JPH1048678A - Nonlinear optical material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an optically stable thiophene compd. or its compsn. showing high nonlinearity and having fast relaxing time by incorporating a specified polythiophene. SOLUTION: The material contains at least one kind of polythiophene having structural units expressed by formula I and formula II. In formulae I and II, X, Y are straight-chain or branched-chains alkyl groups having 1 to 22 carbon atoms or straight-chain of branched-chain alkoxyl groups having 1 to 22 carbon atoms, or X and Y with atoms bonded to these may form a cyclic structure containing carbon atoms. The cyclic structure contains not only carbon atoms but nitrogen (N) heteroatoms, oxygen (O) heteroatoms, sulfur (S) heteroatoms or (P) phosphorus heteroatoms or two or more kinds of these heteroatoms. Moreover, the cyclic structure may have substltuents Z on the position of carbon atoms, nitrogen atoms or phosphorus atoms, and each Z independently represents the same groups as defined as X and Y.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to the compounds of the general formulas (I) and (II)

[0002]

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Wherein X and Y may be the same or different independently of one another and are linear or branched C ₁ -C ₂₂ alkyl groups; linear or branched C ₁ -C ₂₂ Alkoxy groups; linear or branched C ₁ -C ₂₂ alkyloxyalkyl groups;
Linear or branched C ₁ -C ₂₂ acyl group; linear or branched C ₁ -C ₂₂ thioacyl group; linear or branched C ₁ -C ₂₂
An acyloxy group; a linear or branched C ₁ -C ₂₂ thioacyloxy group; a C ₅ -C ₈ cycloalkyl group, a C ₆ -C ₁₈ aryl group or a C ₅ -C ₈ heterocyclic group. One or more linear or branched C ₁ -C ₂₂ alkyl groups, one or more linear or branched C ₁ -C ₂₂ alkoxy groups, one or more linear or branched C ₁ -C ₂₂ alkoxy groups, ₁ -C ₂₂ alkyloxy group, C ₁ -C one or more linear or branched
₂₂ acyl groups or one or more linear or branched C ₁ -C ₂₂
NO ₂ ; which may be substituted by a thioacyl group);
Or NHR ¹ , wherein R ¹ may be the same or different;
Each hydrogen; or a linear or branched C ₁ -C ₂₂ alkyl group, a linear or branched C ₁ -C ₂₂ alkoxy group, a linear or branched C ₁ -C ₂₂ alkyloxyalkyl group Represents a linear or branched C ₁ -C ₂₂ acyl group or a linear or branched C ₁ -C ₂₂ thioacyl group, or X and Y together with the atoms to which they are attached To form a carbon-containing ring system which, in addition to carbon, comprises a nitrogen (N) heteroatom, an oxygen (O) heteroatom, a sulfur (S) heteroatom or a phosphorus (P) heteroatom, or Wherein the ring system may be further substituted with a group Z at each of a carbon atom, a nitrogen atom and a phosphorus atom, wherein each Z is Represents independently the same as defined for X and Y above, or two Adjacent groups Z together are the following general formula (III) ~ (VI)

[0004]

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Wherein A represents carbon (C), nitrogen (N), phosphorus (P) or a mixture of two or more of these atoms;
In this case, as long as A is a carbon atom, each A is 1
Or may be further substituted with those defined above for X and Y)
Which forms a group represented by the formula: [1] and a nonlinear optical material containing at least one kind of polythiophene having a structural unit represented by the formula:

[0006]

It is already known that conjugated organic materials can provide a nonlinear optical effect. This fact is caused by the easy polarization of delocalized π-electrons in this system. In this case, the number of double bonds has a decisive influence on the nonlinear optical properties of the conjugated polyene.

[0007] Nonlinear optics is completely or generally engaged in the interaction of electromagnetic fields and materials and can produce a refractive index that depends on the intensity of the light beam. RN Prasad and
DJ.Williams says `` Introduction to non-linear optica
l effects in molecules and polymers (Wiley 1991) ''
Book contains detailed information on this subject.

[0008] Three-dimensional order (dritte Ordnung)
Dielectric susceptibility of ⁽³⁾ (dielektrischenSuszeptibitaet)
Has a strength-dependent refractive index. χ ⁽³⁾ is the material constant (Materialkonstante) that depends on the molecular structure, crystal structure, light frequency and temperature. This constant is known as "4-wave-mixing-method (Vier-Wellen-Misch-M
ethode) ”(Degenerate For Wave Mixing, DFWM) or triple frequency test (Frequenzverdreifachungs-Experimen
t) (Third Harmonic Generation, THG). These methods are described in principle by Prasad and Williams, for example, in the above-mentioned literature.

[0009] Materials having a high χ ⁽³⁾ value are suitable just for the production of optical switches and thus for use in optical telecommunications or in optically operated computers. Other potential uses for this type of material include, for example, DR Ulrich Molecular Crystals Liquid
Crystals, 160, (1988), S. 1-31.

For the application of non-linear optical materials (here: materials having high χ ⁽³⁾ values ⁾ in optical members, various combinations of material properties are required. A high χ ⁽³⁾ value alone does not satisfy the requirements for optical members. Other,
It is preferred that the relaxation time and thus the switching time be very short (in the range of picoseconds and femtoseconds), and that optical losses due to absorption, scattering, etc., be minimized. In particular, it is advantageous to have good workability of the material in the form of a layer, for example an optical waveguide.

The application of this material is generally performed in electronics using a variety of thin film techniques that apply thin layers on a variety of supports. A relatively simple method for producing layers for optical materials is the so-called Spin-Coat-Verfah method.
ren). This method provides a homogeneous, transparent layer composed of pure non-linear optically active material or composed of a mixture of a transparent matrix polymer and an NLO-material. For the industrial realization of this process, the material to be coated must be pure or homogeneously dissolved in combination with the polymer. The layer thickness of the layers obtained in the case of the spin-coating process depends on the rheological properties of the solution in the case of coating as well as on the speed of rotation of the support.

For the production of films having a layer thickness of> 1 μm, blade coating techniques and casting techniques can also be applied. After coating is complete, careful drying must be observed to avoid crack formation or non-uniformity.

It is known that polythiophenes can be manufactured as thin layers (in particular, "Introduction to nonlinear o
ptical effects in molecules and polymers ", P. Pras
ad and DJ Williams, Wiley, 1991; "Third-oder opt
ical nonlinearity in polycondensed thiophene-based
polymers and polysilane polymers ", L. Yang, R. Do
rsinville, QZ Wang, WK Zou, PPHo, NL Yang
e, RR Alfano, R. Zamboni, R. Daniel; J. Opt. Soc.
Am. B .: Opt. Phys., 6 (4) (1989), S. 753- 756; "No.
nlinear-optical response in polythiophene films us
ing four-wave mixing techniques ", R. Dorsinville,
L. Yang, RRAlfano, R. Zamboni, R. Danieli, G. Rua
ni. C. Taliani; Opt. Lett., 14 (1989), S. 1321-13
23; "Frequency variation of cubic susceptibility in
the new conjugated polymers (polythieno (3,2-b) thi
ophene) and poly [1,4-di (2-thienyl) benzene] ", F. Kaj
zar, G. Ruani, C. Taliani, R. Zamboni; Synth. Me
t., 37 (1990), S. 223-229; "Conjugated poly (thio
phenes): synthesis, functionalization, andapplicat
ions ", J. Roncali; Chem. Rev., 92 (1992), S. 711-
738; Photoexcitation and nonlinear optical proper
ties in thiophene based conjugatedsystems, C. Tali
ani, AJ Pal, G. Ruani, R. Zamboni, RR Alfano,
R. Dorsinville, L. Yang; Proc. SPIE-Int. Soc. Opt.
Eng., 1599 (Recent Adv.UsesLight Phys., Chem., En
g., Med.) (1992), S. 24-33).

However, a disadvantage of this layer is that it has a disadvantage of about 80, which is important industrially, for example for electronic communications or semiconductor lasers.
It does not exhibit high nonlinearity in a wavelength range of 0 nm to 1600 nm. For polythiophene, L.
Yang et al. ("Third-order optical nonlinearity in p
olycondensed thiophene-based polymers and polysila
ne polymers ", J. Opt. Soc. Am. B .: Opt. Phys., 6
(4) (1989), S.753-756) gives a χ ⁽³⁾ value (DFW ⁾ of 3 × 10 ^-11 esu with a switching time of <12 ps.
M, 1064 nm).

Heretofore, thiophenes or homopolymers of substituted thiophenes have been known almost exclusively.
In this case, mostly simple 3-alkyl- or 3,4-dialkylthiophenes were polymerized and tested for possible industrial applications. The appearance of polythiophene produced so far and its frequently used method of manufacture is described in Hans R. Kricheldorf "Handbook of polymer syn
thesis ", Teil B, S. 1383-1390 (1992), M. Pomeran
tz "Processable polymers and copolymers of 3-alkyl
thiophenes and their blends ", Synthetic Metals, 41
-43 (1991), S.825-830, and EP-A-0 339 340.

Soluble poly (2,3-dihexylthieno [3,4-b] pyrazine) was prepared by M. Pomerantz et al. By iron chloride-oxygen polymerization of the corresponding monomers (M. Pomerantz). "New processable low band-g
ap, conjugated polyheterocycles, Synthetic Metals,
55-57, S. 960-965 (1993)). In this way, only a doped substance (dotierte Substanzen) can be produced. EP in NMR spectra, even after treatment with aqueous ammonia or hydrazine
An R-signal and a linear distribution (Linienverbreitung) are observed, indicating the presence of a paramagnetic species.

The production process heretofore mainly involves chemical oxidation (for example with FeCl ₃ ) or electrochemical oxidation of individual precursors or mixtures of two different 3-alkylthiophenes, correspondingly. A polymer linked at the 2,5-position was formed (M. Pomerantz "Processable po
lymers and copolymers of 3-alkylthiophenes and the
ir blends ", Synthetic Metals, 41-43 (1991), S. 8
25-830, especially S. 828, and M. Berggren et al. "Li
ght-emitting diodes with variable colorsfrom poly
mer blends ", Nature, 372 (1994), S. 444-446, especially S. 444).

Another common batch for the preparation of oligo- or polythiophenes is the catalytic ligation of metal-organic reactants, often Grignard reagents (see Kricheldorf, supra).

In this case, however, it is noted that thiophenes having functional groups such as nitro-, carbonyl-, imino-, amido-, nitrile-, pyridine- and pyrazine groups cannot be used during the process. There must be.

[0020] A relatively new method for the production of the novel CC linkage is the so-called Stille-Umsetzung reaction. By this reaction, the organic electrophile is reacted with an organotin reagent in the presence of a suitable solvent and a Pd (0) or Pd (II) complex (JKStille "The palladium-c
atalysed cross-coupling reactions of organotin rea
gents with organic electrophils ", Angew. Chem. In
t. Ed. Engl. 25, S. 508-542 (1986)). This reaction was effectively performed for the production of poly (2,5-thieno-1,4-phenylene) (Z. Bao et al., J. A.
m. Chem. Soc., 117, 12426-12435 (1995)).

Generally, this doping is preferred for certain applications, such as, for example, high conductivity, but is undesirable for other applications, such as, for example, producing thin films with good optical quality. The properties of the doped material are:
Frequently changes with time. Furthermore, the reproducibility of this property is likewise generally low compared to the properties of the undoped material.

This consideration is made, for example, in the use of doped and undoped copoly- and co-oligothiophenes having substituted and unsubstituted structural units as materials having nonlinear optical (NLO) properties. Shows the possibility of

[0023]

Accordingly, an object of the present invention was to produce photostable thiophene compounds or compositions thereof having high non-linearity and rapid relaxation times. This material is preferably capable of being produced in a simple manner as a thin film of high optical quality.

[0024]

The above object is achieved according to the invention by a non-linear optical material containing a polythiophene as defined above and a composition containing this polythiophene. Due to variations in the reactants used and their relative components, high non-linearities of more than 10 ^-10 esu are achieved in the industrially important wavelength range from about 800 nm to 1600 nm. This relaxation time is clearly 10p
s, allowing for significantly higher switching speeds. The optical quality of this layer is good. The polythiophenes and the compositions containing them as defined in the claims and explained in more detail below can be used in customary solvents such as THF.
The production of thin layers can be carried out by simple spin coating or casting, because of their good dissolution in them.

FIGS. 1 and 3 graphically show the results of DFWM measurements on the copolythiophenes used according to the invention.

FIGS. 2 and 4 are graphs showing the absorption spectrum of this copolythiophene.

[0027]

DETAILED DESCRIPTION OF THE INVENTION The polythiophenes used within the scope of the present invention and the compositions containing them are described in detail below.

The structural units (I) present in the polythiophenes used according to the invention are derived from thiophenes.

In the structural unit (II), X and Y, if they do not form a ring system containing carbon atoms together with the atoms to which they are attached, can each represent the radicals mentioned at the outset and are advantageously X and Y are the same. If X and Y each represent the group NHR ¹ , both groups R ¹ are preferably likewise identical. Of the above-mentioned alkyl, alkoxy, alkyloxyalkyl, acyl and thioacyl groups having 1 to 22 C atoms, those having 1 to 20 carbon atoms are advantageous, and those having 60 to 20 carbon atoms are advantageous. Those having 5 carbon atoms are furthermore advantageous,
Those having 6 carbon atoms are particularly advantageous.

Particularly preferred substituents X and Y are the aforementioned acyl groups, thioacyl groups and NHR ¹ .

The expression "thioacyl group" within the scope of the present invention denotes a group of the general formula -C (S) -R, wherein R is alkyl. The expression “heterocyclic groups” mentioned at the outset denotes saturated alicyclic, unsaturated alicyclic and aromatic heterocyclic groups.

In addition, X and Y can be taken together with the atoms to which they are attached to form a carbon-containing ring system which, in addition to carbon, has a nitrogen (N) heteroatom, It has an oxygen (O) heteroatom, a sulfur (S) heteroatom or a phosphorus (P) heteroatom or a mixed form of two or more heteroatoms. In this case, X and Y preferably form a divalent radical, which radical has 2 to 8 atoms, more preferably 3 to 6 atoms, and both Form a ring system with 4 to 10 or 5 to 8 atoms. The number of said heteroatoms which can be present in this ring system is advantageously up to three,
More preferably, up to two. Of the aforementioned heteroatoms, nitrogen (N) is preferred. The ring systems mentioned are preferably those having at least one, more preferably two or more, double bonds. In a particularly advantageous embodiment of the invention,
The double bond of the ring system is in conjugation with the double bond of the thiophene fragment attached to the ring system, and optionally further comprises a compound of the formula (I) III) to (VI) are conjugated with a double bond.

The ring system can here again be substituted at the carbon, nitrogen or phosphorus atom by a radical Z, each Z being independently of one another X and Substituents which represent a radical as defined for Y, again stated as being advantageous for X and Y, are again considered to be advantageous.

Two adjacent radicals Z can further form one radical selected from the radicals mentioned at the beginning of the general formulas (III) to (IV),
The position "A" represents carbon (C), nitrogen (N), phosphorus (P) or a mixture of two or more of these atoms, as long as A is carbon, it has a hydrogen atom, or even here,
It may be substituted as defined for X and Y above. In this case, the radicals together with the atoms to which they are attached form another ring, which advantageously forms a conjugated unsaturated system with the remaining rings in the structural unit.

The advantageous ring which has formed in this case is the cyclobutene ring.

An advantageous group of polythiophenes used according to the invention are those of the general formulas (VII) and / or (VI)
Which have the structural unit of II):

[0037]

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Wherein X and Y are as described above, and n, m and k are each independently an integer from 1 to 10,
Advantageously represents an integer from 1 to 6, 1 is an integer from 1 to 3000,
It preferably represents an integer from 1 to 1000, in particular an integer from 1 to 100. In this case, an alternating sequence of substituted and unsubstituted thiophene units is advantageous.

The polythiophenes used with particular advantage are:
In the structural unit (II), the following general formula:

[0040]

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[0041]

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Wherein R ² ＣＨCH ₂ R ¹ or R ² ＣＨCH
R ¹ _2, is such that is selected from the group consisting of groups represented by R ¹ = H or an those mentioned above.

Of the structural units (II) described above, the following individually listed structural units are particularly advantageous. in this case,
It is, of course, obvious that this is derived from the corresponding compound which is disubstituted adjacent to the thiophene sulfur atom.

3,4-di (decyl) thiophene-,
4-di (undecyl) thiophene-3,4-di (dodecyl) thiophene-, 3,4-di (tridecyl) thiophene-, 3,4-di (tetradecyl) thiophene-, 3,
4-di (pentadecyl) thiophene-, 3,4-di (hexadecyl) thiophene-, 3,4-di (heptadecyl) thiophene- and 3,4-di (octadecyl) thiophene-structural units; 3,4-di ( (Decyloxy) thiophene-, 3,4-di (undecyloxy) thiophene-, 3,4-di (dodecyloxy) thiophene-, 3,
4-di (tridecyloxy) thiophene-, 3,4-di (tetradecyloxy) thiophene-, 3,4-di (pentadecyloxy) thiophene-, 3,4-di (hexadecyloxy) thiophene-, Preference is given to 3,4-di (heptadecyloxy) thiophene- and 3,4-di (octadecyloxy) thiophene structural units; furthermore, structural units in which the above-defined ether groups are replaced by the corresponding thioether groups. 3,4-di (decyloxyethyl) thiophene-, 3,4-di (undecyloxyethyl) thiophene-, 3,4-di (dodecyloxyethyl) thiophene-, 3,4-di (tridecyl) Oxyethyl) thiophene-, 3,4-di (tetradecyloxyethyl) thiophene-, 3,4- (pentadecyloxyethyl) thio Ene-, 3,4-di (hexadecyloxyethyl) thiophene-, 3,4-di (heptadecyloxyethyl) thiophene- and 3,4-di (octadecyloxyethyl) thiophene-structural units; Further, among the alkyloxyalkyl groups defined in detail above, the oxygen atom is, for example, 3-, 3,6-, 3,6,9-, 3,6,9,12- depending on the total length of the substituent. Structural units present at positions etc. are advantageous, for example 3,4-
Di (ethyl-2-oxydecyl) thiophene; 3,4-
Di (propyl-3-oxydecyl) thiophene; 3,4
-Di (butyl-4-oxydecyl) thiophene; 3,4
-Di (2- (2- (decyloxy) ethoxy) ethyl)
Thiophene; 3,4-di (2- (2- (undecyloxy) ethoxy) ethyl) thiophene; 3,4-di (2-
(2- (dodecyloxy) ethoxy) ethyl) thiophene; and the like, in which case the total number of C atoms does not exceed 22;
In addition, structural units in which the oxygen atom of the alkyloxyalkyl substituent as defined above is replaced by a sulfur atom are also advantageous; 3,4-di (cyclopentyl) thiophene-, 3,4-di (cyclopentenyl) Thiophene-, 3,4-di (cyclohexyl) thiophene-, 3,
4-di (cyclohexenyl) thiophene-, 3,4-di (cyclohexadienyl) thiophene-, 3,4-di (phenyl) thiophene- and 3,4-di (benzyl)
Thiophene-structural units, in which the abovementioned substituents can again be substituted by one or more groups defined for R ¹ ; 3,4-di (decanoyl) thiophene-, 3,4- Di (undecanoyl) thiophene-, 3,4-di (dodecanoyl) thiophene-, 3,4
-Di (tridecanoyl) thiophene-, 3,4-di (tetradecanoyl) thiophene-, 3,4-di (pentadecanoyl) thiophene-, 3,4-di (hexadecanoyl) thiophene-, 3,4 Di- (heptadecanoyl) thiophene- and 3,4-di (octadecanoyl) thiophene structural units; and corresponding alkanoyloxy structural units, for example 3,4-di (decanoyloxy) thiophene, 3,4-di- (Undecayloxy) thiophene and the like; also here, substituents in which the carbonyl groups present are replaced by thiocarbonyl groups are advantageous; 3,4-di (decanoylamino) thiophene-, 3, 4-di (undecanoylamino) thiophene-, 3,4-di (dodecanoylamino) thiophene-,
3,4-di (tridecanoylamino) thiophene-,
3,4-di (tetradecanoylamino) thiophene-,
3,4-di (pentadecanoylamino) thiophene-,
3,4-di (hexadecanoylamino) thiophene-,
3,4-di (heptadecanoylamino) thiophene- and 3,4-di (octadecanoylamino) thiophene-
Structural units, in which oxygen can also be replaced by sulfur; 2,3-dipentylthieno [3,4-
b] pyrazine, 2,3-didecylthieno [3,4-b]
Pyrazine-, 2,3-diundecylthieno [3,4-
b] pyrazine-, 2,3-didodecylthieno [3,4-
b] pyrazine-, 2,3-ditridecylthieno [3,4
-B] pyrazine-, 2,3-ditetradecylthieno [3,4-b] pyrazine-, 2,3-dipentadecylthieno [3,4-b] pyrazine-, 2,3-dihexadecylthieno [3,4-b] pyrazine-, 2,3-diheptadecylthieno [3,4-b] pyrazine- and 2,3-dioctadecylthieno [3,4-b] pyrazine-structural units; 2-methyl -3-decyloxythieno [3,4-
b] Pyrazine-, 2-methyl-3-undecyloxythieno [3,4-b] pyrazine-, 2-methyl-3-dodecyloxythieno [3,4-b] pyrazine-, 2-methyl-3- Tridecyloxythieno [3,4-b] pyrazine-, 2-methyl-3-tetradecyloxythieno [3,4-b] pyrazine-, 2-methyl-3-pentadecyloxythieno [3,4-b ] Pyrazine-, 2-methyl-3-hexadecyloxythieno [3,4-b] pyrazine-, 2-methyl-3-octadecyloxythieno [3,4-b] pyrazine-, 2-methyl-3-eico Siloxythieno [3,4-b] pyrazine-, 2-methyl-3-docosyloxythieno [3,4-b] pyrazine-, 2-ethyl-3-decyloxythieno [3,4-
b] Pyrazine-, 2-ethyl-3-undecyloxythieno [3,4-b] pyrazine-, 2-ethyl-3-dodecyloxythieno [3,4-b] pyrazine-, 2-ethyl-3- Tridecyloxythieno- [3,4-b] pyrazine-, 2-ethyl-3-tetradecyloxythieno [3,4-b] pyrazine-, 2-ethyl-3-pentadecyloxythieno [3,4- b] Pyrazine-, 2-ethyl-3-hexadecyloxythieno [3,4-b] pyrazine-, 2-ethyl-3-octadecyloxythieno [3,4-b] pyrazine-, 2-ethyl-3- Eicosyloxythieno [3,4-b] pyrazine-, 2-ethyl-3-dodecyloxythieno [3,4-b] pyrazine-
Structural unit, 2-phenyl-3-decyloxythieno [3,4-b] pyrazine-, 2-phenyl-3-undecyloxythieno [3,4-b] pyrazine-, 2-phenyl-3-tridecyl Oxythieno [3,4-b] pyrazine-, 2-phenyl-3-tetradecyloxythieno [3,4-b] pyrazine-, 2-phenyl-3-pentadecyloxythieno [3,4-b] pyrazine -, 2-phenyl-3-hexadecyloxythieno [3,4-b]
Pyrazine-, 2-phenyl-3-heptadecyloxythieno [3,4-b] pyrazine-, 2-phenyl-3-octadecyloxythieno [3,4-b] pyrazine-, 2
-Phenyl-3-eicosyloxythieno [3,4-
b] pyrazine- and 2-phenyl-3-docosyloxythieno [3,4-b] pyrazine-structural units, in which oxygen can also be replaced by sulfur;
3-di (decyloxy) thieno [3,4-b] pyrazine-, 2,3-di (undecyloxy) thieno [3,4-
b] Pyrazine-, 2,3-di (dodecyloxythieno [3,4-b] pyrazine-, 2,3-di (tridecyloxy) thieno [3,4-b] pyrazine-, 2,3-di (Tetradecyloxy) thieno [3,4-b] pyrazine-, 2,3-di (pentadecyloxy) thieno [3,4
-B] pyrazine-, 2,3-di (hexadecyloxy)
Thieno [3,4-b] pyrazine-, 2,3-di (heptadecyloxy) thieno [3,4-b] pyrazine-, 2,
3-di (octadecyloxy) thieno [3,4-b] pyrazine-, 2,3-di (eicosyloxy) thieno [3,4-b] pyrazine- and 2,3-di (docosyloxy) thieno [3 2,4-b] pyrazine structural units; furthermore, structural units in which the above-defined ether groups are replaced by the corresponding thioether groups;
3-di (decyloxyethyl) thieno [3,4-b] pyrazine-, 2,3-di (undecyloxyethyl) thieno [3,4-b] pyrazine-, 2,3-di (dodecyloxyethyl) ) Thieno [3,4-b] pyrazine-, 2,3
-Di (tridecyloxyethyl) thieno [3,4-b]
Pyrazine-, 2,3-di (tetradecyloxyethyl)
Thieno [3,4-b] pyrazine-, 2,3-di (pentadecyloxyethyl) thieno [3,4-b] pyrazine-, 2,3-di (hexadecyloxyethyl) thieno [3,4- b] Pyrazine-, 2,3-di (heptadecyloxyethyl) thieno [3,4-b] pyrazine- and 2,3-di (octadecyloxyethyl) thieno [3
4-b] pyrazine-structural units, wherein the oxygen atoms in the alkyloxyalkyl groups defined further above are, depending on the total length of the substituents, for example 3-, 3,6-, 3,
Structural units which are present at the 6,9-, 3,6,9,12-position and the like are advantageous; for example, 2,3-di (ethyl-2-oxydecyl) thieno [3,4-b] pyrazine; , 3-
Di (propyl-3-oxydecyl) thieno [3,4-
b] pyrazine; 2,3-di (2,3-di (butyl-4-oxydecyl) thieno [3,4-b] pyrazine and the like;
-(2- (decyloxy) ethoxy) ethyl) thieno [3,4-b] pyrazine; 2,3-di (2- (2- (undecyloxy) ethoxy) ethyl) thieno [3,4-
b] pyrazine; 2,3-di (2- (2- (dodecyloxy) ethoxy) ethyl) thieno [3,4-b] pyrazine and the like; in each case the total number of C atoms does not exceed 22; Preference is given to structural units in which the oxygen atom of the alkyloxyalkyl substituent as defined above is replaced by sulfur; 2,3-di (cyclopentyl) thieno [3,4-b] pyrazine-, 2,3- Di (cyclopentenyl) thieno [3,4-b] pyrazine-, 2,3-di (cyclohexyl) thieno [3,4-b] pyrazine-,
2,3-di (cyclohexenyl) thieno [3,4-b]
Pyrazine-, 2,3-di (cyclohexadienyl) thieno [3,4-b] pyrazine-, 2,3-di (phenyl)
Thieno [3,4-b] pyrazine- and 2,3-di (benzyl) thieno [3,4-b] pyrazine-structural units, in which the abovementioned substituents are again defined by one or more R ¹ 5,6-di (decyloxy) cyclobuta [b] thieno [3,4-
e] Pyrazine-, 5,6-di (undecyloxy) cyclobuta [b] thieno [3,4-e] pyrazine-, 5,6
-Di (dodecyloxy) cyclobuta [b] thieno [3
4-e] pyrazine-, 5,6-di (tridecyloxy)
Cyclobuta [b] thieno [3,4-e] pyrazine-,
3,4-di (tetradecyloxy) cyclobuta [b] thieno [3,4-e] pyrazine-, 5,6-di (pentadecyloxy) cyclobuta [b] thieno [3,4-e] pyrazine-, 5,6-di (hexadecyloxy) cyclobuta [b] thieno [3,4-e] pyrazine-, 5,6-di (heptadecyloxy) cyclobuta [b] thieno [3
4-e] pyrazine- and 5,6-di (octadecyloxy) cyclobuta [b] thieno [3,4-e] pyrazine-
Preference is given to structural units in which the above-defined ether groups are replaced by the corresponding thioether groups; 5,6-di (cyclopentyloxy) cyclobuta [b] thieno [3,4-e] Pyrazine-, 5,6-
Di (cyclopentenyloxy) cyclobuta [b] thieno [3,4-e] pyrazine-, 5,6-di (cyclohexyloxy) cyclobuta [b] thieno [3,4-e] pyrazine-, 5,6-di (Cyclohexenyloxy) cyclobuta [b] thieno [3,4-e] pyrazine-, 5,6-
Di (cyclohexadienyloxy) cyclobuta [b] thieno [3,4-e] pyrazine-, 5,6-di (phenyl) cyclobuta [b] thieno [3,4-e] pyrazine-
And 5,6-di (benzyl) cyclobuta [b] thieno [3,4-e] pyrazine structural units, wherein said substituents are again substituted by one or more groups defined for R ¹ 2-decyl-1H-thieno [3,4-d] imidazole-, 2-undecyl-1H
-Thieno [3,4-d] imidazole-, 2-dodecyl-1H-thieno [3,4-d] imidazole-, 2-tridecyl-1H-thieno [3,4-d] imidazole-, 2-tetradecyl- 1H-thieno [3,4-d] imidazole-, 2-pentadecyl-1H-thieno [3,
4-d] imidazole-, 2-hexadecyl-1H-thieno [3,4-d] imidazole-, 2-heptadecyl-1H-thieno [3,4-d] imidazole- and 2-
Octadecyl-1H-thieno [3,4-d] imidazole structural unit; 2-cyclopentyl-1H-thieno [3,
4-d] Imidazole-, 2-cyclopentenyl-1H
-Thieno [3,4-d] imidazole-, 2-cyclohexyl-1H-thieno [3,4-d] imidazole-,
2-cyclohexenyl-1H-thieno [3,4-d] imidazole-, 2-cyclohexadienyl-1H-thieno [3,4-d] imidazole-, 2-phenyl-1H
-Thieno [3,4-d] imidazole- and 2-benzyl-1H-thieno [3,4-d] imidazole structural units, 2-butylthio-1H-thieno [3,4-d] imidazole-, 2-pentylthio -1H-thieno [3,4
-D] imidazole-, 2-hexylthio-1H-thieno [3,4-d] imidazole-, 2-heptylthio-
1H-thieno [3,4-d] imidazole-, 2-octylthio-1H-thieno [3,4-d] imidazole-, 2-nonylthio-1H-thieno [3,4-d] imidazole-, 2-decylthio -1H-thieno [3,4-
d] Imidazole-, 2-undecylthio-1H-thieno [3,4-d] imidazole-, 2-dodecylthio-
1H-thieno [3,4-d] imidazole-, 2-tridecylthio-1H-thieno [3,4-d] imidazole-, 2-tetradecylthio-1H-thieno [3,4-
d] Imidazole-, 2-pentadecylthio-1H-thieno [3,4-d] imidazole-, 2-hexadecylthio-1H-thieno [3,4-d] imidazole-, 2
-Heptadecylthio-1H-thieno [3,4-d] imidazole-, 2-octadecylthio-1H-thieno [3,4-d] imidazole structural units, wherein the substituents are again one or more R Can be substituted by the groups defined in ¹ ; the proportion of the above defined structural units (I) and (II) in the polythiophenes used according to the invention is from about 1 to about 99 mol% ( I) and about 99 to about 1 mole% (II), preferably about 30 to about 70 mole% (I) and about 70 to about 30 mole% (II), and especially about 50 mole% (I) to about 50 mole%. Mol% (II), where the proportions of both structural units add up to 1
00 mol%. The order of the two structural units (I) and (II) is preferably alternating.

The weight average molecular weight (M _w ) of the polythiophene prepared according to the invention, determined by gel permeation chromatography using polystyrene as standard.
Is generally from about 1000 to about 500,000, preferably about 1
000 to about 250,000, especially about 30,000 to about 80
000. The non-uniformity of the molecular weight distribution, i.e. the quotient ( _Mw / _Mn ) of the weight average molecular weight and the number average molecular weight, is about 2 to about 4, preferably about 2 to about 3, especially about 2 to about 2.5. is there.

The polythiophenes used according to the invention can be polymerized using any reaction suitable for the polymerization of polyols or thiophenes, such as the chemical or electrochemical oxidation mentioned at the outset; Some polythiophenes having alkoxy-, acylamino- or alkyloxyalkyl substituents can also be reacted by catalytic ligation of metal organic reagents (mostly Grignard reagents). Reference is made to the literature reported at the outset for details of this reaction.

However, the advantageous processes for the preparation of the polythiophenes used according to the invention are described in the reaction with Stille and the reaction with Suzuki already mentioned at the outset (A. Suzuki et al. "Stereoselective synthe
sis of arylated (E) -alkanes by the reaction of alk
-1-enylboranes with aryl halides in the presenceof
palladium catalyst ", JCS Chem. Comm., 1979,
S. 866-867), which is described in more detail below.

In the case of the Suzuki reaction, 2,5-dihalogen or 2,5 corresponding to the structural unit (II) according to the invention
The triflate-substituted thiophene is reacted with a thiophene diborate or a thiophene diborate, a base, preferably sodium ethoxide and a palladium complex of the structure PdL ₄ (L = ligand), preferably Pd (PPh ₃ ) ₄ React in presence.

[0049]

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Sub = halogen or triflate X, Y = as defined above R = H or alkyl As the preferred borane, thiophene-2,
5-Diboric acid and its esters are used. For further details of this reaction, reference is made to the above reported literature.

Of course, within the scope of the Suzuki reaction, the thiophene derivative corresponding to the diboric acid (ester) derivative of the structural unit (II) can be replaced with the 2,5-dihalogen- or 2- , 5-triflate-substituted thiophene.

However, a particularly advantageous process for preparing polythiophenes according to the invention is the Stille reaction already mentioned at the outset. In this reaction, 2,5-dihalogenthiophene or 2,5-ditriflatethiophene and a bis (trialkyltin) -substituted thiophene derivative at a carbon atom adjacent to sulfur (this is a structural unit defined above) (II)), or 2,5-bis (trialkyltin) thiophene and a bis (halogen)-or bis (triflate) -substituted thiophene derivative at a carbon atom adjacent to sulfur (this is described above). According to the following reaction scheme, in mutually suitable solvents, in the presence of a suitable Pd (0) or Pd (II) complex as a catalyst.

[0053]

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Sub = halogen or triflate
k ′ = 1, 2, 3,... 10 Of the substituents “Sub” mentioned in the above reaction scheme, halogen-substituted derivatives are advantageously used. Bis (triflate) substituted, ie (CF ₃ SO ₃ )
If substituted starting materials are used, for example LiC
l can be added to improve reactivity.

Based on the mild conditions of its practice, this reaction allows all kinds of substituents, for example amine-, acyl-, ester-, ether- and nitro groups.

Pd (II)-or Pd
The (0) complex is used. Advantageous catalysts include in particular: tris (dibenzylideneacetone)
Dipalladium (Pd ₂ dba ₃ ), Pd (Ph ₃ P) ₂ Cl
₂ , wherein “Ph” represents C ₆ H ₅ and Pd (Ph ₃
P) ₄ . When using tris (dibenzylideneacetone) dipalladium, a variety of ligands are added, with the catalytic PdL ₄ being catalyzed in situ.
Formed by ligand exchange between Pd ₂ dba ₃ , which is weakly coordinated with the above, and this ligand. In this case, PPh ₃ , AsPH ₃ , [2- (CH ₃ ) C ₆ H ₄ ] as ligands
₃ P, P (OPh) ₃ and (2-furyl) ₃ P are used, where “furyl” represents a furyl group. The amount of catalyst used is about 2 to about 10 mol%, preferably about 2 to about 5 mol%, based on the amount of bis (trialkyltin) substituted starting material used.

In general, all solvents capable of holding the starting materials and catalysts used in solution can be used, but DMF, NMP and cyclic ethers such as THF and dioxane are particularly suitable solvents. . Among them, DMF and THF are advantageously used.

The reaction is generally carried out at a temperature from room temperature to the boiling point of the solvent, wherein temperatures from about 50 ° C. to about 100 ° C. are advantageous. The reaction times vary from 1 day to 1 month, preferably from 1 day to 1 week, depending on the starting materials and / or catalyst used.

By this relatively mild reaction, it is also possible to produce polythiophenes having the following advantageous properties: the resulting thiophene has little or no structural defects, doping or excessive oxidation; -A large number of functional groups can be used, including acceptors, donors and π-systems with multiple bonds between carbon and heteroatoms; and-exact alternating coordination with variously substituted rings. It is possible to carry out the reaction of polymeric copolythiophenes, for example thiophenes substituted in the 3- and 4-position, with unsubstituted thiophenes, a process which has hitherto been commonly used for the preparation of polythiophenes. It was extremely difficult.

The Suzuki reaction also has the above-mentioned advantages over the conventional method, but within the scope of the present invention the Stille reaction is advantageous, since this reaction is opposite to the Suzuki reaction Because no additional base is required.

Accordingly, the present invention relates to a 2,5-dihalogenthiophene or a 2,5-ditriflate thiophene, and a thiophene derivative substituted with bis (trialkyltin) at at least one carbon atom adjacent to sulfur ( This corresponds to the structural unit (II) defined above)
In a suitable solvent, a suitable Pd (0) complex or Pd (I
I) at least one prepared by reaction in the presence of the complex
The use of certain polythiophenes in nonlinear optical materials according to the invention is also described. Further, a 2,5-bis (trialkyltin) thiophene and a thiophene derivative bis (halogen) -substituted or bis (triflate) -substituted at at least one carbon atom adjacent to sulfur (this is described above) At least one polythiophene prepared by reaction in the presence of a suitable Pd (0) complex or a Pd (II) complex as a catalyst in a suitable solvent with a defined structural unit (II) Are also described as non-linear optical materials.

The invention furthermore relates to the following components (a) and (b): (a) at least one polythiophene as defined above; (b) at least one other polymer, wherein component (a) ) And (b) relate to compositions having non-linear optical properties that are different from each other.

[0063] Component (b) of the composition is an amorphous polymer. For example, polymers based on vinyl acetate, vinylamine, vinylimidazole or vinylpyrrolidone. Others include polymers based on acrylamides, such as acrylamide or alkylacrylamide, preferably methacrylamide. Similarly, polymers based on acrylimides, acrylimide or alkylacrylimide, preferably methacrylimide, can also be used as component B.

[0064] Random or block copolymers as well as mixtures of different polymers B can also be included in the composition. Particularly advantageous are copolymers based on polyvinylpyrrolidone and monomers selected from the group of N-vinylpyrrolidone, N-vinylimidazole and vinyl acetate. Particular preference is given to polymers based on N-vinylpyrrolidone and vinyl acetate.

These polymers are well known and generally have 2
0000 to 1500000, preferably 40000 to 120
It has a molecular weight (weight average) of 0000. The production of these polymers is likewise known, or these polymers can be produced by known methods,
Reference is made here to relevant documents.

Generally, the proportion of polymer component (b) in the composition is from 79.9 to 95% by weight. An advantageous composition is
Polymer (b) contains from 81.8 to 92, in particular from 84.6 to 90% by weight. The balance of the composition is the polythiophene used according to the invention, whereby components (a) and (b) make up 100%.

The thin films of polythiophene used according to the invention can be prepared by casting a carefully filtered or centrifuged solution in chloroform or trichlorethylene onto a glass support. In this way, a homogeneous film with a thickness of up to 300 nm can be obtained. The optical quality of this coating is high and does not show the noticeable light scattering. In particular, polymers having structural units (I) and (IIb) alternately comprise from about 850 to about 9
It has a maximum in the absorption spectrum at 00 nm and shows high transparency in the visible region, where it is approximately 42
It has a weak maximum at 0 nm and a minimum at about 520 nm. This value is measured in THF, in which the substance has a green color. The same applies to the coating obtained for this polymer. Polymers with amide- or sulfamide-substituents are typical for polythiophenes as a film and in the form of a THF solution (λ _max = 410-4).
30 nm).

The thieno [3,4-b] pyrazine unit (II
The maximum position in the long wavelength region of the solution or coating of all copolymers having b-IIe) is determined by their relative proportions and is in the range from about 400 to about 1000, especially from about 410 to about 900 nm. .

The invention therefore also relates to the use of a coating or sheet containing at least one polythiophene as defined above, or at least one composition as defined above, as a nonlinear optical material.

The present invention further provides a nonlinear optical material comprising at least one polythiophene as defined above, or at least one composition as defined above.

The present invention will be described in more detail with reference to the following examples.

[0072]

【Example】

Model test of advantageous polythiophenes used according to the invention 2,3-Didecylthieno [3,4-b] pyrazine-thiophene-oligomer Co-oligomer used according to the invention (Co-Oligomere)
n) or to obtain a copolymer,
The reaction is carried out in F in the presence of (Ph ₃ P) ₄ Pd or (Ph ₃ P) ₂ PdCl ₂ , which are used in a catalytic amount of 2 to 5 mol% based on the component 1 shown in the following reaction formula. did. In the case of dibromide 1 shown below, the reaction had already started at room temperature.

To obtain more accurate information on the structure of the resulting polymer, it was first necessary to investigate the structure of the oligomer formed during the early stages of the polymerization. This type of test is generally possible when starting materials are used in excess and interfere with the reaction at low conversion rates. Examples of this type of reaction are given below.

[0074]

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In this reaction formula, m and k are each an integer of 1 to 10, 1 is an integer of 1 to 3000, R is alkyl, and λ _max is the maximum absorption wavelength in the visible region.

The "short" oligomers 7, 8 and 9 were separated from the reaction mixture and, after separation, were obtained as pure compounds using a silica gel column. The fraction obtained after separation, “long oligomer”, is called MALDI (matrix-assisted laser-desorption ionization).
Tested by mass spectrometry using n). By this method it is possible to obtain a complete molecular substance without decomposition.
It should be noted that the tin groups still present in the oligomer are separated off when separating on a silica gel column. The results of the mass spectrometry test are shown in Table 1 below.

[0077]

[Table 1]

4, 1-2 each having the same number of thieno [3,4-b] pyrazine units (Σl = 2,3,4)
Similar to the comparison of the resulting materials in columns 3, 4-5-6 and 7-8, in this reaction using one of the starting materials in excess, the 3,4-unsubstituted thiophene ring and thieno [3 , 4-
b] There was no regular alternating arrangement between the pyrazine rings. In some cases, the pyrazine rings are separated from one another by one or more thiophene rings. Thus, for example, a molecular weight of 17
38 corresponds to three thienopyrazine fragments (Σ = 3) and six thiophene rings (Σ (k + m) = 6). Possible values of m are 1, 2 and 3 since Σk ≧ Σl. When m is 1, the combination of k values is 1,
2,2 or 1,1,3, which can be changed in the first set, which results in 2,1,2 or a combination of 2,2,1 which is 3 Corresponds to an oligomer of the isomer of

This form of “homocoupling” is less pronounced when reacting the same molar amounts of the two starting materials (1 and 3). After purification, a polymer having a ratio of two monomers of approximately 1: 1 is obtained in this embodiment by elemental analysis. The weight average molecular weight (M _w ) of the polymer of general formula 4 obtained starting from 1 and 3 obtained within this reaction range is approximately 2000 as determined by GPC using polystyrene as standard respectively.
0 to almost 100,000, preferably about 50,000. Polydispersity ( _Mw / _Mn ) of approximately 2.0 to approximately 3.0;
Advantageously it is approximately 2.0-2.5.

The following reaction formula:

[0081]

Embedded image

Wherein T = H or a trialkyltin m, l, k = as defined above R = alkyl, preferably CH ₃ R ′ = alkanoyl having 16 to 22 C atoms, or

[0083]

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In this case, R ″ = alkyl having 10 to 22 C atoms or alkoxyl R ′ ″ = alkyl having 10 to 22 C atoms), in an analogous reaction of other copolythiophene,
Copolythiophenes having a weight average molecular weight of 0000 to about 60000, preferably up to about 50,000 and a polydispersity of about 2.0 to about 3.0 are obtained.

Formula 4 having an alkyl (or alkoxyalkyl) substituent having 10 to 22 carbon atoms,
The polythiophenes 5 and 6 are dissolved in organic solvents such as chloroform and THF.

In all these cases, of course, an alternating sequence of substituted and unsubstituted thiophenes is advantageous.

A very important modification of the thieno [3,4-b] pyrazine fragment involves the extension of conjugation inside the pyrazine component to be polymerized. The additional conjugated system may be heterocyclic or non-heterocyclic. 4 in the latter case
It may be composed of one, two or more C ＝ C double bonds by forming a ring such as a six-membered ring or a six-membered ring. The 4-membered ring system of cyclobuta [b] thieno [3,4-e] pyrazine is particularly advantageous, since this use results in particularly advantageous nonlinear optical properties.

General Procedure for the Preparation of the Monomers to Generate the Polythiophenes Used According to the Invention The synthesis of some of the monomers giving the polythiophenes which are particularly advantageously used within the scope of the invention will now be described in detail.

5,7-Dibromothieno [3,4-b] of the general formula 11 which is an important monomer for synthesizing the undoped or doped polythiophenes and oligothiophenes of the general formulas 4 and 6 defined above. The pyrazine is advantageously obtained as follows:

[0090]

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R '= H, C ₁ -C ₂₂ alkyl or C ₁ -C
₂₂ alkoxyalkyl, i: reaction with bromine-dioxane complex in THF, ii: R'-CO-CO- in the presence of triethylamine in a solvent mixture consisting of ethanol and methylene chloride
Reaction of R 'The synthesis of 3,4-diaminothiophene is described in the literature (F. Outurquin et al. "Syntheses du diamino-3,4t
hiophene de quelques derives de substitution ", Bull
etin de la Societe Quimiqie de France 1983, S.II-15
3-II-158 and WO 87/05296). Alkyl- or alkoxyalkyl-substituted 1,2-
Diketones can be obtained in a simple manner by oxidation of acetylene (DGLee "The preparation of α-diones. Phase-tra
nsfer assisted oxidation of alkynes by potassium p
ermanganate ", Synthesis, 1978. S. 462-46
3). The reaction is illustrated by the following equation.

[0092]

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A preferred embodiment of the above monomer 11 is a monomer of the general formulas 14 and 17 described below.

The 2,3-dialkoxy-5 of the general formula 14
7-Dibromothieno [3,4-b] pyrazine is obtained as follows:

[0095]

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I: Br ₂ -dioxane (1: 1) complex, THF, -10 ° C. to room temperature (X = Br) or I ₂ / K
IO ₃ / aqueous H ₂ SO ₄ / ACOH / CCl ₄ , reflux (X =
I) ii: R'CH ₂ I, Ag ₂ CO ₃ , toluene, room temperature,
Reflux, ultrasonic R ¹ = the above X = halogen 5,6-dialkoxy-1,3-dibromocyclobuta [b] thieno [3,4-e] pyrazine of general formula 17 is obtained as follows. :

[0097]

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I:

[0099]

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Anhydrous EtOH, room temperature ii: Br ₂ -dioxane (1: 1) -complex, TH
F, −10 ° C. to room temperature iii: R′CH ₂ I, Ag ₂ CO ₃ , toluene, room temperature,
Reflux, C ₁ -C ₂₂ alkyl 5,7-dibromo ultrasonic R '= a linear or branched - or 5,7-diiodo-1,2,
3,4-tetrahydro-2,3-dioxothieno [3,
4-b] pyrazine 13 is a known compound 12 (F. Outurquin
et al. Bull.Chem. Soc. France 1983, 5-6, II-153-II-15
Starting from 4), it is obtained as a yellowish brown to dark brown powder in a yield of 60-90%. It has very low solubility in all practical solvents, but its quality can be determined by microanalysis for Br or I content (see F. Outurquin et al., Supra).

Monomers 14 and 17 were obtained starting with amide 13 or compound 16 and starting with GCHopkins et al. J. Org.
It can be produced by O, O′-alkylation using the corresponding iodide (RCH ₂ I) under the same conditions as described in Chem. 32 S. 4040 (1967). When the silver salt of an amide is used, if the reaction is carried out in an aprotic, non-polar solvent, preferably a hydrocarbon, the O, O′-alkylation is preferred over the N, N′-alkylation. Dominant. Particular preference is given to using toluene, since reactions at elevated temperatures are possible. In order to accelerate the rate of the heterogeneous reaction, it is necessary that the reaction be carried out under standard stirring and treated with ultrasound at regular time intervals. Under these conditions, the reaction proceeds completely within a few days with yields of approximately 40% to approximately 70%. Products resulting from N, N'- and O, O-alkylation are not isolated. Starting compound 15
Is 3,4-diaminothiophene (GCHopkins et al. J.
Org. Chem. 32 S. 4040 (1967)) and AH starting from commercially available 1,2-diethoxy-2,3-dioxocyclobutene.
The method described in Schmidt et al. Synthesis, S869 (1978) can be obtained in a simple manner and in high yield. Subsequently, bromination and O, O-dialkylation are carried out in the same manner as described above to obtain the monomer 17.

The isolation and purification of monomers 14 and 17 is carried out by chromatography on silica gel and subsequent recrystallization. The compound obtained is stable in air at room temperature. Its thermal stability is likewise sufficient for subsequent reactions, with no decomposition into solution at temperatures up to 100-120 ° C. under a protective gas atmosphere for several hours.

Other advantageous monomer types are those of the general formula 18
N, N-substituted 3,4-diamino-2,5-diiodothiophene. This is obtained as follows.

[0104]

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I: RCOCl or RSO ₂ Cl or RCSCl, pyridine ii: I ₂ / KIO ₃ , AcOH / H ₂ SO ₄ / CC
l ₄ , reflux iii: (only when R ′ is RC (O)) Lawesson's reagent (Lawesson-Reagenz), toluene, reflux R ′ = RC (O), RSO ₂ , RC (S), and R =
Represents a linear or branched C ₁ -C ₂₂ -alkyl or a linear or branched C ₁ -C ₂₂ -alkoxyalkyl.

Starting compound and the monomer docosane-11,12-dione 3H ₂₁ C ₁₀ -C≡C—C ₁₀ H ₂₁ + 4KMnO ₄ + 2H ₂ O used according to the invention
→ 3H ₂₁ C ₁₀ -CO-CO-C ₁₀ H ₂₁ +4 MnO ₂ +4
KOH 11-docosin was prepared according to the general method described above (DGLee et al.
Synthesis, 1978. S. 462-463).

11-docosin (TMFyles, J. Org. Chem. 1
984, manufactured by the method described in S. 753 to 761) (15.
3 g, 0.05 mol) and Adogen 464 (5.7 g, obtained from ALDRICH) were dissolved in a mixture consisting of 360 ml of dichloromethane and 18 ml of glacial acetic acid. Potassium permanganate (21.6 g,
(0.136 mol) was finely powdered and added to the vigorously stirred solution, which was kept at reflux. The mixture is refluxed for 4 hours.
Stirred for hours. Excess oxidant and precipitated manganese dioxide were decomposed by adding a solution of sodium nitrite or sodium sulfite and adding diluted inorganic acid until complete decolorization. The organic layer was separated, and the aqueous layer was extracted with 250 ml of dichloromethane. Combine organic layers with water, 2% N
Washed sequentially with aOH, water and saline solution. After drying over magnesium sulfate, the organic solvent was evaporated and the resulting waxy material was recrystallized from methanol. Melting point 68.5-6
10.8 g of docosan-11,12-dione as a pale yellow solid having 9 ° C. (methanol) (64
%)was gotten.

3,4-diamino-2,5-dibromothio
Phen (-dihydrobromide) 3,4-diaminothiophene (F. Outurqui
(prepared by the method of n) (1.14 g, 10 mmol) was dissolved in 30 ml of dry THF under a nitrogen atmosphere. Subsequently, at −10 ° C., 4.96 g (20 mmol) of the bromo-1,4-dioxane (1: 1) complex were added little by little to the stirred solution. The solution turned black and a black solid precipitated. The reaction mixture was warmed to room temperature and stirred for another 2 hours. Subsequently, dry diethyl ether was added (100 ml), the precipitate was separated off, washed with dry ether and dried under nitrogen. 4.22 g of a black-brown powder were obtained. (Yield: 98% based on 3,4-diamino-2,5-dibromothiophene-dihydrobromide) This material has limited stability and was used in other reactions without further purification.

5,7-dibromo-2,3-didecylthier
No [3,4-b] pyrazine (1) 3,4-diamino-2,5-dibromothiophene-dihydrobromide (5.2 g, 12 mmol) and docosan-11,12-dione (3.4 g, 10 mmol) ) Under nitrogen in 35 ml of dichloromethane and 35 ml of absolute ethanol
ml mixed with each other. To the stirred mixture at 0 ° C. was added dropwise triethylamine (2.6 g, 26 mmol), which was subsequently kept at 60 ° C. for 1.5 hours. Subsequently, chloroform (200 ml) was added and the black suspension was filtered through Celite®, Manville, Filtration and Minerals ^™ to remove the solids formed. The filter cake was washed with chloroform and the combined solution was briefly stirred and warmed with activated carbon. Filtration through celite and evaporation of the solvent under reduced pressure gave a brown solid which was washed with methanol and subsequently recrystallized from methanol. Melting point 50.9 ° C (decomposition)
5,7-dibromo-2,3 as yellow needles having
3.3 g of decylthieno [3,4-b] pyrazine (57
%)was gotten.

3,4-di (hexadecanoylamino) thio
Ophene 3,4-diaminothiophene (2.0 g, 17 mmol) was dissolved in pyridine and palmitoyl chloride (1.
To a stirred solution of 9.33 g (34 mmol) at 4 mbar (bp 141 ° C.) was added dropwise by injection. Stirred overnight. The reaction mixture was poured into ice water to which concentrated hydrochloric acid was added, and extracted three times with 150 ml of chloroform. The organic layer was washed with water, 2% N
aOH (2 × 100 ml), washed again with water, followed by Mg added with activated carbon to remove colored impurities
And dried over SO _4. After evaporating the solvent, a solid with a yield of 70% was obtained, which was recrystallized from a toluene-hexane mixture. The solid had a melting point of 107-109 ° C.

3,4-di (hexadecanoylamino)-
2,5-diiodothiophene (18, R '= C (O) C
₁₅ H ₃₁ ) The iodination method described in RFHeck, Organic Reactions, 27, S.345ff (1982) was used. 2.35 g (4 mmol) of 3,4-di (hexadecanoylamino) thiophene, 0.9 g (3.6 mmol) of iodine, potassium iodate 0.
A mixture of 5 g (2.4 mmol), 2.0 ml of 30% sulfuric acid, 12 ml of carbon tetrachloride and 7.0 ml of glacial acetic acid was stirred under heating (75 ° C.) for 2 hours. After cooling to 0 ° C., the precipitate was collected, washed with methanol and recrystallized from a toluene-ethanol mixture. Di (hexadecanoylamino) -2,5-diiodothiophene having a melting point of 201 DEG to 203 DEG C. (decomposition) (toluene-ethanol) was obtained in a yield of 83% of theory.

2,5-bis (trimethyltin) thiophene
Down (3, alkyl = CH ₃₎ H.Zimmer, J.Org.Chem.49, was prepared by the method of S.5250~5253 (1984).

5,5′-bis (trimethyltin) -2,
2'-bithiophene (20) S. Kotani et al. J. Organomet. Chem. 429, S. 403-413 (199
It was produced by the method described in 2).

5,7-dibromo-1,2,3,4-tetra
Lahydro-2,3-dioxothieno [3,4-b] pyra
Gin (13, X = Br) Starting material 12 is F. Outurquin, Bull. Chem. Soc. France, 198
3, II-153 to 159 (method A).
Activated carbon was added from water and the mother liquor was evaporated to a small volume. Dioxane-bromine complex (1: 1
1,1.75 g, 7.1 mmol) were added in portions to a stirred suspension of compound 12 (0.49 g, 2.9 mmol) in 20 ml of dry THF. After the addition was completed, the cooling bath was removed and the reaction mixture was warmed to room temperature and further stirred for 6-10 hours. The brown precipitate is filtered, washed with ether,
Dried. 0.64 g (67% of theory) of the crude product of compound 13 was obtained.

The 5,7-dibromo-2,3-di (hexade
Siloxy) thieno [3,4-b] pyrazine (14,
R ′ = C ₁₆ H ₃₃ ) Starting material 13 (0.59 g, 1.8 mmol), silver carbonate (1.10 g, 4.9 mmol), hexadecyl iodide (7.0 g, 20 mmol) were dissolved in toluene ( 70ml)
In an ultrasonic bath at room temperature under nitrogen for 30 minutes. At that time, generation of gas was recognized. The reaction mixture was subsequently stirred at 100 ° C. under nitrogen for 6-8 hours and kept in an ultrasonic bath (30 minutes, room temperature, nitrogen atmosphere). This operation is 6 ~
It was repeated eight times, at which time the incidence of bright natural light was eliminated.
After removing the precipitate, the dark reaction mixture was carefully filtered through celite under moderate vacuum, and the filter cake was washed with a hexane-ether mixture until the flowing-through solvent flowed out colorless. The filtrate was evaporated under reduced pressure, the residue was dissolved in hexane and separated on a silica gel column. Hexadecyl iodide is eluted with hexane to give the desired product 1
4 was eluted with a hexane-ether mixture (50: 1). 0.56 g (40%) of a pale yellow solid having a melting point of 68 ° C. (acetone-methanol) was obtained.

¹ H-NMR (400 MHz, CDCl ₃ ,
δ, ppm): 0.88 t (6H, J 6.5 Hz, CH
_{3), 1.25m (48H CH 2} x24), 1.45m
(4H, CH ₂ (CH ₂ CH ₂ O)), 1.89 quin
_{t (4H, J6.5Hz, CH 2} (CH 2 O)), 4.4
8t (4H, J 6.5 Hz, CH ₂ O) ¹³ C-NMR (100 MHz, CDCl ₃ , δ, pp
_{m): 14.33 (CH 3)} , 22.71,25.9
6, 28.37, 29.31, 29.38, 29.6
1,29.72 (4-5 times the intensity), 31.94 (CH
₂ ), 67.86 (CH ₂ O), 98.63 (CB
r), 136.24 (= C (N)), 151.08 (C
= N).

General Polymerization Method The halothiophene derivatives 1,14,18 (or their mixtures of different components) were used in a total amount of approximately 1 mmol. Bis (trialkyltin) thiophenes 3 and 20 were used alone or in equivalent amounts as a mixture. This starting material was dissolved in water-free THF (20-200 ml) and introduced into an oven-dried or annealed two-necked flask, where a weak stream of nitrogen or argon flowed through the solution for 10-15 minutes. Bis (triphenylphosphine) palladium (II) chloride or tetrakis (triphenylphosphine) palladium (0) was added to the oxygen-free solution at 2 to 5 mol%. The flask was equipped with a reflux condenser and
The reaction was carried out at a temperature between 0 ° C. and approximately 70 ° C. for 1-7 days under a nitrogen or argon atmosphere.

After completion of the reaction, the solvent was evaporated and the residue was dissolved by adding methanol from the wall of the flask. The precipitate was collected and washed with methanol and hexane, removing the trialkyltin halide. Further purification was performed by soxlet extraction with methanol, hexane or acetone (for substances with low solubility). Chloroform, THF polymer
Or dissolved in another solvent (optionally using an ultrasonic bath) to remove insoluble particles from the solution (3000-5000 r.
Additional purification is possible by centrifugation (at pm) and precipitation of the higher molecular weight material with methanol, hexane or other suitable solvent, followed by centrifugation. If necessary, these purification steps can be repeated, for example to obtain a polymer with a high molecular weight and / or a low polydispersity.

DFWM Measurement The DFWM experiment in which the wavelength can be varied is measured using a folding box structure (Fold
ed-Boxcars Konfiguration). As a light source,
Pulse 100 fs time, tunable 720-920 nm
A mode-coupled Ti sapphire laser with As a result, the time resolution of the DFWM experiment is 100 f
s. The number of laser repetitions is determined by the pulse picker (Puls
The frequency was adjusted to 100 kHz with a picker. The overlap of the two focused partial lights at the sample position created a refractive index grating due to the non-linearity of the thiophene layer, which was scanned with interrogation radiation. The intensity of the interrogation radiation off the index grating was the measured signal. A Si photodiode with a back-connected amplifier was used for detection. To improve the signal-to-noise ratio, an additional lock-in amplifier was used in combination with a spatial filter in front of the detector and two optical choppers. The non-linearity value, χ ⁽³⁾ value, can be obtained from the measurement signal by performing additional measurements with reference material CS ₂ under the same optical ambient conditions and taking into account the absorption and layer thickness of the reference sample and the measurement sample. Could be calculated. The relaxation time of the optical nonlinearity was measured by repeating the experiment periodically, in which the interrogation pulse was gradually delayed in time with respect to the grating forming pulse. At that time, the measurement signal decreased as the delay increased. The relaxation time could be measured directly from the decrease in time (see measurement curve).

Example 1 Monomers 1, 18 and 3 were reacted with each other according to the general polymerization method described above, and a copolymer 1 was obtained according to the following reaction formula. Copolymer 1 was obtained with a yield of 60%. It had a weight average molecular weight M _w 40000 measured by GPC using polystyrene as a standard and a polydispersity, ie a ratio of weight average molecular weight to number average molecular weight of 2.8. The relative amounts used and the catalysts used are likewise described in the formula below.

[0121]

Embedded image

A thin film of Copolymer 1 on a piece of glass plate was cast using a chloroform solution of the copolymer. It had a layer thickness of 755 nm.

⁽³⁾ Value (DFWM, 755 nm): 0.1.
52 · 10 ^{- 9} esu relaxation time: 170 fs, are reacted with one another monomer 1,14,20 and 3 by 2.5ps Example 2 above general polymerization method, copolymers 2 by the following reaction scheme
was gotten. Copolymer 2 was obtained with a yield of 51%. It has a weight average molecular weight M _w 51000 measured by GPC using polystyrene as a standard and a polydispersity of 2.
7 had. The relative amounts used and the catalysts used are likewise described in the reaction schemes below.

[0124]

Embedded image

A thin film of copolymer 2 on a glass plate was cast using a chloroform solution of the copolymer. It had a layer thickness of 395 nm.

⁽³⁾ Value (DFWM, 840 nm): 0.1.
99 · 10 ^{- 9} esu relaxation time: 180fs, described in 1.6 ps DFWM measurement results and and 1 absorption spectra of these copolymers 2 (copolymer 1) and 3 and 4 (copolymer 2).

[Brief description of the drawings]

FIG. 1 graphically shows the DFWM-signal of the polythiophene layer according to Example 1 at a wavelength of 755 nm.

FIG. 2 is an absorption spectrum of a polythiophene layer according to Example 1. Layer thickness is 755 nm

FIG. 3 graphically shows the DFWM-signal of the polythiophene layer according to example 2 at a wavelength of 840 nm.

FIG. 4 is an absorption spectrum of a polythiophene layer according to Example 2. Layer thickness is 395nm

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Fradimir Beloff Germany Ludwigshafen Londner Ring 13 (72) Inventor Elmar Meier Augsburg Geschwister-Schor-Strase 12 (72) Inventor Edwald Koylen Mie 3-33-5 Sasaohigashi, Toin-cho, Toin-cho

Claims (2)

[Claims] 1. General formulas (I) and (II) Wherein X and Y may be the same or different independently of one another and are linear or branched C ₁ -C ₂₂ alkyl groups; linear or branched C ₁ -C ₂₂ alkoxy groups; A linear or branched C ₁ -C ₂₂ alkyloxyalkyl group; a linear or branched C ₁ -C ₂₂ acyl group; a linear or branched C ₁ -C ₂₂ thioacyl group; A branched C ₁ -C ₂₂ thioacyloxy group; a linear or branched C ₁ -C ₂₂ acyloxy group;
C ₅ -C ₈ cycloalkyl group, C ₆ -C ₁₈ aryl group or C ₅ -C ₈ heterocyclic group (C ₁ -C ₂₂ alkyl group of one or more linear or branched They further respectively, One or more linear or branched C ₁ -C ₂₂ alkoxy groups, one or more linear or branched C ₁ -C ₂₂ alkyloxyalkyl groups, one or more linear or branched chains NO ₂ ; or NHR ¹ , which may be substituted by a C ₁ -C ₂₂ acyl group or one or more linear or branched C ₁ -C ₂₂ thioacyl groups);
Wherein R ¹ may be the same or different and are each hydrogen; or a linear or branched C ₁ -C ₂₂ alkyl group, a linear or branched C ₁ -C ₂₂ alkoxy group, a linear or A branched C ₁ -C ₂₂ alkyloxyalkyl group, a linear or branched C ₁ -C ₂₂ acyl group or a linear or branched C ₁ -C ₂₂
X represents a thioacyl group or X and Y together with the atoms connecting them form a carbon-containing ring system which, in addition to carbon, comprises a nitrogen (N) heteroatom, an oxygen (O) heteroatoms, sulfur (S) heteroatoms or phosphorus (P) heteroatoms or a mixture of two or more of these heteroatoms, wherein the ring system further comprises carbon atoms, nitrogen At each of the atoms or phosphorus atoms may be substituted by a group Z, each Z being independently of one another,
Represents the same as defined for X and Y above, or two adjacent groups Z together form the following general formula (I
II) to (VI) (Wherein, A represents carbon (C), nitrogen (N), phosphorus (P) or a mixture of two or more of these atoms. In this case, as long as A is a carbon atom, A represents 1 Or may be further substituted with the same as defined above for X and Y).
Nonlinear optical material containing polythiophene. 2. The following components (a) and (b): (a) at least one polythiophene as defined in claim 1, and (b) at least one other polymer, wherein the components (A) and (b) are mutually different compositions having non-linear optical properties.