JP2009120542A - Polymerizable abietic acid derivative - Google Patents

Abstract

【選択図】なしDisclosed is a polymerizable optically active compound which has a large HTP, is excellent in compatibility with other liquid crystal materials, and can be produced by an economical method.
An R-P-X- (A- Z) m -Y [R is ^{_{CH 2 = C (R 1)}} -COO, polymerizable groups such as CH ₂ = CH (R ¹ is hydrogen or methyl) and P represents a single bond or alkylene having 1 to 12 carbon atoms, and X represents a single bond, O, S, COO, OCO, CON (R ³ ), N (R ³ ) CO or OCOO (R ³ Represents hydrogen or methyl), A represents an aromatic ring or an aliphatic ring, Z represents a single bond, COO, OCO or CH ₂ CH ₂ , m represents an integer of 0 to 3, Y represents a formula (3- 1) A group represented by (3-2) or (3-3). ] The compound represented by this.

[Selection figure] None

Description

  The present invention relates to a novel abietic acid derivative. More specifically, the present invention relates to a polymerizable abietic acid derivative that is an optically active compound that can be used as a chiral agent, a liquid crystal composition containing the abietic acid derivative, a polymer obtained from the composition, and uses thereof.

  Cholesteric liquid crystal molecules have a helical structure in their liquid crystal state. Therefore, when cholesteric liquid crystal is polymerized to fix the helical structure and irradiated with light, circularly polarized light in a specific wavelength region corresponding to the direction of rotation of the spiral of the liquid crystal molecules and the length of the pitch is reflected. For example, when visible light is irradiated, light of blue, green, yellow, and red wavelengths corresponding to the pitch length of the liquid crystal is selectively reflected. These color tones are different from pigments and dyes that exhibit color by light absorption, and have a viewing angle dependency that changes in color tone depending on the viewing angle. Furthermore, since the pitch length of the cholesteric liquid crystal can be controlled by the temperature and the type of compound, not only visible light but also light in the near infrared and ultraviolet regions can be selectively reflected.

  Materials that selectively reflect light of various wavelengths within a wide wavelength range have been provided by utilizing such characteristics of cholesteric liquid crystals. Examples thereof include liquid crystal pigments, paints, spray inks, printing inks, cosmetics, anti-counterfeit printed matter, and decorative items. In addition, it has also been proposed for optical films such as polarizing plates, compensation plates, and color filters in optical elements such as liquid crystal display elements and holographic elements. As cholesteric liquid crystal pigments, which are existing materials, flaky cholesteric liquid crystal polymers and microencapsulated cholesteric liquid crystals are used. These applications include automotive paints and cosmetics.

  Cholesteric liquid crystals can be usually prepared by adding an optically active compound (chiral agent) to nematic liquid crystals. In order to reflect circularly polarized light from the ultraviolet region to the visible light region, the cholesteric liquid crystal needs to exhibit a spiral structure with a very short pitch. For this purpose, an optically active compound having a large helical induction force (HTP) is required. When an optically active compound having a small HTP is used, the amount of addition must be increased, so that it is difficult to adjust other physical properties, particularly the temperature range of the cholesteric liquid crystal and the selective reflection wavelength range. In many cases, since the optically active compound does not exhibit liquid crystallinity, the liquid crystallinity of the composition disappears when the addition amount is increased, and the intended cholesteric liquid crystal phase cannot be obtained.

Further, even if HTP is a large optically active compound, since it is difficult to synthesize if it has a complicated structure, it may be a very expensive material that is inappropriate for industrial bulk specifications.
Bull. Chem. Soc. Jpn., Vol. 80, No. 3, 589-593 (2007) (Non-patent Document 1) describes the use of an abietic acid derivative as a chiral agent. However, the abietic acid derivative described in Non-Patent Document 1 is a non-polymerizable compound, and no polymerizable abietic acid derivative has been reported so far. When a polymerizable optically active compound is used as the chiral agent, the hardness of the liquid crystal composition polymer can be controlled as compared with a non-polymerizable optically active compound, and the optically active compound itself oozes out from the molded product. Can be prevented.
Bull. Chem. Soc. Jpn., Vol. 80, No. 3, 589-593 (2007)

An object of the present invention is an economical method having a large HTP, excellent compatibility with other liquid crystal materials, easy adjustment of characteristics required as a cholesteric material, and suitable for industrial bulk specifications The present invention provides a polymerizable optically active compound that can be produced by the following process.
Note that the liquid crystal material is a generic term including a liquid crystal compound and a liquid crystal composition.

As a result of intensive studies, the present inventors have found a novel polymerizable optically active compound that can solve the above-mentioned problems. A specific configuration example of the present invention is shown below.
[1] A compound represented by the following formula (1).

RP-X- (AZ) _m -Y (1)
[In Formula (1),
R is CH ₂ ═C (R ¹ ) —COO—, CH ₂ ═CH—, or the following formula (2-1) or (
2-2), R ¹ represents hydrogen or methyl,
P represents a single bond or alkylene having 1 to 12 carbon atoms, and any —CH ₂ — in the alkylene represents —O—, —S—, —CH═CH—, —CO—, —COO— or -OCO- may be substituted,
X represents a single bond, —O—, —S—, —COO—, —OCO—, —CON (R ³ ) —, —N (
R ³ ) represents CO— or —OCOO—, R ³ represents hydrogen or methyl,
A independently represents an aromatic ring or an aliphatic ring, and in these rings, any hydrogen may be replaced by alkyl having 1 to 3 carbon atoms;
Z independently represents a single bond, —COO—, —OCO— or —CH ₂ CH ₂ —;
m represents an integer of 0 to 3,
Y represents a group represented by the following formula (3-1), (3-2) or (3-3). ]

[In the formula (2-1), R ² represents hydrogen, methyl or ethyl. ]

[2] The compound according to item [1], wherein in the formula (1), m is 0 and P is alkylene having 2 to 10 carbon atoms.
[3] In the formula (1), m is 1, and A is a group represented by the following formula (4-1), (4-2), or (4-3). The compound according to [1].

[4] The compound according to item [3], wherein in the formula (1), P, Z and X are a single bond.
[5] The compound according to item [3], wherein in the formula (1), P is alkylene having 2 to 10 carbon atoms.

[6] In the formula (1),-(AZ) _m -is any one of structures represented by the following formulas (5-1) to (5-9) [1] ] The compound of description.

[7] The compound according to item [6], wherein in the formula (1), P and X are a single bond.
[8] The compound according to item [6], wherein in the formula (1), P is alkylene having 2 to 10 carbon atoms.

[9] In the formula (1),-(AZ) _m -is any one of structures represented by the following formulas (6-1) to (6-8). ] The compound of description.

[10] The compound according to item [9], wherein in the formula (1), P and X are a single bond.
[11] The compound according to item [9], wherein in the formula (1), P is alkylene having 2 to 10 carbon atoms.

[12] In the formula (1), R—P—X— is CH ₂ ═CH—COO— or C
The compound according to item [1], wherein H ₂ = C (CH ₃ ) —COO—.
[13] In the formula (1), R—P—X— represents CH ₂ ═CH—CO—OCH ₂ CH ₂ OCH ₂ CH ₂ O—COO— or CH ₂ ═CH—CO—OCH ₂ CH ₂ OCH. The compound according to item [1], which is ₂ CH ₂ OCH ₂ CH ₂ O—COO—.

[14] In the formula (1), R—P—X— represents CH ₂ ═C (CH ₃ ) —CO—OCH ₂ CH ₂ OCH ₂ CH ₂ O—COO— or CH ₂ ═C (CH ₃ ). The compound according to item [1], which is —CO—OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ O—COO—.

[15] The compound according to any one of items [1] to [14], wherein in the formula (1), Y is a group represented by the formula (3-1).
[16] A liquid crystal composition comprising the compound according to any one of items [1] to [15] and a liquid crystal compound.

[17] The liquid crystal composition according to item [16], wherein the liquid crystal compound includes at least one polymerizable liquid crystal compound.
[18] A polymer obtained by polymerizing the liquid crystal composition according to item [17].

[19] The polymer according to item [18], which exhibits a cholesteric liquid crystal phase.
[20] Use of the liquid crystal composition according to item [16] or [17] for an application selected from liquid crystal pigments, paints, spray inks, printing inks, cosmetics, anti-counterfeit prints, ornaments and optical films.

  [21] Use of the polymer according to item [18] or [19] for use selected from liquid crystal pigments, paints, spray inks, printing inks, cosmetics, anti-counterfeit printed matter, decorative products, and optical films.

  The compound of the present invention has high polymerization reactivity, large HTP, excellent compatibility with other liquid crystal materials, easy adjustment of properties required as a cholesteric material, and industrial bulk specifications. Since it can be produced by a suitable and economical method, it can be suitably used as a chiral agent.

Hereinafter, the compound according to the present invention and its use will be described in detail.
In the following, the compound represented by the formula (1) may be referred to as “compound (1)”. In the chemical formula, when one compound has a plurality of A, any two A may be the same or different. This rule also applies to symbols such as Z.

〔Compound〕
As shown in the above formula (1), the compound (1) of the present invention has a polymerizable group at one end and any one of the above formulas (3-1) to (3-3) at the other end. Since it has an abietic acid residue represented by the formula, it exhibits characteristics such as high polymerization reactivity, optical activity and good miscibility.

In the above formula (1), R represents CH ₂ ═C (R ¹ ) —COO— (R ¹ represents hydrogen or methyl), CH ₂ ═CH—, or the above formula (2-1) or (2- 2), and among them, CH ₂ ═C (R ¹ ) —COO because of excellent compatibility with other components in the composition and solubility in a solvent. - and CH ₂ = CH- are preferred.

In the above formula (1), P represents a single bond or alkylene having 1 to 12 carbon atoms, and any —CH ₂ — in the alkylene represents —O—, —S—, —CH═CH—, —CO. -, -COO
-Or -OCO- may be substituted.

Here, the meaning of the phrase “any —CH ₂ — in alkylene may be replaced by —O—, —CH═CH—, etc.” is shown as an example. The group in which arbitrary —CH ₂ — in —C ₄ H ₈ — is replaced by —O— or —CH═CH— is, for example, —C ₃ H ₆ O—, —CH ₂ —O— (
CH ₂ ) ₂ —, —CH ₂ —O—CH ₂ —O—, —HC═CH— (CH ₂ ) ₃ —, —CH ₂ —CH
_{= CH- (CH 2) 2 -} , - is a _{CH 2 -CH = CH-CH 2} -O- or the like. Thus, the term “arbitrary” means “at least one selected without distinction”. In consideration of the stability of the compound, —CH ₂ —O—CH ₂ —O— in which oxygen and oxygen are not adjacent to each other than —CH ₂ —O—O—CH ₂ — in which oxygen and oxygen are adjacent to each other. Is preferred.

In the above formula (1), X represents a single bond, —O—, —S—, —COO—, —OCO—, —CON (R ³ ) —, —N (R ³ ) CO— or —OCOO—. (R ³ represents hydrogen or methyl), and among these, a single bond and —COO— are preferable.

In the above formula (1), preferred examples of the site represented by R—P—X—
_{(I) CH 2 = CH-} COO- or _{CH 2 = C (CH 3)} -COO-,
_{(Ii) CH 2 = CH-} CO-OCH 2 CH 2 OCH 2 CH 2 O-COO- or _{CH 2 = CH-CO-OCH} 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 O-COO-,
_{(Iii) CH 2 = C (} CH 3) -CO-OCH 2 CH 2 OCH 2 CH 2 O-COO- or _{CH 2 = C (CH 3)} -CO-OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 O-COO-
Etc. When the site represented by R—P—X— is the above (i) to (iii), it is effective for improving the compatibility with other components and causing HTP to appear.

  In the above formula (1), A independently represents an aromatic ring or an aliphatic ring, and in these rings, arbitrary hydrogen may be replaced with alkyl having 1 to 3 carbon atoms. Examples of such A include 1,4-cyclohexylene, 1,3-phenylene, 1,4-phenylene, naphthalene-2,6-diyl, and the like. In these, since it is a structure effective in making HTP appear, group represented by the said Formula (4-1), (4-2) or (4-3) is preferable.

In the above formula (1), Z independently represents a single bond, —COO—, —OCO— or —CH ₂ CH ₂ —, and among these, a single bond, —COO— and —OCO— are preferred. .
In said formula (1), m shows the integer of 0-3.

  When m = 0, P is preferably an alkylene having 1 to 12 carbons, more preferably an alkylene having 2 to 10 carbons, and particularly preferably an alkylene having 4 to 10 carbons.

  When m = 1, A is preferably any one of groups represented by the above formulas (4-1) to (4-3). In this case, it is more preferable that P, Z and X are a single bond, or P is alkylene having 2 to 10 carbon atoms. In addition, it is more preferable that the carbon number of P is 4-10.

In the case of m = 2, the site represented by-(AZ) _m -is preferably any one of the structures represented by the above formulas (5-1) to (5-9). In this case, it is more preferable that P and X are single bonds, or P is alkylene having 5 to 12 carbon atoms. In addition, it is more preferable that the carbon number of P is 4-10.

In the case of m = 3, it is preferable that the site represented by-(AZ) _m -is any one of the structures represented by the formulas (6-1) to (6-8). In this case, it is more preferable that P and X are single bonds, or P is alkylene having 2 to 10 carbon atoms. In addition, it is more preferable that the carbon number of P is 4-10.

  In the above formula (1), Y represents an abietic acid residue represented by the above formula (3-1), (3-2) or (3-3), and among these, the formula (3-1) It is preferable that it is group represented by these.

The example of the synthesis method of the compound (1) of this invention is demonstrated below.
(I) In the above formula (1), the compound (1) in which m = 0 and P is alkylene having 1 to 12 carbons can be synthesized according to the following synthesis scheme.

  As shown in the above scheme, dehydroabietic acid [a] is first chlorinated to give carboxylic acid chloride [b]. Next, compound [d] can be synthesized by esterifying carboxylic acid chloride [b] and 2-hydroxyethyl acrylate [c]. The compound (1) having the group represented by the above formula (3-2) or (3-3) is synthesized by using abietic acid or dihydroabietic acid instead of dehydroabietic acid [a]. Can do. Moreover, 4-hydroxybutyl acrylate etc. can be used instead of 2-hydroxyethyl acrylate [c].

(Ii) In the above formula (1), m = 1 and A is a group represented by the above formula (4-1), (4-2) or (4-3), or (1) m = 2,-(AZ) _m
Compound (1) in which the moiety represented by — is a structure represented by the above formula (5-5) can be synthesized according to the following synthesis scheme.

Dehydroabietic acid chloride [b] obtained in the same manner as in the above method (i) is esterified with hydroquinone [e] to obtain compound [f]. Subsequently, compound [h] can be obtained by esterification reaction of compound [f] and (meth) acrylic acid chloride [g]. Resorcinol, 2,6-naphthalenediol or 4-4 ′ biphenol can be used in place of hydroquinone [e]. In place of (meth) acrylic acid chloride [g], ethylene glycol monoacrylate chloroformate, 4-acryloyloxybutyl chloroformate, diethylene glycol acrylate chloroformate or triethylene glycol acrylate chloroformate may be used. it can.

(Iii) In the above formula (1), m = 2, and any of the structures represented by the above formulas (5-1) to (5-9) is represented by-(AZ) _m- Any one of the structures represented by the above formulas (6-1) to (6-8), wherein the compound (1) is m = 3 and the site represented by-(AZ) _m -is Compound (1) can be synthesized according to the following synthesis scheme.

First, an abietic acid derivative ester compound is synthesized by esterifying the compound [f] obtained in the same manner as in the above method (ii) and the compound [i]. For the esterification reaction, a condensing agent such as dicyclohexylcarbodiimide (DCC) can be suitably used. Note that DMAP in the above scheme is an abbreviation for N, N-dimethyl-4-aminopyridine. Next, deprotection of the acetoxy group is performed under alkaline conditions to obtain compound [j]. Furthermore, compound [k] can be obtained by esterification reaction of compound [j] and (meth) acrylic acid chloride [g].

In addition, when synthesizing the compound [f], resorcinol, 2,6-naphthalenediol or 4-4 ′ biphenol can be used as described above. Instead of the compound [i], resorcinol, 2,6-naphthalenediol, 4-4 ′ biphenol or the like in which one hydroxy group is protected with a protecting group such as an acetoxy group can be used. Moreover, as mentioned above, instead of (meth) acrylic acid chloride [g], ethylene glycol monoacrylate chloroformate, 4-acryloyloxybutyl chloroformate, diethylene glycol acrylate chloroformate or triethylene glycol acrylate chloroformate Etc. can be used.

  Specific examples of the compound (1) synthesized by the above method are shown below. The structure of the compound (1) synthesized as described above can be confirmed by, for example, a proton NMR spectrum.

[Liquid crystal composition]
The liquid crystal composition of the present invention contains the above-described compound (1) of the present invention and a liquid crystal compound. Compound (1) may be used alone or in combination of two or more. Similarly, the liquid crystal compounds may be used singly or in combination of two or more. The liquid crystal compound may be non-polymerizable or polymerizable, but at least one kind is preferably a polymerizable liquid crystal compound.

The non-polymerizable liquid crystal compound is described in, for example, a liquid crystal compound database (LiqCryst, LCI Publisher GmbH, Hamburg, Germany).
Examples of the polymerizable liquid crystal compound include compounds represented by the following formulas (M1a), (M1b), (M1c), (M2a), (M2b), and (M2c).

In the formulas (M1a) to (M2c),
P ¹ is independently a group represented by any of the following formulas (P1) to (P8);
R ¹ is independently hydrogen, fluorine, chlorine, —CN, or alkyl having 1 to 20 carbons;
In the alkyl, any —CH ₂ — may be replaced with —O—, —COO— or —OCO—, and any hydrogen may be replaced with halogen;
Ring A ³ is independently 1,4-cyclohexylene or 1,4-phenylene;
W ¹ is independently hydrogen, halogen, alkyl having 1 to 3 carbon atoms or alkyl halide having 1 to 3 carbon atoms;
X ¹ is independently a single bond or alkylene having 1 to 20 carbon atoms, and any —CH ₂ — in the alkylene may be replaced by —O—, —COO— or —OCO—;
Z ¹ is independently —COO—, —OCO—, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —,
_{-CH 2 CH 2 COO -, -} OCOCH 2 CH 2 -, - CH = CHCOO- or -OCOCH = CH- and is;
p and q are each independently 0 or 1, and n is an integer of 0 to 10.

In formulas (P1) to (P8), W represents hydrogen, halogen, alkyl having 1 to 3 carbon atoms, or alkyl halide having 1 to 3 carbon atoms.
The liquid crystal composition of the present invention has a wide cholesteric liquid crystal phase region around room temperature (about 10 to 40 ° C.), and the cholesteric phase is changed by changing the composition ratio of each component and the temperature at which the composition is polymerized. The wavelength range of the reflected light can be controlled, and it is possible to form a polymer that reflects light having a wavelength according to a desired color or purpose.

  In the liquid crystal composition of the present invention, the compound (1) is preferably 5 to 40% by weight, more preferably 5 to 30% by weight with respect to 100% by weight in total of the compound (1) and the liquid crystal compound. More preferably, it is contained in an amount of 5 to 25% by weight. When the content of the compound (1) is within the above range, the selected wavelength range of the liquid crystal composition can be controlled as necessary.

  In addition to the compound (1) and the liquid crystal compound, the liquid crystal composition of the present invention includes, for example, a non-liquid crystalline polymerizable compound, a solvent, a polymerization initiator, a surfactant, an antioxidant, an ultraviolet absorber, a filler, A sensitizer and the like may be further contained as long as the object of the present invention is not impaired. In order to optimize the properties of the composition, an optically active compound other than the compound (1) may be added to the liquid crystal composition of the present invention.

(Polymer)
The polymer of the present invention is obtained by polymerizing the liquid crystal composition of the present invention described above, and the cholesteric liquid crystal phase (helical structure) of the composition is fixed by the polymerization, and has a wavelength corresponding to a desired color and purpose. Reflects light. The polymerization reaction of the composition may be thermal polymerization by heating, photopolymerization by light irradiation, or a method combining both.

  Preferred types of light used for photopolymerization are ultraviolet rays, visible rays, infrared rays, and the like, and electromagnetic waves such as electron beams and X-rays may be used. Usually, ultraviolet rays or visible rays are used. The wavelength range is preferably 150 to 500 nm, more preferably 250 to 450 nm, and particularly preferably 300 to 400 nm. As light sources, low-pressure mercury lamps (sterilization lamps, fluorescent chemical lamps, black lights), high-pressure discharge lamps (high-pressure mercury lamps, metal halide lamps), short arc discharge lamps (super-high pressure mercury lamps, xenon lamps, mercury xenon lamps), etc. Among them, an ultrahigh pressure mercury lamp is preferable.

The light from the light source may be irradiated to the composition as it is, or the composition may be irradiated with a specific wavelength (or a specific wavelength region) selected by a filter. Irradiation energy density is preferably in the range 2~5000mJ / cm ^2, more preferably 10~3000mJ / cm ^2, particularly preferably of 100 to 2000 mJ / cm ^2. Illuminance is preferably 0.1-5000m
W / cm ² , more preferably in the range of 1 to 2000 mW / cm ² .

  The shape of the polymer is not particularly limited, and may be a film shape (film shape) or a plate shape, and the polymer may be molded. The film can be obtained by a method of applying the liquid crystal composition of the present invention to a substrate and polymerizing it.

[Use]
Applications of the liquid crystal composition and polymer of the present invention include color materials in general, for example, liquid crystal pigments, paints, spray inks, printing inks, and the like. Moreover, it can also be used for cosmetics, anti-counterfeit printed matter, ornaments, optical films and the like.

EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to these Examples at all. The structure of the compound was confirmed by nuclear magnetic resonance spectrum.
[Example 1]
(First stage)
Dehydroabietic acid (15 g) and thionyl chloride (30 mL) were mixed, and a small amount of DMF (N, N-dimethylformamide) was added dropwise, followed by stirring for 2 hours while refluxing. After cooling to room temperature, toluene solvent was added to the reaction mixture, and thionyl chloride and toluene solvent were removed under reduced pressure. To the residue after removal of the solvent (brown liquid) was added THF (tetrahydrofuran, 100 mL) and about 2 equivalents of hydroquinone (11 g), and then triethylamine (7 mL).
After dropping, the mixture was stirred at room temperature for 8 hours. After completion of the reaction, part of THF was distilled off, ethyl acetate (300 mL) and water (100 mL) were added, and the ethyl acetate layer was separated. The ethyl acetate layer was thoroughly washed with hydrochloric acid water, saturated sodium hydrogen carbonate and water successively, and dried over anhydrous magnesium sulfate. The solvent was removed from the organic layer under reduced pressure, and the obtained residue was purified by column chromatography (silica gel, eluent: toluene / ethyl acetate = 10/1 (V / V)) to give a tan solid. 4-hydroxyphenyl dehydroabietic acid ester was obtained.

(Second stage)
The obtained 4-hydroxyphenyl dehydroabietic acid ester (1.8 g), acrylic acid chloride (1 g), triethylamine (0.7 mL), and THF (50 mL) were mixed and stirred at room temperature for 5 hours. After completion of the reaction, part of THF was distilled off, ethyl acetate (300 mL) and water (100 mL) were added, and the ethyl acetate layer was separated. The ethyl acetate layer was thoroughly washed with hydrochloric acid water, saturated sodium hydrogen carbonate and water successively, and dried over anhydrous magnesium sulfate. The solvent was removed from the organic layer under reduced pressure, and the resulting residue was purified by column chromatography (silica gel, eluent: toluene / ethyl acetate = 10/1 (V / V)) to obtain the desired tan solid. I got a thing. The structure of the obtained compound is shown in Table 1.

[Example 2]
(First stage)
In the same manner as in the first step of Example 1, 4-hydroxyphenyl dehydroabietic acid ester as a tan solid was obtained.

(Second stage)
The target tan solid was obtained in the same manner as in the second step of Example 1 except that ethylene glycol monoacrylate chloroformate was used instead of acrylic acid chloride. The structure of the obtained compound is shown in Table 1.

Example 3
(First stage)
In the same manner as in the first step of Example 1, 4-hydroxyphenyl dehydroabietic acid ester as a tan solid was obtained.

(Second stage)
The target tan solid was obtained in the same manner as in the second step of Example 1, except that 4-acryloyloxybutyl chloroformate was used instead of acrylic acid chloride. The structure of the obtained compound is shown in Table 1.

Example 4
(First stage)
In the same manner as in the first step of Example 1, 4-hydroxyphenyl dehydroabietic acid ester as a tan solid was obtained.

(Second stage)
The resulting 4-hydroxyphenyl dehydroabietic acid ester (1.8 g), 85% potassium hydroxide (3.3 g) and DMF (20 mL) were mixed and stirred with heating for 30 minutes. The mixture was cooled to room temperature, 4- (p-tosyloxy) butyl acrylate (2 g) was added, and the mixture was heated to reflux for 1 hour. After completion of the reaction, a portion of DMF was distilled off, toluene (100 mL) and water (100 mL) were added, and the toluene layer was separated. The toluene layer was sufficiently washed with hydrochloric acid water and water successively and dried over anhydrous magnesium sulfate. The solvent was removed from the organic layer under reduced pressure, and the resulting residue was purified by column chromatography (silica gel, eluent: toluene / ethyl acetate = 10/1 (V / V)) to obtain the desired tan solid. I got a thing. The structure of the obtained compound is shown in Table 1.

Example 5
(First stage)
In the same manner as in the first step of Example 1, 4-hydroxyphenyl dehydroabietic acid ester as a tan solid was obtained.

(Second stage)
The resulting 4-hydroxyphenyl dehydroabietic acid ester (1.8 g), 4-acryloyloxybenzoic acid (1 g), DCC (1.2 g), DMAP (0.06 g) and methylene chloride (50 mL) were mixed, Stir at room temperature for 1 hour. The precipitated crystals were removed by filtration, water (50 mL) was added to the filtrate, and the methylene chloride solvent was separated, and then washed thoroughly with aqueous hydrochloric acid, saturated sodium bicarbonate, and water successively, and anhydrous magnesium sulfate. Dried. The solvent was removed under reduced pressure, and the resulting residue was purified by column chromatography (silica gel, eluent: toluene / ethyl acetate = 10/1 (V / V)) to obtain the desired tan solid. It was. The NMR analysis values of the obtained compound are shown below, and the structure is shown in Table 1.

¹ H-NMR (CDCl ₃ ): δ (ppm); 1.23 (d, 6H), 1.27 (s, 3H), 1.41 (s, 3H), 1.48-1.97 (m 7H), 2.34-2.45 (m, 2H), 2.83-2.96 (m, 3H), 6.06 (dd, 2H), 6.34 (dd, 2H), 6. 63 (dd, 2H) 6.90-8.24 (m, 11H).

Example 6
(First stage)
In the same manner as in the first step of Example 1, 4-hydroxyphenyl dehydroabietic acid ester as a tan solid was obtained.

(Second stage)
The resulting 4-hydroxyphenyl dehydroabietic acid ester (1.8 g), 4-
(6-Acryloylhexyloxy) benzoic acid (1.3 g), DCC (1.2 g), DMAP (0.06 g) and methylene chloride (50 mL) were mixed and stirred at room temperature for 1 hour. The precipitated crystals were removed by filtration, water (50 mL) was added to the filtrate, and the methylene chloride solvent was separated, and then washed thoroughly with aqueous hydrochloric acid, saturated sodium bicarbonate, and water successively, and anhydrous magnesium sulfate. Dried. The solvent was removed under reduced pressure, and the resulting residue was purified by column chromatography (silica gel, eluent: toluene / ethyl acetate = 10/1 (V / V)) to give a tan solid. The structure of the obtained compound is shown in Table 2.

Example 7
A dehydroabietic acid ester of a tan solid was obtained in the same manner as in the first step of Example 1, except that 2-naphthylic acid-6-hydroxy-4-acryloyloxybutyl ester was used instead of hydroquinone. . The structure of the obtained compound is shown in Table 2.

Example 8
In the same manner as in the first step of Example 1, 4-hydroxyphenyl dehydroabietic acid ester as a tan solid was obtained.

(Second stage)
The target tan solid was obtained in the same manner as in the second step of Example 1 except that diethylene glycol acrylate chloroformate was used instead of acrylic acid chloride. The structure of the obtained compound is shown in Table 2.

Example 9
(First stage)
In the same manner as in the first step of Example 1, 4-hydroxyphenyl dehydroabietic acid ester as a tan solid was obtained.

(Second stage)
The resulting 4-hydroxyphenyl dehydroabietic acid ester (1.8 g), 4-acetoxybenzoic acid (0.9 g), DCC (1.2 g), DMAP (0.06 g) and methylene chloride (50 mL) were mixed. And stirred at room temperature for 1 hour. The precipitated crystals were removed by filtration, water (50 mL) was added to the filtrate, and the methylene chloride solvent was separated, and then washed thoroughly with aqueous hydrochloric acid, saturated sodium bicarbonate, and water successively, and anhydrous magnesium sulfate. Dried. The solvent was removed under reduced pressure, and the resulting residue was purified by column chromatography (silica gel, eluent: toluene / ethyl acetate = 10/1 (V / V)) to give a tan solid.

(3rd stage)
Methanol (20 mL) was added to the solid, and 30% aqueous ammonia (2 mL) was added dropwise at room temperature. After stirring at room temperature for 2 hours, 6N hydrochloric acid (30 mL) was added to neutralize the reaction mixture, extracted with ethyl acetate (200 mL), and dried over anhydrous magnesium sulfate. The solvent was removed from the organic layer under reduced pressure.

(Fourth stage)
To the obtained residue, THF (50 mL), triethylamine 3 mL and diethylene glycol acrylate chloroformate (1.0 g) were added, and the mixture was stirred at room temperature for 5 hours. After completion of the reaction, a part of THF was distilled off, ethyl acetate (300 mL) and water (100 mL) were added, and the ethyl acetate layer was separated, and then washed thoroughly using hydrochloric acid water, saturated sodium bicarbonate and water successively. And dried over anhydrous magnesium sulfate. The solvent was removed from the organic layer under reduced pressure, and the resulting residue was purified by column chromatography (silica gel, eluent: toluene / ethyl acetate = 10/1 (V / V)) to obtain the desired tan color. A solid was obtained. The structure of the obtained compound is shown in Table 2.

Example 10
(First stage)
A tan solid 3-hydroxyphenyl dehydroabietic acid ester was obtained in the same manner as in Example 1 except that resorcinol was used instead of hydroquinone.

(Second stage)
The obtained 3-hydroxyphenyl dehydroabietic acid ester (1.8 g), acrylic acid chloride (1 g), triethylamine (0.7 mL) and THF (50 mL) were mixed and stirred at room temperature for 5 hours. After completion of the reaction, part of THF was distilled off, ethyl acetate (300 mL) and water (100 mL) were added, and the ethyl acetate layer was separated. The ethyl acetate layer was thoroughly washed with hydrochloric acid water, saturated sodium hydrogen carbonate and water successively, and dried over anhydrous magnesium sulfate. The solvent was removed from the organic layer under reduced pressure, and the resulting residue was purified by column chromatography (silica gel, eluent: toluene / ethyl acetate = 10/1 (V / V)) to obtain the desired tan solid. I got a thing. The structure of the obtained compound is shown in Table 2.

Example 11
(First stage)
In the same manner as in the first step of Example 10, a tan solid 3-hydroxyphenyl dehydroabietic acid ester was obtained.

(Second stage)
The target tan solid was obtained in the same manner as in the second step of Example 10, except that ethylene glycol monoacrylate chloroformate was used instead of acrylic acid chloride (1 g). Table 3 shows the structure of the obtained compound.

Example 12
(First stage)
In the same manner as in the first step of Example 10, a tan solid 3-hydroxyphenyl dehydroabietic acid ester was obtained.

(Second stage)
The target tan solid was obtained in the same manner as in the second stage of Example 10, except that 4-acryloyloxybutyl chloroformate was used instead of acrylic acid chloride. Table 3 shows the structure of the obtained compound.

Example 13
(First stage)
In the same manner as in the first step of Example 10, a tan solid 3-hydroxyphenyl dehydroabietic acid ester was obtained.

(Second stage)
The target tan solid was obtained in the same manner as in the second step of Example 10 except that 4-acryloyloxybenzoic acid was used instead of acrylic acid chloride. The NMR analysis values of the obtained compound are shown below, and the structure is shown in Table 3.

¹ H-NMR (CDCl ₃ ): δ (ppm); 1.23 (d, 6H), 1.27 (s, 3
H), 1.41 (s, 3H), 1.48-1.97 (m, 7H), 2.34-2.45 (m, 2H), 2.83-2.96 (m, 3H) 6.06 (dd, 2H), 6.34 (dd, 2H), 6.63 (dd, 2H) 7.00-8.22 (m, 11H).

Example 14
(First stage)
In the same manner as in the first step of Example 10, a tan solid 3-hydroxyphenyl dehydroabietic acid ester was obtained.

(Second stage)
The target tan solid was obtained in the same manner as in the second step of Example 10, except that 4- (6-acryloylhexyloxy) benzoic acid was used instead of acrylic acid chloride. Table 3 shows the structure of the obtained compound.

Example 15
(First stage)
In the same manner as in the first step of Example 10, a tan solid 3-hydroxyphenyl dehydroabietic acid ester was obtained.

(2nd to 4th stages)
After carrying out the same operation as in the second to third steps of Example 9, except that 3-hydroxyphenyl dehydroabietic acid ester obtained instead of 4-hydroxyphenyl dehydroabietic acid ester was used, In the same manner as in the second step of Example 4, the target tan solid was obtained. Table 4 shows the structure of the obtained compound.

Example 16
(First stage)
In the same manner as in the first step of Example 10, a tan solid 3-hydroxyphenyl dehydroabietic acid ester was obtained.

(2nd to 4th stages)
Except for using 4-hydroxyphenyl dehydroabietic acid ester instead of 4-hydroxyphenyl dehydroabietic acid ester and using 4-acryloyloxybutyl chloroformate instead of diethylene glycol acrylate chloroformate, The target tan solid was obtained in the same manner as in the second to fourth stages of Example 9. Table 4 shows the structure of the obtained compound.

Example 17
(First stage)
In the same manner as in the first step of Example 10, a tan solid 3-hydroxyphenyl dehydroabietic acid ester was obtained.

(2nd to 4th stages)
The target tan color was obtained in the same manner as in the second to fourth steps of Example 9, except that the obtained 3-hydroxyphenyl dehydroabietic acid ester was used instead of 4-hydroxyphenyl dehydroabietic acid ester. A solid was obtained. The NMR analysis values of the obtained compound are shown below, and the structure is shown in Table 4.

¹ H-NMR (CDCl ₃ ): δ (ppm); 1.1-1.95 (m, 19H), 2.36-2.42 (m, 2H), 2.83-2.95 (m, 3H), 3.80-4.45 (m
, 8H) 5.80 (dd, 2H), 6.16 (dd, 2H), 6.43 (dd, 2H) 6.98-8.22 (m, 11H).

Example 18
Dihydroabietic acid (1.5 g) and thionyl chloride (3 mL) were mixed and a small amount of DMF was added dropwise, followed by stirring for 2 hours while refluxing. After cooling to room temperature, toluene solvent was added to the reaction mixture, and thionyl chloride and toluene solvent were removed under reduced pressure. To the residue after removal of the solvent (brown liquid), THF (20 mL) and 1 equivalent of 2-hydroxyethyl acrylate (
0.6 g) was added, and then 1.5 equivalents of triethylamine was added dropwise, followed by stirring at room temperature for 8 hours. After completion of the reaction, part of THF was distilled off, ethyl acetate (300 mL) and water (100 mL) were added, and the ethyl acetate layer was separated. The ethyl acetate layer was thoroughly washed with hydrochloric acid water, saturated sodium hydrogen carbonate and water successively, and dried over anhydrous magnesium sulfate. The solvent was removed from the organic layer under reduced pressure, and the resulting residue was purified by column chromatography (silica gel, eluent: toluene / ethyl acetate = 10/1 (V / V)) to obtain the desired tan solid. (1.2 g) was obtained. Table 4 shows the structure of the obtained compound.

Example 19
In Example 3, the target product was obtained in the same manner as in the first and second steps of Example 3, except that dihydroabietic acid was used instead of dehydroabietic acid. Table 4 shows the structure of the obtained compound.

Example 20
In Example 12, the target product was obtained in the same manner as in the first and second steps of Example 12, except that dihydroabietic acid was used instead of dehydroabietic acid. Table 4 shows the structure of the obtained compound.

<Measurement of helical pitch and HTP>
The helical pitch was measured as follows. First, the compound (about 0.01 g) obtained in the above example was placed in a glass sample bottle, the following composition (M-1) was added thereto, and the content of the compound obtained in the above example was It mixed so that it might become about 1 weight%. Subsequently, this mixture was heated, and after the mixture dissolved and became a complete isotropic liquid, it was left to stand and allowed to cool. A part of the composition thus obtained was poured into a wedge-shaped cell, and the pitch was measured at 25 ° C. according to the Cano wedge method (Applied Physics, 1974, 43, 125). HTP
Was calculated from the formula [HTP = p ⁻¹ × c ⁻¹ ] based on the obtained pitch. Here, c is% by weight of the sample compound, and p is the pitch (μm). The helical pitches and HTPs of the compounds obtained in Examples 1 to 20 (excluding the compounds of Examples 7 and 12) are shown in Tables 1 to 4 below.

Claims (21)

A compound represented by the following formula (1).
RP-X- (AZ) _m -Y (1)
[In Formula (1),
R is CH ₂ ═C (R ¹ ) —COO—, CH ₂ ═CH—, or the following formula (2-1) or (
2-2), R ¹ represents hydrogen or methyl,
P represents a single bond or alkylene having 1 to 12 carbon atoms, and any —CH ₂ — in the alkylene represents —O—, —S—, —CH═CH—, —CO—, —COO— or -OCO- may be substituted,
X represents a single bond, —O—, —S—, —COO—, —OCO—, —CON (R ³ ) —, —N (
R ³ ) represents CO— or —OCOO—, R ³ represents hydrogen or methyl,
A independently represents an aromatic ring or an aliphatic ring, and in these rings, any hydrogen may be replaced by alkyl having 1 to 3 carbon atoms;
Z independently represents a single bond, —COO—, —OCO— or —CH ₂ CH ₂ —;
m represents an integer of 0 to 3,
Y represents a group represented by the following formula (3-1), (3-2) or (3-3). ]

[In the formula (2-1), R ² represents hydrogen, methyl or ethyl. ]

  In the said Formula (1), m is 0 and P is a C2-C10 alkylene, The compound of Claim 1 characterized by the above-mentioned. 2. In the formula (1), m is 1, and A is a group represented by the following formula (4-1), (4-2) or (4-3). The described compound.

  The compound according to claim 3, wherein P, Z and X in the formula (1) are single bonds. In the said Formula (1), P is a C2-C10 alkylene, The compound of Claim 3 characterized by the above-mentioned. The said Formula (1) WHEREIN:-(AZ) _m- is either of the structures represented by following formula (5-1)-(5-9), It is characterized by the above-mentioned. Compound.

  The compound according to claim 6, wherein P and X are a single bond in the formula (1).   The compound according to claim 6, wherein in the formula (1), P is alkylene having 2 to 10 carbon atoms. The said Formula (1) WHEREIN:-(AZ) _m- is either of the structures represented by following formula (6-1)-(6-8), It is characterized by the above-mentioned. Compound.

  In the said Formula (1), P and X are single bonds, The compound of Claim 9 characterized by the above-mentioned.   In the said Formula (1), P is a C2-C10 alkylene, The compound of Claim 9 characterized by the above-mentioned. In the formula (1), R—P—X— is
CH ₂ = CH-COO- or _{CH 2 = C (CH 3)} -COO-
The compound according to claim 1, wherein In the formula (1), R—P—X— is
_{CH 2 = CH-CO-OCH} 2 CH 2 OCH 2 CH 2 O-COO- or _{CH 2 = CH-CO-OCH} 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 O-COO-
The compound according to claim 1, wherein In the formula (1), R—P—X— is
_{CH 2 = C (CH 3)} -CO-OCH 2 CH 2 OCH 2 CH 2 O-COO- or _{CH 2 = C (CH 3)} -CO-OCH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 O-COO −
The compound according to claim 1, wherein   In the said Formula (1), Y is group represented by the said Formula (3-1), The compound in any one of Claims 1-14 characterized by the above-mentioned.   A liquid crystal composition comprising the compound according to claim 1 and a liquid crystal compound.   The liquid crystal composition according to claim 16, comprising at least one polymerizable liquid crystal compound as the liquid crystal compound.   A polymer obtained by polymerizing the liquid crystal composition according to claim 17.   The polymer according to claim 18, which exhibits a cholesteric liquid crystal phase.   Use of the liquid crystal composition according to claim 16 or 17 for an application selected from liquid crystal pigments, paints, spray inks, printing inks, cosmetics, anti-counterfeit prints, ornaments and optical films.   20. Use of the polymer according to claim 18 or 19 for an application selected from liquid crystal pigments, paints, spray inks, printing inks, cosmetics, anti-counterfeit prints, ornaments and optical films.