JPH03504172A - Nonlinear optical materials in which donor and acceptor groups are vicinally linked - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Donor and acceptor groups are vicina nonlinear optical material bonded to the The present invention relates to nonlinear optical materials based on side chain polymers. In type optical materials, the main chain has an aliphatic chain member, and the side chain has nonlinear optical emission. As a chromophore, it has a conjugated system, and an electron donating group (D) is bonded to one end. and the other end is derived from a side chain polymer to which an electron accepting group (A) is bonded. In the nonlinear optical material to come, at least one selected from the group consisting of D and A One additional substituent is further attached to the above system, and all of the substituents and and substituent A are in each case vicinally bonded to the aromatic system. This relates to nonlinear optical materials derived from side chain polymers, which are characterized by be.

The invention also relates to low molecular weight compounds containing the system substituted in this manner. Ru.

Materials that exhibit nonlinear optical behavior are characterized by having field strength-dependent dielectric sensitivity. It is a substance that This nonlinearity of dielectric sensitivity is of interest in a large number of applications. It is an effect and brings about many effects.

Frequency doubling (second harmonic, 5HG) means that the wavelength is half that of the incident light. give rise to a certain light. This electro-optical effect (Pockets effect) is applied This term refers to the change in the refractive index of a material in an electric field. sum of frequencies and frequency Frequency mixing and frequency division methods that create a difference in number allow continuous tuning of laser light. enable.

Nonlinear optical materials are suitable for manufacturing optical components. These parts include, for example, electrical Air-optic modulators, electro-optic switches, electro-optic directional couplers and frequency doubling Vessels are included.

As an example, these components are used in optical communication technology to modulate and control optical signals. As a spatial light modulator in optical signal processing, semiconductor lasers can be used as spatial light modulators. Used in doubling, in optical data storage, in sensor technology, and also in xerography be done.

Materials with tertiary dielectric sensitivity can be used in the production of line-light optical switches, i.e. pure light Suitable for use with computers.

In order to be suitable for use in the field of second-order nonlinear optics, this kind of material meets a number of requirements. must be met.

To be industrially suitable, it is necessary to have as high a dielectric sensitivity value χ(2) as possible. First of all, it is necessary. This can be achieved, for example, by creating a non-centrosymmetric molecular arrangement in the crystal. let

Many inorganic substances, such as potassium dihydrogen phosphate or lithium niobate, , exhibiting nonlinear optical properties.

However, all of these materials are associated with a wide range of drawbacks. These inorganic In addition to having inadequate secondary dielectric sensitivity values, compounds often have high When treated with light intensity, these inorganic compounds lose sufficient photostability or Difficult to manufacture and process.

La5er Focus 18 (1982) by Gar i to etc. and EP-0091838 describe organic compounds of the nitroaniline type. There is. However, their relatively good photochemical stability and secondary dielectric sensitivity values associated with poor crystal formation and insufficient mechanical stability. In particular, accumulation These materials should not be used to produce thin films such as those required by optical components. I can't do it.

Polymers containing a dissolved or conjugated NLO chromophore are In general, the second-order nonlinear sensitivity (χ(ri)) is obtained only after an electric field is applied in the liquid state. In this case, the NLO chromophore is oriented in a dipolar manner.

This bipolar orientation can be permanently frozen by cooling below the glass transition temperature. It will be done. Therefore, χ11+, as a first approximation, depends on the concentration of the NLO chromophore and the electric field strength. degree is proportional to the hyperpolarizability β and also to the dipole moment μ.

For this reason, compounds with high dipole moments and at the same time high β values are This is especially important. For this reason, we have a conjugated π system, and one end of this π system has an electron donor. NLO chromophores with bound bodies and electron acceptors, respectively, have been studied. There is. Known examples of such substances include pp' to dimethylaminonitrostilbe. (DANS) and 2-methyl-4-nitroaniline (MNA). donation Systems in which the body/receptor is polysubstituted are primarily known in the form of quinodimethane systems. (e.g. systems described in EP 214.828, EP 205.731, E P 243,806), these donors and acceptors are Each is bound to a gem.

Furthermore, Tectile Che+o by W, Ingamells, etc. .

Co2or, + vol. 16, p. 55/II, p. 11 (1984) contains the ortho position. describes an azo compound carrying two NO, groups.

However, this compound has been used as a disperse dye.

These materials, on the other hand, exhibit insufficient nonlinear optical properties in some cases; On the other hand, these materials meet the requirements for effective use as nonlinear optical media. We have not yet reached the point where we can meet these requirements.

Therefore, it has improved nonlinear optical properties and enables the production of nonlinear optical devices. , yet another type of nonlinear structure that does not require the presence of a noncentrosymmetric crystal structure type optical materials are needed. This purpose is achieved by providing the substance according to the invention. is achieved.

Surprisingly, it has a conjugated system in its side chain, and one end of this system has an electron-donating group. or in a side chain polymer to which an electron-accepting group is attached; vicinal to at least one of the donor or acceptor groups present; If additional donor or acceptor groups are attached, the polymer becomes nonlinear. It has been found that it is extremely suitable as an optical material.

In this case, the electron donor group has an electron acceptor group adjacent to the electron donor group (vicinal). are located adjacent to (vicinal) the electron acceptor group, respectively.

In the substance according to the present invention, β and μ expected for the additionally introduced substituents are The increase in product is surprisingly significant. That is, the actual value of this product can be twice or even higher than the expected value.

The values for χfil simply apply to conventional systems with terminal donor/acceptor substituents. In comparison, it has a factor of 2-20 higher.

Furthermore, the introduction of additional donor or acceptor substituents can further improve absorption. Move to a longer wavelength range. This movement is caused by the dispersion of nonlinear optical coefficients in the NIR region. Since it leads to an increase in the electro-optic coefficient and an increase in the frequency doubling ratio, The effect is particularly advantageous.

Therefore, the present invention provides a side chain type polymer, the main chain of which contains an aliphatic chain moiety. and its side chain contains the system in conjugation as a nonlinear optical chromophore, and this system An electron donor (D) is bound to one end, and to this the other end of the system is is a nonlinear optical substance derived from a side chain type polymer to which an electron acceptor (A) is bonded. In terms of quality, the W system includes at least one member selected from the group consisting of D and A. Additional substituents are further attached, and all of the substituents and all of the substituents A are Each side chain type is characterized by being vicinally bonded to the aromatic system. This invention relates to nonlinear optical materials derived from polymers.

The present invention particularly relates to a substance according to claim "Jl", the conjugate of which has a system represented by the following formula: Regarding substances corresponding to the nonlinear optical chromophores shown: [In the formula, D is NR', O or S, and DI is each independently , H1NR', ,OR' or SR1, AI and A2 are respectively independently H, No, CN, Halo Gen, CF,, GOOR', C0NR'! , 5o3R', So□R113 OR' or So, NR', and zl and 2g are each independent of each other. , single bond, -(-C(R')-c(R'')-3-rr-1-N=N-1-C= N-1-N=C- or -C=C-, m is l or 2, B is a carbocyclic or heterocyclic system, the cyclic system having from 5 to 18 ring atoms. and up to 3 N.

contains a heterocyclic atom selected from the group consisting of 0 and S, n is 0, l, 2 or 3; p is 0 or l, R1 is each independently H or C8-C0-alkyl, and R2 is each independently H or C,-C,-alkyl, However, when p is 1, AI is hydrogen.

The present invention also relates to a compound represented by the following formula (1) [wherein D'li, each independently of each other, HSNR', ,OR'' or SR'; D"+1., NR'xma/:, HasR'te, zl and Z! are respectively Mutually independently, a single bond, (-C(R") -C(R+1, -C=N-1-N =C- or -C=C~, m is 1 or 2, B is a carbocyclic or heterocyclic system, the cyclic system having from 5 to 18 ring atoms. and up to 3 heterocyclic ring atoms selected from the group consisting of N10 and S Contains n is 0, l, 2 or 3; A1 is, independently of each other, HlNO,, CN, Haloken, CF3, GOOR”, C0NR”, SO, R”, So, R3, SOR” t f:, So, NR', R1 is each independently H or C8-C*t-alkyl; do R2 is each independently H or CI-c, -alkyl, and R3 is each independently 01-C□-alkyl, However, at least one group selected from the group consisting of DI and AI is hydrogen ].

The present invention furthermore provides a non-linear Regarding type optical materials.

The present invention also relates to the use of the nonlinear optical material according to the present invention in optical components, Furthermore, the invention relates to an optical component containing the substance according to the invention.

The nonlinear optical material according to the present invention can be illustrated in FIGS. 1 and 2 below: The nonlinear optical chromophore according to the present invention has an electron donor (D) at one end and an electron donor (D) at the other end. Contains a conjugated system with an electron acceptor (A). This binding site is an aromatic hydrocarbon be. This system also contains one aromatic ring (A''), preferably a heteroatom. Aromatic rings that do not have, for example 1. ．． 4-7z nylene, 2.6-8 and 2,7 - Can also be naphthalene, anthracenediyl and phenanthrenediyl Wear.

This system is preferably a combination of 2, 3, 4 or 5 of the following groups: consisting of: aromatic systems and double and triple bonds, such as -C=C-1-C=N -1-N=C-1-(jC- and -N=N-, etc. Particularly preferably, the system is aromatic group rings are connected to double or triple bonds, and also not more than two, A system in which double and/or triple bonds are interconnected. suitable aroma Family systems have up to 18 ring atoms, but no more than 3 heteroatoms. Terocyclic ring and carbocyclic ring, preferred aromatic system is 1,4-phenylene , 2,6- and 2,7-naphthylene, anthracenediyl and phenanthre 7-randiyl, pyrrolodiyl, 7randiyl, thiophenediyl, imidazolediyl yl, pyrazolediyl, oxazolediyl, thiazolediyl, pyridinediyl yl, pyrimidinediyl, thiazindiyl, quinolindiyl, inquinolindiyl quinoxalinediyl, indolediyl, benzimidazolediyl and It is benzothiazolediyl.

In the present invention, the electron-rich heteroaromatic ring is preferably bonded to a donor ring. and the heteroaromatic ring, which is devoid of electrons, is bound to acceptor A. especially Preferred compounds are those in which no more than two heteroaromatic rings are present.

The substance according to the invention has at least 1 fli already present in its molecule. one or more additions at the vicinal position relative to the donor or acceptor group. It has additional donor and/or acceptor groups.

That is, according to FIGS. 1 and 2, up to 4 additional groups of this type are attached. and in this case the donor group is vicinal to the donor group and its The acceptor group is vicinal to the acceptor group.

Suitable electron donors include amino groups, alkoxy groups, alkylthio groups, and also These are alkyl groups, vinyl groups, hydroxyl groups and thiol groups.

Among the electron acceptors, nitro groups, cyano groups, alkoxycarbonyl groups and amino do group, halogen and -CN- and/or -GOOR = substituted ethylene, Furthermore, a halogen atom is preferred. Acyl groups, haloalkyl groups and alkoxy Sulfonyl groups are also preferred.

The nonlinear optical chromophore according to the present invention may optionally be added to the polymer main chain (PoI2). They are conjugated together via a spacer (Sp).

Suitable spacers are in particular linear or branched chains having 2 to 20 CyK molecules. is a lekylene group, and one or more (II, groups present in this group are - It may be replaced by 〇-1-S-S and/or -NR'-. R ' is an alkyl group having 1 to 6 CM atoms.

Examples of suitable spacers include: ethylene, propylene, butylene, ben Tylene, hexylene, octylene, decylene, undecylene, dodecylene, octylene Tadecylne, ethyleneoxyethylene, ethylenethioethylene, ethylene-N- Methyliminoethylene or ]-methylalkylene.

The attachment of a nonlinear optical chromophore to the polymer backbone, optionally via a spacer. The chromophore can in principle be any C atom in this chromophore.

The structure of the polymer backbone is not critical. Therefore, polystyrenes, polyester polyurethanes, polysiloxanes, poly(meth)acrylates, poly( meth)acrylamides and their polymers and polymer admixtures or Other polymeric materials can be used.

A suitable non-linear optical chromophore corresponds to formula (2). These colors are based on donor groups. or the donor group is attached to the polymer backbone via a structure of the polymer backbone. It is a component of

D is NR', O or S1, preferably NR' and O. D is the main chain structure If it is a part, then D is just N.

DI is H%NR', , OR' or SR', each independently of the other; Preferably, DI is H,NR'! or "OR".

AI and A1 are each independently H or an electron accepting group. , for example NO, CN or halogen (for example p, ca or Br), Or CF,,C0OR'.

C0NRI, and sulfoxide, sulfonate and sulfonamide groups. Preferably No, CN1F, (41CF.

and GOOR'. However, if p is 1, both groups A1 Both are H.

Zl and Z of the bonding moiety are each independently a single bond, -(-C(R1 ) -C(R')3-r-1 (in the formula, m is 1 or 2), -C=C-, - C=N, -N-C-1-N=N- or -C=C-.

Particularly preferred are single bonds, -C(R")=C(R")- and -C= I can give C-.

B is a carbocyclic or heterocyclic system having 5 to 18 ring atoms.

In particular, B is 1,4-phenylene, 2,6- and 2,7-naphthylene or anthracene, 2,5-pyrrolediyl, -7landiyl and monothiophenedi Furthermore, B is pyridinediyl, pyrimidinediyl, triazidine indolediyl and indolediyl. However, B also has other heterogeneous These rings may contain no more than 3 heterocyclic atoms, although they may also be aromatic rings. have Preferred side-chain polymers according to the invention have no more than two polymers in their side chains. It has a heteroaromatic ring.

ρ寞 is H or branched chain or straight chain with up to 24 C atoms is an alkyl group. R'lt, preferably H or a linear group; preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, Butyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetyl Radecyl, pentadecyl, hexadecyl, octadecyl, eicosyl and toco It is Sill.

R2 is preferably H1 methyl, ethyl, propyl, butyl, pentyl or It's Xyl.

Particularly preferred non-linear optical chromophores, denoted by 2), have the following formula 1a-Iu: Equivalent to. For brevity, above and below, Phe is l, 4-7 Enylene is one of the aromatic rings, 2,5-pyrrolediyl, -7rane diyl and -thiophenediyl, pyridinediyl, pyrimidinediyl, thoria Zingiyl and indolediyl.

-D-Phe, -Phe, -A c-D-Phe, -Z"-Pha2-A I d-D-Phe, -Phe-P he, -A I e-D-Phe, -Hat-Phel-A I 1-D-Phe, -Phe-Z''-Pha, -A I g-D-Phet-Het-Z”-Phez-A I h-D-Phe, -Z'-Phe-Phe-A I 1-D -Phet-Z'-Het-Phet-A I j-D-P het-Z’-Pbe-Z”-Phe, -A I k-D-Ph et-Z’-Het-Z”-Phet-A I 1-D-Phe r-Phe-Phe-Z″-Phel-A I m-D-Phe , -Phe-Het-Z"-Phe, -A I n-D-Phe, - HeL-Phe-Z"-Pbe2-A I.

-D-Phet-Z'-Phe-Phe-Z"-Phe, -A Ip -D-Phet-Z'-Phe-Het-Z'i-Phel-A　　　　　q- D-Phe, -Z'-Het-Phe-Z"-Phel-A I r-D -Phe, -Z'-Phe-Phe-Pbe2-A I 5-D- Phet-Z'-Phe-HeL-Phel-A I t-D-P het-Z'-Het-Phe-Phel-A I u attached formula Ia~I Among the substances according to the present invention containing a nonlinear optical chromophore represented by u, particularly preferred are The new substances are D, D', A, A', A8, zl, Z8, B, R' and R. 8 is a substance having the preferred meanings given above.

In these sub-formulas, %-D-Phe, - is preferably CQ.

The compound itself, for example, a mononuclear compound (JP60/However, the present invention In the chromophore represented by the formula ■, DI, AI and A! from the group consisting of At least one selected group is a group other than H.

Low molecular weight compounds containing non-linear optical chromophores of formula I may also be used as described above. It exhibits the following advantageous physical properties. Chromophore dissolution shift for aminonitrostilbene derivatives The following comparison of solvatochromic 5hift (△λ) is clearly demonstrated the positive effect of vicinal substituents on the nonlinear optical properties of compounds. There is.

Hllnm 15nmCN 14nm 18nmF 20nNO1-” 23n+i* indicates that it was not measured.

This chromophore dissolution shift occurs when the solvent is changed from cyclohexane to acetonitrile. , is particularly striking.

178.427-A) and compounds of formula I in which D is OH or OR ( JP 62/156.628-A, EP 250099-A) are respectively It is a known compound. The novel compound according to the present invention corresponds to the following formula (■): [In the formula, DI is each independently H%NR", , OR" or SR" and D-modulus is NR'□ or SR', and zl and 21 are each mutually independent. Then, a single bond, -(-C(R") -C(R")", -C=N-1-N=C- tf:, bar CWC-tea'l, m is,! or 2, B is a carbocyclic or heterocyclic system, the cyclic system having from 5 to 18 ring atoms. and up to 3 N.

contains a heterocyclic atom selected from the group consisting of O and S, n is 0, L2 or 3, A'1 magazine, independently of each other, H, NOI, CN, Haroken, CF, , GOOR”, C0NR”! , 5OIR”, So, R3, SOR’ *t: 　So、NR」、、 R1 is each independently H or C7-ci4-alkyl; do R2 is each independently H or C0-C1-alkyl, and each R3 is independently CI"""CI4-alkyl, However, at least one group selected from the group consisting of Dl and AI is hydrogen ].

These compounds are also the subject of the present invention.

Dl is preferably H, NR", and is preferably OR". D2 is preferably N R'.

21 and Z! are preferably -C(1?s·C(R Li-1-C=C- or a single bond. B is preferably 1.4-] two elms, 2,6- and 2,7-naphthylene or monoanthracene, 2,5-viroldi yl, -7randiyl and -thiophenediyl, and also pyridine diyl, pyrimidinediyl, triazinediyl and indolediyl.

However, B can also be another heterocyclic ring, in which case , the ring has no more than 3 peteroatoms.

n is preferably 0. It is l or 2. A is preferable and AI is mutually exclusive. independently preferably H, NO, CN or halogen (e.g. F, CQ or Br), CF,, GOOR” and C0NH”! It is. Especially preferred Examples include H1NO□, CN%F, CQ, COOR3 and CF, can be given.

R1 is preferably H or a linear group having up to 24 C atoms , i.e. methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl. ru, oc≠ru, nonyl, decyl, undecyl, dodecyl, tridecyl, tetrade Sil, pentadecyl, hexadecyl, octadecyl, eicosyl and tocosyl It is.

R2 is preferably H1 methyl, ethyl, propyl, butyl, pentyl or It's Xyl.

R3 preferably has the preferred meanings given above for R1, while H removed.

Particularly preferred compounds of formula (1) correspond to sub-formulas IIa to IIs below. Ru: D"-Pbe, -Phe, -A-If aD"-Phel-Z"-Phes-A 　　　　　　　　n　hD2-Pher-Phe-Phe, -A II cD”-Phet-Het-Pbe3-A n dD"-Pher-Phe-Z"-Phes-A IF eD"- Phet-HeL-Z"-Phes-A n fD'-Phe, -Z’-Phe-Phes-A　　　　　　　　　n　gD”-Phe, -Z’-Het-Phe, -A n hD”-Phe, -Z’-Phe-Z”-Phe, -A If iD’-Phe , -Z’-HeL-Z’-Pbe3-A n jD”-Phe , -Phe-Phe-Z"-Phe, -A n kD"-Phe , -Phe-HeL-Z"-Phe, -A II ID"-Ph e, -Het-Phe-Z'-Phe, -A n mD"-Ph e, -Z'-Phe-Phe-Z"-Phe, -A II nD"-P her-Z'-Phe-Het-Z"-Phe-A n.

D"-Phe, -Z'-Het-Phe-Z'-Pbe3-A n pD'-Phe, -Z'-Phe-Phe-Pbe3-A I QD'-Phe, -Z'-Phe-Hat-Phe, -A II rD"-Pher-Z'-8et-Phe-Pbe3-A I Is Among the compounds represented by the attached formulas 1 [a to Tls according to the present invention, Dl, D 2, A, A', Z', Z'', B, n%R', R' and R3 are the above Compounds with preferred meanings are particularly preferred.

In these formulas, D"-Phe,- is preferably CI2.

Similar to the chromophore represented by formula I, in the compound represented by 2) according to the present invention, At least one group selected from the group consisting of DI and A1 is a group other than H It is.

A compound containing a nonlinear optical chromophore represented by formula l, from which the substance according to the present invention is derived Compounds of formula ■ and can be produced by standard methods of organic chemistry. Wear.

This reaction condition can be found in standard academic texts on organic chemistry production, such as HOUBEN-W. Methoden der OrganischenChemie by EYL (Georg Thiew+e Publisher, StuttgarL), 0RGA NIC5YNTHESES (J, Wiley, New York-Lond on-Sydney) or HETEROCYCLIC COMPOUND S, Volume 14, (J, Wiley, NewYork-London-5 ydney).

That is, zl or the corresponding compound where Zl is -C=C- double bond is For example, by combining the corresponding alkyl compound with a suitable aldehyde or ketone compound, They can be prepared by condensation in a manner customary per se. This contraction In this case, dehydrating agents such as acetic anhydride, bases such as ammonia, such as ethylamine, piperidine or pyridine, or salts such as ammonium acetate. This is done by adding monium or piperidinium acetate. Inert solvent, e.g. Hydrocarbons such as hexane, cyclohexane, benzene, toluene or xylene It is also preferable to add an element. The reaction temperature is usually 06 to 250°C, preferably +20° to The temperature is 150°C. At these temperatures, the reaction generally takes between 15 minutes and 48 hours. completed later. Stilbene derivatives are e.g. the corresponding aromatic aldehyde compounds. and from the corresponding arylmethylphosphonium salt or monophosphonate compound , produced by Wittig-Horner reaction or WitLig reaction be able to.

C=N or N=N double bonds can be formed by aldehyde by an advantageously carried out condensation reaction. from hydride compounds and primary amine compounds, or from nitroso compounds and primary amine compounds. amine compounds by methods known to those skilled in the art.

In another method for producing the above compound, a (hetero)aryl halide compound is React with the olefin in the presence of a tertiary amine and a palladium catalyst Acc, Chem, Res, 12 (1979) 1 by F. Heck See page 46]. Suitable (hetero)aryl halide compounds include, for example, chloride. bromide and iodite, especially bromide. This coupling anti Tertiary amine compounds, such as triethylamine, which are necessary for successful reactions, may also be added to the solution. Also suitable as a medium. Suitable palladium catalysts are, for example, salts thereof, especially Pd( If) acetate, which is an organophosphorus (I[) compound, e.g. It is used together with other drugs such as phosphine. This method requires the presence of an inert solvent or at a temperature of about θ″ to 150°C, preferably about 20° to 100°C, in the absence of I can. Suitable solvents include, for example, nitriles such as acetonitrile; or hydrocarbons such as benzene or toluene. used as starting material The (hetero)aryl halide compounds and olefins used are quite often are available commercially or by methods known from the literature, e.g. by halogenation of the parent compound, or by the corresponding alcohol compound or halide. It can be produced by an elimination reaction on a ride compound.

Furthermore, in order to combine (hetero)aromatic compounds, (hetero)aryl halide The ride compound is a (hetero)aryltin compound or a (hetero)arylbox Can be reacted with acid compounds. These reactions are preferably carried out using a catalyst, e.g. An inert solvent such as hydrocarbon water is added to the palladium(0) complex compound. under a protective gas atmosphere at an elevated temperature, e.g. boiling xylene. Do it below.

The vicinal position of the electron donating group on the aromatic C atom, which is a feature of the substance according to the present invention, and the vicinal position of the electron-accepting group, respectively, are already present in the starting compound. can be done. On the other hand, many vicinally substituted starting compounds, even Baphthalonitrile, 0-dinitrobenzene, 3.4-dinitrotoluene, 3.4 -Dinitrobenzyl alcohol, 3-fluoro-4-nitrotoluene, 〇-Fni Further herein, such as nylene diamine and O-dihaloaromatic compounds, If an electron-donating or electron-accepting group is vicinally substituted, not specified in detail. The aromatic compounds are already commercially available (Messrs.

Merck, Darmstadt) On the other hand, these compounds have substituents It can also be produced from a precursor compound with a small amount by an appropriate substitution reaction, such as For example, 3-cyano-4-nitrotoluene is produced by nitration of 3-cyanotoluene. If desired, this nitro group can be prepared by subsequent diazotization. can be converted to a nitrile via an amine. 0-722 Renjia min can be alkylated and then by Vilsmeier formylation. can be converted into benzaldehyde derivatives. These enumerated reactions are , only a small part of the wide range of possible transformations. Its manufacturing method is known to those skilled in the art. and commonly used reference books, such as Metho by HOUBEN-WEYL. den der Organischen Chemie (Georg-Th ieIIIe Publisher, Stuttgart). The starting compound They are either known per se or can be prepared in the same manner as known compounds by conventional methods. can be manufactured.

The polyurethanes according to the invention contain vicinal donor groups/acceptor groups and A compound containing a bis(ω-hydroxyalkyl)amino group is produced by reacting with isocyanates or alkyl diisocyanates. can be done.

Preferred poly(meth)acrylates and poly(meth)acrylates according to the present invention Amides are appropriately substituted alcohol or amine compounds ( meth)acrylic acid or its reactive derivatives and then polymerized. Thus, more particularly, reaction conditions which are customary per se and known to the person skilled in the art It can be produced by carrying out the above reaction and polymerization under the following conditions. seven Zimmer also includes halogen (preferably bromine or iodine) substitution in the alkoxy group. An acrylate or methacrylate compound having a group derived from formula I It can be produced by reacting with a compound. Overall, polymer Polymers containing a nonlinear optical chromophore attached to the backbone via a donor are Particularly preferred. These 7-year-olds are also the subject of the present invention.

Comonomers suitable for the preparation of the copolymers are in particular acrylic acid and/or meth C3-~C of acrylic acid! . -alkyl ester, preferably CI- to C1-a rukyle esters, mixtures of these esters, and acrylates with these esters. Rylonitrile, methacrylonitrile, styrene, 4-methylstyrene, acrylic and/or methacrylamide.

Among the acrylates, the following compounds are suitable, for example: Methyl acrylate, ethyl acrylate, globyl acrylate, n-butyl Acrylate, isobutyl acrylate, hexyl acrylate, n-octyl Acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl Acrylate, dodecyl acrylate, hexadecyl acrylate, octadecy acrylate and corresponding methacrylates.

Preference is given to the above acrylics of alkanols having up to 8 CWL molecules. ester compounds and methacrylate compounds.

Alternatively, polyesters with halogen substituents, preferably bromine or iodine, in the side chains can be used. It is also possible to react the mer with a compound derived from formula I. Starting from this halogen substitution Polymers are produced by homopolymerization of halogenated monomers, or by copolymerization thereof, preferably Preferably, it is obtained by copolymerization with the above-mentioned comonomers.

The polymer is prepared by known methods, preferably free radical bulk polymerization or free radical solution polymerization. It is manufactured as follows.

For initiation of polymerization, for example Pappas (Preparation).

UV Curing: 5science and Technology (T technology Marketing Corp, Stamford CT, 1978) or 0cian.

Pr1nciples or Po1y+++erizaLion(McGra A number of known inceptions, as described in W-Old II, New York) agent is appropriate. Examples of thermally decomposed free radical initiators include azoisobutyronite. AIBN or decomposed compounds such as potassium persulfate, dibenzoy peroxide and cyclohexanone peroxide, an initiator that decomposes under the action of radiation. Examples include benzophenone compounds, alkyl ethers of benzoin, and benzyl kets. There are compounds such as alcohol compounds and σ-hydroxyalkylphenone compounds.

The ethylenically unsaturated septamer is reacted, optionally in the presence of additives. be able to.

- For example, small amounts of light stabilizers, such as benzophenone derivatives, benzotriazo derivatives, tetraalkylpiperidine compounds or phenyl salicylate compounds things can be added.

Depending on the application, plasticizers, wetting agents or silicones may be used to improve surface quality. Organic additives such as are suitable.

The photopolymerization is carried out by methods known per se at 250 to 500 ne+, preferably 30 This is carried out by light irradiation or ultraviolet irradiation in the wavelength range of 0 to 400 nm. light As a radiation source, a solar source or an artificial light source can be used. high pressure, medium pressure or low pressure mercury vapor lamps, cannon lamps and tungsten lamps are examples of advantageous light sources. be. Laser light sources can be used as well.

High-energy radiation, such as X-rays, electrons, neutrons and other radiation, can also Suitable for initiating polymerization. This irradiation can reduce the amount of photoinitiator added or It can be omitted completely.

Thermal polymerization can be carried out, for example, by ultrasound or microwaves, or This is done by exposure to the action of IR radiation or simply by heating.

The substance according to the present invention has amphiphilic properties or has a strong mutual interaction with the substrate surface. For example, brush coating, printing, dipping or The substance according to the invention can be applied in dissolved form or by spin coating. is in liquid form and by application to a substrate a nonlinear optical arrangement is obtained. present invention The compound represented by the formula Their non-containing properties are dissolved in polymers, as single crystals, or as crystalline powders. It can exhibit linear optical physical properties.

The polymeric material according to the invention is arranged in a bipolar manner in an electric DC field. be able to. This occurs at temperatures within the glass transition temperature of the polymeric material. . The material according to the invention is subsequently cooled in an electric field.

This results in polymeric materials with advantageous nonlinear optical properties.

The materials according to the invention are suitable for use in optical components. i.e. these things On the one hand, the quality can be used for bulk materials, and on the other hand, its electro-optic effect For waveguide structures that utilize the , can be used. If desired, substances according to the invention, e.g. The polymers themselves can function as waveguides.

The material according to the invention can therefore be used, for example, in integrated optics, sensors and communication technologies. For parts in the field of laser beam frequency doubling, directional kagler, switches switching elements, modulators, parametric amplifiers, waveguide structures, optical pulp and their Other suitable optical components known to those skilled in the art. These optical components are For example, it is described in EP0218938.

Legal examples illustrate the invention: AIBN Azobisisobutyronitrile DIRALH diisobutyl aluminum Nium hydride DMEU 1,3-dimethyl-2-imidazolinone DMF Dimethylformamide POT Potassium tart, Butalt M, p, Melting point NBS N-bromosuccinimide NMP N-methylpyrrolidine -2-one TBME Lert, butyl methyl ether THE Trahydrofuran Example 1 4-Amino-3'-cyano-4'-nitrostilbene a) 4-acetylamino- 3'-cyano-4'-nitrostilpene 135 g of 2-nitro-5-methylbenzonitrile in 600 mQ of pyridine (0, 83 mol) (this compound is obtained by nitration of m-tolnitrile), 4-acetylaminobenzaldehyde 1359 (0.83 mol) and piperi Heat the solution of Jin3Qw12 at 140° C. for 4 hours. Let this mixture cool and The formed precipitate is separated by furnace. Orange crystals are obtained. m, p-: 217-21 8℃b) 4-amino-4'-cyano-4'-nitrostilbene 4-acetyl Amino-3'-cyano-4'-nitrostilvea 1359 (0.44 mol) 37% hydrochloric acid aqueous solution 260 m<2 to 9/-100 m (in the mixture with 2 The suspension is heated at boiling point for 48 hours.

The mixture is allowed to cool and the precipitate is filtered out. This product was dissolved in 35% sodium hydroxide. solution 200IIQ and the mixture was then stirred for 4 hours and then filtered. do. The residue is recrystallized from acetone/ethanol. Dark red crystals are obtained .

Example 2 4-amino-3',4'-dinitrostilbene a) l-j lomomethyl-3,4- Dinitrobenzene 3.4-Dinitrobenzyl alcohol 89.6g (452ml mol) was added in portions to 2.250 mol of 48% hydrobromic acid maintained at 90°C. Ru. The mixture was stirred for 2 hours at 90°C, allowed to cool, diluted with water 2.0 and then Extract with TBME. The organic phase was washed with water and seeded sodium carbonate solution. , dried over sodium sulfate and then evaporated. Re-residue from ethanol crystallize. Yellow crystals are obtained.

City, p: 48℃ b) (3,4-dinitrobenzyl)-triphenylphosphonium bromide 1-Bromomethyl-3,4-dinitrobenzene in acetone 2.5a 92.09 (352 mmol) and triphenylphosphine 92.4 g (352 mmol) Heat the solution of 1) at 70° C. for 2 hours. This mixture is cooled and the precipitate is separated from the furnace. and then washed with ether. Yellow crystals are obtained.

c) 4-acetylamino-3',4'-dinitrostilbene POT 34. 7 g (309 mmol) of (7)(3,4-dinito) in 1.5Q dichloromethane lobenzyl)-triphenylphosphonium bromide 1479 (281 mmol ) and stir the mixture for 20 minutes at room temperature. In this red solution, Add 45.89 (281 mmol) of 4-acetylaminobenzaldehyde and mix. The mixture is stirred at room temperature for 18 hours. Pour this mixture into water and separate the organic phase. , the aqueous phase is extracted with dichloromethane. The organic phase was dried with sodium sulfate and then and evaporate the residue on a silica gel column using dichloromethane/methane as eluent. Chromatograph using tanol (95:5). red crystals are obtained Ru.

d) 4-Amino-3',4'-dinitrostilbene 4 in 500 tQ of ethanol -acetylamino-3',4'-dinitrostilbene 58.09 (177 mm A solution of 50 ml of 37% hydrochloric acid is heated at the boiling point for 2 hours. This mixture Pour things into water and make alkaline using 32% sodium hydroxide solution, Then extract with TBME. The organic phase is dried over sodium sulfate and then evaporated The residue was purified with silica gel using dichloromethane/methanol (95: 5). Red crystals are obtained.

Example 3 4-Amino-3',4'-dinitrostilbene a) Diethyl 3,4-dinito lobenzylphosphonate l-bromomethyl-3,4-dinitrobenzene 43g ( 165 mmol) (compound of Example 2a) and 82 g (494 mmol) of triethyl phosphite mmol) mixture is heated at 120° C. for 30 minutes.

Excess triethyl phosphite was removed by vacuum distillation, and the residue was transferred to a silica gel column. Chromatography was performed using dichloromethane/methanol (95:5) as the eluent. tography processing. A yellow oil is obtained.

b) 4-acetylamino-3',4'-dinitrostilbene powder sodium hydroxide 5.7 g (82 mmol) of Nodiethyl 3.4-dini in 100 mQ of THF. 13 g (41 mmol) of trobenzylphosphonate and 4-acetylaminobenzylphosphonate Add to a solution of 6.7 g (41 mmol) of nzaldehyde. This mixture is then and stir at room temperature for 1 hour. The mixture was poured onto ice and then extracted with TBME. put out The organic phase is washed with sodium chloride solution, dried over sodium sulfate and then Evaporate with water. The residue was purified on a silica gel column using dichloromethane as eluent. /methanol (95:5).

c) 4-amino-3',4'-dinitrostilbene This compound is described in Example 2d Manufactured according to the following.

Example 4 4-amino-3'-fluoro-4'-nitrostilbene a) 1-bromomethy -3-fluoro-4-nitrobenzene 125+m of carbon tetrachloride (15.1 g of 3-fluoro-4-'nitrotoluene in 2 (97.3 mmol), NES 26.0g (146 mmol) and diben A solution of 1.4] g (5.9 mmol) of zoyl peroxide was heated at boiling point for 54 hours. heat. The mixture is allowed to cool, undissolved material is separated, and the furnace liquid is evaporated. Residue The distillate was passed through a silica gel column using petroleum ether/ethyl acetate (95:5) as eluent. chromatography.

A yellowish oil is obtained.

b) (3-fluoro-4-nitrobenzyl)-phosphonium bromide ■-Bromomethyl-3-fluoro-4-nitroin 300+mi2 Benzene 9.09 (38.5 mmol) and triphenylphosphine IO, 1 g (38.5 mmol) of the solution is heated at 70° C. for 2 hours. Cool this mixture. The precipitate is filtered off and washed with diethyl ether. , yellow crystals are obtained.

c) 4-acetylamino-3'-fluoro-4'-nitrostilbene 3.5 g (31.0 mmol) of POT ( 3-Fluoro-4-nitrobenzyl)-triphenylphosphonium bromide 1 4.0 g (28.8 mmol) of the suspension and the mixture was stirred for 20 minutes at room temperature. Stir. To this red solution was added 4.6 g of 4-acetylaminobenzaldehyde (2 8.2 mmol) is added and the mixture is stirred at room temperature for 28 hours. This mixture in water The organic phase is separated and the aqueous phase is extracted with dichloromethane. Sulfurize the organic phase dried over sodium chloride, then evaporated and the residue was purified on a silica gel column. Chromatograph using dichloromethane/methanol (95:5) as eluent. Filing process. Orange-red crystals are obtained.

d) 4-amino-3'-fluoro-4'-nitrostilbeethanol 125 vi (4-acetylamino-3'-fluoro-4'-nitrostilbene in ．． 59 (28.2 mmol) and 37% hydrochloric acid 25 m (2) at boiling point for 4 hours. Heat. Pour this mixture into water and use 32% sodium hydroxide solution. , made alkaline and then extracted with dichloromethane.

The organic phase was dried over sodium sulfate, then evaporated and the residue was filtered onto silica gel. chromatograph using toluene/methanol (95:5) as eluent. Raffi processing. The product obtained in this way was then recrystallized from ethanol. let Orange-red crystals are obtained.

Example 5 N-hexyl-4-amino-3'-cyano-4'-nitrostilbene 16.8g (0.20 mol) of sodium bicarbonate A, DMEU 170+mff 4-amino-3'-cyano-4'-nitrostilbene 52.99 (0,20 mol) (compound of Example 1) and 33.0y of I-bromohexane (0.20 mol) ) and heat the mixture at 100° C. for 3 hours. Cool this mixture Pour into water and extract with dichloromethane. Organic phase over sodium sulfate After drying and evaporation, the residue was passed through a silica gel column using petroleum air as eluent. Chromatography using tel/ethyl acetate (1:1). dark red color Crystals are obtained. m-p: i34-135°C.

Similarly, the following compound is prepared: N-methyl-4-amino-3'-cya No-4'-Nitros still pen N-ethyl-4-amino-3'-cyano-4'-nitrostilbene N-propyl-4-amino-3'-cyano-4'-nitrostilbene N-butyl-4-amino-3'-cyano-4'-nitrostilbene N-pentyl-4-amino-3'-cyano-4'-nitrostilbene N-heptyl-4-amino-3'-cyano-4'-nitrostilpene N-octyl-4-amino-3'-cyano-4'-nitrostilbene N-nonyl-4-amino-3'-cyano-4'-nitrostilbene N-decyl-4-amino-3'-cyano-4'-nitrostilbene N-dodecyl-4-amino-3'-cyano-4'-nitrostilbene N-tetradecyl-4-amino-3'-cyano-4'-nitrostilbene N-hexadecyl-4-amino-3'-cyano-4'-nitrostilbene N-octadecyl-4-amino-3'-cyano-4'-nitrostilbene N-eicosyl-4-amino-3'-cyano-4'-nitrostilpene N-docon-4-amino-3'-cyano-4'-nitrostilbene N-methyl-4-amino-3',4'-dinitrostilbe N-ethyl-4-amino No-3',4'-dinitrostyl N-butyl-4-amino-3',4'-dinito Rostil N-butyl-4-amino-3',4'-dinitrostil N-butyl-4 -amino-3',4'-dinitrostyl N-hexyl-4-amino-3',4' -Dinitrostilbene, m, p: 97°C N-hebutyl-4-amino-3',4'-dinitrostilbene N-cutyl-4-amino-3',4'-dinitrostilbene N-nonyl-4-amino-3',4'-dinitrostilbe N-decyl-4-amino No-3',4'-dinitrostilbe N-dodecyl-4-amino-3',4'-di Nitrostilbene N-tetradecyl-4-amino-3',4'-dinitrostilbene N-hexadecyl-4-amino-3',4'-dinitrostilbene N-octadecyl-4-amino-3',4'-dinitrostilbene N-eicosyl-4-amino-3',4'-dinitrostilbene N-tocosyl-4-amino-3',4'-dinitrostilbene N-methyl-4-amino-3'-fluoro-4'-nitrostilbene N-ethyl-4-amino-3'-fluoro-4'-nitrostilbene N-propyl-4-amino-3'-fluoro-4'-nitrostilbene N-butyl-4-amino-3'-fluoro-4'-nitrostilbene N-pentyl-4-amino-3'-fluoro-4'-nitrostilbene N-hexyl-4-amino-3'-fluoro-4'-nitrostilbene N-hebutyl-4-amino-3'-fluoro-4'-nitrostilbene N-octyl-4-amino-3'-fluoro-4'-nitrostilbene N-nonyl-4-amino-3'-fluoro-4'-nitrostilbene N-decyl-4-amino-3'-fluoro-4'-nitrostilbene N-dodecyl-4-amino-3'-fluoro-4'-nitrostilbene N-tetradecyl-4-amino-3'-fluoro-4'-nitrostilbene N-hexadecyl-4-amino-3'-fluoro-4'-nitrostilpene 1 N-octadecyl-4-amino-3'-fluoro-4'-nitrostilbe hmm N-eicosyl-4-amino-3'-fluoro-4'-nitrostilbene N-tocosyl-4-amino-3'-fluoro-4'-nitrostilbene Example 6 N,N-dihexyl-4-amino-3'-cyano-4'-nitrostilbene 2.5 g (30 mmol) of sodium bicarbonate in DMEU 3OrRff -amino-3'-cyano-4'-nitrostilbene 2.0 g (7.5 mmol) (compound of Example 1) and 5.0 g (30 mmol) of l-bromohexane. and heat the mixture at 100° C. for 48 hours. Let the mixture cool and then add water and then extracted with dichloromethane. Organic phase over sodium sulfate Dry, then evaporate and transfer the residue to a silica gel column using petroleum as eluent. Chromatography was performed using ether/ethyl acetate (9:1). red knot Crystals are obtained. m, p,: 74°C.

Similarly, the following compound is prepared: N,N-dimethyl-4-amino-3' -cyano-4'-nitrostilbene N,N-diethyl-4-amino-3'-cyano-4'-nitrostilpene N,N-dipropyl-4-amino-3'-cyano-4'-nitrostilbene N,N-dibutyl-4-amino-3'-cyano-4'-nitrostilbene N,N-dipentyl-4-amino-3'-cyano-4'-nitrostilbene N,N-diheptyl-4-amino-3'-cyano-4'-nitrostilbene N,N-dioctyl-4-amino-3'-cyano-4'-nitrostilbene N,N-dinonyl-4-amino-3'-cyano-4'-cytoN,N,-dido Decyl-4-amino-3'-cyano-4'-nitrostilbene N,N-ditetradecyl-4-amino-3'-cyano-4'-nitrostilbene N,N-dihexadecyl-4-amino-3'-cyano-4'-nitrostilbene N,N-dioctadecyl-4-amino-3'-cyano-4'-nitrostilbene , dark red crystal N,N-dicosyl-4-amino-3'-cyano-4'-nitrostilbene N,N-cytocosyl-4-amino-3'-cyano-4'-nitrostilpene N,N-dimethyl-4-amino-3'-fluoro-4'-nitrostilbene N,N-diethyl-4-amino-3'-fluoro-41-nitrostilbene N,N-dipropyl-4-amino-3'-fluoro-4'-nitrostilbene N,N-dibutyl-4-amino-3'-fluoro-4'-nitrostilpene N,N-diben-4-amino-3'-fluoro-47-nitrostilbene N,N-dihexyl-4-amino-3'-fluoro-4'-nitrostilbene, purple crystal N,N-diheptyl-4-amino-3'-fluoro-4'-nitrostilbene N,N-dioctyl-4-amino-3'-fluoro-4'-nitrostilbene N,N-dinonyl-4-amino-3'-fluoro-4'-nitrostilbene N,N-didecyl-4-amino-3'-fluoro-4'-nitrostilbene N,N-didodecyl-4-amino-3'-fluoro-4'-nitrostilpene N,N-ditetradecyl-4-amino-3'-fluoro-4'-nitrostilbe hmm N,N-dihexadecyl-4-amino-3'-fluoro-4'-nitrostilbe hmm N,N-dioctadecyl-4-amino-3'-fluoro-4'-nitrostilbe hmm N,N-dicosyl-4-amino-3'-fluoro-4'-nitrostilbene N,N-cytocosyl-4-amino-3'-fluoro-4'-nitrostilbene N,N-dimethyl-4-amino-3',4'-dinitrostyl N,N-diethyl -4-amino-3',4'-dinitrostilbene N,N-dipropyl-4-amino-3',4'-dinitrostilbene N,N-dibutyl-4-amino-3',4'-dinitrostilbene N,N-dipentyl-4-amino-3',4'-dinitrostilbene N,N-dimxyl-4-amino-3',4'-dinitrostilbene, n+,p ,: 82℃ N,N-diheptyl-4-amino-3',4'-dinitrostilbene N,N-dioctyl-4-amino-3',4'-dinitrostilbene N,N-dinonyl-4-amino-3',4'-dinitrostilbene N,N-didecyl-4-amino-3',4'-dinitrostilbene N,N-didodecyl-4-amino-3',4'-dinitrostilbene N,N-ditetradecyl-4-amino-3',4'-dinitrostilbene N,N-dihexadecyl-4-amino-3',4'-dinitrostilbene N,N-dioctadecyl-4-amino-3',4'-dinitrostilbene N,N-dicosyl-4-amino-3',4'-dinitrostilbene N,N-cytocosyl-4-amino-3',4'-dinitrosti-2-C2-(3 -cyano-4-nitrophenyl)-ethynyl)-5-(2-(4-dihexyl) minophenyl)-ethynylcupyridine a) 2-(2-(3-cyano-4-nitrophenyl)-ethynyl)]-]5-meth Chilpyridi 24.2 g of 2-nitro-5-methylbenzonitrile in pyridine 15112 ( 149 mmol), 2-formyl-5-methylpyridine 18.17 g (150 mmol) [This compound was prepared according to the method of Mathes, (Sauermilch, Manufactured by Chew, Ber, 9 (L p. 758 (1957)) ] and 15 ml of piperidine was heated at 140° C. for 4 hours. this mixture Cool and separate the precipitate. Yellowish crystals are obtained.

b) 2-C2-(3-cyano-4-nitrophenyl)-ethynyl)-5-(2- (4-dihexylaminophenyl)-ethynylcupyridine 2-C2-(3-cyano-4-nitrophenyl)-nitenyl]-5-methylpi Lysine 13.3 g (50 mmol), 4-dihexylaminobenzaldehyde 1 4.5 g (50 mmol) (this compound was converted from N,N-dihexylaniline to Vi lsweier formylation) and 5 mM of piperidine. The solution in gin 50 mff is heated at 140° C. for 16 hours. Let the mixture cool and settle. The filtrate is filtered and then recrystallized from ethanol. Dark red crystals are obtained.

In the same way, the following compound is prepared: 2-(2-(3-cyano-4-ditho lophenyl)-ethynyl)-5-(2-(4-dimethylaminophenyl)-ethene ]-pyridine 2-(2-(3-cyano-4-nitrophenyl)-ethynyl)-5-[2-( 4-Diethylaminophenyl)-ethynylcupyridine 2-(2-(3-cyano-4-nitrophenyl)-ethynyl)-5-(2-( 4-dibutylaminophenyl)-ethenyl]-pyridine 2-(2-(3-cyano-4-nitrophenyl)-ethynyl)-5-(2-( 4-Diethylaminophenyl)-ethenyl]-pyridine 2-(2-(3-cyano-4-nitrophenyl)-ethynyl)-5-(2-( 4-diethylaminophenyl)-5-(2-(4-dioctylaminophenyl) (phenyl)-ethynylcupyridine 2-C2-(3-cyano-4-nitrophenyl)-ethynyl)-5-(2-(4 -dinonylaminophenyl)-ethynylcopyridine 2-(2-(3-cyano-4-nitrophenyl)-ethynyl)-5-(2-( 4-Didecylaminophenyl)-ethenyl]-pyridine 2-(2-(3-cyano-4-nitrophenyl)-ethynyl)-5-[2-( 4-Dioctylaminophenyl)-ethynylcupyridine 2-(2-(3-cyano-4-nitrophenyl)-ethynyl)-5-[2-( 4-ditetradecylaminophenyl)-ethynylcupyridine 2-(2-(3-cyano-4-nitrophenyl)-ethynyl)-5-[2-' (4-dihexadecylaminophenyl)-ethynylcupyridine 2-(2-(3-cyano-4-nitrophenyl)-ethynyl)-5-(2-( 4-dioctadecylaminophenyl)-ethynylcupyridine 2-C2-(3-cyano-4-nitrophenyl)-ethynyl)-5-(2-( 4-dicosylaminophenyl)-ethynyl]-pyridine 2-(2-(3-cyano-4-nitrophenyl)-ethynyl)-5-(2-( 4-Dioctylaminophenyl)-ethynylcupyridine 2-C2-(3-fluoro-4-nitrophenyl)-ethynyl)-5-C2 -(4-dimethylaminophenyl)-ethynylcupyridine 2-(2-(3-fluoro-4-nitrophenyl)-ethynyl)-5-(2- (4-diethylaminophenyl)-ethenyl]-pyridine 2-[2-(3-fluoro-4-nitrophenyl)-ethynyl)-5-(2- (4-dipropylaminophenyl)-ethynylcupyridine 2-C2-(3-fluoro-4-nitrophenyl)-ethynyl)-5-[2- (4-dibutylaminophenyl)-ethynylcupyridine 2-(2-(3-fluoro-4-nitrophenyl)-ethynyl)'-5-(2 -(4-dipentylaminophenyl)-ethynylcupyridine 2-C2-(3-fluoro-4-nitroenyl)-ethynyl)-5-(2 -(4-didecylaminophenyl)-ethynylcupyridine 2-(2-(3-fluoro-4-nitrophenyl)-ethynyl)-5-(2- (4-diheptylaminophenyl)-ethynylcupyridine 2-(2-(3-fluoro-4-nitrophenyl)-ethynyl)-5-(2- (4-Dioctylaminophenyl)-ethynylcupyridine 2-(2-(3-fluoro-4-nitrophenyl)-ethynyl)-5-(2- (4-Dinonylaminophenyl)-ethynylcupyridine 2-C2-(3-fluoro-4-nitrophenyl)-ethynyl)-5-(2- (4-Didecylaminophenyl)-ethenyl]-pyridine 2-(2-(3-fluoro-4-nitrophenyl)-ethynyl)-5-(2 -(4-didecylaminophenyl)-ethynylcupyridine 2-(2-(3-fluoro-4-nitrophenyl)-ethynyl)-5-(2- (4-ditetradecylaminophyl)-ethynylcupyridine 2-(2-(3-fluoro-4-nitrophenyl)-ethynyl)-5-(2-( 4-dihexadecylaminophenyl)-ethynylcupyridine 2-(2-(3-fluoro-4-nitrophenyl)-ethynyl)-5-(2- (4-dioctadecylaminophenyl)-ethynylcupyridine 2-C2-(3-fluoro-4-nitrophenyl)-ethynyl)-5-(2- (4-dicosylaminophenyl)-ethynylcupyridine 2-(2-(3-fluoro-4-nitrophenyl)-ethynyl)-5-C2- (4-cytocosylaminophenyl)-ethynylcupyridine 2-C2-(3,4-dinitrophenyl)-ethynyl]-5-(2-(4-di Methylaminophenyl)-ethynylcupyridine 2-(2-(3,4-dinitrophenyl)-ethynyl)-5-(2-(4-' ;ethylaminophenyl)-ethynylcupyridine 2-(2-(3,4-dinitrophenyl)-ethynyl]-5-[2-C4-dip (ropylaminophenyl)-ethynylcupyridine 2-C2-(3,4-dinitrophenyl)-ethynyl]-5-(2-(4-dinitrophenyl)-ethynyl) (ph'thylaminophenyl)-ethynylcupyridine 2-(2-(3,4-dinitrophenyl)-ethynyl]-5-(2-<4-dipe (anthylaminophenyl)-ethynylcupyridine 2-C2-(3,4-dinitrophenyl)-ethynyl]-5-(2-(4-di ethylaminophenyl)-ethynylcupyridine 2-(2-(3,4-dinitrophenyl)-ethynyl)-5-C2-(4-di heptylaminophenyl)-ethynylcupyridine 2-(2-(3,4-dinitrophenyl)-ethynyl]-5-C2-(4-dio (cutylaminophenyl)-ethynylcupyridine 2-(2-(3,4-dinitrophenyl)-ethynyl)-5-[2-(4-di nonylaminophenyl)-ethynyl]-pyridine 2-(2-(3,4-dinitrophenyl)-ethynyl] = 5-[2-(4-dide cylaminophenyl)-ethynyltwopyridine 2-[2-(3,4-dinitrophenyl)-ethynyl]=5- C2-(4- didodecylaminophenyl)-ethynyltwopyridine 2-(2-(3,4-dinitrophenyl)-ethynyl)-5-(2-(4-dinitrophenyl)-ethynyl) Tetradecylaminophenyl)-ethynyltwopyridine 2-(2-(3,4-dinitrophenyl)-ethynyl)=5-(2-(4- Dihexadecylaminophenyl)-ethynyltwopyridine 2-(2-(3,4-dinitrophenyl)-ethynyl]-5-C2-(4-dio (ctadecylaminophenyl)-ethynyltwopyridine 2-(2-(3,4-dinitrophenyl)-ethynyl)-5-(2-(4-dide cylaminophenyl)-ethynyl]-pyridine 2-(2-(3,4-dinitrophenyl)-ethynyl]-5-(2-(4-dido) Decylaminophenyl)-etheny3-cyano4-nitro-4'-(2-(4- Dioctadecylaminophenyl)-ethynyl)-stilbene a) 4-cyano -4'-dioctadecylaminostilvejethyl 4-cyano-phenyl-methyl 13.4 g (52.9 mmol) of phosphonate and 4-dioctadecylamino 33.1 g (52.9 mmol) of phenyl) redehyde was added to 100 m (1 Add to the suspension of 5-9 g (106 mmol) of powdered potassium hydroxide in the mixture Stir at room temperature for 18 hours. Pour this mixture into water, filter out the precipitate, and evaporate. Recrystallized from nol and petroleum ether. Yellow fluorescent crystals are obtained.

b) 4'-dioctadecylamino-4-formyl stilbe kept at 5°C , 4-cyano-4'-dioctadecylaminostilbene 18.29 (25,1 mmol) of DIBALH in hexane in 250 ml of hexane. 1 molar solution33. b++12 (33.1 mmol) is added dropwise. This mixture The mixture is stirred at room temperature for 1.5 hours, then 2 mQ of methanol are added. this mixture Pour into water, acidify using concentrated hydrochloric acid, separate and collect the organic phase, and remove the aqueous phase. Extract with TBME. The organic phase is dried over sodium sulfate and then evaporated, The residue was passed through a silica gel column using petroleum ether/ethyl acetate (95: 5) for chromatography. Yellow crystals are obtained.

c) 3-cyano-4-nitro-4'-(2-(4-dioctadecylaminof) (phenyl)-ethynyl)-stilbene 4'-dioctadecylamino-4-formyl 1.0 g (9-6 mmol) of stilbene, 5-methyl-2-nitropenzonitri 1.69 (9.1 mmol) and piperidine ltQ in pyridine 3OtQ The solution is stirred for 48 hours at a temperature of 100°C.

The mixture is allowed to cool, poured into water and extracted with TBME. The organic phase is diluted with sodium sulfate. Dry over thorium, then evaporate and transfer the residue to a silica gel column with eluent Chromatography using petroleum ether/ethyl acetate (95:5) as do. Purple crystals are obtained.

Example 9 3-cyano-4-nitro-4'-(2-(4-didecylaminophenyl)ethini a) 3-cyano-4-nitro-4'-hydroxymethylstyl ben 4-formylbenzyl alcohol 50.0 g (370 mmol), 5-methyl- 2-nitropenzonitrile 59.59 (370 mmol) and piperidine 3 ．． A solution of 70aQ in pyridine 37OtQ is heated at 100° C. for 100 hours.

The mixture is poured into water and extracted with dichloromethane. Sodium sulfate organic phase evaporated on a silica gel column with dichloromethane as eluent. Chromatography using lomethane/methanol (95:5). yellow Crystals are obtained.

b) 4-7' lomomethyl-3'-cyano-4'-nitrostilbene 3-cyano-4-nitro-4'-hydroxymethylstilbene 19.59 (6 9.6 mmol) was added little by little to 350+ml of 47% hydrobromic acid and the mixture was Heat the mixture at 90° C. for 4 hours.

The mixture is allowed to cool and the precipitate is filtered off with suction. Remove the residue using a silica gel column. Chromatograph using oil ether/ethyl acetate (8:2). yellow Crystals are obtained.

c) (3'-cyano-4'-nitro-1-stilbenylmethyl)-triphe Nylphosphonium bromide 4-bromomethyl-3'-cyano-4'-nitros Chirpene 13.89 (40.2 mmol) and triphenyl phosphite 10. 59 (40.2 mmol) in 300 tQ of acetone at 70 °C for 4 hours Heat. The mixture was evaporated and then passed through a silica gel column in dichloromethane/ Chromatograph using methanol (9:1). yellow crystals are obtained Ru.

d) 3-cyano-4-nitro 4'-(2-(4-acetylaminophenyl )-ethynyl)-stilbene POT 3.249 (28.9 mmol) was diluted with (3'-cyano-4'-nitro-1-stilbenyl) in 200 mg of chloromethane methyl)-triphenylphosphonium puromyF 15.99 (26,3 mm ) and the mixture is stirred at room temperature for 20 minutes. In this dark green suspension, Add 4.72y (28.9 mmol) of 4-acetyl aminobenzaldehyde, The mixture is stirred at room temperature for 18 hours. Pour this mixture into water and remove the precipitate using a suction furnace. Separate. Orange crystals are obtained.

e) 3-cyano-4-nitro-4'-(2-(4-aminophenyl)-ethyl )-Stilbene 3-cyano-4-nitro-4'-(2-(4-acetylaminophenyl)-ethyl 11.3 g (27.6 mmol) of 37% hydrochloric acid A suspension in a mixture of Q and NMP 4.4 rQ and x9 nor L40 rtrQ Heat at boiling point for 18 hours.

This mixture is poured into fNNaOH. The precipitate was separated in a suction furnace, and then silica Chromatograph using dichloromethane/ethyl acetate (97:3) on a gel column. Filing process. Orange crystals are obtained.

0 3-cyano-4-nitro 4'-(2-(4-dihexylaminophenyl) -ethynyl)-stilbene sodium bicarbonate 1.559 (18.5 mmol) , 3-cyano-4-nitro 4'-(2-(4-amino) in NMP lO+mff nophenyl)-ethynyl)-stilbene 1.709 (4.63 mmol) and The mixture was added to a solution of 3.059 (18.5 mmol) of 1-bromohexane and Heat at 00°C for 40 hours. The mixture is allowed to cool and then poured into water, Separate the precipitate by suction. The residue was purified with petroleum ether/ethyl acetate ( 8: Chromatography using 2). Black crystals are obtained.

Analogously to Example 8 or Example 9, the following compounds are prepared: 3-cyano-4-nitro-4'-(2-(4-dimethylaminophenyl)-ethyl nyl)-stilbene 3-cyano-4-nitro-4'-(2-(4-diethylamide) nophenyl)-ethynyl)-stilbene 3-cyano-4-nitro-4'-(2- (4-dibutylaminophenyl)-ethynyl)-stilbene 3-cyano-4-di Trow 4'-(2-(4-dibentylaminophenyl)-ethynyl)-stilbe cyano-4-nitro-4'-(2-(4-dihexylaminophenyl) -ethynyl)-stilbene 3-cyano-4-nitro-4'-(2-(4-dihep tylaminophenyl)-ethynyl)-stilbene 3-cyano-4-nitro-4' -(2-(4-dioctylaminophenyl)-ethynyl)-stilbene 3-sia No-4-nitro-4'-(2-(4-dinonylaminophenyl)-ethynyl)- Stilbene 3-cyano-4-nitro-4'-(2-(4-didecylaminophenyl) )-ethynyl)-stilbene 3-cyano-4-nitro4'-(2-(4-di dodecylaminophenyl)-ethynyl)-stilbene 3-cyano-4-nitro 4'-(2-(4-ditetradecylaminophenyl)-ethynyl)-stilbene 3-cyano-4-nitro 4'-(2-(4-dihexadecylaminophenyl) -ethynyl)-stilbene 3-cyano-4-nitro4'-(2-(4-dicosy (ruaminophenyl)-ethynyl)-stilbene 3-cyano-4-nitro4'- (2-(4-cytocosylaminophenyl)-ethynyl)-stilbene 3-fluoro rho-4-nitro-4'-(2-(4-dimethylaminophenyl)-ethynyl)- Stilbene 3-fluoro-4-nitro-4'-(2-(4-diethylaminophe) 3-fluoro-4-nitro-4'-(2-(4 -diethylaminophenyl)-ethynyl)-stilbene 3-fluoro-4-nito rho-4'-(2-(4-dibutylaminophenyl)-ethynyl)-stilbene 3 -fluoro-4-nitro-4'-(2-(4-dibentylaminophenyl)-ethyl thinyl)-stilbene 3-fluoro-4-nitro-4'-(2-(4-dihexy Ruaminophenyl)-ethynyl)-stilbene 3-fluoro-4-nitro-4' -(2-(4-diheptylaminophenyl)-ethynyl)-stilbene 3-flu Oro-4-nitro-4'-(2-(4-dioctylaminophenyl)-ethynyl )-stilbene 3-fluoro-4-nitro 4'-(2-(4-dinonylamino phenyl)-ethynyl)-stilbene 3-fluoro-4-nitro 4'-(2- (4-didecylaminophenyl)-ethynyl)-stilbene 3-fluoro-4- Nitro 4'-(2-(4-didecylaminophenyl)-ethynyl)-styl Ben 3-fluoro-4-nitro 4'-(2-(4-ditetradecylaminophe) 117-4'-(2- (4-Dihexadecylaminophenyl)-ethynyl)-stilbene 3-fluoro -4-diF.rho4'-(2-(4-dioctatecylaminophenyl)-ethini )-stilbene 3-fluoro-4-nitro-4'-(2-(4-dicosylamine) nophenyl)-ethynyl)-stilbene 3-fluoro-4-nitro-4'-(2 -(4-cytocosylaminophenyl 3,4-dinitro-4'-(2-(4-dimethylaminophenyl)-ethynyl) -Stilbene 3,4-dinitro-4'-(2-(4-gelthiaminophenyl)-ethynyl) -Stilbene 3,4-dinitro-4'-(2-(4-dibutylaminophenyl)-ethynyl) -Stilbene 3,4-dinitro-4'-(2-(4-dibutylaminophenyl)-ethynyl) -Stilbene 3,4-dinitro-4'-(2-(4-dibentylaminophenyl)-ethynyl ) - stilbene 3,4-dinitro-4'-(2-(4-dihexylaminophenyl)-ethynyl ) - stilbene 3,4-dinitro-4'-(2-(4-diheptylaminophenyl)-ethynyl ) - stilbene 3,4-dinitro-4'-(2-(4-dioctylaminophenyl)-ethynyl ) - stilbene 3.4-dinitro-4'-(2-(4-dinonylaminophenyl)-ethynyl) -Stilbene 3.4-dinitro-4'-(2-(4-didecylaminophenyl)-ethynyl) -Stilbene 3.4-Dinitro-4'-(2-(4-didecylamino7enyl)-ethynyl ) - stilbene 3.4-dinitro-4'-(2-(4-ditetradecylaminophenyl)-ethyl 3,4-dinitro-4'-(2-(4-dihexadecylamide) nophenyl)-ethynyl)-stilbene 3,4-dinitro-4'-(2-(4- Dioctadecylaminophenyl)-ethynyl)-stilbene 3,4-dinitro- 4'-(2-(4-dicosylaminophenyl)-ethynyl)-stilbene 3.4-dinitro-4'-(2-(4-cytocosylaminophenyl)-ethynyl ) - stilbene Example 10 3'-cyano-4-(4-dioctadecylaminophenyl)-4'-nitrosti Reuben a) 4-Cyano-4'-dioctadecylaminophenyl sodium bicarbonate 7.0 g (83.4 mmol) of 4'-amino-4-cya in DMEU 20 taQ. nobiphenyl 5.4t;t (27,8 mmol) and l-bromooctadeca 27.8 g (83.4 mmol) of water and the mixture was heated at 100° C. for 18 hours. Heat. The mixture is allowed to cool, poured into water and then extracted with TBME. . The organic phase was dried over sodium sulfate, then evaporated and the residue was purified on silica gel. The column was chromatographed using petroleum ether/ethyl acetate (95:5) as the eluent. tography processing. Yellowish crystals are obtained. ■, p,: 77-78°C0 b) (7) D in 4'-dioctadecylamino-4-formylbiphenyhexane 17.6 mg (17.6 mmol) of IRALH (7) l molar solution was heated at 5°C. 4-cyano-4'-dioctadecyla in hexane 80Ila maintained at Add dropwise to a suspension of 9.44 g (13.5 mmol) of minobiphenyl. Living The resulting solution is stirred at room temperature for 1.5 hours. Add 1 mα of methanol dropwise, The mixture is poured into water and the organic phase is separated and collected.

The organic phase was dried over sodium sulfate, then evaporated and the residue was dissolved in ethanol. recrystallize from Yellow crystals are obtained. m, p,: 66-67°C.

c) 3'-cyano-4-(4-dioctadecylaminophenyl)-4'-di tros still pen 1.62 g (10 mmol) of 2-nitro-5-methylbenzonitrile, 4'-di Octadecylamino-4-formylbiphenyl 3.079 (10 mmol) and Heat a solution of 1 tx (l) and piperidine at 140°C for 4 hours. Cool the mixture. Boil, pour into water and then extract with TBME. Organic phase over sodium sulfate The residue was dried on a silica gel column using petroleum as eluent. Chromatography using ether/ethyl acetate (9:1). red knot Crystals are obtained.

Similarly, the following compound is obtained: 3'-cyano 4-(4-dimethylamino) (nophenyl)-4'-nitrostilbene 3'-cyano-4-(4-diethylaminophenyl)-4'-nitrostilbene 3'-cyano-4-(4-dipropylaminophenyl)-4'-nitrostilbe hmm 3'-cyano-4-(4-dibutylaminophenyl)-4'-nitrostilpene 3'-cyano-4-(4-dibentylaminophenyl)-4'-nitrostilbe hmm 3'-cyano-4-(4-diethylaminophenyl)-4'-nitrostilbene 3'-cyano-4-(4-diheptylaminophenyl)-4'-nitrostilbe hmm 3'-cyano-4-(4-dioctylaminophenyl)-4'-nitrostilbe hmm 3'-cyano-4-(4-dinonylaminophenyl)-4'-nitrostilpene 3'-cyano-4-(4-didecylaminophenyl)-4'-nitrostilbene 3'-cyano-4-(4-didecylaminophenyl)-4'-nitrostilbe hmm 3'-cyano-4-(4-ditetradecylaminophenyl)-4'-nitrosti J leben 3'-cyano-4-(4-dihexadecylaminophenyl)-4'-nitrosti Reuben 3'-cyano-4-(4-dicosylaminophenyl)-4'-nitrostilbene 3'-cyano-4-(4-cytocosylaminophenyl)-4'-nitrostilbe hmm 3'-Fluoro-4-(4-dimethylaminophenyl) = 4'-nitrostilbe hmm 3'-Fluoro-4-(4-diethylaminophenyl)-4'-nitrostilbe hmm 3'-fluoro-4-(4-'; dipropylaminophenyl-4'-nitrosti Reuben 3'-Fluoro-4-(4-dibutylaminophenyl)-4'-nitrostilbe hmm 3/-Fluoro-4-(4-dibentylaminophenyl)-4'-nitros chilbane 3'-Fluoro-4-(4-diethylaminophenyl)-4'-nitrostilbe hmm 3'-Fluoro-4-(4-diheptylaminophenyl)-4'-nitrostyl ben 3'-fluoro-4-(4-dioctylaminophenyl)-4'-nitrosti Reuben 3'-Fluoro-4-(4-dinonylaminophenyl)-4'-nitrostilbe hmm 3'-Fluoro-4-(4-didecylaminophenyl)-4'-nitrostilbe hmm 3'-Fluoro-4-(4-didecylaminophenyl)-4'-nitrostyl ben 3'-Fluoro-4-(4-ditetradecylaminophenyl)-4'-nitros chilbane 3'-Fluoro-4-(4-dihexadecylaminophenyl)-4'-nitros chilbane 3'-Fluoro-4-(4-dioctadecylaminophenyl)-4'-nitros chilbane 3'-Fluoro-4-(4-dicosylaminophenyl)-4'-nitrostilbe hmm 3 / ++-y fluoro-4-(4-di)'cosylaminophenyl)-4'-2 Trostilbene 4-(4-dimethylaminophenyl')-3',4'-dinitrostilbene 4-C4-diethylaminophenyl)-3',4'-dinitrostilbene 4-(4-dipropylaminophenyl)-3',4'-dinitrostilbene 4-C4-dibutylaminophenyl)-3',4'-dinitrostilbene 4-(4-diethylaminophenyl)-3',4'-dinitrostilbene 4-(4-diethylaminophenyl)-3',4'-dinitrostilbene 4-(4-diethylaminophenyl)-3',4'-dinitrostilbene 4-・(4-dioctylaminophenyl)-3',4'-dinitrostilbene 4-(4-dinonylaminophenyl)-3',4'-dinitrostilbene.

4-(4-didecylaminophenyl)-3',4'-dinitrostilbene 4-(4-didecylaminophenyl)-3',4'-dinitrostilbene 4-(4-ditetradecylaminophenyl')-3',4'-dinitrostyl ben 4-(4-dihexadecylaminophenyl)-3',4'-dinitrostilbe hmm 4-(4-dioctadecylaminophenyl)-3',4'-dinitrostilbe hmm 4-(4-dicosylaminophenyl)-3',4'-dinitrostilbene 4-(4-cytocosylaminophenyl)-3',4'-dinitrostilbene Example 11 4-(3,4-sinitrophenyla/)-N-ethylaniline 8.19 (0.12 mol) of sodium nitrite was mixed with 300 g of glacial acetic acid and 37% salt. 3,4-dinitroaniline 18.39 (0,1 mol) in a mixture with 100 m<1 ) [This compound includes O, N, Witt and E.

Produced by the method of Witte (Chew, Bar, p. 41.3090). Add to the solution. 12.29 N-ethylaniline in 100 m6 of glacial acetic acid (0.1 mol) is added dropwise. The mixture was stirred at room temperature for 2 hours and the precipitation Separate the lord. Red crystals are obtained.

Similarly, the following compound is prepared: 4-(3,4-'; nitrophenyl azo)-N-methylaniline 4-(3,4-dinitroaniline'/')-N-': l loviraniline 4-(3,4-dinitrophenylazo)-N-pentylaniline 4-(3,4-dinitrophenylazo)-N-hexylaniline 4-(3,4-dinitrophenylazo)-N-hebutylaniline 4-(3,4-dinitrophenylazo)-N-octylaniline 4-(3,4-dinitrophenylazo)-N-nonylaniline 4-(3,4-dinitrophenylazo)-N-decylaniline 4-(3,4-dinitrophenylazo)-N-F decylaniline 4-(3,4-dinitrophenylazo)-N-tetradecylaniline 4-(3,4-dinitrophenylazo)-N-hexadecylaniline 4-(3,4-dinitrophenylazo)-N-octadecylaniline 4-(3,4-dinitrophenylazo)-N-eicosylaniline 4-(3,4-dinitrophenylazo)-N-tocosylua N, N, N', N '-Tetrahexyl-3,4-diamino-4'-nitrostilbene a) N, N, N', N'-tetrahexyl-〇-7 22-diamine Sodium bicarbonate 5809 (6.9 mol) was dissolved in 〇-Funirelene difluoride in DMEUI. 150 g (1,38 mol) of amine and 1.14 g (6, 9 mol) and the mixture is heated at 120° C. for 48 hours. this mixture Allow to cool, filter out undissolved material, and then remove solvent by vacuum distillation.

The residue was purified on a silica gel column using petroleum ether/ethyl acetate (6:4). Geography, chromatography. A colorless liquid is obtained.

b) N, N, N', N'-tetrahexyl-3,4-diaminobenzalde Hido N,N,N',N'-tetrahexyl-〇-phenyle in DMF 130+mQ 61.1 g (138 mmol) of diamine and 27.59 g (138 mmol) of phosphorus oxytrichloride ( A solution of 179 mmol) is heated at 100° C. for 22 hours. Let this mixture cool , poured into water and then extracted with dichloromethane. Sodium sulfate organic phase The residue was dried on a silica gel column using petroleum as the eluent. Chromatograph using ether/ethyl acetate (8:2). viscosity A brown oil is obtained.

c) N,N,N',N'-tetrahexyl-3,4-diamino-4'-dito rostilbene N,N,N',N'-tetrahexyl-3,4-diami in pyridine 30mI2 2.30 g (4.90 mmol) of Novenzaldehyde, 4-ditrophenylacetic acid A solution of 1.359 (7.35 mmol) and piperidine 0.3vrQ at boiling point Heat for 22 hours. The mixture was allowed to cool, poured into water and then dichloromethane. Extract with tongue. The organic phase is dried over sodium sulfate and then evaporated to remove the residual The material was purified through a silica gel column using petroleum ether/ethyl acetate (92:8) as the eluent. used and chromatographically processed. A red, highly viscous oil is obtained.

In the same way, the following compound is prepared: N,N,N',N'-tetramethyl- 3,4-diamino-4'-nitrostilbene N, N, N', N'-tetraethyl-3,4-diamino-4'-nitrostyl ben N,N,N',N'-tetrapropyl-3,4-diamino-4'-nitrostyl ben N, N, N', N'-tetrabutyl-3,4-diamino-4'-nitrostyl ben N, N, N', N'-tetrapentyl-3,4-diamino-4'-nitrosti Reuben N,N,N',N'-tetraheptyl-3,4-diamino-4'-nitrostyl ben N,N,N',N'-tetraoctyl-3,4-diamino-4'-nitrostyl ben N,N,N',N'-tetranonyl-3,4-diamino-4'-nitrostilbe hmm N,N,N',N'-tetradecyl-3,4-diamino-4'-nitrostilbe hmm N, N, N', N'-tetradodecyl-3,4-diamino-4'-nitrosti Reuben N,N,N',N'-tetradodecyl-3,4-diamino-3'-cyano-4' - Nitrostilbene N,N,N',N'-tetramethyl-3,4-diamino-3',4'-dinitro stilbene N,N,N',N'-tetraethyl-3,4-diamino-3',4'-dinito rostilbene N, N, N', N'-tetrapropyl-3,4-diamino-3',4'-di Nitrostilbene N,N,N',N'-tetrabutyl-3,4-diamino-3',4'-dinitro stilbene N, N, N', N'-tetrapentyl-3,4-diamino-3',4'-dini Trostilbene N, N, N', N'-tetrahexyl-3,4-diamino-3',4'-dini Trostilbene N, N, N', N'-tetraheptyl-3,4-diamino-3',4'-dini tros still pen N, N, N', N'-tetraoctyl-3,4-diamino-3',4'-dini Trostilbene N, N, N', N'-tetranonyl-3,4-diamino-3',4'-dinito rostilbene N, N, N', N'-tetradecyl-3,4-diamino-3',4'-dinito rostilbene N, N, N', N'-tetradodecyl-3,4-diamino-3',4'-dini Trostilbene N,N,N',N'-tetramethyl-3,4-diamino-3'-fluoro-4' - Nitrostilbene N, N, N', N'-tetraethyl-3,4-diamino-3'-fluoro-4 ′-nitrostilbene N, N, N', N'-tetrapropyl-3,4-diamino-3'-fluoro- 4'-nitrostilbene N, N, N', N'-tetrabutyl-3,4-diamino-3'-fluoro-4 ′-nitrostilbene N, N, N', N'-tetrapentyl-3,4-diamino-3'-fluoro- 4'-nitrostilbene N, N, N', N'-tetrahexyl-3,4-diamino-3'-fluoro- 4'-nitrostilbene N,N,N',N'-tetraheptyl-3,4-diamino-3'-fluoro-4 ′-nitrostilbene N, N, N', N'-tetraoctyl-3,4-diamino-3'-fluoro- 4'-nitrostilbene N,N,N',N'-tetranonyl-3,4-diamino-3'-fluoro-4' - Nitrostilbene N, N, N', N'-tetradecyl-3,4-diamino-3'-fluoro-4 ′-Nitro Still Pen N, N, N', N'-tetradodecyl-3,4-diamino-3'-fluoro- 4'-nitrostilbene Example 13 N, N, N', N'-tetrahexyl-3,4-diamino-3'-cyano-4 ′-Nitrostilbene N,N,N',N'-tetrahexyl-3,4-diaminobenzaldehyde2. 39 (4,9 mmol) and 0-8 g of 5-methyl-2-nitropenzonitrile (4,9 mmol) and piperidine Q, in pyridine 30III2 with 5m<1 The solution is heated at boiling point for 18 hours. Let the mixture cool, pour it into water, and Extract with chloromethane. The organic phase was dried over sodium sulfate and then evaporated. The residue was chromatographed on a silica gel column using toluene as the eluent. Raffi processing. A red, highly viscous oil is obtained.

Similarly, the following compound is prepared: N,N,N',N'-tetramethyl -3,4-diamino-3'-cyano-4'-nitrostilbene N, N, N', N'-tetraethyl-3,4-diamino-3'-cyano-4' - Nitrostilbene N, N, N', N'-tetrapropyl-3,4-diamino-3'-cyano-4 ′-nitrostilbene N, N, N', N'-tetrabutyl-3,4-diamino-3'-cyano-4' - Nitrostilbene N, N, N', N'-tetrapentyl-3,4-diamino-3'-cyano-4 ′-nitrostilbene N, N, N', N'-tetraheptyl-3,4-diamino-3'-cyano-4 ′-nitrostilbene N,N,N',N'-tetraoctyl-3,4-diamino-3'-cyano-4' - Nitros still pen N,N,N',N'-tetranonyl-3,4-diamino-3'-cyano-4'- Nitrostilbene N,N,N',N'-tetradecyl-3,4-diamino-3'-cyano-4'- Nitrostilbene N,N,N',N'-tetradodecyl-3,4-diamino-3'-cyano-4' - Nitrostilbene Example 14 polyurethane a) N,N-bis-(3-hydroxypropyl)-4'-amino-3-sia 57 g (678 mmol) of nor-4-nitrostilbene sodium bicarbonate was added to NM 4'-amino-3-cyano-4-nitrostilbene in P 500 mn 60.0 g (226 mmol) and 126 g (678 mmol) of 3-iodopropanol ) and heat the mixture at 100° C. for 4 hours. Let this mixture cool, Then pour it into the water. The precipitate was purified with dichloromethane/methane on a silica gel column. Chromatography is carried out using Aqueous solution (95:5) as eluent. green faint light Violet crystals with . City, p.: 168℃.

Similarly, the following compound is prepared: N,N-bis(3-hydroxyethyl )-4'-amino-3-cyano-4-nitrostilbene N,N-bis(3-hydroxypropyl)-4-amino-3',4'-dinitro stilbene N,N-bis(3-hydroxypropyl)-4-amino-3'-fluoro-4' -Nitrostilbene b) Polyurethane N,N-bis-(3-hydroxypropyl)-4'-a in 11.1g of NMP Mino-3-cyano-4-nitrostilbene 7.609 (i9.9 mmol) and Mixture of 2,4-diisocyanatotoluene and 2,6-diisocyanatotoluene A solution of 3.479 (19.9 mmol) of compound (80:20) was heated to 130°C. Heat gently and maintain at this temperature for 2 hours.

This viscous solution was diluted with NMP 80 taQ, and then this NMP solution was diluted with ethanol. The polymer is precipitated by adding dropwise to the tube 2a. red polymer - is obtained.

Similarly, diisocyanate mixtures and N,N-his(3-hydroxypropanol) Pill=)-4-amino-3',4'-dinitrostilbene N,N-bis(3-hydroxypropyl)-4-amino-3'-fluoro-4' - Polyurethane is produced from nitrostilbene.

Example 15 N-hexyl-N-(4-methacryloyloxybutyl)-4-amino-3' -cyano-4'-nitrostilbene N-hexyl-4-amino-3'-cyano- 4'-nitrostilbene 22.49 (64.1 mmol) (compound of example 5), 20.6 g (76.9 mmol) of 4-iodobutyl methacrylate and 2, 6-tert-butyl-4-methylphenol 5 mg DMEU 10 Add 6.5 g (76.9 mmol) of sodium bicarbonate to the solution in 0 mff, Heat the mixture at 100° C. for 16 hours. Let this mixture cool and pour it into water , then extracted with dichloromethane. The organic phase was dried over sodium sulfate and evaporated. Then, petroleum ether/ethyl acetate (8:2) was added to the silica gel column. Use as eluent and chromatography. A dark red oil is obtained.

Example 16 methacrylate homopolymer N-hexyl-N-(4-methacryloyloxybutyl) in NMP lOmρ )-4-amino-3'-cyano-4'-nitrostilbene 4.2 g (9.2 mm mol) (compound of example 15) and AIBN 30.219 (0.18 mmol) Heat the solution at 60° C. for 48 hours. The polymer was precipitated from methanol and NM P, reprecipitated from methanol and then dried. Obtains dark red powder It will be done.

Similarly, the following heptadmer compounds (these heptamers were prepared in the same manner as in Example 15) homopolymers are produced from: N-methyl-4-amino-3'-cyano-4'-nitrostilbene N-ethyl-4-amino-3'-cyano-4'-nitrostilpene N-propyl-4-amino-3'-cyano-4'-nitrostilbene N-pentyl-4-amino-3'-cyano-4'-nitrostilbene N-hebutyl-4-amino-3'-cyano-4'-nitrostilpene N-cutyl-4-amino-3'-cyano-4'-nitrostilbene N-nonyl-4-amino-3'-cyano-4'-nitrostilbene N-decyl-4-amino-3'-cyano-4'-nitrostilpene N-dodecyl-4-amino-3'-cyano-4'-nitrostilbene N-tetradecyl-4-amino-3'-cyano-4'-nitrostilbene N-hexadecyl-4-amino-3'-cyano-4'-nitrostilpene N-octadecyl-4-amino-3'-cyano-4'-nitrostilbene N-eicosyl-4-amino-3'-cyano-4'-nitrostilbene N-tocosyl-4-amino-3'-cyano-4'-nitrostilbene N-methyl-4-amino-3',4'-dinitrostilbe N-ethyl-4-amino No-3',4'-dinitrostilbe N-propyl-4-amino-3',4'-di Nitrostilbene N-pentyl-4-amino-3',4'-dinitrostilbene N-hexyl-4-amino-3',4'-dinitrostilbene N-hebutyl-4-amino-3',4'-dinitrostilbene N-octyl-4-amino-3',4'-dinitrostilbene N-nonyl-4-amino-3',4'-dinitrostilpe N-decyl-4-amino No-3',4'-dinitrostilbene N-Fy-syl-4-amino-3',4'-dinitrostilbene N-tetradecyl-4-amino-3',4'-dinitrostilbene N-hexadecyl-4-amino-3',4'-dinitrostilbene N-octadecyl-4-amino-3',4'-dinitrostilbene N-eicosyl-4-amino-3',4'-dinitrostilbene N-tocosyl-4-amino-3',4'-dinitrostilbene N-methyl-4-amino-3'-fluoro-4'-nitrostilbene N-ethyl-4-amino-3'-fluoro-4'-nitrostilpene N-propyl-4-amino-3'-fluoro-4'-nitrostilpene N-pentyl-4-amino-3'-fluoro-4'-nitrostilbene N-hebutyl-4-amino-3'-fluoro-4'-nitrostilbene N-octyl-4-amino-3'-fluoro-4'-nitrostilbene N-nonyl-4-amino-3'-fluoro-4'-nitrostilbene N-decyl-4-amino-3'-fluoro-4'-nitrostilbene N-dodecyl-4-amino-3'-fluoro-4'-nitrostilpene N-tetradecyl-4-amino-3'-fluoro-4'-nitrostilpene N-hexadecyl-4-amino-3'-fluoro-4'-nitrostilbene N-ctadecyl-4-amino-3'-fluoro-4'-nitrostilbene N-eicosyl-4-amino-3'-fluoro-4'-nitrostilbene N-tocosyl-4-amino-3'-fluoro-4'-nitrostilbene 4-(3,4-dinitrophenylazo)-N-methylaniline 4-(3,4-dinitrophenylazo)-N-ditylaniline 4-(3,4-dinitrophenylazo)-N-propylaniline 4-(3,4-dinitrophenylazo)-N-butylaniline 4-(3,4-dinitrophenylazo)-N-pentylaniline 4-(3,4-dinitrophenylazo)-N-hexylaniline 4-(3,4-dinitrophenyl/)-N-hebutylaniline 4-(3,4-dinitrophenylazo)-N-octylaniline 4-(3,4-';nitrophenylazo)-N-nonylaniline 4-(3,4-dinitrophenylazo)-N-decylaniline 4-(3,4-dinitrophenylazo)-N-dodecylaniline 4-(3,4-dinitrophenylazo)-N-tetradecylaniline 4-(3,4-dinitrophenylazo)-N-hexadecylaniline 4-(3,4-dinitrophenylazo)-N-octadecylaniline 4-(3,4-dinitrophenylazo)-N-eicosylaniline 4-(3,4-dinitrophenylazo)-N-tocosylaniline 3-cyano-4-nitro-N-methylaniline (this compound and the homologation below) The compounds are described in U.S. Pat. No. 2.195.076 or Beilstein 141 [ 1,1021h) 3-cyano-4-nitro-N-ethylaniline 3-cyano-4-nitro-N-propylene 3-cyano-4-nitro-N-butylaniline 3-cyano-4- Nitro-N-pentylaniline 3-cyano-4-nitro-N-hexylaniline 3-cyano-4-nitro-N-hebutylaniline 3-cyano-4-nitro-N- Octylaniline 3-cyano-4-nitro-N-nonylaniline 3-cyano-4 -Nitro-N-decylaniline 3-cyano-4-nitro-N-dodecylaniline 3-cyano-4-nitro-N-tetradecylanili 3-cyano-4-nitro-N -hexadecyl 3-cyano-4-nitro-N-octadecyl 3-cyano Funo 4-nitro N-eicosylaniline 3-cyano-4-nitro-N-toco Silaniline example 17 methacrylate copolymer N-hexyl-N-(4-methacryloyloxybutyl )-4-amino-3'-cyano-4'-nitrostilpene 5.89 (11,8 mi) (compound of Example 15), methyl methacrylate 10.79 (107 molar) A solution of AIBN 38919 (2.4 mmol) and AIBN 38919 (2.4 mmol) was Cook for 4 hours. The polymer was precipitated from methanol and dissolved in dichloromethane. , reprecipitation from methanol and then drying. A dark red powder is obtained.

A copolymer with methyl meth 7' acrylate can be prepared in the same manner by the following monomer compound: N- Methyl-4-amino-3'-cyano-4'-nitrostilbene N-ethyl-4-amino-3'-cyano-4'-nitrostilbene N-propyl-4-amino-3'-cyano-4'-nitrostilbene N-pentyl-4-amino-3'-cyano-4'-nitrostilbene N-hebutyl-4-amino-3'-cyano-4'-nitrostilbene N-cutyl-4-amino-3'-cyano-4'-nitrostilbene N-nonyl-4-amino-3'-cyano-4'-nitrostilbene N-decyl-4-amino-3'-cyano-4'-nitrostilbene N-dodecyl-4-amino-3'-cyano-4'-nitrostilbene N-tetradecyl-4-amino-3'-cyano-4'-nitrostilbene N-hexadecyl-4-amino-3'-cyano-4'-nitrostilbene N-ctadecyl-4-amino-3'-cyano-4'-nitrostilbene N-eicosyl-4-amino-3'-cyano-4'-nitrostilbene N-tocosyl-4-amino-3'-cyano-4'-nitrostilbene N-methyl-4-amino-3'-4'-dinitrostilpe N-ethyl-4-amino No-3'-4'-dinitrostilbe N-propyl-4-amino-3'-4'-di Nitrostilbene N-pentyl-4-amino-3'-4'-'; nitrostilbene N-hexyl-4-amino-3'-4'-dinitrostilbene N-hebutyl-4-amino-3'-4'-dinitrostilbene N-cutyl-4-amino-3'-4'-dinitrostilbene N-nonyl-4-amino-3'-4'-dinitrostilbe N-decyl-4-a Mino-3'-4'-dinitrostilpe N-dodecyl-4-amino-3'-4' -Dinitrostilbene N-tetradecyl-4-amino-3'-4'-dinitrostilbene N-hexadecyl-4-amino-3'-4'-dinitrostilbene N-octadecyl-4-amino-3'-4'-dinitrostilbene N-eicosyl-4-amino-3'-4'-dinitrostilbene N-tocosyl-4-amino-3'-4'-dinitrostilbene N-methyl-4-amino-3'-fluoro-4'-nitrostilpene N-ethyl-4-amino-3'-fluoro-4'-nitrostilpene N-propyl-4-amino-3'-fluoro-4'-nitrostilbene N-pentyl-4-amino-3'-fluoro-4'-nitrostilbene N-hexyl-4-amino-3'-fluoro-4'-nitrostilbene N-heptyl-4-amino-3'-fluoro-4'-nitrostilbene N-cutyl-4-amino-3'-fluoro-4'-nitrostilpene N-nonyl-4-amino-3'-fluoro-4'-nitrostilbene N-decyl-4-amino-3'-fluoro-4'-nitrostilbene N-dodecyl-4-amino-3'-fluoro-4'-nitrostilbene N-tetradecyl-4-amino-3'-fluoro-4'-nitrostilpene N-hexadecyl-4-amino-3'-fluoro-4'-nitrostilbene N-octadecyl-4-amino-3'-fluoro-a-47-nitrostilbene N-eicosyl-4-amino-3'-fluoro-4'-nitrostilbene N-tocosyl-4-amino-3'-fluoro-4'-nitrostilbene 4-(3,4-dinitrophenyl/)-N-methylaniline 4-(3,4-dinitrophenylazo)-N-ethylaniline 4-(3,4-dinitrophenylazo)-N-propylaniline 4-(3,4-dinitrophenylazo)-N-butylaniline 4-(3,4-dinitrophenylazo)-N-pentylaniline 4-(3,4-dinitrophenylazo)-N-hexylaniline 4-(3,4-dinitrophenylazo)-N-hebutylaniline 4-(3,4-dinitrophenylazo)-N-octylaniline 4-(3,4-dinitrophenyla'/)-N-nonylaniline 4-(3,4-dinitrophenylazo)-N-decylaniline 4-(3,4-dinitrophenylazo)-N-dodecylaniline 4-(3,4-dinitrophenylazo)-N-tetradecylaniline 4-(3,4-dinitrophenylazo)-N-hexadecylaniline 4-(3,4-dinitrophenylazo)-N-octadecylaniline 4-(3,4-';nitrophenylazo)-N-eicosylaniline 4-(3,4-dinitrophenylazo)-N-tocosylaniline 3-cyano-4-nitro-N-methylaniline 3-cyano-4-nitro-N-di Tylaniline 3-cyano-4-nitro-N-propylaniline 3-cyano-4- Nitro-N-butylaniline 3-cyano-4-nitro-N-pentylaniline 3 -cyano-4-nitro-N-hexylaniline to 3-cyano-4-nitro-N- Butylaniline 3-cyano-4-nitro-N-octylaniline 3-cyano-4 -Nitro-N-nonylaniline 3-cyano-4-nitro-N-decylaniline 3 -cyano-4-nitro-N-dodecylaniline 3-cyano-4-nitro-N-te Tradecyl Ayuri 3-cyano-4-nitro-N-hexadecyl Ayuri 3-cyano -4-nitro-N-octadecyl ayuri 3-cyano-4-nitro-N-eikosi Luaniline 3-cyano-4-nitro N-tocosylaniline Example 18 NMP of copolymer (0,69) from Example 17 1.61? and 2-ethoxy A solution in 1.6 g of ethyl acetate is prepared. Filter this solution with a pore size of 2μ. filter) to remove contaminant particles.

Glass plate (4cm x) coated with ITO (indium/tin/oxide) 4 crs, thickness: 1.1m+*) with a neutral soap solution (Extran, Messrs, manufactured by Merck) for 10 minutes using ultrasonic waves, and then Strain and rinse with double distilled water, then wash with Improper Tools. this glass plate Spin coating the polymer solution on top (LOOORPM), followed by Dry for 4 hours at 100° C. in vacuum. The density of this film is approximately 1.3 It is called μ. A translucent gold electrode is deposited onto this film.

This film was heated to 100°C in a vacuum open, and then a 100V DC current was applied. Apply pressure for 10 minutes at 120°C. This sample was cooled to room temperature at 1°C/min in an electric field. Then turn off the electric field.

To measure the nonlinear magnetic susceptibility of this material, this film was Insert into the laser irradiation line (λ = 1.06μ scrap, Hals fa time = 7 n5ec, pulse energy force 0.5mJ, 7 angle to the ilm surface - 50'). The frequency and intensity of the doubled light of this sample are measured. This is the sample frequency It is a measure of the number and doubling rate. A photomultiplier signal of 32 V is obtained.

Similarly, another polymer film is prepared and measured as described above.

The structure of this polymer lacked the vicinal CN group, but the rest of the structure was similar to Example 1. The structure of the polymer from 7.

The thickness of this film is about lθμ, and the applied DC voltage is 200v. . A photomultiplier signal of 35+sV is obtained.

The film thickness of the polymer according to the invention is approximately one-eighth of the thickness of this comparative film. Despite this, signals of almost uniform size are detected. Sunawa In other words, the material according to the invention exhibits a higher frequency doubling ratio than the comparative material.

Example I9 Using the polymer from Example 17, as described by R. LyLel et al. Proc, 5PIE, vol. 824, p. 152 (1988)), manufacturing optical components. Build. This material exhibits excellent waveguide properties.

international search report 1111＾-”””　l’L　PCT/EP　90100190International Search Report EP 9000190 SA 34B52

Claims (7)

[Claims] 1. Nonlinear optical materials based on side chain polymers, the main chain of which has aliphatic chain members. and the side chain has a conjugated π-system as a nonlinear optical chromophore, and one end has an electron donor (D) bound to it, and the other end has an electron acceptor (A ) are bonded to nonlinear optical materials based on side chain polymers, such as D and A. at least one additional substituent selected from the group consisting of: and all of the substituents D and all of the substituents A are in each case A nonlinear optical material characterized by being vicinally bonded to an aromatic system. 2. The conjugated π-thread has the formula I ▲There are mathematical formulas, chemical formulas, tables, etc.▼I [In the formula, D is NR1, O or S, and D1 is each independently, H, NR12, OR1 or SR1, A is NO2 or CN, or A1 and A2 are each mutually unique. Stand up, H, NO2, CN, halogen, CF3, COOR1, CONR12, S O5R1, SO2R1, SOR1 or SO2NR12, and Z1 and Z2 are each independently a single bond or −[C(R2)=C( R2)] -m, -N=N-, -C=N-, -N=C- or -C=C-, m is 1 or 2, B has 5 to 18 ring atoms and is a group consisting of up to 3 N, O and S A carbocyclic or heterocyclic system having heterocyclic atoms selected from n is 0, 1, 2 or 3, p is 0 or 1, R1 is each independently H or C1-C24-alkyl, and R2 is each independently H or C1-C6-alkyl, However, when p is 1, A1 is hydrogen]. 2. A substance according to claim 1, which corresponds to a group. 3. Formula II ▲There are mathematical formulas, chemical formulas, tables, etc.▼II [In the formula, D1 is independent of each other. is H, NR32, OR3 or SR3, D2 is NR12 or SR1, and Z1 and Z2 are each independent of each other. and a single bond, -[C(R2=C(R2)]-m, -C=N-, -N=C- or is -C≡C-, m is 1 or 2, B has 5 to 18 ring atoms and is a group consisting of up to 3 N, O and S is a carbocyclic or heterocyclic system having heterocyclic atoms selected from , 0, 1, 2 or 3; A is NO2, CN, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ mathematical formulas, chemical formulas, tables, etc. There are ▼ or ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼, and A1 is Each independently of the other, H, NO2, CN, halogen, CF3, COOR3, CO NR32, SO3R3, SO2R3, SOR3 or SO2NR32, R1 is each independently of the other H or C1-C24-alkyl; do R2 is each independently H or C1-C6-alkyl, and each R3 is independently C1-C24-alkyl; However, at least one group selected from the group consisting of D1 and A1 is hydrogen Compounds that are other than atoms. 4. characterized by containing at least one compound represented by the above formula II nonlinear optical material. 5. A nonlinear optical material containing at least one polymeric thread portion, the material comprising At least one of the components is a compound represented by formula II. Linear optical material. 6. Optical component according to at least one of claims 1, 2, 4 and 5. The use of nonlinear optical materials. 7. Non-linear according to at least one of claims 1, 2, 4 and 5 An optical component characterized by containing an optical substance.