JP2003238551A - Polymerizable compound and optical element using its matrix - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a compound useful as a nonlinear optical material having no or suppressed orientation relaxation, to provide an optical element using its matrix and uses thereof. <P>SOLUTION: The polymerizable compound is represented by formula (I) or (II) [wherein, X denotes O or S; Ar<SP>1</SP>and Ar<SP>2</SP>denote each a single bond, an aromatic ring, biphenyl group or terphenyl group (with the proviso that Ar<SP>1</SP>and Ar<SP>2</SP>are not simultaneously single bonds); D denotes oxygen atom, sulfur atom or an electron-bonating group; A denotes an electron-attracting group; S<SP>1</SP>and S<SP>2</SP>denote each a bivalent connecting group; and P<SP>1</SP>and P<SP>2</SP>denote each a polymerizable group]. The optical element uses the matrix thereof. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a compound useful as a novel nonlinear optical material useful in the fields of optoelectronics and photonics, and various elements utilizing the nonlinear optical effect such as electro-optical elements.

[0002]

2. Description of the Related Art With the progress of the advanced information society, many attempts have been made to use optical technology for transmission, processing and recording of information. Under such circumstances, a nonlinear optical material exhibiting a nonlinear optical effect has attracted attention in the fields of optoelectronics and photonics. The nonlinear optical effect is a phenomenon that when a strong electric field is applied to a substance, a nonlinear response is exhibited between the generated electric polarization and the applied electric field.
A non-linear optical material refers to a material that remarkably exhibits such non-linearity. Known nonlinear optical materials that utilize the second-order nonlinear response include materials that generate second harmonics and materials that exhibit the Pockels effect (first-order electro-optical effect) that causes a change in the refractive index in proportion to the linearity of the applied electric field strength. Has been
In particular, the latter is being studied for application to electro-optic (EO) light modulators.

Conventionally, for these nonlinear optical materials, material search and element fabrication have been performed mainly on inorganic nonlinear optical materials, but in recent years, 1) large nonlinearity is shown, 2) response speed is fast, 3 ) Organic materials are attracting attention because of their high photo-damage threshold, 4) a wide variety of molecular designs are possible, and 5) excellent manufacturing suitability. However, in order for the second-order nonlinear optical effect to appear, the polarization induced by the electric field needs to lack an inversion symmetry center. Therefore, it is necessary to arrange a molecule exhibiting a nonlinear optical effect or a nonlinear optical response group in a material in a structure lacking the center of inversion symmetry.

According to the prior art, in order to arrange a molecule exhibiting a non-linear optical effect or a non-linear optical response group in a structure lacking inversion symmetry, a molecule exhibiting a non-linear optical effect or a non-linear optical response group is arranged in an organic polymer. Is used to orient the dipoles by, for example, an electric field. Poling the orientation control by this electric field
The polled organic polymer is called an electric field oriented polymer (polled polymer). That is, by applying a high voltage at a temperature higher than the glass transition temperature of the base polymer, the dipoles of the molecule or the responsive group exhibiting the second-order nonlinear optical effect are aligned, and then cooled and aligned by the electric field. Is a method of freezing. For example, SPIE magazine, first
213, p. 7 (1990), describes examples of electro-optic (EO) light modulators made by this method. However, these materials undergo thermal orientation relaxation with time, electro-optical characteristics deteriorate, and lack stability, and are not practical or applicable to a wide range. The solution was desired (see, for example, Mol. Cryst. Liq. Cryst., Vol. 189, p. 3, (1990)).

Also, for example, Thin Solid Film magazine, 2nd
Vol. 10, p. 195 (1992), synthesizes a polymerizable long-chain alkylamino derivative of 2-amino-5-nitropyridine as a compound that is amphiphilic and exhibits a nonlinear optical effect, and polymerizes it after forming an LB film. Have reported an example in which the orientation is fixed. However, in the fabrication of devices using the LB method,
Defects such as pin poles and lack of suitability for industrial manufacturing were regarded as problems. Furthermore, for example, the Handbook of Liquid
Crystals, Volume 3, Chapter IV, Section 4 (1998)
Although an example of using a liquid crystal polymer having a non-linear optically active group in the side chain has been reported in J. et al., None of them has ensured sufficient long-term stability, and further improvement has been desired.

Next, for example, New J. Chem., Vol. 24,
A benzofuran derivative is disclosed on page 977 (2000), JP-A-7-179856 and the like. Also,
A benzothiophene derivative is disclosed in Japanese Patent Publication No. 11-502855. However, none of them have concrete examples of the compounds of the present invention, and do not suggest the present invention. For example, the above-mentioned Japanese Patent Laid-Open No. 7-1798.
The compounds exemplified in Japanese Patent Publication No. 56 and Japanese Patent Publication No. 11-502855 are not developed for the purpose of exhibiting nonlinear optical characteristics, and are polymerizable compounds, that is, capable of undergoing a polymerization reaction at both ends of the compound. A compound having two or more substituents is not exemplified. Therefore, none of the compounds disclosed in these publications can form a matrix three-dimensionally, and even if they have a group exhibiting nonlinear optical characteristics, orientation relaxation cannot be suppressed, so that they are useful. Lack. Further, the benzofurans described in New J. Chem. Magazine have non-linear optical properties, but are not polymerizable compounds, so that the orientation cannot be fixed by a three-dimensional matrix as in the present invention.

[0007]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a novel polymerizable compound which is useful for a non-linear optical material made of an organic material which has no orientation relaxation or is suppressed, and an optical element using the matrix. To provide.

[0008]

As a result of intensive studies, the present inventors have found that the following materials can achieve the object of the present invention. That is, (1) a polymerizable compound represented by the following general formula (I) or (II).

[0009]

[Chemical 5]

[0010]

[Chemical 6]

(In each formula, X is -O- or-
Indicates S-, Ar¹, Ar²Are each independently a single bond, or
Indicates an aromatic ring, biphenyl group, or terphenyl group
You However, Ar¹, Ar²Are not single bonds at the same time. D is oxygen source
Child (-O-), sulfur atom (-S-) or electron donating group,
A is an electron-withdrawing group, S¹, S²Are each independently bivalent linked
Base, P¹, P²Each independently represents a polymerizable group. ) (2) The polymerizable compound according to item (1), wherein X is -O-.
object. (3) Ar¹Is a single bond, Ar²Wherein (1) is a benzene ring
Alternatively, the polymerizable compound according to the item (2). (4) S¹, S²Are each independently an alky having 2 to 12 carbons.
Polymerization of the above (1) to (3), which is a len group.
Compound (5) P¹, P²The polymerizable groups of
Is an yloxy group or a methacryloyloxy group
The polymerizable compound according to any one of items (1) to (4). (6) D is an oxygen atom (-O-) or a sulfur atom (-S-).
Rui or substituted imino group (-NR-: where R is 1 to 6 carbon atoms
Lower alkyl group, or hydrogen atom, or P ¹-S
¹An imino group having a ring structure, which represents a substituent represented by-
May be ) And A is an ester group (-COO
-), Sulfonyl group (-SO₂-) Or sulfoxy group (-S
O_Three-) Is an electron-withdrawing group selected from
The polymerizable compound according to any one of (1) to (5) above. (7) In an optical element using a nonlinear optical material, a nonlinear
The optical material is shaped by the general formula (I) or (II) below.
Optics characterized by a matrix of compatible compounds
element.

[0012]

[Chemical 7]

[0013]

[Chemical 8]

(In each formula, X is -O- or-
S- represents, Ar ¹ and Ar ² each independently have a single bond, or an aromatic ring which may have a substituent, a biphenyl group which may have a substituent, or a substituent. Represents a terphenyl group which may be present. However, Ar ¹ and Ar ² are not single bonds at the same time. D is an oxygen atom (-O-) or a sulfur atom (-S-) or an electron-donating group, A is an electron-withdrawing group,
S ¹ and S ² each independently represent a divalent linking group, and P ¹ and P ² each independently represent a polymerizable group. (8) The optical element according to the item (7), wherein the optical element is a non-linear optical element, an electro-optical element, or a wavelength conversion element.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. First, Ar ¹ in the general formulas (I) and (II) and
It is preferable that one of Ar ² is a single bond. Ar ¹ or Ar ² is a divalent group, preferably an aromatic ring having 6 to 12 carbon atoms, a biphenyl group or a terphenyl group, more preferably a benzene ring, a naphthalene ring, a biphenyl group or a terphenyl group. In the present invention, Ar ¹ and Ar ² may have a substituent. When Ar ¹ and Ar ² represent an aromatic ring having a substituent, examples of the preferable substituent include a lower alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, an isopropyl group. , Butyl group, sec
-Butyl group, tert-butyl group, pentyl group, hexyl group and the like can be mentioned.

In the general formulas (I) and (II), D is an oxygen atom (-O-), a sulfur atom (-S-), -NH-, or -NR- (R has 1 to 6 carbon atoms. A substituent of or P ¹ −
A group represented by S ^1- is preferable, and a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group and a hexyl group are particularly preferable. ), Or the groups shown below

[0017]

[Chemical 9]

Etc. are preferred, and an oxygen atom is particularly preferred. Preferred examples of A, a carbonyl group (-CO-), carbonyloxy group (-COO-), a sulfonyl group _(-SO 2 -), or a sulfonyloxy group (-SO ₃ -) and others as mentioned, carbonyl Oxy and sulfonyloxy groups are particularly preferred.

S ¹ and S ^{2 of the} above general formulas (I) and (II)
The number of carbon atoms of the linking group represented by is preferably 2 to 12, and more preferably 2 to 6. Further, S ¹ and S ² may have a ring structure, and when they have a ring structure, a cyclohexane ring is preferable. Furthermore, an alkylene group is mentioned as an example of a preferable coupling group. The linking group may have one or more substituents. At this time, examples of the preferable substituent include a substituent having 1 to 4 carbon atoms and a halogen atom, and particularly preferably a methyl group, an ethyl group, a propyl group and an isopropyl group. Also,
When the carbon atom having a substituent is an asymmetric carbon, the configuration may be any of R, S and any mixture thereof.

In the general formulas (I) and (II), P ¹ and P ²
Represents a polymerizable group, and preferable examples thereof include an acryloyloxy group, a methacryloyloxy group, a glycidyl group, and a vinyloxy group, and an acryloyloxy group and a methacryloyloxy group are particularly preferable. In the general formula (I) or (II), the D-Ar ¹ -benzotheophene ring or benzofuran ring -Ar ² -A moiety exerts an action as a nonlinear optical response group. Specific examples of the compounds represented by the general formulas (I) and (II) include the following compounds.

[0021]

[Chemical 10]

[0022]

[Chemical 11]

[0023]

[Chemical 12]

[0024]

[Chemical 13]

The compounds of the particularly preferred examples of the present invention can be synthesized, for example, by the methods of Schemes 1 to 4 shown below. However, the present invention is not limited to this. Scheme 1

[0026]

[Chemical 14]

(In the formula, Ar ¹ , Ar ² and D have the same meanings as described above.
K is a leaving group, Y is a protecting group, and R is an alkyl group. )

In the method of Scheme 1, the compounds represented by the compounds I and II (the compound II is preferably 1 to 3 equivalents, more preferably 1 to 1.5 equivalents based on the compound I).
It is equivalent. ) As a starting material in the presence of base I (base I
Is preferably 1 to 4 equivalents, more preferably 1 to 2 equivalents, relative to compound II. 5) in an organic solvent
The reaction suitably proceeds under heating at about 0 to 150 ° C. to obtain the compound represented by the compound III. Compound I
The protecting group Y in is, for example, te when D is an amino group.
An rt-butoxycarbonyl group (Boc), a benzoylcarbonyl group (Dbz) group, an acetyl group (Ac) and the like can be mentioned.
If D is any other substituent, Protective Groups in Organic Chemistry, (Plenham Press) (London and New York, 1973) [Protecti
ve Groups in Organic Chemistry, Plenum Press];
Green Tea W (Green, TW), Protective Groups in Organic Synthesis, (Willie, New York, 1981) [Protective
Groups in Organic Synthesis, Wiley New York, 198
1]; and peptides, Vol. I, Schroeder and Lubke (Academic Press (London and New York) 19
65) [Peptides, Vol. I, Schrooder and Lubke, Acade
mic Press (London and New York, 1965)] for protection and deprotection. Compound II
Examples of the leaving group K in are a halogen atom, an alkylsulfonyloxy group, or an arylsulfonyloxy group, and examples of the alkyl group R are a methyl group, an ethyl group, a propyl group, an isopropyl group, and the like. Examples of the organic solvent used include N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMA), tetrahydrofuran (THF), chloroform, dichloromethane, dimethylsulfoxide (DMSO) and the like. As the base I, inorganic and organic bases can be adopted,
Examples of preferable bases include potassium carbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium acetate, sodium acetate, sodium phosphate, ammonia and the like.

Next, the compound III thus obtained is allowed to stand at a temperature of about 100 ° C. in the presence of the base II (wherein the base II is preferably 1 to 4 equivalents, more preferably 1 to 2 equivalents relative to the compound III). The reaction proceeds properly when stirred at
The compound shown in compound IV is obtained. Inorganic and organic bases can be adopted as the base II, and examples of preferable bases include tert-butoxy potassium and tert.
-Sodium butoxy, sodium methoxide, sodium hydride, lithium hydride and the like.

Finally, the compound IV is hydrolyzed in the presence of the base III (however, the base III is preferably 1 to 4 equivalents, more preferably 1 to 2 equivalents relative to the compound IV) to obtain the compound V. To be Examples of preferable base III include sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, lithium hydroxide and the like. Scheme 2

[0031]

[Chemical 15]

(In the formula, Ar ¹ , Ar ² , S ¹ , S ² , P ¹ and P ² have the same meanings as described above. Y represents a protecting group and K represents a leaving group.)

Then, in Scheme 2, thionyl chloride (SOCl ₂ ) was added to the compound V obtained above in an organic solvent.
(1 to 3 equivalents, preferably 1 to 1.5 equivalents relative to compound V) are allowed to act, and then H
Compound VI is obtained by reacting a compound represented by OS ² -P (preferably 1 to 3 equivalents, more preferably 1 to 1.5 equivalents based on compound V).

Next, the protecting group Y is deprotected by the method described in Protective Groups in Organic Chemistry, (Plenham Press) (London and New York, 1973) to give compound VII. To be Finally, in the presence of a base I (1 to 4 equivalents relative to compound VII, preferably 1 to 2 equivalents), a compound represented by K-S ¹ -P ¹ ( ¹ relative to compound VII To 3 equivalents, more preferably 1 to 1.5 equivalents) are reacted under heating at about 50 ° C to 150 ° C to obtain the desired compound VIII. Examples of the leaving group K in this compound include a halogen atom,
Examples thereof include an alkylsulfonyloxy group and an arylsulfonyloxy group. As the base I, inorganic and organic bases can be adopted, and preferred examples of the base include potassium carbonate, sodium carbonate, sodium hydroxide,
Examples thereof include potassium hydroxide, lithium hydroxide, potassium acetate, sodium acetate, sodium phosphate and the like. Scheme 3

[0035]

[Chemical 16]

(In the formula, Ar ¹ , Ar ² and D have the same meanings as described above.
T is a halogen atom, Y is a protecting group, and R is an alkyl group. )

In Scheme 3, the compound IX is represented in Table 11
It can be synthesized by the method described in JP-A-502855. This compound IX and a compound represented by Y-D-Ar ¹ -B (OH) ₂ (1 to 3 equivalents relative to compound IX, preferably 1 to 2 equivalents) are tetrakistriphenylphosphine. Palladium (preferably 0.3 to 5 mol% relative to compound IX, more preferably 1
To 3 mol%. Compound X is obtained by the reaction (Suzuki coupling reaction). Examples of the protecting group Y include a tert-butoxycarbonyl group (Boc), a benzoylcarbonyl group (Dbz) group, an acetyl group (Ac) and the like.

Next, for compound X, base III (compound x
On the other hand, it is preferably 1 to 4 equivalents, more preferably 1 to 2 equivalents. ) Is reacted with T ₂ to give compound XI. The halogen atom T is preferably an iodine atom or a bromine atom. Next, compound XI and (HO) ₂ B
A compound represented by —Ar ² —CO ₂ —R (1 to 3 equivalents relative to compound XI is preferable, and 1 to 2 is more preferable.
It is equivalent. ) Is reacted with Suzuki coupling reaction to obtain compound XII. Finally, the above-mentioned Protective Groups in Organic Chemistry, (Plenham Press) (London and New York, 19
By deprotecting the protecting group Y of compound XII according to the method described in 73), compound XIII can be obtained. Scheme 4

[0039]

[Chemical 17]

(In the formula, Ar ¹ , Ar ² , S ¹ , S ² , P ¹ and P ² have the same meanings as described above. Y represents a protecting group and K represents a leaving group.)

In Scheme 4, the target compound XVI can be synthesized from the compound XIII by a method similar to the method described in the above Scheme 2.

Next, a preferred embodiment of the optical element of the present invention will be described. It is preferable that a layer containing the polymerizable molecule represented by the general formula as at least a part of the constituent components is provided on one substrate or between a pair of substrates. The layer containing the polymerizable molecule as at least a part of the constituents contains the molecule in an amount of 80% by weight or more,
It is preferable to contain 90% or more. If necessary, an appropriate polymerization initiator, polymerization inhibitor, photosensitizer, crosslinking agent, etc. may be added.

A preferred example of the substrate is a transparent substrate such as glass or a transparent plastic substrate. If necessary, a transparent electrode layer, an insulating film, etc. may be provided on the substrate. It may or may not have a transparent electrode, but I
It is preferable that TO is vapor-deposited, but it is not particularly limited thereto. Although an insulating film may or may not be included, a polyimide-based or polyvinyl alcohol insulating film is a preferred example when the insulating film is included. When using a pair of substrates, a spacer, a sealant or the like may be used if necessary.

A well-known method can be used as a method for providing a layer containing a molecule having a non-linear optical response group and a plurality of polymerization-reactive functional groups at the same time as at least a part of constituent components on one substrate. Adopted. As the coating method, known methods such as curtain coating method, extrusion coating method, roll coating method, spin coating method, dip coating method, bar coating method, spray coating method, slide coating method, and printing coating method are adopted. It As a method for injecting between the substrates, a general method such as a dispenser method or a bell jar method is adopted.

Then, an external electric field or an external magnetic field is applied to the layer containing at least a molecule having a nonlinear optical response group and a plurality of functional groups capable of undergoing polymerization reaction at least as a part of the constituents. Orient the polymerizable molecules. As the orientation method, a method using an external electric field is preferable,
It is preferable to employ a contact poling method (planar electrode poling method, electrode sandwich poling method) or a corona poling method. These polling methods are described in "A Handbook of Optoelectronic Functional Organic Materials", published by Asakura Shoten (199
5 years). The external electric field or the external magnetic field is preferably applied within a temperature range around the melting point. As the strength of the external electric field or the external magnetic field used, a strength suitable for controlling the orientation of the polymerizable molecules used is adopted.

Finally, in a state in which the polymerizable molecule having a non-linear optical response group and a plurality of functional groups capable of polymerization reaction at the same time is oriented, the polymerizable molecule is two-dimensionally applied under the application of an external electric field or an external magnetic field. It is possible to obtain the desired non-linear optical material by polymerizing mechanically, the polymer chains are entangled three-dimensionally as a whole, and by forming a matrix, the orientation of the non-linear optical response group is fixed. For the polymerization reaction, various known polymerization methods using heat or electromagnetic waves can be adopted, but radical polymerization using a photopolymerization initiator by ultraviolet light is particularly preferable. The non-linear optical response layer obtained as described above may or may not have one insulating film. In the non-linear optical material provided on the transparent electrode substrate, the non-linear optical response layer is further formed on the upper layer. An electrode layer may be provided. An example thereof is an electrode formed by vapor-depositing a metal such as aluminum or gold. 1 and 2 show typical examples of the layer structure of the nonlinear optical material according to the present invention. In FIG. 1 and FIG. 2, 1 is a layer made of a matrix of the polymerizable compound of the present invention (nonlinear optical response layer), 2 is an insulating layer, and 3 is a transparent electrode substrate.

[0047]

The present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to the following examples.

Example 1 4- (6-Hydroxy-benzofuran-2-yl) -benzoic
Acid synthesis

[0049]

[Chemical 18]

2-Hydroxy-4-methoxy-benzaldehyde (16.1 g, 105.8 mmol) and methyl 4- (bromoethyl) benzoate (24.5 g, 107.0 mmol) were dissolved in 280 ml of dimethylformamide (DMF) and potassium carbonate (34.6 g) was added. g, 250m
mol) was added. After stirring at 100 ° C for 10 hours,
400 ml of water was added and extracted with ethyl acetate. After washing with saturated saline, the extract was dried over anhydrous magnesium sulfate, and the solvent was distilled off with a rotary evaporator. Then recrystallize with hexane / ethyl acetate to give 30.1 g of 4-
White crystals of (2-formyl-5-methoxy-phenoxymethyl) -benzoic acid methyl ester were obtained.

Next, 4- (2-formyl-5-methoxy-phenoxymethyl) -benzoic acid methyl ester (3
0.1 g, 99.9 mmol) was dissolved in 300 ml of dimethylformamide (DMF), and potassium ter-butoxide (12.9 g, 115 mmol) was added.
Was gradually added. After stirring at room temperature for 8 hours, water was added. The precipitate was filtered and washed with water to give 11.9 g of 4- (6-methoxy-benzofuran-2-yl) -benzoic acid methyl ester as a white solid.

Next, 4- (6-methoxy-benzofuran-2-yl) -benzoic acid methyl ester (11.9 g, 42.
(2 mmol) is dissolved in 150 ml of dichloromethane, and 100 ml of a 1.0 mol / L dichloromethane solution of boron tribromide (BBr3) is dissolved.
(100 mmol) was added dropwise under ice cooling, and the mixture was stirred at room temperature for 4 hours. After that, water was added to the reaction solution, and the formed precipitate was filtered and washed with water to obtain 25.1 g of 4- (6-hydroxy-benzofuran-2-yl) -benzoic acid. FAB-MS (M + H) ⁺ = 254 ¹ H NMR (DMSO-d ₆ , 300MHz, δ): 6.78-6.81 (dd, J =
8.4, 2.1Hz, 1H), 6.99-7.00 (d, J = 1.5Hz, 1H), 7.46
-7.49 (d, J = 8.4Hz, 1H), 7.47 (s, 1H), 7.93-7.96 (d,
J = 8.4Hz, 1H), 8.01-8.04 (d, J = 8.4Hz, 1H)

Example 2 Synthesis of 4- (6-hydroxy-benzo [b] thiophen-2-yl) -benzoic acid

[0054]

[Chemical 19]

First, 2-bromo-6-methoxy-benzo [b] thiophene was synthesized by the method described in Japanese Patent Publication No. 11-502855. Then 2-bromo-6-methoxy-benzo [b] thiophene (12.2 g, 50.0 mmo in toluene (200 ml).
l) Add 4-methoxycarbophenylboronic acid to the solution.
(9.9 g, 55.0 mmol) and tetrakistriphenylphosphine palladium (1.13 g, 1.00 mmol) were sequentially added. To this solution was added 50 ml of 2N sodium carbonate solution. The resulting mixture was heated under reflux for 5 hours. Upon cooling, white 4- (6-methoxy-benzo [b] thiophen-2-yl) -benzic acid methyl ester was formed. The solid was collected by filtration and washed with ethyl acetate. On the other hand, the filtrate was extracted with ethyl acetate and saturated aqueous sodium hydrogen carbonate, and the organic layer was washed with saturated saline and dried over sodium sulfate. Further 4- (6-methoxy-benzo-
[b] Thiophen-2-yl) -benzoic acid methyl
The ester was obtained, which was collected by filtration. The total yield of product was 11.7 g (81% yield).

Next, 4- (6-methoxy-benzo [b] thiophen-2-yl) -benzoic acid methyl ester (1
0.0 g, 33.5 mmol) was dissolved in 130 ml of dichloromethane, 80 ml (80 mmol) of a 1.0 mol / L dichloromethane solution of boron tribromide (BBr3) was added dropwise under ice cooling, and then at room temperature.
It was stirred for 4 hours. Thereafter, water was added to the reaction solution, and the resulting precipitate was filtered and washed with water to give 7.8 g of 4- (6-hydroxy-benzofuran-2-yl) -benzoic acid (yield 87
%). FAB-MS (M + H) ⁺ = 270

Example 3: 4- [6- (4-acryloyloxy-
Butoxy) -benzofuran-2-yl] -benzoic acid
4-acryloyloxy-butyl ester (Compound 3)
Synthesis of

[0058]

[Chemical 20]

4- (6-hydroxy-benzofuran-2-yl)-
Benzoic acid (1.46 g, 5.74 mmol) was dissolved in 15 ml of dimethylformamide (DMF), and potassium carbonate (6.22 g, 45.
0 mmol) was added. Acrylic acid 4-methanesulfonyloxy butyl ester (5.11 g, 23.0 mmol) was added, and the mixture was stirred at 120 ° C. for 12 hours. After that, water was added to the reaction solution and the mixture was extracted with ethyl acetate. The extract was washed with saturated aqueous sodium hydrogen carbonate solution and saturated saline and dried over anhydrous magnesium sulfate. Concentrate with a rotary evaporator and purify the concentrate with silica gel chromatography (developing solution: hexane / ethyl acetate = 3/1) to give 4- [6-
1.2 g of (4-acryloyloxy-butoxy) -benzofuran-2-yl] -benzoic acid 4-acryloyloxy-butyl ester was obtained.

FAB-MS (M + H) ⁺ = 506 ¹ H NMR (CDCl ₃ , 300 MHz, δ): 1.66-1.78 (m, 8H), 3.6
9-3.73 (t, J = 6.2Hz, 2H), 4.19-4.23 (t, J = 6.5Hz,
2H), 4.24-4.28 (t, J = 6.1Hz, 2H), 4.35-4.39 (t, J =
6.1Hz, 2H), 5,82-5.86 (dd, J = 10.3, 1.5Hz, 1H),
6.09-6.17 (dd, J = 17.4, 10.2Hz, 1H), 6.39-6.46 (dd,
J = 18.6, 1.2Hz, 1H), 6.80-6.83 (d, J = 7.5Hz, 1H),
7.03-7.; 7.07 (dd, J = 10.4, 2.0Hz, 2H), 7.42-7.44
(d, J = 8.4Hz, 1H), 7.84-7.87 (d, J = 8.6Hz, 2H),
8.07-8.09 (d, J = 8.7Hz, 2H)

Example 4: 4- [6- (4-acryloyloxy-
Butoxy) -benzo [b] thiophen-2-yl] -benzoic acid 4-acryloyloxy-butyl ester (Compound 4) synthesis

[0062]

[Chemical 21]

4- (6-hydroxy-benzofuran-2-yl)-
The benzoic acid was changed to 4- (6-hydroxy-benzo [b] thiophen-2-yl) -benzoic acid and synthesized according to the method of Example 3. FAB-MS (M + H) ⁺ = 522

Example 5: Synthesis of 4- (6-acryloyloxymethoxy-benzofuran-2-yl) -benzoic acid acryloyloxymethyl ester (Compound 1)

[0065]

[Chemical formula 22]

Acrylic acid 4-methanesulfonyloxy-butyl ester was replaced with acrylic acid methanesulfonyloxymethyl ester, and synthesis was performed according to the method of Example 3. Melting point 108 ° C (measured by DSC). FAB-MS (M + H) ⁺ = 422

Example 6: Synthesis of 4- (6-acryloyloxymethoxy-benzo [b] thiophen-2-yl) -benzic acid acryloyloxymethyl ester (Compound 2)

[0068]

[Chemical formula 23]

4- (6-hydroxy-benzofuran-2-yl)-
The benzoic acid was changed to 4- (6-hydroxy-benzo [b] thiophen-2-yl) -benzoic acid and synthesized according to the method of Example 5. FAB-MS (M + H) ⁺ = 438

Example 7: 4- [6- (6-acryloyloxy-
Hexyloxy) -benzofuran-2-yl] -benzoic
Synthesis of acid 6-acryloyloxy-hexyl ester (Compound 5)

[0071]

[Chemical formula 24]

Acrylic acid 4-methanesulfonyloxy butyl ester was replaced with acrylic acid 6-methanesulfonyloxy-hexyl ester, and synthesis was performed according to the method of Example 3. FAB-MS (M + H) ⁺ = 562

Example 8: 4- [6- (6-acryloyloxy-
Hexyloxy) -benzo [b] thiophen-2-yl] -benzoic acid 6-Acryloyloxy-hexyl ester (Compound 6) synthesis

[0074]

[Chemical 25]

4- (6-hydroxy-benzofuran-2-yl)-
Example 3 with the benzoic acid changed to 4- (6-hydroxy-benzo [b] thiophen-2-yl) -benzoic acid
It was synthesized according to the method of. FAB-MS (M + H) ⁺ = 578

Example 9: 4- [6- (12-acryloyloxy-
Dodecyloxy) -benzofuran-2-yl] -benzoic
Synthesis of acid 12-acryloyloxy-dodecyl ester (Compound 7)

[0077]

[Chemical formula 26]

Acrylic acid 4-methanesulfonyloxy butyl ester was replaced with acrylic acid 12-methanesulfonyloxy-dodecyl ester, and synthesis was performed according to the method of Example 3. FAB-MS (M + H) ⁺ = 730

Example 10: 4- [6- (12-acryloyloxy-dodecyloxy) -benzo [b] thiophen-2-yl] -benzoic acid 12-acryloyloxy-dodecyl
Synthesis of ester (Compound 8)

[0080]

[Chemical 27]

Example 4 was changed to acrylic acid 12-methanesulfonyloxy-dodecyl ester instead of acrylic acid 4-methanesulfonyloxy-butyl ester.
It was synthesized according to the method of. FAB-MS (M + H) ⁺ = 746

Example 11 4- [6- (4-acryloyloxy-butoxy) -benzofuran
-2-yl] -benzoic acid 6-acryloyloxy-
Synthesis of hexyl ester (Compound 9)

[0083]

[Chemical 28]

4- (6-hydroxy-benzofuran-2-yl)-
Benzoic acid (5.0 g, 19.7 mmol) was dissolved in 50 ml of tetrahydrofuran (THF) and thionyl chloride (3.5 g, 29.7 mmol) was added.
9.5 mmol) was added dropwise. Acrylic after stirring for 3 hours at 50 ℃
Acid 6-hydroxy-hexyl ester (6.6g, 38.4mm
ol) and diisopropylethylamine (10.2g, 78.8mmo
l) was added and the mixture was stirred at 70 ° C. for 12 hours. Phosphate buffer was added and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline and dried over anhydrous magnesium sulfate. After distilling off the solvent, the residue was purified by silica gel chromatography (developing solution: hexane / ethyl acetate = 2/1) to give 4- (6-hydroxy-benzofuran-2-yl) -benzic acid 6-acryloyloxy-hexyl. Ester (4.58 g, yield 57
%). Finally, using 4- (6-hydroxy-benzofuran-2-yl) -benzoic acid 6-acryloyloxy-hexyl ester and acryl acid 4-methanesulfonyloxy-butyl ester, the method of Example 2 was followed. 4- [6- (4-Acryloyloxy-butoxy) -benzofuran-2-yl] -benzoic acid 6-
Acryloyloxy-hexyl ester was obtained. FAB-MS (M + H) ⁺ = 535

Example 12 Synthesis of 4- [6- (4-acryloyloxy-butoxy) -benzo [b] thiophen-2-yl] -benzoic acid 6-acryloyloxy-hexyl ester (Compound 10)

[0086]

[Chemical 29]

4- (6-hydroxy-benzofuran-2-yl)-
Example 1 with the benzoic acid changed to 4- (6-hydroxy-benzo [b] thiophen-2-yl) -benzoic acid
It was synthesized according to the method of 1. FAB-MS (M + H) ⁺ = 550

Example 13: 4- [5- (4-acryloyloxy-butoxy) -benzofuran-2-yl] -benzoic acid 4-acryloyloxy-butyl ester (Compound 1
Synthesis of 1)

[0089]

[Chemical 30]

2-Hydroxy-4-methoxy-benzaldehyde was replaced by 2-hydroxy-5-methoxy-benzaldehyde and 4- (5-hydroxy-benzofuran-2-yl) -benzoic acid was prepared according to the method of Example 1. First synthesized. Then, 4- (6-hydroxy-benzofuran-2-yl) -benzoic acid was changed to 4- (5-hydroxy-benzofuran-2-yl) -benzoic acid, and the target compound was prepared according to the method of Example 3. -[5- (4-Acryloyloxy-butoxy) -benzofuran-2-yl] -benzoic acid 4-
Acryloyloxy-butyl ester was synthesized. FAB-MS (M + H) ⁺ = 506 ¹ H NMR (CDCl ₃ , 300MHz, δ): 1.87-1.94 (m, 8H), 4.0
5-4.6 (m, 2H), 4.23-4.27 (m, 2H), 4.37-4.42 (m, 2H),
5,81-5.86 (dd, J = 9.6, 1.5Hz, 1H), 6.11-6.17 (dd,
J = 17.4, 8.4Hz, 1H), 6.39-6.46 (dd, J = 17.4, 1.2H
z, 1H), 6.90-6.94 (dd J = 7.5, 1.2Hz, 1H), 7.04-7.0
8 (dd, J = 9.6, 2.7Hz, 2H), 7.40-7.43 (d, J = 8.4Hz,
1H), 7.89-7.91 (d, J = 8.4Hz, 2H), 8.09-8.12 (d, J
= 8.7Hz, 2H)

Example 14: Synthesis of 4- [5- (4-acryloyloxy-butoxy) -benzo [b] thiophen-2-yl] -benzoic acid 4-acryloyloxy-butyl ester (Compound 12)

[0092]

[Chemical 31]

4- (5-hydroxy-benzofuran-2-yl)-
Example 1 was changed to 4- (5-hydroxy-benzo [b] thiophen-2-yl) -benzoic acid instead of benzoic acid.
4- [5- (4-acryloyloxy-butoxy) -benzo [b] thiophen-2-yl] -benzoic acid 4-acryloyloxy-butyl ester was synthesized according to the method of 3. FAB-MS (M + H) ⁺ = 522

Example 15: Synthesis of 4- [5- (12-acryloyloxy-dodecyloxy) -benzofuran-2-yl] -benzoic acid 12-acryloyloxy-dodecyl ester (compound 13)

[0095]

[Chemical 32]

4- (5-hydroxy-benzofuran-2-yl)-
Example 9 was changed to 4- (5-hydroxy-benzo [b] thiophen-2-yl) -benzoic acid instead of benzoic acid.
It was synthesized according to the method of. FAB-MS (M + H) ⁺ = 730

Example 16: 4- [5- (12-acryloyloxy-dodecyloxy) -benzo [b] thiophen-2-yl] -benzoic acid 12-acryloyloxy-dodecyl
Synthesis of ester (compound 14)

[0098]

[Chemical 33]

4- (6-hydroxy-benzo [b] thiophene-2-
Yl) -benzoic acid 4- (5-hydroxy-benzo
[b] thiophen-2-yl) -benzoic acid
Synthesized according to the method of Example 10. FAB-MS (M + H) ⁺ = 746

Example 17: Synthesis of 4 '-[6- (4-Acryloyloxy-butoxy) -benzofuran-2-yl] -biphenyl-4-carboxylic acid 4-acryloyloxy-butyl ester (Compound 15)

[0101]

[Chemical 34]

First, methyl 4- (bromoethyl) benzoate was changed to 4'-bromomethyl-biphenyl-4-carboxylic acid methyl ester, and 4 '-(6-hydroxy-benzofuran-2-yl) was prepared according to the method of Example 1. -Biphenyl-4-carboxylic acid was synthesized. Then 4-
(6-Hydroxy-benzofuran-2-yl) -benzoic acid is changed to 4 '-(6-hydroxy-benzofuran-2-yl) -biphenyl-4-carboxylic acid and the desired compound is prepared according to the method of Example 3. 15 was synthesized. FAB-MS (M + H) ⁺ = 582

Example 18: 4 '-[6- (4-acryloyloxy-butoxy) -benzo [b] thiophen-2-yl] -biphenyl-4-carboxylic acid 4-acryloyloxy-
Synthesis of butyl ester (Compound 16)

[0104]

[Chemical 35]

First, 4-methoxycarbonylphenylboronic acid was converted into 4'-methoxycarbonyl-biphenyl-4-
4 '-(6-Hydroxy-benzo [b] thiophen-2-yl)-according to the method of Example 1 substituting for a carboxylic acid.
Biphenyl-4-carboxylic acid was synthesized. Next, 4- (6-hydroxy-benzofuran-2-yl) -benzoic acid was converted to 4 '-(6-hydroxy-benzo [b] thiophene-2-
Yl) -biphenyl-4-carboxylic acid,
The target compound 16 was synthesized according to the method of Example 3. FAB-MS (M + H) ⁺ = 598

Example 19: 4- [6- (4-Acryloyloxy-butoxy) -benzofuran-2-yl]-[1,1 ';4', 1 "] terphenyl-4" -carboxyl Synthesis of acid 4-acryloyloxy-butyl ester (Compound 17)

[0107]

[Chemical 36]

First, methyl 4- (bromoethyl) benzoate was replaced with 4-bromomethyl- [1,1 ′; 4 ′, 1 ″] terphenyl-4 ″.
-Carboxylic acid, 4- (6-hydroxy-benzofuran-2-yl)-[1,1 ';4', according to the method of Example 1
1 ″] terphenyl-4 ″ -carboxylic acid was synthesized. Next, 4- (6-hydroxy-benzofuran-2-yl) -benzoic acid was added to 4- (6-hydroxy-benzofuran-2-yl).
Yield)-[1,1 ′; 4 ′, 1 ″] terphenyl-4 ″ -carboxylic acid, and the target compound 17 was synthesized according to the method of Example 3. FAB-MS (M + H) ⁺ = 658

Example 20: 4- [6- (4-acryloyloxy-butoxy) -benzo [b] thiophen-2-yl]-[1,1 ';4',
Synthesis of 1 "] terphenyl-4" -carboxylic acid 4-acryloyloxy-butyl ester (Compound 18)

[0110]

[Chemical 37]

First, 4-methoxycarbonylphenylboronic acid is converted into 4-methoxycarbonyl- [1,1 ';4', 1 ''].
Change to terphenyl-4 ''-carboxylic acid methyl ester and follow the procedure of Example 2 to prepare 4- (6-hydroxy)
-Benzo [b] thiophen-2-yl)-[1,1 ';4', 1 "] terphenyl-4" -carboxylic acid was synthesized. Then 4
-(6-Hydroxy-benzofuran-2-yl) -benzoic
The acid was changed to 4- (6-hydroxy-benzo [b] thiophen-2-yl)-[1,1 ′; 4 ′, 1 ″] terphenyl-4 ″ -carboxylic acid and the acid of Example 3 was used. Compound 18 of interest was synthesized according to the method. FAB-MS (M + H) ⁺ = 674

Example 21: 6- [6- (4-Acryloyloxy-butoxy) -benzofuran-2-yl] -naphthalene-2-carboxylic acid 4-acryloyloxy-butyl
Synthesis of ester (compound 19)

[0113]

[Chemical 38]

First, methyl 4- (bromoethyl) benzoate was replaced with 6-bromomethyl-naphthalene-2-carboxylic acid methyl ester, and 6- (6-hydroxy-benzofuran-2-yl) -naphthalene was prepared according to the method of Example 1. -2-Carboxylic acid was synthesized. Then 4-
(6-Hydroxy-benzofuran-2-yl) -benzoic acid was changed to 6- (6-hydroxy-benzofuran-2-yl) -naphthalene-2-carboxylic acid to obtain the desired compound 19 according to the method of Example 3. Was synthesized. FAB-MS (M + H) ⁺ = 556

Example 22: 6- [6- (4-Acryloyloxy-butoxy) -benzo [b] thiophen-2-yl] -naphthalene
-2-Carboxylic acid 4-acryloyloxy-
Synthesis of butyl ester (Compound 20)

[0116]

[Chemical Formula 39]

First, 4-methoxycarbonylphenylboronic acid was changed to 6-methoxycarbonylphenyl-naphthalene-2-carboxylic acid and 6- (6-hydroxy-benzofuran-2-yl)-was prepared according to the method of Example 1. Naphthalene-2-carboxylic acid was synthesized. Then, 4- (6-hydroxy-benzofuran-2-yl) -benzoic acid was added to 6- (6-hydroxy-benzo [b] thiophene-2.
The target compound 19 was synthesized according to the method of Example 3 by changing to (-yl) -naphthalene-2-carboxylic acid. FAB-MS (M + H) ⁺ = 572

Example 23: Synthesis of 6- [4- (4-acryloyloxy-butoxy) -phenyl] -benzofuran-2-carboxylic acid 4-acryloyloxy-butyl ester (Compound 21)

[0119]

[Chemical 40]

First, 2-hydroxy-4-methoxy-benzaldehyde was changed to 3-hydroxy-4'-methoxy-biphenyl-4-carbaldehyde, and 6- (4-
Hydroxy-phenyl) -benzofuran-2-carboxylic acid was synthesized. Then, 4- (6-hydroxy-benzofuran-2-yl) -benzoic acid was changed to 6- (4-hydroxy-phenyl) -benzofuran-2-carboxylic acid to obtain the desired compound 21 according to the method of Example 3. Was synthesized. FAB-MS (M + H) ⁺ = 506

Example 24: Synthesis of 6- [4 '-(4-acryloyloxy-butoxy) -biphenyl-4-yl] -benzofuran-2-carboxylic acid 4-acryloyloxy-butyl ester (Compound 22)

[0122]

[Chemical 41]

First, 2-hydroxy-4-methoxy-benzaldehyde was converted into 3 ″ -hydroxy-4-methoxy- [1,1 ′; 4 ′, 1 ″].
Example 1 was changed to terphenyl-4 ″ -carbaldehyde.
6- (4'-hydroxy-biphenyl-4-yl)-according to the method of
Benzofuran-2-carboxylic acid was synthesized.
After that, 4- (6-hydroxy-benzofuran-2-yl) -benzoic acid was changed to 6- (4'-hydroxy-biphenyl-4-yl) -benzofuran-2-carboxylic acid,
Compound 22 of interest was synthesized according to the method of Example 3. FAB-MS (M + H) ⁺ = 582

Example 25: 6- [6- (4-Acryloyloxy-butoxy) -naphthalen-2-yl] -benzofuran-2-carboxylic acid 4-acryloyloxy-butyl
Synthesis of ester (compound 23)

[0125]

[Chemical 42]

First, 2-hydroxy-4-methoxy-benzaldehyde was treated with 2-hydroxy-4- (6-methoxy-naphthalene-2-
6- (6-Hydroxy-naphthalen-2-yl) -benzofuran-in accordance with the method of Example 1
2-Carboxylic acid was synthesized. Then 4- (6-
Hydroxy-benzofuran-2-yl) -benzoic acid was changed to 6- (6-hydroxy-naphthalen-2-yl) -benzofuran-2-carboxylic acid to synthesize the desired compound 23 according to the method of Example 3. . FAB-MS (M + H) ⁺ = 556

Example 26 4- {6- [4- (4-acryloyloxy-butoxy) -phenyl]
-Benzofuran-2-yl} -benzoic acid 4-acryloyloxy-butyl ester (Compound 24)

[0128]

[Chemical 43]

2-Hydroxy-4-methoxybenzaldehyde was changed to 3-hydroxy-4'-methoxy-biphenyl-4-carbaldehyde and the 4-
[6- (4-Hydroxy-phenyl) -benzofuran-2-yl] -benzoic acid was first synthesized. Then, 4- (6-hydroxy-benzofuran-2-yl) -benzoic acid
4- [6- (4-hydroxy-phenyl) -benzofuran-2-yl]-
The desired compound 24 was synthesized according to the method of Example 3 by changing to benzoic acid. FAB-MS (M + H) ⁺ = 582

Example 27 Synthesis of acrylic acid 4- {2- [4- (4-acryloyloxy-butoxysulfonyl) -phenyl] -benzofuran-6-yloxy} -butyl ester (Compound 25)

[0131]

[Chemical 44]

Methyl 4- (bromoethyl) benzoate
-Bromomethyl-benzene sulphonic 4- (6-hydroxy-benzofuran-2-yl) -benzene sulphonic according to the method of Example 1 substituting for the acid methyl ester.
The acid was first synthesized. Thereafter, 4- (6-hydroxy-benzofuran-2-yl) -benzoic acid was changed to 4- [6- (4-hydroxy-phenyl) -benzofuran-2-yl] -benzoic acid, and the method of Example 3 was followed. The target compound 25 was synthesized. FAB-MS (M + H) ⁺ = 542

Example 28: Synthesis of 4- {6-[(4-acryloyloxy-butyl) -ethyl-amino] -benzofuran-2-yl} -benzoic acid 4-acryloyloxy-butyl ester (Compound 26)

[0134]

[Chemical formula 45]

First, 2-hydroxy-4-methoxy-benzaldehyde was changed to 4-bromo-2-hydroxy-benzaldehyde, and 4- (6-bromo-benzofuran-2-yl) -benzoic acid was prepared according to the method of Example 1. The acid methyl ester was first synthesized. Then 4- (6-bromo-benzofuran-2-yl)
-Benzoic Acid Methyl Ester (14.8g, 44.7m
mol) and N-ethyl-acetamide (4.67 g, 53.6 mmol) were dissolved in 100 ml of toluene. Pd (dba) ₂ (2
60 mg, 0.45 mmol) and tri-tert-butylphosphine (9
1.0 mg, 0.45 mmol) was added, and the mixture was stirred at 80 ° C. After 10 hours, a phosphate buffer was added and the mixture was extracted with ethyl acetate. The extract was washed with saturated saline and dried over anhydrous magnesium sulfate. After the solvent was distilled off, the residue was purified by silica gel chromatography (developing solution: hexane / ethyl acetate = 2/1), and 4- [6- (acetyl-ethyl-amino) -benzofuran-2-yl] -benzoic Acid methyl ester
(12.8 g, yield 85%) was obtained. Next, 4- [6- (acetyl-ethyl-amino) -benzofuran-2-yl] -benzoic acid methyl ester (12.5 g, 37.9 mmol) was added to methylene chloride.
Dissolve in 200 ml and under ice cooling, BF ₃・ Et ₂ O (14.0 g, 98.9 mmol)
Was dripped. After stirring at room temperature for 5 hours, water was added under surface cooling and the precipitate was collected by filtration. The precipitate was washed with saturated aqueous sodium hydrogencarbonate and water, dried under vacuum and dried, and then 4- (6-ethylamino-benzofuran-2-yl) -benzoic acid (1
0.2 g, 36.1 mmol) was obtained. Finally, 4- (6-ethylamino-benzofuran-2-yl) -benzoic acid and acrylic acid 4-methanesulfonyloxy-butyl ester were reacted according to the method of Example 3 to obtain the desired 4- {6-
[(4-Acryloyloxy-butyl) -ethyl-amino] -benzofuran-2-yl} -benzoic acid 4-acryloyloxy-butyl ester was obtained. FAB-MS (M + H) ⁺ = 533

Example 29: Synthesis of 4- {6-[(4-acryloyloxy-butyl) -isopropyl-amino] -benzofuran-2-yl} -benzoic acid 4-acryloyloxy-butyl ester (Compound 27)

[0137]

[Chemical formula 46]

N-Ethyl-acetamide was replaced with N-isopropyl-acetamide and synthesized according to the method of Example 28. FAB-MS (M + H) ⁺ = 547

Example 30: Synthesis of 4- {6- [bis- (4-acryloyloxy-butyl) -amino] -benzofuran-2-yl} -benzoic acid 4-acryloyloxy-butyl ester (Compound 28)

[0140]

[Chemical 47]

First, using N-acetyl-3-amino-phenol as a starting material, New J. Chem., Vol. 24, 977.
4- (6-acetylamino-benzofuran-2-yl) -benzic acid methyl ester was synthesized by the method described on page (2000). Next, 4- (6-acetylamino-
Benzofuran-2-yl) -benzoic acid methyl ester (2.0 g, 6.47 mmol) was dissolved in 70 ml of methylene chloride, and BF ₃ .Et ₂ O (2.7 g, 19.4 mmol) was added dropwise under ice cooling. After stirring at room temperature for 5 hours, water was added under ice cooling and the precipitate was collected by filtration. The precipitate was washed with saturated aqueous sodium hydrogen carbonate solution and water, dried under vacuum, and dried with 4- (6-amino-benzofuran-2).
-Yl) -benzoic acid (1.15 g, yield 76%) was obtained.
Finally, 4- (6-hydroxy-benzofuran-2-yl) -benzoic acid is converted to 4- (6-amino-benzofuran-2-yl)-
Substituting benzoic acid, the desired compound 28 was synthesized according to the method of Example 3. FAB-MS (M + H) ⁺ = 631

Example 31: 4- [6- (4-acryloyloxy
-Butylsulfanyl) -benzofuran-2-yl] -benzoic acid 4-acryloyloxy-butyl ester (Compound 29)

[0143]

[Chemical 48]

2-Hydroxy-4-methoxy-benzaldehyde was changed to 2-hydroxy-4-methylsulfanyl-benzaldehyde and 4- (6-mercapto- was prepared according to the method of Example 1.
Benzofuran-2-yl) -benzoic acid was first synthesized. Then, the target compound 29 was synthesized according to the method of Example 3. FAB-MS (M + H) ⁺ = 522

Example 32: 4- {6- [4- (2-Methyl-acryloyloxy) -butoxy] -benzofuran-2-yl} -benzoic acid 4- (2-methyl-acryloyloxy) -butyl ester ( Synthesis of compound 30)

[0146]

[Chemical 49]

Example 3 Acrylic acid 4-methanesulfonyloxy butyl ester was replaced with metaclic acid 4-methanesulfonyloxy butyl ester, Example 3
Compound 30 was synthesized according to the method described in 1. FAB-MS (M + H) ⁺ = 534

Example 33: 4- {6- [4- (2-Methyl-acryloyloxy) -butoxy] -benzo [b] thiophen-2-yl}-
Synthesis of benzoic acid 4- (2-methyl-acryloyloxy) -butyl ester (Compound 31)

[0149]

[Chemical 50]

Example 4 Acrylic acid 4-methanesulfonyloxy butyl ester was replaced with metaclic acid 4-methanesulfonyloxy butyl ester, Example 4
Compound 31 was synthesized according to the method described in 1. FAB-MS (M + H) ⁺ = 550

Example 34: Synthesis of 6- [4- (4-acryloyloxy-butoxy) -phenyl] -benzofuran-2-carboxylic acid 4-acryloyloxy-butyl ester (Compound 32)

[0152]

[Chemical 51]

2-hydroxy-4-methoxybenzaldehyde was changed to 3-hydroxy-4'-methoxy-biphenyl-4-carbaldehyde, methyl 4- (bromoethyl) benzoate was changed to bromo-acetic acid acid methyl ester, According to the method of Example 1, 6- (4-hydroxy-phenyl) -benzofuran-2-carboxylic acid was first synthesized. Then, the target compound 32 was synthesized according to the method of Example 3. FAB-MS (M + H) ⁺ = 506

Example 35: 4- [6- (4 -Acryloyloxy-butoxy) -benzofuran-2-yl] -benzoic acid 4-acryloyloxy-butyl ester (Compound 3) (92.7 parts by weight), phenothiazine (1.3 parts by weight), polymerization initiator (IRGACURE 651 Product name, manufactured by Ciba Geigy) (4
(Parts by weight) and hydroquinone monomethyl ether (2 parts by weight). Next, while applying a DC voltage of 200 V between the transparent electrodes, the obtained sample was kept at 80 ° C. and UV irradiation (254 nm, 10 W
/ cm, 3 min) to prepare the nonlinear optical material shown in FIG. The sample obtained above was irradiated with infrared light of a YHG laser (1.06 μm), and generation of the second harmonic was confirmed. The second harmonic intensity of the sample was retained after 6 months.

Example 36: Glass substrate having ITO transparent electrode portion coated with polyimide thin film as insulating film (glass substrate thickness 0.7 mm, polyimide thin film thickness 0.3 μm)
4- [6- (4-acryloyloxy-butoxy) -benzofuran-2-yl] -benzoic acid 4-acryloyloxy-butyl ester (Compound 3) (92.7 parts by weight), phenothiazine (1.3 parts by weight) Part), Irgacure 651 (4 parts by weight), and hydroquinone monomethyl ether (2 parts by weight) are applied by spin coating (1000 rpm, 20 seconds).
And dried under reduced pressure for 12 hours to obtain a resin layer (thickness 1.0 μm
m) was formed. Next, the obtained sample is kept at 60 ° C.,
Voltage application using the corona poling method (applied voltage: 5.0k
V, 20 min) and then UV irradiation (254 nm, 10 W / cm, 3 min) while applying voltage. An aluminum electrode was carried on the polymerized non-linear optical response portion by vapor deposition to prepare the non-linear optical material shown in FIG. 1 having electrodes at both ends. The sample obtained above was irradiated with infrared light (1.06 μm) of a YHG laser to confirm the generation of the second harmonic and the electro-optical effect. The intensity of the second harmonic and electro-optic effect of the sample was retained after 6 months. Compound 3
A sample in which a matrix of the compound was sandwiched was prepared in exactly the same manner as in Example 35 except that the compound was replaced by any one of the compounds 1, 2, and 4 to 30. It was confirmed that all the samples generated the second harmonic and the intensity was maintained for a long time.

[0156]

Industrial Applicability According to the present invention, an organic non-linear optical material having an electro-optic effect or the attenuation of the generation of second harmonics over time significantly suppressed can be obtained.

[Brief description of drawings]

FIG. 1 is a schematic view of an example showing a layer structure of a nonlinear optical material of the present invention.

FIG. 2 is a schematic view of another example showing the layer structure of the nonlinear optical material of the present invention.

[Explanation of symbols]

1 Non-linear optical response layer 2 insulating film 3 Transparent electrode substrate

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G02F 1/361 G02F 1/361 F term (reference) 2K002 AB12 CA06 HA13 HA20 4C037 PA05 PA06 QA12 4J100 AL66P AL67P BA02P BA15P BA28P BA55P BC43P BC44P BC49P BC53P BC83P CA01 JA32

Claims (2)

[Claims] 1. A polymerizable compound represented by the following general formula (I) or (II). [Chemical 1] [Chemical 2] (In each formula, X represents -O- or -S-, and A
r ¹ and Ar ² each independently represent a single bond, an aromatic ring, a biphenyl group, or a terphenyl group. However, Ar
¹ and Ar ² are not single bonds at the same time. D is an oxygen atom (-O-),
Sulfur atom (-S-) or electron-donating group, A is an electron-withdrawing group, S ¹ and S ² are independently divalent linking groups, and P ¹ and P ² are independently polymerizable groups. Show. ) 2. An optical element using a nonlinear optical material, wherein the nonlinear optical material is a matrix of a polymerizable compound represented by the following general formula (I) or (II). [Chemical 3] [Chemical 4] (In each formula, X represents -O- or -S-, and A
r ¹ and Ar ² each independently represent a single bond, an aromatic ring, a biphenyl group, or a terphenyl group. However, Ar
¹ and Ar ² are not single bonds at the same time. D is an oxygen atom (-O-) or sulfur atom (-S-) or an electron-donating group, A is an electron-withdrawing group, S ¹ and S ² are each independently a divalent linking group, P
¹ and P ² each independently represent a polymerizable group. )