JPH06340593A - Tetrahydronaphthalenone derivative and layer element containing same - Google Patents

Abstract

PURPOSE: To provide the new subject compd. having high dipole moment and extrapolarizability, useful as nonlinear optical materials.

CONSTITUTION: The compd. of formula (wherein R¹, R², R³ and R⁴ are each H or 1-4C alkyl; A and A¹ are each NO₂, CN, halogen, CF₃ or the like; D is NR⁸ ₂ [R⁸ is 1-22C alkyl (substd. by OH, SH, prim. amino or sec. amino at terminal) or the like], OR⁸ or the like; Q is residue from aromatic carbon ring or the like having at least ≤3 rings; (n) is 1-3; (p) is 0 or 1). For example, 2-dicyanomethylene-7-(4'(N(-2-hydroxyethyl)-N-methyl-amino)-styryl)-4,4'- dimethyl-4,4a,5,6-tetrahydro(3H)naphthalene is provided. The exemplified compd. is obtained by reacting the reaction mixtures obtained by adding acetic acid and acetic anhydride to malonic acid dinitrile and 4,4a,5,6-tetrahydro-(3H) naphthalene with 4-(N-(2-hydroxyethyl)-N-methylamino)benzaldehyde.

COPYRIGHT: (C)1994,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention contains an electron donating group at the 7-position and the keto group is exchanged for an olefinic double bond bearing at least one electron accepting group 4,4.
It relates to derivatives of a, 5,6-tetrahydro-2- (3H) -naphthalenone. The invention further relates to layer elements containing these compounds in the form of layers on a support and the use of said compounds for the purposes of non-linear optical materials.

[0002]

The molecules of the above compounds are non-centrosymmetric due to various substituents. They therefore mostly show dipole moments. Moreover, they have an expanded π-electron system with many chromophores. This is suitable for the purpose of the nonlinear optical material.

Non-linear optical materials make it possible, with suitable equipment, to obtain new frequencies corresponding to the difference or the sum from two different rays of different frequencies, and from optical fluxes of optical frequencies several times this frequency. To be able to obtain. Non-linear optical materials make it possible to convert electrical information into optical information and can therefore lead to a fundamental transformation of the recording medium and the technology of storage of recording in the long run.

It is suitable for the production of linear optical components such as electro-optical regulators, electro-optical switches, electro-optical directional couplers and frequency doubling means. These structural elements are used, for example, in communication technology (for adjusting and controlling optical signals) as spatial light adjusting means in optical signal processing, for optical data storage, sensor technology for frequency doubling of semiconductor lasers. And used for xerography.

The main purpose is the production of electro-optical or purely optical devices which can be operated at low voltages and at usable light intensities of semiconductor lasers. These requirements are due to the large electro-optic coefficient (especially Boc (Boc).
kel) coefficients = r and y) and are only satisfied by materials which are suitable (for workability) for the production of efficient optical waveguide systems.

A large number of inorganic crystals have been tested as NLO materials, such as potassium dihydrogen phosphate and lithium niobate. Regulators consisting of lithium niobate and frequency doublers based on potassium dihydrogen phosphate are commercially available.

Other organic NLO materials, however, are of great interest. There are many reasons for this. The first lies in the NLO-activity (= NLO-sensitivity) of organic materials, which is often many times more than inorganic materials. The refractive index and dielectric constant are generally low. This allows a large internal electric field, small polarizability and small return loss, all of which result in high efficiency.

Furthermore, organic materials can be synthesized "custom-made", for example for the purpose of obtaining highly transparent materials under specific operating wavelengths. A wide variety of organic materials can be processed.
The production of monolayers of organic materials is easier than the production of inorganic crystals, for example. These crystals must be grown at relatively high temperatures, then cut, ground and oriented. Therefore, there is a need for organic materials for use in the field of secondary non-linear optical materials.

The (macroscopic) polarity P induced by the electric field in the medium can be expressed by an exponential series of the electric field strength E. P = X ⁽¹⁾ E + X ⁽²⁾ E ² + X ⁽³⁾ E ³ + ... X ⁽ⁱ⁾ is a so-called electrical sensitivity function. Susceptibility X
⁽²⁾ and X ⁽³⁾ are so-called molecular hyperpolarizabilities (Hype).
rpolarisierbarkeiten) β and y.

X ⁽²⁾ (-ω3, ω2, ω1) _XYZ = Nf
_{x, w3} , f _{x, w2} , f _{x, w1} D _XYZxyz β _XYZ P ₁ = αE + βE ² + γE ³ ... In this case, P ₁ is the polarity of the molecule; α, β and γ are polarizabilities . N is the number of molecules per volume unit, f is the local field factor and D _XYZxyz is the tensor that describes the molecular arrangement of the macroscopic system.

NLO-interactions can give rise to new frequencies in the NLO-medium and can change the index of refraction of the medium. The important nonlinear optical effect depending on X ⁽²⁾ is
Frequency doubling of the laser beam, parametric enhancement of weak optical signals and electro-optical conversion of electrical signals. In order to achieve the quadratic effect, the active molecule must be non-centrosymmetrically oriented since X ⁽²⁾ = 0 for centrosymmetric molecules or crystals.

Experiments can be conducted to grow crystals of NLO-compounds. When it crystallizes in a non-centrosymmetric manner, the crystal has a second-order macroscopic susceptibility X ⁽²⁾ that does not disappear without any further treatment. Since the chromophores and very high ranks are achieved and the non-centrosymmetric array is the lowest free energy state, there are no further problems with array relaxation.
Already, many crystals are poorly machinable and the manufacture of finished optical structural elements with single crystals is usually not practical. In addition, asymmetric molecules can lead to centrosymmetric crystals.

J. Langmuir and K.K. B. Bl
The method of manufacturing thin layers according to the oddgett (= LB method) offers the greatest freedom in the case of chemical plans, but requires extensive experience. In this method, the molecules are spread parallel to the surface of the water, the surfaces are made smaller so that they are aligned parallel to each other and are deposited on the substrate by dipping and removing the support material in a fixed aliquot. . With each dipping step, the molecular layer is transferred, maintaining its alignment. To construct the LB-layer, amphipathic molecules are used, ie molecules with hydrophilic ends (“head”) and hydrophobic ends (“tail”).

In order to enable an LB-layer with a high secondary susceptibility, an organic compound exhibiting a high secondary molecular hyperpolarizability β and amphipathic properties is produced. If the amphiphiles consisting of some molecular species are arranged in multiple layers according to the LB-method, three different possible immersion behaviors can appear. That is, X-type membranes (transferred only during immersion) or Z-type membranes (transferred during removal) appear, both of which have the advantage of a non-centrosymmetric structure. Most often, however, Y-type membranes are formed in which the molecules show head-to-head and tail-to-tail arrangements (transitions during immersion and removal).

In most cases, Y-type membranes have a centrosymmetric structure. In the case of a few compounds that show one orientation on the surface of the support (essentially a non-centrosymmetric structure), the susceptibility that can be achieved is relatively small. Three methods can be used to achieve multi-layered arrangements of asymmetrical structures in compounds that lead to Y-type membranes: a) Active and non-active layers (amphiphilic molecules or chromophores without chromophore). Polymers such as trimethylsilylcellulose or polymethacrylate) form alternating films. This method has the disadvantage that the NLO-active molecules do not effectively utilize the available volume, because the inert layer makes the system "thin". Therefore such films exhibit low NLO-activity. b) Control the transfer process to obtain a Z-type film. However, for this purpose a special multichamber device for coating the substrate is required. Immersion and removal takes place in different rooms. c) Alternating membranes consisting of two different NLO-active amphiphilic molecules, one of which has a dipole moment directed towards the hydrophobic long-chain alkyl residue (tail) and the other away from it. In this case, two adjacent dipole moments add without canceling despite the Y-structure. Therefore the effective dipole moment is still of a magnitude of interest for NLO-purposes.

Another method of aligning chromophores in a material having a non-centrosymmetric structure is N 2 in a polymer matrix.
It incorporates an LO-active chromophore ("polarized polymer"). For example, low molecular weight NLO-active compounds may be dissolved directly in the polymer. Due to the strong electric field, some of the chromophores can be aligned. However, there is a rapid loosening of the sequence after that, so that relatively little alignment of the chromophore is achievable with this method. Furthermore, there is the drawback that the solubility of the low molecular weight NLO-active compounds in the polymer is limited.

The sequence stability and the concentration of chromophore groups can be further improved if they are covalently bound in the polymer, for example as part of the side chains or polymer backbone.
The orientation can be sufficiently stabilized by increasing the glass transition temperature or by post-crosslinking.

It is always desirable for NLO-active compounds to have as large an optical nonlinearity (= second-order hyperpolarizability) as possible. A compound has a large value of β when it has a conjugated π electron system (eg, a stilbene residue) and at least one electron donor and at least one electron acceptor group are present. The value of β increases when the molecule absorbs light at the wavelength of the incident electric field or NLO-obtained field (so-called resonance increase). Already absorption is not desired for many applications. Because it is exhausted and the optical stability is negatively affected. Without causing material damage in a durable manner
A compound is considered "photostable" when the light intensity can withstand for a long time. The ideal compound has a large hyperpolarizability β but no residual absorption in the desired wavelength range. Already, most compounds with sufficiently high β values
Under the desired wavelength for frequency doubling, the frequency 83
0 nm is generated by doubling IR-light (diode-
Laser) still exhibits a significant residual absorption, especially in the range of 415 nm.

Compounds exhibiting a large value of β at the same time as a large dipole moment are of interest, so that the chromophore consists of a conjugated π-system and has an NLO-activity having an electron acceptor and an electron donor at the end. The compound has already been tested.
Known compounds include, for example, 4-dimethylamino-4'-nitrostilbene (DANS) and 2-methyl-4-nitroaniline (MNA). From European patent applications 0,364,313 and 0,390,655, derived from cyclohexenone and 3 or 4
NLO-active compounds with a single conjugated double bond are known. A particularly preferred electron acceptor is the cyano residue and a particularly preferred electron donor is the p-dimethylaminophenyl group. This product μ · β is 1.
It's only 9 times bigger.

However, the NLO of these known compounds
-Characteristics are, for example, satisfactory electro-optical coefficients (γ> 60p
It is still not sufficient to obtain a polarized polymer with m).

[0021]

The object of the present invention is therefore to provide novel organic NLO-active compounds which exhibit a high value of .mu..beta. For their products. Another problem relates to providing a device for frequency doubling or a compound that can be used for the modulation of light.

[0022]

The symmetry of the present invention is represented by the general formula I

[0023]

[Chemical 5] [Wherein R ¹ and R ² are independently of each other H or C ₁
~ C ₄ -alkyl, R ³ and R ⁴ are C ₁ -C ₄ -alkyl or hydrogen atoms, A and A ¹ independently of each other NO ₂ , CN, halogen atoms, CF ₃ , COOR ⁵ ,
CONR ⁶ _2, SO ₂ R ⁷ or one of the residues A and A ¹ is a hydrogen _{atom, -CO 2 (CH 2) x} ZH, SO 3 R
_{^{5, SOR 7, SO 2 NR}} 6 2 or S (NSO ₂ CF
₃ ) means CF ₃ , where x is 2, 3, 4 or 5;
Z is O, S or NH, R ⁵ is C ₁ -C ₄ -alkyl, R ⁶ is C ₁ -C ₄ -alkyl or hydrogen atom, R ⁷ is C ₁ -C ₄ -alkyl, C ₁ -C ₄ - perfluoroalkyl or phenyl residue optionally substituted, D is meant _{^{NR 8 2, oR 8, SR}} 8, R
⁸ is a C ₁ -C ₂₂ -alkyl optionally substituted at the end with a hydroxyl group, a thiol group or a primary- or secondary amino group or is the group H (OCH ₂ CH ₂ ) _m and Q is 3 A (n + 1) -valent residue derived from an aromatic carbocyclic- or heterocyclic ring system having up to 3 rings, p being 0
Or 1, n is 1, 2 or 3 and m is 1, 2, 3, 4, 5 or 6. ] It is a compound represented by these.

Residue D is effective as an electron donor and ^one of residues A and A ¹ is effective as an electron acceptor. One of the residues A and A ¹ is CO ₂ (CH ₂ ) _x ZH
Where R ⁸ is a C ₁ -C ₂₂ -alkyl residue.

The residue Q acts as a bridge for π-electrons. Examples of carbocyclic ring systems are benzene, naphthalene,
There is anthracene. Examples of heterocyclic ring systems from which the residue Q is derived are pyrrole, furan, thiophene, imidazole, pyrazole, oxazole, thiazole, pyridine, pyrimidine, quinoline, isoquinoline, quinoxaline, indole, benzimidazole and benzthiazole. .

Residue Q is 1, 2 or 3 residues D, for example 3 methoxy residues. Advantageously, D is a dimerylamino-, methoxy- or methylthio group.

Advantageously, Q is derived from benzene or thiophene. In both cases, D is HZ- (C
H _{2) x} is -Y-, Z is O, NR ^9, S, x
Is a number from 1 to 18, Y is O, S, NR ¹⁰ , and R
⁹ , R ¹⁰ independently of _one another are C ₁ -C ₄ -alkyl or hydrogen atoms.

Not only are these compounds NLO-active, but they also have a functional group HZ- which is capable of reacting with other low-molecular or high-molecular compounds which are themselves NLO-inactive. Reactive compounds in which Z is oxygen and Y is oxygen or NCH ₃ are particularly preferred.

A compound of the general formula I in which D is NR ⁸ R ¹⁰ , OR ⁸ or SR ⁸ , R ¹⁰ is C ₁ -C ₄ -alkyl or H and R ⁸ is C ₁₆ -C ₂₂ -alkyl. Contains a long-chain alkyl group as well as at least one polar group A or A ¹ . Hence they are amphipathic and Langmuir Brodgett (Langmu
It can be arranged on the support in the form of a monolayer or a multilayer by the method of ir-Blodgett).

The subject of the invention is therefore also layer elements which have at least one monolayer of a compound of the formula I. The layer element preferably has on a support at least two monolayers of the amphiphilic compounds according to the invention. For purposes of non-linear optics, the film thickness should be at least 0.1 μm
Is advantageous. This is because a conventional light wave conductor having a very thin film thickness is possible. The thickness of only one monolayer is approximately 3 nm depending on its size.

In order to manufacture the membrane element of the present invention with Langmuir Brodgett-film, a solution of an amphipathic compound dissolved in a highly volatile solvent is spread on a clean water surface. The average area per molecule is calculated from the dimensions of the surface, the spreading volume and the concentration of the solution. The phase transition when compressing molecules is shear-area-isothermal (Schub-Flaeche).
n-Isotherme) method.

Molecules are clustered at the barrier or by other techniques such as the use of hydrodynamic forces, where the chains are oriented substantially perpendicular to the boundary layer under growing compaction. During compression, the self-function of the molecules in the boundary layer results in a highly oriented monolayer whose constant layer thickness is determined by the chain length of the molecule. The typical thickness of such a film is 2 to
It is 3 nm.

The invention further relates to polymers containing tetrahydro-naphthalene residues in the main chain or side chains.
The polymer is deposited as a thin layer on a support by centrifugation. It is then heated to near the glass transition temperature of the polymer and at this temperature a strong voltage field (about 150 V / μ
m) is applied thereby aligning at least a portion of the polar chromophore. When this layer is slowly cooled while maintaining the voltage, the orientation of the chromophore is sufficiently frozen. The covalent attachment of the NLO-active chromophore in the polarized polymer stabilizes the chromophore alignment and allows a relatively high proportion of chromophore to be incorporated into the polymer.

The polymers of the present invention preferably contain at least 10% by weight of residue E.

[0035]

[Chemical 6] [Wherein R ¹ , R ² , R ³ , R ⁴ , A and A ¹ are the formula I
Z has the meanings described above, Z is O, NR ⁹ , S, x is a number from 1 to 18, Y is O, S, NR ¹⁰ and R ⁹ , R ¹⁰ are C independently of one another. ₁ -C ₄ - alkyl or a hydrogen atom. ] Is included.

The backbone of the polymers of the present invention is preferably derived from polyacrylic acid and the side chains contain the residue E. To produce this polymer, an activated derivative,
For example, when the acid chloride of this polyacid is used, D is H-Z- (C
H _{2) x} -Y- as or A is CO ₂ (CH _{2) x}
It can be reacted with a reactive compound of general formula I which is ZH, where x and Z have the meanings given in formula I. Low molecular weight acrylic acid derivatives containing residue E
In some cases, the polymerization may be carried out in the presence of another monomer. In this case, polymerization can be difficult depending on the substituents present. Particularly suitable comonomers are alkyl esters of methacrylic acid and acrylic acid.

According to this method, the general formula II

[0038]

[Chemical 7] [Wherein R ¹¹ and R ¹³ are independently of each other H, CH ₃ ,
Cl, F or CF ₃ , G is CO ₂ R ¹² , CON
HR ^12, a CONR ¹² _2, or -CN, R ¹² is H or C ₁ -C ₁₀ - alkyl a is and E have the abovementioned meanings. ] The homopolymer or copolymer represented by this is manufactured.

Reaction of a compound of formula I in which D is a bis (ω-hydroxyalkyl) amino residue with an arylene- or alkylene diisocyanate gives a polyurethane of the following structure:

[0040]

[Chemical 8] The material according to the invention in dissolved or liquid form, for example by brushing, printing, dipping or spraying (Aufschleud).
Ern) gives a non-linear optical alignment when the material has amphipathic properties or is associated with strong interactions (physical sorption, chemical sorption) with the substrate surface. . The compounds of formula I can also take advantage of their NLO-characteristics, either as single crystals or as crystalline powders, either incorporated into inclusion compounds or dissolved in polymers.

The materials of the present invention can be manufactured by standard methods of organic chemistry. The reaction conditions can be taken from standard practice of manufacturing organic chemistry (eg Houben-Wey.
1, Methoden der Organische
n Chemie (Method of Organic Chemistry), Georg T
(Hieme Publisher, Stuttgart). For example, A = A
^The above compounds wherein ¹ = -CN are prepared by the known condensation of dimethyl-tetrahydronaphthalenone (US Pat. No. 3,217,717) with malodinitrile and the aldehyde R-CHO. The reaction proceeds according to the following reaction scheme:

[0042]

[Chemical 9] Ketones react similarly. The condensation reaction is an azeotropic agent with water,
Preference is given to carrying out in a solvent such as dimethylformamide with the addition of, for example, acetic anhydride, a base such as ethylamine, piperidine or salts such as ammonium acetate or piperidinium acetate. In order to determine the reaction conditions and improve the yield, it has been found to be advantageous to add an inert solvent, such as toluene, in combination with heating at the water separator.

When both the residues R ¹ and R ² are alkyl residues, the residue R ¹ can be easily prepared.
Compounds of the general formula III in which R ² and R ² are at the same carbon atom are particularly preferred.

[0044]

[Chemical 10] A compound in which R ¹ and R ² are hydrogen atoms is also easily available. Compounds in which Q is a phenylene residue and p = 1, that is to say compounds with two conjugated vinyl groups in addition to the ring system, can be prepared with the corresponding substituted cinnamic aldehydes (eg p-dimethylamino-cinnamic aldehyde) and 4,4 , 7-Trimethyl-tetrahydronaphthalene derivative. Compounds with p = 0 are prepared when starting from compounds having an aldehyde group attached to the ring system Q.

As a support, a solid having a clean surface,
There are, for example, glass, ceramic- or metal plates, synthetic resin layers such as PMMA, polystyrene, polycarbonate, polyethylene, polypropylene or polytetrafluoroethylene, or metal layers on the substrate.

In order to experimentally measure the value of the second-order susceptibility (X ⁽²⁾ ) with a Langmuir-Brodget-film, a laser beam having a frequency of ω and a frequency of 2ω was used in the active substance.
An optical frequency doubling phenomenon can be used to convert the light rays into In this case, the obtained harmonic intensity 2ω grows squarely with the incident intensity ω of the fundamental ray. So-called "marker fringes (M
ker-Fringes) "method is most often used.

As a source of electromagnetic waves at an angular frequency ω, a Nd: YAG-laser which produces a short (generally 30 ps to 30 ns) light impulse is typically used. The light impulse is split into two lights in the sample groove and the control groove by the light splitting means. In the sample groove, the layer system to be measured is mounted on a rotating plate. A small part of the incident light is NL
It is converted to doubled frequency light by the O-active system. Harmonic wave intensity is measured by a photomultiplier, captured by a data acquisition electro-optics and control computer as a function of angle of incidence, and measured by a number of firings per angle. Polarizer and filter
Care should be taken to measure only the harmonic waves that occur in the sample under controlled polarization conditions.

The control groove is likewise fitted with an NLO-active substance, for example powdered 2-methyl-4-nitroaniline. That is, the substance serves to tune the control of the measured intensity due to the weakening of the energy and the stereoscopic light profile. Next, the measured sample, for example, a quartz crystal having a susceptibility of about 1 pm / V, is measured in the sample groove. From the angular dependence of the harmonic intensities and its value in comparison with the intensity of the measured sample, it is possible to obtain information for lining the NLO-sensitivity as well as the chromophore.

The NLO-activity of crystals, in particular of the crystals of the compounds according to the invention, can be investigated by the so-called Kurtz powder method. The compound to be tested is ground in a mortar and fixed in a layer about 0.2 mm thick between the glazings. Control samples (eg 2-methyl-
-4-Nitroaniline). The sample is irradiated with a pulsating Nd: YAG-laser beam and the controlled light intensity before the doubled frequency is measured by a photomultiplier for the sample and the control.

The hyperpolarizability β of a molecule can be evaluated by measuring the integrated intensity of the absorption band in the donor-acceptor system and the rubbing of the absorption maximum in various solvents. The basis of this method is the assumption that the optical non-linearity is dominated by the charge rub between the base state and the initial applied state. In this case β is proportional to the transition moment for absorbing the lowest energy that can be measured by measuring the integrated band intensity. Hyperpolarizability is also proportional to the difference between the dipole moments of the two states. This difference can be evaluated by rubbing the absorption wavelength between two solvents with different dielectric constants.

The compounds according to the invention, especially when present as polarised polymers or Langmuir-Brodgett films in layer elements or in the form of non-central control crystals,
It is possible to manufacture an optical system having good nonlinear optical characteristics. Such a system is suitable, for example, as an electro-optical switch, a diode laser frequency multiplier or an optical parameter reinforcement means (for example as a so-called reinforcement of weak optical signals in an optical signal transmission net).

The materials of the present invention are suitable for use in optical structural elements. The special polymer can itself be manufactured as a wave propagator. They are suitable as components in the production of directional couplers, switching elements, modulation means, parametric amplifiers, for example for frequency doubling of the laser beam, for example in the field of integrated optics, sensors and reporting technology.

The figures described below illustrate the basic construction of corresponding structural elements. FIG. 1 shows a structural element (100) for doubling the frequency of light waves. Base (switch support) 1
An NLO-active layer 103 is embedded between 04 and the covering layer 105. The indices of refraction of (103) and (105) should be less than 104, which allows for total reflection.

Light 101 is transmitted through the front side of layer 103 or through prism 108 or a diffraction grating (not shown). The cover layer (105) serves only to protect the active layer. The active layer 103 may also constitute side surfaces, so that light is guided in two dimensions (perpendicular and parallel to the layer plane).

The active layer preferably contains a compound according to the invention which exhibits a high (> 10 ⁻⁸ esu) second-order optical sensitivity. If the thickness and width of the layer 103 and the index of refraction of the substrate (104) are in the correct ratio for the wavelength of the incident light, the layer velocity of the frozen fundamental wave matches that of the harmonic second order wave. Then you can achieve. At that time (103)
There is a special lot of light at twice the frequency at. The light ray (106) leaves from another front face (107) at the NLO-active layer or through a prism (109) or a diffraction grating (not shown). The light of the incident wavelength is (1
Move away from 06) through a filter.

In another embodiment (not shown), the frozen fundamental wave in the light wave is guided and the Tscheme described above is used.
According to the rekow principle, a harmonic light wave is coupled out into the substrate and the light wave conductor is arranged to leave the front of the substrate.

FIG. 2 illustrates another embodiment of a structural element having a substrate 204 and a cover layer 205. The incident light ray 201 similarly enters through the front surface 202. A ray of light (206) with an additional frequency leaves the structural element through the front face (207). This light guide is in turn composed of an NLO-inactive layer (203) and an NLO-active layer 208 having a high refractive index, the NLO-active layer comprising the compounds according to the invention, especially in the LB-composite layer state or polarity. It is contained in the state of polymerized.

3 and 3b, a component 300 capable of adjusting the intensity of a light wave is shown. Incident light 30
1 is transmitted through the front face 302, a prism (not shown) or a diffraction grating (not shown) into the active lightwave conductor layer 303. Layer 303 is Mas viewed from the side
It is configured as a ch-Zehnder interferometer.

According to FIG. 3, which illustrates a partial cross section of the structure, two electrodes (304) are on either side of the lightwave conductor 303, which are mounted on a light-transmissive substrate.
According to FIG. 4, the electrodes 304 are located below and above the arms of the interferometer when viewed from the side. This interferometer has a base 3
It is located above 08.

When a voltage is applied to the electrode 304, the refractive index at 303 changes due to the linear electro-optic effect and the layer velocity of the light at that arm of the interferometer changes. The original light waves then additionally or subtractively overlap and modulate the intensity of the light exiting through the flanks 307. Most compounds of the invention of the general formula I, II or III have a strong intrinsic color and are therefore well suited for such light modulators.

That is to say, FIG. 5 shows a structural element 400 providing an interaction between a first ray of frequency ω1 and a second ray of frequency ω2. In this case, light is generated whose frequency corresponds to the sum and difference of ω3 and ω4. Rays at frequencies ω 1 (401) and ω 2 (402) pass through side 403 or prisms (not shown) or diffraction gratings (not shown) to the light guide texture 404 disposed on substrate 408. Sent. The light guide structure 404 may be covered with a protective layer 409.

The active layer 404 having a light conductor function is NLO.
-Composed of active LB-composite layer (similar to Figure 1). That is, it may have an additional inert layer of high refractive index (similar to FIG. 2).

Layer 404 may be laterally structured to produce a two-dimensional lightwave conductor. The frequencies ω1 and ω2 are mixed by the NLO-interaction in layer 404. That is, a part of the transmitted intensity is at frequencies ω1 and ω
It is converted into a frequency corresponding to the sum of 2 and the difference. Light containing these frequencies exits through front face 407 or through a prism (not shown) or a diffraction grating (not shown).

A = COOR ⁵ and A ¹ = SO ₂ R ⁷
The compound of general formula I which is R. It can be manufactured based on the research of Duncan et al. [Synthesis (19
80), 10, 806-807].

Compounds of general formula I in which A = NO ₂ and A ¹ = COOR ⁵ are described by W. Manufactured based on Lehnet's work [Tetrahedron, 1972,
28, 663-666].

Compounds of general formula I in which A = COOR ⁵ and A ¹ = SOR ⁷ can be prepared according to R. It can be produced based on the research of Tanikaga [J. Chem. Soc. , P
erkin Trans. I, N4, 825-83
0].

A and A ¹ are CN, CO ₂ R ⁷ and C
Compounds of general formula I selected from ONH ₂ are described in J. Zab
It can be manufactured based on Ricky's research [J. Che
m. Soc. , 1901, 683].

Compounds of the general formula I in which A = and A ¹ = SO ₂ R ⁷ are described by M. L. It can be produced based on the research of Oftedahl [J. Org. Chem. , 30 (1
965) 296].

[0069]

The present invention will be described in more detail by the following examples. Example 1 2-Dicyanomethylene-7- (4 '(N (-2-hydroxyethyl) -N-methylamino) -styryl) -4,
4'-dimethyl-4,4a, 5,6-tetrahydro (3
H) Naphthalene 1.04 g of malonic acid dinitrile and 3 g of 4,4
7-trimethyl-4,4a, 5,6-tetrahydro (3
H) -naphthalenone was added to dimethylformamide (25 m
Piperidine (0.2 g), concentrated acetic acid (0.05 g) and acetic anhydride (0.03 g) are added to the solution dissolved in l). The reaction mixture is stirred overnight at room temperature under a nitrogen atmosphere. Thereafter, the reaction mixture was charged with 2.83 g of 4-
(N- (2-hydroxyethyl) -N-methylamino)
Stir for 1/2 hour at 80 ° C. before adding benzaldehyde. The mixture is then stirred at 80 ° C. for 2 hours. To confirm the end of the reaction, mix with toluene and heat at the water separator. The toluene mixture is slowly distilled while fresh toluene is added to the mixture.
Repeat this many times. Thereafter, the mixture is cooled and the solvent is distilled off under reduced pressure. The distillation residue is stirred in water and extracted with dichloromethane. The organic phase is MgSO
Dry at ₄ and remove solvent. The product is purified by medium pressure liquid chromatography (isohexane: ethyl acetate = 1: 1, silica gel-column). Yield 1.2
5g (20%).

¹ H-NMR (300 MHz, D-trichloromethane): δ (ppm) 0.80 (s, 3H);
1.19 (s, 3H); 2.07 (m, 2H); 2.3
8 (m, 3H); 2.79 (m, 2H); 3.05
(S, 3H); 3.55 (m, 2H); 3.85 (m,
2H); 6.33 (s, 1H); 6.56 (s, 1
H); 6.73 (d, 1H); 6.75 (d, 2H);
6.83 (d, 1H); 7.37 (d, 2H).

MS EI (70 eV): (M ⁺ ) 39
9, melting point: 187 ° C. λ _max (acetonitrile) = 515 nm The compounds of Examples 2 to 7 were also produced according to the formulation described in Example 1. At that time, the reaction time and the post-treatment were changed only so as not to be sufficient.

Example 2 2-Dicyanomethylene-7- (5'-dibutylamino-
2'-thienylvinyl) -4,4-dimethyl-4,4
a, 5,6-Tetrahydro (3H) naphthalene ¹ H-NMR (300 MHz, D-trichloromethane): δ (ppm) 0.96 (t, 6H); 1.26
(S, 6H); 1.36 (m, 4H); 1.64 (m,
4H); 2.29 (m, 3H); 2.42 (m, 2
H); 2.74 (m, 2H); 3.29 (t, 4H);
5.72 (d, 1H); 6.23 (s, 1H); 6.2
8 (s, 1H); 6.48 (d, 1H); 6.84
(D, 1H); 6.92 (d, 1H).

Λ _max (acetonitrile) = 598 nm Example 3 2-Dicyanomethylene-7- (4′-methylthiostyryl) -4,4-dimethyl-4,4a, 5,6-tetrahydro (3H) naphthalene ¹ H- NMR (300 MHz, D-trichloromethane): δ (ppm) 0.81 (s, 3H); 1.20
(S, 3H); 2.10 (m, 2H); 2.39 (m,
3H); 2.50 (s, 3H); 2.80 (m, 2
H); 6.39 (s, 1H); 6.61 (s, 1H);
6.80 (d, 1H); 6.88 (d, 1H); 7.2
2 (d, 2H); 7.39 (d, 2H).

Λ _max (acetonitrile) = 448 nm,
Melting point: 203 ° C. EFISH: μβ (1600 nm) = 700 · 10 ⁻⁴⁸
esu μβ. = 420 · 10 ⁻⁴⁸ esu Example 4 2-Dicyanomethylene-7- (2 ′, 4′-dimethoxystyryl) -4,4-dimethyl-4,4a, 5,6-tetrahydro (3H) naphthalene ¹ H- NMR (300 MHz, D-trichloromethane): δ (ppm) 0.81 (s, 3H); 1.19
(S, 3H); 2.07 (m, 2H); 2.39 (m,
3H); 2.81 (m, 2H); 3.85 (s, 3
H); 3.87 (s, 3H); 6.36 (s, 1H);
6.45 (d, 1H); 6.52 (m, 1H); 6.5
9 (s, 1H); 6.84 (d, 1H); 7.19
(D, 1H); 7.48 (d, 1H).

Λ _max (acetonitrile) = 453 nm,
Melting point: 197 to 199 ° C. EFISH: μβ (1600 nm) = 1060/10
^-48 esu μβ. = 640 · 10 ⁻⁴⁸ esu Example 5 2-Dicyanomethylene-7- (4 ′-(dimethylaminophenyl) -1′-butanedienyl) -4,4-dimethyl-4,4a, 5,6-tetrahydro (3H ) Naphthalene ¹ H-NMR (300 MHz, D-trichloromethane): δ (ppm) 0.81 (s, 3H); 1.18
(S, 3H); 2.00 to 2.10 (m, 2H);
25-2.47 (m, 3H); 2.69-2.87
(M, 2H); 3.00 (s, 6H); 6.27 (s,
1H); 6.32 to 6.42 (m, 1H); 6.57
(S, 1H); 6.63 to 6.80 (m, 5H);
34 (d, 2H) λ _max (acetonitrile) = 518 nm, melting point: 2
05-206 ° C. Example 6 2-Dicyanomethylene-7- (4′-dimethylaminosilyl) -4,4-dimethyl-4,4a, 5,6-tetrahydro (3H) naphthalene ¹ H-NMR (300 MHz, CDCl ₃ ): δ (pp
m) 0.80 (s, 3H); 1.26 (s, 3H);
2.07 (m, 2H); 2.38 (m, 3H); 2.7
9 (m, 2H); 3.02 (s, 6H); 6.30
(S, 1H); 6.56 (s, 1H); 6.67 (d,
2H); 6.79 (m, 2H); 7.38 (d, 2
H).

Λ _max (acetonitrile) = 508 nm Example 7 2-Dicyanomethylene-7- (4′-dimethoxysilyl) -4,4-dimethyl-4,4a, 5,6-tetrahydro (3H) naphthalene ¹ H- NMR (300 MHz, D-trichloromethane): δ (ppm) 0.81 (s, 3H); 1.20
(S, 3H); 2.03 to 2.13 (m, 2H);
29-2.49 (m, 3H); 2.70-2.90.
(M, 2H); 3.84 (s, 3H); 6.36 (s,
1H); 6.60 (s, 1H); 6.81 (d, 2
H); 6.90 (m, 2H); 7.43 (d, 2H).

Λ _max (acetonitrile) = 447 nm,
Melting point: 169 to 172 ° C. EFISH: μβ (1600 nm) = 550 · 10 ⁻⁴⁸
esu μβ. = 330 · 10 ⁻⁴⁸ esu In the table below, R ³ = R ⁴ = H, p = 0, Q = 1,
4-phenylene and compounds of general formula III with n = 1 are likewise obtained:

[0078]

[Table 1]

[0079]

[Table 2] Example 8 (Polymer) In a 100 ml round-bottomed flask with protective gas atmosphere, 0.7 ml of a solution of 19.02% by weight of polyacrylic acid chloride in dioxane is initially introduced. to this,
0.3 g of 2-dicyanomethylene-7- (4 '-(N (2-hydroxyethyl) -N-methylstyryl) -4,4-dimethyl-4,4a, 5,6 was added to dried dioxane.
A solution of tetrahydro (3H) naphthalene (Example 1) in solution is added dropwise. The reaction mixture is stirred at room temperature for a few minutes. Add 0.16 ml dry pyridine and stir overnight at room temperature. Then the reaction solution is heated to 50 ° C. for 8 hours. Then 1 ml of methanol is added to the cooled solution and again stirred overnight at room temperature. It is then stirred for a further 8 hours at 50 ° C. and the cooled solution is precipitated with slightly acidified methanol. The black-red polymer which precipitates is dissolved in dichloromethane for the purpose of purification and until low molecular weight components are no longer present (DC-
Control is carried out and examined) Precipitate again with methanol.
Yield: 151 mg (35%).

UV power-Determination of incorporation rate in dye by spectroscopy [λ _max polymer (CHCl ₃ ) = 5
10 nm], the chromophore group 58. in the original acid chloride group.
It is 3 mol%.

The molecular hyperpolarizability β can be evaluated in the donor-acceptor system by measuring the integrated intensity of the absorption band and the absorption maximum in various solvents. The basis of these methods is that optical non-linearity is predominant due to the charge shift between the basic state and the initial voltage application state. In this case β is proportional to the transition moment for the lowest energy absorption that can be measured by measuring the integrated bandguru. Hyperpolarizability is also proportional to the difference between the two states' dipole moments. This difference can be evaluated by the difference in absorption wavelength between two kinds of solvents having different dielectric constants.

By the solvate chromic method for μ · β of some compounds (solvatochromi
sch) The measured values are shown in Table 1. D. J. Willi
The method disclosed by Ams (Angew. Chem.
IE 96, 1984, p. 640), an electric-field-induced second-order harmonic generator (Electric-field-in
duced second-harmonic generation) is used to measure the value of β and the associated β · μ. This EFISH-value is more accurate than the value measured by the sorbate chromic method. Table 3 compares the compounds of the present invention with two prior art compounds.

[0083]

[Table 3]

[0084]

[Table 4]

[Brief description of drawings]

1 is a cross-sectional view of a structural element for doubling the frequency of light waves.

FIG. 2 is a sectional view of a structural element having a substrate and a coating layer.

FIG. 3 is a sectional view of a component capable of adjusting the intensity of light waves.

FIG. 4 is a perspective view of a component capable of adjusting the intensity of light waves.

FIG. 5 shows the first ray of frequency ω1 and frequency ω2.
FIG. 6 is a cross-sectional view of a structural element that causes an interaction with a second ray of light.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C07C 323/60 323/62 C07D 333/36 C08F 8/00 MJB 246/00 MPY C09K 9/02 Z 7188-4H G02F 1/35 504 9316-2K (72) Inventor Shinfong Su, 86th Hoxist Serenese Corporation, Maurice Avenyu, Summit, NJ, USA

Claims (15)

[Claims] 1. A compound represented by the general formula (I): [Wherein R ¹ and R ² are independently of each other H or C ₁
˜C ₄ -alkyl, R ³ and R ⁴ are C ₁ -C ₄ -alkyl or hydrogen atoms, A and A ¹ are independently NO ₂ , CN, halogen atoms, CF ₃ , COOR ⁵ , CONR ⁶ ₂ , SO ₂ R ⁷
Or, one of the residues A and A ¹ is a hydrogen atom, —CO ₂ (C
_{H 2) x ZH, SO 3} R 5, SOR 7, SO 2 NR 6 2
Or S (NSO ₂ CF ₃ ) CF ₃ , x is 2, 3, 4 or 5, Z is O, S or NH, R ⁵ is C ₁ -C ₄ -alkyl, R ⁶ C ₁ -C ₄ is - alkyl or hydrogen atom, R ⁷ is C ₁ -C ₄ - alkyl, C ₁ -C ₄ - perfluoroalkyl or phenyl residue optionally substituted, D is NR ⁸ ₂ , OR ⁸ , SR ⁸ , R ⁸ is C ₁ -C ₂₂ -alkyl optionally substituted at the end with a hydroxyl group, a thiol group or a primary- or secondary amino group, or the group H (OCH a ₂ CH _{2) m,} Q is an aromatic carbocyclic ring having up to three rings - or derived from the heterocyclic ring system (n + 1) -valent residue, p is 0 or 1 , N is 1, 2 or 3 and m is 1, 2, 3, 4,
Means 5 or 6. ] The compound represented by these. 2. The compound according to claim 1, wherein Q is phenylene or thiophenylene. 3. D is N (CH ₃ ) ₂ , CH ₃ O or C
The compound according to claim 1, which is H ₃ S. 4. Q is phenylene and D is HZ
- (CH ₂₎ a _x -Y-, Z is O, NR ^9, S, x is a number of 1 to 18, Y is O, S, an NR ^10, R ^9, R ¹⁰ is independently of one another C ₁ -C ₄ - alkyl or a compound according to claim 2 is a hydrogen atom. 5. The compound according to claim 4, wherein Z is O and Y is NCH ₃ or O. 6. D is NR ⁸ R ¹⁰ , OR ⁸ or SR ⁸ , R ¹⁰ is C ₁ -C ₄ -alkyl or H and R ⁸ is C ₁₆ -C ₂₂ -alkyl. The compound according to. 7. A layer element having at least two monomolecular films of an amphipathic compound on a support, characterized in that the amphipathic compound is the compound of claim 6. 8. The layer element according to claim 7, wherein the layer thickness, which depends on the number of layers, is at least 0.1 μm. 9. At least 10% by weight of residue E [Wherein R ¹ , R ² , R ³ , R ⁴ , A and A ¹ have the meanings given in claim 1 and Z, x and Y have the meanings given in claim 4]. ] The polymer containing. 10. General formula II: [Wherein R ¹¹ and R ¹³ are independently of each other H, CH ₃ ,
Cl, F or CF _3, G is _{^{CO 2 R 12, CONHR 12,}} CONR 12 2 , or -
CN, R ¹² is H or C ₁ -C ₁₀ -alkyl and E has the meaning given in claim 9. ] The polymer of Claim 9 which has these. 11. The polymer according to claim 9, wherein the chromophore groups E are arranged sterically exclusively in the same meaning. 12. The polymer according to claim 11, which is in the form of an intimate layer having a thickness of at least 0.1 μm. 13. A device for voltage-dependent light conditioning, comprising two electrodes for voltage application arranged parallel to one another and a light-wave conductor partly arranged between the two electrodes. Device according to claim 12, characterized in that the light guide is a layer element according to claim 8 or a polymer layer according to claim 12. 14. The method of claim 1 for the purpose of a non-linear optical material.
A method of using the compound according to any one of 10 to 10. 15. The general formula III: The compound of claim 1 represented by: