JP5376359B2 - Nonlinear optical compound, nonlinear optical material, and nonlinear optical element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a nonlinear optical compound which has both nonlinearity and heat resistivity in a sufficiently high level. <P>SOLUTION: The nonlinear optical compound is expressed in a general formula (1). Here, in the general formula (1), n is an integer between 2 and 4, R<SP>1</SP>shows a 1-4C alkyl group, n pieces of R<SP>1</SP>may be the same, or different from each other. p and q are integers between 0 and 2 independently, and p+q is two or less. Ar<SP>1</SP>and Ar<SP>2</SP>show a predetermined aryl group or a predetermined hetero-aryl group independently, and when p+q is two, Ar<SP>1</SP>and Ar<SP>2</SP>may be the same, or different from each other. D and A show a predetermined electron donor group and a predetermined electronic acceptance group respectively. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a nonlinear optical compound, a nonlinear optical material, and a nonlinear optical element.

  Devices such as optical modulators, optical switches, optical memories, and wavelength converters utilize the electro-optic effect of nonlinear optical materials. Conventionally, inorganic materials such as lithium niobate and potassium dihydrogen phosphate have been widely used as nonlinear optical materials, but organic nonlinear optical materials are used in order to meet the demands for higher nonlinear optical performance and manufacturing cost reduction. Attention has been attracted and various studies have been conducted for its practical application.

  The organic nonlinear optical material is obtained by dispersing or bonding a compound having nonlinear optical activity (hereinafter simply referred to as “nonlinear optical compound”) to a host material such as a polymer material. As a nonlinear optical compound, a push-pull type π-conjugated compound having an electron-donating group and an electron-accepting group positioned at both ends of a molecular structure and a π-conjugated chain connecting them is known. For example, Patent Document 1 below describes a nonlinear optical compound having a polyene chain represented by the following formula (7).

  Patent Documents 2 to 5 below describe nonlinear optical compounds having a thiophene ring in a π-conjugated chain. Further, Patent Documents 6 to 8 below describe efforts to improve the heat resistance of the nonlinear optical compound by adopting a predetermined electron donating group or electron accepting group.

US Pat. No. 6,067,186 JP-T-2004-501159 JP-T-2004-506630 JP-T-2004-508430 JP 2006-507403 A JP 2005-227376 A JP 2005-227378 A JP 2007-99739 A

  By the way, when producing an optical element in which an optical waveguide is formed of a nonlinear optical material, an alignment treatment of the nonlinear optical compound may be performed in order to generate a second-order nonlinear optical activity of the nonlinear optical material. An electric field poling method is generally used as a method of aligning the nonlinear optical compound. The electric field poling method is a method in which an electric field is applied to a nonlinear optical material, and the nonlinear optical compound is oriented in the applied electric field direction by the Coulomb force between the dipole moment of the nonlinear optical compound and the applied electric field.

  In the electric field poling method, an electric field is usually applied in a state where the host material is heated to a temperature near the glass transition temperature of the host material and the molecular motion of the nonlinear optical compound is promoted. Therefore, in order to obtain a non-linear optical element that exhibits excellent non-linear optical performance, in addition to the non-linear optical compound having excellent non-linearity, it is required that the non-linear optical compound has heat resistance that does not change due to heating in the alignment treatment. Is done.

  Although the nonlinear optical compounds described in Patent Documents 1 to 5 have relatively high nonlinearity, the heat resistance is insufficient. The low heat resistance of these nonlinear compounds is presumed to be caused by the porin chain or thiophene ring in the π-conjugated chain. On the other hand, although the nonlinear optical compounds described in Patent Documents 6 to 8 have been improved in heat resistance, on the other hand, nonlinearity tends to be insufficient, and there is still room for improvement in this respect. It was.

  The present invention has been made in view of such a situation, and an object thereof is to provide a nonlinear optical compound that can achieve both nonlinearity and heat resistance at a sufficiently high level. Another object of the present invention is to provide a nonlinear optical material and a nonlinear optical element using the nonlinear optical compound.

The nonlinear optical compound according to the present invention is represented by the following general formula (1). In general formula (1), n represents an integer of 2 to 4, R ¹ represents an alkyl group having 1 to 4 carbon atoms, and n R ¹ in the same molecule may be the same or different from each other, p and q each independently represent an integer of 0 to 2, p + q is 2 or less, and Ar ¹ and Ar ² each independently represent a group represented by the following formula (2-a) or (2-b): As shown, when p + q is 2, Ar ¹ and Ar ² may be the same as or different from each other. D represents an electron donating group represented by the following formula (3). A represents an electron accepting group represented by the following formula (4). In the following formulas (2-a) and (2-b), m represents an integer of 0 to 4, h represents an integer of 0 to ^2, and R ² and R ³ each independently represent a halogen atom or a carbon number of 1 is alkyl or _-C x _H 2x ^oR 4 (x of 10 indicates an integer of 1 or more, ^{R 4} is a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, a substituent An aryl group having 6 to 10 carbon atoms that may have, a triorganosilyl group having 3 to 18 carbon atoms, an alkylacyl group having 2 to 11 carbon atoms that may have a substituent, or a substituent An arylacyl group having 7 to 11 carbon atoms which may be present), and m R ² in the formula (2-a) may be the same or different from each other, in the formula (2-b) H R ^{3 s} may be the same as or different from each other. In the following formula (3), R ⁵ and R ⁶ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or an optionally substituted group having 6 to 6 carbon atoms. 10 aryl groups are shown. In the following formula (4), R ⁷ and R ⁸ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, and an optionally substituted carbon atom having 6 to 6 carbon atoms. The C1-C12 heteroaryl group which may have a 10 aryl group or a substituent is shown.

The nonlinear optical compound according to the present invention includes a phenylene group in which a π-conjugated chain connecting the electron donating group D and the electron accepting group A has a plurality of substituents R ¹ as represented by the general formula (1). contains. According to the nonlinear optical compound of the present invention, both nonlinearity and heat resistance can be achieved at a sufficiently high level. The main reason why high nonlinearity is obtained is presumed to be that the predetermined electron donating group D and the electron accepting group A represented by the above formulas (3) and (4) are connected by a π-conjugated chain. On the other hand, the main reason why high heat resistance is obtained is presumed to be that the π-conjugated chain contains a phenylene group having a plurality of substituents R ¹ .

Examples of the nonlinear optical compound include nonlinear optical compounds in which R ¹ represents a methyl group in the general formula (1).

  Examples of the nonlinear optical compound include nonlinear optical compounds in which n is 2 in the general formula (1).

In the nonlinear optical compound according to the present invention, in the above formulas (2-a) and (2-b), R ² and R ³ are each independently a halogen atom, an alkyl group having 1 to 3 carbon atoms, or —CH ₂ OSiR ^9. ₃ (R ⁹ represents an alkyl group having 1 to 4 carbon atoms, a phenyl group, or an alkoxy group having 1 to 10 carbon atoms, and a plurality of R ⁹ in the same molecule may be the same or different from each other). Is preferred. The nonlinear optical compound has an advantage of being excellent in nonlinearity and being relatively easy to synthesize.

In the nonlinear optical compound according to the present invention, in the general formula (1), Ar ¹ and Ar ² preferably each independently represent a phenylene group or a thiophenediyl group. The nonlinear optical compound has an advantage of being excellent in nonlinearity and being relatively easy to synthesize.

In the nonlinear optical compound according to the present invention, in the above formula (3), R ⁵ and R ⁶ preferably each independently represent an alkyl group having 1 to 10 carbon atoms or a phenyl group, and the alkyl group and the phenyl group are substituted. As a group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or —OR ¹⁰ (R ¹⁰ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a carbon number. A 3-18 triorganosilyl group or an alkylacyl group having 2-11 carbon atoms). The nonlinear optical compound has an advantage that it is excellent in nonlinearity and compatibility with a host material and is relatively easy to synthesize.

In the nonlinear optical compound according to the present invention, the electron donating group represented by D in the general formula (1) is preferably a group represented by the following formula (5). In the following formula (5), j and k each independently represent an integer of 1 to 6, R ¹¹ and R ¹² are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or —OR ¹³ (R ¹³ is A hydrogen atom, a triorganosilyl group having 3 to 18 carbon atoms, or an alkylacyl group having 2 to 11 carbon atoms). The nonlinear optical compound has an advantage that it is excellent in nonlinearity and compatibility with a host material and is relatively easy to synthesize.

  Examples of the nonlinear optical compound include nonlinear optical compounds in which j and k are both 2 in the above formula (5).

In the nonlinear optical compound according to the present invention, the electron donating group represented by D in the general formula (1) is preferably a group represented by the following formula (6-a) or (6-b). In the following formulas (6-a) and (6-b), R ¹⁴ represents a hydrogen atom, a methyl group, an ethyl group or —OR ¹⁵ (R ¹⁵ represents a hydrogen atom, a t-butyldiphenylsilyl group, an acetyl group or a pivaloyl group. Show.) The nonlinear optical compound has an advantage that it is excellent in nonlinearity and compatibility with a host material and is relatively easy to synthesize.

In the nonlinear optical compound according to the present invention, in the above formula (4), R ⁷ and R ⁸ are each independently an alkyl group having 1 to 4 carbon atoms, a fluorinated alkyl group having 1 to 4 carbon atoms, or a substituent. It is preferable to show a phenyl group or a phenyl group or a thienyl group which may have a C1-C10 alkyl group. The nonlinear optical compound has an advantage that it is excellent in nonlinearity and compatibility with a host material and is relatively easy to synthesize.

In the nonlinear optical compound according to the present invention, in the above formula (4), it is preferable that R ⁷ and R ⁸ each independently represent an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a trifluoromethyl group. The nonlinear optical compound has an advantage that it is excellent in nonlinearity and compatibility with a host material and is relatively easy to synthesize.

  The nonlinear optical material according to the present invention contains the nonlinear optical compound of the present invention and a host material in which the nonlinear optical compound is dispersed. As described above, since the nonlinear optical compound of the present invention has high nonlinearity, the nonlinear optical material containing it can also achieve sufficiently high nonlinearity. In addition, since the nonlinear optical compound of the present invention has high heat resistance, it is possible to use a material having a relatively high glass transition temperature as a host material, thereby suppressing the orientational relaxation of the nonlinear compound subjected to electric field poling. A highly durable nonlinear optical material can be obtained.

  The nonlinear optical material according to the present invention contains a resin having a reactive functional group capable of forming a covalent bond between the host material and the nonlinear optical compound, and at least a part of the nonlinear optical compound is bonded to the resin. It is preferable that By combining the nonlinear optical compound and the resin, aggregation of the nonlinear optical compound can be sufficiently prevented, and deterioration of the nonlinear optical performance accompanying aggregation can be made difficult to occur. In addition, the durability of the nonlinear optical material can be further improved.

  The nonlinear optical element according to the present invention has an optical waveguide formed by the nonlinear optical material of the present invention. The nonlinear optical element according to the present invention exhibits excellent nonlinear optical performance. In addition, by forming the optical waveguide with a highly durable nonlinear optical material, a nonlinear optical element having a sufficiently high level of reliability and durability can be manufactured.

  The present invention provides a nonlinear optical compound that can achieve both nonlinearity and heat resistance at a sufficiently high level. In addition, according to the present invention, a nonlinear optical material and a nonlinear optical element using the nonlinear optical compound are provided.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings.

The nonlinear optical compound according to this embodiment is a nonlinear optical compound represented by the following general formula (1). In general formula (1), n represents an integer of 2 to 4, R ¹ represents an alkyl group having 1 to 4 carbon atoms, and n R ¹ in the same molecule may be the same or different from each other, p and q each independently represent an integer of 0 to 2, p + q is 2 or less, and Ar ¹ and Ar ² each independently represent a group represented by the following formula (2-a) or (2-b): As shown, when p + q is 2, Ar ¹ and Ar ² may be the same as or different from each other. D represents an electron donating group represented by the following formula (3). A represents an electron accepting group represented by the following formula (4). In the following formulas (2-a) and (2-b), m represents an integer of 0 to 4, h represents an integer of 0 to ^2, and R ² and R ³ each independently represent a halogen atom or a carbon number of 1 is alkyl or _-C x _H 2x ^oR 4 (x of 10 indicates an integer of 1 or more, ^{R 4} is a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, a substituent An aryl group having 6 to 10 carbon atoms that may have, a triorganosilyl group having 3 to 18 carbon atoms, an alkylacyl group having 2 to 11 carbon atoms that may have a substituent, or a substituent And m R ² in the formula may be the same as or different from each other, and h R ³ in the formula may be the same as each other. It may be different. In the following formula (3), R ⁵ and R ⁶ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or an optionally substituted group having 6 to 6 carbon atoms. 10 aryl groups are shown. In the following formula (4), R ⁷ and R ⁸ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, and an optionally substituted carbon atom having 6 to 6 carbon atoms. The C1-C12 heteroaryl group which may have a 10 aryl group or a substituent is shown.

In the general formula (1), when p is 0, it indicates that D and a phenylene group having a plurality of substituents R ¹ are directly bonded. Also shows when q is 0, and A, and a double bond to bond to phenylene group having a plurality of substituents R ¹ is the direct bond. That is, the compound in which p and q are 0 represents a compound represented by the following formula (8). In the formula (8), D represents the electron donor, and A represents the electron acceptor.

The nonlinear optical compound according to the present embodiment includes an electron donor represented by D in the general formula (1), an electron acceptor represented by A, and a π-conjugated chain that connects them, and the π-conjugated chain includes A phenylene group having a plurality of substituents R ¹ is included.

Here, the π-conjugated chain means a partial structure represented by the following formula (9) in the nonlinear optical compound. In formula (9), n represents an integer of 2 to 4, R ¹ represents an alkyl group having 1 to 4 carbon atoms, and n R ¹ in the same molecule may be the same or different from each other, p And q each independently represents an integer of 0 to 2, p + q is 2 or less, and Ar ¹ and Ar ² each independently represent a group represented by the above formula (2-a) or (2-b). , P + q is 2, Ar ¹ and Ar ² may be the same or different from each other.

The nonlinear optical compound can achieve both nonlinearity and heat resistance at a sufficiently high level by including a phenylene group in which the π-conjugated chain has a plurality of substituents R ¹ .

Examples of R ¹ include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Of these, R ¹ is preferably a methyl group from the viewpoint of relatively easy synthesis.

The phenylene group having a plurality of the substituents R ^1, from the viewpoint of relatively easy synthesis, a phenylene group is preferable to have two substituents R ^1.

In the π-conjugated chain, Ar ¹ and Ar ² each independently represent a group represented by the above formula (2-a) or (2-b), and when p + q is 2, Ar ¹ and Ar ² are the same as each other But it can be different. For example, in the case of a π-conjugated chain in which p is 2 and q is 0, the two Ar ¹ in the π-conjugated chain may be the same as or different from each other. In the case of a π-conjugated chain in which p is 0 and q is 2, two Ar ² in the π-conjugated chain may be the same as or different from each other.

The group represented by the formula ^{(2-a), R} 2 is a halogen atom, an alkyl group or _{^{-C x H 2x OR 9 3 (}} x from 1 to 3 carbon atoms is an integer of 1 to 10, R ⁹ represents an alkyl group having 1 to 4 carbon atoms, a phenyl group, or an alkoxy group having 1 to 10 carbon atoms, and a plurality of R ⁹ in the same molecule may be the same or different from each other. More preferably, R ² represents an alkyl group having 1 to 3 carbon atoms. Non-linear optical compounds in which Ar ¹ and / or Ar ² are these groups have the advantages of being more excellent in non-linearity and heat resistance and being relatively easy to synthesize.

The group represented by the formula (2-b), ^{R 3} is a halogen atom, an alkyl group or _{^{-C x H 2x SiR 9 3 (}} x from 1 to 3 carbon atoms is an integer of 1 to 10, R ⁹ represents an alkyl group having 1 to 4 carbon atoms, a phenyl group, or an alkoxy group having 1 to 10 carbon atoms, and a plurality of R ⁹ in the same molecule may be the same or different from each other. Non-linear optical compounds in which Ar ¹ and / or Ar ² are these groups have advantages that they are more excellent in non-linearity and compatibility with a host material and are relatively easy to synthesize.

The formula (2-a), in _(2-b), the group represented by -CH 2 OSiR ⁹ _3, ^{R 9} is a methyl group, an ethyl group, normal propyl group, an isopropyl group, normal butyl group, isobutyl A group showing a group, sec-butyl group, tert-butyl group or phenyl group is preferred. Incidentally, a plurality in the same molecule R ⁹ may be the same or different.

A nonlinear optical compound in which Ar ¹ and Ar ² in the π-conjugated chain each independently represent a phenylene group or a thiophenediyl group is preferable from the viewpoint of being excellent in nonlinearity and being relatively easy to synthesize.

The nonlinear optical compound according to the present invention is a nonlinear optical compound represented by the above general formula (1). In the general formula (1), D represents an electron donating group represented by the following formula (3). In formula (3), R ⁵ and R ⁶ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or an optionally substituted carbon group having 6 to 10 carbon atoms. An aryl group of

In formula (3), the alkyl group having 1 to 10 carbon atoms represented by R ⁵ and R ⁶ includes a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a tert-butyl group, and a normal hexyl group. , 2-ethylhexyl group, cyclohexyl group, adamantyl group and the like. Examples of the aryl group having 6 to 10 carbon atoms represented by R ⁵ and R ⁶ include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. These may have one or more substituents. When the group represented by R ⁵ and / or R ⁶ is a phenyl group, the phenyl group preferably has a substituent containing an oxygen atom.

  Examples of such electron donating groups include electron donating groups used in known push-pull type π-conjugated compounds. Examples of the electron donating group used in the known push-pull type π-conjugated compound include an electron donating group selected from the functional group represented by the following formula (10).

In the electron donating group, in formula (3), it is preferable that R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 10 carbon atoms or a phenyl group, and the alkyl group and the phenyl group have a carbon number as a substituent. An alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or —OR ¹⁰ (R ¹⁰ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkyl group having 3 to 18 carbon atoms. A triorganosilyl group or an alkylacyl group having 2 to 11 carbon atoms). The nonlinear optical compound has an advantage that it is excellent in nonlinearity and compatibility with a host material and is relatively easy to synthesize.

In the above formula (3), examples of the alkyl group having 1 to 10 carbon atoms represented by R ¹⁰ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a normal butyl group, a tert-butyl group, a normal hexyl group, Examples include 2-ethylhexyl group, cyclohexyl group, adamantyl group and the like. Examples of the aryl group having 6 to 10 carbon atoms represented by R ¹⁰ include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. Examples of the triorganosilyl group having 3 to 18 carbon atoms represented by R ¹⁰ include a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, a tert-butyldimethylsilyl group, and a tert-butyldiphenylsilyl group. Examples of the alkyl acyl group having 2 to 11 carbon atoms represented by R ¹⁰ include an acetyl group, an ethylcarbonyl group, a propylcarbonyl group, an isopropylcarbonyl group, a normal butylcarbonyl group, a sec-butylcarbonyl group, a tert-butylcarbonyl group, and the like. Is mentioned.

The electron donating group is more preferably a group represented by the following formula (5). In formula (5), j and k each independently represent an integer of 1 to 6, R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or —OR ¹³ (R ¹³ represents hydrogen An atom, a triorganosilyl group having 3 to 18 carbon atoms, or an alkylacyl group having 2 to 11 carbon atoms). The nonlinear optical compound has an advantage that it is excellent in nonlinearity and compatibility with a host material and is relatively easy to synthesize.

In the above formula (3), the triorganosilyl group having 3 to 18 carbon atoms represented by R ¹³ is a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, a tert-butyldimethylsilyl group, or a tert-butyldiphenylsilyl group. Etc. Examples of the alkyl acyl group having 2 to 11 carbon atoms represented by R ¹³ include acetyl group, ethylcarbonyl group, propylcarbonyl group, isopropylcarbonyl group, normal butylcarbonyl group, sec-butylcarbonyl group, tert-butylcarbonyl group, and the like. Can be mentioned.

  As such an electron-donating group, an electron-donating group in which both j and k in the above formula (5) are 2 can be suitably used from the viewpoint that synthesis is relatively easy.

Furthermore, the electron donating group is a group represented by the following formula (6-a) or (6-b) from the viewpoint of being more excellent in nonlinearity and compatibility with the host material and being easier to synthesize. It is preferable that In the following formulas (6-a) and (6-b), R ¹⁴ represents a hydrogen atom, a methyl group, an ethyl group or —OR ¹⁵ (R ¹⁵ represents a hydrogen atom, a t-butyldiphenylsilyl group, an acetyl group or a pivaloyl group. Show.)

The nonlinear optical compound according to the present invention is a nonlinear optical compound represented by the above general formula (1). In the general formula (1), A represents an electron accepting group represented by the following formula (4). In the following formula (4), R ⁷ and R ⁸ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, and an optionally substituted carbon atom having 6 to 6 carbon atoms. The C1-C12 heteroaryl group which may have a 10 aryl group or a substituent is shown.

In the formula (4), the alkyl group having 1 to 10 carbon atoms represented by ^{R 7} and ^{R 8,} methyl group, ethyl group, n- propyl group, an isopropyl group, normal butyl group, tert- butyl group, normal Examples include a hexyl group, a 2-ethylhexyl group, a cyclohexyl group, and an adamantyl group. Examples of the aryl group having 6 to 10 carbon atoms represented by R ⁷ and R ⁸ include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. Examples of the heteroaryl group having 1 to 12 carbon atoms represented by R ⁷ and R ⁸ include a furyl group, a thienyl group, a pyrrolyl group, an oxazolyl group, a pyridyl group, a quinolinyl group, and a carbazolyl group. These may have one or more substituents.

  Examples of such electron accepting groups include electron accepting groups used in known push-pull type π-conjugated compounds. As an electron-accepting group used for a well-known push-pull type (pi) conjugated compound, the electron-accepting group chosen from the functional group group shown to following formula (11) etc. is mentioned, for example.

In the above formula (4), R ⁷ and R ⁸ are each independently an alkyl group having 1 to 4 carbon atoms, a fluorinated alkyl group having 1 to 4 carbon atoms, or a phenyl group or 1 to 10 carbon atoms as a substituent. It is preferable to show a phenyl group or a thienyl group optionally having an alkyl group, and it is more preferable that each independently represents an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a trifluoromethyl group. Such a nonlinear optical compound having an electron-accepting group is advantageous in that it is excellent in nonlinearity and compatibility with a host material and is relatively easy to synthesize.

  The nonlinear optical compound can be synthesized, for example, as follows.

  As an example of a method for synthesizing the nonlinear optical compound, 2- [3-cyano-4- [2- [5- [2- [4- [2- [4- (dibutylamino]] represented by the following formula (VII): Synthesis examples of) phenyl] vinyl] -2,5-dimethylphenyl] vinyl] -2-thienyl] vinyl] -5,5-dimethyl-2 (5H) -furanylidene] propanedinitrile are shown below.

  According to the reaction scheme represented by the following formula (7-1), 4- [2- [4- (dibutylamino) phenyl] vinyl] -2,5-dimethylbenzyl alcohol is synthesized.

  Specifically, for example, 0.7 g (8.5 mmol) of phenyl lithium is added to 30 ml of tetrahydrofuran under a stream of argon, and further 1.8 g (3 of 4- (hydroxymethyl) -2,5-dimethylbenzyltriphenylphosphonium bromide). .66 mmol) is added. After stirring, 0.86 g (3.68 mmol) of 4- (dibutylamino) benzaldehyde is added. After stirring for 1 hour, pour into 150 ml of water and extract with toluene. The extract solution is washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated. The residue is purified by silica gel column chromatography to give 4- [2- [4- (dibutylamino) phenyl] vinyl] -2,5-dimethylbenzyl alcohol.

  Next, 4- [2- [4- (dibutylamino) phenyl] vinyl] -2,5-dimethylbenzaldehyde is synthesized according to the reaction scheme represented by the following formula (7-2).

  Specifically, 4- [2- [4- (dibutylamino) phenyl] vinyl]-in which 3.86 g (44.4 mmol) of active manganese dioxide is suspended in 30 ml of dichloromethane and dissolved in 20 ml of dichloromethane with stirring is used. 805 mg (2.2 mmol) of 2,5-dimethylbenzyl alcohol are added. The mixture is stirred at room temperature for 22 hours, filtered, and concentrated. The residue is purified by silica gel column chromatography to give 4- [2- [4- (dibutylamino) phenyl] vinyl] -2,5-dimethylbenzaldehyde.

  Next, according to the reaction scheme represented by the following formula (7-3), N, N-dibutyl-N- [4- [2- [2,5-dimethyl-4- [2- (2-thienyl) vinyl] Synthesize [phenyl] vinyl] phenylamine.

  Specifically, for example, 0.2 g (2.26 mmol) of phenyl lithium is added to 15 ml of tetrahydrofuran under a stream of argon, and 0.78 g (1.98 mmol) of tenenyltriphenylphosphonium chloride is added while cooling. After stirring, 0.72 g (1.98 mmol) of 4- [2- [4- (dibutylamino) phenyl] vinyl] -2,5-dimethylbenzaldehyde is dissolved in 3 ml of tetrahydrofuran and added dropwise. After stirring for 1.5 hours, it is poured into 70 ml of water and extracted with toluene. Wash with saturated brine, dehydrate with anhydrous sodium sulfate, and concentrate. The residue was purified by silica gel column chromatography to obtain N, N-dibutyl-N- [4- [2- [2,5-dimethyl-4- [2- (2-thienyl) vinyl] phenyl] vinyl] phenyl. An amine is obtained.

  Next, according to the reaction scheme represented by the following formula (7-4), 5- [2- [4- [2- [4- (dibutylamino) phenyl] vinyl] -2,5-dimethylphenyl] vinyl] Synthesize thiophene-2-carbaldehyde.

  Specifically, for example, N, N-dibutyl-N- [4- [2- [2,5-dimethyl-4- [2- (2-thienyl) vinyl] phenyl] vinyl] is added to 10 ml of tetrahydrofuran under an argon stream. 600 mg (1.35 mmol) of phenylamine is dissolved, and 1.27 ml (2.03 mmol) of n-butyllithium (1.6 M hexane solution) is added dropwise under cooling. After stirring for 1 hour, 0.13 ml (1.69 mol) of N, N-dimethylformamide is added dropwise and stirred. The temperature is raised slowly, water is injected, the mixture is extracted with ethyl acetate, washed with saturated brine, and dehydrated over anhydrous sodium sulfate. After concentration, the residue was purified by silica gel column chromatography to obtain 5- [2- [4- [2- [4- (dibutylamino) phenyl] vinyl] -2,5-dimethylphenyl] vinyl] thiophene-2. -Carbaldehyde is obtained.

  Next, according to the reaction scheme represented by the following formula (7-5), 2- [3-cyano-4- [2- [5- [2- [4- [2- [4- (dibutylamino) phenyl] ] Vinyl] -2,5-dimethylphenyl] vinyl] -2-thienyl] vinyl] -5,5-dimethyl-2 (5H) -furanylidene] propanedinitrile is synthesized.

  Specifically, for example, 5- [2- [4- [2- [4- (dibutylamino) phenyl] vinyl] -2,5-dimethylphenyl] vinyl] thiophene-2-carbaldehyde in ethanol (200 mg (0 .424 mmol). To this, 90 mg (0.452 mmol) of 2- (3-cyano-4,5,5-trimethyl-2 (5H) -furanylidene] propanedinitrile and 33 mg (0.428 mmol) of ammonium acetate are added and stirred at room temperature. The black liquid was filtered and washed with a small amount of ethanol to purify 274 mg of crystals by silica gel column chromatography, and the resulting crystals were washed with ethanol to give 2- [3-cyano-4- [2- [ 5- [2- [4- [2- [4- (Dibutylamino) phenyl] vinyl] -2,5-dimethylphenyl] vinyl] -2-thienyl] vinyl] -5,5-dimethyl-2 (5H) -Furanylidene] propanedinitrile is obtained.

  The nonlinear optical material according to this embodiment contains the nonlinear optical compound and a host material in which the nonlinear optical compound is dispersed. In order for the nonlinear optical material to have excellent nonlinearity, it is preferable that the nonlinear optical compound is uniformly dispersed at a high concentration in the host material. From this viewpoint, the host material preferably exhibits high compatibility with the nonlinear optical compound.

  Examples of the host material include resins such as polymethyl methacrylate, polycarbonate, polystyrene, silicone resin, epoxy resin, polysulfone, polyethersulfone, and polyimide. These resins are preferable because they are excellent in compatibility with a nonlinear optical compound and are excellent in transparency and moldability when used as a nonlinear optical element.

  Examples of the dispersion method for the host material include, for example, a nonlinear optical material in which a nonlinear optical compound and a host material are dissolved in an organic solvent at an appropriate mixing ratio, and then applied onto a substrate by spin coating and heat treatment is performed. Examples include a method for obtaining a thin film.

  As the nonlinear optical material, the host material contains a resin having a reactive functional group capable of forming a covalent bond with the nonlinear optical compound, and at least a part of the nonlinear optical compound binds to the resin. You may do it. Such a nonlinear optical material can disperse the nonlinear optical compound in the host material at a high density, and can realize high nonlinearity.

Examples of the reactive functional group include a halogenated alkyl group (—C _n H _2n X (n represents an integer of 1 or more, X represents a halogen atom), a halogenated acyl group, an alkoxycarbonyl group, an aryloxy group. Examples of the functional group include a carbonyl group, a hydroxy group, an amino group, an isocyanate group, an epoxy group, and a carboxyl group, such as a hydroxy group, an amino group, and an alkoxycarbonyl group in the nonlinear optical compound. It can react to form a covalent bond.

  The nonlinear optical element according to this embodiment is manufactured using the nonlinear optical material. By using a nonlinear optical material excellent in nonlinearity and heat resistance, a nonlinear optical element having excellent optical performance and excellent durability that can withstand long-term use can be obtained.

  FIG. 1 is a schematic cross-sectional view showing an optical waveguide constituting an arm of a Mach-Zehnder modulator. In the optical waveguide 10 shown in the figure, a lower electrode 2, a first cladding layer 3, a core layer 5, a second cladding layer 6 and an upper electrode 8 are laminated in this order from the substrate 1 side. In this optical waveguide 10, the core layer 5 is formed of the nonlinear optical material subjected to the electric field poling process, the optical waveguide core 9 is formed by reactive ion etching or the like, and constitutes a Mach-Zehnder interferometer. Yes. When an electric field is applied by the lower electrode 2 and the upper electrode 8, the refractive index of the core layer 5 located between these electrodes changes, so that the phase difference between the Mach-Zehnder arms changes, and the propagating light is transmitted. The intensity can be modulated.

  The first clad layer 3 and the second clad layer 6 are not particularly limited as long as the refractive index is lower than that of the core layer 5. For example, UV-curing or thermosetting such as acrylic, epoxy-based, or silicone-based. Resin, organic-inorganic composite sol-gel curable materials such as polyimide and glass, silicon oxide and the like can be suitably used. The lower electrode 2 is a conductive film made of a metal, a conductive oxide film, a conductive organic polymer, or the like, and is used as an electrode at the time of polling or operation as an element. The upper electrode 8 is an electrode for applying an input electric signal.

  Here, an example in which the optical waveguide 10 constitutes a Mach-Zehnder modulator is shown, but the present invention is not limited to the Mach-Zehnder type, and may be another type (for example, a directional coupler type). In addition, the nonlinear optical element according to the present invention is not limited to a modulator, and may be anything provided with an optical waveguide formed of the above nonlinear optical material. For example, an optical switch, an optical memory, a wavelength converter Etc.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

[Example 1]
In this example, 2- [3-cyano-4- [2- [4- [2- [4- [2- [4- (dibutylamino) phenyl] vinyl]] represented by the following formula (I) was used. [Phenyl] vinyl] -2,5-dimethylphenyl] vinyl] -5,5-dimethyl-2 (5H) -furanylidene] propanedinitrile is subjected to the following synthesis examples (1-1) to (1-11). Was obtained by

(Synthesis Example 1-1)
According to the reaction scheme represented by the following formula (1-1), 4-bromomethylbenzyl alcohol was synthesized.

Specifically, 5.0 g (36.2 mmol) of p-xylene glycol and 12.4 g (37.4 mmol) of carbon tetrachloride were dissolved in tetrahydrofuran. The solution was cooled and 9.8 g (37.4 mmol) of triphenylphosphine was added with stirring. After stirring, 80 mL of hexane was added to the reaction solution, and the supernatant was concentrated under reduced pressure. Purified by silica gel column chromatography. 2.89 g of 4-bromomethylbenzyl alcohol was obtained as colorless crystals (yield 39.6%).
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 4.50 (2H, s), 4.70 (2H, s), 7.35 (2H, d, J = 8.2 Hz), 7.40 (2H , D, J = 8.2 Hz)
¹³ C-NMR (600 MHz, CDCl ₃ ) δ: 33.2, 64.8, 127.2, 129.2, 137.1, 141.1

(Synthesis Example 1-2)
According to the reaction scheme represented by the following formula (1-2), 4- (hydroxymethyl) benzyltriphenylphosphonium bromide was synthesized.

Specifically, 2.01 g (0.01 mol) of 4- (bromomethyl) benzyl alcohol and 2.62 g (0.01 mol) of triphenylphosphine were added to 30 mL of acetonitrile, and the mixture was stirred for 6 hours on a 60 ° C. oil bath. The crystals reprecipitated when heated were collected by filtration, washed with acetonitrile and dried. 4.57 g of 4- (hydroxymethyl) benzyltriphenylphosphonium bromide was obtained as colorless crystals. (Yield 98.6%)
¹ H-NMR (600 MHz, DMSO-d ₆ ) δ: 4.43 (2H, d, J = 1.6 Hz), 5.14 (2H, d, J = 15.4 Hz), 5.17 (1H, t, J = 5.5 Hz), 6.92 (2H, d, J = 8.2 Hz), 7.16 (2H, d, J = 7.7 Hz), 7.65-7.68 (6H, m ), 7.73-7.76 (6H, m), 7.90-7.92 (3H, m)
¹³ C-NMR (600 MHz, DMSO-d ₆ ) δ: 27.8, 62.2, 117.5, 118.1, 126.6, 130.5, 130.0, 134.0, 135.0, 142.9

(Synthesis Example 1-3)
Diethyl 2,5-dimethylterephthalate was synthesized according to the reaction scheme represented by the following formula (1-3).

Specifically, 20.0 g (0.103 mol) of 2,5-dimethylterephthalic acid was suspended in ethanol, 2 mL of concentrated sulfuric acid was added, and the mixture was stirred for 100 hours under reflux and then concentrated with ice cooling to filter the precipitated crystals. Taken, washed with cold ethanol and dried. 22.43 g of diethyl 2,5-dimethylterephthalate was obtained as colorless needle crystals. The mother liquor was again stirred under reflux, concentrated and ice-cooled. The precipitated crystals were collected by filtration and washed with cold ethanol to obtain 2.70 g of crystals. Total yield 25.13 g (97.5% yield)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.40 (6H, t, J = 7.2 Hz), 2.57 (6H, s), 4.37 (4H, q, J = 7.2 Hz) , 7.74 (2H, s)
¹³ C-NMR (600 MHz, CDCl ₃ ) δ: 14.4, 21.0, 61.1, 132.8, 133.5, 136.9, 167.3

(Synthesis Example 1-4)
According to the reaction scheme represented by the following formula (1-4), 4- (hydroxymethyl) -2,5-dimethylbenzyl alcohol was synthesized.

Specifically, 5.7 g (0.15 mol) of lithium aluminum hydride was added to tetrahydrofuran under an argon atmosphere. Under cooling, 25.13 g (0.1 mol) of diethyl 2,5-dimethylterephthalate was added dropwise. The mixture was stirred at room temperature for 1 hour and then cooled on ice. After stirring for 15 minutes, the mixture was filtered, and the back solution and the washing solution washed with tetrahydrofuran were combined and concentrated. The mixture was cooled with ice, and the precipitated crystals were collected by filtration and recrystallized from 400 mL of ethyl acetate. 14.92 g of 4- (hydroxymethyl) -2,5-dimethylbenzyl alcohol was obtained as colorless crystals. The mother liquor was concentrated and ice-cooled to obtain 1.28 g. Total yield 16.2 g (97.1% yield)
¹ H-NMR (600 MHz, DMSO-d ₆ ) δ: 2.20 (6H, s) 4.43 (4H, d, J = 5.5 Hz), 4.92 (2H, t, J = 5.5 Hz) ), 7.08 (2H, s)
¹³ C-NMR (600 MHz, DMSO-d ₆ ) δ: 17.8, 60.9, 128.5, 131.7, 138.2

(Synthesis Example 1-5)
According to the reaction scheme represented by the following formula (1-5), 4- (bromomethyl) -2,5-dimethylbenzyl alcohol was synthesized.

Specifically, 7.0 g (42.1 mmol) of 4- (hydroxymethyl) -2,5-dimethylbenzyl alcohol and 15.36 g (46.3 mmol) of carbon tetrachloride were dissolved in tetrahydrofuran. While maintaining ice cooling, 12.15 g (46.3 mmol) of triphenylphosphine was added. Tetrahydrofuran was distilled off, and the residue was purified by silica gel column chromatography to obtain 1.6 g of 4- (bromomethyl) -2,5-dimethylbenzyl alcohol as colorless crystals. (Yield 16.6%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 2.30 (3H, s), 2.38 (3H, s), 4.49 (2H, s), 4.66 (2H, d, J = 5) .5 Hz), 7.12, (1H, s), 7.19 (1H, s)
¹³ C-NMR (600 MHz, CDCl ₃ ) δ: 18.0, 18.2, 32.1, 63.1, 130.0, 131.9, 133.9, 134.8, 135.0, 139. 4

(Synthesis Example 1-6)
According to the reaction scheme represented by the following formula (1-6), 4- (hydroxymethyl) -2,5-dimethylbenzyltriphenylphosphonium bromide was synthesized.

Specifically, 4- (bromomethyl) -2,5-dimethylbenzyl alcohol 1.19 g (5.2 mmol) and 1.37 g (5.15 mmol) of triphenylphosphine were added to 25 mL of acetonitrile, and the mixture was stirred at 60 ° C. After cooling, the precipitated crystals were collected by filtration, washed with acetonitrile, and dried. 1.94 g of 4- (hydroxymethyl) -2,5-dimethylbenzyltriphenylphosphonium bromide was obtained as colorless crystals. The filtrate was concentrated and ice-cooled to obtain 0.24 g of crystals. Total yield 2.18 g (yield 85.4%)
¹ H-NMR (600 MHz, DMSO-d ₆ ) δ: 1.63 (3H, s), 1.93 (3H, s), 4.40 (2H, dd, J = 2.2 Hz, 5.5 Hz) 4.96 (2H, d, J = 24.8 Hz), 5.06 (1 H, t, J = 5.5 Hz), 6.06 (1 H, d, J = 2.2 Hz), 7.09 ( 1H, s), 7.61-7.65 (6H, m), 7.72-7.77 (6H, m), 7.91-7.947 (3H, m)
¹³ C-NMR (600 MHz, DMSO-d ₆ ) δ: 18.1, 19.0, 26.5, 26.8, 61.1, 118.0, 118.6, 124.2, 129.8, 130.6, 132.9, 134.6, 135.7, 136.0, 141.3

(Synthesis Example 1-7)
According to the reaction scheme represented by the following formula (1-7), 4- [2- [4- (dibutylamino) phenyl] vinyl] benzyl alcohol was synthesized.

Specifically, 1.52 g (18.09 mmol) of phenyllithium was added to 40 mL of tetrahydrofuran under an argon stream, and 3.81 g (8.22 mmol) of 4- (hydroxymethyl) benzyltriphenylphosphonium bromide was added while cooling. . After stirring at the same temperature, 2.0 g (8.57 mmol) of 4- (dibutylamino) benzaldehyde was added. The mixture was stirred at the same temperature for 1 hour, added to 250 mL of water, and extracted with toluene. The extract was washed with saturated brine and dehydrated with anhydrous sodium sulfate. Toluene was distilled off and the residue was purified by silica gel column chromatography to obtain 2.37 g of 4- [2- [4- (dibutylamino) phenyl] vinyl] benzyl alcohol as a yellow liquid. (Yield 85.5%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 0.96 (6H, t, J = 7.7 Hz), 1.33-1.39 (4H, m), 1.55-1.60 (4H, m), 3.28 (4H, t, J = 7.7 Hz), 4.66 (2H, d, J = 4.9 Hz), 6.62 (2H, d, J = 8.8 Hz), 6. 86 (1H, d, J = 16.5 Hz), 7.02 (1 H, d, J = 16.5 Hz), 7.31 (2H, d, J = 8.3 Hz), 7.37 (2H, d , J = 8.8 Hz), 7.45 (2H, d, J = 8.3 Hz)
¹³ C-NMR (600 MHz, CDCl ₃ ) δ: 14.0, 20.3, 29.5, 50.8, 65.3, 111.6, 123.2, 124.1, 126.1, 127. 4,127.7,129.0,138.0,139.2,148.0

(Synthesis Example 1-8)
According to the reaction scheme represented by the following formula (1-8), 4- [2- [4- (dibutylamino) phenyl] vinyl] benzaldehyde was synthesized.

Specifically, 6.0 g (69.0 mmol) of active manganese dioxide was suspended in 30 mL of dichloromethane, and 1.165 g (3.45 mmol) of 4- [2- [4- (dibutylamino) phenyl] vinyl] benzyl alcohol was suspended. Was dissolved in 20 mL of dichloromethane and added. After stirring at room temperature, the mixture was filtered, the solvent was distilled off, and the residue was purified twice by silica gel column chromatography. 742 mg of 4- [2- [4- (dibutylamino) phenyl] vinyl] benzaldehyde was obtained as yellow crystals. (Yield 64.1%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 0.97 (6H, t, J = 7.7 Hz), 1.34-1.40 (4H, m), 1.56-1.62 (4H, m), 3.30 (4H, t, J = 7.7 Hz), 6.63 (2H, d, J = 8.2 Hz), 6.89 (1H, d, J = 15.9 Hz), 7. 19 (1H, d, J = 15.9 Hz), 7.40 (2H, d, J = 8.8 Hz), 7.59 (2H, d, J = 8.3 Hz), 7.82 (2H, d , J = 8.3 Hz), 9.95 (1H, s)
¹³ C-NMR (600 MHz, CDCl ₃ ) δ: 14.0, 20.3, 29.5, 50.8, 111.6, 122.0, 123.5, 126.1, 128.4, 130. 2,132.7, 134.4, 144.8, 148.5, 191.6

(Synthesis Example 1-9)
According to the reaction scheme represented by the following formula (1-9), 4- [2- [4- [2- [4- (dibutylamino) phenyl] vinyl] phenyl] vinyl] -2,5-dimethylbenzyl alcohol is used. Synthesized.

Specifically, 0.37 g (4.38 mmol) of phenyllithium was added to 15 mL of tetrahydrofuran under an argon stream, and 0.94 g (1) of 4- (hydroxymethyl) -2,5-dimethylbenzyltriphenylphosphonium bromide while cooling. .9 mmol) was added. After stirring, 0.64 g (1.9 mmol) of 4- [2- [4- (dibutylamino) phenyl] vinyl] benzaldehyde was added. After stirring for 1 hour, the mixture was added to 100 mL of water and extracted with toluene. The extract was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated. The residue was purified by silica gel column chromatography, and 4- [2- [4- [2- [4- (dibutylamino) phenyl] vinyl] phenyl] vinyl] -2,5-dimethylbenzyl alcohol as yellow crystals. 806 mg was obtained. (Yield 60.6%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 0.96 (6H, t, J = 7.7 Hz), 1.33-1.40 (4H, m), 1.56-1.61 (4H, m), 2.36 (3H, s), 2.41 (3H, s), 3.29 (4H, t, J = 7.7 Hz), 4.67 (2H, d, J = 5.5 Hz) , 6.63 (2H, d, J = 8.8 Hz), 6.87 (1 H, d, J = 16.5 Hz), 6.99 (1 H, d, J = 15.9 Hz), 7.05 (1H, d, J = 15.9 Hz), 7.16 (1 H, s), 7.28 (1 H, d, J = 16.5 Hz), 7.38 (2 H, d, J = 8.8 Hz) 7.42 (1H, s), 7.45 (2H, d, J = 8.8 Hz), 7.48 (2H, d, J = 8.8 Hz)
¹³ C-NMR (600 MHz, CDCl ₃ ) δ: 14.0, 18.3, 19.4, 20.3, 29.5, 50.8, 63.4, 111.7, 123.2, 124. 5, 125.3, 126.2, 126.8, 127.2, 127.8, 128.9, 129.6, 129.9, 133.4, 133.7, 135.86, 135.91, 137.8, 147.9

(Synthesis Example 1-10)
According to the reaction scheme represented by the following formula (1-10), 4- [2- [4- [2- [4- (dibutylamino) phenyl] vinyl] phenyl] vinyl] -2,5-dimethylbenzaldehyde is synthesized. did.

4- [2- [4- [2- [4- (Dibutylamino) phenyl] vinyl] phenyl] vinyl] -2,5-dimethylbenzyl alcohol (467 mg, 1.0 mmol) was dissolved in 30 ml of dichloromethane, and activated dioxide. 1.74 g (20.0 mmol) of manganese was added. After stirring at room temperature, the mixture was filtered and the solvent was distilled off. The resulting residue was purified by silica gel column chromatography. 390 mg of 4- [2- [4- [2- [4- (dibutylamino) phenyl] vinyl] phenyl] vinyl] -2,5-dimethylbenzaldehyde was obtained as an orange oil. (Yield 83.9%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 0.96 (6H, t, J = 7.7 Hz), 1.33-1.40 (4H, m,), 1.56-1.61 (4H M), 2.46 (3H, s,), 2.66 (3H, s), 3.29 (4H, t, J = 7.7 Hz), 6.63 (2H, d, J = 8. 8 Hz), 6.88 (1 H, d, J = 15.9 Hz), 7.07 (1 H, d, J = 15.9 Hz), 7.13 (1 H, d, J = 15.9 Hz), 7 .27 (1H, d, J = 15.9 Hz), 7.38 (2H, d, J = 8.8 Hz), 7.47 (2H, d, J = 8.2 Hz), 7.48 (1H, s,), 7.50 (2H, d, J = 8.2 Hz), 7.60 (1H, s), 10.21 (1H, s)
¹³ C-NMR (600 MHz, CDCl ₃ ) δ: 14.0, 19.2, 19.3, 20.3, 29.5, 50.8, 111.7, 123.0, 124.2, 124. 3, 126.3, 127.2, 127.9, 128.2, 129.5, 132.6, 132.8, 133.6, 134.1, 135.1, 138.1, 138.7, 141.8, 148.0, 192.2

(Synthesis Example 1-11)
Therefore, 2- [3-cyano-4- [2- [4-[-2- [4- [2- [4- (dibutylamino) phenyl] vinyl] is represented by the reaction scheme represented by the following formula (1-11). ] Phenyl] vinyl] -2,5-dimethylphenyl] vinyl] -5,5-dimethyl-2 (5H) -furanylidene] propanedinitrile was synthesized.

Specifically, 190 mg (0.408 mmol) of 4- [2- [4- [2- [4- (dibutylamino) phenyl] vinyl] phenyl] vinyl] -2,5-dimethylbenzaldehyde was dissolved in ethanol. 2- (3-Cyano-4,5,5-trimethyl-2 (5H) -furanylidene] propanedinitrile (92 mg, 0.462 mmol) was added thereto, and the mixture was stirred at room temperature for 18 hours. After washing with a small amount of ethanol and then with ether, 248 mg of black crystals were purified by silica gel column chromatography, and 2- [3-cyano-4- [2- [4- [2- [4- [2- [4- ( 229 mg of dibutylamino) phenyl] vinyl] phenyl] vinyl] -2,5-dimethylphenyl] vinyl] -5,5-dimethyl-2 (5H) -furanylidene] propanedinitrile as black crystals at mp 250-251 ° C. (Yield 86.7%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 0.97 (6H, t, J = 7.7 Hz), 1.34-1.40 (4H, m), 1.57-1.63 (4H, m), 1.80 (6H, s), 2.48 (3H, s), 2.50 (3H, s), 3.30 (4H, t, J = 7.7 Hz), 6.64 (2H) , D, J = 8.8 Hz), 6.88 (1H, d, J = 16.5 Hz), 6.93 (1H, d, J = 15.9 Hz), 7.08 (1H, d, J = 16.5 Hz), 7.15 (1 H, d, J = 15.9 Hz) 7.28 (1 H, d, J = 15.9 Hz), 7.39 (2 H, d, J = 8.8 Hz), 7 .48 (2H, d, J = 8.8 Hz), 7.50 (2H, d, J = 8.3 Hz), 7.54 (1H, s), 7.57 (1H, s), 8.07 (1H, d, = 15.9Hz)
¹³ C-NMR (600 MHz, CDCl ₃ ) δ: 14.0, 19.4, 19.6, 20.3, 26.5, 29.5, 50.8, 57.4, 97.4, 98. 4, 110.8, 111.1, 111.9, 111.8, 126.4, 127.3, 127.8, 128.0, 128.4, 124.3, 131.4, 134.6, 135.1, 137.6, 138.9, 141.5, 148.2, 114.1, 122.9, 123.9, 129.7, 132.6, 144.6, 174.0, 175. 5

[Example 2]
In this example, 2- [3-cyano-4- [2- [4- [2- [4- [2- [4- [N, N-bis [2]] represented by the following formula (II) was used. -(2,2-dimethylpropionyloxy) ethyl] amino] phenyl] vinyl] phenyl] vinyl] -2,5-dimethylphenyl] vinyl] -5,5-dimethyl-2 (5H) -furanylidene] propanedinitrile It was obtained through the following synthesis examples (2-1) to (2-8).

(Synthesis Example 2-1)
2-[[2- (2,2-dimethylpropionyloxy) ethyl] phenylamino] ethyl 2,2-dimethylpropionate was synthesized according to the reaction scheme represented by the following formula (2-1).

Specifically, 15.0 g (27.59 mmol) of N-phenyldiethanolamine was dissolved in 150 ml of acetonitrile, and 15.3 g (110.7 mmol) of potassium carbonate and 13.3 g (110.3 mmol) of pivaloyl chloride were added. 9.8 g (81.28 mmol) of pivaloyl chloride and 15.3 g (110.7 mmol) of potassium carbonate were added and stirred for 5 hours. The filtrate was filtered, and the filtrate was cooled with ice. The precipitated colorless crystals were removed by filtration. The back solution was concentrated, dissolved in 100 ml of ethyl acetate, and washed with saturated aqueous sodium hydrogen carbonate. Dehydrated and concentrated with anhydrous sodium sulfate, the residue was purified by silica gel column chromatography, and 2-[[2- (2,2-dimethylpropionyloxy) ethyl] phenylamino] ethyl 2,2-dimethylpropionate Was obtained as a colorless oil. (Yield 95.0%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.18 (18H, s), 3.63 (4H, t, J = 6.3 Hz), 4.23 (4H, t, J = 6.3 Hz) 6.72 (1H, t, J = 7.2 Hz), 6.78 (2H, d, J = 7.7 Hz), 7.23 (2H, dd, J = 7.2 Hz, 8.8 Hz)

(Synthesis Example 2-2)
According to the reaction scheme represented by the following formula (2-2), 2- [N- (4-formylphenyl) -N- [2- (2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2- Dimethylpropionate was synthesized.

Specifically, 2.64 g (17.2 mmol) of phosphoryl chloride was added dropwise to 10 ml of N, N-dimethylformamide under ice cooling (8-10 ° C.). After stirring for 1 hour at the same temperature, 6.0 g (17.2 mmol) of 2- [N- [2- (2,2-dimethylpropionyloxy) ethyl] -N-phenylamino] ethyl 2,2-dimethylpropionate was added. It was dripped. After stirring at room temperature for 2 hours, 20 ml of 20% aqueous sodium acetate was added, and the mixture was extracted 3 times with ethyl acetate. The extract was washed successively with saturated aqueous sodium hydrogen carbonate and saturated brine, dried over anhydrous sodium sulfate, and concentrated. Purified by silica gel column chromatography, 2- [N- (4-formylphenyl) -N- [2- (2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate was colorless 4.86 g of crystals were obtained. (Yield 75.0%) This crystallized at room temperature.
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.17 (18H, s), 3.73 (4H, t, J = 6.0 Hz), 4.27 (4H, t, J = 6.0 Hz) 6.85 (2H, d, J = 9.3 Hz), 7.75 (2H, d, J = 9.3 Hz), 9.76 (1H, s)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 27.2, 38.8, 49.3, 61.2, 111.5, 126.3, 132.3, 152.4, 178.5, 190 .3

(Synthesis Example 2-3)
According to the reaction scheme represented by the following formula (2-3), 2- [N- [4- [2- [4- (hydroxymethyl) phenyl] vinyl] phenyl] -N- [2- (2,2- Dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate was synthesized.

  Specifically, 0.36 g (4.34 mmol) of phenyllithium was added to tetrahydrofuran under an argon stream, and 1.0 g (2.16 mmol) of 4- (hydroxymethyl) benzyltriphenylphosphonium bromide was added while stirring under cooling. did. After stirring, 0.84 g (2.22 mmol) of 2- [N- (4-formylphenyl) -N- [2- (2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate Was dripped. The mixture was stirred at the same temperature for 45 minutes, poured into ice water, and extracted twice with toluene. The extract was washed with saturated brine, dehydrated with anhydrous sodium sulfate, concentrated, and the residue was purified by silica gel column chromatography. 2- [N- [4- [2- [4- (hydroxymethyl) phenyl] vinyl] phenyl] -N- [2- (2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpro 0.82 g of pionate was obtained as a yellow-orange oil. (Yield 78.9%)

(Synthesis Example 2-4)
In accordance with the reaction scheme represented by the following formula (2-4), 2- [N- [4- [2- (4-formylphenyl) vinyl] phenyl] -N- [2- (2,2-dimethylpropionyloxy) ) Ethyl] amino] ethyl 2,2-dimethylpropionate was synthesized.

Specifically, 2- [N- [4- [2- [4- (hydroxymethyl) phenyl] vinyl] phenyl] -N- [2- (2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2 , 2-dimethylpropionate (0.96 g, 1.99 mmol) was dissolved in dichloromethane, and active manganese dioxide (3.5 g, 40.3 mmol) was added. After stirring, the mixture was filtered, and the concentrated residue was purified by silica gel column chromatography. 2- [N- [4- [2- (4-Formylphenyl) vinyl] phenyl] -N- [2- (2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate 0.81 g was obtained as a yellow-orange oil. (Yield 84.7%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.19 (18H, s), 3.67 (4H, t, J = 6.0 Hz), 4.26 (4H, t, J = 6.0 Hz) 6.80 (2H, d, J = 18.8 Hz), 6.94 (1 H, d, J = 16.0 Hz), 7.19 (1 H, d, J = 16.0 Hz), 7.44 ( 2H, d, J = 8.8 Hz), 7.60 (2H, d, J = 8.3 Hz), 7.83 (2H, d, J = 8.3 Hz), 9.77 (1H, s)
¹³ C-NMR (600 MHz, CDCl ₃ ) δ: 27.3, 38.8, 49.5, 61.5, 112.3, 123.3, 125.7, 126.4, 128.6, 130. 3, 132.2, 134.7, 144.5, 147.8, 178.6, 191.7

(Synthesis Example 2-5)
According to the reaction scheme represented by the following formula (2-5), 2- [N- [4- [2- [4- [2- (4-hydroxymethyl-2,5-dimethylphenyl) vinyl] phenyl] vinyl ] Phenyl] -N- [2- (2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate was synthesized.

Specifically, 0.288 g (3.40 mmol) of phenyllithium was added to 12 ml of tetrahydrofuran under a stream of argon, and 0.83 g (1. of 1. 4- (hydroxymethyl) -2,5-dimethylbenzyltriphenylphosphonium bromide under cooling). 69 mmol) was added. After stirring, 2- [N- [4- [2- (4-formylphenyl) vinyl] phenyl] -N- [2- (2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpro 0.81 g (1.69 mmol) of pionate was added dropwise. After stirring for 1 hour, the reaction solution was poured into ice water and 40 ml of toluene and extracted. The aqueous layer was extracted again with 30 ml of toluene, and the organic layers were combined, washed with saturated brine, and then dried over anhydrous sodium sulfate. After concentration, the residue was subjected to silica gel column chromatography repeatedly to obtain 2- [N- [4- [2- [4- [2- (4-hydroxymethyl-2,5-dimethylphenyl) vinyl] phenyl] vinyl] phenyl]. 204 mg of -N- [2- (2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate was obtained as a slightly yellowish orange oil. (Yield 19.7%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.20 (18H, s), 2.37 (3H, s), 2.42 (3H, s), 3.67 (4H, t, J = 6) .0 Hz), 4.26 (4H, t, J = 6.0 Hz), 4.68 (2H, d, J = 5.5 Hz), 6.78 (2H, d, J = 8.8 Hz), 6 .91 (1H, d, J = 16.0 Hz), 6.99 (1H, d, J = 16.0 Hz), 7.05 (1H, d, J = 16.0 Hz), 7.16 (1H, s), 7.29 (1H, d, J = 16.0 Hz), 7.41 (2H, d, J = 8.8 Hz), 7.42 (1H, s), 7.47 (2H, d, J = 8.8 Hz), 7.49 (2H, d, J = 8.8 Hz)

(Synthesis Example 2-6)
According to the reaction scheme represented by the following formula (2-6), 2- [N- [4- [2- [4- [2- (4-formyl-2,5-dimethylphenyl) vinyl] phenyl] vinyl] Phenyl] -N- [2- (2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate was synthesized.

Specifically, 2- [N- [4- [2- [4- [2- (4-hydroxymethyl-2,5-dimethylphenyl) vinyl] phenyl] vinyl] phenyl] -N- [2- ( 2,2-Dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate 204 mg (0.33 mmol) was dissolved in 10 ml of dichloromethane and 580 mg (6.67 mmol) of active manganese dioxide was added. The mixture was stirred overnight at room temperature and filtered, and the concentrated residue was purified by silica gel column chromatography. 2- [N- [4- [2- [4- [2- (4-Formyl-2,5-dimethylphenyl) vinyl] phenyl] vinyl] phenyl] -N- [2- (2,2-dimethylpropionyl) 182 mg of oxy) ethyl] amino] ethyl 2,2-dimethylpropionate was obtained as yellow-orange crystals. (Yield 92.0%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.19 (18H, s), 2.47 (3H, s), 2.67 (3H, s), 3.67 (4H, t, J = 6) .0Hz), 4.26 (4H, t, J = 6.0 Hz), 6.79 (2H, d, J = 8.8 Hz), 6.94 (1H, d, J = 15.9 Hz), 7 .07 (1H, d, J = 15.9 Hz), 7.16 (1 H, d, J = 15.9 Hz), 7.29 (1 H, d, J = 15.9 Hz), 7.42 (2H, d, J = 8.8 Hz), 7.48 (1H, s), 7.49 (2H, d, J = 8.8 Hz), 7.52 (2H, d, J = 8.8 Hz), 7. 60 (1H, s), 10.21 (1H, s)
¹³ C-NMR (600 MHz, CDCl ₃ ) δ: 19.3, 19.4, 27.3, 38.8, 49.5, 61.6, 112.3, 124.3, 124.5, 126. 3,126.5,127.3,128.1,128.3,129.1,132.6,133.0,133.7,134.2,135.67,138.2,138.4 141.8, 147.3, 178.6, 192.3

(Synthesis Example 2-7)
According to the reaction scheme represented by the following formula (2-7), 2- [3-cyano-4- [2- [4- [2- [4- [2- [4- [N, N-bis [2] -(2,2-dimethylpropionyloxy) ethyl] amino] phenyl] vinyl] phenyl] vinyl] -2,5-dimethylphenyl] vinyl] -5,5-dimethyl-2 (5H) -furanylidene] propanedinitrile Synthesized.

Specifically, 2- [N- [4- [2- [4- [2- (4-formyl-2,5-dimethylphenyl) vinyl] phenyl] vinyl] phenyl] -N- [2- (2 , 2-Dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate 97.2 mg (0.159 mmol) and 2- (3-cyano-4,5,5-trimethyl-2 (5H) -furanylidene 33.0 mg (0.165 mmol) of propanedinitrile was dissolved in ethanol, stirred at room temperature for 24 hours and then ice-cooled, and the precipitated crystals were collected by filtration, and the filtrate and washings were concentrated and subjected to silica gel column chromatography. Purify and add 2- [3-cyano-4- [2- [4- [2- [4- [2- [4-N, N-bis [2-[(2,2-dimethylpropionyloxy) ethyl]]. Amino] phenyl] Sulfonyl] phenyl] vinyl] -2,5-dimethylphenyl] vinyl] -5,5-dimethyl -2 (5H) -. Furaniriden] to give 110mg of propanedinitrile as a black crystal (87.3% yield)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.20 (18H, s), 1.80 (6H, s), 2.48 (3H, s), 2.50 (3H, s), 3. 67 (4H, t, J = 6.3 Hz), 4.26 (4H, t, J = 6.3 Hz), 6.79 (2H, d, J = 8.8 Hz), 6.91 (1H, d) , J = 16.5 Hz), 6.93 (1H, d, J = 16.5 Hz), 7.08 (1H, d, J = 16.5 Hz), 7.15 (1H, d, J = 16. 5 Hz), 7.29 (1 H, d, J = 16.5 Hz), 7.42 (2 H, d, J = 8.8 Hz), 7.49 (2 H, d, J = 8.3 Hz), 7. 51 (2H, d, J = 8.3 Hz), 7.54 (1H, s), 7.55 (1H, s), 8.06 (1H, d, J = 16.5 Hz)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 19.5, 19.7, 26.7, 27.2, 38.8, 49.5, 57.5, 61.6, 97.5, 98 6,110.8,111.1,111.9,112.3,114.1,124.1,126.2,126.6,127.4,127.8,128.1,128.4 , 129.2, 131.4, 132.6, 134.6, 135.4, 137.6, 138.6, 141.5, 144.6, 147.3, 174.2, 175.6, 178 .6

[Example 3]
In this example, 2- [3-cyano-4- [2- [4- [2- [4- [2- [4- [N, N-bis [2]] represented by the following formula (III) was used. -(2,2-dimethylpropionyloxy) ethyl] amino] phenyl] vinyl] -2,5-dimethylphenyl] vinyl] phenyl] vinyl] -5,5-dimethyl-2 (5H) -furanylidene] propanedinitrile It was obtained through the following synthesis examples (3-1) to (3-13).

(Synthesis Example 3-1)
According to the reaction scheme represented by the following formula (3-1), 4- (tert-butyldiphenylsiloxymethyl) -2,5-dimethylbenzyl alcohol was synthesized.

Specifically, 8.0 g (48.0 mmol) of 4- (hydroxymethyl) -2,5-dimethylbenzyl alcohol and 6.5 g (95.0 mmol) of imidazole were dissolved in N, N-dimethylformamide. 15.5 g (56.4 mmol) of tert-butylchlorodiphenylsilane was added dropwise, stirred at room temperature for 4 hours, poured into water, and extracted twice with 250 ml of ethyl acetate. The extract was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated. Purification by silica gel column chromatography gave 9.71 g of 4- (tert-butyldiphenylsiloxymethyl) -2,5-dimethylbenzyl alcohol as a colorless oil. (Yield 49.9%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.09 (9H, s), 2.16 (3H, s), 2.34 (3H, s), 4.67 (2H, d, J = 6) .0Hz), 4.69 (2H, s), 7.11 (1H, s), 7.27 (1H, s), 7.36-7.39 (4H, m), 7.42-7. 45 (2H, m), 7.69-7.71 (4H, m)
¹³ C-NMR (600 MHz, CDCl ₃ ) δ: 18.2, 18.5, 19.4, 27.0, 63.5, 63.9, 127.8, 129.1, 129.6, 129. 8, 132.9, 133.4, 133.7, 135.7, 137.2, 138.4

(Synthesis Example 3-2)
According to the reaction scheme represented by the following formula (3-2), 4- (tert-butyldiphenylsiloxymethyl) -2,5-dimethylbenzyl bromide was synthesized.

Specifically, 4- (tert-butyldiphenylsiloxymethyl) -2,5-dimethylbenzyl alcohol 10.89 g (26.9 mmol) and carbon tetrachloride 10.71 g (32.3 mmol) were dissolved in 85 ml of tetrahydrofuran. 8.47 g (32.3 mmol) of triphenylphosphine was added, and the mixture was concentrated and purified by silica gel column chromatography. 4-[(tert-butyldiphenylsiloxy) methyl] -2,5-dimethylbenzyl bromide was obtained as a colorless oil. As a result, 11.13 g was obtained. (Yield 88.5%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.09 (9H, s), 2.12 (3H, s), 2.39 (3H, s), 4.51 (2H, s), 4. 67 (2H, s), 7.06 (1H, s), 7.28 (1H, s), 7.36-7.39 (4H, m), 7.41-7.44 (2H, m) , 7.68-7.69 (4H, m)
¹³ C-NMR (600 MHz, CDCl ₃ ) δ: 18.0, 18.5, 19.4, 26.9, 32.6, 63.7, 127.8, 129.2, 129.8, 131. 5, 133.1, 133.5, 134.1, 134.5, 135.7, 139.7

(Synthesis Example 3-3)
According to the reaction scheme represented by the following formula (3-3), 4- (tert-butyldiphenylsiloxymethyl) -2,5-dimethylbenzyl triphenylphosphonium bromide was synthesized.

Specifically, 5.0 g (10.69 mmol) of 4- (tert-butyldiphenylsiloxymethyl) -2,5-dimethylbenzyl bromide and 2.8 g (10.68 mmol) of triphenylphosphine were added to acetonitrile at 60 ° C. For 6 hours. Acetonitrile was distilled off, ether was newly added, and the mixture was allowed to stand overnight in a refrigerator for crystallization. This was collected by filtration, washed with ether and dried to obtain 6.67 g of 4- (tert-butyldiphenylsiloxymethyl) -2,5-dimethylbenzyl triphenylphosphonium bromide as white powder crystals. (Yield 85.6%)
¹ H-NMR (600 MHz, DMSO-d ₆ ) δ: 1.63 (3H, s), 1.93 (3H, s), 4.40 (2H, dd, J = 2.2 Hz, 5.5 Hz) 4.96 (2H, d, J = 24.8), 5.06 (1H, t, J = 5.5 Hz), 6.06 (1H, d, J = 2.2 Hz), 7.09 ( 1H, s), 7.61-7.65 (6H, m), 7.72-7.77 (6H, m), 7.91-7.947 (3H, m)
¹³ C-NMR ((600 MHz, DMSO-d ₆ ) δ: 18.1, 19.0, 26.5, 26.8, 61.1, 118.0, 118.6, 124.2, 129.8 130.6, 132.9, 134.6, 135.7, 136.0, 141.3

(Synthesis Example 3-4)
In accordance with the reaction scheme represented by the following formula (3-4), diethyl 4- (tert-butyldiphenylsiloxymethyl) -2,5-dimethylbenzylphosphonate was synthesized.

Specifically, 5.57 g (11.9 mmol) of 4- (tert-butyldiphenylsiloxymethyl) -2,5-dimethylbenzyl bromide and 2.08 g (12.5 mmol) of triethyl phosphite were heated and stirred. The reaction solution was purified by silica gel column chromatography to obtain 2.95 g of diethyl 4- (tert-butyldiphenylsiloxymethyl) -2,5-dimethylbenzylphosphonate as a colorless oil. (Yield 7.2%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.09 (9H, s), 1.25 (6H, t, J = 7.1 Hz), 2.13 (3H, s), 2.35 (3H , S), 3.14 (2H, d, J = 22.0 Hz), 4.00 (4H, t, J = 7.1 Hz), 4.66 (2H, s), 7.02 (1H, d) , J = 2.2 Hz), 7.23 (1H, s), 7.37-7.39 (4H, m), 7.42-7.44 (2H, m), 7.68-7.70. (4H, m)

(Synthesis Example 3-5)
In accordance with the reaction scheme represented by the following formula (3-5), 2- [N- [4- [2- [4- (tert-butyldiphenylsiloxymethyl) -2,5-dimethylphenyl] vinyl] phenyl]- N- [2- (2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate was synthesized.

Specifically, 1.44 g of 2- [N- (4-formylphenyl) -N- [2- (2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate (3. 81 mmol) and 2.0 g (3.81 mol) of diethyl 4- (tert-butyldiphenylsiloxymethyl) -2,5-dimethylbenzylphosphonate were dissolved in tetrahydrofuran, and 0.47 g (4 of potassium tert-butoxide was stirred at room temperature). 19 mol) was added. After stirring for 30 minutes, the mixture was poured into saturated aqueous sodium hydrogen carbonate and extracted twice with ethyl acetate. The extract was washed with saturated brine, dehydrated with anhydrous sodium sulfate, concentrated, and the residue was purified by silica gel column chromatography. 2- [N- [4- [2- [4- (tert-Butyldiphenylsiloxymethyl) -2,5-dimethylphenyl] vinyl] phenyl] -N- [2- (2,2-dimethylpropionyloxy) ethyl ] 1.31 g of amino] ethyl 2,2-dimethylpropionate was obtained as a colorless oil. (Yield 46.0%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.09 (9H, s), 1.20 (18H, s), 2.20 (3H, s), 2.39 (3H, s), 3. 66 (4H, t, J = 6.0 Hz), 4.26 (4H, t, J = 6.0 Hz), 4.70 (2H, s), 6.77 (2H, d, J = 8.8 Hz) ), 6.92 (1H, d, J = 16.5 Hz), 7.11 (1H, d, J = 16.5 Hz), 7.22 (1 H, s), 7.35 (1 H, s), 7.38-7.45 (8H, m), 7.70-7.72 (4H, m)

(Synthesis Example 3-6)
According to a reaction scheme represented by the following formula (3-6), 2- [N- [4- [2- (4-hydroxymethyl-2,5-dimethylphenyl) vinyl] phenyl] -N- [2- ( 2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate was synthesized.

Specifically, 2- [N- [4- [2- [4- (tert-butyldiphenylsiloxymethyl) -2,5-dimethylphenyl] vinyl] phenyl] -N- [2- (2 , 2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate (1.31 g, 1.75 mmol) was dissolved, and 35 ml of tetrabutylammonium fluoride was added dropwise with stirring at room temperature. After stirring, the mixture was poured into water and extracted twice with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated. Purified by silica gel column chromatography, 2- [N- [4- [2- (4-hydroxymethyl-2,5-dimethylphenyl) vinyl] phenyl] -N- [2- (2,2-dimethylpropionyloxy) 0.8 g of ethyl] amino] ethyl 2,2-dimethylpropionate was obtained as an orange oil. (Yield 89.9%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.19 (18H, s), 2.36 (3H, s), 2.38 (3H, s), 3.66 (4H, t, J = 6) .3 Hz), 4.25 (4 H, t, J = 6.3 Hz), 4.66 (2 H, s), 6.79 (2 H, d, J = 8.8 Hz), 6.92 (1 H, d) , J = 15.9 Hz), 7.09 (1H, d, J = 15.9 Hz), 7.14 (1H, s), 7.40 (1H, s), 7.41 (2H, d, J = 8.8Hz)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 16.5, 17.6, 25.4, 37.0, 47.8, 59.7, 61.6, 110.5, 120.5, 125 1,126.1,127.7,128.2,131.2,131.8,134.5,135.4,145.1,176.8

(Synthesis Example 3-7)
According to the reaction scheme represented by the following formula (3-7), 2- [N- [4- [2- [4- (tert-butyldiphenylsiloxymethyl] -2,5-dimethylphenyl] vinyl] phenyl]- N- [2- (2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate was synthesized.

  Specifically, 0.38 g (4.5 mmol) of phenyllithium was added to tetrahydrofuran under an argon stream, and 3.0 g of 4- (tert-butyldiphenylsiloxymethyl) -2,5-dimethylbenzyltriphenylphosphonium bromide under cooling. (4.11 mmol) was added. After stirring, 1.58 g (4.19 mmol) of 2- [N- (4-formylphenyl) -N- [2- (2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate Was dripped. The mixture was stirred for about 1.5 hours, poured into water, and extracted twice with 50 ml of ethyl acetate. The extract was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated. Purified by silica gel column chromatography. 2- [N- [4- [2- [4- (tert-Butyldiphenylsiloxymethyl) -2,5-dimethylphenyl] vinyl] phenyl] -N- [2- (2,2-dimethylpropionyloxy) ethyl Amino] ethyl 2,2-dimethylpropionate was obtained as a yellow oil to obtain 2.72 g. (Yield 88.5%)

(Synthesis Example 3-8)
According to the reaction scheme represented by the following formula (3-8), 2- [N- [4- [2- (4-hydroxymethyl-2,5-dimethylphenyl) vinyl] phenyl] -N- [2- ( 2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate was synthesized.

Specifically, 2- [N- [4- [2- [4- (tert-butyldiphenylsiloxymethyl) -2,5-dimethylphenyl] vinyl] phenyl] -N- [2- (2,2- Dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate (2.72 g) was dissolved in tetrahydrofuran, and 70 ml of tetrabutylammonium fluoride (1 molar tetrahydrofuran solution) was added dropwise at room temperature. After stirring for about 1 hour, the mixture was poured into water and extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated. The residual liquid was purified by silica gel column chromatography, and 2- [N- [4- [2- (4-hydroxymethyl-2,5-dimethylphenyl) vinyl] phenyl] -N- [2- (2,2- 1.71 g of dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate was obtained as a brown oil. (Yield 92.3%)
(Cis isomer): ¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.16 (18H, s), 2.20 (3H, s), 2.25 (3H, s), 3.58 (4H, t, J = 6.3 Hz), 4.18 (4H, t, J = 6.3 Hz), 4.68 (2H, s), 6.38 (1H, d, J = 12.1 Hz), 6. 46 (1H, d, J = 12.1 Hz), 6.55 (2H, d, J = 8.8 Hz), 7.00 (2H, d, J = 8.8 Hz), 7.05 (1H, s ), 7.18 (1H, s)
(Trans isomer): ¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.19 (18H, s), 2.36 (3H, s), 2.38 (3H, s), 3.66 (4H, t, J = 6.3 Hz), 4.25 (4H, t, J = 6.3 Hz), 4.66 (2H, s), 6.79 (2H, d, J = 8.8 Hz), 6. 92 (1H, d, J = 15.9 Hz), 7.09 (1 H, d, J = 15.9 Hz), 7.14 (1 H, s), 7.40 (1 H, s), 7.41 ( 2H, d, J = 8.8Hz)

(Synthesis Example 3-9)
According to a reaction scheme represented by the following formula (3-9), 2- [N- [4- [2- (4-hydroxymethyl-2,5-dimethylphenyl) vinyl] phenyl] -N- [2- ( 2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate was synthesized.

(Synthesis Example 3-9)
According to a reaction scheme represented by the following formula (3-9), 2- [N- [4- [2- (4-formyl-2,5-dimethylphenyl) vinyl] phenyl] -N- [2- (2 , 2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate was synthesized.

Specifically, 2- [N- [4- [2- (4-hydroxymethyl-2,5-dimethylphenyl) vinyl] phenyl] -N- [2- (2,2-dimethylpropionyloxy) ethyl] 1.92 g (3.77 mmol) of amino] ethyl 2,2-dimethylpropionate was dissolved in dichloromethane and 5.4 g (62.2 mmol) of active manganese dioxide was added. The mixture was stirred at room temperature for 18 hours and filtered, and the concentrated residue was purified by silica gel column chromatography. 2- [N- [4- [2- (4-formyl-2,5-dimethylphenyl) vinyl] phenyl] -N- [2- (2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2, 1.55 g of 2-dimethylpropionate was obtained as a yellow oil. (Yield 81.1%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.20 (18H, s), 2.43 (3H, s), 2.66 (3H, s), 3.67 (4H, t, J = 6) .3 Hz), 4.26 (4 H, t, J = 6.3 Hz), 6.80 (2 H, d, J = 8.8 Hz), 7.07 (1 H, d, J = 15.9 Hz), 7 .10 (1H, d, J = 15.9 Hz), 7.45 (2H, d, J = 8.8 Hz), 7.16 (1H, s), 7.58 (1H, s), 10.2. (1H, s)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 17.36, 17.45, 25.3, 36.9, 47.6, 59.5, 110.3, 119.1, 124.2, 125 8, 126.5, 130.5, 130.7, 131.3, 132.2, 136.2, 140.5, 145.7, 176.7, 190.3
¹ H-NMR (600 MHz, DMSO-d ₆ ) δ: 1.11 (18H, s), 2.42 (3H, s), 2.60 (3H), 3.68 (4H, t, J = 6) .0 Hz), 4.19 (4H, t, J = 6.0 Hz), 6.84 (2H, d, J = 8.8 Hz), 7.13 (1H, d, J = 16.0 Hz), 7 .25 (1H, d, J = 16.0 Hz), 7.51 (2H, d, J = 8.8 Hz), 7.61 (1 H, s), 7.62 (1 H, s), 10.1 (1H, s)
¹³ C-NMR ((600 MHz, DMSO-d ₆ ) δ: 17.3, 17.5, 25.4, 36.8, 47.2, 60.2, 110.6, 118.3, 123.6. 125.8, 127.0, 130.4, 131.3, 131.5, 132.2, 136.2, 140.5, 146.3, 176.1, 191.0.

(Synthesis Example 3-10)
According to the reaction scheme represented by the following formula (3-10), 2- [N- [4- [2- [4- [2- [4- (hydroxymethyl) phenyl] vinyl] -2,5-dimethylphenyl ] Vinyl] phenyl] -N- [2- (2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate was synthesized.

Specifically, 0.24 g (2.9 mmol) of phenyllithium was added to tetrahydrofuran under an argon atmosphere, and 0.64 g (1.38 mmol) of 4- (hydroxymethyl) benzyltriphenylphosphonium bromide was added under cooling. After stirring for 10 minutes at the same temperature, 2- [N- [4- [2- (4-formyl-2,5-dimethylphenyl) vinyl] phenyl] -N- [2- (2,2-dimethylpropionyloxy) Ethyl] amino] ethyl 2,2-dimethylpropionate 0.7 g (1.38 mmol) was added dropwise. After stirring, the mixture was poured into water and extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated. The residue was purified by silica gel column chromatography. 2- [N- [4- [2- [4- [2- [4- (hydroxymethyl) phenyl] vinyl] -2,5-dimethylphenyl] vinyl] phenyl] -N- [2- (2,2 -Dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate was obtained as an orange oil. (Yield 41.8%)
1H-NMR (600 MHz, CDCl ₃ ) δ: 1.19 (18H, s), 2.41 (3H, s), 2.42 (3H, s), 3.65 (4H, t, J = 6. 3 Hz), 4.24 (4 H, t, J = 6.3 Hz), 4.66 (2 H, s), 6.78 (2 H, d, J = 8.8 Hz), 6.95 (1 H, d, J = 16.0 Hz), 7.09 (1 H, d, J = 16.0 Hz), 7.00 (1 H, d, J = 16.0 Hz), 7.29 (1 H, d, J = 16.0 Hz) ), 7.33 (2H, d, J = 8.2 Hz,), 7.40 (1H, s), 7.41 (1H, s), 7.42 (2H, d, J = 8.2 Hz) , 7.50 (2H, d, J = 8.2Hz)
13C-NMR ((600 MHz, CDCl ₃ ) δ: 19.5, 27.1, 38.6, 49.4, 61.4, 65.0, 110.3, 120.3, 124.4, 124. 75, 124.83, 125.0, 125.2, 125.5, 126.1, 126.7, 127.4, 131.2, 131.6, 132.7, 134.3, 135.4. 138.3, 145.0, 178.5

(Synthesis Example 3-11)
According to the reaction scheme represented by the following formula (3-11), 2- [N- [4- [2- [4- [2- (4-formylphenyl) vinyl] -2,5-dimethylphenyl] vinyl] Phenyl] -N- [2- (2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate was synthesized.

Specifically, 2- [N- [4- [2- [4- [2- [4- (hydroxymethyl) phenyl] vinyl] -2,5-dimethylphenyl] vinyl] phenyl] -N- [2 148 mg (0.24 mmol) of-(2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate was dissolved in dichloromethane, and 420 mg (4.83 mmol) of active manganese dioxide was added. After stirring, the mixture was filtered, and the concentrated residue was purified by silica gel column chromatography. 2- [N- [4- [2- [4- [2- (4-Formylphenyl) vinyl] -2,5-dimethylphenyl] vinyl] phenyl] -N- [2- (2,2-dimethylpropionyl) 111 mg of oxy) ethyl] amino] ethyl 2,2-dimethylpropionate was obtained as yellow-orange crystals. (Yield 75.2%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.20 (18H, s), 2.43 (3H, s), 2.46 (3H, s), 3.67 (4H, t, J = 6) .3 Hz), 4.26 (4 H, t, J = 6.3 Hz), 4.66 (2 H, s), 6.80 (2 H, d, J = 8.8 Hz), 6.98 (1 H, d) , J = 15.9 Hz), 7.10 (1H, d, J = 15.9 Hz), 7.05 (1H, d, J = 15.9 Hz), 7.43 (2H, d, J = 8. 8Hz), 7.436 (1H, s), 7.443 (1H, s), 7.48 (1H, d, J = 15.9 Hz), 7.66 (2H, d, J = 8.2 Hz) , 7.87 (2H, d, J = 8.2 Hz), 9.99 (1H, s)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 19.65, 19.70, 27.3, 38.8, 49.6, 61.6, 113.0, 126.8, 127.4, 127 6, 128.1, 129.8, 129.9, 130.4, 133.3, 133.9, 134.1, 135.2, 137.2, 144.1, 147.1, 178.6 , 191.7

(Synthesis Example 3-12)
According to a reaction scheme represented by the following formula (3-12), 2- [3-cyano-4- [2- [4- [2- [4- [2- [4-N, N-bis [2- [(2,2-dimethylpropionyloxy) ethyl] amino] phenyl] vinyl] -2,5-dimethylphenyl] vinyl] phenyl] vinyl] -5,5-dimethyl-2 (5H) -furanylidene] propanedinitrile Synthesized.

Specifically, 2- [N- [4- [2- [4- [2- (4-formylphenyl) vinyl] -2,5-dimethylphenyl] vinyl] phenyl] -N- [2- (2 , 2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate 219 mg (0.359 mmol) and 2- (3-cyano-4,5,5-trimethyl-2 (5H) -furanylidene] propane Dinitrile (78.0 mg, 0.392 mmol) was dissolved in ethanol, and the mixture was stirred at room temperature for 18 hours, and then the precipitate was collected by filtration and washed with ethanol to purify the powdery crystals by silica gel column chromatography. The obtained powder was washed again with ethanol and dried under reduced pressure.2- [3-Cyano-4- [2- [4- [2- [4- [2- [4-N, N-bis [2] − [( , 2-dimethylpropionyloxy) ethyl] amino] phenyl] vinyl] -2,5-dimethylphenyl] vinyl] phenyl] vinyl] -5,5-dimethyl-2 (5H) -furanylidene] propanedinitrile mp252-255 240 mg was obtained as a black powder at 0 ° C. (Yield: 84.5%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.20 (18H, s), 1.82 (6H, s), 2.43 (3H, s), 2.47 (3H, s), 3. 67 (4H, t, J = 6.3 Hz), 4.26 (4H, t, J = 6.3 Hz), 6.80 (2H, d, J = 8.8 Hz), 6.99 (1H, d , J = 15.9 Hz), 7.04 (1H, d, J = 15.9 Hz), 7.05 (1H, d, J = 16.0 Hz), 7.10 (1H, d, J = 16.0. 0 Hz), 7.43 (2H, d, J = 8.8 Hz), 7.44 (1 H, s), 7.45 (1 H, s), 7.49 (1 H, d, J = 16.0 Hz) 7.63 (1H, d, J = 16.0 Hz), 7.61 (2H, d, J = 8.8 Hz), 7.64 (2H, d, J = 8.8 Hz)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 19.67, 19.71, 26.7), 27.3, 38.8, 49.6, 57.8, 61.5, 97.6 99.6, 110.4, 111.0, 111.8, 112.3, 114.2, 121.9, 126.7, 127.0, 127.36, 127.40, 127.49, 128. 1, 129.7, 129.8, 130.0, 132.7, 133.3, 133.8, 134.2, 137.4, 142.9, 146.9, 147.2, 173.7, 175.4, 178.6

[Example 4]
In this example, 2- [N- [4- [2- [4- [2- [4- [2- (4-cyano-5-dicyanomethylene-2, represented by the following formula (IV)] is represented. 2-Dimethyl-2,5-dihydrofuran-3-yl) vinyl] phenyl] vinyl] -2,5-dimethylphenyl] vinyl] phenyl] -N-ethylamino] ethyl acetate was synthesized by the following synthesis example (4- Obtained by going through 1) to (4-9).

(Synthesis Example 4-1)
2- (N-ethyl-N-phenylamino) ethyl acetate was synthesized according to the reaction scheme represented by the following formula (4-1).

Specifically, 2- (N-ethyl-N-phenylamino) ethanol 25.0 g (0.15 mol), acetic anhydride 25 ml and pyridine 1.0 ml were mixed and stirred for 2 hours. After cooling, the mixture was poured into water and extracted with 100 ml of ethyl acetate. The extract was washed 3 times with saturated aqueous sodium hydrogen carbonate and once with saturated brine, then dried over anhydrous sodium sulfate and concentrated. The residual liquid was distilled under reduced pressure to obtain 29.99 g of 2- (N-ethyl-N-phenylamino) ethyl acetate as a colorless oil of bp 103-105 ° C./0.8 mmHg. (Yield 92.4%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.17 (3H, t, J = 7.16 Hz), 2.05 (3H, s), 3.40 (2H, q, J = 7.1 Hz) 3.55 (2H, t, J = 6.6 Hz), 4.22 (2H, t, J = 6.6 Hz), 6.67-6.73 (3H, m), 7.20-7. 23 (2H, m)

(Synthesis Example 4-2)
2- [N-ethyl-N- (4-formylphenyl) amino] ethyl acetate was synthesized according to the reaction scheme represented by the following formula (4-2).

Specifically, 11.1 g (72.4 mmol) of phosphoryl chloride was added dropwise to 45 ml of N, N-dimethylformamide with stirring. After stirring, 15.0 g (72.4 mmol) of 2- (N-ethyl-N-phenylamino) ethyl acetate was added dropwise. The reaction solution was stirred at 60 ° C. for 5 hours and further at 70 ° C. for 1 hour and then ice-cooled, and 100 ml of 20% aqueous sodium acetate was added dropwise. After stirring for 1 hour, the mixture was extracted with ethyl acetate, and the extract was washed with saturated brine. The mixture was dehydrated with anhydrous sodium sulfate, concentrated, and purified by silica gel column chromatography to obtain 11.99 g of 2- [N-ethyl-N- (4-formylphenyl) amino] ethyl acetate as a colorless oil. (Yield 70.4%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.23 (3H, t, J = 7.1 Hz), 2.05 (3H, s), 3.50 (2H, q, J = 7.1 Hz) 3.65 (2H, t, J = 6.3 Hz), 4.26 (2H, t, J = 6.3 Hz), 6.75 (2H, d, J = 8.8 Hz), 7.73 ( 2H, d, J = 8.8 Hz), 9.74 (1H, s)

(Synthesis Example 4-3)
In accordance with the reaction scheme represented by the following formula (4-3), 2- [N- [4- [2- [4- (tert-butyldiphenylsiloxymethyl) -2,5-dimethylphenyl] vinyl] phenyl]- N-ethylamino] ethyl acetate was synthesized.

  Specifically, 0.55 g (6.6 mmol) of phenyl lithium was added to 20 ml of tetrahydrofuran under an argon stream, and 4- (tert-butyldiphenylsiloxymethyl) -2,5-dimethylbenzyltriphenylphosphonium bromide 4 was added while cooling. 0.03 g (5.52 mmol) was added. After stirring, 1.3 g (5.53 mmol) of 2- [N-ethyl-N- (4-formylphenyl) amino] ethyl acetate was added dropwise. After stirring, the mixture was poured into water and extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated. The residue was purified by silica gel column chromatography and 2- [N- [4- [2- [4- (tert-butyldiphenylsiloxymethyl) -2,5-dimethylphenyl] vinyl] phenyl] -N-ethyl. 1.76 g of amino] ethyl acetate was obtained. (Yield 52.5%)

(Synthesis Example 4-4)
According to the reaction scheme represented by the following formula (4-4), 2- [N-ethyl-N- [4- [2- (4-hydroxymethyl-2,5-dimethylphenyl) vinyl] phenyl] amino] ethyl Acetate was synthesized.

Specifically, 2- [N- [4- [2- [4- (tert-butyldiphenylsiloxymethyl) -2,5-dimethylphenyl] vinyl] phenyl] -N-ethylamino] ethyl acetate 1.75 g (2.89 mmol) was dissolved in tetrahydrofuran, and 20.2 ml (20.2 mmol) of tetrabutylammonium fluoride (1 molar tetrahydrofuran solution) was added dropwise with stirring at room temperature. After stirring, the mixture was poured into 100 ml of water and extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated. The residue was purified by silica gel column chromatography (2- [N-ethyl-N- [4- [2- (4-hydroxymethyl-2,5-dimethylphenyl) vinyl] phenyl] amino] ethyl acetate was yellow. As a liquid, 0.82 g was obtained (yield 77.4%).
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.13 (Z) (3H, t, J = 7.1 Hz), 1.19 (E) (3H, t, J = 7.1 Hz), 2. 02 (Z) (3H, s), 2.06 (E) (3H, s), 2.21 (Z) (3H, s), 2.25 (Z) (3H, s), 2.36 ( E) (3H, s), 2.38 (E) (3H, s), 3.36 (Z) (2H, q, J = 7.1 Hz), 3.44 (E) (2H, q, J = 7.1 Hz), 3.50 (Z) (2H, t, J = 6.6 Hz), 3.58 (E) (2H, t, J = 6.6 Hz), 4.17 (Z) (2H , T, J = 6.6 Hz), 4.24 (E) (2H, t, J = 6.6 Hz), 4.66 (E) (2H, d, J = 5.5 Hz), 4.68 ( Z) (2H, d, J = 5.5 Hz), 6.35 (Z (1H, d, J = 12.6 Hz), 6.45 (Z) (1 H, d, J = 12.6 Hz), 6.49 (Z) (2H, d, J = 8.8 Hz), 6. 71 (E) (2H, d, J = 8.8 Hz), 6.92 (E) (1 H, d, J = 15.9 Hz), 7.02 (Z) (2H, d, J = 8.8 Hz) ), 7.07 (E) (1H, d, J = 15.9 Hz), 7.08 (Z) (1 H, s), 7.13 (E) (1 H, s), 7.18 (Z) (1H, s), 7.40 (E) (1H, s), 7.41 (E) (2H, d, J = 8.8 Hz)

(Synthesis Example 4-5)
According to the reaction scheme represented by the following formula (4-5), 2- [N-ethyl-N- [4- [2- (4-formyl-2,5-dimethylphenyl) vinyl] phenyl] amino] ethyl acetate Was synthesized.

Specifically, 0.82 g of 2- [N-ethyl-N- [4- [2- (4-hydroxymethyl-2,5-dimethylphenyl) vinyl] phenyl] amino] ethyl acetate in 40 ml of dichloromethane (2. 23 mmol was dissolved, 3.9 g (44.86 mmol) of active manganese dioxide was added, and the mixture was stirred at room temperature for 18 hours.The reaction solution was filtered, concentrated, and purified by silica gel column chromatography. [2- [N-ethyl-N] 677 mg of [4- [2- (4-formyl-2,5-dimethylphenyl) vinyl] phenyl] amino] ethyl acetate was obtained as an orange oil (yield 83.1%).
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.20 (3H, t, J = 7.1 Hz), 2.07 (3H, s), 2.43 (3H, s), 2.66 (3H , S), 3.45 (2H, q, J = 7.1 Hz), 3.60 (2H, t, J = 6.6 Hz), 4.25 (2H, t, J = 6.6 Hz), 6 .73 (2H, d, J = 8.8 Hz), 7.06 (1H, d, J = 15.9 Hz), 7.09 (1H, d, J = 15.9 Hz), 7.44 (2H, d, J = 8.8 Hz), 7.46 (1H, s), 7.58 (1H, s), 10.19 (1H, s)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 12.4, 19.3, 19.4, 21.0, 45.4, 48.9, 61.6, 112.0, 120.6, 125 .3, 127.7, 128.5, 132.3, 132.9, 133.2, 134.2, 138.2, 142.6, 147.9, 171.1, 192.3

(Synthesis Example 4-6)
According to a reaction scheme represented by the following formula (4-6), 2- [N-ethyl-N- [4- [2- [4-2-2- [4- (hydroxymethyl) phenyl] vinyl] -2,5 -Dimethylphenyl] vinyl] phenyl] aminoethyl acetate was synthesized.

  Specifically, 0.34 g (4.06 mmol) of phenyllithium was added to tetrahydrofuran under an argon stream, and 856 mg (1.85 mmol) of 4- (hydroxymethyl) benzyltriphenylphosphonium bromide was added while cooling. After the reaction solution was stirred for 10 minutes, 675 mg (1.85 mmol) of 2- [N-ethyl-N- [4- [2- (4-formyl-2,5-dimethylphenyl) vinyl] phenyl] amino] ethyl acetate was added. It was dripped. The mixture was stirred at the same temperature for 1 hour, poured into 200 ml of water and extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated. The residue was purified by silica gel column chromatography, and 2- [N-ethyl-N- [4- [2- [4-2-2- [4- (hydroxymethyl) phenyl] vinyl] -2,5-dimethylphenyl was obtained. 198 mg of vinyl] phenyl] aminoethyl acetate as an orange liquid was obtained. (Yield 22.8%)

(Synthesis Example 4-7)
According to the reaction scheme represented by the following formula (4-7), 2- [N-ethyl-N- [4- [2- [4- [2- (4-formylphenyl) vinyl] -2,5-dimethyl Phenyl] vinyl] phenyl] amino] ethyl acetate was synthesized.

Specifically, 2- [N-ethyl-N- [4- [2- [4-2-2- [4- (hydroxymethyl) phenyl] vinyl] -2,5-dimethylphenyl] vinyl] phenyl] is added to dichloromethane. 0.196 g of aminoethyl acetate (0.42 mmol was dissolved, 0.72 g (8.28 mmol) of active manganese dioxide was added, and the mixture was stirred at room temperature for 20 hours. The reaction solution was filtered and concentrated, and the residual solution was subjected to silica gel column chromatography. 2- [N-ethyl-N- [4-[-2- [4- [2- (4-formylphenyl) vinyl] -2,5-dimethylphenyl] vinyl] phenyl] amino] ethyl acetate Was obtained as orange crystals (yield 52.3%).
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.20 (3H, t, J = 7.1 Hz), 2.06 (3H, s), 2.42 (3H, s), 2.45 (3H , S), 3.44 (2H, q, J = 7.1 Hz), 3.59 (2H, t, J = 6.6 Hz), 4.25 (2H, t, J = 6.6 Hz), 6 .72 (2H, d, J = 8.8 Hz), 6.98 (1H, d, J = 15.9 Hz), 7.05 (1H, d, J = 15.9 Hz), 7.09 (1H, d, J = 15.9 Hz), 7.41 (1H, s), 7.43 (1H, s), 7.43 (2H, d, J = 8.8 Hz), 7.48 (1H, d, J = 15.9 Hz), 7.65 (2H, d, J = 8.2 Hz), 7.86 (2H, d, J = 8.2 Hz), 9.99 (1H, s)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 12.4, 19.6, 19.7, 21.0, 45.4, 48.9, 61.7, 112.1, 121.6, 126 0.0, 126.91, 126.93, 127.4, 127.5, 128.1, 129.8, 130.1, 130.3, 133.2, 133.8, 134.1, 135.2 , 137.3, 144., 147.4, 171.1, 191.7

(Synthesis Example 4-8)
According to the reaction scheme represented by the following formula (4-8), 2- [N- [4- [2- [4- [2- [4- [2- (4-cyano-5-dicyanomethylene-2, 2-Dimethyl-2,5-dihydrofuran-3-yl) vinyl] phenyl] vinyl] -2,5-dimethylphenyl] vinyl] phenyl] -N-ethylamino] ethyl acetate was synthesized.

Specifically, 2- [N-ethyl-N- [4- [2- [4- [2- (4-formylphenyl) vinyl] -2,5-dimethylphenyl] vinyl] phenyl] amino] in ethanol 83 mg (0.178 mmol) of ethyl acetate and 39 mg (0.196 mmol) of 2- (3-cyano-4,5,5-trimethyl-2 (5H) -furanylidene] propanedinitrile were dissolved and stirred at room temperature for 23 hours. The solvent was distilled off, and the residue was purified by silica gel column chromatography, and the obtained crystals were washed with methanol and 2- [N- [4- [2- [4- [2- [4- [2- (4-Cyano-5-dicyanomethylene-2,2-dimethyl-2,5-dihydrofuran-3-yl) vinyl] phenyl] vinyl] -2,5-dimethylphenyl] vinyl] phenyl]- -. Give 94mg ethylamino] ethyl acetate as a black crystal (81.6% yield)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.20 (3H, t, J = 7.1 Hz), 1.81 (6H, s), 2.07 (3H, s), 2.43 (3H , S), 2.47 (3H, s), 3.45 (2H, q, J = 7.1 Hz), 3.59 (2H, t, J = 6.6 Hz), 4.26 (2H, t , J = 6.6 Hz), 6.72 (2H, d, J = 8.8 Hz), 6.99 (1H, d, J = 15.9 Hz), 7.038 (1H, d, J = 15. 9 Hz), 7.043 (1 H, d, J = 15.9 Hz), 7.09 (1 H, d, J = 15.9 Hz), 7.42 (2 H, d, J = 8.8 Hz), 7. 437 (1H, s), 7.444 (1H, s), 7.49 (1H, d, J = 15.9 Hz), 7.61 (2H, d, J = 8.8 Hz), 7.630 ( 1 , D, J = 15.9Hz,) 7.633 (2H, d, J = 8.8Hz)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 12.4, 19.67, 19.72, 21.0, 26.7, 45.5, 48.9, 59.7, 61.7, 97.6, 99.5, 110.4, 111.0, 111.8, 112.0, 114.2, 121.4, 125.9, 126.9, 127.3, 127 4, 127.5, 128.1, 129.8, 130.2, 132.7, 133.3, 133.7, 134.2, 137.5, 142.9, 146.9, 147.4 , 166.8, 173.7, 175.4

[Example 5]
In this example, 2- [3-cyano-4- [2- [4- [2- [4- [2- [4- [N-ethyl-N- () represented by the following formula (V) is used. 2-hydroxyethyl) amino] phenyl] vinyl] -2,5-dimethylphenyl] vinyl] phenyl] vinyl] -5,5-dimethyl-2 (5H) -furanylidene] propanedinitrile was synthesized by the following synthesis example (5 -1) to (5-11).

(Synthesis Example 5-1)
2- (N-ethyl-N-phenylamino) ethyl 2,2-dimethylpropionate was synthesized according to the reaction scheme represented by the following formula (5-1).

Specifically, 8.26 g (0.05 mol) of 2- (N-ethyl-N-phenylamino) ethanol and 15.5 g (0.12 mol) of N-ethyldiisopropylamine were dissolved in 150 ml of toluene. At room temperature, 12.0 g (0.1 mol) of pivaloyl chloride was added dropwise, the reaction solution was gradually heated, and stirred at 80 ° C. for 1.5 hours. After cooling, water was added, stirred and separated. The organic layer was washed successively with saturated aqueous sodium hydrogen carbonate and saturated brine, dried over anhydrous sodium sulfate, and concentrated. The residual liquid was purified by silica gel column chromatography to obtain 12.05 g of 2- (N-ethyl-N-phenylamino) ethyl 2,2-dimethylpropionate as a yellow liquid. (Yield 96.7%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.17 (3H, t, J = 7.1 Hz), 1.19 (9H, s), 3.41 (2H, q, J = 7.1 Hz) , 3.54 (2H, t, J = 6.6 Hz), 4.21 (2H, t, J = 6.6 Hz), 6.68 (1H, d, J = 7.1 Hz), 6.73 ( 2H, d, J = 8.8 Hz), 7.20-7.23 (2H, m)

(Synthesis Example 5-2)
2- [N-ethyl-N- (4-formylphenyl) amino] ethyl 2,2-dimethylpropionate was synthesized according to the reaction scheme represented by the following formula (5-2).

Specifically, 7.6 g (49.6 mmol) of phosphoryl chloride was added dropwise while stirring N, N-dimethylformamide. Further, 12.0 g (48.0 mmol) of 2- (N-ethyl-N-phenylamino) ethyl 2,2-dimethylpropionate was added dropwise. Stir for 3 hours. While cooling with a water bath, 20% aqueous sodium acetate was added dropwise. The mixture was extracted with ethyl acetate, and the extracts were combined and washed with saturated aqueous sodium hydrogen carbonate and then saturated brine. After dehydration with anhydrous sodium sulfate, the solvent was distilled off and the residue was purified by silica gel column chromatography. 2- [N-ethyl-N- (4-formylphenyl) amino] ethyl 2,2-dimethylpropionate was pale brown oil As a product, 10.03 g was obtained. (Yield 75.2%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.18 (9H, s), 1.23 (3H, t, J = 7.1 Hz), 3.51 (2H, q, J = 7.1 Hz) 3.65 (2H, t, J = 6.3 Hz), 4.25 (2H, t, J = 6.3 Hz), 6.77 (2H, d, J = 8.8 Hz), 7.73 ( 2H, d, J = 8.8 Hz), 9.73 (1H, s)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 12.2, 27.2, 38.8, 45.4, 48.6, 61.5, 111.1, 125.6, 132.3, 152 .5,178.6,190.2

(Synthesis Example 5-3)
According to a reaction scheme represented by the following formula (5-3), 2- [N-ethyl-N- [4- [2- [4- (tert-butyldiphenylsiloxymethyl) -2,5-dimethylphenyl] vinyl ] Phenyl] amino] ethyl 2,2-dimethylpropionate was synthesized.

  Specifically, 0.61 g (7.23 mmol) of phenyl lithium was added to 25 ml of tetrahydrofuran under an argon stream, and 4- (tert-butyldiphenylsiloxymethyl) -2,5-dimethylbenzyltriphenylphosphonium bromide 4 was added while cooling. 0.8 g (6.58 mmol) was added. After stirring, 1.83 g (6.59 mmol) of 2- [N-ethyl-N- (4-formylphenyl) amino] ethyl 2,2-dimethylpropionate was added dropwise. The mixture was stirred at the same temperature for 2 hours, poured into water and extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated. The residue was purified by silica gel column chromatography, and 2- [N-ethyl-N- [4- [2- [4- (tert-butyldiphenylsiloxymethyl] -2,5-dimethylphenyl] vinyl] phenyl] was obtained. 2.96 g of amino] ethyl 2,2-dimethylpropionate was obtained (yield 69.5%).

(Synthesis Example 5-4)
According to the reaction scheme represented by the following formula (5-4), 2- [N-ethyl-N- [4- [2- (4-hydroxymethyl-2,5-dimethylphenyl) vinyl] phenyl] amino] ethyl 2,2-dimethylpropionate was synthesized.

Specifically, 2- [N-ethyl-N- [4- [2- [4- (tert-butyldiphenylsiloxymethyl) -2,5-dimethylphenyl] vinyl] phenyl] amino] ethyl 2,2- 2.96 g (4.57 mmol) of dimethylpropionate was dissolved in tetrahydrofuran, and 15 ml (15.0 mmol) of tetrabutylammonium fluoride solution was added dropwise over 20 minutes while stirring at room temperature. After stirring for 2 hours, the mixture was poured into water and extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated. The residue was purified by silica gel column chromatography, and 2- [N-ethyl-N- [4- [2- (4-hydroxymethyl-2,5-dimethylphenyl) vinyl] phenyl] amino] ethyl 2,2- 1.68 g of dimethylpropionate was obtained as a yellow liquid. (Yield 89.8%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.13 (Z) (3H, t, J = 7.1 Hz), 1.16 (Z) (9H, s), 1.19 (E) (3H , T, J = 7.1 Hz), 1.20 (E) (9H, s), 2.21 (Z) (3H, s), 2.25 (Z) (3H, s), 2.36 ( E) (3H, s), 2.38 (E) (3H, s), 3.37 (Z) (2H, q, J = 7.1 Hz), 3.45 (E) (2H, q, J = 7.1 Hz), 3.50 (Z) (2H, t, J = 6.6 Hz), 3.58 (E) (2H, t, J = 6.6 Hz), 4.17 (Z) (2H , T, J = 6.6 Hz), 4.23 (E) (2H, t, J = 6.6 Hz), 4.66 (E) (2H, d, J = 6.0 Hz), 4.68 ( Z) (2H, d, J = 6.0 Hz), 6.35 (Z (1H, d, J = 12.1 Hz), 6.45 (Z) (1 H, d, J = 12.1 Hz), 6.50 (Z) (2H, d, J = 8.8 Hz), 7. 00 (Z) (2H, d, J = 8.8 Hz), 6.73 (E) (2H, d, J = 8.8 Hz), 7.41 (E) (2H, d, J = 8.8 Hz) ), 6.92 (E) (1H, d, J = 15.9 Hz), 7.07 (E) (1 H, d, J = 15.9 Hz), 7.07 (Z) (1 H, s), 7.18 (Z) (1H, s), 7.13 (E) (1H, s), 7.40 (E) (1H, s)

(Synthesis Example 5-5)
2- [N-ethyl-N- [4- [2- (4-formyl-2,5-dimethylphenyl) vinyl] phenyl] amino] ethyl 2 according to the reaction scheme represented by the following formula (5-5) , 2-dimethylpropionate was synthesized.

Specifically, 2- [N-ethyl-N- [4- [2- (4-hydroxymethyl-2,5-dimethylphenyl) vinyl] phenyl] amino] ethyl 2,2-dimethylpropionate in dichloromethane 1.68 g (4.1 mmol) was dissolved, 7.13 g (82.0 mmol) of active manganese dioxide was added, and the mixture was stirred at room temperature for 17 hours. The reaction solution was filtered and concentrated, and the residue was purified by silica gel column chromatography. 1.37 g of 2- [N-ethyl-N- [4- [2- (4-formyl-2,5-dimethylphenyl) vinyl] phenyl] amino] ethyl 2,2-dimethylpropionate as an orange oil Obtained. (Yield 82.0%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.20 (9H, s), 1.21 (3H, t, J = 7.1 Hz), 2.43 (3H, s), 2.66 (3H , S), 3.46 (2H, q, J = 7.1 Hz), 3.59 (2H, t, J = 6.6 Hz), 4.24 (2H, t, J = 6.6 Hz), 6 .74 (2H, d, J = 8.8 Hz), 7.06 (1H, d, J = 16.5 Hz), 7.09 (1H, d, J = 16.5 Hz), 7.44 (2H, d, J = 8.8 Hz), 7.46 (1H, s), 7.58 (1H, s), 10.18 (1H, s,)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 12.4, 19.3, 19.4, 27.3, 38.8, 45.3, 48.8, 61.8, 112.0, 120 5, 125.3, 127.7, 128.5, 132.3, 132.9, 133.2, 134.2, 138.2, 142.6, 147.9, 178.7, 192.3

(Synthesis Example 5-6)
According to the reaction scheme represented by the following formula (5-6), 2- [N-ethyl-N- [4- [2- [4- [2- [4- (hydroxymethyl) phenyl] vinyl] -2, 5-Dimethylphenyl] vinyl] phenyl] amino] ethyl 2,2-dimethylpropionate was synthesized.

  Specifically, 0.27 g (3.23 mmol) of phenyllithium was added to 20 l of tetrahydrofuran under an argon stream, and 680 mg (1.47 mmol) of 4-hydroxymethylbenzyltriphenylphosphonium bromide was added while cooling. After stirring, 2- [N-ethyl-N- [4- [2- (4-formyl-2,5-dimethylphenyl) vinyl] phenyl] amino] ethyl 2,2-dimethylpropionate 600 mg (1.47 mmol) ) Was added dropwise. The mixture was stirred at the same temperature for 2 hours, poured into water and extracted with ethyl acetate. The extract was washed with saturated brine, dehydrated with anhydrous sodium sulfate, and concentrated. The residue was purified by silica gel column chromatography, and 2- [N-ethyl-N- [4- [2- [4- [2- [4- (hydroxymethyl) phenyl] vinyl] -2,5-dimethyl was obtained. 485 mg of phenyl] vinyl] phenyl] amino] ethyl 2,2-dimethylpropionate were obtained. (Yield 64.7%)

(Synthesis Example 5-7)
According to the reaction scheme represented by the following formula (5-7), 2- [N-ethyl-N- [4- [2- [4- [2- (4-formylphenyl) vinyl] -2,5-dimethyl Phenyl] vinyl] phenyl] amino] ethyl 2,2-dimethylpropionate was synthesized.

Specifically, 2- [N-ethyl-N- [4- [2- [4- [2- [4- (hydroxymethyl) phenyl] vinyl] -2,5-dimethylphenyl] vinyl] phenyl in dichloromethane is used. Amino] ethyl 2,2-dimethylpropionate (480 mg, 0.938 mmol was dissolved, activated manganese dioxide (1.63 g, 18.75 mmol) was added, and the mixture was stirred at room temperature for 19 hours. The reaction solution was filtered, concentrated, The residue was purified by silica gel column chromatography (ethyl acetate / hexane-1 / 2), and 2- [N-ethyl-N- [4-[-2- [4- [2- (4-formylphenyl) vinyl] ] -2,5-dimethylphenyl] vinyl] phenyl] amino] ethyl 2,2-dimethylpropionate was obtained as orange crystals (316 mg, yield 66.1%).
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.20 (3H, t, J = 7.1 Hz), 1.20 (9H, s), 2.43 (3H, s,), 2.46 ( 3H, s), 3.45 (2H, q, J = 7.1 Hz), 3.58 (2H, t, J = 6.6 Hz), 4.24 (2H, t, J = 6.6 Hz), 6.74 (2H, d, J = 8.8 Hz), 6.98 (1H, d, J = 15.9 Hz), 7.05 (1H, d, J = 15.9 Hz), 7.09 (1H , D, J = 15.9 Hz), 7.41 (1H, s), 7.43 (2H, d, J = 8.8 Hz), 7.43 (1H, s), 7.48 (1H, d) , J = 15.9 Hz), 7.66 (2H, d, J = 8.2 Hz), 7.82 (2H, d, J = 8.2 Hz), 10.00 (1H, s)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 12.3, 19.56, 19.62, 27.2, 38.8, 45.3, 48.7, 61.8, 112.0, 121 4, 125.9, 126.8, 126.9, 127.3, 127.5, 127.9, 129.8, 130.0, 130.3, 133.2, 133.7, 134.0 135.1, 137.3, 144.1, 147.4, 178.6, 191.6.

(Synthesis Example 5-8)
According to the reaction scheme represented by the following formula (5-8), 4- [2- [4- [2- [4- [N-ethyl-N- (2-hydroxyethyl) amino] phenyl] vinyl] -2 , 5-Dimethylphenyl] vinyl] benzaldehyde was synthesized.

Specifically, 2- [N-ethyl-N- [4- [2- [4- [2- (4-formylphenyl) vinyl] -2,5-dimethylphenyl] vinyl] phenyl] amino] ethyl 2 , 2-dimethylpropionate (167 mg) was dissolved in a tetrahydrofuran / methanol mixed solvent. To this was added 1.3 ml of 10% aqueous sodium hydroxide, and the mixture was stirred at room temperature for 0.5 hour and further at 50 ° C. with heating for 0.5 hour. Water was added and extracted with ethyl acetate. The extract was washed with saturated brine, dehydrated with anhydrous sodium sulfate, and concentrated. 140 mg of 4- [2- [4- [2- [4- [N-ethyl-N- (2-hydroxyethyl) amino] phenyl] vinyl] -2,5-dimethylphenyl] vinyl] benzaldehyde was obtained as orange crystals. It was. (Rough yield 100%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.19 (3H, t, J = 7.1 Hz), 2.43 (3H, s), 2.46 (3H, s), 3.46 (2H , Q, J = 7.1 Hz), 3.51 (2H, t, J = 6.6 Hz), 3.83 (2H, br), 6.77 (2H, d, J = 8.8 Hz), 6 .98 (1H, d, J = 15.9 Hz), 7.05 (1H, d, J = 15.9 Hz), 7.09 (1H, d, J = 15.9 Hz), 7.42 (2H, d, J = 8.8 Hz), 7.43 (1H, s), 7.44 (1H, s), 7.48 (1H, d, J = 15.9 Hz), 7.66 (2H, d, J = 8.2 Hz), 7.87 (2H, d, J = 8.2 Hz), 10.00 (1H, s)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 12.0, 19.5, 19.6, 45.7, 52.5, 60.4, 112.7, 121.7, 126.3, 126 .8, 126.9, 127.3, 127.5, 127.9, 129.8, 130.0, 130.3, 133.2, 133.8, 134.0, 135.1, 137.3 , 144.1, 147.9, 191.6

(Synthesis Example 5-9)
According to the reaction scheme represented by the following formula (5-9), 2- [3-cyano-4- [2- [4- [2- [4- [2- [4- [N-ethyl-N- ( 2-hydroxyethyl) amino] phenyl] vinyl] -2,5-dimethylphenyl] vinyl] phenyl] vinyl] -5,5-dimethyl-2 (5H) -furanylidene] propanedinitrile was synthesized.

Specifically, 4- [2- [4- [2- [4- [N-ethyl-N- (2-hydroxyethyl) amino] phenyl] vinyl] -2,5-dimethylphenyl] vinyl] was added to ethanol. Benzaldehyde 140 mg (0.33 mmol) and 2- (3-cyano-4,5,5-trimethyl-2 (5H) -furanilidene] propanedinitrile 72 mg (0.36 mmol) were dissolved and stirred at room temperature for 24 hours. The precipitated crystals were collected by filtration and washed with ethanol to obtain 157 mg of crude crystals, which were purified by silica gel column chromatography and further washed with methanol. [2- [3-cyano-4- [2- [4- [ 2- [4- [2- [4- [N-ethyl-N- (2-hydroxyethyl) amino] phenyl] vinyl] -2,5-dimethylphenyl] vinyl] phenyl] Sulfonyl] -5,5-dimethyl -2 (5H) -. Furaniriden] propane dinitrile was obtained 157mg as a black crystalline powder of mp> 300 ℃ (78.7% yield)
¹ H-NMR (600 MHz, DMSO-d ₆ ) δ: 1.10 (3H, t, J = 7.1 Hz), 1.81 (6H, s), 2.39 (3H, s), 2.44 (3H, s), 3.38 (2H, t, J = 6.6 Hz), 3.41 (2H, q, J = 7.1 Hz), 3.55 (2H, dt, J = 6.0 Hz, 5.5 Hz), 4.72 (1H, t, J = 5.5 Hz), 6.68 (2H, d, J = 8.8 Hz), 7.04 (1H, d, J = 15.9 Hz), 7.07 (1H, d, J = 15.9 Hz), 7.24 (1 H, d, J = 15.9 Hz), 7.42 (2H, d, J = 8.8 Hz), 7.45 (1H , S), 7.57 (1H, s), 7.57 (1H, d, J = 15.9 Hz), 7.78 (2H, d, J = 8.8 Hz), 7.92 (2H, d , J = 8. Hz), 7.95 (1H, d, J = 16.5Hz)
¹³ C-NMR ((600 MHz, DMSO-d ₆ ) δ: 12.3, 19.45, 19.48, 25.5, 44.9, 53.1, 54.5), 58.7, 99. 0, 99.6, 111.2, 112.213.0, 111.7, 115.0, 120.1, 124.6, 126.5, 127.4, 127.5, 127.8. 128.2, 130.2, 130.3, 132.8, 133.6, 134.1, 136.8, 141.9, 146.0, 147.2, 147.8, 175.4, 177. 3

[Example 6]
In this example, 2- [3-cyano-4- [2- [4- [2- [5- [2- [4- (dibutylamino) phenyl] vinyl]] represented by the following formula (VI) was used. 2-thienyl] vinyl] -2,5-dimethylphenyl] vinyl] -5,5-dimethyl-2 (5H) -furanylidene] propanedinitrile was synthesized from the following synthesis examples (6-1) to (6-9). )

(Synthesis Example 6-1)
2-Chloromethylthiophene was synthesized according to the reaction scheme represented by the following formula (6-1).

Specifically, 12.8 g (0.112 mol) of 2-thiophene methanol was dissolved in 200 ml of chloroform, and 0.3 ml of pyridine was added. While heating and stirring, 40.0 g (0.336 mol) of thionyl chloride was added dropwise. The mixture was further stirred for 1 hour, cooled, poured into ice water, and stirred. The organic layer was separated, washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off and the residual liquid was distilled under reduced pressure. 11.27 g of 2-chloromethylthiophene was obtained as a colorless oil having a bp of 53-54 ° C./10 mmHg. (Yield 75.8%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 4.80 (2H, s), 6.95 (1H, dd, J = 3.9 Hz, 5.0 Hz), 7.08 (1H, d, J = 3.9 Hz), 7.30 (1 H, dd, J = 1.1 Hz, 5.0 Hz)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 40.3, 126.86, 126.89, 127.6, 140.

(Synthesis Example 6-2)
According to the reaction scheme represented by the following formula (6-2), 2-thienyltriphenylphosphonium chloride was synthesized.

Specifically, 3.0 g (22.7 mmol) of 2-chloromethylthiophene and 5.93 g (22.6 mmol) of triphenylphosphine were dissolved in acetonitrile. The mixture was stirred on a 70 ° C. oil bath and then cooled, and the precipitated crystals were collected by filtration. After washing with acetonitrile and drying, 8.09 g of 2-thienyltriphenylphosphonium chloride as colorless crystals was obtained. (Yield 90.6%)
¹ H-NMR (600 MHz, DMSO-d ₆ ) δ: 5.56 (2H, d, J = 14.8 Hz), 6.78-6.79 (1H, m), 6.96-6.98 ( 1H, m), 7.48-7.49 (1H, m), 7.68-7.71 (6H, m), 7.75-7.78 (6H, m), 7.91-7. 93 (3H, m)

(Synthesis Example 6-3)
N, N-dibutyl-N- [4-2 (2-thienyl) vinyl] phenylamine was synthesized according to the reaction scheme represented by the following formula (6-3).

Specifically, 1.98 g (23.6 mmol) of phenyllithium was added to 70 ml of tetrahydrofuran under an argon stream, and 8.09 g (20.5 mmol) of 2-thienyltriphenylphosphonium chloride was added while cooling. After stirring the dark reddish brown liquid, 4.92 g (21.0 mmol) of 4- (dibutylamino) benzaldehyde was added dropwise. The mixture was stirred at the same temperature for 1 hour, poured into water and extracted with toluene. The extract was washed with saturated brine, dehydrated with anhydrous sodium sulfate, and concentrated. The residue was purified by silica gel column chromatography to obtain 6.32 g of N, N-dibutyl-N- [2- (2-thienyl) vinyl] phenylamine as an orange liquid. (Yield 98.4%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 0.96 (6H, t, J = 7.7 Hz), 1.32-1.39 (4H, m), 1.55-1.60 (4H, m), 3.28 (4H, t, J = 7.7 Hz), 6.60 (2H, d, J = 8.8 Hz), 6.84 (1H, d, J = 15.9 Hz), 6. 95 (1H, d, J = 3.9 Hz), 6.96 (1H, d, J = 3.9 Hz), 6.99 (1H, d, J = 15.9 Hz), 7.09 (1H, t , J = 3.0 Hz), 7.31 (2H, d, J = 8.8 Hz)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 14.0, 20.3, 29.5, 50.8, 116.9, d128.8, 111.7, 122.7, 124.1, 124 .2, 127.4127.6, 128.8, 144.2, 147.8

(Synthesis Example 6-4)
5- [2- [4- (dibutylamino) phenyl] vinyl] thiophene-2-carbaldehyde was synthesized according to the reaction scheme represented by the following formula (6-4).

Specifically, 3.0 g (9.57 mmol) of N, N-dibutyl-N- [2- (2-thienyl) vinyl] phenylamine was dissolved in tetrahydrofuran under an argon stream. While cooling, 9.0 ml (14.35 mmol) of n-butyllithium (hexane solution) was added dropwise. After stirring for 1 hour, 0.87 g (11.9 mmol) of N, N-dimethylformamide was added dropwise. After 20 minutes, the temperature was raised to 5 ° C., 30 ml of water was added dropwise, and then tetrahydrofuran was distilled off, followed by extraction with chloroform. The mixture was dehydrated with anhydrous sodium sulfate and concentrated, and the residual liquid was purified by silica gel column chromatography (chloroform). 3.12 g of 5- [2- [4- (dibutylamino) phenyl] vinyl] thiophene-2-carbaldehyde was obtained as a red-orange oil. (Yield 95.5%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 0.96 (6H, t, J = 7.7 Hz), 1.33-1.39 (4H, m), 1.55-1.61 (4H, m), 3.30 (4H, t, J = 7.7 Hz), 6.61 (2H, d, J = 8.8 Hz), 6.96 (1H, d, J = 15.9 Hz), 7. 03 (1H, d, J = 4.2 Hz), 7.07 (1H, d, J = 15.9 Hz), 7.35 (2H, d, J = 8.8 Hz), 7.61 (1H, t , J = 4.2 Hz), 9.81 (1H, s)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 14.0, 20.3, 29.4, 50.7, 115.5, 133.7, 111.5, 122.8, 124.7, 128 .5, 137.6, 140.0, 148.7, 154.5, 182.2

(Synthesis Example 6-5)
According to the reaction scheme represented by the following formula (6-5), N, N-dibutyl-N- [4- [2- [5- [2- [4- (tert-butyldiphenylsiloxymethyl) -2,5 -Dimethylphenyl] vinyl] -2-thienyl] vinyl] phenyl] amine was synthesized.

  Specifically, 0.24 g (2.89 mmol) of phenyllithium was added to 15 ml of tetrahydrofuran under an argon stream, and 4- (tert-butyldiphenylsiloxymethyl) -2,5-dimethylbenzyltriphenylphosphonium bromide 1 was added while cooling. .84 g (2.52 mmol) was added. After stirring, 0.87 g (2.54 mmol) of 5- [2- [4- (dibutylamino) phenyl] vinyl] thiophene-2-carbaldehyde was added dropwise. The mixture was stirred at the same temperature for 30 minutes, poured into water, extracted with toluene, and washed with saturated brine. The mixture was dehydrated with anhydrous sodium sulfate and concentrated, and the residue was purified by silica gel column chromatography. N, N-dibutyl-N- [4- [2- [5- [2- [4- (tert-butyldiphenylsiloxymethyl] -2,5-dimethylphenyl] vinyl] -2-thienyl] vinyl] phenylamine Was obtained as a red liquid (yield 78.2%).

(Synthesis Example 6-6)
According to a reaction scheme represented by the following formula (6-6), 4- [2- [5- [2-[(4-dibutylamino) phenyl] vinyl] -2-thienyl] vinyl] -2,5-dimethyl Benzyl alcohol was synthesized.

Specifically, N, N-dibutyl-N- [4- [2- [5- [2- [4- (tert-butyldiphenylsiloxymethyl] -2,5-dimethylphenyl] vinyl]-in 20 ml of tetrahydrofuran was added. 2-thienyl] vinyl] phenylamine (1.4 g, 1.966 mmol) was dissolved, and 39 ml of tetrabutylammonium fluoride (tetrahydrofuran solution) was added dropwise with stirring at room temperature, and the mixture was poured into water and extracted with ethyl acetate. The extract was washed with saturated brine, dehydrated with anhydrous sodium sulfate, concentrated, and purified by silica gel column chromatography to obtain 0.65 g as orange crystals (yield 69.9%).
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 0.97 (6H, t, J = 7.7 Hz), 1.33-1.40 (4H, m), 1.55-1.61 (4H, m), 2.36 (3H, s), 2.40 (3H, s), 3.29 (4H, t, J = 7.7 Hz), 4.67 (2H, d, J = 6.0 Hz) , 6.61 (2H, d, J = 8.8 Hz), 6.84 (1H, d, J = 15.9 Hz), 6.84 (1H, d, J = 3.8 Hz), 6.92 ( 1H, d, J = 3.8 Hz), 6.95 (1H, d, J = 15.9 Hz), 7.04 (1H, d, J = 15.9 Hz), 7.09 (1H, d, J = 15.9 Hz), 7.16 (1 H, s), 7.32 (2 H, d, J = 8.8 Hz), 7.38 (1 H, s)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 14.0, 18.3, 19.3, 20.3, 29.5, 50.8, 63.4, 111.7, 117.0, 123 0.0, 124.0, 124.9, 125.2, 126.8, 127.2, 127.7, 129.2, 130.0, 133.3, 133.7, 135.4, 137.8 , 140.7, 143.4, 147.9

(Synthesis Example 6-7)
According to a reaction scheme represented by the following formula (6-7), 4- [2- [5- [2-[(4-dibutylamino) phenyl] vinyl] -2-thienyl] vinyl] -2,5-dimethyl Benzaldehyde was synthesized.

Specifically, 4- [2- [5- [2-[(4-dibutylamino) phenyl] vinyl] -2-thienyl] vinyl] -2,5-dimethylbenzyl alcohol 0.65 g (1.37 mmol) Was dissolved in dichloromethane and 2.38 g (27.4 mmol) of activated manganese dioxide was added. After stirring at room temperature, the mixture was filtered, and the concentrated residue was purified by silica gel column chromatography. 0.61 g of 4- [2- [5- [2-[(4-dibutylamino) phenyl] vinyl] -2-thienyl] vinyl] -2,5-dimethylbenzaldehyde was obtained as reddish brown crystals. (Yield 94.1%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 0.96 (6H, t, J = 7.7 Hz), 1.33-1.39 (4H, m), 1.56-1.61 (4H, m), 2.44 (3H, s, Me), 2.65 (3H, s, Me), 3.29 (4H, t, J = 7.7 Hz), 6.61 (2H, d, J = 8.8 Hz), 6.86 (1H, d, J = 3.8 Hz), 6.87 (1H, d, J = 15.9 Hz), 6.95 (1H, d, J = 15.9 Hz), 6.99 (1H, d, J = 3.8Hz), 7.01 (1H, d, J = 15.9Hz), 7.23 (1H, d, J = 15.9Hz), 7.33 (2H , D, J = 8.8 Hz), 7.42 (1H, s), 7.58 (1H, s), 10.19 (1H, s)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 14.0, 19.2, 19.3, 20.3, 29.5, 50.8, 111.7, 116.7, 123.5, 123 .8,125.3,125.9,127.7,127.8,128.7,129.9,132.7,133.4,134.2,138.1,139.9,141.3 , 144.7, 148.1, 192.1

(Synthesis Example 6-8)
According to the reaction scheme represented by the following formula (6-8), 2- [3-cyano-4- [2- [4- [2- [5- [2- [4- (dibutylamino) phenyl] vinyl] -2-thienyl] vinyl] -2,5-dimethylphenyl] vinyl] -5,5-dimethyl-2 (5H) -furanylidene] propanedinitrile was synthesized.

Specifically, 250 mg (0 of 4- [2- [5- [2-[(4-dibutylamino) phenyl] vinyl] -2-thienyl] vinyl] -2,5-dimethylbenzaldehyde in an ethanol / tetrahydrofuran mixed solvent). .53 mmol) was dissolved. To this was added 112 mg (0.56 mmol) of 2- (3-cyano-4,5,5-trimethyl-2 (5H) -furanylidene] propanedinitrile, and the mixture was stirred at room temperature. The crystals obtained were washed with ethanol and washed with 2- [3-cyano-4- [2- [4- [2- [5- [2- [4- (dibutylamino) phenyl] vinyl]]. 289 mg of 2-thienyl] vinyl] -2,5-dimethylphenyl] vinyl] -5,5-dimethyl-2 (5H) -furanylidene] propanedinitrile as mp216-218 ° C. black crystals were obtained (yield). 83.5%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 0.97 (6H, t, J = 7.7 Hz), 1.33-1.40 (4H, m), 1.56-1.61 (4H, m), 1.78 (6H, s), 2.44 (3H, s), 2.46 (3H, s), 3.30 (4H, t, J = 7.7 Hz), 6.61 (2H) , D, J = 8.8 Hz), 6.86 (1H, d, J = 15.9 Hz), 6.87 (1H, d, J = 3.8 Hz), 6.90 (1H, d, J = 15.9 Hz), 6.94 (1H, d, J = 15.9 Hz), 6.98 (1H, d, J = 15.9 Hz), 6.99 (1H, d, J = 3.8 Hz), 7.24 (1H, d, J = 15.9 Hz), 7.32 (2H, d, J = 8.8 Hz), 7.46 (1 H, s), 7.52 (1 H, s), 8. 03 (1H, d J = 15.9Hz),
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 14.0, 19.4, 19.5, 20.3, 26.5, 29.5, 50.8, 57.0, 97.4, 98 2,110.8,111.0,111.8,111.7,113.8,116.6,123.2,123.7,125.4,125.8,127.2,127.9 , 128.4, 129.1, 130.2, 131.2, 134.3, 137.5, 139.9, 141.0, 144.4, 145.2, 148.2, 174.0, 175 .5

[Example 7]
In this example, 2- [3-cyano-4- [2- [5- [2- [4- [2- [4- (dibutylamino) phenyl] vinyl]] represented by the following formula (VII) was used. -2,5-dimethylphenyl] vinyl] -2-thienyl] vinyl] -5,5-dimethyl-2 (5H) -furanylidene] propanedinitrile was synthesized from the following synthesis examples (7-1) to (7-5). )

(Synthesis Example 7-1)
According to the reaction scheme represented by the following formula (7-1), 4- [2- [4- (dibutylamino) phenyl] vinyl] -2,5-dimethylbenzyl alcohol was synthesized.

  Specifically, 0.71 g (8.5 mmol) of phenyllithium was added to tetrahydrofuran under an argon stream, and 1.8 g of 4- (hydroxymethyl) -2,5-dimethylbenzyltriphenylphosphonium bromide under ice-cooling and stirring. 3.66 mmol) was added. At the same temperature, 0.86 g (3.68 mmol) of 4- (dibutylamino) benzaldehyde was added dropwise. After stirring at the same temperature for 1 hour, the mixture was poured into water and extracted with toluene. The extract was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated. The residue was purified by silica gel column chromatography to obtain 805 mg as a yellow liquid (yield 60.1%).

(Synthesis Example 7-2)
According to the reaction scheme represented by the following formula (7-2), 4- [2- [4- (dibutylamino) phenyl] vinyl] -2,5-dimethylbenzaldehyde was synthesized.

Specifically, 3.86 g (44.4 mmol) of active manganese dioxide was suspended in dichloromethane, and 805 mg of 4- [2- [4- (dibutylamino) phenyl] vinyl] -2,5-dimethylbenzyl alcohol was stirred. (2.2 mmol) was added. After stirring at room temperature, the mixture was filtered, and after concentration, the residue was purified by silica gel column chromatography. 721 mg of 4- [2- [4- (dibutylamino) phenyl] vinyl] -2,5-dimethylbenzaldehyde was obtained as an orange oil. (Yield 90.1%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 0.97 (6H, t, J = 7.7 Hz), 1.34-1.40 (4H, m), 1.56-1.61 (4H, m), 2.42 (3H, s), 2.65 (3H, s), 3.30 (4H, t, J = 7.7 Hz), 6.64 (2H, d, J = 8.8 Hz) 7.04 (1H, d, J = 15.9 Hz), 7.09 (1H, d, J = 15.9 Hz), 7.41 (2H, d, J = 8.8 Hz), 7.45 ( 1H, s,), 7.51 (1H, s), 10.17 (1H, s)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 14.0, 19.2, 19.3, 20.3, 29.5, 50.8, 111.6, 119.7, 124.1, 127 5, 128.3, 132.1, 132.9, 133.1, 134.1, 138.1, 142.7, 148.4, 192.2

(Synthesis Example 7-3)
According to the reaction scheme represented by the following formula (7-3), N, N-dibutyl-N- [4- [2- [2,5-dimethyl-4- [2- (2-thienyl) vinyl] phenyl] Vinyl] phenylamine was synthesized.

  Specifically, 0.19 g (2.26 mmol) of phenyllithium was added to tetrahydrofuran under an argon stream, and 0.78 g (1.98 mmol) of tenenyltriphenylphosphonium chloride was added while cooling. After stirring, 0.72 g (1.98 mmol) of 4- [2- [4- (dibutylamino) phenyl] vinyl] -2,5-dimethylbenzaldehyde was added dropwise. After stirring at the same temperature, the mixture was poured into water and extracted with toluene. The extract was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated. The residue was purified by silica gel column chromatography, and N, N-dibutyl-N- [4- [2- [2,5-dimethyl-4- [2- (2-thienyl) vinyl] phenyl] vinyl] phenyl] phenyl 606 mg of amine was obtained as a yellow liquid. (Yield 69.2%)

(Synthesis Example 7-4)
According to the reaction scheme represented by the following formula (7-4), 5- [2- [4- [2- [4- (dibutylamino) phenyl] vinyl] -2,5-dimethylphenyl] vinyl] thiophene-2 -Carbaldehyde was synthesized.

Specifically, N, N-dibutyl-N- [4- [2- [2,5-dimethyl-4- [2- (2-thienyl) vinyl] phenyl] vinyl] phenylamine 600 mg in tetrahydrofuran under an argon stream. (1.35 mmol) was dissolved, and 1.27 ml (2.03 mmol) of n-butyllithium (hexane solution) was added dropwise under cooling. After stirring for 1 hour, 0.13 ml (1.69 mol) of N, N-dimethylformamide was added dropwise at the same temperature and stirred. Water was added dropwise at 5 ° C. The mixture was extracted with ethyl acetate, washed with saturated brine, and dried over anhydrous sodium sulfate. Concentrate and purify the residue by silica gel column chromatography to obtain 5- [2- [4- [2- [4- (dibutylamino) phenyl] vinyl] -2,5-dimethylphenyl] vinyl] thiophene-2- 339 mg of carbaldehyde was obtained as a red liquid. (Yield 53.2%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 0.96 (6H, t, J = 7.7 Hz), 1.33-1.40 (4H, m), 1.56-1.61 (4H, m), 2.40 (3H, s), 2.43 (3H, s), 3.30 (4H, t, J = 7.7 Hz), 6.63 (2H, d, J = 8.8 Hz) , 6.98 (1H, d, J = 16.5 Hz), 7.04 (1H, d, J = 16.5 Hz), 7.12 (1H, d, J = 16.5 Hz), 7.14 ( 1H, d, J = 3.8 Hz), 7.38 (1H, d, J = 16.5 Hz), 7.39 (2H, s), 7.41 (2H, d, J = 8.8 Hz), 7.66 (1H, d, J = 3.8 Hz), 9.85 (1H, s)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 14.0, 19.5, 19.6, 20.3, 29.5, 50.8, 111.8, 120.6, 120.7, 124 8, 126.2, 126.9, 127.3, 128.0, 130.6, 130.7, 132.8, 133.2, 134.2, 137.3, 137.9, 141.3 , 148.1, 153.4, 182.5

(Synthesis Example 7-5)
According to the reaction scheme represented by the following formula (7-5), 2- [3-cyano-4- [2- [5- [2- [4- [2- [4- (dibutylamino) phenyl] vinyl]] -2,5-Dimethylphenyl] vinyl] -2-thienyl] vinyl] -5,5-dimethyl-2 (5H) -furanylidene] propanedinitrile was synthesized.

Specifically, 200 mg (0.424 mmol) of 5- [2- [4- [2- [4- (dibutylamino) phenyl] vinyl] -2,5-dimethylphenyl] vinyl] thiophene-2-carbaldehyde in ethanol. ) Was dissolved. To this was added 90 mg (0.452 mmol) of 2- (3-cyano-4,5,5-trimethyl-2 (5H) -furanylidene] propanedinitrile, and the mixture was stirred at room temperature. The crystals obtained by washing with silica gel were purified by silica gel column chromatography, and the obtained crystals were washed with ethanol to give 2- [3-cyano-4- [2- [5- [2- [4- [2 -[4- (dibutylamino) phenyl] vinyl] -2,5-dimethylphenyl] vinyl] -2-thienyl] vinyl] -5,5-dimethyl-2 (5H) -furanylidene] propanedinitrile mp212-214 As a result, 249 mg of black crystals were obtained at 9 ° C. (Yield 90.0%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 0.97 (6H, t, J = 7.7 Hz), 1.34-1.40 (4H, m), 1.57-1.62 (4H, m), 1.77 (6H, s), 2.41 (3H, s), 2.47 (3H, s), 3.30 (4H, t, J = 7.7 Hz), 6.64 (1H) , D, J = 15.9 Hz), 6.64 (2H, d, J = 8.8 Hz), 7.00 (1H, d, J = 15.9 Hz), 7.04 (1H, d, J = 15.9 Hz), 7.11 (1H, d, J = 3.8 Hz), 7.15 (1H, d, J = 15.9 Hz), 7.38 (1H, d, J = 15.9 Hz), 7.39 (1H, d, J = 3.8 Hz), 7.40 (2H, d, J = 8.8 Hz), 7.41 (1H, s), 7.44 (1H, s,), 7 .78 (1H, , J = 15.9Hz),
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 14.1, 19.6, 19.7, 20.4, 26.6, 29.6, 50.9, 57.0, 97.1, 97 2, 110.9, 111.3, 112.1, 111.8, 112.7, 120.3, 120.5, 124.6, 126.9, 127.3, 128.1, 129.6 130.9, 131.1, 131.4, 132.6, 133.3, 134.6, 137.1, 138.4, 139.3, 145.4, 148.2, 153.0, 170 .1, 172.9

[Example 8]
In this example, 2- [N- [4- [2- [4- [2- [5- [2- (4-cyano-5-dicyanomethylene-2,] represented by the following formula (VIII) was used. 2-Dimethyl-2,5-dihydrofuran-3-yl) vinyl] thiophen-2-yl] vinyl] -2,5-dimethylphenyl] vinyl] phenyl] -N- [2- (2,2-dimethylpropionyl) Oxy) ethyl] amino] ethyl 2,2-dimethylpropionate was obtained through the following synthesis examples (8-1) to (8-9).

(Synthesis Example 8-1)
According to the reaction scheme represented by the following formula (8-1), tert-butyldiphenyl 2-tenyloxysilane was synthesized.

Specifically, 12.0 g (0.105 mol) of 2-tenyl alcohol and 17.9 g (0.263 mol) of imidazole were dissolved in N, N-dimethylformamide. At room temperature, 31.8 g (0.116 mol) of tert-butylchlorodiphenylsilane was added dropwise. The mixture was stirred overnight at room temperature, poured into water, and extracted twice with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated. The obtained oil was purified by silica gel column chromatography to obtain 32.83 g of tert-butyldiphenyl 2-tenyloxysilane as a colorless oil. (Yield 88.6%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.08 (9H, s), 4.89 (2H, s), 6.82-6.83 (1H, m), 6.92-6.94 (1H, m), 7.23-7.24 (1H, m), 7.37-7.40 (4H, m), 7.42-7.45 (2H, m), 7.69-7 .71 (4H, m)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 19.4, 26.9, 61.6, 123.7, 124.6, 126.6, 144.9, 127.8, 129.99133.4 , 135.7

(Synthesis Example 8-2)
According to the reaction scheme represented by the following formula (8-2), 5- (tert-butyldiphenylsiloxymethyl) thiophene-2-carbaldehyde was synthesized.

Specifically, 10.0 g (28.4 mmol) of tert-butyldiphenyl 2-tenyloxysilane was dissolved in tetrahydrofuran under an argon stream, and 23.2 ml (37.1 mmol) of n-butyllithium (hexane solution) was added under cooling. It was dripped. After stirring, the temperature was increased and the mixture was stirred for 2 hours, and then 3.04 g (41.6 mmol) of N, N-dimethylformamide was added dropwise. After stirring for 30 minutes, water was added dropwise and the mixture was extracted twice with ether. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated. The residue was recrystallized from methanol to obtain 8.79 g of 5- (tert-butyldiphenylsiloxymethyl) thiophene-2-carbaldehyde as colorless crystals. The mother liquor was concentrated and purified by silica gel column chromatography, and then recrystallized from methanol to obtain 0.53 g of crystals. 9.32 g in total (yield 86.4%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.10 (9H, s), 4.91 (2H, d, J = 1.1 Hz), 6.91 (1H, m), 7.38-7 .41 (4H, m), 7.44-7.47 (2H, m), 7.63 (1H, m), 7.68-7.69 (4H, m), 9.87 (1H, s )
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 19.3, 26.7, 61.86, 123.8, 127.9, 130.0, 132.7, 135.5, 136.6, 142 .3, d156.8, 183.0

(Synthesis Example 8-3)
According to the reaction scheme represented by the following formula (8-3), 5- (tert-butyldiphenylsiloxymethyl) -2-enyl alcohol was synthesized.

Specifically, 2.7 ml of 0.2N sodium hydroxide was added to ethanol, and 0.54 g (14.3 mol) of sodium borohydride was dissolved therein. While stirring, 8.37 g (22.0 mol) of 5- (tert-butyldiphenylsiloxy) methylthiophene-2-carbaldehyde was added. After stirring, water and ethyl acetate were added for extraction. The aqueous layer was re-extracted with ethyl acetate, and the organic layers were combined and washed with saturated brine. The mixture was dehydrated with anhydrous sodium sulfate, concentrated, and purified by silica gel column chromatography. There were obtained 8.22 g of 5-[(tert-butyldiphenylsiloxy) methyl] -2-thenyl alcohol as a colorless oil. (Yield 97.7%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.08 (9H, s), 4.79 (2H, d, J = 6.0 Hz), 4.84 (2H, s), 6.69 (1H , D, J = 3.3 Hz), 6.83 (1H, d, J = 3.3 Hz), 7.37-7.40 (4H, m), 7.42-7.45 (2H, m) , 7.69-7.71 (4H, m)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 19.4, 26.9, 60.4, 61.7, 123.5, 125.1, 127.9, 129.9, 133.4, 135 .7, 143.2, 145.4

(Synthesis Example 8-4)
According to the reaction scheme represented by the following formula (8-4), 5-bromomethyl-2-enyloxy tert-butyldiphenyl silane was synthesized.

Specifically, 8.2 g (21.43 mmol) of 5- (t-butyldiphenylsiloxymethyl) -2-enyl alcohol and 8.9 g (26.84 mmol) of carbon tetrachloride were dissolved in tetrahydrofuran. Under ice-cooling, 7.04 g (26.84 mmol) of triphenylphosphine was added. After stirring, tetrahydrofuran was distilled off, ethyl acetate / hexane (1/4) was added, and insoluble crystals were removed by filtration. After concentration, the residue was purified by silica gel column chromatography to obtain 7.32 g of 5-bromomethyl-2-enyloxy tert-butyldiphenyl silane as a colorless oil. (Yield 76.7%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.08 (9H), 4.73 (2H, s), 4.82 (2H, s), 6.64 (1H, d, J = 3.3 Hz) )), 6.94 (1H, d, J = 3.8 Hz), 7.38-7.40 (4H, m), 7.42-7.45 (2H, m), 7.68-7. 70 (4H, m)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 19.2, 26.7, 27.4, 61.6, 123.3, 127.8, 129.8, 133.0, 135.6, 139 .3, 147.0

(Synthesis Example 8-5)
According to the reaction scheme represented by the following formula (8-5), 5- (tert-butyldiphenylsiloxymethyl) -2-enyltriphenylphosphonium bromide was synthesized.

Specifically, 0.68 g (1.53 mmol) of 5-bromomethyl-2-thenyloxy tert-butyldiphenyl silane and 0.4 g (1.53 mmol) of triphenylphosphine were added to acetonitrile and the oil bath was heated at 60 ° C. for 7 hours. Stir. After cooling to room temperature, the precipitated crystals were removed by filtration, and ether was added to the filtrate and allowed to stand. The precipitated crystals were collected by filtration, washed with ether, and dried under reduced pressure. 0.72 g of 5- (tert-butyldiphenylsiloxymethyl) -2-enyl triphenylphosphonium bromide was obtained as colorless crystals (yield 66.7%).
¹ H-NMR (600 MHz, DMSO-d ₆ ) δ: 0.94 (9H, s), 4.80 (2H, d, J = 2.2 Hz), 5.49 (2H, d, J = 14. 3 Hz), 6.65 (1 H, t, J = 3.3 Hz), 6.74 (1 H, d, J = 3.3 Hz), 7.40-7.42 (4 H, m), 7.47- 7.50 (2H, m), 7.54-7.56 (4H, m), 7.68-7.72 (6H, m), 7.74-7.77 (6H, m), 7. 91-7.93 (3H, m)

(Synthesis Example 8-6)
In accordance with the reaction scheme represented by the following formula (8-6), 2- [N- [4- [2- [4- [2- [5- (tert-butyldiphenylsiloxymethyl) -2-thienyl] vinyl] -2,5-Dimethylphenyl] vinyl] phenyl] -N- [2- (2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate was synthesized.

  Specifically, 0.15 g (1.81 mmol) of phenyl lithium was added to tetrahydrofuran under an argon atmosphere, and 1.07 g (1) of 5- (tert-butyldiphenylsiloxymethyl) -2-enyltriphenylphosphonium bromide under ice cooling. .51 mmol) was added. After stirring at the same temperature, 2- [N- [4- [2- (4-formyl-2,5-dimethylphenyl) vinyl] phenyl] -N- [2- (2,2-dimethylpropionyloxy) ethyl] Amino] ethyl 2,2-dimethylpropionate 0.768 g (1.51 mmol) was added dropwise. After stirring, the mixture was poured into water and extracted twice with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated. The dark reddish brown residue was purified by silica gel column chromatography (ethyl acetate / hexane = 1/2). 2- [N- [4- [2- [4- [2- [5- (tert-Butyldiphenylsiloxymethyl] -2-thienyl] vinyl] -2,5-dimethylphenyl] vinyl] phenyl] -N- 1.16 g of [2- (2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate was obtained as an orange oil (yield 89.7%).

(Synthesis Example 8-7)
According to a reaction scheme represented by the following formula (8-7), 2- [N- [4- [2- [4- [2- (5-hydroxymethyl-2-thienyl) vinyl] -2,5-dimethyl Phenyl] vinyl] phenyl] -N- [2- (2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate was synthesized.

Specifically, 2- [N- [4- [2- [4- [2- [5- (tert-butyldiphenylsiloxymethyl) -2-thienyl] vinyl] -2,5-dimethylphenyl] was added to tetrahydrofuran. 1.16 g (1.36 mmol) of vinyl] phenyl] -N- [2- (2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate are dissolved, and the mixture is stirred at room temperature with stirring. 27 ml of tetrabutylammonium bromide (tetrahydrofuran solution) was added dropwise. After stirring, the mixture was poured into water and extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated. The residue was purified by silica gel column chromatography and 2- [N- [4- [2- [4- [2- (5-hydroxymethyl-2-thienyl) vinyl] -2,5-dimethylphenyl] vinyl]. 0.35 g of phenyl] -N- [2- (2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate was obtained as an orange oil. (Yield 41.7%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.19 (18H, s), 2.39 (6H, s), 3.65 (4H, t, J = 6.0 Hz), 4.24 (4H , T, J = 6.0 Hz, OCH ₂ ), 4.77 (2H, s), 6.78 (2H, d, J = 8.8 Hz), 6.88 (1H, d, J = 15.9 Hz) ), 6.89 (1H, d, J = 15.9 Hz), 6.94 (1H, d, J = 15.9 Hz), 7.08 (1H, d, J = 15.9 Hz), 7.07 (2H, s), 7.35 (1H, s), 7.39 (1H, s), 7.41 (2H, d, J = 8.8 Hz)

(Synthesis Example 8-8)
According to the reaction scheme represented by the following formula (8-8), 2- [N- [4- [2- [4- [2- (5-formylthiophen-2-yl) vinyl] -2,5-dimethyl Phenyl] vinyl] phenyl] -N- [2- (2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate was synthesized.

Specifically, 2- [N- [4- [2- [4- [2- (5-hydroxymethyl-2-thienyl) vinyl] -2,5-dimethylphenyl] vinyl] phenyl] -N in dichloromethane is used. -[2- (2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate (349 mg, 0.565 mmol) was dissolved, and active manganese dioxide (980 mg, 11.3 mmol) was added at room temperature. Stir. Filtration, concentration, and purification by silica gel column chromatography. 2- [N- [4- [2- [4- [2- (5-formylthiophen-2-yl) vinyl] -2,5-dimethylphenyl] vinyl] phenyl] -N- [2- (2, 236.7 mg of 2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate was obtained as red-orange crystals. (Yield 68.0%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.20 (18H, s), 2.41 (3H, s), 2.43 (3H, s), 3.67 (4H, t, J = 6) .3 Hz), 4.25 (4 H, t, J = 6.3 Hz), 6.79 (2 H, d, J = 8.8 Hz), 6.98 (1 H, d, J = 15.9 Hz), 7 .08 (1H, d, J = 15.9 Hz), 7.14 (1 H, d, J = 15.9 Hz), 7.38 (1 H, d, J = 15.9 Hz), 7.151 H, d, J = 4.4 Hz), 7.40 (1H, s), 7.43 (1H, s), 7.43 (2H, d, J = 8.8 Hz), 7.67 (1H, d, J = 3.8 Hz), 9.86 (1 H, s)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 19.69.7, 27.3, 38.8, 49.6, 61.6, 112.3, 120.8, 121.9, 126.3 , 126.7, 127.0, 127.3, 128.1, 130.1, 130.6, 133.1, 133.3, 134.3, 137.4, 137.6, 141.4, 147 .2,178.6,)

(Synthesis Example 8-9)
According to the reaction scheme represented by the following formula (8-9), 2- [N- [4- [2- [4- [2- [5- [2- (4-cyano-5-dicyanomethylene-2, 2-Dimethyl-2,5-dihydrofuran-3-yl) vinyl] thiophen-2-yl] vinyl] -2,5-dimethylphenyl] vinyl] phenyl] -N- [2- (2,2-dimethylpropionyl) Oxy) ethyl] amino] ethyl 2,2-dimethylpropionate was synthesized.

Specifically, 2- [N- [4- [2- [4- [2- (5-formyl) thiophen-2-yl] vinyl] -2,5-dimethylphenyl] vinyl] phenyl-N in ethanol. -[2- (2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate 236.7 mg (0.384 mmol) and 2- (3-2- (3-cyano-4,5) , 5-Trimethyl-2 (5H) -furanylidene] propanedinitrile 84.2 mg (0.423 mmol) was dissolved and stirred at room temperature, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography. And then washed with 2- [N- [4- [2- [4- [2- [5- [2- (4-cyano-5-dicyanomethylene-2,2-dimethyl-2,5-dihydrofuran- 3 Yl) vinyl] thiophen-2-yl] vinyl] -2,5-dimethylphenyl] vinyl] phenyl] -N- [2- (2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpro 227 mg of pionate was obtained as black powdery crystals of mp 197-203 ° C. (yield 74.2%).
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.20 (18H, s), 1.77 (6H, s), 2.42 (3H, s), 2.47 (3H, s), 3. 67 (4H, t, J = 6.3 Hz), 4.26 (4H, t, J = 6.3 Hz), 6.64 (1H, d, J = 15.4 Hz), 7.77 (1H, d , J = 15.4 Hz), 6.80 (2H, d, J = 8.8 Hz), 7.00 (1H, d, J = 15.9 Hz), 7.09 (1H, d, J = 15. 9 Hz), 7.11 (1 H, d, J = 4.4 Hz), 7.16 (1 H, d, J = 15.9 Hz), 7.37 (1 H, d, J = 15.9 Hz), 7. 39 (1H, d, J = 3.8 Hz), 7.42 (2H, d, J = 8.8 Hz), 7.441 (1 H, s) 7.444 (1 H, s)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 19.65, 19.7, 26.6, 27.3, 38.8, 49.6, 56.9, 61.5, 97.2, 97 4, 110.9, 111.3, 112.1, 112.3, 112.7, 120.6, 121.7, 126.6, 127.1, 127.3, 128.15, 128.20 , 130.4, 131.3, 132.9, 133.4, 134.6, 137.1, 138.0, 138.4, 139.3, 147.2, 152.9, 173.0, 175 .6,178.6

[Example 9]
In this example, 2- [N- [4- [2- [5-[-2- [4- [2- (4-cyano-5-dicyanomethylene-2] represented by the following formula (IX)] was used. , 2-Dimethyl-2,5-dihydrofuran-3-yl) vinyl] -2,5-dimethylphenyl] vinyl] -2-thienyl] vinyl] phenyl] -N- [2- (2,2-dimethylpropionyl) Oxy) ethyl] amino] ethyl 2,2-dimethylpropionate was obtained through the following synthesis examples (9-1) to (9-10).

(Synthesis Example 9-1)
According to the reaction scheme represented by the following formula (9-1), 2- [N- [4- [2- [5- (tert-butyldiphenylsiloxymethyl) -2-thienyl] vinyl] phenyl] -N- [ 2- (2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate was synthesized.

  Specifically, 0.36 g (4.25 mmol) of phenyllithium was added to tetrahydrofuran under an argon atmosphere, and 2.5 g of 5- (tert-butyldiphenylsiloxymethyl) -2-enyltriphenylphosphonium bromide under ice-cooling and stirring. 3.53 mmol) was added. After stirring at the same temperature, 2- [N- (4-formylphenyl) -N- [2- (2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate 1.34 g (3 .55 mmol) was added dropwise. After stirring, the mixture was poured into water and extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated. The residue was purified by silica gel column chromatography, and 2- [N- [4- [2- [5- (tert-butyldiphenylsiloxymethyl) -2-thienyl] vinyl] phenyl] -N- [2- (2 , 2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate as a yellow-orange oil. (Yield 81.9%)

(Synthesis Example 9-2)
According to the reaction scheme represented by the following formula (9-2), 2- [N- [4- [2-[(5-hydroxymethyl) -2-thienyl] vinyl] phenyl] -N- [2- (2 , 2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate was synthesized.

  Specifically, 2- [N- [4- [2- [5- (tert-butyldiphenylsiloxymethyl) -2-thienyl] vinyl] phenyl] -N- [2- (2,2-dimethyl) was added to tetrahydrofuran. 1.6 g (2.2 mmol) of propionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate was dissolved, and 11 ml of tetrabutylammonium fluoride (tetrahydrofuran solution) was added dropwise with stirring. After stirring, the mixture was poured into water and extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated. Purification by silica gel column chromatography gave 2- [N- [4- [2-[(5-hydroxymethyl) -2-thienyl] vinyl] phenyl] -N- [2- (2,2-dimethylpropionyloxy). 0.93 g of ethyl] amino] ethyl 2,2-dimethylpropionate was obtained as an orange oil. (Yield 86.2%)

(Synthesis Example 9-3)
According to a reaction scheme represented by the following formula (9-3), 2- [N- [4- [2-[(5-formyl) -2-thienyl] vinyl] phenyl] -N- [2- (2, 2-Dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate was synthesized.

Specifically, 2- [N- [4- [2-[(5-hydroxymethyl) -2-thienyl] vinyl] phenyl] -N- [2- (2,2-dimethylpropionyloxy) ethyl] amino ] 1.14 g (2.34 mmol) of ethyl 2,2-dimethylpropionate was dissolved in dichloromethane, and 3.0 g (34.5 mmol) of active manganese dioxide was added. After stirring at room temperature, the mixture was filtered, and after concentration, the residue was purified by silica gel column chromatography. 2- [N- [4- [2-[(5-formyl) -2-thienyl] vinyl] phenyl] -N- [2- (2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2- 0.92 mg of dimethylpropionate was obtained as an orange oil. (Yield 92.0%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.19 (18H, s), 3.67 (4H, t, J = 6.3 Hz), 4.25 (4H, t, J = 6.3 Hz) , 6.78 (2H, d, J = 8.8Hz), 7.00 (1H, d, J = 15.9Hz), 7.08 (1H, d, J = 15.9Hz), 7.07 ( 1H, d, J = 3.8 Hz), 7.39 (2H, d, J = 8.8 Hz), 7.64 (1H, d, J = 3.8 Hz), 9.82 (1H, s)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 27.2, 38.8, 49.3, 61.4, 112.2, 116.7, 124.7, 125.2, 128.6, 133 .2, 137.5, 140.4, 148.0, 153.9, 178.5, 182.4

(Synthesis Example 9-4)
According to the reaction scheme represented by the following formula (9-4), 2- [N- [4- [2- [5- [2- [4- (tert-butyldiphenylsiloxy) methyl-2,5-dimethylphenyl] ] Vinyl] -2-thienyl] vinyl] phenyl] -N- [2- (2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate was synthesized.

  Specifically, diethyl 4- (tert-butyldiphenylsiloxymethyl) -2,5-dimethylbenzylphosphonate 171 mg (0.326 mmol) and 2- [N- [4- [2-[(5-formyl) -2] -Thienyl] vinyl] phenyl] -N- [2- (2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate 158 mg (0.325 mmol) was dissolved in tetrahydrofuran and stirred at room temperature. Then, 42 mg (0.374 mmol) of potassium t-butoxide was added dropwise. After stirring, the mixture was poured into saturated aqueous sodium hydrogen carbonate and extracted twice with ethyl acetate. The extract was washed with saturated brine, dehydrated with anhydrous sodium sulfate, concentrated, and the residue was purified by silica gel column chromatography. 2- [N- [4- [2- [5- [2- [4- (tert-Butyldiphenylsiloxymethyl) -2,5-dimethylphenyl] vinyl] -2-thienyl] vinyl] phenyl] -N- 110 mg of [2- (2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate was obtained as a yellow oil. (Yield 40.2%)

(Synthesis Example 9-5)
According to the reaction scheme represented by the following formula (9-5), 2- [N- [4- [2- [5- [2- [4- (tert-butyldiphenylsiloxymethyl) -2,5-dimethylphenyl] ] Vinyl] -2-thienyl] vinyl] phenyl] -N- [2- (2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate was synthesized.

  Specifically, 0.16 g (1.86 mmol) of phenyllithium was added to tetrahydrofuran under an argon stream, and 4- (tert-butyldiphenylsiloxymethyl) -2,5-dimethylbenzyltriphenylphosphonium bromide was added while cooling. 135 g (1.55 mmol) was added. After stirring the orange liquid, 2- [N- [4- [2-[(5-formyl) -2-thienyl] vinyl] phenyl] -N- [2- (2,2-dimethylpropionyloxy) ethyl] amino Ethyl 2,2-dimethylpropionate (0.755 g, 1.55 mmol) was added dropwise. The mixture was stirred at room temperature, poured into water, and extracted with ethyl acetate. The extract was washed with saturated brine, dehydrated with anhydrous sodium sulfate, and concentrated. The residue was purified by silica gel column chromatography, and 2- [N- [4- [2- [5- [2- [4- (tert-butyldiphenylsiloxymethyl) -2,5-dimethylphenyl] vinyl] was obtained. There were obtained 1.27 g of 2-thienyl] vinyl] phenyl] -N- [2- (2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate as an orange oil. (Yield 95.5%)

(Synthesis Example 9-6)
According to a reaction scheme represented by the following formula (9-6), 2- [N- [4- [2- [5- [2- (4-hydroxymethyl-2,5-dimethylphenyl) vinyl] -2- Thienyl] vinyl] phenyl] -N- [2- (2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate was synthesized.

Specifically, 2- [N- [4- [2- [5- [2- [4- (tert-butyldiphenylsiloxymethyl) -2,5-dimethylphenyl] vinyl] -2-thienyl] is added to tetrahydrofuran. 1.38 g (1.61 mmol) of vinyl] phenyl] -N- [2- (2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate are dissolved, and the mixture is stirred at room temperature with stirring. 8.5 ml of tetrabutylammonium bromide (tetrahydrofuran solution) was added dropwise. After stirring, the mixture was poured into water and extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated. Purification by silica gel column chromatography gave 2- [N- [4- [2- [5- [2- (4-hydroxymethyl-2,5-dimethylphenyl) vinyl] -2-thienyl] vinyl] phenyl]-. 473 mg of N- [2- (2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate was obtained as an orange oil. (Yield 95.0%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.19 (18H, s), 2.35 (3H, s), 2.40 (3H, s), 3.66 (4H, t, J = 6) .3 Hz), 4.25 (4 H, t, J = 6.3 Hz), 4.67 (2 H, d, J = 4.4 Hz), 6.77 (2 H, d, J = 8.8 Hz), 6 .84 (1H, d, J = 15.9 Hz), 7.00 (1H, d, J = 15.9 Hz), 6.87 (1H, d, J = 3.3 Hz) 6.93 (1H, d , J = 3.3 Hz), 7.05 (1H, d, J = 15.9 Hz), 7.10 (1H, d, J = 15.9 Hz), 7.16 (1H, s), 7.36 (2H, d, J = 8.8 Hz), 7.38 (1H, s)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 18.4, 19.4, 27.3, 38.8, 49.5), 61.6, 63.5, 112.3, 118.2. 1213.0, 125.3, 125.8, 126.0, 126.9, 127.3, 127.9, 128.7, 130.1, 133.4, 133.8, 135.4, 138. 0, 141.2, 143.0, 147.2, 178.6

(Synthesis Example 9-7)
According to the reaction scheme represented by the following formula (9-7), 2- [N- [4- [2- [5- [2- (4-formyl-2,5-dimethylphenyl) vinyl] -2-thienyl) ] Vinyl] phenyl] -N- [2- (2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate was synthesized.

Specifically, 2- [N- [4- [2- [5- [2- (4-hydroxymethyl-2,5-dimethylphenyl) vinyl] -2-thienyl] vinyl] phenyl] -N is added to dichloromethane. -[2- (2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate 855 mg (1.38 mmol) was dissolved and 1.8 g (20.7 mmol) of active manganese dioxide was added. . After stirring at room temperature, the mixture was filtered, concentrated, and purified by silica gel column chromatography. 2- [N- [4- [2- [5- [2- (4-Formyl-2,5-dimethylphenyl) vinyl] -2-thienyl] vinyl] phenyl] -N- [2- (2,2 -Dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate was obtained as red-orange crystals in 792 mg. (Yield 93.0%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.19 (18H, s), 2.45 (3H, s), 2.65 (3H, s), 3.66 (4H, t, J = 6) .3 Hz), 4.25 (4 H, t, J = 6.3 Hz), 6.77 (2 H, d, J = 8.8 Hz), 6.87 (1 H, d, J = 15.9 Hz), 6 .99 (1H, d, J = 15.9 Hz), 6.89 (1H, d, J = 3.3 Hz) 7.00 (1H, d, J = 3.3 Hz), 7.03 (1H, d , J = 15.9 Hz), 7.24 (1H, d, J = 15.9 Hz), 7.36 (2H, d, J = 8.8 Hz), 7.43 (1H, s), 7.59 (1H, s), 10.29 (1H, s)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 19.3, 19.4, 27.3, 38.8, 49.5, 61.6, 112.3, 117.9, 123.9, 125 .8, 125.9, 127.9, 128.0, 128.7, 129.4, 132.8, 133.6, 134.3, 138.2, 140.4, 141.3, 144.3 , 147.3, 178.6, 192.2

(Synthesis Example 9-8)
According to the reaction scheme represented by the following formula (9-8), 2- [N- [4- [2- [5- [2- [4- [2- (4-cyano-5-dicyanomethylene-2, 2-dimethyl-2,5-dihydrofuran-3-yl) vinyl] -2,5-dimethylphenyl] vinyl] -2-thienyl] vinyl] phenyl] -N- [2- (2,2-dimethylpropionyloxy) ) Ethyl] amino] ethyl 2,2-dimethylpropionate was synthesized.

Specifically, 2- (3-cyano-4,5,5-trimethyl-2 (5H) -furanilidene] propanedinitrile 0.25 g (1.255 mmol) and 2- [N- [4- [2- [5- [2- (4-Formyl-2,5-dimethylphenyl) vinyl] -2-thienyl] vinyl] phenyl-N- [2- (2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2, 0.64 g (1.039 mmol) of 2-dimethylpropionate was dissolved in ethanol and stirred at room temperature, and the precipitated crystals were collected by filtration to obtain 0.59 g of crystals. 2- [N- [4- [2- [5- [2- [4- [2- (4-cyano-5-dicyanomethylene-2,2-dimethyl-2,5-dihydrofuran] -3-yl) vinyl] 2,5-dimethylphenyl] vinyl] -2-thienyl] vinyl] phenyl] -N- [2- (2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate mp186-187 0.67 g was obtained as black powdery crystals at a temperature of 8 ° C. (Yield 80.8%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.19 (18H, s), 1.77 (6H, s), 2.46 (3H, s), 2.28 (3H, s), 3. 67 (4H, t, J = 6.3 Hz), 4.25 (4H, t, J = 6.3 Hz), 6.78 (2H, d, J = 8.8 Hz), 6.87 (1H, d , J = 15.9 Hz), 7.00 (1H, d, J = 15.9 Hz), 6.90 (1H, d, J = 2.7 Hz), 6.92 (1H, d, J = 5. 9 Hz), 8.05 (1 H, d, J = 5.9 Hz), 7.01 (1 H, d, J = 3.9 Hz), 7.03 (1 H, d, J = 15.9 Hz), 7. 26 (1H, d, J = 15.9 Hz), 7.37 (2H, d, J = 8.8 Hz), 7.48 (1 H, s), 7.54 (1 H, s)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 19.5, 19.6, 26.7, 27.3, 38.8, 49.5, 57.3, 61.5, 97.5, 98 4, 110.8, 111.1, 111.8, 112.3, 114.0, 117.9, 123.6, 125.7, 125.9, 126.0, 127.4, 128.1 , 128.5, 129.1, 129.7, 131.4, 134.5, 137.6, 140.4, 141.0, 144.5, 144.7, 147.4, 174.1, 175 .6,178.6

[Example 10]
In this example, 2- [3-cyano-4- [2- [4- [2- [5- [2- [4- [N, N-bis [2]] represented by the following formula (X) is used. -(Tert-Butyldiphenylsiloxy) ethyl] amino] phenyl] vinyl] -2-thienyl] vinyl] -2,5-dimethylphenyl] vinyl] -5,5-dimethyl-2 (5H) -furanylidene] propanedinitrile Was obtained through the following synthesis examples (10-1) to (10-9).

(Synthesis Example 10-1)
According to the reaction scheme represented by the following formula (10-1), 2- [N- [2- (2,2-dimethylpropionyloxy) ethyl] -N- [4- [2- (2-thienyl) vinyl] Phenyl] amino] ethyl 2,2-dimethylpropionate was synthesized.

Specifically, 0.61 g (7.28 mmol) of phenyllithium was added to tetrahydrofuran under an argon stream, and 2.6 g (6.58 mmol) of tenenyltriphenylphosphonium bromide was added with cooling and stirring. After stirring at the same temperature, 2- [N- (4-formylphenyl) -N- [2- (2,2-dimethylpropionyloxy) ethyl] amino] ethyl 2,2-dimethylpropionate 2.5 g (6 0.62 mmol) was added dropwise. The mixture was poured into water after stirring and extracted with toluene. The extract was washed with saturated brine, dehydrated with anhydrous sodium sulfate, concentrated, and purified by silica gel column chromatography. 2- [N- [2- (2,2-dimethylpropionyloxy) ethyl] -N- [4- [2- (2-thienyl) vinyl] phenyl] amino] ethyl 2,2-dimethylpropionate yellow 2.1 g was obtained as an oil. (Yield 69.8%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.19 (18H, s), 3.65 (4H, t, J = 6.0 Hz), 4.24 (4H, t, J = 6.0 Hz) , 6.76 (2H, d, J = 8.8 Hz), 6.84 (1 H, d, J = 15.9 Hz), 7.03 (1H, d, J = 15.9 Hz), 6.97- 6.99 (2H, m), 7.12 (1H, d, J = 5.0 Hz), 7.35 (2H, d, J = 8.8 Hz)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 27.3, 38.8, 49.5, 61.6, 112.3, 118.1, 123.3, 124.8, 126.1, 127 .6,127.8,128.4,143.9,147.1,178.6

(Synthesis Example 10-2)
2- [N- (2-hydroxyethyl) -N- [4- [2- (2-thienyl) vinyl] phenyl] amino] ethanol was synthesized according to the reaction scheme represented by the following formula (10-2). .

Specifically, 4.0 g (0.1 mol) of sodium hydroxide was dissolved in 6.5 ml of water, and 25 ml of ethanol was added. To this was added 2- [N- [2- (2,2-dimethylpropionyloxy) ethyl] -N- [4- [2- (2-thienyl) vinyl] phenyl] amino] ethyl 2,2-dimethylpropionate. 1.71 g (4.98 mmol) was added and stirred. The reaction solution was poured into water and stirred, and the precipitated crystals were collected by filtration. Washed repeatedly with water and dried under reduced pressure. 1.07 g of 2- [N- (2-hydroxyethyl) -N- [4- [2- (2-thienyl) vinyl] phenyl] amino] ethanol was obtained as yellow crystals. (Yield 74.3%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 3.15 (2H, s), 3.61 (4H, t, J = 4.7 Hz), 3.88 (4H, t, J = 4.7 Hz) , 6.67 (2H, d, J = 8.8Hz), 6.75 (1H, d, J = 16.5Hz), 7.03 (1H, d, J = 16.5Hz), 6.97- 6.99 (2H, m), 7.13 (1H, d, J = 4.4 Hz), 7.34 (2H, d, J = 8.8 Hz)

(Synthesis Example 10-3)
According to the reaction scheme represented by the following formula (10-3), N, N-bis [2- (tert-butyldiphenylsiloxy) ethyl] -N- [4- [2- (2-thienyl) vinyl] phenyl] An amine was synthesized.

Specifically, 1.06 g (3.66 mmol) of 2- [N- (2-hydroxyethyl) -N- [4- [2- (2-thienyl) vinyl] phenyl] amino] ethanol and 1.25 g of imidazole. (18.36 mmol) was dissolved in N, N-dimethylformamide. While stirring at room temperature, 2.23 g (8.11 mmol) of tert-butylchlorodiphenylsilane was added dropwise. After stirring, ethyl acetate was added to dissolve the precipitated crystals, which were washed successively with water and then with saturated brine. After dehydration with anhydrous sodium sulfate and concentration, the precipitated crystals were recrystallized from ethanol. 2.53 g of N, N-bis [2- (tert-butyldiphenylsiloxy) ethyl] -N- [4- [2- (2-thienyl) vinyl] phenyl] amine was obtained as yellow crystals. (Yield 90.2%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.04 (18H, s), 3.41 (4H, t, J = 6.6 Hz), 3.76 (4H, t, J = 6.6 Hz) , 6.27 (2H, d, J = 8.8Hz), 6.79 (1H, d, J = 15.9Hz), 6.95 (1H, d, J = 15.9Hz), 6.95- 6.97 (2H, m), 7.10 (1H, d, J = 4.9 Hz), 7.11 (2H, d, J = 8.8 Hz), 7.33-7.35 (8H, m ), 7.40-7.43 (4H, m), 7.62-7.63 (8H, m)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 19.1, 26.9, 53.0, 60.9, 111.5, 117.2, 122.9, 124.4, 124.6, 127 5, 127.6, 127.8, 128.9, 129.8, 133.5, 135.7, 144.2, 147.5

(Synthesis Example 10-4)
According to the reaction scheme represented by the following formula (10-4), 2- [2- [4- [N, N-bis [2-[(tert-butyldiphenylsiloxy) ethyl] amino] phenyl] vinyl] thiophene- 5-carbaldehyde was synthesized.

20 ml of tetrahydrofuran was added 2.53 g (3.3 mmol) of N, N-bis [2- (tert-butyldiphenylsiloxy) ethyl] -N- [4- [2- (2-thienyl) vinyl] phenyl] amine under an argon atmosphere. Then, 3.1 ml (4.95 mmol) of n-butyllithium (hexane solution) was added dropwise with cooling. After stirring, 0.3 g (4.1 mmol) of N, N-dimethylformamide was added dropwise. After stirring, the temperature was raised and water was slowly added dropwise. The mixture was extracted with ethyl acetate, washed with saturated brine, and dried over anhydrous sodium sulfate. Concentrated and purified by silica gel column chromatography. Subsequently, recrystallization from an ethyl acetate / hexane mixed solvent gave 2- [2- [4- [N, N-bis [2-[(tert-butyldiphenylsiloxy) ethyl] amino] phenyl] vinyl] thiophene-5-carba. 2.41 g of aldehyde was obtained as yellow crystals. (Yield 91.9%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.04 (18H, s), 3.48 (4H, t, J = 6.6 Hz), 3.75 (4H, t, J = 6.6 Hz) 6.29 (2H, d, J = 19.3 Hz), 6.92 (1 H, d, J = 15.9 Hz), 7.03 (1 H, d, J = 15.9 Hz), 7.04 ( 1H, d), 7.15 (2H, d, J = 9.3 Hz), 7.33-7.36 (8H, m), 7.41-7.44 (4H, m), 7.62 ( 1H, d, J = 3.3 Hz), 7.62-7.63 (8H, m)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 19.2, 26.9, 53.0, 60.9, 111.6, 115.8, 123.5, 124.9, 127.8, 128 .5, 129.8, 133.4, 133.7, 135.7, 137.6, 140.2, 148.5, 154.5, 182.4)

(Synthesis Example 10-5)
According to the reaction scheme represented by the following formula (10-5), 4- [2- [5- [2- [4- [N, N-bis [2- (tert-butyldiphenylsiloxy) ethyl] amino] phenyl] ] Vinyl] -2-thienyl] vinyl] -2,5-dimethylbenzyl acetate was synthesized.

Specifically, 0.11 g (1.31 mmol) of phenyllithium was added to tetrahydrofuran under an argon stream, and the mixture was cooled with ice and stirred with 0.67 g (1. 4-acetoxymethyl-2,5-dimethylbenzyltriphenylphosphonium bromide). 26 mmol) was added. At the same temperature, 1.0 g (1.26 mmol) of 2- [2- [4- [N, N-bis [2-[(tert-butyldiphenylsiloxy) ethyl] amino] phenyl] vinyl] thiophene-5-carbaldehyde Was dripped. After 20 minutes, the ice bath was removed and the mixture was stirred at room temperature for 1 hour. The reaction mixture was poured into water and extracted twice with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated. The residue was purified by silica gel column chromatography, and 4- [2- [5- [2- [4- [N, N-bis [2- (tert-butyldiphenylsiloxy) ethyl] amino] phenyl] vinyl]- 0.693 g of 2-thienyl] vinyl] -2,5-dimethylbenzyl acetate was obtained as a red oil. (Yield 56.8%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.05 (18H, s), 2.04 (3H, s), 2.34 (3H, s), 2.39 (3H, s), 3. 40 (4H, t, J = 6.6 Hz), 3.74 (4H, t, J = 6.6 Hz), 5.08 (2H, s), 6.27 (2H, d, J = 8.8 Hz) ), 6.80 (1H, d, J = 15.9 Hz), 6.85 (1H, d, J = 3.3 Hz), 6.91 (1H, d, J = 15.9 Hz), 6.92 (1H, d, J = 3.8 Hz), 7.03 (1H, d, J = 15.9 Hz), 7.09 (1H, d, J = 15.9 Hz), 7.12 (1H, s) , 7.12 (2H, d, J = 8.8 Hz), 7.33-7.36 (9H, m), 7.38 (1H, s), 7.41-7.44 (4H, m) , 7.62-7 64 (8H, m)

(Synthesis Example 10-6)
According to the reaction scheme represented by the following formula (10-6), 4- [2- [5- [2- [4- [N, N-bis [2- (tert-butyldiphenylsiloxy) ethyl] amino] phenyl] [Vinyl] -2-thienyl] vinyl] -2,5-dimethylbenzyl alcohol was synthesized.

Specifically, 4- [2- [5- [2- [4- [N, N-bis [2- (tert-butyldiphenylsiloxy) ethyl] amino] phenyl] vinyl] -2-thienyl] vinyl] 693 mg (0.716 mmol) of -2,5-dimethylbenzyl acetate was dissolved in dioxane, and 12 ml of 10% aqueous sodium hydroxide was added. After stirring at room temperature, the mixture was added to water and extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated. The residual liquid was purified by silica gel column chromatography, and 4- [2- [5- [2- [4- [N, N-bis [2- (tert-butyldiphenylsiloxy) ethyl] amino] phenyl] vinyl]- 432 mg of 2-thienyl] vinyl] -2,5-dimethylbenzyl alcohol was obtained as an orange oil. (Yield 65.2%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.05 (18H, s), 2.35 (3H, s), 2.40 (3H, s), 3.47 (4H, t, J = 6) _{.6Hz 2), 3.74 (4H,} t, J = 6.6Hz 2), 4.66 (2H, s), 6.27 (2H, d, J = 8.8Hz), 6.79 (1H , D, J = 15.9 Hz), 6.84 (1H, d, J = 3.8 Hz), 6.91 (1H, d, J = 15.9 Hz), 6.91 (1H, d, J = 3.8 Hz), 7.04 (1H, d, J = 15.9 Hz), 7.09 (1 H, d, J = 15.9 Hz), 7.12 (2H, d, J = 8.8 Hz), 7.15 (1H, s), 7.33-7.36 (9H, m), 7.37 (1H, s,), 7.41-7.44 (4H, m), 7.62-7 .64 (8H, )
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 18.4, 19.2, 19.4, 26.9, 53.1, 61.0, 63.5, 111.6, 117.3, 123 1,124.6,125.1,125.4,126.9,127.3,127.7,127.8,129.2,129.8,130.1,133.4,133.5 , 133.8, 135.4, 135.7, 137.9, 140.9, 143.3, 147.6.

(Synthesis Example 10-7)
According to the reaction scheme represented by the following formula (10-7), 4- [2- [5- [2- [4- [N, N-bis [2- (tert-butyldiphenylsiloxy) ethyl] amino] phenyl] [Vinyl] -2-thienyl] vinyl] -2,5-dimethylbenzaldehyde was synthesized.

Specifically, 4- [2- [5- [2- [4- [N, N-bis [2- (tert-butyldiphenylsiloxy) ethyl] amino] phenyl] vinyl] -2-thienyl] was added to dichloromethane. Vinyl] -2,5-dimethylbenzyl alcohol 0.448 g (0.484 mmol was dissolved, activated manganese dioxide 0.85 g (9.78 mmol) was added, and the mixture was stirred at room temperature. Was purified by silica gel column chromatography 4- [2- [5- [2- [4- [N, N-bis [2- (tert-butyldiphenylsiloxy) ethyl] amino] phenyl] vinyl] -2- 0.42 g of thienyl] vinyl] -2,5-dimethylbenzaldehyde was obtained as a red oil (94.0% yield).
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.05 (18H, s), 2.45 (3H, s), 2.65 (3H, s), 3.48 (4H, t, J = 6) .6 Hz), 3.75 (4H, t, J = 6.6 Hz), 6.28 (2H, d, J = 8.8 Hz), 6.82 (1H, d, J = 15.9 Hz), 6 .87 (1H, d, J = 3.8 Hz), 6.92 (1H, d, J = 15.9 Hz), 6.99 (1H, d, J = 3.8 Hz), 7.02 (2H, d, J = 15.9 Hz), 7.13 (2H, d, J = 8.8 Hz), 7.24 (1H, d, J = 15.9 Hz), 7.34-7.36 (8H, m) ), 7.41-7.44 (5H, m), 7.59 (1H, s), 7.62-7.64 (8H, m), 10.20 (1H, s)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 19.2, 19.3, 19.4, 53.1), 60.9, 111.6, 117.0, 123.7, 124.4. 125.5, 126.0, 127.8, 128.8, 128.9, 129.8, 129.9, 131.0, 132.8, 133.5, 134.3, 135.7, 138. 2, 140.1, 141.4, 144.6, 147.8, 192.2

(Synthesis Example 10-8)
According to the reaction scheme represented by the following formula (10-8), 2- [3-cyano-4- [2- [4- [2- [5- [2- [4- [N, N-bis [2] -(Tert-Butyldiphenylsiloxy) ethyl] amino] phenyl] vinyl] -2-thienyl] vinyl] -2,5-dimethylphenyl] vinyl] -5,5-dimethyl-2 (5H) -furanylidene] propanedinitrile Was synthesized.

Specifically, 4- [2- [5- [2- [4- [N, N-bis [2- (tert-butyldiphenylsiloxy) ethyl] amino] phenyl] vinyl] -2-thienyl] was added to ethanol. Vinyl] -2,5-dimethylbenzaldehyde 420 mg (0.454 mmol) and 2- (3-cyano-4,5,5-trimethyl-2 (5H) -furanylidene] propanedinitrile 108.6 mg (0.545 mmol) Dissolved and stirred at room temperature, the solvent was distilled off, and the residue was purified by silica gel column chromatography 2- [3-cyano-4- [2- [4- [2- [5- [2- [4] -[N, N-bis [2- (tert-butyldiphenylsiloxy) ethyl] amino] phenyl] vinyl] -2-thienyl] vinyl] -2,5-dimethylphenyl] vinyl]- , 5-dimethylamino -2 (5H) -. Furaniriden] to give 427mg of propanedinitrile as a black powdery crystals mp211-214 ℃ (85.0% yield)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.05 (18H, s), 1.80 (6H, s), 2.46 (3H, s), 2.48 (3H, s), 3. 48 (4H, t, J = 6.6 Hz), 3.75 (4H, t, J = 6.6 Hz), 6.29 (2H, d, J = 8.8 Hz), 6.83 (1H, d , J = 15.9 Hz), 6.88 (1H, d, J = 3.8 Hz,), 6.92 (1H, d, J = 15.9 Hz), 7.01 (1H, d), 7. 01 (2H, d, J = 15.9 Hz), 7.13 (2H, d, J = 8.8 Hz), 7.26 (1H, d, J = 15.9 Hz), 7.34-7.36 (8H, m), 7.41-7.44 (4H, m), 7.48 (1H, s), 7.54 (1H, s), 7.62-7.64 (8H, m), 8.06 (1H, , J = 15.9Hz)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: δ: 19.2, 19.6, 26.7, 26.9, 53.1, 57.4, 60.9, 60.4), 97. 5,98.3,110.8,111.111.9,111.6,113.9,116.9,123.4,124.3,125.6,126.0,127.3,127. 8, 127.9, 128.5, 129.2, 129.8, 130.2, 131.3, 133.5, 134.5, 135.7, 137.6, 140.1, 141.1, 144.5, 145.1, 147.9, 174.1, 175.6

[Example 11]
In this example, 2- [4- [2- [4- [2- [3-bromo-5- [2- [4- (dibutylamino) phenyl] vinyl]] represented by the following formula (XI) was used. [Thiophen-2-yl] vinyl] -2,5-dimethylphenyl] vinyl] -3-cyano-5,5-dimethyl-2 (5H) -furanilidene] propanedinitrile was synthesized by the following synthesis example (11-1). It was obtained by going through (11-8).

(Synthesis Example 11-1)
4-Bromo-2-thienylmethanol was synthesized according to the reaction scheme represented by the following formula (11-1).

Specifically, 0.13 g of sodium hydroxide was dissolved in 17 ml of water, and 25.0 g (0.13 mol) of 4-bromo-2-thiophenecarbaldehyde was dissolved in methanol and added dropwise while keeping the temperature at 5 ° C. or lower. After stirring for 1 hour, methanol was distilled off under reduced pressure. The residue was extracted by adding 50 ml of water and 300 ml of ethyl acetate. The crystals precipitated in the organic layer were filtered off and concentrated, and the residue was purified by silica gel column chromatography (chloroform / methanol = 20/1) to give 4-bromo-2-thienylmethanol as a slightly yellow oil. 84 g was obtained. (Yield 82.5%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 4.79 (2H, d, J = 6.1 Hz), 6.93 (1H, s), 7.17 (1H, s)
¹³ C-NMR (600 MHz, CDCl ₃ ) δ: 59.6, 109.3, 122.6, 127.7, 145.3

(Synthesis Example 11-2)
4-Bromo-2- (chloromethyl) thiophene was synthesized according to the reaction scheme represented by the following formula (11-2).

Specifically, 20.8 g (0.108 mol) of 4-bromo-2-thienylmethanol was added dropwise while stirring and stirring 180 ml of 36% hydrochloric acid. The mixture was stirred at 5 ° C. for 1.5 hours, and the precipitated crystals were extracted with chloroform. The extract was washed twice with a small amount of water, dehydrated with anhydrous sodium sulfate, and concentrated. The residual liquid was distilled under reduced pressure to obtain 20.3 g of 4-bromo-2- (chloromethyl) thiophene as a colorless oil of bp 96-99 ° C./10 mmHg. (Yield 89.1%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 4.73 (2H, s), 7.00 (1H, s), 7.20 (1H, s)

(Synthesis Example 11-3)
According to the reaction scheme represented by the following formula (11-3), diethyl 4-bromo-2-enyl phosphonate was synthesized.

Specifically, 15.0 g (0.071 mol) of 4-bromo-2- (chloromethyl) thiophene and 12.96 g (0.078 mol) of triethyl phosphite were stirred at 140 ° C. for 18 hours. Concentration under reduced pressure afforded 22.14 g of diethyl 4-bromo-2-tenylphosphonate as a yellow-orange oil. (Rough yield 99.7%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.30 (6H, t, J = 7.2 Hz), 3.31 (2H, d, J = 21.4 Hz), 4.07-4.12 ( 4H, m), 6.90 (1H, m), 7.09 (1H, t, J = 1.6 Hz)
¹³ C-NMR (600 MHz, CDCl ₃ ) δ: 16.3, 16.4, 27.6, 28.6), 62.5, 62.6), 109.4, 122.1, 129.8, 134.3

(Synthesis Example 11-4)
N- [4- [2- (4-bromo-2-thienyl) vinyl] phenyl] -N, N-dibutylamine was synthesized according to the reaction scheme represented by the following formula (11-4).

Specifically, 7.4 g (23.6 mmol) of diethyl 4-bromo-2-tenylphosphonate and 5.0 g (0.0214 mol) of 4- (dibutylamino) benzaldehyde were dissolved in 15 ml of tetrahydrofuran and stirred at room temperature. 2.7 g (0.0241 mol) of potassium tert-butoxide was dissolved in 55 ml of tetrahydrofuran and added dropwise over 8 minutes (24 to 47 ° C.). After stirring for 30 minutes, the mixture was poured into 200 ml of saturated aqueous sodium hydrogen carbonate and extracted twice with 100 ml of ethyl acetate. The extract was washed with saturated brine, dehydrated with anhydrous sodium sulfate, concentrated, and the residue was purified by silica gel column chromatography. 7.94 g of N- [4- [2- (4-bromo-2-thienyl) vinyl] phenyl] -N, N-dibutylamine was obtained as a yellow oil. (Yield 94.5%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 0.96 (6H, t, J = 7.7 Hz), 1.32-1.39 (4H, m), 1.55-1.60 (4H, m), 3.28 (4H, t, J = 7.7 Hz), 6.60 (2H, d, J = 8.8 Hz), 6.83 (1H, d, J = 15.9 Hz), 6. 88 (1H, d, J = 15.9 Hz), 6.86 (1 H, d, J = 1.1 Hz), 6.97 (1 H, d, J = 1.6 Hz), 7.30 (2H, d , J = 8.8 Hz)

(Synthesis Example 11-5)
According to the reaction scheme represented by the following formula (11-5), 3-bromo-5- [2- [4- (dibutylamino) phenyl] vinyl] -2-thiophenecarbaldehyde was synthesized.

Specifically, 4.0 g (10.19 mmol) of N- [4- [2- (4-bromo-2-thienyl) vinyl] phenyl] -N, N-dibutylamine was dissolved in 50 ml of tetrahydrofuran and cooled. 13.4 ml (21.44 mmol) of n-butyllithium (1.6-mol hexane solution) was added dropwise. After stirring, 1.5 g (20.54 mmol) of N, N-dimethylformamide was added dropwise. After stirring for 30 minutes, the temperature was raised, and 20% aqueous sodium acetate was slowly added dropwise. The mixture was extracted with ethyl acetate, washed with saturated brine, and dried over anhydrous sodium sulfate. Concentrate and purify the dark red-brown oil by silica gel column chromatography to give 1.03 g of 3-bromo-5- [2- [4- (dibutylamino) phenyl] vinyl] -2-thiophenecarbaldehyde as dark red crystals. Obtained. (Yield 24.0%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 0.96 (6H, t, J = 7.1 Hz), 1.33-1.40 (4H, m), 1.56-1.61 (4H, m), 3.03 (4H, t, J = 7.7 Hz), 6.61 (2H, d, J = 8.8 Hz), 6.87 (1H, d, J = 16.0 Hz), 7. 07 (1H, d, J = 16.0 Hz), 6.99 (1 H, s), 7.35 (2H, d, J = 8.8 Hz), 9.86 (1 H, s)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 14.0, 20.3, 29.4, 50.8, 114.2, 127.5), 111.6, 121.2, 122.3. (128.9, 132.6, 134.8, 149.1, 157.0, 182.3)

(Synthesis Example 11-6)
According to the reaction scheme represented by the following formula (11-6), 4- [2- [3-bromo-5- [2- [4- (dibutylamino) phenyl] vinyl] -2-thienyl] vinyl] -2 , 5-Dimethylbenzyl alcohol was synthesized.

Specifically, 0.38 g (4.47 mmol) of phenyllithium was added to 10 ml of tetrahydrofuran under an argon stream, and 4- (hydroxymethyl) -2,5-dimethylbenzyltriphenyl bromide was cooled and stirred (7 to 9 ° C.). Phosphonium 1.0 g (2.035 mmol) was added in 15 minutes. After stirring for 10 minutes at the same temperature, 0.69 g (1.65 mmol) of 3-bromo-5- [2- [4- (dibutylamino) phenyl] vinyl] -2-thiophenecarbaldehyde was added to 3 ml of tetrahydrofuran. And dissolved in 5 minutes. The mixture was stirred at the same temperature for 1.5 hours, poured into 40 ml of ice water, and extracted twice with 30 ml toluene. The extract was washed with saturated brine, dehydrated with anhydrous sodium sulfate and concentrated. The residue was purified by silica gel column chromatography, and 4- [2- [3-bromo-5- [2- [4- (dibutylamino)] was purified. Phenyl] vinyl] -2-thienyl] vinyl] -2,5-dimethylbenzyl alcohol was obtained. Total yield 0.77g (Yield 84.6%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 0.97 (6H, t, J = 7.1 Hz), 1.34-1.40 (4H, m), 1.56-1.61 (4H, m), 2.37 (3H, s), 2.41 (3H, s), 3.30 (4H, t, J = 7.7 Hz), 4.68 (2H, s), 6.61 (2H) , D, J = 8.8 Hz), 6.83 (1H, s), 6.85 (1H, d, J = 16.0 Hz), 6.887.09 (1H, d, J = 15.9 Hz) 7.15 (1 H, d, J = 15.9 Hz), 7.17 (1 H, s), 7.32 (2 H, d, J = 8.8 Hz), 7.43 (1 H, s)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 14.0, 18.36, 19.3, 20.3, 29.5, 50.8, 63.3, 111.4, 111.7, 115 7, 121.3, 123.4, 126.8, 127.2, 127.5, 128.1, 130.0, 130.4, 133.6, 133.9, 134.5, 135.2 , 138.4, 142.3, 148.3

(Synthesis Example 11-7)
According to the reaction scheme represented by the following formula (11-7), 4- [2- [3-bromo-5- [2- [4- (dibutylamino) phenyl] vinyl] -2-thienyl] vinyl] -2 , 5-Dimethylbenzaldehyde was synthesized.

Specifically, 574 mg of 4- [2- [3-bromo-5- [2- [4- (dibutylamino) phenyl] vinyl] -2-thienyl] vinyl] -2,5-dimethylbenzyl alcohol in 25 ml of dichloromethane (1.04 mmol) was dissolved and 1.8 g (20.7 mmol) of active manganese dioxide was added. The mixture was stirred at room temperature for 21 hours, filtered and concentrated. Crystals crystallized from ethyl acetate / hexane were collected by filtration to give 4- [2- [3-bromo-5- [2- [4- (dibutylamino) phenyl] vinyl] -2-thienyl] vinyl] -2, 367 mg of 5-dimethylbenzaldehyde was obtained as orange crystals. The mother liquor was concentrated, purified by silica gel column chromatography, and crystallized from ethyl acetate / hexane in the same manner to obtain 166 mg. Total yield 0.53g (93.2% yield)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 0.96 (6H, t, J = 7.1 Hz), 1.33-1.40 (4H, m), 1.56-1.61 (4H, m), 2.45 (3H, s), 2.67 (3H, s), 3.30 (4H, t, J = 7.7 Hz), 6.61 (2H, d, J = 8.8 HzH) ), 6.85 (1H, s), 6.86 (1H, d, J = 15.9 Hz), 6.89 (1H, d, J = 15.9 Hz), 7.06 (1H, d, J = 15.9 Hz), 7.29 (1 H, d, J = 15.9 Hz), 7.32 (2 H, d, J = 8.8 Hz), 7.47 (1 H, s), 7.60 (1 H) , S), 10.21 (1H, s)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 14.0, 19.2, 19.3, 20.3, 29.5, 50.8, 111.6, 112.9, 115.3, 123 .2,124.0,125.3,127.5,128.1,131.0,133.0,133.6,133.7,134.1,138.2,141.0,143.5 , 148.4, 192.1

(Synthesis Example 11-8)
According to the reaction scheme represented by the following formula (11-8), 2- [4- [2- [4- [2- [3-bromo-5- [2- [4- (dibutylamino) phenyl] vinyl]] [Thiophen-2-yl] vinyl] -2,5-dimethylphenyl] vinyl] -3-cyano-5,5-dimethyl-2 (5H) -furanylidene] propanedinitrile was synthesized.

Specifically, 4- [2- [3-bromo-5- [2- [4- (dibutylamino) phenyl] vinyl] -2-thienyl] vinyl] -2,5-dimethylbenzaldehyde 200 mg (0.363 mmol) ) And 2- (3-cyano-4,5,5-trimethyl-2 (5H) -furanilidene] propanedinitrile 74 mg (0.371 mmol) were dissolved in ethanol 7 ml and tetrahydrofuran 3.5 ml and stirred at room temperature. The precipitated crystals were collected by filtration and washed with ethanol to obtain 221 mg of crystals, which were purified by silica gel column chromatography to give 2- [4- [2- [4- [2- [3-bromo-5]. [2- [4- (Dibutylamino) phenyl] vinyl] thiophen-2-yl] vinyl] -2,5-dimethylphenyl] vinyl] -3-cyano-5 5-dimethylamino -2 (5H) -. Furaniriden] to give 196mg of propanedinitrile as a black powdery crystals mp249-252 ℃ (73.7% yield)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 0.97 (6H, t, J = 7.1 Hz), 1.34-1.40 (4H, m), 1.56-1.61 (4H, m), 1.79 (6H, s), 2.45 (3H, s), 2.49 (3H, s), 3.30 (4H, t, J = 7.7 Hz), 6.61 (2H) , D, J = 8.8 Hz), 6.85 (1H, s), 6.85 (1H, d, J = 15.9 Hz), 6.88 (1H, d, J = 15.9 Hz), 6 .93 (1H, d, J = 15.9 Hz), 8.02 (1H, d, J = 15.9 Hz), 7.02 (1H, d, J = 15.9 Hz), 7.29 (1H, d, J = 15.9 Hz), 7.51 (1H, s), 7.53 (1H, s)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 14.1, 19.5, 19.7, 20.4, 26.7, 29.6, 50.9, 57.5, 97.5, 98 6,110.8,111.1,111.9,111.7,113.3,114.2,115.3,123.1,123.9,125.0,127.6,127.7 , 128.3, 128.5, 131.4, 131.7, 133.8, 134.6, 137.7, 140.7, 143.9, 144.4148.5, 174.1, 175.6.

[Example 12]
In this example, 2- [3-cyano-4- [2- [4- [2- [5- [2- [4- (dibutylamino) phenyl] vinyl]] represented by the following formula (XII) was used. -3-[(tert-Butyldiphenylsiloxy) methyl] -2-thienyl] vinyl] -2,5-dimethylphenyl] vinyl] -5,5-dimethyl-2 (5H) -furanylidene] propanedinitrile It was obtained through Synthesis Examples (12-1) to (12-6).

(Synthesis Example 12-1)
According to the reaction scheme represented by the following formula (12-1), 5- [2- [4- (dibutylamino) phenyl] vinyl] -3-thiophenemethanol was synthesized.

Specifically, 0.56 g (1.64 mmol) of 5- [2- [4- (dibutylamino) phenyl] vinyl] -3-thiophenecarbaldehyde was dissolved in 12 ml of methanol. To this was added 40 mg (1.06 mmol) of sodium borohydride dissolved in 0.5 ml of 0.2M sodium hydroxide under cooling with ice water. After stirring for 1 hour, the mixture was poured into 50 ml of water and extracted twice with 30 ml of ethyl acetate. The extract was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated. The residue was purified by silica gel column chromatography to obtain 0.51 g of the title compound as a pale yellow oil. (Yield 90.7%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 0.96 (6H, t, J = 7.2 Hz), 1.32-1.38 (4H, m), 1.54-1.60 (4H, m), 3.28 (4H, t, J = 7.7 Hz), 4.61 (2H, d, J = 5.5 Hz), 6.60 (2H, d, J = 8.8 Hz), 6. 83 (1H, d, J = 15.9 Hz), 6.94 (1 H, d, J = 15.9 Hz), 6.95 (1 H, s), 6.97 (1 H, s), 7.31 ( 2H, d, J = 8.8Hz)

(Synthesis Example 12-2)
According to the reaction scheme represented by the following formula (12-2), 5- [2- [4- (dibutylamino) phenyl] vinyl] -3-hydroxymethylthiophene-2-carbaldehyde was synthesized.

Specifically, 162 mg (0.472 mmol) of 5- [2- [4- (dibutylamino) phenyl] vinyl] -3-thiophene methanol was dissolved in 20 ml of tetrahydrofuran, and n-butyl was cooled in a dry ice / acetone bath. Lithium (1.6-mol hexane solution) 0.74 ml (1.18 mmol) was added dropwise in 17 minutes. After stirring for 1.5 hours, N.P. 0.55 ml (7.92 mmol) of N-dimethylformamide was added dropwise over 10 minutes. After stirring for 1 hour, the bath was removed, the temperature was raised to -20 ° C, and 20 ml of water was slowly added dropwise. The mixture was extracted with ethyl acetate, washed with saturated brine, and dried over anhydrous sodium sulfate. Concentrate and purify the dark red-brown oil by silica gel column chromatography. 104 mg of 5- [2- [4- (dibutylamino) phenyl] vinyl] -3-hydroxymethylthiophene-2-carbaldehyde was obtained as a red oil. (Yield 59.4%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 0.97 (6H, t, J = 7.1 Hz), 1.33-1.40 (4H, m), 1.56-1.61 (4H, m), 3.30 (4H, t, J = 7.7 Hz), 4.86 (2H, d, J = 6.6 Hz), 6.61 (2H, d, J = 8.8 Hz), 6. 93 (1H, d, J = 15.9 Hz), 7.09 (1 H, d, J = 15.9 Hz), 7.05 (1 H, s), 7.35 (2 H, d, J = 8.8 Hz) ), 9.80 (1H, s, CHO)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 14.1, 20.4, 29.5, 50.9, 59.8, 111.7, 115.2, 122.7, 126.5, 128 .7, 133.9, 134.1, 148.9, 151.2, 154.5, 182.3

(Synthesis Example 12-3)
According to the reaction scheme represented by the following formula (12-3), 5- [2- [4- (dibutylamino) phenyl] vinyl] -3-[(tert-butyldiphenylsiloxy) methyl] -2-thiophenecarbaldehyde Was synthesized.

Specifically, 104 mg (0.28 mmol) of 5- [2- [4- (dibutylamino) phenyl] vinyl] -3-hydroxymethylthiophene-2-carbaldehyde and 35 mg (0.51 mmol) of imidazole were added to N, N -Dissolved in 2 ml of dimethylformamide. While stirring at room temperature, 88.5 mg (0.32 mmol) of tert-butylchlorodiphenylsilane was added dropwise. The mixture was stirred overnight at room temperature, poured into 10 ml of water, and extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated. Purification by silica gel column chromatography gave 163 mg of 5- [2- [4- (dibutylamino) phenyl] vinyl] -3-[(tert-butyldiphenylsiloxy) methyl] -2-thiophenecarbaldehyde as a red-orange oil. Obtained. (Yield 95.5%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 0.97 (6H, t, J = 7.7 Hz ₃ ), 1.09 (9H, s), 1.34-1.40 (4H, m), 1.56-1.61 (4H, m), 3.30 (4H, t, J = 7.7 Hz), 4.97 (2H, s), 6.61 (2H, d, J = 8.8 Hz) ), 6.92 (1H, d, J = 15.9 Hz), 7.03 (1H, d, J = 15.9 Hz), 7.02 (1H, s), 7.37-7.45 (6H) , M), 7.67-7.69 (4H, m), 9.85 (1H, s)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 14.1, 19.3, 20.4, 26.9, 29.6, 50.9, 60.8, 111.7, 115.7, 123 0.0, 126.0, 128.0, 128.6, 130.0, 133.0, 133.6, 133.9, 135.6, 148.8, 151.5, 153.1, 181.7

(Synthesis Example 12-4)
According to the reaction scheme represented by the following formula (12-4), 4- [2- [3- (tert-butyldiphenylsiloxy) methyl-5- [2-[(4-dibutylamino) phenyl] vinyl] -2 -Thienyl] vinyl] -2.5-dimethylbenzyl alcohol was synthesized.

Specifically, 49.4 mg (2.89 mmol) of phenyllithium was added to 5 ml of tetrahydrofuran under an argon stream, and 131 mg (0.266 mmol) of 4- (hydroxymethyl) -2,5-dimethylbenzyltriphenylphosphonium bromide while cooling. ) Was added. After stirring, 163 mg (0.267 mmol) of 5- [2- [4- (dibutylamino) phenyl] vinyl] -3-[(tert-butyldiphenylsiloxy) methyl] -2-thiophenecarbaldehyde was dissolved in 2 ml of tetrahydrofuran. And it was dripped in 5 minutes. The mixture was stirred at the same temperature for 2.5 hours, poured into 35 ml of water and extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated. The residue was purified by silica gel column chromatography to give 4- [2- [3- (tert-butyldiphenylsiloxy) methyl-5- [2-[(4-dibutylamino) phenyl] vinyl] -2-thienyl] vinyl. ] 121 mg of -2.5-dimethylbenzyl alcohol was obtained as a red-orange liquid. (Yield 61.0%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 0.96 (6H, t, J = 7.7 Hz), 1.08 (9H, s), 1.33-1.39 (4H, m), 1 .55-1.61 (4H, m), 2.30 (3H, s), 2.36 (3H, s), 3.29 (4H, t, J = 7.7 Hz), 4.65 (2H) , S), 4.74 (2H, s)), 6.61 (2H, d, J = 8.8 Hz), 6.82 (1H, d, J = 15.9 Hz), 6.92 (1H, d, J = 15.9 Hz), 6.84 (1H, s), 6.97 (1H, d, J = 16.0 Hz), 7.04 (1H, d, J = 16.0 Hz), 7. 12 (1H, s), 7.22 (1H, s), 7.33 (2H, d, J = 8.8 Hz), 7.37-7.44 (6H, m), 7.71-7. 73 (4H, m)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 14.1, 18.3, 19.40, 19.43, 20.5, 26.9, 29.6, 50.9, 60.3, 63 5, 111.8, 115.4, 117.1, 121.1, 124.2, 125.1, 127.0, 127.8, 127.9, 129.2, 129.7, 129.9 130.1, 130.2, 133.4, 133.5, 133.7, 135.6, 135.8, 137.8, 139.9, 141.7, 148.0

(Synthesis Example 12-5)
According to a reaction scheme represented by the following formula (12-5), 4- [2- [3- (tert-butyldiphenylsiloxymethyl) -5- [2-[(4-dibutylamino) phenyl] vinyl] -2 -Thienyl] vinyl] -2.5-dimethylbenzaldehyde was synthesized.

Specifically, 4- [2- [3- (tert-butyldiphenylsiloxymethyl) -5- [2-[(4-dibutylamino) phenyl] vinyl] -2-thienyl] vinyl] -2 in 8 ml of dichloromethane. .121 mg (0.163 mmol) of 5-dimethylbenzyl alcohol was dissolved, 230 mg (2.65 mmol) of active manganese dioxide was added, and the mixture was stirred at room temperature for 17 hours. 8 ml of dichloromethane and 230 mg (2.65 mmol) of active manganese dioxide were added, and the mixture was further stirred for 4.5 hours. The reaction solution was filtered and concentrated, and the residue was purified by silica gel column chromatography. 4- [2- [3- (tert-Butyldiphenylsiloxymethyl) -5- [2-[(4-dibutylamino) phenyl] vinyl] -2-thienyl] vinyl] -2.5-dimethylbenzaldehyde was red oily. 112 mg was obtained as a product. (Yield 92.8%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 0.97 (6H, t, J = 7.7 Hz), 1.08 (9H, s), 1.34-1.40 (4H, m,), 1.56-1.62 (4H, m), 2.42 (3H, s), 2.60 (3H, s), 3.30 (4H, t, J = 7.7 Hz), 4.77 ( 2H, si), 6.62 (2H, d, J = 8.8 Hz), 6.85 (1H, d, J = 15.9 Hz), 6.93 (1H, d, J = 15.9 Hz), 6.85 (1H, s), 6.95 (1H, d, J = 15.4 Hz), 7.21 (1H, d, J = 15.4 Hz), 7.25 (1H, s), 7. 34 (2H, d, J = 8.8 Hz), 7.37-7.44 (6H, m), 7.57 (1H, s), 7.71-7.73 (4H, m), 10. 19 (1H, s)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 14.1, 14.3, 19.2, 19.4, 20.4, 26.9, 29.6, 50.9, 60.3, 60 5, 111.7, 116.8, 123.6, 123.9, 124.0, 127.0, 127.88, 127.92, 129.9, 130.0, 132.7, 133.4 133.5, 134.2, 135.1, 135.7, 138.1, 141.4, 141.5, 143.0, 148.1, 192.2

(Synthesis Example 12-6)
According to the reaction scheme represented by the following formula (12-6), 2- [3-cyano-4- [2- [4- [2- [5- [2- [4- (dibutylamino) phenyl] vinyl]- 3-[(tert-Butyldiphenylsiloxy) methyl] -2-thienyl] vinyl] -2,5-dimethylphenyl] vinyl] -5,5-dimethyl-2 (5H) -furanylidene] propanedinitrile was synthesized.

Specifically, 4- [2- [3- (tert-butyldiphenylsiloxymethyl) -5- [2-[(4-dibutylamino) phenyl] vinyl] -2-thienyl] vinyl in 3 ml of ethanol and 1 ml of tetrahydrofuran ] -2.5-dimethylbenzaldehyde 112.0 mg (0.15 mmol) and 2- (3-cyano-4,5,5-trimethyl-2 (5H) -furanylidene] propanedinitrile 36.0 mg (0.18 mmol) The obtained crystals were collected by filtration and washed with methanol.2- [3-cyano-4- [2- [4- [2- [5- [2- [4] -(Dibutylamino) phenyl] vinyl] -3- (tert-butyldiphenylsiloxymethyl) -2-thienyl] vinyl] -2,5-dimethylphenyl] bi 47.2 mg of [Lu] -5,5-dimethyl-2 (5H) -furanylidene] propanedinitrile as black powdery crystals at mp 165-167 ° C. The filtrate was concentrated and purified by silica gel column chromatography, It was then washed with methanol to obtain an additional 32.8 mg, total yield 80.0 mg (yield 57.4%).
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 0.97 (6H, t, J = 7.1 Hz), 1.08 (9H, s), 1.34-1.40 (4H, m), 1 .56-1.61 (4H, m), 1.79 (6H, s), 2.41 (3H, s), 2.42 (3H, s), 3.30 (4H, t, J = 7) .1 Hz), 4.77 (2 H, s), 6.62 (2 H, d, J = 8.8 Hz), 6.85 (1 H, d, J = 15.9 Hz), 6.85 (1 H, s) ), 6.90 (1H, d, J = 15.9 Hz), 6.92 (1H, d, J = 15.9 Hz), 6.93 (1H, d, J = 15.9 Hz), 7.25. (1H, d, J = 15.9 Hz), 7.30 (1 H, s), 7.34 (2H, d, J = 8.8 Hz), 7.37-7.44 (6H, m), 7 .52 (1H, s , 7.71-7.73 (4H, m), 8.05 (1H, d, J = 15.9Hz)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 14.1, 19.39, 19.4, 19.42, 20.4, 26.7, 26.9, 29.5, 50.9, 57 3, 60.4, 97.5, 98.1, 110.9, 111.1, 112.0, 111.7, 113.8, 116.7, 123.3, 123.8, 124.1 , 127.0, 127.3, 127.9, 128.0, 128.4, 129.9, 130.3, 131.2, 133.4, 134.4, 135.1, 135.7, 137 6,141.3,141.8,143.5,144.6,148.2,174.1,175.7

[Example 13]
In this example, 2- [3-cyano-4- [2- [4- [2- [4- [N-ethyl-N- (2-hydroxyethyl) amino] represented by the following formula (XIII) was used. ] Phenyl] vinyl] -2,5-dimethylphenyl] vinyl] -5,5-dimethyl-2 (5H) -furanylidene] propanedinitrile, the following synthesis examples (13-1) to (13-2) Got through.

(Synthesis Example 13-1)
According to the reaction scheme represented by the following formula (13-1), 4- [2- [4- [N-ethyl-N- (2-hydroxyethyl) amino] phenyl] vinyl] -2,5-dimethylbenzen An aldehyde was synthesized.

Specifically, 2- [N-ethyl-N- [4- [2- (4-formyl-2,5-dimethylphenyl) vinyl] phenyl] amino] ethyl 2,2-dimethylpropionate 1.0 g (2.45 mmol) was dissolved in ethanol, and 5 ml of 20% aqueous sodium hydroxide was added thereto. The mixture was stirred under heating, added to 100 ml of water, extracted with ethyl acetate, washed with saturated brine, dried over anhydrous sodium sulfate and concentrated. The residue was purified by silica gel column chromatography to give 4- [2- [4- [N-ethyl-N- (2-hydroxyethyl) amino] phenyl] vinyl] -2,5-dimethylbenzaldehyde as orange crystals. As a result, 0.76 g was obtained. (Yield 95.8%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.02 (3H, t, J = 7.1 Hz), 2.43 (3H, s), 2.65 (3H, s), 3.47 (2H , Q, J = 7.1 Hz), 3.52 (2H, t, J = 6.0 Hz), 3.83 (2H, q, J = 6.0 Hz), 6.76 (2H, d, J = 8.8 Hz), 7.06 (1H, d, J = 16.5 Hz), 7.09 (1 H, d, J = 16.5 Hz), 7.43 (2H, d, J = 8.8 Hz), 7.45 (1H, s), 7.57 (1H, s), 10.18 (1H, s)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 12.0, 19.3, 19.4, 45.7, 52.5, 60.4, 112.6, 120.7, 125.6, 127 .8, 128.4, 132.3, 132.8, 133.2, 134.2, 138.2, 142.5, 148.5, 192.3

(Synthesis Example 13-2)
According to the reaction scheme represented by the following formula (13-2), 2- [3-cyano-4- [2- [4- [2- [4- [N-ethyl-N- (2-hydroxyethyl) amino] ] Phenyl] vinyl] -2,5-dimethylphenyl] vinyl] -5,5-dimethyl-2 (5H) -furanylidene] propanedinitrile was synthesized.

Specifically, 4- [2- [4- [N-ethyl-N- (2-hydroxyethyl) amino] phenyl] vinyl] -2,5-dimethylbenzaldehyde 0.76 g (2.35 mmol) in ethanol. ) And 2- (3-cyano-4,5,5-trimethyl-2 (5H) -furanilidene] propanedinitrile (0.52 g, 2.61 mmol) were dissolved and stirred at room temperature. The resulting black powder (990 mg) was purified by silica gel column chromatography and further washed with methanol.2- [3-cyano-4- [2- [4- [2- [4- [ N-ethyl-N- (2-hydroxyethyl) amino] phenyl] vinyl] -2,5-dimethylphenyl] vinyl] -5,5-dimethyl-2 (5H) -furanylidene] propa The dinitrile was obtained 0.93g as a black powdery crystals. (78.4% yield)
¹ H-NMR (600 MHz, DMSO-d ₆ ) δ: 1.10 (3H, t, J = 7.1 Hz), 1.75 (6H, s), 2.42 (3H, s), 2.45 (3H, s), 3.39 (2H, t, J = 6.6 Hz), 3.43 (2H, q, J = 7.1 Hz), 3.55 (2H, t, J = 6.6 Hz) 6.70 (2H, d, J = 8.8 Hz), 7.09 (1H, d, J = 15.9 Hz), 7.26 (1H, d, J = 15.9 Hz), 7.15 ( 1H, d, J = 15.9 Hz), 8.28 (1H, d, J = 15.9 Hz), 7.47 (2H, d, J = 8.8 Hz), 7.65 (1H, s), 7.89 (1H, s), 8.28 (2H, d, J = 8.8 Hz)
¹³ C-NMR ((600 MHz, DMSO-d ₆ ) δ: 12.6, 19.4, 19.6, 25.5, 40.4, 52.6, 54.2, 59.0, 96.5 99.8, 112.6, 113.5, 114.6, 112.0, 112.6, 113.5, 114.6, 119.5, 124.5, 127.0, 129.1, 129 5, 131.2, 133.3, 133.9, 138.1, 141.8, 144.9, 148.7, 176.3, 178.0

[Comparative Example 1]
In this comparative example, 2- [3-cyano-4- [2- [4- [2- [4- [N- (2-hydroxyethyl) -N-ethylamino] represented by the following formula (A) is used. ] Phenyl] vinyl] phenyl] vinyl] -5,5-dimethyl-2 (5H) -furanylidene] propanedinitrile was obtained through the following synthesis examples (A-1) to (A-6).

(Synthesis Example A-1)
4- [N-ethyl-N- (2-hydroxymethyl) amino] benzaldehyde was synthesized according to the reaction scheme represented by the following formula (A-1).

Specifically, 8.5 g (0.213 mol) of sodium hydroxide was dissolved in water, and ethanol was added. To this was added 10.14 g (0.043 mol) of 2- [N-ethyl-N- (4-formylphenyl) amino] ethyl acetate, and the mixture was stirred at room temperature. The pH was adjusted to 8 with 2.5% hydrochloric acid and then extracted three times with ethyl acetate. The extracts were combined, washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated. The residual liquid was purified by silica gel column chromatography to obtain 8.39 g of 4- [N-ethyl-N- (2-hydroxymethyl) amino] benzaldehyde as a pale yellow oil. (Yield 100%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.22 (3H, t, J = 7.1 Hz), 2.53 (2H, q, J = 7.1 Hz), 3.58 (2H, t, J = 6.1 Hz), 3.86 (2H, t, J = 6.1 Hz), 6.74 (2H, d, J = 8.8 Hz), 7.69 (2H, d, J = 8.8 Hz) ), 9.68 (1H, d, J = 3.3 Hz)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 12.0, 45.8, 52, 60.1, 111.8, 125.2, 132.4, 152.9, 190.3

(Synthesis Example A-2)
According to the reaction scheme represented by the following formula (A-2), 4- [N-ethyl-N- [2- (tert-butyldiphenylsiloxy) ethyl] amineno] benzaldehyde was synthesized.

Specifically, 4.0 g (20.7 mmol) of 4- [N-ethyl-N- (2-hydroxymethyl) amino] benzaldehyde and 2.47 g (36.3 mmol) of imidazole are dissolved in N, N-dimethylformamide. did. At room temperature, 6.26 g (22.8 mmol) of tert-butylchlorodiphenylsilane was added dropwise. After stirring overnight, the mixture was poured into 150 ml of water and extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated. The residual liquid was purified by silica gel column chromatography to obtain 8.39 g of 4- [N-ethyl-N- [2- (tert-butyldiphenylsiloxy) ethyl] amineno] benzaldehyde as slightly yellow crystals. (Yield 91.7%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.04 (9H, s), 1.14 (3H, t, J = 7.1 Hz), 3.41 (2H, q, J = 7.1 Hz, ), 3.49 (2H, t, J = 6.6 Hz), 3.80 (2H, t, J = 6.6 Hz), 7.35-7.38 (4H, m), 7.42-7 .45 (2H, m), 7.61 (2H, d, J = 8.8 Hz), 7.63-7.64 (4H, d, J = 8.8 Hz), 9.68 (1H, s)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 12., 19.2, 26.9, 45., 51.9, 60.9, 110.8, 125.0, 127.9, 130.0 , 132.2, 133.3, 135.7, 152.6, 190.1

(Synthesis Example A-3)
According to the reaction scheme represented by the following formula (A-3), 4- [2- [4- [N-ethyl-N- [2- (tert-butyldiphenylsiloxy) ethyl] amino] phenyl] vinyl] benzyl alcohol Was synthesized.

Specifically, 1.08 g (12.8 mmol) of phenyllithium was added to tetrahydrofuran under an argon stream, and 2.7 g (5.83 mmol) of 4- (hydroxymethyl) benzyltriphenylphosphonium bromide was added while cooling. After stirring the reaction solution, 2.5 g (5.79 mmol) of 4- [N-ethyl-N- [2- (tert-butyldiphenylsilyloxy) ethyl] amineno] benzaldehyde was added dropwise. After stirring at the same temperature, the mixture was poured into water and extracted with chloroform. The extract was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated. The residue was purified by silica gel column chromatography, and 4- [2- [4- [N-ethyl-N- [2- (tert-butyldiphenylsiloxy) ethyl] amino] phenyl] vinyl] benzyl alcohol was purified. 74 g was obtained. (Yield 88.4%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.06 (9H, s), 1.17 (3H, t, J = 7.2 Hz), 3.35 (2H, q, J = 7.2 Hz ₂ ), 3.44 (2H, t, J = 6.6 Hz), 3.79 (2H, t, J = 6.6 Hz), 4.68 (2H, d, J = 6.0 Hz), 6.48 (2H, d, J = 8.8 Hz), 6.85 (1H, d, J = 16.5 Hz), 7.01 (1H, d, J = 16.5 Hz), 7.28 (2H, d, J = 8.8 Hz), 7.32 (2H, d, J = 8.2 Hz), 7.36-7.39 (4H, m), 7.42-7.45 (2H, m), 7. 46 (2H, d, J = 8.2Hz)

(Synthesis Example A-4)
According to the reaction scheme represented by the following formula (A-4), 4- [2- [4- [N-ethyl-N- [2- (tert-butyldiphenylsiloxy) ethyl] amino] phenyl] vinyl] benzaldehyde is obtained. Synthesized.

Specifically, 2.74 g (5.11 mmol) of 4- [2- [4- [N-ethyl-N- [2- (tert-butyldiphenylsiloxy) ethyl] amino] phenyl] vinyl] benzyl alcohol was added to dichloromethane. After dissolution, 8.9 g (102.4 mmol) of active manganese dioxide was added and stirred at room temperature, the reaction mixture was filtered and concentrated, and the residue was purified by silica gel column chromatography. 1.32 g of N-ethyl-N- [2- (tert-butyldiphenylsiloxy) ethyl] amino] phenyl] vinyl] benzaldehyde was obtained as orange crystals (yield 48.4%).
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.06 (9H, s), 1.12 (3H, t, J = 7.1 Hz), 3.37 (2H, q, J = 6.6 Hz) 3.46 (2H, t, J = 6.6 Hz), 3.80 (2H, t, J = 6.6 Hz), 6.50 (2H, d, J = 8.8 Hz), 6.88 ( 1H, d, J = 15.9 Hz), 7.17 (1H, d, J = 15.9 Hz), 7.32 (2H, d, J = 8.8 Hz), 7.36-7.39 (4H , M), 7.42-7.45 (2H, m), 7.59 (2H, d, J = 8.2 Hz), 7.65-7.67 (4H, m), 7.82 (2H) , D, J = 8.2 Hz), 9.66 (1H, s)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 12.3, 19.2, 26.9, 45.5, 52.1, 61.2, 111.6, 122.2, 126.3, 127 .8, 128.4, 129.8, 130.3, 132.7, 133.5, 134.5, 135.7, 144.8, 148.3, 191.7

(Synthesis Example A-5)
According to the reaction scheme represented by the following formula (A-5), 4- [2- [4- [N-ethyl-N- (2-hydroxyethyl) amino] phenyl] vinyl] benzaldehyde was synthesized.

Specifically, 1.49 g (2.79 mmol) of 4- [2- [4- [N-ethyl-N- [2- (tert-butyldiphenylsiloxy) ethyl] amino] phenyl] vinyl] benzaldehyde was added to tetrahydrofuran. After dissolution, 9 ml (9 mmol) of tetrabutylammonium fluoride (tetrahydrofuran solution) was added dropwise with stirring at room temperature. After stirring, it was poured into water and extracted three times with chloroform. The extract was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated. The residue was purified by silica gel column chromatography, and the obtained crystals were further recrystallized from ethanol. 0.643 g of 4- [2- [4- [N-ethyl-N- (2-hydroxyethyl) amino] phenyl] vinyl] benzaldehyde was obtained as orange crystals. (Yield 77.4%)
¹ H-NMR (600 MHz, CDCl ₃ ) δ: 1.20 (3H, t, J = 7.1 Hz), 1.65 (1H, t, J = 6.0 Hz), 3.47 (2H, q, J = 7.1 Hz), 3.53 (2H, t, J = 6.0 Hz), 3.83 (2H, dd, J = 6.0 Hz, 6.0 Hz), 6.76 (2H, d, J = 8.8 Hz), 6.93 (1H, d, J = 16.5 Hz), 7.20 (1 H, d, J = 16.5 Hz), 7.42 (2H, d, J = 8.8 Hz) 7.60 (2H, d, J = 8.2 Hz), 7.83 (2H, d, J = 8.2 Hz), 9.96 (1H, s)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 12.0, 45.6, 52.4), 60.3, 112.4, 122.8, 124.9, 126.3, 128.4 130.3, 132.3, 134.4, 144.3, 148.4, 191.6

(Synthesis Example A-6)
According to the reaction scheme represented by the following formula (A-6), 2- [3-cyano-4- [2- [4- [2- [4- [N- (2-hydroxyethyl) -N-ethylamino] ] Phenyl] ethenyl] phenyl] vinyl] -5,5-dimethyl-2 (5H) -furanylidene] propanedinitrile was synthesized.

Specifically, 4- [2- [4- [N-ethyl-N- (2-hydroxyethyl) amino] phenyl] vinyl] benzaldehyde (500 mg, 1.69 mmol) and 2- (3-cyano-4) were added to ethanol. , 5,5-trimethyl-2 (5H) -furanylidene] propanedinitrile (370 mg, 1.86 mmol) was dissolved and stirred at room temperature, and the precipitated crystals were collected by filtration and purified by silica gel column chromatography. The crystals were washed with methanol and 2- [3-cyano-4- [2- [4- [2- [4- [N- (2-hydroxyethyl) -N-ethylamino] phenyl] vinyl] phenyl] vinyl -5,5-dimethyl-2 (5H) -furanylidene] propanedinitrile as black crystals, 618 mg (yield 76.6%).
¹ H-NMR (600 MHz, DMSO-d ₆ ) δ: 1.10 (3H, t, J = 7.1 Hz), 1.80 (6H, s), 3.39 (2H, t, J = 6. 6 Hz), 3.43 (2H, q, J = 7.1 Hz, 3.55 (2H, dd, J = 6.6 Hz, 5.5 Hz), 4.75 (1H, t, J = 5.5 Hz) 6.70 (2H, d, J = 8.8 Hz), 7.02 (1H, d, J = 16.5 Hz), 7.20 (1H, d, J = 16.5 Hz), 7.35 ( 1H, d, J = 16.5 Hz), 7.45 (2H, d, J = 8.8 Hz), 7.65 (2H, d), 7.88 (2H, d, J = 8.8 Hz), 7.93 (1H, d, J = 16.5 Hz)
¹³ C-NMR ((600 MHz, DMSO-d ₆ ) δ: 12.6, 25.8, 40.4, 52.6, 54.4 ₂ ), 59.0, 98.6, 99.8, 111 7, 112.6, 113.4, 112.0, 114.5, 122.4, 124.1, 127.0, 129.1, 130.8, 132.8, 132.9, 143.2 , 147.9, 148.7, 175.8, 177.7

For the compounds obtained in Examples 1 to 13 and Comparative Example 1, thermal decomposition onset temperature (Td), maximum absorption spectrum (λmax), hyperpolarizability (β), non-resonant hyperpolarizability (β ₀₎ ) Was measured. The results are shown in Table 1.

[Measurement of thermal decomposition start temperature (Td)]
The thermal decomposition start temperature (Td) was measured using a differential thermal analyzer TG-DTA2000S manufactured by Bruker AXS Co., Ltd. under the conditions of a measurement sample of 5 mg and a heating rate of 10 ° C./min.

[Measurement of hyperpolarizability (β)]
Ultra-polarizability (β), the reference paper ( "Intermolecular Coupling Enhancement of the Molecular Hyperpolarizability in Multuchromophoric Dipolar Dendron", Shiyoshi Yokoyama, Tatsuo Nakahama, Akira Otomo, and Shinro Mashiko, Journal of the American Chemical Society, vol. 122, pages 3174-318 (2000).). As a laser light source, an Nd: YAG solid state laser (CLYAG-2000G, wavelength 1.31 μm, pulse width 28 nsec, output 86 mW) manufactured by Cyber Laser Co., Ltd. was used. As the photodetector, a photomultiplier tube (R3896) manufactured by Hamamatsu Photonics Co., Ltd. was used. The nonlinear optical compound was adjusted to a concentration of 5 μmol / l in chloroform to prepare a measurement sample. Laser light is irradiated by the method described in the reference paper, the second optical harmonic intensity generated is detected by a photomultiplier tube, and compared with the hyperpolarizability of the reference sample, the hyperpolarizability (β ) As a reference sample, the hyperpolarizability of chloroform used as a solvent (−0.49 × 10 ⁻³⁰ esu), or a reference paper (“Modulated Conjugation as a Means for Attaching a Record High Intensive Hyperpolarizer,” JM The hyperpolarizability of the nonlinear optical compound (No. 4) described in Yuxia Ahao, Koen Cray, and Mark G. Kuzyk, Optics Letters, col. 32, pages 59-61 (2007).) Was used.

[Measurement of non-resonant hyperpolarizability (β ₀ )]
Non-resonant super polarizability (β _0), the reference paper ( "Intermolecular Coupling Enhancement of the Molecular Hyperpolarizability in Multuchromophoric Dipolar Dendron", Shiyoshi Yokoyama, Tatsuo Nakahama, Akira Otomo, and Shinro Mashiko, Journal of the American Chemical Society, vol. 122, pages 3174-318 (2000).). The maximum absorption wavelength (λmax) of the nonlinear optical compound was measured by adjusting the nonlinear optical compound at a concentration of 5 μmol / l in chloroform and using an ultraviolet-visible spectrophotometer (UVmini 1240) manufactured by Shimadzu Corporation. Using the maximum absorption wavelength, a β / β ₀ value was determined in the same manner as in the reference paper. Using the calculated β / β ₀ value and the actually measured β value, the nonresonant hyperpolarizability (β ₀ ) was obtained.

1 is a schematic cross-sectional view showing an embodiment of a nonlinear optical element according to the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Substrate, 2 ... Lower electrode, 3 ... 1st cladding layer, 5 ... Core layer, 6 ... 2nd cladding layer, 8 ... Upper electrode, 9 ... Optical waveguide core, 10 ... Optical waveguide (nonlinear optical element).

Claims (14)

A nonlinear optical compound represented by the following general formula (1).

[In formula (1), n represents an integer of 2 to 4, R ¹ represents an alkyl group having 1 to 4 carbon atoms, and n R ¹ in the same molecule may be the same or different from each other, p and q each independently represent an integer of 0 to 2, p + q is 2 or less, and Ar ¹ and Ar ² each independently represent a group represented by the following formula (2-a) or (2-b): As shown, when p + q is 2, Ar ¹ and Ar ² may be the same as or different from each other.

{In the formula, m represents an integer of 0 to 4, h represents an integer of 0 to 2, R ² and R ³ each independently represent a halogen atom, an alkyl group having 1 to 10 carbon atoms, or —C _x H _2x OR ⁴ (x represents an integer of 1 or more, R ⁴ represents a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or an optionally substituted carbon atom having 6 to 10 carbon atoms. An aryl group having 3 to 18 carbon atoms, an alkyl acyl group having 2 to 11 carbon atoms which may have a substituent, or an aryl having 7 to 11 carbon atoms which may have a substituent And m R ² in the formula (2-a) may be the same or different from each other, and h R ³ in the formula (2-b) may be the same or different from each other. May be. }
D represents an electron donating group represented by the following formula (3).

{In Formula (3), R ⁵ and R ⁶ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or an optionally substituted carbon group having 6 to 6 carbon atoms. 10 aryl groups are shown. }
A represents an electron accepting group represented by the following formula (4).

(In Formula (4), R ⁷ and R ⁸ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or an optionally substituted carbon atom having 6 to 6 carbon atoms. A C1-C12 heteroaryl group optionally having 10 aryl groups or substituents.]] The nonlinear optical compound according to claim 1, wherein in the general formula (1), R ¹ represents a methyl group.   The nonlinear optical compound according to claim 1 or 2, wherein n represents 2 in the general formula (1). In the above formulas (2-a) and (2-b), R ² and R ³ are each independently a halogen atom, an alkyl group having 1 to 3 carbon atoms, or —CH ₂ OSiR ⁹ ₃ (R ⁹ is 1 to 1 carbon atoms). 4 is an alkyl group, a phenyl group, or an alkoxy group having 1 to 10 carbon atoms, and a plurality of R ⁹ in the same molecule may be the same or different from each other. The nonlinear optical compound according to Item. The nonlinear optical compound according to claim 1, wherein Ar ¹ and Ar ² each independently represent a phenylene group or a thiophenediyl group in the general formula (1). In the above formula (3), R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 10 carbon atoms or a phenyl group, and the alkyl group and the phenyl group each have an alkyl group having 1 to 10 carbon atoms and a carbon as a substituent. An aryl group having 6 to 10 carbon atoms or -OR ¹⁰ (R ¹⁰ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, a triorganosilyl group having 3 to 18 carbon atoms, or 2 carbon atoms. The nonlinear optical compound of any one of Claims 1-5 which may have an alkylacyl group of -11. The nonlinear optical compound according to any one of claims 1 to 6, wherein the electron donating group represented by D in the general formula (1) is a group represented by the following formula (5).

[In the formula (5), j and k each independently represent an integer of 1 to 6, R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or —OR ¹³ (R ¹³ represents A hydrogen atom, a triorganosilyl group having 3 to 18 carbon atoms, or an alkylacyl group having 2 to 11 carbon atoms). ]   The nonlinear optical compound according to claim 7, wherein j and k are both 2 in the formula (5). The electron donating group represented by D in the general formula (1) is a group represented by the following formula (6-a) or (6-b), according to any one of claims 1 to 8. Nonlinear optical compound.

[Wherein, R ¹⁴ represents a hydrogen atom, a methyl group, an ethyl group or —OR ¹⁵ (R ¹⁵ represents a hydrogen atom, a t-butyldiphenylsilyl group, an acetyl group or a pivaloyl group). ] In the above formula (4), R ⁷ and R ⁸ are each independently an alkyl group having 1 to 4 carbon atoms, a fluorinated alkyl group having 1 to 4 carbon atoms, or a phenyl group or 1 to 10 carbon atoms as a substituent. The nonlinear optical compound of any one of Claims 1-9 which shows the phenyl group or thienyl group which may have an alkyl group. In the above formula (4) shows the R ⁷ and R ⁸ are each independently an alkyl group having 1 to 4 carbon atoms, a phenyl group or a trifluoromethyl group. The nonlinear optical compound of any one of Claims 1-10.   A nonlinear optical material containing the nonlinear optical compound according to claim 1 and a host material in which the nonlinear optical compound is dispersed.   The host material contains a resin having a reactive functional group capable of forming a covalent bond with the nonlinear optical compound, and at least a part of the nonlinear optical compound is bonded to the resin. 13. The nonlinear optical material according to 12.   A nonlinear optical element having an optical waveguide formed of the nonlinear optical material according to claim 12.

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