path
evaporator (10.sup.-3 mbar, 180.degree. C.).
[0265] .sup.1H NMR (CDCl.sub.3): [ppm]=7.34 (m, 2 H, H-6, H-5'),
7.28 (d, 1 H, H-3, J.sub.H-F=10 Hz), 6.92 (m, 3 H, H-2', H-4',
H-6'), 4.64, 4.48 (2.times.s, 2.times.2 H, CH.sub.2Cl), 4.04 (m, 2
H, O--CH.sub.2), 1.83 (m, 1 H, H-3"), 1.60 (m, 3 H, H-2", H-7"),
1.25 (m, 6 H, H-4", H-5", H-6"), 0.95 (d, 3 H, Me, J=7.5 Hz), 0.87
(d, 6 H, Me, J=7.5 Hz).
EXAMPLE E7
Synthesis of
2,5-bischloromethyl-4-fluoro-3',4'-bis(2-methylpropyl)bipheny-
l
[0266] Procedure analogous to Example E3. The product was obtained
as a viscous oil in a yield of 70% by distillation in a short-path
evaporator (10.sup.-3 mbar, 185.degree. C.).
[0267] .sup.1H NMR (CDCl.sub.3): [ppm].delta.=7.33 (d, 1 H, H-6,
J.sub.H-F=7 Hz), 7.26 (d, 1 H, H-3, J.sub.H-F=10 Hz), 6.93 (d; 1 H;
H-5', J=8 Hz), 6.91 (d; 1 H; H-2', J=2 Hz), 6.84 (dd; 1 H; H-6',
J=8 Hz, J=2 Hz), 4.65, 4.47 (2.times.s, 2.times.2 H, CH.sub.2Cl),
3.80, 3.77 (2.times.d, 2.times.2 H, O--CH.sub.2, J=8 Hz), 2.16 (m,
2 H, CH), 1.06 (m, 12 H, CH.sub.3).
EXAMPLE E8
Synthesis of
2,5-bischloromethyl-4-chloro-4'-(3,7-dimethyloctyloxy)bipheny-
l
[0268] Procedure analogous to Example E3. The product was obtained
as a viscous oil in a yield of 65% by distillation in a short-path
evaporator (10.sup.-3 mbar, 190.degree. C.).
[0269] .sup.1H NMR (CDCl.sub.3): [ppm].delta.=7.58, 7.38
(2.times.s, 2.times.1 H, H-3, H-6), 7.29, 6.97 (AA'BB', 4 H,
H-aryl), 4.70, 4.47 (2.times.s, 2.times.2 H, CH.sub.2Cl), 4.05 (m,
2 H, O--CH.sub.2), 1.85 (m, 1 H, H-3"), 1.63 (m, 3 H, H-2", H-7"),
1.28 (m, 6 H, H-4", H-5", H-6"), 0.97 (d, 3 H, Me, J=7.5 Hz), 0.88
(d, 6 H, Me, J=7.5 Hz).
EXAMPLE E9
Synthesis of 2
,5-bischloromethyl-4-(3,7-dimethyloctyloxy)biphenyl
[0270] Procedure analogous to Example E3. The product was obtained
as a viscous oil in a yield of 44% by double distillation in a
short-path evaporator (10.sup.-3 mbar, 1. 135.degree. C., 2.
190.degree. C.).
[0271] .sup.1H NMR (CDCl.sub.3): =[ppm]7.40 (m (AA'BB'C), 5 H,
H-phenyl), 7.29, 7.05 (2.times.s, 2.times.1 H, H-3, H-6), 4.66,
4.51 (2.times.s, 2.times.2 H, CH.sub.2Cl), 4.13 (m, 2 H,
O--CH.sub.2), 1.90 (m, 1 H, H-3"), 1.66 (m, 3 H, H-2", H-7"), 1.28
(m, 6 H, H-4", H-5", H-6"), 0.99 (d, 3 H, Me, J=7.5 Hz), 0.88 (d, 6
H, Me, J=7.5 Hz).
EXAMPLE E10
Synthesis of
2,5-bis(chloromethyl)-4-methoxy-3',5'-bisfluorobiphenyl
[0272] Procedure analogous to Example E1. The product was purified
by crystallization from heptane.
[0273] Melting point: 117.degree. C.
[0274] .sup.1H NMR (CDCl.sub.3): [ppm].delta.=7.54, 7.24
(2.times.s, 2.times.1 H, H-3, H-6), 7.00-6.92 (m, 2 H, H-2', H-6'),
6.86 (tt, 1 H, H-4', J=8.7 Hz, J=2 Hz), 4.60, 4.48 (2.times.s,
2.times.2 H, CH.sub.2Cl), 3.99 (s, 3 H, O--Me).
[0275] Z. Synthesis of Comonomers
Z1. Synthesis of
2,5-bis(chloromethyl)-1-methoxy-4-(3,7-dimethyloctyloxy)b-
enzene
a) Preparation of 3,7-dimethyloctyl-1-chloride
[0276] 275 ml (1.46 mol) of 3,7-dimethyl-1-octanol were introduced
into a 1 l four-necked round-bottomed flask fitted with dropping
funnel, high-efficiency condenser and magnetic stirrer bar, and
cooled to -3.degree. C. 0.7 ml of pyridine was then added, and 129
ml (1.77 mol, 1.2 eq) of thionyl chloride were added dropwise at
such a rate that the temperature did not exceed 15.degree. C. (75
minutes). The HCl gas formed was trapped in a wash bottle
containing Ca(OH).sub.2/water. The mixture was then heated to
130.degree. C. over the course of 40 minutes. After two hours at
this temperature, the mixture was cooled to 50.degree. C., and
volatile constituents were distilled off by applying a reduced
pressure of 100 mbar. The residue was then cooled to room
temperature, diluted with 200 ml of n-hexane and washed firstly
twice with 50 ml of 10% strength NaOH solution in water each time,
then with 50 ml of water and finally with 50 ml of saturated
aqueous NaHCO.sub.3 solution. The solution was dried using
Na.sub.2SO.sub.4, and the solvent was removed by distillation in a
rotary evaporator. The residue was purified by distillation under
reduced pressure (13 mbar, 86-87.degree. C.), giving 178.9 g (1.01
mol, 69%) of 3,7-dimethyl-1-octyl chloride as a colorless oil.
[0277] Boiling point: 86-87.degree. C., 13 mbar. .sup.1H NMR (400
MHz, CDCl.sub.3): (ppm)=3.61-3.49 (m, 2H, CH.sub.2Cl); 1.82-1.74
(m, 1H); 1.69-1.48 (m, 3H); 1.37-1.21 (m, 3H); 1.19-1.09 (m, 3H);
0.89 (d, J=6.7 Hz, 3H; CH.sub.3); 0.87 (d, J=6.7 Hz, 6H;
2.times.CH.sub.3).
b) Preparation of 1-methoxy-4-(3,7-dimethyloctyloxy)benzene
[0278] 184.4 g (1.48 mol) of p-methoxyphenol, 275.9 g (1.56 mol,
1.05 eq) of 3,7-dimethyl-1-octyl chloride, 106.9 g of KOH (85%
strength, 1.62 mol, 1.09 eq) and 15.04 g of sodium iodide were
dissolved in 620 ml of dry ethanol in a 2 l four-necked
round-bottomed flask fitted with dropping funnel, high-efficiency
condenser, gas outlet and magnetic stirrer bar, and heated at the
boil for 64 hours with magnetic stirring. The mixture was cooled to
room temperature, and the reaction solution was decanted off from
the solid formed. The reaction solution was evaporated in a rotary
evaporator. The solid was taken up in 400 ml of 10% strength
aqueous NaOH solution. This solution was extracted twice with 400
ml of toluene each time. The organic phases were combined, washed
with 100 ml of 10% strength aqueous NaOH solution and dried using
Na.sub.2SO.sub.4. The solvent was distilled off under reduced
pressure in a rotary evaporator. The residue was distilled under
reduced pressure (1 mbar, head temperature: 159-162.degree. C.),
giving 372.4 g (1.41 mol, 95%) of
1-methoxy-4-(3,7-dimethyloctyloxy)benzene as a colorless oil.
[0279] Boiling point: 159-162.degree. C./1 mbar. .sup.1H NMR (400
MHz, CDCl.sub.3): (ppm)=6.82 (d, J=0.8 Hz, 4H; H.sub.arom);
3.97-3.88 (m, 2H; OCH.sub.2); 3.75 (s, 3H; OCH.sub.3); 1.84-1.75
(m, 1H); 1.71-1.47 (m, 3H); 1.38-1.23 (m, 3H); 1.22-1.09 (m, 3H);
0.93 (d, J=6.6 Hz, 6H; CH.sub.3); 0.86 (d, J=6.7 Hz, 6H;
2.times.CH.sub.3).
c) Preparation of
2,5-bis(chloromethyl)-1-methoxy-4-(3,7-dimethyloctyloxy)-
benzene
[0280] 304.96 g (1.03 mol) of
1-(3,7-dimethyloctyloxy)-4-methoxybenzene and 85.38 g (2.84 mol) of
paraformaldehyde were introduced under N.sub.2 in a 4 l four-necked
flask fitted with mechanical stirrer, reflux condenser, thermometer
and dropping funnel, and 490 ml (580.6 g, 5.89 mol) of 37 percent
HCl were added; a yellow suspension was obtained. 990 ml (1070 g,
10.5 mol) of acetic anhydride were then added dropwise at such a
rate that the internal temperature did not exceed 70.degree. C.
(duration: 1.5 hours). The final 100 ml were added in one portion;
during this addition, a temperature increase from 70.degree. C. to
75.degree. C. occurred; the reaction mixture changed color from
beige-brown to reddish. The batch was stirred at 70-75.degree. C.
for 3.5 hours and then cooled to room temperature with stirring,
during which a pale solid crystallized out at 32.degree. C., and a
temperature increase to 35.degree. C. occurred. The batch was left
to stand at room temperature overnight, during which a pale solid
precipitated out. 940 ml of cold-saturated Na acetate solution were
added to the reaction mixture (duration: about 15 minutes). 700 ml
of 25% strength NaOH were then added dropwise at such a rate that
the internal temperature did not exceed 30.degree. C. (duration:
about 35 minutes). The batch was then heated to 52.degree. C.
(duration: about 30 minutes) and then cooled in an ice bath with
rapid stirring (duration: about 30 minutes). The cream-colored,
granular solid was filtered off with suction and washed with 200 ml
of H.sub.2O. 2500 ml of hexane were added to the solid (451 g), the
mixture was stirred at room temperature, and 300 ml of boiling
H.sub.2O were then added. The mixture was stirred for 20 minutes,
and the aqueous phase was separated off. The yellowish organic
phase was stirred 3.times. with 300 ml of H.sub.2O each time, and
the pH was 5. The organic phase was dried over Na.sub.2SO.sub.4 and
filtered. The filtrate was evaporated and crystallized in the
freezer.
[0281] The crystallized precipitate (447 g) was filtered off with
suction, washed with hexane at -20.degree. C. and, for
recrystallization, dissolved in 1000 ml of hexane at 60.degree. C.
The product was crystallized at -20.degree. C., and the solid was
filtered off with suction and dried at room temperature under
reduced pressure, giving 279.6 g (0.774 mol, 75%) of
2,5-bis(chloromethyl)-1-methoxy-4-(3,7-dimeth- yloctyloxy)benzene
as a colorless solid.
[0282] Melting point: 65.degree. C.;
[0283] .sup.1H NMR (400 MHz, CDCl.sub.3): (ppm)=6.92 (d, J=2.0 Hz,
2H; H.sub.arom); 4.63 (d, J=2.6 Hz, 4 H; CH.sub.2Cl); 4.07-3.98 (m,
2H; OCH2); 3.85 (s, 3H; OCH.sub.3); 1.88-1.80 (m, 1H); 1.76-1.66
(br. m, 1H); 1.65-1.49 (m, 2H); 1.40-1.26 (m, 3H); 1.23-1.12 (m,
3H); 0.95 (d, J=6.8 Hz, 3H; CH.sub.3); 0.87 (d, J=6.8 Hz, 6H;
2.times.CH.sub.3). .sup.13C NMR (100 MHz, CDCl.sub.3): (ppm)=151.0,
150.7 (C1, C4); 127.1, 126.8 (C2, C5); 114.4, 113.3 (C3, C6); 67.5
(OCH.sub.2); 56.3 (OCH.sub.3); 41.3 (2.times.CH.sub.2Cl); 39.2
(C2'); 37.3, 36.3 (C4', C6'); 29.9 (C3'); 28.0 (C7'); 24.7 (C5');
22.7, 22.6, 19.7 (3.times.CH.sub.3).
Z2. Synthesis of preparation of
2,5-bis(chloromethyl)-1,4-bis(3,7-dimethyl- octyloxy)benzene
a) Preparation of 1,4-bis(3,7-dimethyloctyloxy)benzene
[0284] 84.2 g of KOH (85% strength, 1.28 mol, 1.28 eq) and 14.9 g
of sodium iodide (0.10 mol) were dissolved in 600 ml of dry ethanol
in a 2 l four-necked round-bottomed flask fitted with dropping
funnel, high-efficiency condenser, gas inlet and magnetic stirrer
bar. During this, the temperature rose to 35.degree. C. 55.1 g
(0.50 mol) of hydroquinone were then added to the cloudy solution,
and 221 g of 3,7-dimethyl-1-octyl chloride (1.25 mol, 1.25 eq) were
slowly added dropwise. The pale-brown suspension was heated at the
boil for 10 hours with magnetic s.tirring. A further 21 g of KOH
(85% strength, 0.32 mol) and 55 g of 3,7-dimethyl-1-octyl chloride
(0.31 mol, 0.31 eq) were then added, and the mixture was then
heated at the boil for a further 84 hours.
[0285] The mixture was cooled to room temperature, and the reaction
solution was evaporated in a rotary evaporator. The solid was
extracted with 500 ml of ethyl acetate. This solution was washed
three times each with 200 ml of 10% strength aqueous NaOH solution
each time and 200 ml of water and then dried using MgSO.sub.4. The
solvent was distilled off under reduced pressure in a rotary
evaporator. The residue was distilled under reduced pressure (0.05
mbar, head temperature: 166-170.degree. C.), giving 147.4 g (0.37
mol, 75%) of 1,4-bis(3,7-dimethyloctyloxy)benzene as a colorless
oil.
[0286] Boiling point: 166-170.degree. C./0.05 mbar. .sup.1H NMR
(400 MHz, CDCl.sub.3): (ppm)=6.82 (s, 4H; H.sub.arom); 3.98-3.88
(m, 4H; OCH.sub.2); 1.84-1.75 (m, 2H); 1.71-1.61 (br. m, 2H);
1.59-1.49 (m, 4H); 1.40-1.09 (m, 12H); 0.93 (d, J=6.5 Hz, 6H;
2.times.CH.sub.3); 0.86 (d, J=6.5 Hz, 12H; 4.times.CH.sub.3).
b) Preparation of
2,5-bis(chloromethyl)-1,4-bis(3,7-dimethyloctyloxy)benze- ne
[0287] 58.6g (150 mmol) of 1,4-bis(3,7-dimethyloctyloxy)benzene and
12.43g (414 mmol) of paraformaldehyde were introduced under N.sub.2
into a 1 l four-necked flask fitted with mechanical stirrer, reflux
condenser, thermometer and dropping funnel, and 71.4 ml (858 mmol)
of 37 percent HCl were added; a yellow suspension was obtained. 144
ml (156 g, 1.53 mol) of acetic anhydride were then added dropwise
at such a rate that the internal temperature did not exceed
70.degree. C. (duration: 2 hours). The batch was stirred at
70-75.degree. C. for 9 hours. A further 110 ml (119 g, 1.17 mol) of
acetic anhydride were then added, and the mixture was again stirred
at 70-75.degree. C. for 8 hours and then cooled to room temperature
with stirring, during which a pale solid crystallized out. 240 ml
of cold-saturated Na acetate solution were added to the reaction
mixture (duration: about 15 minutes), and 100 ml of 25% strength
NaOH were then added dropwise at such a rate that the internal
temperature did not exceed 30.degree. C. (duration: about 35
minutes). The granular solid was partitioned between 300 ml of
hexane and 300 ml of water. The organic phase was dried over
Na.sub.2SO.sub.4 and filtered. The filtrate was evaporated and
crystallized in the refrigerator. The product was again
recrystallized from 170 ml of hexane (washing with hexane at
-20.degree. C.), giving 28.3 g (58.0 mmol, 39%) of
2,5-bis(chloromethyl)-1,4-bis(3,7-- dimethyloctyloxy)benzene as a
colorless solid.
[0288] Melting point: 55.degree. C.; .sup.1H NMR (400 MHz,
CDCl.sub.3): (ppm)=6.92 (s, 2H; H.sub.arom); 4.62 (s, 4 H;
CH.sub.2Cl); 4.07-3.97 (m, 4H; OCH.sub.2); 1.88-1.80 (m, 2H);
1.76-1.66 (br. m, 2H); 1.65-1.49 (m, 4H); 1.40-1.13 (m, 12H); 0.95
(d, J=6.5 Hz, 6H; 2.times.CH.sub.3); 0.87 (d, J=6.8 Hz, 12H;
2.times.CH.sub.3).
Z3. Synthesis of
2,5-bischloromethyl-3'-(3,7-dimethyloctyloxy)biphenyl
a) Synthesis of dimethyl
2-(3'-(3,7-dimethyloctyloxy)phenyl)terephthalate
[0289] Dimethyl bromoterephthalate (49.7 g, 182 mmol, purchased
from TransWorld, Rockville Md., USA, or prepared analogously to
Example A1), K.sub.2CO.sub.3 (50.3 g, 364 mmol) and 170 ml of
toluene and 170 ml of H.sub.2O were initially introduced, and the
apparatus was flushed with argon for 30 minutes.
3-(3,7-Dimethyloctyloxy)boronic acid (55.7 g, 200 mmol) (cf. B1)
and Pd(PPh.sub.3).sub.4 (0.93 g, 0.8 mmol) were subsequently added
under a protective gas. The yellow-greenish, cloudy mixture was
stirred vigorously at an internal temperature of 85.degree. C.
under a protective-gas blanket. The reaction was complete after 24
hours. After the phases had been separated, the organic phase was
washed (until neutral) by shaking with dilute HCl/H.sub.2O. The
aqueous phase was extracted by shaking with ethyl acetate, and the
organic phases were combined, evaporated and dried at 2 mbar,
giving the product as a yellow oil in adequate purity (greater than
95%): 76.1 g (98%).
[0290] .sup.1H NMR (400 MHz; CDCl.sub.3): [ppm]=8.07 (d; 1 H; J=2
Hz; H-3), 8.05 (dd; 1 H; J.sub.1=8, J.sub.2=2 Hz; H-5), 7.82 (d; 1
H; J=8 Hz; H-6), 7.29 (t; 1 H, J=8 Hz; H-5), 6.90 (m; 3 H; H-2',
H-4', H-6'), 4.01 (m; 2 H; O--CH.sub.2), 3.94, 3.67 (each: s; 3 H;
CO.sub.2--CH.sub.3), 1.84 (m; 1 H; O--CH.sub.2--CH.sub.2--CH),
1.63-1.48 (m; 3 H; H-alkyl), 1.37-1.12 (m; 6 H; H-alkyl), 0.96 (d;
3 H; J=7.8 Hz; CH.sub.3), 0.87 (d; 6 H; J=7.7 Hz; CH.sub.3).
b) Synthesis of
2,5-bishydroxymethyl-3'-(3,7-dimethyloctyloxy)biphenyl
[0291] LiAlH.sub.4 (9.4 g, 248 mmol) was initially introduced in
300 ml of THF under N.sub.2. Dimethyl
2-(3'-(3,7-dimethyloctyloxy)phenyl)terephthal- ate (75.5 g, 177
mmol), dissolved in 120 ml of THF, was then slowly added dropwise
at RT. The mixture was subsequently stirred under reflux for 4
hours and cooled. Excess LiAlH4 was then carefully destroyed by
addition of H.sub.2O. Semiconcentrated H.sub.2SO.sub.4 was
subsequently carefully added dropwise (about 50 ml). The batch was
of very low viscosity at this point. After a subsequent stirring
time of 1 hour, a clear solution and a gray precipitate at the
bottom of the flask were observed. The clear solution was decanted
off, and the solvent was stripped off. The precipitate which
remained was stirred with plenty of water and ethyl acetate and
filtered, the organic phase was separated off, the solvent was
stripped off, and combined with the first organic phase. The
combined organic phases were taken up in ethyl acetate and
extracted five times with water. After the extracts had been dried
over MgSO.sub.4, the solvent was stripped off. The resultant oil
was stirred a number of times with hexane and dried in an oil-pump
vacuum, giving the product as a pure, pale-yellow, high-viscosity
oil (54 g, 82%).
[0292] .sup.1H NMR (400 MHz; CDCl.sub.3): [ppm]=7.50 (d; 1 H; J=7.8
Hz; H-6), 7.34 (dd; 1 H; J.sub.1=7.8, J.sub.2=1.9 Hz; H-5), 7.30
(dt; 1 H; J.sub.1=8, J.sub.2=1 Hz; H-5'), 7.26 (d; 1 H; J=1.9 Hz;
H-3), 6.88 (m; 3 H; H-2', H-4', H-6'), 4.69, 4.59 (each: s; 2 H;
CH.sub.2--OH), 4.00 (m; 2 H; O--CH.sub.2), 1.97 (s; 2 H; OH), 1.82
(m; 1 H; O--CH.sub.2--CH.sub.2--- CH), 1.67-1.50 (m; 3 H; H-alkyl),
1.40-1.13 (m; 6 H; H-alkyl), 0.95 (d; 3 H; J=7.5 Hz; CH.sub.3),
0.87 (d; 6 H; J=7.6 Hz; CH.sub.3).
c) Synthesis of
2,5-bischloromethyl-3'-(3,7-dimethyloctyloxy)biphenyl
[0293] 2,5-Bishydroxymethyl-3'-(3,7-dimethyloctyloxy)biphenyl (50.7
g, 137 mmol) was initially introduced under N.sub.2, and thionyl
chloride (20 ml, 274 mmol) was carefully added. 2 ml of thionyl
chloride were added twice (after 2 and after 8 hours), and the
batch was finally stirred at room temperature of a total of 20
hours. The batch was carefully poured into aqueous NaHCO.sub.3
solution and extracted with ethyl acetate, and finally the organic
phase was washed until neutral and dried over MgSO.sub.4. The ethyl
acetate was stripped off, and the batch was subjected to fractional
distillation under reduced pressure, giving the product (39 g, 70%)
as a high-viscosity, colorless oil (boiling point: 212.degree. C.
at 0.67 mbar).
[0294] .sup.1H NMR (300 MHz; CDCl.sub.3): [ppm]=7.54 (d; 1 H; J=8.3
Hz; H-6), 7.41 (dd; 1 H; J.sub.1=8.2, J.sub.2=2.1 Hz; H-5), 7.34
(d; 1 H; J.sub.1=8, J.sub.2=1 Hz; H-5'), 7.31 (d; 1 H; J=2 Hz;
H-3), 6.94 (m; 3 H; H-2'; H-4', H-6'); 4.61, 4.52 (each: s; 2 H;
CH.sub.2Cl), 4.04 (m; 2H; O--CH.sub.2), 1.84 (m; 1 H;
O--CH.sub.2--CH.sub.2--CH), 1.72-1.46 (m; 3 H; H-alkyl), 1.38-1.10
(m; 6 H; H-alkyl), 0.94 (d; 3 H; J=6.7 Hz; CH.sub.3), 0.86 (d; 6 H;
J=6.9 Hz; CH.sub.3).
Z4. Synthesis of
2,5-bischloromethyl-4'-(3,7-dimethyloctyloxy)biphenyl
[0295] The synthesis is described in WO98/25874 as Example E6.
Z5: Synthesis of
2,5-bischloromethyl-3',4'-bis(2-methylpropyl)biphenyl
[0296] The synthesis is described in WO98/25874 as Example E7.
[0297] Part 2: Synthesis and Characterization of the Polymers
[0298] The composition of the copolymers P1 to P17 and V1 to V7 was
confirmed by oxidative degradation followed by qualitative and
quantitative analysis of the monomer units thus obtained again. It
was found that the proportion of monomer units in the copolymer was
equal to the monomer ratio employed in the synthesis.
[0299] P: Synthesis of Polymers According to the Invention
EXAMPLE P1
[0300] Copolymer comprising 50% of
2,5-bis(chloromethyl)-1,4-bis(3,7-dimet- hyloctyloxy)benzene and
50% of 2,5-bis(chloromethyl)-3'-(3,7-dimethyloctyl-
oxy)-4-methoxybiphenyl (polymer P1):
[0301] Preparation of
poly(2,5-(3,7-dimethyloctyloxy)-p-phenylenevinylene)-
co(2-(3'-(3,7-dimethyloctyloxy)phenyl-5-methoxy)-p-phenylenevinylene).
[0302] 590 g of dry and O.sub.2-free 1,4-dioxane were heated to
99.degree. C. in a dry 1 l four-necked flask fitted with mechanical
Teflon stirrer, reflux condenser, thermometer and dropping funnel.
A solution of 1.95 g (4.00 mmol) of
2,5-bis(chloromethyl)-1,4-bis(3',7'-dimethyloctyloxy)benze- ne and
1.75 g (4.00 mmol) of
2,5-bis(chloromethyl)-3'-(3,7-dimethyloctylox- y)-4-methoxybiphenyl
in 30 ml of dry 1,4-dioxane was then added. A solution of 2.36 g
(21 mmol) of potassium tert-butoxide in 21 ml of dry 1,4-dioxane
was then added dropwise to the vigorously stirred mixture over the
course of 5 minutes. During this addition, the color changed from
colorless via yellow to orange-red. After 5 minutes, a further 1.79
g (16 mmol) of potassium tert-butoxide, dissolved in 16 ml of
1,4-dioxane, were added. After the mixture had been stirred at
98-100.degree. C. for 2 hours, it was cooled to 55.degree. C., and
a mixture of 4 ml of acetic acid and 4 ml of 1,4-dioxane was added.
The solution, which was then orange, was poured into 0.85 l of
vigorously stirred water. The polymer which precipitated was
isolated by filtration through a polypropylene filter and was dried
under reduced pressure. The crude yield was 2.22 g (5.70 mmol,
71%).
[0303] The polymer was dissolved in 250 ml of THF with heating to
60.degree. C. and precipitated by addition of 250 ml of methanol at
40.degree. C. After the mixture had been dried under reduced
pressure, this step was repeated. Drying under reduced pressure
gave 1.37 g (=3.52 mmol, 44%) of the polymer P1 as pale-orange
fibers.
[0304] .sup.1H NMR (400 MHz, CDCl.sub.3): .delta.(ppm)=7.8-6.6 (br.
m, 6 H); 4.2-3.6 (br. m, 4.5 H); 2.87 (br. s, bisbenzyl); 2.0-0.9
(br. m, 15 H); 0.85, 0.84 (2 s, 13.5 H). The .sup.1H NMR spectrum
of polymer P1 is reproduced in FIG. 1. Integration of the signal at
2.87 ppm gave the content of TBB groups as 1.4%.
[0305] GPC: THF+0.25% oxalic acid; column set SDV500, SDV1000,
SDV10000 (PSS), 35.degree. C., UV detection 254 nm, polystyrene
standard: M.sub.w=1.35.times.10.sup.6 g/mol,
M.sub.n=1.27.times.10.sup.5 g/mol.
EXAMPLE P2
[0306] Copolymer comprising 50% of
2,5-bis(chloromethyl)-4-methoxy-3'-(3,7- -dimethyloctyloxy)biphenyl
and 50% of 2,5-bis(chloromethyl)-3',4'-bis(2-me-
thylpropoxy)biphenyl (polymer P2):
[0307] Preparation of
poly(2-(3'-(3,7-dimethyloctyloxy)phenyl)-5-methoxy)--
p-phenylenevinylene)co(2-(3',4'-bis(2-methylpropoxy))phenyl)-p-phenylenevi-
nylene).
[0308] 3400 ml of dry and O.sub.2-free 1,4-dioxane were heated to
99.degree. C. in a heat-dried 6 l four-necked flask fitted with
mechanical Teflon stirrer, reflux condenser, thermometer and
dropping funnel. A solution of 12.45 g (28.5 mmol) of
2,5-bis(chloromethyl)-4-meth- oxy-3'-(3,7-dimethyloctyloxy)biphenyl
(Ex. E2) and 11.25 g (28.5 mmol) of
2,5-bis(chloromethyl)-3',4'-bis(2-methylpropoxy)biphenyl (Ex. Z5)
in 50 g of dry 1,4-dioxane was then added. A solution of 16.6 g
(148 mmol) of potassium tert-butoxide in 148 ml of dry 1,4-dioxane
was then added dropwise to the vigorously stirred mixture over the
course of 5 minutes. During this addition, the color changed from
colorless via yellow to yellow-orange. After 5 minutes, a further
15.4 g (137 mmol) of potassium tert-butoxide, dissolved in 140 ml
of 1,4-dioxane, were added. After the mixture had been stirred at
98-100.degree. C. for 2 hours, it was cooled to 50.degree. C., and
a mixture of 33 ml of acetic acid and 35 ml of 1,4-dioxane was
added. The solution, which was then orange, was poured into 3.8 l
of vigorously stirred water. The fibrous polymer which precipitated
was isolated by filtration through a polypropylene filter, washed
twice with methanol and dried under reduced pressure. The crude
yield was 15.33 g (78%).
[0309] The polymer was dissolved in 1.7 l of THF with heating to
60.degree. C. and precipitated by addition of the same amount of
methanol at 40.degree. C. After the mixture had been washed with
methanol and dried under reduced pressure, this step was repeated
(1.2 l of THF/1.2 l of methanol). Drying under reduced pressure
gave 8.68 g (=25.3 mmol, 44%) of the polymer P2 as yellow-orange
fibers.
[0310] .sup.1H NMR (400 MHz, CDCl.sub.3): .delta.[ppm]=7.7-6.5 (br.
m, 8 H; H.sub.arom, olefin-H); 4.2-3.6 (br. m, 4.5 H; OCH3, OCH2);
2.8-2.7 ppm (br. m, bisbenzyl), 2.1-0.6 (br. m, 19H; aliph. H).
[0311] Integration of the signal at 2.8-2.7 ppm gave the content of
TBB groups as 4.8%. The .sup.1H NMR spectrum of polymer P2 is
reproduced in FIG. 2.
[0312] GPC: THF+0.25% oxalic acid; column set SDV500, SDV1000,
SDV10000 (PSS), 35.degree. C., UV detection 254 nm, polystyrene
standard: M.sub.w=1.5.times.10.sup.6 g/mol,
M.sub.n=2.8.times.10.sup.5 g/mol.
EXAMPLE P3
[0313] Copolymer comprising 75% of
2,5-bis(chloromethyl)-4-methoxy-3'-(3,7- -dimethyloctyloxy)biphenyl
and 25% of 2,5-bis(chloromethyl)-3',4'-bis(2-me-
thylpropoxy)biphenyl (polymer P3):
[0314] Preparation of
poly(2-(3'-(3,7-dimethyloctyloxy)-5-methoxy)phenyl)--
p-phenylenevinylene)co(2-(3',4'-bis(2-methylpropoxy))phenyl)-p-phenylenevi-
nylene).
[0315] 2.62 g (6.00 mmol) of
2,5-bis(chloromethyl)-4-methoxy-3'-(3,7-dimet- hyloctyloxy)biphenyl
and 0.79 g (2.00 mmol) of 2,5-bis(chloromethyl)-3',4'-
-bis(2-methylpropoxy)biphenyl and 540 ml of dry 1,4-dioxane were
polymerized analogously to Example P2. Double reprecipitation from
THF/MeOH gave 1.30 g (=46%) of the polymer P3 as a fine orange
powder.
[0316] .sup.1H NMR (400 MHz, CDCl.sub.3): .delta.(ppm)=7.7-6.5 (br.
m, 8 H; H.sub.arom, olefin-H); 4.2-3.7 (br. m, 4.75 H; OCH.sub.3,
OCH.sub.2); 2.8-2.7 ppm (br, bisbenzyl), 2.1-0.6 (br. m, 17.75 H;
aliph. H).
[0317] Integration of the signal at 2.8-2.7 ppm gave the content of
TBB groups as 1.8%)
[0318] GPC: THF+0.25% oxalic acid; column set SDV500, SDV1000,
SDV10000 (PSS), 50.degree. C., UV detection 254 nm, polystyrene
standard: M.sub.w=1.2.times.10.sup.6 g/mol,
M.sub.n=1.8.times.10.sup.5 g/mol.
EXAMPLE P4
[0319] Copolymer comprising 25% of
2,5-bis(chloromethyl)-1,4-bis(3,7-dimet- hyloctyloxy)benzene and
75% of 2,5-bis(chloromethyl)-3'-(3,7-dimethyloctyl-
oxy)-4-methoxybiphenyl (polymer P4):
[0320] Preparation of
poly(2,5-(3,7-dimethyloctyloxy)-p-phenylenevinylene)-
co(2-(4'-(3,7-dimethyloctyloxy)phenyl-5-methoxy)-p-phenylenevinylene).
[0321] 0.97 g (2.00 mmol) of
2,5-bis(chloromethyl)-1,4-bis(3',7'-dimethylo- ctyloxy)benzene and
2.62 g (6.00 mmol) of 2,5-bis(chloromethyl)-3'-(3,7-di-
methyloctyloxy)-4-methoxybiphenyl in 590 g of 1,4-dioxane were
polymerized analogously to Example P1. Purification was
accomplished by double dissolution in 300 ml of chlorobenzene
(110.degree. ) and precipitation using ethylene glycol. 1.50 g
(50%) of polymer P4 were obtained as orange flakes.
[0322] .sup.1H NMR (400 MHz, C.sub.2D.sub.2Cl.sub.4, 363K):
.delta.(ppm)=8.0-6.8 (br. m, 6.5 H; H.sub.arom, H.sub.olefin);
4.4-3.7 (br. m, 4.75 H, OCH.sub.3, OCH.sub.2); 2.7 (br. s,
bisbenzyl); 2.0-0.9 (br. m, 23.75 H). Integration of the signal at
2.7 ppm gave a TBB content of 1.0%.
EXAMPLE P5:
[0323] Quaternary copolymer comprising 25% of
2,5-bis(chloromethyl)-1-meth- oxy-4-(3,7-dimethyloctyloxy)benzene,
25% of 2,5-bis(chloromethyl)-1,4-bis(-
3,7-dimethyloctyloxy)benzene, 25% of
2,5-bis(chloromethyl)-3'-(3,7-dimethy- loctyloxy)biphenyl and 25%
of 2,5-bis(chloromethyl)-4-methoxy-3'-(3,7-dime-
thyloctyloxy)biphenyl (polymer P5):
[0324] Preparation of
poly(2-methoxy-5-(3,7-dimethyloctyloxy)-p-phenylenev-
inylene)co(2-(3'-(3,7-dimethyloctyloxy)phenyl)-p-phenylenevinylene)co-(2,5-
-bis(3,7-dimethyloctyloxy)-p-phenylenevinylene)co(5-methoxy-2-(3'-(3,7-dim-
ethyloctyloxy)phenyl)-p-phenylenevinylene) 600 g of dry and
O.sub.2-free 1,4-dioxane were introduced into a dry 1 l four-necked
flask fitted with mechanical stirrer, reflux condenser, thermometer
and dropping funnel, and heated to 98.degree. C. with stirring.
2,5-bis(chloromethyl)-1-methox- y-4-(3,7-dimethyloctyloxy)benzene
(723 mg), 2,5-bis(chloromethyl)-1,4-bis(-
3,7-dimethyloctyloxy)benzene (975 mg),
2,5-bis(chloromethyl)-3'-(3,7-dimet- hyloctyloxy)biphenyl) (815 mg)
and 2,5-bis(chloromethyl)-4-methoxy-3'-(3,7-
-dimethyloctyloxy)biphenyl (875 mg) (2 mmol each), dissolved in 50
ml of dry 1,4-dioxane, were then added. A solution of 2.36 g (21
mmol) of potassium tert-butoxide in 21 ml of dry 1,4-dioxane was
then added dropwise to the vigorously stirred mixture over the
course of 5 minutes. The viscosity of the solution increased
slightly. After the mixture had been stirred at 98.degree. C. for 5
minutes, a further 1.79 g (16 mmol, 2.0 eq) of potassium
tert-butoxide in 16 ml of 1,4-dioxane were added over the course of
one minute. After the mixture had been stirred at
97.degree.-98.degree. C. for a further 2 hours, it was cooled to
45.degree. C., and a mixture of 2.2 ml of acetic acid and 2.2 ml of
1,4-dioxane were then added. After the mixture had been stirred for
a further 20 minutes, the polymer was precipitated by addition of
the reaction solution to 1 l of vigorously stirred water. The
polymer obtained in this way was filtered off and washed twice with
100 ml of methanol each time. Drying at room temperature under
reduced pressure gave 1.71 [lacuna] of crude polymer.
[0325] The crude product was dissolved in 200 ml of THF with
heating to 60.degree. C. and precipitated by addition of 200 ml of
methanol. After the product had been dried under reduced pressure
and washed with 100 ml of methanol, this step was repeated (200 ml
of THF/200 ml of methanol). Drying for two days under reduced
pressure gave 1.13 g (=3.2 mmol, 40%) of the polymer P5 as
pale-orange fibers.
[0326] .sup.1H NMR (400 MHz, CDCl.sub.3): .delta.(ppm)=7.9-6.6 (br.
m; about 9 H); 4.2-3.7 (br. s, 4 H); 2.9-2.8 (br. m, bisbenzyl);
1.9-0.8 (br. m, about 19 H). Integration of the signal at 2.9-2.8
ppm gave a TBB content of 4.7 ppm. GPC: THF+0.25% oxalic acid;
column set SDV500, SDV1000, SDV10000 (PSS), 35.degree. C., UV
detection 254 nm, polystyrene standard: Mw=1.0.times.10.sup.6
g/mol, Mn=1.9.times.10.sup.5 g/mol.
EXAMPLE P6
[0327] Copolymer comprising 50% of
2,5-bis(chloromethyl)-3',4'-bis(2-methy- lpropoxy)biphenyl and 50%
of 2,5-bis(chloromethyl)-4-methoxy-3',4'-bis(2-m-
ethylpropoxy)biphenyl (polymer P6):
[0328] Preparation of
poly[2-(3',4'-bis(2-methylpropoxy))-phenyl-p-phenyle-
nevinylene]co[2-(3',4'-bis(2-methylpropoxy)phenyl)-5-methoxy-p-phenylenevi-
nylene].
[0329] 11.42 g (28.9 mmol) of
2,5-bis(chloromethyl)-3',4'-bis(2-methylprop- oxy)biphenyl (Ex. Z5)
and 12.28 g (28.9 mmol) of 2,5-bis(chloromethyl)-4-m-
ethoxy-3',4'-bis(2-methylpropoxy)biphenyl (Ex. E3) in 3400 ml of
dry 1,4-dioxane were polymerized analogously to Example P2. Double
reprecipitation from THF/MeOH gave 10.5 g (=53%) of the polymer P6
as yellow fibers.
[0330] .sup.1H NMR (400 MHz, CDCl.sub.3): .delta.[ppm]=7.6-6.5 (br.
m, 7.5 H; H.sub.arom, olefin-H); 4.1-3.7 (br. m, 5.5 H; OCH.sub.3,
OCH.sub.2); 2.8-2.7 ppm (br. m, bisbenzyl), 2.1 (br. s, 2H, CH),
1.2-0.8 (br. m, 12 H; aliph. H).
[0331] Integration of the signal at 2.8-2.7 ppm gave the content of
TBB groups as 4.4%).
[0332] GPC: THF+0.25% oxalic acid; column set SDV500, SDV1000,
SDV10000 (PSS), 50.degree. C., UV detection 254 nm, polystyrene
standard: M.sub.w=1.1.times.10.sup.6 g/mol,
M.sub.n=2.5.times.10.sup.05 g/mol.
EXAMPLE P7
Copolymer comprising 50% of
2,5-bis(chloromethyl)-4-methoxy-3'-(3,7-dimeth- yloctyloxy)biphenyl
and 50% of 2,5-bis(chloromethyl)-3'-(3,7-dimethyloctyl-
oxy)biphenyl (polymer P7)
Preparation of
poly[2-(3'-(3,7-dimethyloctyloxy))phenyl-5-methoxy-p-phenyl-
enevinylene]co[2-(3'-(3,7-dimethyloctyloxy))-phenyl-p-phenylenevinylene]
[0333] 12.45 g (28.5 mmol) of
2,5-bis(chloromethyl)-4-methoxy-3'-(3,7-dime- thyloctyloxy)biphenyl
(Ex. E2) and 11.60 g (28.5 mmol) of
2,5-bis(chloromethyl)-3'-(3,7-dimethyloctyloxy)biphenyl (Ex. Z3) in
3400 ml of dry 1,4-dioxane were polymerized at 98.degree. C.
analogously to Example P2. Double reprecipitation from THF/MeOH
gave 8.7 g (=44%) of the polymer P7 as yellow fibers.
[0334] .sup.1H NMR (400 MHz, CDCl.sub.3): .delta.[ppm]=7.8-6.5 (br.
m, 8.5 H; H.sub.arom, olefin-H); H); 4.1-3.6 (br. m, 3.5 H;
OCH.sub.3, OCH.sub.2); 3.0-2.7 ppm (br. m, bisbenzyl); 1.9-0.8 (br.
m, 19 H; aliph. H).
[0335] Integration of the signal at 3.0-2.7 ppm gave the content of
TBB groups as 4.6%.
[0336] GPC: THF+0.25% oxalic acid; column set SDV500, SDV1000,
SDV10000 (PSS), 50.degree. C., UV detection 254 nm, polystyrene
standard: M.sub.w=1.0.times.10.sup.6 g/mol,
M.sub.n=2.4.times.10.sup.5 g/mol.
EXAMPLE P8
Copolymer comprising 50% of
2,5-bis(chloromethyl)-3'-(3,7-dimethyloctyloxy- )biphenyl and 50%
of 2,5-bis(chloromethyl)-4-methoxy-3',4'-bis(2-methylpro-
poxy)biphenyl (polymer P8)
Preparation of
poly[(2-(3'-(3,7-dimethyloctyloxy))phenyl-p-phenylenevinyle-
ne)co(2-(3',4'-bis(2-methylpropoxy))phenyl-5-methoxy-p-phenylenevinylene]
[0337] 11.60 g (28.5 mmol) of
2,5-bis(chloromethyl)-3'-(3,7-dimethyloctylo- xy)biphenyl (Ex. Z3)
and 12.11 g (28.5 mmol) of 2,5-bis(chloromethyl)-4-me-
thoxy-3',4'-bis(2-methylpropoxy)biphenyl (Ex. E3) in 3400 ml of dry
1,4-dioxane were polymerized at 99.degree. C. analogously to
Example P2. Double reprecipitation from THF/MeOH gave 8.13 g (=42%)
of the polymer P8 as fine polymer fibers.
[0338] .sup.1H NMR (400 MHz, CDCl.sub.3): .delta.[ppm]=7.9-6.6 (br.
m, 8 H; H.sub.arom, olefin-H); 4.1-3.6 (br. m, 4.5 H; OCH.sub.3,
OCH.sub.2); 2.9-2.6 ppm (br. m, bisbenzyl); 2.13 (br. s, 1H, CH);
1.9-0.8 (br. m, 15.5 H; aliph. H).
[0339] Integration of the signal at 2.9-2.6 ppm gave the content of
TBB groups as 5.0%)
[0340] GPC: THF+0.25% oxalic acid; column set SDV500, SDV1000,
SDV10000 (PSS), 50.degree. C., UV detection 254 nm, polystyrene
standard: M.sub.w=1.3.times.10.sup.6 g/mol,
M.sub.n=2.3.times.10.sup.5 g/mol.
EXAMPLE P9
Copolymer comprising 50% of
2,5-bis(chloromethyl)-3'-(3,7-dimethyloctyloxy- )biphenyl and 50%
of 2,5-bis(chloromethyl)-4-fluoro-3',4'-bis(2-methylprop-
oxy)biphenyl (polymer P9)
Preparation of
poly[(2-(3'-(3,7-dimethyloctyloxy))phenyl-p-phenylenevinyle-
ne)co(2-(3',4'-bis(2-methylpropoxy))phenyl-5-fluoro-p-phenylenevinylene]
[0341] 5.80 g (14.23 mmol) of
2,5-bis(chloromethyl)-3'-(3,7-dimethyloctylo- xy)biphenyl (Ex. Z3)
and 5.88 g (14.23 mmol) of 2,5-bis(chloromethyl)-4-fl-
uoro-3',4'-bis(2-methylpropoxy)biphenyl (Ex. E7) in 3200 ml of dry
1,4-dioxane were polymerized at 98.degree. C. analogously to
Example P2. Double reprecipitation from THF/MeOH gave 8.13 g (=42%)
of the polymer P9 as a yellow powder.
[0342] .sup.1H NMR (400 MHz, CDCl.sub.3): .delta.[ppm]=8.0-6.6 (br.
m, 8 H; H.sub.arom, olefin-H); 4.2-3.6 (br. m, 3 H; OCH.sub.3,
OCH.sub.2); 3.0-2.6 ppm (br. m, bisbenzyl); 2.1 (br. s, 1H, CH);
1.9-0.8 (br. m, 15.5 H; aliph. H).
[0343] Integration of the signal at 3.0-2.6 ppm gave the content of
TBB groups as 8.5%)
[0344] GPC: THF+0.25% oxalic acid; column set SDV500, SDV1000,
SDV10000 (PSS), 50.degree. C., UV detection 254 nm, polystyrene
standard: M.sub.w=9.5.times.10.sup.5 g/mol,
M.sub.n=1.1.times.10.sup.5 g/mol.
EXAMPLE P10
Copolymer comprising 40% of
2,5-bis(chloromethyl)-4-chloro-4'-(3,7-dimethy- loctyloxy)biphenyl
and 60% of 2,5-bis(chloromethyl)-3',4'-bis(2-methylprop-
oxy)biphenyl (polymer P10)
Preparation of
poly[(2-(4'-(3,7-dimethyloctyloxy)phenyl)-5-chloro-p-phenyl-
enevinylene)co(2-(3',4'-bis(2-methylpropoxy))phenyl-p-phenylenevinylene]
[0345] 2.83 g (6.4 mmol) of
2,5-bis(chloromethyl)-4-chloro-4'-(3,7-dimethy- loctyloxy)biphenyl
(Ex. E8) and 3.79 g (9.6 mmol) of
2,5-bis(chloromethyl)-3',4'-bis(2-methylpropoxy)biphenyl (Ex. Z5)
in 1100 ml of dry 1,4-dioxane were polymerized at 98.degree. C.
analogously to Example P2. Double reprecipitation from
chlorobenzene/MeOH gave 1.6 g (=42%) of the polymer P10 as a yellow
powder.
[0346] .sup.1H NMR (400 MHz, CDCl.sub.3): .delta.[ppm]=8.0-6.6 (br.
m, 8 H; H.sub.arom, olefin-H); 4.1-3.6 (br. m, 3.2 H; OCH.sub.3,
OCH.sub.2); 3.0-2.7 ppm (br. m, bisbenzyl); 2.2 (br. s, 1H, CH);
1.9-0.8 (br. m, 15 H; aliph. H).
[0347] Integration of the signal at 3.0-2.7 ppm gave a content of
TBB groups of 9.5%.
EXAMPLE P11
Copolymer comprising 50% of 1
,4-bis(chloromethyl)-2-(3,7-dimethyloctyloxy- )-5-methoxybenzene,
30% of 2,5-bis(chloromethyl)-4-methoxy-3'-(3,7-dimethy-
loctyloxy)biphenyl and 20% of
2,5-bis(chloromethyl)-3'-(3,7-dimethyloctylo- xy)biphenyl (polymer
P11)
Preparation of
poly[2-methoxy-5-(3,7-dimethyloctyloxy)-p-phenylenevinylene-
]co[2-(3'-(3,7-dimethyloctyloxy)phenyl)-5-methoxy-p-phenylenevinylene]co[2-
-(3'-(3,7-dimethyloctyloxy))-phenyl-p-phenylenevinylene]
[0348] 7.47 g (28.5 mmol) of
1,4-bis(chloromethyl)-2-(3,7-dimethyloctyloxy- )-5-methoxybenzene
(Ex. Z1), 6.22 g (17.1 mmol) of 2,5-bis(chloromethyl)-4-
-methoxy-3'-(3,7-dimethyloctyloxy)biphenyl (Ex. E2) and 4.64 g
(11.4 mmol) of
2,5-bis(chloromethyl)-3'-(3,7-dimethyloctyloxy)biphenyl (Ex. Z3) in
3450 ml of dry 1,4-dioxane were polymerized at 98-100.degree. C.
analogously to Example P2. Double reprecipitation from THF/MeOH
gave 7.9 g (=43%) of the polymer P11 as orange-red fibers.
[0349] .sup.1H NMR (400 MHz, CDCl.sub.3): .delta.[ppm]=7.7-6.4 (br.
m, 6.2 H; H.sub.arom, olefin-H); 4.1-3.6 (br. m, 4.4 H; OCH.sub.3,
OCH.sub.2); 3.0-2.8 ppm (br. m, bisbenzyl); 1.9-0.8 (br. m, 19 H;
aliph. H).
[0350] Integration of the signal at 3.0-2.8 ppm gave the content of
TBB groups as 3.3%.
[0351] GPC: THF+0.25% oxalic acid; column set SDV500, SDV1000,
SDV10000 (PSS), 50.degree. C., UV detection 254 nm, polystyrene
standard: M.sub.w=1.0.times.10.sup.6 g/mol,
M.sub.n=2.4.times.10.sup.5 g/mol.
EXAMPLE P12
Copolymer comprising 25% of
2,5-bis(chloromethyl)-3'-(3,7-dimethyloctyloxy- )biphenyl, 25% of
2,5-bis(chloromethyl)-4-methoxy-3'-(3,7-dimethyloctyloxy-
)biphenyl, 25% of
2,5-bis(chloromethyl)-4-methoxy-3',4'-bis(2-methylpropox-
y)biphenyl and 25% of
2,5-bis(chloromethyl)-3',4'-bis(2-methylpropoxy)biph- enyl (polymer
P12)
[0352] 5.80 g (14.2 mmol) of
2,5-bis(chloromethyl)-3'-(3,7-dimethyloctylox- y)biphenyl (Ex. Z3),
6.22 g (14.2 mmol) of 2,5-bis(chloromethyl)-4-methoxy-
-3'-(3,7-dimethyloctyloxy)biphenyl (Ex. E2), 6.05 g (14.2 mmol) of
2,5-bis(chloromethyl)-4-methoxy-3',4'-bis(2-methylpropoxy)biphenyl
(Ex. E3) and 5.63 g (14.2 mmol) of
2,5-bis(chloromethyl)-3',4'-bis(2-methylpro- poxy)biphenyl (Ex. Z5)
in 3400 ml of dry 1,4-dioxane were polymerized at 99.degree. C.
analogously to Example P2. Neutralization, precipitation and double
reprecipitation from THF/MeOH gave 9.12 g (47%) of the polymer P12
as fine yellow fibers.
[0353] .sup.1H NMR (400 MHz, CDCl.sub.3): .delta.[ppm]=7.7-6.5 (br.
m, 8 H; H.sub.arom, olefin-H); 4.1-3.6 (br. m, 4.5 H; OCH.sub.3,
OCH.sub.2); 2.9-2.6 ppm (br. m, bisbenzyl); 2.14 (br. s, 1H, CH);
1.9-0.8 (br. m, 15.5 H; aliph. H).
[0354] Integration of the signal at 2.9-2.6 ppm gave the content of
TBB groups as 6.0%.
[0355] GPC: THF+0.25% oxalic acid; column set SDV500, SDV1000,
SDV10000 (PSS), 50.degree. C., UV detection 254 nm, polystyrene
standard: M.sub.w=1.1.times.10.sup.6 g/mol,
M.sub.n=1.8.times.10.sup.5 g/mol.
EXAMPLE P13
Copolymer comprising 50% of
2,5-bis(chloromethyl)-3'-(3,7-dimethyloctyloxy- )biphenyl and 50%
of 2,5-bischloromethyl-4-(3,7-dimethyloctyloxy)biphenyl (polymer
P13)
Preparation of
poly[(2-(3'-(3,7-dimethyloctyloxy))phenyl-p-phenylenevinyle-
ne)co(2-phenyl-5-(3,7-dimethyloctyloxy)-p-phenylenevinylene)]
[0356] 8.85 g (21.7 mmol) of
2,5-bis(chloromethyl)-3'-(3,7-dimethyloctylox- y)biphenyl (Ex. Z3)
and 8.85 g (21.7 mmol) of 2,5-bischloromethyl-4-(3,7-d-
imethyloctyloxy)-biphenyl (Ex. E9) in 2250 g of dry 1,4-dioxane
were polymerized at 99.degree. C. analogously to Example P2. Double
reprecipitation from THF/MeOH gave 7.6 g (=52%) of the polymer P13
as a yellow powder.
[0357] .sup.1H NMR (400 MHz, CDCl.sub.3): .delta.[ppm]=7.7-6.6 (br.
m, 9 H; H.sub.arom, olefin-H); 4.4-3.6 (br. m, 2 H; OCH.sub.3,
OCH.sub.2); 2.9-2.6 ppm (br. m, bisbenzyl); 1.9-0.8 (br. m, 19 H;
aliph. H).
[0358] Integration of the signal at 2.9-2.6 ppm gave the content of
TBB groups as 7.0%.
[0359] GPC: THF+0.25% oxalic acid; column set SDV500, SDV1000,
SDV10000 (PSS), 50.degree. C., UV detection 254 nm, polystyrene
standard: M.sub.w=1.1.times.10.sup.6 g/mol,
M.sub.n=1.3.times.10.sup.5 g/mol.
EXAMPLE P14
Copolymer comprising 50% of
2,5-bis(chloromethyl)-3',4'-bis(2-methylpropox- y)biphenyl and 50%
of 2,5-bis(chloromethyl)-3'-(3,7-dimethyloctyloxy)-4-fl-
uorobiphenyl (polymer P14)
Preparation of
poly[(2-(3',4'-bis(2-methylpropoxy)phenyl)-p-phenylenevinyl-
ene)co(2-(3'-(3,7-dimethyloctyloxy))phenyl-5-fluoro-p-phenylenevinylene)]
[0360] 3.26 g (8.25 mmol) of
2,5-bis(chloromethyl)-3',4'-bis(2-methylpropo- xy)biphenyl (Ex. Z5)
and 3.51 g (8.25 mmol) of 2,5-bis(chloromethyl)-4-flu-
oro-3',4'-bis(2-methylpropoxy)biphenyl (Ex. E6) in 1000 ml of dry
1,4-dioxane were polymerized at 98.degree. C. analogously to
Example P2. Double reprecipitation from THF/MeOH gave 3.3 g (=59%)
of the polymer P14 as a yellow powder.
[0361] .sup.1H NMR (400 MHz, CDCl.sub.3): .delta.[ppm]=7.9-6.5 (br.
m, 8 H; H.sub.arom, olefin-H); 4.2-3.5 (br. m, 3 H; OCH.sub.3,
OCH.sub.2); 2.9-2.5 ppm (br. s, bisbenzyl); 2.2-0.8 (br. m, 16.5 H;
aliph. H).
[0362] Integration of the signal at 2.9-2.5 ppm gave the content of
TBB groups as 8.5%.
[0363] .sup.19F NMR (376 MHz, CDCl.sub.3): .delta.[ppm]=120 (br.
m); using an internal reference (C.sub.6F.sub.6), it was found that
the proportion of fluorine-containing groups is 50%.
[0364] GPC: THF+0.25% oxalic acid; column set SDV500, SDV1000,
SDV10000 (PSS), 50.degree. C., UV detection 254 nm, polystyrene
standard: M.sub.w=1.05.times.10.sup.6 g/mol,
M.sub.n=1.9.times.10.sup.5 g/mol.
EXAMPLE P15
Copolymer comprising 50% of
2,5-bis(chloromethyl)-3'-(3,7-dimethyloctyloxy- )biphenyl and 50%
of 2,5-bischloromethyl-4,2',5'-trimethoxybiphenyl (polymer P15)
Preparation of
poly[(2-(3'-(3,7-dimethyloctyloxy))phenyl)-p-phenylenevinyl-
ene)co(2-(2',5'-dimethoxy)phenyl)-5-methoxy-p-phenylenevinylene]
[0365] 3.36 g (8.25 mmol) of
2,5-bis(chloromethyl)-3'-(3,7-dimethyloctylox- y)biphenyl (Ex. Z3)
and 2.82 g (8.25 mmol) of 2,5-bis(chloromethyl)-4,2',5-
'-trimethoxybiphenyl (Ex. E4) in 1000 ml of dry 1,4-dioxane were
polymerized at 98-100.degree. C. analogously to Example P2. Double
reprecipitation from THF/MeOH gave 1.95 g (=54%) of the polymer P15
as a yellow powder.
[0366] .sup.1H NMR (400 MHz, CDCl.sub.3): .delta.[ppm]=7.6-6.6 (br.
m, 8 H; H.sub.arom, olefin-H); 4.4-3.6 (br. m, 5.5 H; OCH.sub.3,
OCH.sub.2); 2.9-2.6 ppm (br. s, bisbenzyl); 2.0-0.8 (br. m, 9.5 H;
aliph. H).
[0367] Integration of the signal at 2.9-2.6 ppm gave the content of
TBB groups as 5.5%.
[0368] .sup.19F NMR (376 MHz, CDCl.sub.3): .delta.[ppm]=116 (br.
s); using an internal reference (C.sub.6F.sub.6) it was found that
the proportion of fluorine-containing groups is 50%.
[0369] GPC: THF+0.25% oxalic acid; column set SDV500, SDV1000,
SDV10000 (PSS), 50.degree. C., UV detection 254 nm, polystyrene
standard: M.sub.w=10.times.10.sup.6 g/mol,
M.sub.n=1.9.times.10.sup.5 g/mol.
EXAMPLE P16
Copolymer comprising 30% of
2,5-bis(chloromethyl)-3'-(3,7-dimethyloctyloxy- )biphenyl, 30% of
2,5-bis(chloromethyl)-3',4'-bis(2-methylpropoxy)biphenyl and 40% of
2,5-bis(chloromethyl)-4-methoxy-2',5'-dimethylbiphenyl (polymer
P16)
[0370] 6.96 g (16.6 mmol) of
2,5-bis(chloromethyl)-3'-(3,7-dimethyloctylox- y)biphenyl (Ex. Z3),
6.75 [lacuna] (16.6 mmol) of 2,5-bis(chloromethyl)-3'-
,4'-bis(2-methylpropoxy)biphenyl (Ex. Z5) and 7.04 g (22.1 mmol) of
2,5-bis(chloromethyl)-4-methoxy-2',5'-dimethylbiphenyl (Ex. E5) in
3400 ml of dry 1,4-dioxane were polymerized at 98.degree. C.
analogously to Example P2. Double reprecipitation from THF/MeOH
gave 6.70 g (=40%) of the polymer P16 as green-yellow fibers.
[0371] .sup.1H NMR (400 MHz, CDCl.sub.3): .delta.[ppm]=7.8-6.6 (br.
m, 7.9 H; H.sub.arom, olefin-H); 4.2-3.6 (br. m, 3 H; OCH.sub.3,
OCH.sub.2); 2.9-2.7 ppm (br. s, bisbenzyl); 2.4-0.8 (br. m, 12.3 H;
aliph. H).
[0372] Integration of the signal at 2.9-2.7 ppm gave the content of
TBB groups as 4.0%.
[0373] GPC: THF+0.25% oxalic acid; column set SDV500, SDV1000,
SDV10000 (PSS), 50.degree. C., UV detection 254 nm, polystyrene
standard: M.sub.w=1.2.times.10.sup.6 g/mol,
M.sub.n=2.7.times.10.sup.5 g/mol.
EXAMPLE P17
Copolymer comprising 50% of
2,5-bis(chloromethyl)-3'-(3,7-dimethyloctyloxy- )biphenyl and 50%
of 2,5-bis(chloromethyl)-4-methoxy-3',5'-bisfluorobiphen- yl
(polymer P9)
Preparation of
poly[(2-(3'-(3,7-dimethyloctyloxy))phenyl)-p-phenylenevinyl-
ene)co(2-3',5'-difluorophenyl-5-methoxy-p-phenylenevinylene)]
[0374] 4.27 g (10.5 mmol) of
2,5-bis(chloromethyl)-3'-(3,7-dimethyloctylox- y)biphenyl (Ex. Z3)
and 3.35 g (10.5 mmol) of 2,5-bis(chloromethyl)-4-meth-
oxy-3',5'-bisfluorobiphenyl (Ex. E10) in 2500 ml of dry 1,4-dioxane
were polymerized at 98.degree. C. analogously to Example P2. Double
reprecipitation from THF/MeOH gave 2.99 g (=49%) of the polymer P9
as a yellow powder.
[0375] .sup.1H NMR (400 MHz, CDCl.sub.3): .delta.[ppm]=8.1-6.6 (br.
m, 8 H; H.sub.arom, olefin-H); 4.2-3.6 (br. m, 2.5 H; OCH.sub.3,
OCH.sub.2); 3.0-2.6 ppm (br. s, bisbenzyl); 2.1 (br. s, 1H, CH);
1.9-0.8 (br. m, 9.5 H; aliph. H).
[0376] Integration of the signal at 3.0-2.6 ppm gave the content of
TBB groups as 4.5%.
[0377] GPC: THF+0.25% oxalic acid; column set SDV500, SDV1000,
SDV10000 (PSS), 50.degree. C., UV detection 254 nm, polystyrene
standard: M.sub.w=9.times.10.sup.5 g/mol,
M.sub.n=1.8.times.10.sup.5 g/mol.
[0378] V. Synthesis of Comparative Examples Not According to the
Invention
EXAMPLE V1
Copolymer comprising 50% of
2,5-bis(chloromethyl)-1-methoxy-4-(3,7-dimethy- loctyloxy)benzene
and 50% of 2,5-bis(chloromethyl)-3'-(3,7-dimethyloctylox-
y)biphenyl (polymer V1)
Preparation of
poly(2-methoxy-5-(3,7-dimethyloctyloxy)-p-phenylenevinylene-
)co(2-(3'-(3,7-dimethyloctyloxy)phenyl)-p-phenylenevinylene)
[0379] 3.5 l of dry and O.sub.2-free 1,4-dioxane were introduced
into a dry 6 l four-necked flask fitted with mechanical stirrer,
reflux condenser, thermometer and dropping funnel, and heated to
95.degree. C. with stirring. 9.00 g (24.9 mmol) of
2,5-bis(chloromethyl)-1-methoxy-4-(3- ,7-dimethyloctyloxy)benzene
and 10.13 g (24.9 mmol) of
2,5-bis(chloromethyl)-3'-(3,7-dimethyloctyloxy)biphenyl, dissolved
in 30 ml of dry 1,4-dioxane, were then added. A solution of 13.97 g
(124.5 mmol, 2.5 eq) of potassium tert-butoxide in 125 ml of dry
1,4-dioxane was then added dropwise to the vigorously stirred
mixture over the course of 5 minutes. During the course of this
addition, the color changed from colorless via yellow to
orange-red. After the mixture had been stirred at 95-96.degree. C.
for 5 minutes, the same amount (13.97 g, 124.5 mmol, 2.5 eq) of
potassium tert-butoxide in 125 ml of 1,4-dioxane was again added
over the course of one minute. After the mixture had been stirred
at 95.degree.-97.degree. C. for a further two hours, it was cooled
to 55.degree. C., and a mixture of 30 ml of acetic acid and 30 ml
of 1,4-dioxane was added. 1.8 l of water were added to the
solution, which was then pale orange, over the course of 5 minutes
with vigorous stirring. The precipitated polymer was filtered off
and washed twice with 100 ml of methanol each time. Drying under
reduced pressure gave 14.1 g of crude polymer.
[0380] The crude polymer was dissolved in 1.8 l of THF with heating
to 60.degree. C. and precipitated by addition of 2 l of methanol.
After the product had been dried under reduced pressure and washed
with 200 ml of methanol, this step was repeated. Drying for two
days under reduced pressure gave 10.80 g (=34.7 mmol, 70%) of the
polymer V1 as pale-orange fibers.
[0381] .sup.1H NMR (400 MHz, CDCl.sub.3): (ppm)=7.9-6.6 (br. m; 6.5
H); 4.2-3.6 (br. m, 3.5 H); 3.0-2.6 (br. M; 7.2% bisbenzyl);
2.0-0.95 (br. m, 10H); 0.86, 0.84 (2 s, 9H).
[0382] GPC: THF+0.25% oxalic acid; column set SDV500, SDV1000,
SDV10000 (PSS), 35.degree. C., UV detection 254 nm, polystyrene
standard: M.sub.w=7.4.times.10.sup.5 g/mol,
M.sub.n=7.times.10.sup.4 g/mol.
[0383] The .sup.1H-NMR spectrum of the polymer V1 is reproduced in
FIG. 1.
EXAMPLE V2
Copolymer comprising 50% of
2,5-bis(chloromethyl)-3'-(3,7-dimethyloctyloxy- )biphenyl and 50%
of 2,5-bis(chloromethyl)-3',4'-bis(2-methylpropoxy)biphe- nyl
(polymer V2)
Preparation of
poly(2-(3'-(3,7-dimethyloctyloxy)phenyl)-p-phenylenevinylen-
e)co(2-(3',4'-2-methylpropoxy)phenyl)-p-phenylenevinylene)
[0384] 600 ml of dry 1,4-dioxane were introduced into a heat-dried
1 l four-necked flask fitted with mechanical Teflon stirrer,
high-efficiency condenser, thermometer and dropping funnel,
degassed by passing through N.sub.2 for 15 minutes and then heated
to gentle reflux (99.degree. C.) with stirring. 1.63 g (4.00 mmol)
of 2,5-bis(chloromethyl)-3'-(3,7-dimeth- yloctyloxy)biphenyl and
1.58 g (4.00 mmol) of [lacuna], dissolved in 20 ml of dry
1,4-dioxane, were subsequently added. A solution of 2.36 g (21
mmol, 2.6 eq) of potassium tert-butoxide in 21 ml of dry
1,4-dioxane was then added dropwise to the vigorously stirred
mixture over the course of 5 minutes. During the addition of the
base, the following color change was observed:
colorless--yellow--yellow-green. After the mixture had been stirred
at this temperature for a further 5 minutes, a further 1.80 g (16
mmol, 2.0 eq) of potassium tert-butoxide in 16 ml of dry
1,4-dioxane were added over the course of one minute. The
temperature was held at 98-99.degree. C. for a further 2 hours;
after this time, the mixture was cooled to 45.degree. C., and a
mixture of 2.5 ml of acetic acid and 2.5 ml of 1,4-dioxane was
added. The color of the reaction mixture became somewhat paler
during this addition, and the viscosity rose. The reaction mixture
was stirred for 20 minutes and poured into 0.65 l of vigorously
stirred water. 100 ml of methanol were added, and the mixture was
stirred for a further 20 minutes. Filtration through a
polypropylene circular filter, rinsing twice with methanol and
drying under reduced pressure gives 1.30 g (3.93 mmol, 49%) of
crude polymer as yellow fibers.
[0385] After the crude polymer has been dried at room temperature
under reduced pressure, purification is carried out by double
dissolution in 100 ml of THF each time and precipitation using 100
ml of methanol each time. Drying gave 0.99 g (3.00 mmol, 38%) of
polymer V2 as yellow fibers.
[0386] .sup.1H NMR (400 MHz, CDCl.sub.3): .delta.(ppm)=7.8-6.5,
beneath this br. s at 6.9 (br. m; 8.8 H); 4.0 (br. s, 1.6 H);
3.0-2.6 ppm (br. m, 12% bisbenzyl); 2.3 (br. s, 0.6 H, CH.sub.3);
2.0 (br. s, 0.6 H, CH.sub.3); 1.8, 1.65, 1.55, 1.3, 1.15
(5.times.s, together 8 H; alkyl-H); 0.91, 0.85 (2.times.s, 7.2H;
3.times.CH.sub.3).
[0387] GPC: THF+0.25% oxalic acid; column set SDV500, SDV1000,
SDV10000 (PSS), 35.degree. C., UV detection 254 nm, polystyrene
standard: M.sub.w=1.8.times.10.sup.6 g/mol,
M.sub.n=3.9.times.10.sup.5 g/mol.
[0388] The .sup.1H-NMR spectrum of the polymer V2 is reproduced in
FIG. 2.
EXAMPLE V3
Copolymer comprising 50% of
2,5-bis(chloromethyl)-1-methoxy-4-(3,7-dimethy- loctyloxy)benzene
and 50% of 2,5-bis(chloromethyl)-4'-(3,7-dimethyloctylox-
y)biphenyl (polymer V3)
Preparation of
poly(2-methoxy-5-(3,7-dimethyloctyloxy)-p-phenylenevinylene-
)co(2-(4'-(3,7-dimethyloxtyloxy)phenyl)-p-phenylenevinylene)
[0389] 3400 ml of dry and O.sub.2-free 1,4-dioxane were heated to
97.degree. C in a dry 6 l four-necked flask fitted with mechanical
Teflon stirrer, reflux condenser, thermometer and dropping funnel.
A solution of 8.44 g (23.35 mmol) of
2,5-bis(chloromethyl)-1-methoxy-4-(3',7'-dimethylo- ctyloxy)benzene
and 9.52 g (23.35 mmol) of 2,5-bis(chloromethyl)-4'-(3,7-d-
imethyloctyloxy)biphenyl in 50 ml of dry 1,4-dioxane was then
added. A solution of 13.10 9 (117 mmol) of potassium tert-butoxide
in 117 ml of dry 1,4-dioxane was then added dropwise to the
vigorously stirred mixture over the course of 5 minutes. During
this addition, the color changed from colorless via yellow to
orange-red. After 5 minutes, a further 10.48 g (93 mmol) of
potassium tert-butoxide, dissolved in 93 ml of 1,4-dioxane, were
added. After the mixture had been stirred at 95-97.degree. C. for 2
hours, it was cooled to 45.degree. C., and a mixture of 19 ml of
acetic acid and 20 ml of 1,4-dioxane was added. The solution, which
was then orange, was poured into 4 l of vigorously stirred water.
The precipitated polymer was isolated by filtration through a
polypropylene filter and dried under reduced pressure. The crude
yield was 12.65 g (40.6 mmol, 87%).
[0390] The polymer was dissolved in 1690 ml of THF with heating to
60.degree. C. and precipitated by addition of 1700 ml of methanol
at 40.degree. C. After the product had been dried under reduced
pressure, this step was repeated. Drying under reduced pressure
gave 7.10 g (=22.79 mmol, 49%) of the polymer V3 as pale-orange
fibers.
[0391] .sup.1H NMR (400 MHz, CDCl.sub.3): .delta.(ppm)=7.9-6.9 (br.
m, 6.5 H); 4.2-3.6 (br. m, 3.5 H); 2.9-2.6 (br. m, 7% bisbenzyl);
2.0-0.9 (br. m, 10H); 0.89, 0.86 (2 s, 9H).
[0392] GPC: THF+0.25% oxalic acid; column set SDV500, SDV1000,
SDV10000 (PSS), 35.degree. C., UV detection 254 nm, polystyrene
standard: M.sub.w=1.5.times.10.sup.6 g/mol,
M.sub.n=2.8.times.10.sup.5 g/mol.
EXAMPLE V4
Quaternary copolymer comprising 2% of
2,5-bis(chloromethyl)-1-methoxy-4-(3- ,7-dimethyloctyloxy)benzene,
13% of 2,5-bis(chloromethyl)-2',5'-dimethylbi- phenyl, 25% of
2,5-bis(chloromethyl)-3'-(3,7-dimethyloctyloxy)biphenyl and 60% of
2,5-bis(chloromethyl)-4'-(3,7-dimethyloctyloxy)biphenyl (polymer
V4)
Preparation of
poly(2-methoxy-5-(3,7-dimethyloctyloxy)-p-phenylenevinylene-
)co(2-(3'-(3,7-dimethyloctyloxy)phenyl)-p-phenylenevinylene)phenylenevinyl-
ene)co(2-(4'-(3,7-dimethyloctyloxy)phenyl)-p-phenylenevinylene)co(2-(2',5'-
-dimethyl)phenyl)-p-phenylenevinylene)
[0393] 3.55 kg (3.40 l ) of dry and O.sub.2-free 1,4-dioxane were
introduced into a dry 6 l four-necked flask fitted with mechanical
stirrer, reflux condenser, thermometer and dropping funnel, and
heated to 98.degree. C. with stirring. A solution of 240 mg (0.66
mmol) of
2,5-bis(chloromethyl)-1-methoxy-4-(3,7-dimethyloctyloxy)benzene,
3.38 g (8.29 mmol) of
2,5-bis(chloromethyl)-3'-(3,7-dimethyloctyloxy)biphenyl, 8.11 g
(19.9 mmol) of 2,5-bis(chloromethyl)-4'-(3,7-dimethyloctyloxy)biph-
enyl and 1.20 g (4.31 mmol) of
2,5-bis(chloromethyl)-2',5'-dimethylbipheny- l, dissolved in 50 ml
of dry 1,4-dioxane, was then added. A solution of 9.30 g (82.9
mmol, 2.6 eq) of potassium tert-butoxide in 83 ml of dry
1,4-dioxane was then added dropwise to the vigorously stirred
mixture over the course of 5 minutes. The viscosity of the solution
increased slightly. After the mixture had been stirred at
98.degree. C. for 5 minutes, a further 7.44 g (66.3 mmol, 2.0 eq)
of potassium tert-butoxide in 66 ml of 1,4-dioxane were added over
the course of one minute. After the mixture had been stirred at
97.degree.-98.degree. C. for a further 2 hours, it was cooled to
45.degree. C., and a mixture of 19.1 ml of acetic acid and 20 ml of
1,4-dioxane was added. The polymer was stirred for a further 20
minutes and precipitated by addition of the reaction solution to 4
l of vigorously stirred water. The polymer obtained in this way was
filtered off and washed twice with 300 ml of methanol each time.
Drying at room temperature under reduced pressure gave 10.40 g
(32.8 mmol, 99%) of crude polymer.
[0394] The crude product was dissolved in 1390 ml of THF with
heating to 60.degree. C. and precipitated by addition of 1.4 l of
methanol. After the product had been dried under reduced pressure
and washed with 100 ml of methanol, this step was repeated (800 ml
of THF/800 ml of methanol). Drying for two days under reduced
pressure gave 7.90 g (=24.9 mmol, 75%) of the polymer V4 as
pale-orange fibers.
[0395] .sup.1H NMR (400 MHz, CDCl.sub.3): .delta.(ppm)=7.9-6.6 (br.
m; about 9 H); 4.0 (br. s, about 2 H); 2.9-2.6 (br. m, 12%
bisbenzyl); 2.4, 2.1 (2.times.br. s, 2.times.each H); 1.9-0.8 (br.
m, about 19 H).
[0396] GPC: THF+0.25% oxalic acid; column set SDV500, SDV1000,
SDV10000 (PSS), 35.degree. C., UV detection 254 nm, polystyrene
standard: M.sub.w=7.8.times.10.sup.5 g/mol,
M.sub.n=1.9.times.10.sup.5 g/mol.
EXAMPLE V5
Copolymer comprising 82% of
2,5-bis(chloromethyl)-1-(3,7-dimethyloctyloxy)- -4-methoxybenzene
and 18% of 2,5-bis(chloromethyl)-3'-(3,7-dimethyloctylox-
y)-4-methoxybiphenyl (polymer V5)
Preparation of
poly(2-(3,7-dimethyloctyloxy)-5-methoxy-p-phenylenevinylene-
)co(2-(3'-(3,7-dimethyloctyloxy)phenyl)-5-methoxy-p-phenylenevinylene)
[0397] 540 ml of dry and O.sub.2-free 1,4-dioxane were heated to
98.degree. C. in a dry 1 l four-necked flask fitted with mechanical
Teflon stirrer, reflux condenser, thermometer and dropping funnel.
A solution of 2.37 g (6.56 mmol) of
2,5-bis(chloromethyl)-1-(3,7-dimethyloc- tyloxy)-4-methoxybenzene
and 0.630 g (1.44 mmol) of
2,5-bis(chloromethyl)-3'-(3,7-dimethyloctyloxy)-4-methoxybiphenyl
in 10 ml of dry 1,4-dioxane was then added. A solution of 2.47 g
(22 mmol) of potassium tert-butoxide in 22 ml of dry 1,4-dioxane
was then added dropwise to the vigorously stirred mixture over the
course of 5 minutes. During this addition, the color changed from
colorless via yellow to orange-red. After 5 minutes, a further 2.47
g (22 mmol) of potassium tert-butoxide, dissolved in 22 ml of
1,4-dioxane, were added. After the mixture had been stirred at
98-99.degree. C. for 2 hours, it was cooled to 42.degree. C. A
mixture of 6 ml of acetic acid and 6 ml of 1,4-dioxane was then
added. The orange, cloudy solution was poured into 0.6 l of
vigorously stirred water. The polymer, which precipitated in flake
form, was isolated by filtration through a polypropylene filter and
dried under reduced pressure. The crude yield was 2.46 g (6.56
mmol, 82%).
[0398] The polymer was dissolved in 330 ml of THF with heating to
reflux. It was precipitated by dropwise addition of 350 ml of
methanol. After the product had been dried under reduced pressure,
it was dissolved in 300 ml of THF and precipitated by addition of
300 ml of methanol. Washing with methanol and drying under reduced
pressure gave 1.62 g (=4.32 mmol, 54%) of polymer V5 as orange
fibers.
[0399] .sup.1H NMR (400 MHz, CDCl.sub.3): .delta.(ppm) =7.9-6.5
(br. m, 4.7 H); 4.4-3.6 (br. m, 5 H); 3.0-2.7 (br. m, 3.5%
bisbenzyl); 2.0-0.7 (br. m, 19 H).
[0400] Owing to the tendency of polymer V5 to gel, a GPC
measurement could not be carried out.
EXAMPLE V6
Polymerization of
2,5-bis(chloromethyl)-3'-(3,7-dimethyloctyloxy)biphenyl (polymer
V6) by dehydrohalogenation
Preparation of
poly[2-(3'-(3,7-dimethyloctyloxy)phenyl)-p-phenylenevinylen- e]
[0401] 640 g (619 ml) of dry 1,4-dioxane were introduced into a dry
reaction apparatus (2 l four-necked round-bottomed flask fitted
with reflux condenser, mechanical stirrer, dropping funnel and
thermometer) and degassed by passing through N.sub.2 for 15
minutes. After switching over to an N.sub.2 blanket, the dioxane
was heated to 98.degree. C. 3.26 g (8.00 mmol) of
2,5-bis(chloromethyl)-3'-(3,7-dimethyloctyloxy)biphenyl (dissolved
in 30 ml of dry 1,4-dioxane) were then added to the boiling
solution. A solution of 2.33 g (20.8 mmol, 2.6 eq) of potassium
tert-butoxide in 21 ml of dry 1,4-dioxane was added dropwise over
the course of 5 minutes; during this addition, the color of the
reaction mixture changed from colorless to green. After 5 minutes,
a further 1.8 g (16 mmol, 2 eq) of potassium tert-butoxide
(dissolved in 18 ml of dry 1,4-dioxane) were added over the course
of one minute. The mixture was stirred at 98.degree. C. for a
further 2 hours, during which the color changed from green to
yellow-green. The reaction solution was cooled to 50.degree. C.,
and a mixture of 3 ml of acetic acid and 3 ml of 1,4-dioxane was
added. The mixture was stirred for a further 20 minutes and then
poured into 700 ml of water with vigorous stirring. After 100 ml of
methanol had been added, the polymer (fine green fibers) was
filtered off with suction through a polypropylene circular filter
and washed with 100 ml of methanol/water 1:1 and then with 100 ml
of pure methanol. Drying at room temperature under reduced pressure
gave 2.60 g (7.77 mmol, 97%) of crude polymer V6.
[0402] The purification was carried out by dissolving the polymer
in 300 ml of THF (60.degree. C.), cooling to 30.degree. C. and
precipitating the product by dropwise addition of 300 ml of
methanol. The product was washed with 100 ml of methanol and dried
at room temperature under reduced pressure. This procedure was
repeated a further twice with 260 ml of THF/260 ml of methanol each
time. 1.85 g (5.53 mmol, 69%) of polymer V6 were obtained as
green-fluorescent fibrous polymer.
[0403] .sup.1H NMR (400 MHz, CDCl.sub.3): (ppm)=7.8-57.02 (br. m, 7
H; H.sub.arom); 6.92, 6.67 (br. s, together 2H; olefin-H); 3.99
(br. s, 2 H; OCH.sub.2); 1.82 (br. s, 1 H; aliph. H); 1.72-1.45 (m,
3H); 1.40-1.08 (m, 6H), 0.91 (s, 3H; CH.sub.3); 0.85 (s, 3H;
CH.sub.3); 0.83 (s, 3H; CH.sub.3).
[0404] GPC: THF+0.25% oxalic acid; column set SDV500, SDV1000,
SDV10000 (PSS), 35.degree. C., UV detection 254 nm, polystyrene
standard: M.sub.w=6.3.times.10.sup.5 g/mol,
M.sub.n=6.8.times.10.sup.4 g/mol.
EXAMPLE V7
Homopolymerization of
2,5-bis(chloromethyl)-1-methoxy-4-(3',7'-dimethyloct- yloxy)benzene
(polymer V7)
Preparation of
poly(2-methoxy-5-(3,7-dimethyloctyloxy)-p-phenylenevinylene- )
[0405] A 4 l four-necked flask fitted with mechanical (Teflon)
stirrer, reflux condenser, thermometer and dropping funnel was
dried by heating (hair drier) and flushed with N.sub.2. It was then
filled with 2.3 l of dry 1,4-dioxane, and, for degassing, N.sub.2
was passed through the solvent for about 15 minutes. The flask was
heated to 98.degree. C. in an oil bath, and 14.0 g (38.7 mmol) of
2,5-bis(chloromethyl)-1-methoxy-4-(3'- ,7'-dimethyloctyloxy)benzene
were added as solid (rinsing with about 10 ml of dry 1,4-dioxane).
11.3 g (100 mmol, 2.6 eq) of potassium tert-butoxide, dissolved in
100 ml of 1,4-dioxane, were added dropwise to the reaction solution
over the course of 5 minutes via the dropping funnel. During this
addition, the reaction mixture changed color from colorless via
greenish to yellow/orange, and the viscosity increased
significantly. When the addition was complete, the mixture was
stirred at 98.degree. C. for about 5 more minutes, and then 8.70 g
of potassium tert-butoxide (77 mmol, 2 eq) in 100 ml of dry
1,4-dioxane were added over the course of one minute, and the
mixture was stirred at 96-98.degree. C. for a further 2 hours. The
solution was then cooled to 50.degree. C. over the course of about
2 hours. 15 ml (260 mmol, 1.5 eq, based on the base) of acetic acid
(diluted with the same amount of dioxane) were finally added to the
reaction, and the mixture was stirred for a further 20 minutes. The
solution was then deep orange. For work-up, the reaction solution
was poured slowly into 2.5 l of vigorously stirred water. The
mixture was stirred for a further 10 minutes, 200 ml of methanol
were added, and the precipitated polymer was filtered off, washed
with 200 ml of methanol and dried at room temperature under reduced
pressure, giving 10.04 g (34.8 mmol, 90%) of crude polymer as red
fibers.
[0406] Purification was carried out by dissolving the polymer in
1.1 l of THF (60.degree. C.), cooling the solution to 40.degree. C.
and precipitating the product by dropwise addition of 1.2 l of
methanol. After the product had been washed with 200 ml of
methanol, it was dried at room temperature under reduced pressure.
This procedure was repeated again with 1.0 l of THF/1.0 l of
methanol. 6.03 9 (20.9 mmol, 54%) of polymer V7 were obtained as
dark-orange fibrous polymer.
[0407] .sup.1H NMR (400 MHz, CDCl.sub.3): (ppm)=7.7-6.5 (br. m, 4
H; H.sub.arom, olefin-H); 4.5-3.6 (br. m, 5 H; OCH.sub.3,
OCH.sub.2); 2.9 (br. s, bisbenzyl (3,5%)); 2.1-0.6 (br. m, 19H;
aliph. H). GPC: THF+0.25% oxalic acid; column set SDV500, SDV1000,
SDV10000 (PSS), 35.degree. C., UV detection 254 nm, polystyrene
standard: M.sub.w=1.2.times.10.sup.6 g/mol,
M.sub.n=1.1.times.10.sup.5 g/mol.
[0408] Part 3: Production and Characterization of LEDs
[0409] LEDs were produced by the general process outlined below.
Naturally, this had to be adapted to the particular circumstances
(for example polymer viscosity and optimum layer thickness of the
polymer in the device) in individual cases. The LEDs described
below were in each case one-layer systems, i.e.
substrate//ITO///polymer//negative electrode.
[0410] General process for the production of high-efficiency
long-life LEDs:
[0411] After the ITO-coated substrates (for example glass support,
PET foil) have been cut to the correct size, they are cleaned in a
number of cleaning steps in an ultrasound bath (for example soap
solution, Millipore water, isopropanol).
[0412] For drying, they are blown with an N.sub.2 gun and stored in
a desiccator. Before coating with the polymer, they are treated
with an ozone plasma unit for about 20 minutes. A solution of the
respective polymer (in general with a concentration of 4-25 mg/ml
in, for example, toluene, chlorobenzene, xylene:cyclohexanone
(4:1)) is prepared and dissolved by stirring at room temperature.
Depending on the polymer, it may also be advantageous to stir the
solution at 50-70.degree. C. for some time. When the polymer has
dissolved completely, it is filtered through a 5 .mu.m or smaller
filter and coated on at variable speeds (400-6000) using a spin
coater. The layer thicknesses can be varied thereby in the range
from about 50 to 300 nm.
[0413] Electrodes are then applied to the polymer films. This is
generally carried out by thermal evaporation (Balzer BA360 or
Pfeiffer PL S 500). The transparent ITO electrode is then connected
as positive electrode and the metal electrode (for example Ca) as
negative electrode, and the device parameters are determined.
[0414] The results obtained using the polymers described are shown
in Table 1:
3TABLE 1 Polymer Polymer Max. luminance EL I/Area for Example conc.
Spin speed TBB efficiency .lambda..sub.max U for 100 100 cd/m.sup.2
[a] [mg/ml] [rpm] content [%] Cd/A [nm] Color cd/m.sup.2 [V]
[mA/cm.sup.2] P1 5 2000 1.4% 3.6 586 yellow-orange 3.2 2.9 P2 5
1800 4.8% 12.8 555 yellow 2.9 0.9 P3 5 2500 1.8% 7.8 565 yellow 3.9
1.4 P4 5 1800 1.0% 3.2 579 yellow-orange 3.2 2.8 P5 5 600 4.7% 2.9
578 yellow-orange 3.4 3.0 P6 5 2000 4.4% 11.8 555 yellow 3.1 0.9 P7
5 1900 4.6% 10.7 544 yellow 3.3 1.1 P8 6 3700 5.0% 9.1 551 yellow
3.1 1.5 P9 5 1000 8.5% 7.3 535 green-yellow 3.9 2.6 P10 5(Cl- 1300
9.5% 4.0 540 yellow-green 4.6 4.0 benzene) P11 5 2000 3.3% 3.1 581
yellow-orange 3.2 1.8 P12 5 800 6.0% 9.7 555 yellow 3.2 1.3 P13
5(Cl- 1000 7.0% 3.4 550 yellow 5.2 4.4 benzene) P14 5 1400 8.5% 8.6
528 green-yellow 3.8 1.4 P15 5 2000 5.5% 9.2 560 yellow 3.4 1.3 P16
5 1500 4.0% 8.6 552 yellow 3.2 1.2 P17 5 1000 4.5% 9.0 549
yellow-green 3.1 1.1 V1 5 [b] 500 7.0% 3.0 587 yellow-orange 4.3
4.4 V2 5 1000 12.3% 4.6 517 green 5.1 4.6 V3 5 3000 7.0% 3.1 581
yellow-orange 4.5 5.0 V4 5 900 12.0% 4.0 547 yellow 5.6 5.6 V5 5
2000 3.5% 1.2 591 orange 3.4 5.1 V6 8 2200 12.5% 5.9 519 green 4.4
3.8 V7 6 [b] 1100 3.5% 1.2 591 orange 3.5 5.3 [a] Device size: 16
mm.sup.2; layer thickness: 80 nm, solutions in toluene [b] 100 nm
layer thickness
[0415] The polymers according to the invention have a structural
difference with respect to certain defect structures compared with
all PPVs known hitherto prepared by dehydrohalogenation; this
difference will be explained in greater detail below without
restricting the invention or making the invention dependent on the
truth content of the model explained. This structural difference
can be correlated in model terms with the obtaining of the desired
properties (long active service life of the corresponding LEDs; low
increase in voltage).
[0416] In the dehydrohalogenation polymerization, the following
takes place--following the outlined model: the stable premonomer
employed (referred to as just monomer in the text above) initially
eliminates HX on contact with a strong base, resulting in the
formation of the actual monomer (quinodimethane). This reactive
intermediate then polymerizes very quickly (presumably anionically
initiated) to give the prepolymer, which is converted into the
actual PPV by further base-induced elimination of HX (cf. following
scheme). 52
[0417] So long as a uniform head/tail polymerization always occurs
here, this results in a defect-free PPV. However, as soon as a
polymer lines up quasi inverted (i.e. head/head and tail/tail
polymerization), this results in the occurrence of triple and
single bonds or a tolan-bisbenzyl defect (TBB); cf. following
scheme. 53
[0418] These defects can also be detected analytically in the NMR
of the corresponding polymers. The bisbenzyl unit gives a broad
signal in the region of 2.6 to 3.0 ppm (.sup.1H NMR; CDCl.sub.3;
about 300 K). Integration of this signal and comparison with other
main signals gives information on the content of defective bonds.
The following is now known from a number of experiments (cf. FIG. 1
and 2 and Comparative Experiments V1-V7): 2,5-dialkoxy-PPVs
generally have a TBB content in the range 3-5% (TBB content:
content of single+triple bonds based on the total number of
"vinylic bonds"). Copolymers containing dialkoxy-PPV units and
aryl-substituted PPV units have a higher TBB content, which is
dependent on the monomer ratio. Homopolymers, which are
2-aryl-substituted PPVs, have a TBB content of greater than 12%. A
surprisingly found feature of the polymers according to the
invention is that the TBB content is significantly lower than that
of comparative polymers which have no further substituents in the
5- or 6-position, i.e. in addition to the aryl substituent on the
phenyl ring: thus, for example, a 50/50 copolymer comprising
dialkoxy-PPV monomers and 5-methoxy-2-aryl-PPV monomers has a TBB
content of about 1.5% (compared with about 6-8% for the
corresponding polymer without methoxy substitution) (cf. Ex. P1).
Analogously, a 50/50 copolymer between aryl-PPV monomers and
5-methoxy-2-aryl-PPV monomers has a TBB content of about 5-6%
(compared with about 12% for the corresponding polymer without
methoxy substitution) (cf. Ex. P2).
[0419] This lower TBB content surprisingly results (cf. table
below) in a significant reduction in the voltage increase (in each
case based on comparable polymers) and also in greater active
service lives. Thus, the structural characteristic described here
for the polymers according to the invention can be regarded
retrospectively as the scientific basis for the desirable
properties surprisingly found.
4TABLE 2 Poly- TBB T.sub.1/2 dU/dt.sup.[a] mer M1 [%] M2 [%] M3 [%]
[%] [h].sup.[a] [mV/h] V1 54 50% 55 50% 7% 90 120 V2 56 50% 57 50%
12.3% 1 1500 V3 58 50% 59 50% 7% 80 120 V4 12% 1.5 1000 V5 60 82%
61 18% 3.5% 80 45 V6 62 100% 12.5% 1 1500 V7 63 100% 3.5% 100 40 P1
64 50% 65 50% 1.4% 280 10 P2 66 50% 67 50% 4.8% 200 15 P3 68 25% 69
75% 1.8% 300 5 P4 70 25% 71 75% 1.0% 800 2 P5 4.7% 750 4 P6 72 50%
73 50% 4.4% 1250 1.5 P7 74 50% 75 50% 4.6% 560 4 P8 76 50% 77 5.0%
1100 1.2 P9 78 50% 79 50% 8.5% 130 30 P10 80 40% 81 60% 9.5% 55 110
P11 82 50% 83 30% 84 20% 3.3% 2600 <1 P12 6.0% 550 5 P13 85 50%
86 50% 7.0% 110 35 P14 87 50% 88 50% 8.5% 180 20 P15 89 50% 90 50%
5.5% 100 50 P16 91 40% 92 30% 93 30% 4.0% 280 8 P17 94 95 50% 4.5%
145 17 Table .sup.[a]in each case at a luminosity of 1000
Cd/m.sup.2. C.sub.10 = 3,7-dimethyloctyl C.sub.4 =
2-methylpropyl
* * * * *