WO1989005843A1

WO1989005843A1 - Non-linear optical material containing a hemicyanine compound and process for producing it

Info

Publication number: WO1989005843A1
Application number: PCT/EP1988/001114
Authority: WO
Inventors: Dieter Dorsch; Bernhard Rieger; Eike Poetsch; Gerd Marowsky
Original assignee: MERCK Patent Gesellschaft mit beschränkter Haftung
Priority date: 1987-12-23
Filing date: 1988-12-07
Publication date: 1989-06-29
Also published as: DD276487A5; DE3743833A1; EP0348497A1; JPH02503005A; KR900700570A

Abstract

Amphiphilic hemicyanines of formula (I) and polymer materials containing a chromophore covalently bonded according to formula (I), in which W, X, Y, Z, A, Q, n, R?1, R?2, R?3 and V?$g(U) have the meaning given in claim 1, are useful as non-linear optical media.

Description

Nonlinear optical material which contains a hemicycline compound and process for its production.

The invention relates to nonlinear optical .Materials containing amphiphilic hemicyanines and polymers which contain the corresponding chromophores covalently bound, a process for their preparation and their use as nonlinear optical media.

Nonlinear optics deals with the interaction of electromagnetic fields in various media and the associated creation of new fields with changed properties. Materials with nonlinear optical properties have a second order dielectric susceptibility, which results in a number of dispersive processes: frequency doubling (second har onic generation = SHG) allows the generation of light of half the wavelength compared to the incident light; the electro-optical effect (Pockels effect) enables the refractive index to be changed when an electric field is applied; Methods of sum and difference frequency mixing as well as frequency division allow the continuous tuning of laser light. A large number of technical applications result from the effects listed above. Electro-optical switches, frequency and intensity control in laser technology, holography and the areas of information processing and integrated optics are areas of application for materials with non-linear optical properties

2nd order.

Materials with electrical susceptibility functions

3rd order are suitable for the production of purely optical switches and thus as waveguides for the construction of purely optical computers.

In order to be suitable for use in the field of 2nd order nonlinear optics, such materials have to meet a number of requirements.

In addition to a non-centrosymmetric molecular arrangement in the

Crystal requires a technical usability the highest possible values for the dielectric susceptibility X ( ^v 2)

A number of inorganic substances such as potassium dihydrogen phosphate or lithium niobate show non-linear optical properties. However, all of these connections have various disadvantages. In addition to ^• insufficient values for second order dielectric susceptibility, inorganic compounds often lack sufficient photostability when treated with high light intensities or are difficult to manufacture and process.

Organic compounds of the nitroaniline type are known from Garito et al., Faser Focus 8 (1982) and EP-0091-838. Their relatively good values for photochemical stability and dielectric susceptibility are second However, order goes hand in hand with poor crystallizability and poor mechanical stability. In particular, the production of thin layers, as required by the integrated optics, does not succeed with these materials.

An interesting class of substance that has already been examined several times is that of hemicyanine dyes, in particular those with the following general structure:

X compatible anion

So D.J. Williams, Angew. Chem. 96_, 637 (1984) carried out on the corresponding compound m t R 1, R2 and R3 equal to CH_ powder tests. I.R. Girling et al.,

Thin Solid Films 132, 101 (1985) examined the frequency

Doubling at the connection with R equal to C H and

R 2, R3 equal to CH_ based on Langmuir-Blodgett films

(LB files). EP-A2-203780 discloses multilayer LB films which consist of alternating layers of two

Connections exist. In one of the two compounds R 1 and R2 is H or lower alkyl and R3 is a long alkyl chain, in the second R 2 and R3 is lower alkyl and

R is a long alkyl chain. Furthermore, G.H. Cross et al. in J. Opt. Soc. At the. B / Vol. 4, No. 6, June 1987

Measurements on LB monolayers of hemicyanines with betaine

Structure and the same alkyl radicals R 2 and R3 have been carried out.

Similar structured polymers are described in Japanese Patent Laid-Open J6 1148-433-A and J6 1167-930-A described. However, in contrast to the inventive chro-ophores, they contain short-chain alkyl radicals or also H or aryl on the donor nitrogen.

The materials still have unsatisfactory nonlinear optical properties and do not adequately meet the requirements placed on commercial use as nonlinear optical media.

There is therefore a need for further nonlinear optical materials which do not have the disadvantages described or only have them to a minor extent and in particular allow the production of nonlinear optical arrangements without the need for noncentrosymmetric crystal structures.

This object is achieved by providing the amphiphilic hemicyanines according to the invention.

It has surprisingly been found that compounds of the formula I and polymers which contain the chromophore corresponding to the formula I covalently bonded are particularly suitable as materials with nonlinear optical properties.

The invention therefore relates to nonlinear optical materials, characterized in that they contain at least one compound of the formula I,

wherein

R ^{1 C} l " ^C 6 ^Alk -"

W, X, Y and 2 each independently CH,

C-alkyl (C- _{j ^} -Cg) or C-halogen, one or two of the radicals W, X, Y or Z also N,

A single bond, -N = N-, -C (R ⁴ ) = C (R ⁴ ) - or -C≡C-,

Q unsubstituted or substituted by C -, - C _ß - alkyl and / or halogen

1,4-phenylene, in which one or more CH groups can also be replaced by N,

n 1, 2, 3 or 4

R 2, R3 j ■ each independently

^C ₆ ~ ^C ₃₀ ^A - * - kyl, in which one or two non-adjacent CH, groups can also be replaced by -0-, -S- or CH = CH,

R each independently of one another H and / or C -, - C ₆ alkyl and

Vθ ei.n kompati.bles Ani.on means.

The invention also relates to nonlinear optical materials containing at least one polymeric component, characterized in that the chromophore is covalently bonded to the polymer chain in accordance with formula I, optionally via a spacer. The invention furthermore relates to a process for the production of nonlinear optical materials, characterized in that a layer of polymerizable compounds containing a chromophore of the formula I, optionally in a mixture with other polymerizable compounds, is applied to a substrate and then polymerized, or that the compounds are first polymerized and the polymer is subsequently applied as a film to the substrate, the chromophores of the polymer applied to the substrate being oriented non-centrosymmetrically.

Finally, the invention relates to the use of the nonlinear optical materials according to the invention as optical media in electronics or as organic substrates in film and fiber technology and in nonlinear optical arrangements.

In formula I, W, X, Y and Z each independently represent CH, C-alkyl (C -, - C ₆ ) or C-halogen. C -.- C, accordingly means methyl, ethyl, propyl, butyl, pentyl, hexyl, 2-methylethyl, 2-methylpropyl, 2-methylbutyl, 2-ethylpropyl or 2-ethylbutyl, halogen, for example fluorine, chlorine or bromine . One or two of the radicals W, X, Y or Z also denote N, preferably X and / or Z.

Accordingly, the nitrogen-containing six-membered ring preferably denotes an unsubstituted or substituted pyridine, pyrimidine or 1,3,5-triazine ring, particularly preferably a pyridine ring.

A each independently of one another preferably denotes a single bond or

Furthermore, preference is also given to compounds in which A is -C≡C- or

-N = N- means. Q each independently of one another is preferably unsubstituted or by at least one alkyl radical having 1 to 6 carbon atoms, such as, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, 2-methylethyl, 2-methylpropyl, 2-methylbutyl, 2 -Ethylpropyl or 2-ethylbutyl and / or 1,4-phenylene substituted by halogen, in particular fluorine or chlorine, in which a CH group can also be replaced by N. Q particularly preferably means 1,4-phenylene which is unsubstituted or substituted in the stated preferred manner.

n is preferably 1, 2 or 3.

R is preferably -, - C ₄ alkyl, that is methyl, ethyl, propyl, 2-methylethyl and butyl.

2 3. . .

R and R preferably each independently of one another denote Co - C-, u--, particularly preferably C-, Δ "-CJ_U_ alkyl, in which one or two non-adjacent CH ₂ groups are also represented by -O- and / or - CH = CH-can be replaced.

R 4 is preferably each independently of the other

H and / or C1 -.- Co ,. Alkyl, particularly preferably H or

^C ₁ ~ ^C ₄ Aiky ¹ ' ^so for example methyl, ethyl, propyl, 2-methylethyl and butyl.

V ^θ means a compatible anion such as a halide, methoxysulfonate, p-toluenesulfonate or another suitable anion of an inorganic or organic acid. CH ₃ OS0 ₃ , CH ₃ - O -S0 ₃ ^θ , Br ^θ , I ^θ , BF ₄ ^Θ and Re0 ₄ ^® are particularly preferred.

The chromophores corresponding to formula I have excellent nonlinear optical properties. It is immaterial whether they are compounds of the formula I or covalently bound to a polymer matrix are used according to the invention. The presence of a donor-acceptor system in the form of the present hemicyanm structure with two long alkyl radicals R 2 and R3 is of importance. The quaternized nitrogen-containing six-membered ring acts as the acceptor and the amino group acts as the donor.

The materials according to the invention can be used in the form of LB layers, applied to a substrate, according to the invention. For example, a non-centrosymmetrically oriented polymer film (non-centrosymmetry of the chromophores) can be produced on a substrate, for example glass or another suitable material, by polymerizing a polymerizable compound containing a chromophore according to formula I, then an LB mono - Layer of the polymer is produced according to known and conventional methods, preferably on a water surface, and then applied to the substrate (M. Sugi, "Langmuir-Blodgett films - a course towards molecular electronics: a review", J Mol. Electron.

1, 3-17 (1985)). But you can also first create an LB layer of the polymerizable compounds on the water surface, then polymerize and transfer the polymer as a film to the substrate. Finally, there is also the possibility of applying the polymerizable compounds to the substrate, for example using the LB technique, and only then polymerizing them.

In this context, the structure of the polymer structure is also not critical. Polystyrenes, polyesters, polysiloxanes, poly (meth) acrylates, poly (meth) acrylamides and their copolymers and polymer mixtures or other polymer materials can be used. Accordingly, according to the invention, in particular those compounds of the general formula I or those polymers which contain a chromophore corresponding to the formula I covalently bonded are preferably used as nonlinear optical materials in which R 1, R 2,

R ³ , R ⁴ , R ⁵ , W, X, Y, A, Q, n and V ^{θ have} the meanings given above.

Preferred compounds of the formula I and compounds of the formula I whose chromophores are covalently bonded to a polymer chain are thus those of the sub-formulas Ia to Ic

R ¹ -Het-AQ-NR ² -R ³ Ia

R ¹ -Het- (AQ) ₂ -NR ² R ³ Ib

R ¹ -Het- (AQ) ₃ -NR ² R ³ IC

For simplicity, means here and below

Het is equal to Pyr ^φ V ^θ , in which Pyr ^denotes an unsubstituted or, in the stated preferred manner, substituted pyridine, pyrimidine or triazine ring. Of the partial formulas Ia, compounds of the sub-formula Ial to Ia3 are accordingly very particularly preferred.

R ¹ -He -Phe-NR ² R ³ Ial

R ¹ -Het-C (R ⁴ ) = C (R ⁴ ) -Phe-NR ² R ³ Ia2

R ¹ -Het-C≡C-Phe-NR ² R ³ Ia3

Here and in the following, Phe means 1,4-phenylene which is unsubstituted or, preferably, substituted, in which one or two CH groups can also be replaced by N.

The preferred compounds of the sub-formulas Ib include those of the sub-formulas Ibl to Ib6

The preferred compounds of sub-formula Ic include those of sub-formulas Icl to Ic7

The compounds of the general formula I can be prepared by standard processes or organic chemistry.

The reaction conditions can be found in the standard works of preparative organic chemistry, e.g. HOUBEN-WEYL, Methods of Organic Chemistry, Georg Thieme Verlag, Stuttgart, ORGANIC SYNTHESES, J. Wiley, New York - London - Sydney, or HETEROCYCLIC COMPOUNDS, Vol. 14, J. Wiley, New York - London - Sydney.

Compounds of the general formula I in which A

C (R 4) = C (R4) means, for example, can be prepared by condensing alkyl compounds with a corresponding aldehyde or ketone in a conventional manner. The condensation is advantageously under Addition of a dehydrating agent such as acetic anhydride, a base such as ammonia, ethylamine, piperidine, pyridine or a salt such as ammonium acetate or piperidinium acetate. The addition of an inert solvent, such as hydrocarbons such as hexane, cyclohexane, benzene, toluene or xylene, has also proven to be expedient. The reaction temperature is usually between 0 ° and 250 ° C, preferably between 20 ° and 150 ° C. At these temperatures, the reactions are usually complete after 15 minutes to 48 hours.

The alkyl six-ring aza compounds and aldehydes or ketones used as the starting material are known or can be obtained in analogy to the known by customary methods.

To uaternize the nitrogen-containing six-membered ring, reagents known to the person skilled in the art are reacted with the nitrogen-containing six-membered ring compounds under reaction conditions which are conventional per se. The process conditions for this are generally known and can also be found in the standard works of preparative organic chemistry.

In a further process for the preparation of the compounds of the formula I, an aryl halide is reacted with an olefin in the presence of a tertiary amine and a palladium catalyst (cf. RF Heck, Acc. Chem. Res. 12_ (1979) 146). Suitable aryl halides are, for example, chlorides, bromides and iodides, in particular bromides. The tertiary amines required for the coupling reaction to succeed, such as triethylamine, are also suitable as solvents. Examples of palladium catalysts include its salts, in particular Pd (II) acetate organic phosphorus (III) compounds such as tri-l-phosphines. You can work in the presence or absence of an inert solvent at temperatures between about 0 ° and 150 °, preferably between about 20 ° and 100 °; Examples of suitable solvents are nitriles such as acetonitrile or hydrocarbons such as benzene or toluene. The aryl halides and olefins used as starting materials are commercially available in many cases or can be prepared by processes known from the literature, for example by halogenation of corresponding parent compounds or by elimination reactions on corresponding alcohols or halides.

Aryl halides can also be reacted with aryltin compounds to couple aromatics. These reactions are preferred with the addition of a catalyst such as e.g. of a palladium (O) complex in inert solvents such as hydrocarbons at high temperatures, e.g. in boiling xylene, carried out under protective gas.

The polymers according to the invention contain at least one chromophore corresponding to the formula I, optionally covalently bound to the polymer chain via a spacer.

In principle, the linkage to the polymer main chain is possible at each carbon atom of a compound of formula I, optionally via a spacer. However, the terminal linkage is particularly preferred, i.e. on a terminal C atom in R 1, R2 or R3 without an additional spacer.

Particularly preferred polymers are poly (meth) acrylates and poly (meth) acrylamides.

Suitable spacers are in particular alkylene groups with 2 to 30 carbon atoms, which are linear or branched and in which one or more CH groups can be replaced by -0-, -S- and / or -NR -. For example, the following can be considered as spacers:

Ethylene, propylene, butylene, pentylene, hexylene, octylene, decylene, undecylene, dodecylene, octadecylene, ethyleneoxyethylene, ethylene thioethylene, ethylene-N-methyliminoethylene or 1-methylalkylene.

Preferred polymers according to the invention are prepared by reacting correspondingly substituted alcohols or amines with (meth) acrylic acid or their reactive derivatives with subsequent polymerization, under reaction conditions which are customary per se and known to the person skilled in the art. The monomers are also the subject of the invention.

The following are particularly suitable comonomers for the preparation of the copolymers:

C - to C _2Q -, preferably C. to Cg alkyl esters of acrylic acid and / or methacrylic acid, mixtures of these esters and mixtures of the esters mentioned with acrylonitrile, methylacrylonitrile, styrene, 4-methylstyrene, acrylic and / or methacrylamide.

The following are preferably preferred as monomers:

Methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, hexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, nonylacrylate, decyl acrylate, dodecyl acrylate, hexadecyl acrylate, octadecyl acrylate and the corresponding methacrylate.

The acrylates and methacrylates mentioned of alkanols having up to 8 carbon atoms are preferred. Alternatively, polymers which contain halogen substituents, preferably bromine or iodine, in the side chains can also be reacted with the pyridine derivatives (without R) on which the formula I is based. In this way, the homo- or copolymers according to the invention are obtained in which the chromophore is preferably terminally linked to R with the polymer structure. The halogen-substituted starting polymers can be obtained by homopolymerizing halogenated monomers or by copolymerizing them with preferably the comonomers mentioned.

The polymers are prepared by known processes, preferably by free-radical polymerization.

A large number of known initiators are suitable for triggering the polymerization, for example in Pappas (ed.), UV Curing: Science and Technology, Technology Marketing Corp., Stamford, CT, 1978, or in Ocian, Principles of Polymerization, McGraw- Hill, New York. Examples of thermally decaying, free radical initiators are azoisobutyronitrile (AIBN) or per compounds such as potassium persulfate, dibenzoyl peroxide and cyclohexanone peroxide, for initiators decaying through the action of radiation, such as benzophenones such as Michler's ketone [4,4'-bis (dimethylamino) benzophenone ], 4,4'-bis (diethylamino) benzophenone, p-dimethylaminobenzophenone, p-chlorobenzophenone, benzophenone; Anthraquinones such as, for example, anthraquinone, 2-chloroanthraquinone, 2-alkylanthraquinones; Xanthones such as 2-halogen xanthones or 2-alkyl xanthones; Thioxanthones such as 2-chlorothioxanthone, 2-alkylthioxanthones; Acridanones such as 2-alkylacridanones or N-substituted Acrida¬ none; Benzoins such as p-dimethylaminobenzoin and alkyl ether of benzoin; Benzil ketals, α-haiogen ketones, Dialkoxyacetophenones, α-hydroxyalkylphenones and α-aminoalkylphenones as described, for example, in DE-OS 27 22 264 and in EP-OS 3003, furthermore, for example, fluorenones, dibenzosuberones, phenanthrenequinones, benzoic acid esters such as hydroxypropyl benzoate and onium salts such as, for example Diaryliodonium or triarylsulfonium salts.

If necessary, the ethylenically unsaturated monomers can be reacted in the presence of additives.

For example, organic amines, phosphines, alcohols and / or thiols, all of which have at least one CH group α-to the heteroatom, can be added as reaction accelerators. Suitable are e.g. primary, secondary and tertiary aliphatic, aromatic, araliphatic or heterocyclic amines, e.g. are described in U.S. Patent No. 3,759,807. Examples of such amines are butylamine, dibutylamine, tributylamine, cyclohexylamine, benzyldimethylamine, di-cyclohexylamine, triethanolamine, N-methyldiethanolamine, phenyldiethanolamine, piperidine, piperazine, morpholine, pyridine, quinoline, p-dimethylamino-benzoic acid - Butyl benzoate, 4,4'-bis-dimethylamino-benzophenone (Michler's ketone) or 4,4'-bis-diethylamino-benzophenone. Tertiary amines such as, for example, trimethylamine, tri-isopropylamine, tributylamine,

Octyl-dimethylamine, dodecyl-dimethylamine, triethanolamine,

N-methyl-diethanolamine, N-butyl-diethanolamine, tris

(hydroxypropyl) amine, dimethylaminobenzoic acid alkyl ester.

Trialkylphosphines, secondary alcohols and thiols are also suitable as reaction accelerators. Small amounts of light stabilizers, such as, for example, benzophenone derivatives, benzotriazole derivatives, tetraalkylpiperidines or phenyl salicylates, can also be added.

Depending on the intended use, organic additives such as thixotropic agents, leveling agents, binders, lubricants, matting agents, plasticizers, wetting agents, silicones for improving the surface properties, anti-floating agents or small amounts of solvents are suitable as an additive to the ethylenically unsaturated monomers.

The photopolymerization is carried out according to methods known per se by irradiation with light or UV radiation in the wavelength range from 250 to 500 nm, preferably from 300 to 400 nm. Sunlight or artificial emitters can be used as radiation sources. Advantages are e.g. High-pressure, medium-pressure or low-pressure mercury vapor lamps, xenon and tungsten lamps; Laser light sources can also be used.

Furthermore, high-energy radiation, such as, for example, X-ray, electron, neutron and other nuclear radiation, is suitable for triggering the polymerization, the amount of photoinitiator added usually being able to be reduced or dispensed with entirely.

The thermal polymerization is achieved, for example, by treatment using ultrasound or microwaves or by the action of IR radiation.

Table 1 shows a comparison of values of the molecular second order hyperpolarizabilities (β) between known compounds and Example 1 according to the invention. It is known that merocyanine dyes, Thus, for example, the compounds (3) and (4) (shown in the literature mostly in the quinoid boundary structure 3b or 4b), have much higher β values than hemicyanine dyes such as (1). A compound with a comparable chromophore is, for example, p, p'-diaminonitrostilbene (DANS) (2), whose ß value is, as expected, in the same order of magnitude as that of (1).

It is surprising, however, that the compounds of the formula I according to the invention, such as, for example, the compound (5), have orders of magnitude better than the already known hemicyanines such as (1) and that even higher ß values than for the merocyanines ( 3) and (4) can be achieved. The hemicyanine dyes according to the invention also offer considerable application advantages over the merocyanines. Because of their high basicity, the merocyanines are already protonated by the action of atomospheric carbon dioxide and water and structurally change into the less polarizable phenol form. In this form, however, the merocyanines have a much smaller ß value than in the phenolate form (3 or 4) (see Table 1). In order to utilize the higher β-value of the merocyanines in a non-centrosymmetric environment in terms of application technology, however, the protonation must be greatly reduced. This only makes sense if the compounds are continuously exposed to a basic atmosphere, for example ammonia gas. As a result, the merocyanines as nonlinear optical materials are not or only of very little economic importance. The hemicyanines according to the invention do not offer such a disadvantage. They are stable under normal conditions and can therefore be used under the influence of the natural atmosphere - with the β value remaining unchanged. Table 1

(Example 1) determined for * λ = 1064 nm, ** λ = 1890 nm, *** λ = 915 nm

a I.R. Girling, N.A. Cade, P.V. Kolinsky, R.J. Jones,

IR Peterson, MM Ahmad, DB Neal, MC Petty, GG Roberts, and WJ Feast: J. Opt. Soc. At the. B 4, 950 (1987). b JF Nicoud and RJ Twieg: see Appendix II in: "Nonlinear Optical Properties of Organic Molecules and Crystals" (eds. DS Chemla and J. Zyss), Vol. 2, Academic Press.

c A.Dulcic and C. Flytzanis: Optics Comm. 25_, 402 (1978).

to you. Girling, P.V. Kolinsky, N.A. Cade, J.D. Earls, and I.R. Peterson: Optics Comm. 5, 289 (1985).

By applying the compounds or polymer materials according to the invention to a substrate in dissolved or liquid form by, for example, painting, printing, dipping or spin coating, nonlinear optical arrangements are obtained. Furthermore, they can also develop their nonlinear optical properties in powder form, as inclusions in other molecular assemblies, such as, for example, polymers, clathrates, solid solutions, as single crystals or solutions.

The materials according to the invention thus open up a wide field of application. They are particularly suitable in the field of integrated optics, for example in sensor and communications technology for frequency doubling of laser light, for producing directional couplers, switching elements, modulators, parametric amplifiers, waveguide structures and the like.

The following examples serve to illustrate the invention. example 1

a) 4- {2- [4- (N, N-Dioctadecylamino) phenyl] ethenyl} pyridine

A solution of 50.0 g of 4-bromo-N, N-dioctadecylaniline (available from 4-bromoaniline and octadecyl bromide), 15.5 g of 4-vinyl pyridine, 7.5 g of triethylamine, 0.16 g of palladium (II) acetate and 0.47 g of tris-o-tolylphosphine in 200 ml of acetonitrile is heated to boiling for 40 hours. After cooling, the precipitate is filtered off with suction and then chromatographed (silica gel; hexane / ethyl acetate 8: 2). Yellow crystals of melting point 74-75 ° C. are obtained.

b) 4- {2- [4- (N, N-Dioctadecylamino) phenyl] ethenyl} -1-methylpyridinium methoxysulfonate

A mixture of 3 g of compound la and 8 g of dimethyl sulfate is stirred at room temperature for 18 hours. 50 ml of tert-butyl methyl ether are then added, and the resulting precipitate is filtered off with suction. After chromatographic purification (silica gel; dichloromethane / methanol 85:15), deep red crystals are obtained.

The hemicyanin 1b is then applied as an LB monolayer to a quartz substrate (G. Marowsky et al. In Optics Comm. 63 ^ 109 (1987). A β value of 6300 x 10 -30 esu at λ = 915 nm is determined .

The same monolayer is obtained by immersing the substrate in a 10 molar solution of the hemicyanin Ib in propanol (2 min), as described by G. Marowsky et al. in J.Opt.Soc.Am.B 4, 956 (1987). The following are produced analogously

4- {2- [4- (N, N-Didecylamino) phenyl] ethenyl} -1-methyl pyridinium methoxysulfonate

4- {2- [4- (N, N-Didodecylamino) phenyl] ethenyl} -1-methyl pyridinium methoxysulfonate

4- {2- [4- (N, N-Ditetradecylamino) phenyl] ethenyl} -1-methyl pyridinium methoxysulfonate

4- {2- [4- (N, N-Dihexadecylamino) phenyl] ethenyl} -1-methyl pyridinium methoxysulfonate 4- {2- [4- (N, N-Dicosylamino) phenyl] ethenyl} -1 -methyl pyridinium methoxysulfonate

4- {2- [4- (N, N-Didocosylamino) phenyl] ethenyl} -1-methyl pyridinium methoxysulfonate

4- {2- [4- (N, N-Didecylamino) phenyl] ethenyl} -1-ethyl pyridinium ethoxysulfonate

4- {2- [4- (N, N-Didodecylamino) phenyl] ethenyl} -1-ethyl pyridinium ethoxysulfonate

4- {2- [4- (N, N-Ditetradecylamino) phenyl] ethenyl} -1-ethyl pyridinium ethoxysulfonate 4- {2- [4- (N, N-Dihexadecylamino) phenyl] ethenyl} - 1-ethyl-pyridinium ethoxysulfonate

4- {2- [4- (N, N-Dioctadecylamino) phenyl] ethenyl} -1-ethyl pyridinium ethoxysulfonate

4- {2- [4- (N, N-Dicosylamino) phenyl] ethenyl} -1-ethyl pyridinium ethoxysulfonate

4- {2- [4- (N, N-Didocosylamino) phenyl] ethenyl} -1-ethyl pyridinium ethoxysulfonate

4- {2- [3-chloro-4- (N, N-didecylamino) phenyl] ethenyl} - 1-methylpyridinium methoxysulfonate 4- {2- [3-chloro-4- (N, N-didodecylamino) - phenyl] ethenyl} - 1-methylpyridinium methoxysulfonate 4- {2- [3-chloro-4- (N, N-ditetradecylamino) phenyl] ethenyl} - 1-methylpyridinium methoxysulfonate

4- {2- [3-chloro-4- (N, N-dihexadecylamino) phenyl] ethenyl} - 1-methylpyridinium methoxysulfonate 4- {2- [3-chloro-4- (N, N-dioctadecylamino) - phenyl] ethenyl} - 1-methylpyridinium methoxysulfonate

4- {2- [3-chloro-4- (N, N-dicosylamino) phenyl] ethenyl} - 1-methylpyridinium methoxysulfonate

4- {2- [3-chloro-4- (N, N-didocosylamino) phenyl] ethenyl} - 1-methylpyridinium methoxysulfonate

4- {2- [3-chloro-4- (N, N-didecylamino) phenyl] ethenyl} -

1-ethylpyridinium ethoxysulfonate

4- {2- [3-chloro-4- (N, N-didodecylamino) phenyl] ethenyl} -

1-ethylpyridinium ethoxysulfonate 4- {2- [3-chloro-4- (N, N-ditetradecylamino) phenyl] ethenyl} -

1-ethylpyridinium ethoxysulfonate

4- {2- [3-chloro-4- (N, N-dihexadecylamino) phenyl] ethenyl} -

1-ethylpyridinium ethoxysulfonate

4- {2- [3-chloro-4- (N, -dioctadecylamino) phenyl] ethenyl} - 1-ethylpyridinium ethoxysulfonate

4- {2- [3-chloro-4- (N, N-dicosylamino) phenyl] ethenyl} -

1-ethylpyridinium ethoxysulfonate

4- {2- [3-chloro-4- (N, N-didocosylamino) phenyl] ethenyl} -

1-ethylpyridinium ethoxysulfonate

3-bromo-4- {2- [4- (N, N-didecylamino) phenyl] ethenyl} -

1-methylpyridinium methoxysulfonate

3-bromo-4- {2- [4- (N, N-didodecylamino) phenyl] ethenyl} -

1-methylpyridinium methoxysulfonate

3-bromo-4- {2- [4- (N, N-ditetradecylamino) phenyl] ethenyl} - 1-methylpyridinium methoxysulfonate

3-bromo-4- {2- [4- (N, N-dihexadecylamino) phenyl] ethenyl} -

1-methylpyridinium methoxysulfonate 3-bromo-4- {2- [4- (N, N-dioctadecylamino) phenyl] ethenyl} - 1-methylpyridinium methoxysulfonate 3-bromo-4- {2- [4- (N, N-dicoylamino) - phenyl] ethenyl} - 1-methylpyridinium methoxysulfonate 3-bromo-4- {2- [4- (N, N-didocosylamino) phenyl] ethenyl} - 1-methylpyridinium methoxysulfonate

3-bromo-4- {2- [4- (N, N-didecylamino) phenyl] ethenyl} -

1-ethylpyridinium ethoxysulfonate

3-bromo-4- {2- [4- (N, N-didodecylamino) phenyl] ethenyl} - 1-ethylpyridinium ethoxysulfonate

3-bromo-4- {2- [4- (N, N-ditetradecylamino) phenyl] ethenyl} -

1-ethylpyridinium ethoxysulfonate

3-bromo-4- {2- [4- (N, N-dihexadecylamino) phenyl] ethenyl} -

1-ethylpyridinium ethoxysulfonate 3-bromo-4- {2- [4- (N, N-dioctadecylamino) phenyl] ethenyl} -

1-ethylpyridinium ethoxysulfonate

3-bromo-4- {2- [4- (N, N-dicosylamino) phenyl] ethenyl} -

1-ethylpyridinium ethoxysulfonate

3-bromo-4- {2- [4- (N, N-didocosyldecylamino) phenyl] ethenyl} 1-ethylpyridinium ethoxysulfonate

Example 2

a) 4- {2- [4 • - (N, N-Dioctadecylamino) biphenyl-4,4'-diyl] ^■ ethenyl} pyridine

Obtainable analogously to example la from 4-bromo-4 ^» - (N, N-di-octadecylamino) biphenyl and 4-vinylpyridine

) 4- {2- [4 '- (N, N-Dioctadecylamino) biphenyl-4,4'-diyl] ethenyl} -1-methylpyridinium iodide A solution of 4.00 g of compound 2a and 1.03 g of methyl iodide in 20 ml of dimethylformamide is stirred at 80 ° C for 6 hours. After cooling, the solvent is removed in vacuo. After chromatographic purification, deep red crystals are obtained.

The following are produced analogously:

4- {2- [4 - (N, N-Didecylamino) biphenyl-4,4 ^! -diyl] - ethenyl -1-methylpyridinium iodide 4- {2- [4 - (N, N-Didodecylamino) biphenyl-4,4'-diyl] - ethenyl -1-methylpyridinium iodide 4- {2- [4 - (N, N-Ditetradecylamino) biphenyl-4,4 * -diyl] - ethenyl -1-methylpyridinium iodide 4- {2- [4 - (N, N-Dihexadecylamino) -biphenyl-4,4'-diyl] - ethenyl -1-methylpyridinium iodide 4- {2- [4 - (N, N-dicosylamino) biphenyl-4,4'-diyl] - ethenyl -1-methylpyridinium iodide 4- {2- [4 - (N, N -Idocosylamino) -biphenyl-4,4'-diyl] -ethenyl-1-methylpyridinium iodide

4- {2- [4 - (N, N-Didecylamino) biphenyl-4,4'-diyl] ethenyl -1-ethylpyridinium iodide 4- {2- [4 - (N, N-Didodecylamino) biphenyl- 4,4'-diyl] - ethenyl -1-ethylpyridinium iodide 4- {2- [4 - (N, N-Ditetradecylamino) biphenyl-4,4'-diyl] - ethenyl -1-ethylpyridinium iodide 4- {2 - [4 - (N, N-Dihexadecylamino) biphenyl-4,4 ^! -diyl] - ethenyl -1-ethylpyridinium iodide 4- {2- [4 - (N, N-dioctadecylamino) -biphenyl-4,4'-diyl] - ethenyl -1-ethylpyridinium iodide 4- {2- [4 - (N, N-Dicosylamino) biphenyl-4, * -diyl] -ethenyl-1-ethylpyridinium iodide 4- {2- [4 - (N, N-Didocosylamino) -biphenyl-4,4 ^f -diyl] -ethenyl -1-ethylpyridinium iodide 4- {2- [4 '- (N, N-Didecylamino) biphenyl-4,4'-diyl] ethenyl} -1-butylpyridinium iodide

4- {2- [4 '- (N, N-Didodecylamino) biphenyl-4,4 • -diyl] -ethenyl} -1-butylpyridinium iodide 4- {2- [4 ^• - (N, N-Ditetradecylamino) -biphenyl-4,4 * -diyl] - ethenyl} -1-butylpyridinium iodide

4- {2- [4 '- (N, N-Dihexadecylamino) biphenyl-4,4'-diyl] ethenyl} -l-butylpyridinium iodide

4- {2- [4 '- (N, N-Dioctadecylamino) biphenyl-4,4'-diyl] ethenyl} -1-butylpyridinium iodide

4- {2- [4 '- (N, N-Dicosylamino) biphenyl-4,4'-diyl] ethenyl} -1-butylpyridinium iodide

4- {2- [4 '- (N, N-Didocosylamino) biphenyl-4,4'-diyl] ethenyl} -1-butylpyridinium iodide

Example 3

a) 4-Cyano-4 '- (dioctadecylamino) biphenyl

A solution of 5.4 g of 4'-amino-4-cyano-biphenyl and 27.8 g of octadecyl bromide in 20 ml of l, 3-dimethyl-2-imidazolidinone is mixed with 7.0 g of NaHCO and at 100 ° C. for 18 h heated. The mixture is poured onto water and extracted with tert-butyl methyl ether. The organic phase is dried over Na ₂ SO ₄ , evaporated and chromatographed on a silica gel column using petroleum ether / ethyl acetate 95: 5 as the eluent. After recrystallization from ethanol, colorless crystals of melting point 77-78 ° C. are obtained. b) 4 '- (Dioctadecylamino) -4-formyl-biphenyl

17.6 ml of an imolar solution of diisobutylaluminum hydride in hexane are added dropwise to a suspension of 9.44 g of compound 3a in 80 ml of hexane, cooled to 5 ° C. After stirring for 1.5 h at room temperature, 1 ml of methanol is added dropwise and the mixture is poured onto water. After acidification with conc. HCl the organic phase is separated off and the aqueous phase is extracted with tert-butyl methyl ether. The combined organic phases are dried over Na ₂ S0 ₄ , evaporated and recrystallized from ethanol. Yellow crystals of melting point 66-67 ° C. are obtained.

c) 4- {1- [4 '- (N, N-Dioctadecylamino) biphenyl-4,4'-diyl] ethenyl} -1-methylpyridinium methoxysulfonate

A solution of 1.53 g (7.0 mmol) of 1,4-dimethylpyridinium methoxysulfonate (obtainable from 4-methylpyridine and dimethyl sulfate), 4.92 g of the compound 3b and 600 mg of piperidine in 30 ml of methanol is heated to boiling for 8 h. After cooling, the precipitate formed is filtered off and recrystallized from methanol. Orange-red crystals are obtained.

Example 4

a) 4- {2- [4- (N, N-Dicosylamino) -2-fluorophenyl] ethenyl] pyridine

The compound is prepared analogously to Example Ia from 4-bromo-3-fluoro-N, N-dicosylaniline and 4-vinylpyridine. b) 4- {2- [4- (N, N-Dicosylamino) -2-fluorophenyl] ethenyl} - 1-methylpyridinium p-toluenesulfonate

A solution of 4.00 g of compound 4a and 1.09 g of methyl p-toluenesulfonate in 20 ml of dimethylformamide is stirred at 80 ° C. for 4 hours. After cooling, the solvent is removed in vacuo. After chromatographic purification, deep red crystals are obtained.

The following are produced analogously:

4- {2- [4- (N, N-Didecylamino) -2-fluorophenyl] ethenyl} -

1-methylpyridinium p-toluo1 sulfonate

4- {2- [4- (N, N-Didodecylamino) -2-fluorophenyl] ethenyl} -

1-methylpyridinium p-toluenesulfonate

4- {2- [4- (N, N-Ditetradecylamino) -2-fluorophenyl] ethenyl} - 1-methylpyridinium p-toluenesulfonate

4- {2- [4- (N, N-Dihexadecylamino) -2-fluorophenyl] ethenyl} -

1-methylpyridinium p-toluenesulfonate

4- {2- [4- (N, N-dioctadecylamino) -2-fluorophenyl] ethenyl} -

1-methylpyridinium p-toluenesulfonate 4- {2- [4- (N, N-Didocosylamino) -2-fluorophenyl] ethenyl} -

1-methylpyridinium p-toluenesulfonate

4- {2- [4- (N, N-Didecylamino) -2-fluorophenyl] ethenyl} -

1-ethylpyridinium p-toluenesulfonate

4- {2- [4- (N, N-Didodecylamino) -2-fluorophenyl] ethenyl} - 1-ethylpyridinium p-toluenesulfonate

4- {2- [4- (N, N-Ditetradecylamino) -2-fluorophenyl] ethenyl} -

1-ethyl pyridinium p-toluenesulfonate

4- {2- [4- (N, N-Dihexadecylamino) -2-fluorophenyl] ethenyl} -

1-ethylpyridinium p-toluenesulfonate 4- {2- [4- (N, N-dioctadecylamino) -2-fluorophenyl] ethenyl} -

1-ethyl pyridinium p-toluenesulfonate 4- {2- [4- (N, N-Dicosylamino) -2-fluorophenyl] ethenyl} - 1-ethyl pyridinium p-toluenesulfonate

4- {2- [4- (N, N-Didocosylamino) -2-fluorophenyl] ethenyl} - 1-ethylpyridinium p-toluenesulfonate

4- {2- [4- (N, N-Didecylamino) -2-fluorophenyl] ethenyl} -

1-butylpyridinium p-toluenesulfonate

4- {2- [4- (N, N-Didodecylamino) -2-fluorophenyl] ethenyl} -

1-butylpyridinium p-toluenesulfonate

4- {2- [4- (N, N-Ditetradecylamino) -2-fluorophenyl] ethenyl} ■ 1-butylpyridinium p-toluenesulfonate

4- {2- [4- (N, N-Dihexadecylamino) -2-fluorophenyl] ethenyl} -

1-butylpyridinium p-toluenesulfonate

4- {2- [4- (N, N-dioctadecylamino) -2-fluorophenyl] ethenyl} -

1-butylpyridinium p-toluenesulfonate 4- {2- [4- (N, N-dicosylamino) -2-fluorophenyl] ethenyl} -

1-butylpyridinium p-toluenesulfonate

4- {2- [4- (N, N-Didocosylamino) -2-fluorophenyl] ethenyl} -

1-butylpyridinium p-toluenesulfonate

Example 5

a) 4- [4- (N, N-Dioctadecylamino) phenyl] pyridine

A solution of 7.6 g of 4- (tributylstannyl) pyridine (available from 4-pyridyllithium and tributylchlorostannan), 14.7 g of 4-bromo-N, N-dioctadecylaniline and 0.286 g of tetrakis (triphenylphosphine) palladium in 150 ml Xylene is heated to boiling for 16 hours.

After cooling, the precipitate formed is filtered off. After chromatographic purification, yellowish crystals are obtained. b) 4- [4- (N, N-Dioctadecylamino) phenyl] -1-methylpyridinium methoxysulfonate

As described in Example 1b, compound 5a is reacted with dimethyl sulfate.

The following are produced analogously:

4- [4- (N, N-Didecylamino) phenyl] -1-methylpyridini m methoxysulfonate

4- [4- (N, N-Didodecylamino) phenyl] -1 ^ methylpyridinium methoxysulfonate

4- [4- (N, N-Ditetradecylamino) phenyl] -1-methylpyridinium methoxysulfonate

4- [4- (N, N-Dihexadecylamino) phenyl] -1-methylpyridinium methoxysulfonate

4- [4- (N, N-Dicosylamino) phenyl] -1-methylpyridinium methoxysulfonate

4- [4- (N, N-Didocosylamino) phenyl] -1-methylpyridinium methoxysulfonate

4- [4- N, N-didecylamino) phenyl] -1-ethylpyridinium ethoxysulfonate

4- [4- N, N-didodecylamino) phenyl] -1-ethylpyridinium ethoxysulfonate

4- [4- N, N-Ditetradecylamino) phenyl] -1-ethylpyridinium ethoxysulfonate

4- [4- N, N-Dihexadecylamino) phenyl] -1-ethylpyridinium ethoxysulfonate

4- [4- N, N-dioctadecylamino) phenyl] -1-ethylpyridinium ethoxysulfonate

4- [4- N, N-dicosylamino) phenyl] -1-ethylpyridinium ethoxysulfonate

4- [4- N, N-Didocosylamino) phenyl] -1-ethylpyridinium ethoxysulfonate Example 6

a) 4- {2- [4- (2- (4- (N, N-Dioctadecylamino) phenyl) ethenyl) phenyl] ethenyl} pyridine

First, 4-bromostyrene and 4-iodo-N, N-dioctadecylaniline (obtainable from 4-iodaniline and octadecylbromide) 4- (N, N-Diocta-decylamino) -phenyl-4'-bromstilbene is prepared analogously to example la. The reaction is then again carried out using 4-vinylpyridine as in Example 1a.

b) 4- {2 - [- 4- (2- (4- (N, N-Dioctadecylamino) phenyl) ethenyl) phenyl] ethenyl} -1-methylpyridinium methoxysulfonate

As described in Example 1b, compound 6a is reacted with dimethyl sulfate.

The following are produced analogously:

4- {2- [4- (2- (4- (N, N-Didecylamino) phenyl) ethenyl) phenyl] ethenyl} -1-methylpyridinium methoxysulfonate

4- {2- [4- (2- (4- (N, N-Didodecylamino) phenyl) ethenyl) phenyl] ethenyl} -1-methylpyridinium methoxysulfonate

4- {2- [4- (2- (4- (N, N-Ditetradecylamino) phenyl) ethenyl) phenyl] ethenyl} -1-methylpyridinium methoxysulfonate 4- {2- [4- (2- ( 4- (N, N-Dihexadecylamino) phenyl) ethenyl) phenyl] ethenyl} -1-methylpyridinium methoxysulfonate 4- {2- [4- (2- (4- (N, N-Dicosylamino) phenyl) ethenyl) phenyl] ethenyl} -1-methylpyridinium methoxysulfonate

4- {2- [4- (2- (4- (N, N-Didocosylamino) phenyl) ethenyl) phenyl] ethenyl} -1-methylpyridinium methoxysulfonate

4- {2- [4- (2- (4- (N, N-Didecylamino) phenyl) ethenyl) phenyl] ethenyl} -1-ethylpyridinium ethoxysulfonate 4- {2- [4- (2- ( 4- (N, N-Didodecylamino) phenyl) ethenyl) phenyl] ethenyl} -1-ethyl pyridinium ethoxysulfonate

4- {2- [4- (2- (4- (N, N-Ditetradecylamino) phenyl) ethenyl) phenyl] ethenyl} -1-ethyl pyridinium ethoxysulfonate

4- {2- [4- (2- (4- (N, N-Dihexadecylamino) phenyl) ethenyl) phenyl] ethenyl} -1-ethyl pyridinium ethoxysulfonate

4- {2- [4- (2- (4- (N, N-Dicosylamino) phenyl) ethenyl) phenyl] ethenyl} -1-ethyl pyridinium ethoxysulfonate

4- {2- [4- (2- (4- (N, N-Didocosylamino) phenyl) ethenyl) phenyl] ethenyl} -1-ethyl pyridinium ethoxysulfonate

Example 7

_a ) 4- {l-Bromo-2- [4- (N, N-dioctadecylamino) phenyl] ethenyl} pyridine

A solution of 35.9 g of compound la and 9 g of bromine in 100 ml of glacial acetic acid is heated to 100 ° C. for 5 hours. The mixture is allowed to cool, the resulting precipitate is filtered off and recrystallized from dichloromethane / ethanol. b) 4- {4- [N, -Dioctadecylamino] phenyl} ethynyl pyridine

A solution of 18.2 g of compound 7a and 2.1 g of potassium hydroxide in 50 ml of ethanol is heated to boiling for 18 hours. The resulting precipitate is filtered off and recrystallized from ethanol / acetone.

c) 4- {4- [N, -Dioctadecylamino] phenyl} ethynyl-1-methylpyridinium methoxysulfonate

As described in Example Ib, compound 7b is reacted with dimethyl sulfate.

The following are produced analogously:

4- {4- [N, N-Didecylamino] phenyl} -ethynyl-1-methylpyridinium methoxysulfonate -4- {4- [N, -Didodecylamino] -phenyl} -ethynyl-1-methylpyridinium methoxysulfonate 4- {4- [ N, N-Ditetradecylamino] phenyl} ethynyl-1-methylpyridinium methoxysulfonate

4- {4- [N, N-Dihexadecylamino] phenyl} ethynyl-1-methylpyridinium methoxysulfonate

4- {4- [N, N-Dicosylamino] phenyl} ethynyl-1-methylpyridinium methoxysulfonate

4- {4- [N, N-Didocosylamino] phenyl} ethynyl-1-methylpyridinium methoxysulfonate

4- {4- [N, N-Didecylamino] phenyl} ethynyl-1-ethylpyridinium ethoxysulfonate 4- {4- [N, N-Didodecylamino] phenyl} -ethynyl-1-ethylpyridinium ethoxysulfonate

4- {4- [N, N-Ditetradecylamino] phenyl} ethynyl-1-ethylpyridinium ethoxysulfonate 4- {4- [N, N-Dihexadecylamino] phenyl} ethynyl-1-ethylpyridinium ethoxysulfonate

4- {4- [N, N-Dioctadecylamino] phenyl} ethynyl-1-ethylpyridinium ethoxysulfonate

4- {4- [N, N-Dicosylamino] phenyl} ethynyl-1-ethylpyridinium ethoxysulfonate

4- {4- [N, N-Didocosylamino] phenyl} ethynyl-1-ethylpyridinium ethoxysulfonate

Example 8

4- {2- [4- (N, N-Dioctadecylamino) phenyl] ethenyl} -1-methylpyridinium iodide

A solution of 10.0 g of 1,4-dimethylpyridinium iodide (available from 4-methylpyridine and methyl iodide), 26.5 g of 4- (N, N-dioctadecylamino) benzaldehyde (available from Vilsmeier formylation of N, N-dioctadecylaniline) and 4.2 ml of piperidine are dissolved in 100 ml of ethanol and heated to boiling for 6 hours. After cooling, the precipitate formed is filtered off and then recrystallized twice from toluene. Red crystals of melting point 228-229 ° C. are obtained.

The following are produced analogously:

4- {2- [4- (N, N-Didecylamino) phenyl] ethenyl} -1-methylpyridinium iodide

4- {2- [4- (N, N-Didodecylamino) phenyl] ethenyl} -1-methylpyridinium iodide

4- {2- [4- (N, N-Ditetradecylamino) phenyl] ethenyl} -1-methylpyridinium iodide

4_ {2- [4- (N, N-Dihexadecylamino) phenyl] ethenyl} -1-methylpyridinium iodide 4- {2- [4- (N, N-Dicosylamino) phenyl] ethenyl} -1-methylpyridinium iodide

4- {2- [4- (N, N-Didocosylamino) phenyl] ethenyl} -1-methylpyridinium iodide

4- {2- [4- (N, N-Didecylamino) phenyl] ethenyl} -1-ethyl pyridinium iodide

4- {2- [4- (N, N-Didodecylamino) phenyl] ethenyl} -1-ethyl pyridinium iodide

4- {2- [4- (N, N-Ditetradecylamino) phenyl] ethenyl} -1-ethyl pyridinium iodide

4- {2- [4- (N, N-Dihexadecylamino) phenyl] ethenyl} -1-ethyl pyridinium iodide

4- {2- [4- (N, N-Dioctadecylamino) phenyl] ethenyl} -1-ethyl pyridinium iodide 4- {2- [4- (N, N-Dicosylamino) phenyl] ethenyl} - 1-ethyl pyridinium iodide

4- {2- [4- (N, N-Didocosylamino) phenyl] ethenyl} -1-ethyl pyridinium iodide

4- {2- [4- (N, N-Didecylamino) phenyl] ethenyl} -1-butyl pyridinium iodide

4- {2- [4- (N, N-Didodecylamino) phenyl] ethenyl} -1-butylpyridinium iodide

4- {2- [4- (N, N-Ditetradecylamino) phenyl] ethenyl} -1-butyl pyridinium iodide 4- {2- [4- (N, N-Dihexadecylamino) phenyl] ethenyl} - 1-butylpyridinium iodide

4- {2- [4- (N, N-Dioctadecylamino) phenyl] ethenyl} -1-butylpyridinium iodide

4_ {2- [4- (N, N-Dicosylamino) phenyl] ethenyl} -1-butylpyridinium iodide

4- {2- [4- (N, N-Didocosylamino) phenyl] ethenyl} -1-butylpyridinium iodide Example 9

Poly (methyl methacrylate-co-4- {4- [2- (4- (N, N-dioctadecylamino) phenyl) ethenyl] pyridyl} butyl methacrylate)

A solution of 4.00 g of poly (methyl methacrylate-co-4-iodide butyl methacrylate) (obtainable by free-radical polymerization of methyl methacrylate and 4-iodobutyl methacrylate in a molar ratio of 9: 1 in toluene as solvent and azobisisobutyronitrile as initiator) and 2.88 g of Compound la in 20 ml of N-methylpyrrolidin-2-one is stirred at 80 ° C. for 8 hours. The polymer is precipitated from methanol. A deep red polymer is obtained. The polymer is then transferred to a quartz substrate as an LB monolayer. Good values for the non-linear second order susceptibility are obtained.

Claims

1) nonlinear optical materials, characterized in that they contain at least one compound of the formula I,

wherein

^{R1 c} ι " ^c ₆ ^Al y ¹ '

W, X, Y and Z are each independently CH,

C-alkyl (C.-C ₈ ) or C-halogen, one or two of the radicals W, X, Y or Z also N,

A single bond, -N = N-, -C (R) = C (R ⁴ ) - or -C≡C-,

Q unsubstituted or by C, -C ₆ -

Alkyl and / or halogen substituted 1,4-phenylene, in which one or more CH groups can also be replaced by N,

n 1, 2, 3 or 4 2 3.

R, R each independently

^C 6 ~ ^C 30 ^A - * - kyl, in which one or two non-adjacent CH ₂ groups can also be replaced by -O-, -S- or CH = CH,

R 4 each independently of one another H and / or C, -C ₆ alkyl and

Q

V means a compatible anion.

2) Nonlinear optical materials according to claim 1, characterized in that the compatible anion

Halide or methoxysulfonate means.

3) Nonlinear optical materials according to claim 1 or 2, characterized in that they consist essentially of one or more successive layers of at least one compound of formula I applied to a substrate.

4) Nonlinear optical materials according to claim 1 or 2, containing at least one polymeric component, characterized in that at least one further component is a compound of formula I.

5) Nonlinear optical materials according to claim 1 or 2, containing at least one polymeric component, characterized in that the chromophore according to formula I, optionally via a spacer, is covalently bound to the polymer chain.

6) Process for the production of nonlinear optical materials, characterized in that a layer of polymerizable compounds containing a chromophore according to formula I, optionally in a mixture with other polymerizable compounds, is applied to a substrate and then polymerized,

or first polymerizing the compounds and then applying the polymer as a film on the substrate,

the chromophores of the polymer applied to the substrate being non-centrosymmetrically oriented.

7) use of nonlinear optical materials, produced by applying polymerizable compounds containing a chromophore according to formula I, optionally in a mixture with other polymerizable compounds, on a substrate with subsequent polymerization,

or vice versa produced by polymerizing the compounds with subsequent application of the polymer produced as a film on a substrate,

the chromophores of the polymer applied to the substrate being non-centrosymmetrically oriented,

as nonlinear optical media. 8) Use of the nonlinear optical materials according to at least one of claims 1 to 5 as optical media in electronics or as organic substrates in film and fiber technology.

9) Use of nonlinear optical materials according to at least one of claims 1 to 5 in nonlinear optical arrangements.