JP2014156459A - Polymerizable compound, and intermediate for producing the compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerizable compound which exhibits excellent solubility to other liquid crystalline compounds, when a polymerizable liquid crystalline composition comprises the polymerizable compound, and which exhibits excellent heat resistance and mechanical strength when the polymerizable liquid crystalline composition is cured and to provide an intermediate from which these polymerizable compounds can efficiently be produced.SOLUTION: The polymerizable compound is shown by general formula (I). The liquid crystalline composition is obtained by using the polymerizable compound as a constituent member. An optically isotropic body or a liquid crystal device is obtained by using the liquid crystalline composition. Since the polymerizable compound exhibits excellent solubility to other liquid crystalline compounds, the polymerizable compound is useful as the constituent member of the polymerizable composition. The intermediate important, when these polymerizable compounds are produced therefrom, is shown by general formula (II).

Description

  The present invention relates to a polymerizable compound, a liquid crystal composition containing the compound, and an optical anisotropic body or a liquid crystal device that is a cured product of the liquid crystal composition, and a hydroxyl group that is a production intermediate of the polymerizable compound. It relates to an aromatic compound having

  In recent years, with the progress of the information society, the importance of optical compensation films used for deflecting plates, retardation plates and the like essential for liquid crystal displays is increasing, and high durability and high functionality are required. An example in which a polymer of a polymerizable liquid crystal composition is used for this optical compensation film has been reported. Optical anisotropic materials used for optical compensation films, etc. are not only optical properties but also important factors such as compound polymerization rate, solubility, melting point, glass transition point, polymer transparency, mechanical strength, surface hardness and heat resistance. It becomes. Furthermore, an example in which a display compound is improved by adding a polymerizable compound to a liquid crystal medium has been reported.

  Conventionally, as a compound constituting a polymerizable liquid crystal composition, a compound having a structure in which 1,4-phenylene groups are linked by an ester bond (see Patent Document 1) and a compound having a fluorene group (see Patent Document 2) are used. Proposed. However, the polymerizable compound described in the cited document has problems such as low solubility. On the other hand, a polymerizable compound having an asymmetric structure has been disclosed in order to improve the solubility (see Patent Document 3), but the solubility is improved as compared with a conventional polymerizable compound. There were problems such as insufficient heat resistance and low mechanical strength. For this reason, further improvement in performance is required.

  Moreover, in order to improve these requirements, the structure of the polymerizable compound has become complicated and its production has become difficult. For this reason, development of the useful intermediate for manufacturing these polymeric compounds efficiently was also earnestly desired.

Japanese National Patent Publication No. 10-513457 JP 2005-60373 A JP-T-2001-527570

  The problem to be solved by the present invention is that when a polymerizable liquid crystal composition is constituted, the polymerizable liquid crystal composition has excellent solubility with other polymerizable compounds and liquid crystal compounds, and the polymerizable liquid crystal composition is cured. It is to provide a polymerizable compound exhibiting excellent heat resistance and mechanical strength, and to provide an intermediate that enables efficient production of these polymerizable compounds.

  As a result of studying various substituents in the polymerizable compound, the present inventors have found that a polymerizable compound having a specific structure can solve the above-described problems, and have completed the present invention.

  Formula (I)

(However, R ¹ is the following formula (R-1) to formula (R-15)

And S ¹ represents an alkylene group having 1 to 12 carbon atoms in which the methylene group may be replaced by an oxygen atom, —COO—, —OCO—, or —OCOO—, assuming that oxygen atoms are not directly bonded to each other. Or Z ¹ is OH, Cl, OC _a H _{2a + 1} (a represents a natural number of 1 to 12, the carbon chain may be linear or branched, L ¹ represents —O—, —COO—, a single bond, or OC _b H _2b (b represents a natural number of 1 to 12). And the carbon chain may be linear or branched, and the methylene group may be replaced by an oxygen atom as an oxygen atom is not directly bonded to each other.), L ² represents —CH═ CH—CO— or —CH ₂ CH ₂ Represents -CO-, ^{M 1} is 1,4-phenylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, 1,4-cyclohexylene Group, or 4,4′-biphenyl group, and M ² and M ³ are each independently 1,4-phenylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene. -2,6-diyl group and tetrahydronaphthalene-2,6-diyl group, M ¹ , M ² and M ³ are each independently unsubstituted or an alkyl group, a halogenated alkyl group, an alkoxy group A group, a halogeno group, a cyano group, or a nitro group, and m represents 0, 1 and 2, but when m represents 2, a plurality of M ² may be the same or different. At best, however ^{M 3} is 1, - For a phenylene group, m represents 1 or 2. As an important intermediate in the production of the compound represented by the general formula (I).

(Wherein Z ² is OH, Cl or OC _c H _{2c + 1} (c represents a natural number of 1 to 12, the carbon chain may be linear or branched, and oxygen atoms are directly bonded to each other) The methylene group may be replaced by an oxygen atom as a non-operating group), S ² is a single bond, or C _d H _2d (d represents a natural number of 1 to 12, and the carbon chain is linear. May be branched, or a carbon atom may be replaced by an oxygen atom assuming that oxygen atoms are not directly bonded to each other.), L ³ represents —O—, —COO—, a single bond, or OC _e H _2e (e represents a natural number of 1 to 12, the carbon chain may be linear or branched, and the methylene group may be replaced by an oxygen atom as a combination of oxygen atoms not directly bonded to each other. L ⁴ represents —CH═CH—C. Represents O— or —CH ₂ CH ₂ —CO—, and M ⁴ and M ⁵ each independently represent 1,4-phenylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, Represents a naphthalene-2,6-diyl group or a tetrahydronaphthalene-2,6-diyl group, and M ⁴ and M ⁵ are each independently unsubstituted or an alkyl group, a halogenated alkyl group, an alkoxy group, It may be substituted with a halogeno group, a cyano group, or a nitro group, and n represents 0, 1 and 2, but when n represents 2, a plurality of M ⁴ may be the same or different. However, when M ⁵ is a 1,4-phenylene group, n represents 1 or 2. This provides an aromatic compound having a hydroxyl group represented by:

  The polymerizable compound derived from the aromatic compound having a hydroxyl group of the present invention has a wide liquid crystal phase temperature range and is useful as an intermediate of a polymerizable compound having excellent solubility with other liquid crystal compounds. In addition, an optical anisotropic body made of a polymerizable composition using a polymerizable compound derived from an aromatic compound having a hydroxyl group of the present invention has high heat resistance, and is used for a polarizing plate, a retardation plate, etc. Useful for molecularly stabilized liquid crystal devices. These polymerizable compounds can be easily produced from the compound represented by formula (I).

In the general formula (I), R ¹ represents a polymerizable group, and specific examples of the polymerizable group include the structures shown below.

  These polymerizable groups are cured by radical polymerization, radical addition polymerization, cationic polymerization, and anionic polymerization. In particular, when performing ultraviolet polymerization as a polymerization method, the formula (R-1), formula (R-2), formula (R-4), formula (R-5), formula (R-7), formula (R -11), formula (R-13) or formula (R-15) are preferred, and formula (R-1), formula (R-2), formula (R-7), formula (R-11) or formula ( R-13) is more preferable, and formula (R-1) and formula (R-2) are more preferable.

S ¹ represents a spacer group or a single bond. As the spacer group, an alkylene group having 1 to 8 carbon atoms or a single bond is preferable, and the alkylene group is a group in which oxygen atoms are not directly bonded to each other. It may be replaced by -COO-, -OCO-, or -OCOO-. A single bond is preferable when excellent polymerizability is required, and an alkylene group having 2 to 6 carbon atoms is particularly preferable when a flexible molecular structure is required.

L ¹ is —O—, —COO—, a single bond or OC _b H _2b (b represents a natural number of 1 to 12, the carbon chain may be linear or branched, and oxygen atoms may be methylene group as no direct bond may be replaced by an oxygen atom.) represent, ^{L 2} is, -CH = CH-CO-, or _-C 2 represents a _H 4 CO-, excellent polymerizable preferably -CH = CH-COO- if required, _-C 2 _H 4 -COO- is preferred if requested excellent compatibility. Z ¹ represents OH, Cl or OC _a H _{2a + 1} (a represents a natural number of 1 to 12, and the carbon chain may be linear or branched), but OH, Cl, OC _a H _{2a + 1} (a represents a natural number from 1 to 8, and the carbon chain may be linear or branched), Ot—C ₄ H ₉ and Os—C ₃ H _7. OH, OC _a H _{2a + 1} (a represents a natural number of 1 to 6 and the carbon chain is linear), Ot—C ₄ H ₉ and Os—C ₃ H ₇ are further preferable.
M ¹ is unsubstituted or is a 1,4-phenylene group, pyridine-2,5- which may be substituted with an alkyl group, a halogenated alkyl group, an alkoxy group, a halogeno group, a cyano group, or a nitro group. Represents a diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, 1,4-cyclohexylene group, 4,4′-biphenyl group, M ³ , M ⁴ , M ⁶ and M ⁷ Are each independently unsubstituted or substituted with an alkyl group, a halogenated alkyl group, an alkoxy group, a halogeno group, a cyano group, or a nitro group, a 1,4-phenylene group, pyridine-2, Represents a 5-diyl group, a pyrimidine-2,5-diyl group, a naphthalene-2,6-diyl group, and a tetrahydronaphthalene-2,6-diyl group, wherein M ² and M ³ are unsubstituted or halo A 1,4-phenylene group and a naphthalene-2,6-diyl group which may be substituted with a geno group are preferred.

  m represents 0, 1 and 2, with 0 and 1 being preferred.

In the general formula (II), Z ² is OH, Cl or OC _c H _{2c + 1} (c represents a natural number of 1 to 12, the carbon chain may be linear or branched, Represents a methylene group that may be replaced by an oxygen atom as a group that is not directly bonded, but OH, Cl, OC _c H _{2c + 1} (c represents a natural number from 1 to 8, and the carbon chain is linear. Or may be branched, and the methylene group may be replaced by an oxygen atom as an oxygen atom is not directly bonded to each other.), Ot-C ₄ H ₉ and Os—C ₃ H ₇ Preferably, OH, OC _c H _{2c + 1} (c represents a natural number of 1 to 6, and the carbon chain is linear), Ot—C ₄ H ₉ and Os—C ₃ H ₇ are more preferable. . S ² represents a single bond or C _d H _2d (d represents a natural number of 1 to 6, the carbon chain may be linear or branched, and methylene as a group in which oxygen atoms are not directly bonded to each other. The group may be replaced by an oxygen atom.), L ³ is —O—, —COO—, a single bond or OC _e H _2e (e represents a natural number from 1 to 12, and the carbon chain is linear. Or a branched methylene group, and a methylene group may be replaced with an oxygen atom as a group in which oxygen atoms are not directly bonded to each other.), L ⁴ represents —CH═CH—CO— or —CH _It represents ₂ CH ₂ —CO—, and —CH═CH—CO— is preferred when excellent polymerizability is required, and —CH ₂ CH ₂ —CO— is preferred for improving compatibility. M ⁴ and M ⁵ are each independently 1,4-phenylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, and tetrahydronaphthalene-2. , 6-diyl group, M ¹ and M ² are each independently unsubstituted or substituted with an alkyl group, a halogenated alkyl group, an alkoxy group, a halogeno group, a cyano group, or a nitro group. However, a 1,4-phenylene group, a pyrimidine-2,5-diyl group, and a naphthalene-2,6-diyl group, which are independent of each other or may be substituted with a halogeno group, are preferable. More preferred are 1,4-phenylene group and naphthalene-2,6-diyl group which may be unsubstituted or substituted by a halogeno group, and n represents 0, 1 and 2, with 0 and 1 being preferred. That's right.

  Specifically, the polymerizable compound represented by the general formula (I) is preferably a compound represented by the following general formula (I-1) to general formula (I-23).

(In the formula, p represents an integer of 0 to 12, but even if p is 0, oxygen atoms are not directly bonded to each other, and in this case, one oxygen atom is removed.)
More specifically, the compound represented by the general formula (II) is preferably a compound represented by the following general formula (II-1) to general formula (II-27).

(In the formula, p represents an integer of 0 to 12.)
The compound of the present invention can be synthesized by the synthesis method described below.
(Production method 1) Production of compounds represented by general formulas (I-1) and (II-1)
The biphenyl derivative (I-1) having a hydroxyl group of the present invention can be obtained by the Mizorogi-Heck reaction of 4-bromo-4'-hydroxybiphenyl and tertiary butyl acrylate with a palladium catalyst. Furthermore, the polymerizable compound (II-1) of the present invention can be obtained by an esterification reaction with methacryloyl chloride.

(Production Method 2) Production of Compounds Represented by General Formulas (I-6) and (II-5) By the Mizorogi-Heck reaction of 2-bromo-6-hydroxynaphthalene and tertiary butyl acrylate with a palladium catalyst, The biphenyl derivative (II-5) having a hydroxyl group of the invention can be obtained. Furthermore, the polymerizable compound (I-6) of the present invention can be obtained by subjecting the obtained biphenyl derivative (II-5) and 6-chlorohexyl acrylate to an etherification reaction in the presence of a base such as potassium carbonate.

(Production Method 3) Production of Compound Represented by General Formula (II-7) A phenylnaphthalene derivative was obtained by reacting a grilinear reagent prepared from 6-methoxy-2-bromonaphthalene and bromoiodobenzene in the presence of a palladium catalyst. Thereafter, it can be hydrolyzed with an acid to obtain a naphthol derivative. By using the obtained compound in place of 2-bromo-6-hydroxynaphthalene in Production Method 2, a compound represented by the general formula (II-7) can be obtained.

(Production Method 4) Production of Compound Represented by General Formula (II-10) The compound represented by General Formula (II-7) obtained by Production Method 3 was removed from the tertiary butyl group with trifluoroacetic acid. Thus, a compound represented by the general formula (II-10) can be obtained.
(Production Method 5) Production of Compound Represented by General Formula (II-15) The compound represented by General Formula (II-1) is generally reduced by reacting with hydrogen gas in the presence of Pd / C. A compound represented by the formula (II-15) can be obtained.
(Manufacturing method 6) Manufacture of the compound represented by general formula (II-17) The compound represented by general formula (II-15) obtained by manufacturing method 5 was made to detach | desorb a tertiary butyl group with trifluoroacetic acid. Thus, a compound represented by the general formula (II-17) can be obtained.
(Manufacturing method 7) Manufacture of the compound represented by general formula (I-15) The compound represented by general formula (II-1) obtained by manufacturing method 1 is dehydrated and condensed with a benzoic acid derivative. The compound represented by -15) can be obtained.

  The aromatic compound having a hydroxyl group of the present invention and the polymerizable compound having these aromatic compounds as intermediates can greatly reduce the production cost by a production method from benzoic acid having a conventional polymerizable group. It is. Furthermore, since the polymerizable group is bonded in the final step, the by-product can be suppressed, and it becomes possible to produce with high purity. In addition, the hydroxybenzoic acid derivative of the present invention is very useful because a variety of polymerizable compounds can be easily produced because different substituents can be introduced into the aromatic ring.

  The compounds of the present invention are polymerizable compounds and intermediates that can be used in nematic liquid crystals, smectic liquid crystals, chiral nematics, chiral smectics, and cholesteric liquid crystal compositions. The polymerizable compound of the present invention preferably has an acryloyloxy group or a methacryloyloxy group as a polymerizable functional group. Moreover, when the liquid crystal composition of the polymerizable compound synthesized from the polymerizable compound or intermediate of the present invention is a cholesteric liquid crystal, addition of a chiral compound is preferable. Further, it may be added to a liquid crystal composition having no polymerizable group, and is a material useful particularly for polymer-stabilized liquid crystal devices.

  Specific examples of the polymerizable compound that can be synthesized from the intermediate or polymerizable compound of the present invention are shown in general formula (IV-1) to general formula (IV-10).

(In the formula, q and r represent integers of 0 to 12, but in the case of 0, one is removed if it represents an oxygen atom directly connected.)
The optically anisotropic body produced by polymerizing the polymerizable compound of the present invention with a liquid crystal composition containing a polymerization initiator and a stabilizer as required can be used for various applications. For example, when the polymerizable liquid crystal composition containing the present invention and the compound to be derived is polymerized in an unaligned state, it can be used as a light scattering plate, a depolarizing plate, or a moire fringe prevention plate. In addition, an optically anisotropic body produced by polymerizing the polymerizable liquid crystal composition in an aligned state has optical anisotropy in physical properties and is useful. Such an optical anisotropic body is, for example, a substrate in which the surface of the polymerizable liquid crystal composition is rubbed with a cloth, or a substrate surface on which an organic thin film is formed is rubbed with a cloth, or SiO ₂ is oblique It can be produced by polymerizing a liquid crystal composition after it is supported on a substrate having a deposited alignment film or sandwiched between substrates.

  The polymerizable liquid crystal composition may be added to a non-polymerizable liquid crystal element. Regarding liquid crystal devices, examples have been reported in which display characteristics are improved by adding a polymerizable compound to a liquid crystal medium, and the present compound can be used to control the alignment of liquid crystal molecules in a liquid crystal cell. Specific compositions include ordinary liquid crystal devices such as STN (super twisted nematic) liquid crystal, TN (twisted nematic) liquid crystal, TFT (thin film transistor) liquid crystal, etc. A liquid crystal composition etc. are mentioned.

  Moreover, it is a compound which has a polymerizable functional group, Comprising: The compound which does not show liquid crystallinity can also be added. Such a compound can be used without particular limitation as long as it is generally recognized as a polymer-forming monomer or polymer-forming oligomer in this technical field. It is necessary to adjust to exhibit sex.

EXAMPLES Hereinafter, although an Example is given and this invention is further explained in full detail, this invention is not limited to these Examples. Further, “%” in the compositions of the following examples and comparative examples means “mass%”.
Example 1
In a reaction vessel equipped with a stirrer, a condenser and a thermometer, 10 g (40.1 mmol) of 4-bromo-4′-hydroxybiphenyl, 6.2 g (48.2 mmol) of tertiary butyl acrylate, 4.8 g of triethylamine (48 mmol), 530 mg of palladium acetate, and 300 ml of dimethylformamide were charged, and the reaction was performed by heating the reactor to 100 ° C. in a nitrogen gas atmosphere. After completion of the reaction, ethyl acetate and THF were added, and the organic layer was washed with 10% aqueous hydrochloric acid solution, pure water and saturated brine. After the solvent was distilled off, purification was performed with a double amount (weight ratio) silica gel column to obtain 11 g of the compound represented by the formula (1).

  Next, a reaction vessel equipped with a stirrer, a cooler and a thermometer was charged with 3 g (10.1 mmol) of the compound represented by the above formula (1), 1 g (11 mmol) of acrylic acid chloride and 50 ml of methylene chloride, and nitrogen was added. The reactor was cooled to 5 ° C. or lower under a gas atmosphere. Next, 1.2 g (12 mmol) of triethylamine was slowly added dropwise. After completion of the dropping, the reaction was carried out at 20 ° C. or lower for 3 hours. After completion of the reaction, methylene chloride was added, and the organic layer was washed with a 10% hydrochloric acid aqueous solution, pure water and saturated brine. After distilling off the solvent, purification was performed with a double amount (weight ratio) silica gel column to obtain 3.6 g of a compound represented by the formula (2).

  Further, 3.6 g of the compound represented by the above formula (2) was dissolved in 10 ml of methylene chloride in a reaction vessel equipped with a stirrer, a cooler, and a thermometer, and then 10 ml of trifluoroacetic acid was added dropwise thereto at room temperature for 30 minutes. Stir. Thereafter, 200 ml of ethyl acetate was added, and the organic layer was washed with pure water and saturated brine. The solvent was distilled off to obtain 2.4 g of the objective compound represented by formula (3).

(Physical property value)
¹ H-NMR (solvent: deuterated dimethyl sulfoxide): δ: 6.16 (dd, 1H), 6.40-6.47 (m, 1H), 6.54-6.60 (m, 2H), 7 .28 (d, 2H), 7.62 (d, 1H), 7.71-7.80 (m, 6H), 12.42 (s, 1H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 119.1, 122.2, 126.9, 127.5, 127.7, 128.8, 130.9, 132.1, 142.1, 150 .6, 164.3, 167.8
Infrared absorption spectrum (IR) (KBr): 1760, 1652-1622, 809 cm ⁻¹
Melting point: 243 ° C
(Example 2)
To a reaction vessel equipped with a stirrer, a cooler, and a thermometer, 12.8 g (96 mmol) of aluminum (III) chloride and 100 ml of dichloromethane were added and stirred. Next, 8.4 g (110 mmol) of acetyl chloride was slowly added dropwise over 90 minutes, and further 80 ml of a dichloromethane solution of 20 g (80 mmol) of 4-bromo-2-fluorobiphenyl was slowly added dropwise over 2 hours. After completion of dropping, the mixture was further stirred for 2 hours. The reaction solution was slowly poured into 500 ml of ice water to terminate the reaction, followed by extraction with dichloromethane, and the organic layer was washed with pure water and saturated brine. After the solvent was distilled off, drying was performed to obtain 23 g of a compound having an acetyl group introduced. Next, 23 g of a compound having an acetyl group introduced therein and 300 ml of formic acid were charged into a reaction vessel equipped with a stirrer, a cooler, and a thermometer, and 20 ml of 34.5% hydrogen peroxide solution was added, followed by heating and refluxing for 6 hours. . After completion of the reaction, 450 ml of 10% aqueous sodium bisulfite solution was used to decompose the peroxide. The precipitated solid was filtered, dissolved with ethyl acetate, and the organic layer was washed with water and saturated brine. After the solvent was distilled off, purification was carried out with a double amount (weight ratio) silica gel column to obtain 18 g of a compound represented by the formula (4).

  In a reaction vessel equipped with a stirrer, a condenser and a thermometer, 10 g (37.4 mmol) of 4-bromo-3-fluorobiphenyl, 5.7 g (44.8 mmol) of tertiary butyl acrylate, 5.6 g of triethylamine ( 56 mmol), 410 mg of palladium acetate and 300 ml of dimethylformamide were charged, and the reactor was heated to 100 ° C. for reaction under a nitrogen gas atmosphere. After completion of the reaction, ethyl acetate and THF were added, and the organic layer was washed with 10% aqueous hydrochloric acid solution, pure water and saturated brine. After distilling off the solvent, purification was performed with a double amount (weight ratio) silica gel column to obtain 10.5 g of the desired compound represented by the formula (5).

  Next, in a reaction vessel equipped with a stirrer, a cooler and a thermometer, 10.5 g (33.4 mmol) of the compound represented by the above formula (5), 3.6 g (40 mmol) of acrylic acid chloride, 100 ml of methylene chloride. And the reactor was cooled to 5 ° C. or lower under a nitrogen gas atmosphere. Next, 4 g (40 mmol) of triethylamine was slowly added dropwise. After completion of the dropping, the reaction was carried out at 20 ° C. or lower for 3 hours. After completion of the reaction, methylene chloride was added, and the organic layer was washed with a 10% hydrochloric acid aqueous solution, pure water and saturated brine. After distilling off the solvent, purification was performed with a double amount (weight ratio) silica gel column to obtain 10.5 g of a compound having an acrylic group.

  Furthermore, 10.5 g of the compound having an acrylic group was dissolved in 20 ml of methylene chloride in a reaction vessel equipped with a stirrer, a cooler and a thermometer, and then 30 ml of trifluoroacetic acid was added dropwise and stirred at room temperature for 30 minutes. Thereafter, 200 ml of ethyl acetate was added, and the organic layer was washed with pure water and saturated brine. The solvent was distilled off to obtain 8.9 g of a compound represented by the formula (6).

(Physical property value)
¹ H-NMR (solvent: deuterated dimethyl sulfoxide): δ: 6.17 (dd, 1H), 6.41-6.45 (m, 1H), 6.55-6.69 (m, 2H), 7 .38 (d, 2H), 7.58-7.69 (m, 5H), 7.74 (d, 2H), 12.42 (s, 1H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 115.1, 115.4, 120.8, 122.0, 124.9, 127.5, 129.9, 130.9, 132.1, 133 .7, 142.1, 150.6, 164.3, 167.8
Infrared absorption spectrum (IR) (KBr): 1760, 1652-1622, 809 cm ⁻¹
Melting point: 218 ° C
(Example 3)
In a reaction vessel equipped with a stirrer, a condenser and a thermometer, 20 g (67.4 mmol) of the compound represented by the formula (1) described in Example 1, 10.5 g (81 mmol) of 2-hydroxyethyl methacrylate, triphenyl 26.5 g (100 mmol) of phosphine and 400 ml of dichloromethane were charged, the reaction vessel was cooled to 10 ° C. or lower under a nitrogen gas atmosphere, and 16.3 g (81 mmol) of diisopropyl azodicarboxylate was slowly added dropwise. After completion of dropping, the reaction vessel was returned to room temperature and reacted for 3 hours. After completion of the reaction, the organic layer was washed with pure water and saturated brine. After distilling off the solvent, purification was performed with a double amount (weight ratio) silica gel column to obtain 20 g of the desired compound represented by the formula (7).

(Physical property value)
¹ H-NMR (solvent: deuterated chloroform): δ: 1.54 (s, 9H), 1.95 (s, 2H) 4.25 (t, 2H), 4.53 (t, 2H), 5. 59 (dd, 1H), 6.15 (s, 1H), 6.37 (d, 1H), 6.98-7.02 (m, 2H), 7.52-759 (m, 6H) , 7.62-7.63 (m, 2H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 18.2, 28.1, 63.0, 66.0, 80.4, 115.0, 119.7, 126.0, 126.9, 128 1,128.4, 133.0, 133.1, 135.9, 142.1, 143.0, 158.5, 166.3, 167.3
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1760, 1652-1622, 809 cm ⁻¹
Melting point: 133 ° C
Example 4
An autoclave vessel equipped with a stirrer was charged with 3.6 g (12 mmol) of the intermediate synthesized in Example 1 shown in formula (1), 180 mg of 5% palladium carbon, 50 ml of tetrahydrofuran, and 5 ml of ethanol, and 0.3 MPa of hydrogen The reduction reaction was carried out at room temperature (8 hours). After the reaction solution was filtered, the solvent was distilled off to obtain 3.6 g of a hydrogenated compound.

  Next, 3.6 g (12 mmol) of the above hydrogenated compound and 3.5 g (12 mmol) of 4- (6-acryloyloxyhexyloxy) benzoic acid were added to a reaction vessel equipped with a stirrer, a condenser and a thermometer. Dimethylaminopyridine 150 mg and diisopropylcarbodiimide 1.8 g (14 mmol) were charged with 150 ml of methylene chloride and reacted for 6 hours in a nitrogen gas atmosphere. After completion of the reaction, 100 ml of methylene chloride was added, and the organic layer was washed with 10% hydrochloric acid aqueous solution, pure water, and saturated brine. After the solvent was distilled off, the residue was purified with a double amount (weight ratio) silica gel column to obtain 4.8 g of the desired compound represented by the formula (8). This compound exhibited a nematic liquid crystal phase at a temperature of 97 ° C to 100 ° C.

(Physical property value)
¹ H-NMR (solvent: deuterated chloroform): δ: 1.43 (s, 9H), 1.47-1.51 (m, 4H), 1.71-1.75 (m, 2H), 1. 83-1.85 (m, 2H), 2.56 (t, 2H), 2.93-2.97 (m, 2H), 4.05 (t, 2H), 4.17 (t, 2H) , 5.81 (dd, 1H), 6.09-6.16 (m, 1H), 6.38 (dd, 1H), 6.95 (d, 2H), 7.24-7.35 (m , 4H), 7.50 (d, 2H), 7.60 (d, 2H), 8.15 (d, 2H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 25.6, 25.7, 28.0, 28.5, 28.9, 30.7, 36.9, 64.4, 68.0, 80 4, 114.2, 121.5, 122.0, 127.0, 127.9, 128.5, 128.7, 130.5, 132.3, 138.3, 138.6, 139.9 , 150.3, 163.4, 164.9, 172.3
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1760, 1652-1622, 809 cm ⁻¹
Melting point: 97 ° C
(Example 5)
In a reaction vessel equipped with a stirrer, a cooler, and a thermometer, 10 g (40.1 mmol) of 4-bromo-4′-hydroxybiphenyl, 7.7 g (60 mmol) of n-butyl acrylate, and 6 g (60 mmol) of triethylamine. Then, 530 mg of palladium acetate and 300 ml of dimethylformamide were charged, and the reactor was heated to 100 ° C. for reaction under a nitrogen gas atmosphere. After completion of the reaction, ethyl acetate and THF were added, and the organic layer was washed with 10% aqueous hydrochloric acid solution, pure water and saturated brine. After distilling off the solvent, purification was performed with a double amount (weight ratio) silica gel column to obtain 9 g of a compound represented by the formula (9).

  In a reaction vessel equipped with a stirrer, a condenser and a thermometer, 9 g (30 mmol) of the compound represented by the above formula (9), 8.7 g (30 mmol) of 4- (6-acryloyloxyhexyloxy) benzoic acid, Dimethylaminopyridine (450 mg) and diisopropylcarbodiimide (4.5 g, 36 mmol) were charged with 150 ml of methylene chloride and reacted in a nitrogen gas atmosphere for 6 hours. After completion of the reaction, after completion of the reaction, 100 ml of methylene chloride was added, and the organic layer was washed with 10% aqueous hydrochloric acid, pure water, and saturated saline. After the solvent was distilled off, purification was carried out with a double amount (weight ratio) silica gel column to obtain 12 g of the desired compound represented by the formula (10). This compound exhibited a smectic liquid crystal phase at a wide temperature range from 90 ° C to 190 ° C.

(Physical property value)
¹ H-NMR (solvent: deuterated chloroform): δ: 0.95-0.99 (m, 3H), 1.44-1.48 (m, 6H), 1.63-1.73 (m, 4H) ), 1.83-1.90 (m, 2H), 4.05 (t, 2H), 4.17-4.24 (m, 4H), 5.81 (dd, 1H), 6.09- 6.16 (m, 1H), 6.38-6.50 (m, 2H), 6.96 (d, 2H), 7.26-7.31 (m, 2H), 7.61 (s, 4H), 7.62-7.68 (m, 2H), 7.70-7.74 (d, 1H), 8.14-8.18 (d, 2H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 13.7, 19.1, 25.6, 28.5, 28.9, 30.7, 64.4, 68.0, 114.2, 118 1, 121.4, 122.2, 127.4, 127.4, 128.0, 128.5, 130.5, 132.4, 137.7, 142.1, 143.9, 150.9 , 163.4, 164.8, 166.2, 167.0
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1760, 1652-1622, 809 cm ⁻¹
Melting point: 90 ° C
(Example 6)
In a reaction vessel equipped with a stirrer, a condenser, and a thermometer, 20 g (90 mmol) of 6-bromo-2-naphthol, 17.2 g (134 mmol) of tertiary butyl acrylate, 14 g (134 mmol) of triethylamine, 1 g of palladium acetate Then, 300 ml of dimethylformamide was charged, and the reactor was heated to 100 ° C. for reaction under a nitrogen gas atmosphere. After completion of the reaction, ethyl acetate and THF were added, and the organic layer was washed with 10% aqueous hydrochloric acid solution, pure water and saturated brine. After the solvent was distilled off, purification was performed with a double amount (weight ratio) silica gel column to obtain 13 g of a compound represented by the formula (11).

  In a reaction vessel equipped with a stirrer, a condenser and a thermometer, 7 g (26 mmol) of the compound represented by the above formula (11), 4.6 g (31 mmol) of 3-chloropropyl acrylate, 4.3 g of potassium carbonate (31 Mmol) and 100 ml of dimethylformamide were charged, and the reactor was heated to 90 ° C. in a nitrogen gas atmosphere and reacted for 6 hours. After completion of the reaction, after completion of the reaction, ethyl acetate was added, and the organic layer was washed with 10% hydrochloric acid aqueous solution, pure water and saturated brine. After distilling off the solvent, purification was performed with a double amount (weight ratio) silica gel column to obtain 8 g of a compound having an acrylic group.

  Furthermore, 10.5 g of the compound having an acrylic group was dissolved in 20 ml of methylene chloride in a reaction vessel equipped with a stirrer, a cooler and a thermometer, and then 20 ml of trifluoroacetic acid was added dropwise and stirred at room temperature for 30 minutes. Thereafter, 300 ml of ethyl acetate was added, and the organic layer was washed with pure water and saturated brine. Thereafter, the solvent was distilled off to obtain 6 g of the desired compound represented by the formula (12). This compound exhibited a nematic liquid crystal phase at a wide temperature range from 153 ° C. to 180 ° C.

(Physical property value)
H-NMR (solvent: deuterated chloroform): δ: 2.17-2.28 (m, 2H), 4.19 (t, 2H), 4.40-4.43 (m, 2H), 5.83 (Dd, 1H), 6.11-6.19 (m, 1H), 6.38-6.46 (m, 1H), 7.13-7.22 (m, 2H), 7.64-7 .81 (m, 3H), 7.89-7.94 (m, 2H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 28.5, 61.3, 63.2, 106.7, 115.9, 119.7, 124.2, 127.5, 128.3, 130 .3, 130.9, 131.0, 137.7, 147.9, 157.0, 163.4, 165.0
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1760, 1652-1622, 809 cm ⁻¹
Melting point: 153 ° C
(Reference Example) Synthesis Method of Polymerizable Compound 10 g (24.4 mmol) of the compound of formula (7) synthesized in Example 3 in a reaction vessel equipped with a stirrer, a cooler and a thermometer, 20 ml of trifluoroacetic acid, dichloromethane After adding 20 ml and stirring at room temperature for 1 hour, 100 ml of ethyl acetate and 150 ml of tetrahydrofuran were added, and the organic layer was washed with pure water and saturated brine. The solvent is distilled off to obtain 8 g of a pale yellow solid. Then, 8.5 g of the above compound, 4.6 g (24 mmol) of acrylic acid = 2- (4-hydroxyphenyl) ethyl, 300 mg of dimethylaminopyridine, methylene chloride in a reaction vessel equipped with a stirrer, a condenser and a thermometer. Charge 100 ml and keep the reaction vessel at 5 ° C or below with an ice-cooled bath. Under an atmosphere of nitrogen gas, 3.5 g (28 mmol) of diisopropylcarbodiimide was slowly added dropwise. After completion of dropping, the reaction vessel was returned to room temperature and reacted for 5 hours. After the reaction solution was filtered, 200 ml of methylene chloride was added to the filtrate, washed with a 10% aqueous hydrochloric acid solution, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After the solvent was distilled off, the residue was purified with a double amount (weight ratio) silica gel column, and 10.3 g of the desired compound represented by the formula (13) was obtained by recrystallization with methylene chloride / methanol. This compound exhibited a liquid crystal phase at a wide temperature from 123 ° C. to 180 ° C. or higher.

  By using the intermediate of Example 3, it was possible to synthesize from the starting material 4-bromo-4'-hydroxybiphenyl in 4 steps, and the total yield was 58%.

(Comparative example) Synthesis method of polymerizable compound To a reaction vessel equipped with a stirrer, a cooler, a Dean Stark, and a thermometer, 16 g (100 mmol) of p-hydroxycinnamic acid, 5 ml of sulfuric acid, and 100 ml of methanol were added and refluxed for 6 hours. 17 g of p-hydroxycinnamic acid methyl ester are obtained. Next, 17 g of p-hydroxycinnamic acid methyl ester synthesized above, 15 g (150 mmol) of triethylamine, and 150 ml of methylene chloride were charged into a reaction vessel equipped with a stirrer, a cooler, and a thermometer, and the temperature was kept at 5 ° C. or less in an ice-cooled bath. Keep the reaction vessel in place. Under an atmosphere of nitrogen gas, 30 g (106 mmol) of trifluoromethanesulfonic anhydride was slowly added dropwise. After completion of dropping, the reaction vessel was returned to room temperature and reacted for 5 hours. After the reaction solution was filtered, 200 ml of methylene chloride was added to the filtrate, washed with a 10% aqueous hydrochloric acid solution, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. The solvent was distilled off to obtain 28 g of a compound represented by the formula (14).

  A reaction vessel equipped with a stirrer and a thermometer was charged with 28 g (90 mmol) of the compound of formula (14), 3.6 g (90 mmol) of sodium hydroxide, 200 ml of methanol, and 20 ml of pure water, and reacted at room temperature for 4 hours. It was. After completion of the reaction, pure water was added to the reaction vessel to precipitate a solid. To the precipitate, 200 ml of dichloromethane and 100 ml of 10% hydrochloric acid were added, and the organic layer was further washed with pure water and saturated brine. The organic layer was distilled off to obtain 19 g of a compound represented by the formula (15).

  In a reaction vessel equipped with a stirrer, a condenser, a Dean Stark and a thermometer, 13.8 g (100 mmol) of p-hydroxyphenylethanol, 1.9 g of p-toluenesulfonic acid-hydrate, 14 g of 3-chloropropionic acid ( 130 mmol) and 150 ml of toluene are added and refluxed for 6 hours. After completion of the reaction, the mixture was washed with saturated sodium bicarbonate and pure water, and the solvent was distilled off to obtain 21 g of a compound represented by the formula (16).

  In a reaction vessel equipped with a stirrer, a condenser and a thermometer, 19 g (64 mmol) of the compound of the above formula (15), 3-chloropropionic acid = 2- (4-hydroxyphenyl) ethyl 17 .5 g (76 mmol), 1 g of dimethylaminopyridine, and 200 ml of methylene chloride were charged, and the reaction vessel was kept at 5 ° C. or lower with an ice-cooled bath. In an atmosphere of nitrogen gas, 9.5 g (76 mmol) of diisopropylcarbodiimide was slowly added dropwise. After completion of dropping, the reaction vessel was returned to room temperature and reacted for 5 hours. After the reaction solution was filtered, 200 ml of methylene chloride was added to the filtrate, washed with a 10% aqueous hydrochloric acid solution, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After the solvent was distilled off, purification was performed with a double amount (weight ratio) silica gel column to obtain 22.7 g of the desired compound represented by the formula (17).

  Then, 22.7 g (45 mmol) of the compound of the formula (17), 8 g (57 mmol) of p-hydroxyphenylboric acid, 10 g (70 mmol) of potassium carbonate, 23.5 g (90 mmol) of phenylphosphine, 500 mg of palladium acetate, 200 ml of tetrahydrofuran and 40 ml of pure water were charged and refluxed for 6 hours. After completion of the reaction, the reaction solution was filtered, 300 ml of ethyl acetate was added to the filtrate, washed with a 10% aqueous hydrochloric acid solution, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After the solvent was distilled off, purification was performed by recrystallization using a double amount (weight ratio) silica gel column to obtain 20.3 g of a compound represented by the formula (18).

In a reaction vessel equipped with a stirrer, a cooler, and a thermometer, 20.3 g (45 mmol) of the compound represented by the above formula (18), 8.7 g (54 mmol) of 3-chloropropyl acrylate, 9.3 g of potassium carbonate (67 mmol) and 150 ml of dimethylformamide were charged, and the reactor was heated to 90 ° C. in a gas atmosphere and reacted for 6 hours. After completion of the reaction, after completion of the reaction, ethyl acetate was added, and the organic layer was washed with 10% hydrochloric acid aqueous solution, pure water and saturated brine. After distilling off the solvent, purification was performed with a double amount (weight ratio) silica gel column to obtain 17 g of a compound represented by the formula (19) having a methacryl group.

  Further, 17 g (30 mmol) of the compound represented by the above formula (19), 6 g (60 mmol) of triethylamine and 100 ml of dichloromethane were added to a reaction vessel equipped with a stirrer, a cooler and a thermometer, and reacted at reflux for 5 hours. . After completion of the reaction, the solvent was distilled off and the residue was purified with a double amount (weight ratio) silica gel column to obtain 13.5 g of the desired compound represented by the formula (13).

In the synthesis method shown in Comparative Example 1, 8 steps were required to obtain the target polymerizable compound, and the yield (total yield 25%) was also poor.
(Example 7)
A polymerizable liquid crystal composition (Composition 1) having the following composition was prepared.

The polymerizable liquid crystal composition had good compatibility stability and exhibited a nematic liquid crystal phase. A photopolymerization initiator Irgacure 907 (manufactured by Ciba Specialty Chemicals) was added to this composition at 3% to prepare a polymerizable liquid crystal composition (Composition 2). The cyclohexanone solution of composition 2 was spin-coated onto a glass with polyimide, and irradiated with 4 mW / cm ² of ultraviolet rays for 120 seconds using a high-pressure mercury lamp, and then heated at 180 ° C. for 30 minutes. The obtained optical anisotropic body maintained a uniform alignment state. The surface hardness (according to JIS-SK-5400) of this optical anisotropic body was H. Assuming that the phase difference before heating of the obtained optical anisotropic body was 100%, the phase difference after heating at 240 ° C. for 1 hour was 89%, and the phase difference reduction rate was 11%. The compound having a tertiary butyl group of the present invention can generate a carboxylic acid by elimination of the tertiary butyl group by heating at a high temperature. As a result, it was possible to suppress a decrease in retardation due to hydrogen bonding by the generated carboxylic acid.
(Comparative Example 2)
A polymerizable liquid crystal composition (Composition 3) having the following composition was prepared.

The polymerizable liquid crystal composition had good compatibility stability and exhibited a nematic liquid crystal phase. A photopolymerization initiator Irgacure 907 (manufactured by Ciba Specialty Chemicals) was added to this composition at 3% to prepare a polymerizable liquid crystal composition (Composition 4). The cyclohexanone solution of this composition 4 was spin-coated on a glass with polyimide, irradiated with 4 mW / cm ² of ultraviolet rays for 120 seconds using a high-pressure mercury lamp, and then heated at 180 ° C. for 30 minutes. The obtained optical anisotropic body maintained a uniform alignment state. The surface hardness (according to JIS-S-K-5400) of this optical anisotropic body was B. Assuming that the phase difference before heating of the obtained optical anisotropic body was 100%, the phase difference after heating at 240 ° C. for 1 hour was 71%, and the phase difference reduction rate was 29%. Since there was no orientation regulating force due to hydrogen bonding, the phase difference was greatly reduced.

Claims (10)

Formula (I)

(However, R ¹ is the following formula (R-1) to formula (R-15)

And S ¹ represents an alkylene group having 1 to 12 carbon atoms in which the methylene group may be replaced by an oxygen atom, —COO—, —OCO—, or —OCOO—, assuming that oxygen atoms are not directly bonded to each other. Or Z ¹ is OH, Cl, OC _a H _{2a + 1} (a represents a natural number of 1 to 12, the carbon chain may be linear or branched, L ¹ represents —O—, —COO—, a single bond, or OC _b H _2b (b represents a natural number of 1 to 12). And the carbon chain may be linear or branched, and the methylene group may be replaced by an oxygen atom as an oxygen atom is not directly bonded to each other.), L ² represents —CH═ CH—CO— or —CH ₂ CH ₂ Represents -CO-, ^{M 1} is 1,4-phenylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, 1,4-cyclohexylene Group, or 4,4′-biphenyl group, and M ² and M ³ are each independently 1,4-phenylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene. -2,6-diyl group and tetrahydronaphthalene-2,6-diyl group, M ¹ , M ² and M ³ are each independently unsubstituted or an alkyl group, a halogenated alkyl group, an alkoxy group A group, a halogeno group, a cyano group, or a nitro group, and m represents 0, 1 and 2, but when m represents 2, a plurality of M ² may be the same or different. At best, however ^{M 3} is 1, - For a phenylene group, m represents 1 or 2. A polymerizable compound represented by Formula (II)

(Wherein Z ² is OH, Cl or OC _c H _{2c + 1} (c represents a natural number of 1 to 12, the carbon chain may be linear or branched, and oxygen atoms are directly bonded to each other) The methylene group may be replaced by an oxygen atom as a non-operating group), S ² is a single bond, or C _d H _2d (d represents a natural number of 1 to 12, and the carbon chain is linear. May be branched, or a carbon atom may be replaced by an oxygen atom assuming that oxygen atoms are not directly bonded to each other.), L ³ represents —O—, —COO—, a single bond, or OC _e H _2e (e represents a natural number of 1 to 12, the carbon chain may be linear or branched, and the methylene group may be replaced by an oxygen atom as a combination of oxygen atoms not directly bonded to each other. L ⁴ represents —CH═CH—C. Represents O— or —CH ₂ CH ₂ —CO—, and M ⁴ and M ⁵ each independently represent 1,4-phenylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, Represents a naphthalene-2,6-diyl group or a tetrahydronaphthalene-2,6-diyl group, and M ⁴ and M ⁵ are each independently unsubstituted or an alkyl group, a halogenated alkyl group, an alkoxy group, It may be substituted with a halogeno group, a cyano group, or a nitro group, and n represents 0, 1 and 2, but when n represents 2, a plurality of M ⁴ may be the same or different. However, when M ⁵ is a 1,4-phenylene group, n represents 1 or 2.) An aromatic compound having a hydroxyl group represented by In the general formula (I), M ¹ , M ² and M ³ are each independently unsubstituted or substituted with a halogeno group, a 1,4-phenylene group or naphthalene-2,6-diyl The polymerizable compound according to claim 1, which represents a group. In the general formula (II), M ⁴ and M ⁵ are each independently unsubstituted or optionally substituted with a halogeno group, a 1,4-phenylene group, a pyrimidine-2,5-diyl group, or a naphthalene The aromatic compound having a hydroxyl group according to claim 1, which represents a -2,6-diyl group. In the general formula (I), Z ¹ is OH, Cl, OC _a H _{2a + 1} (a represents a natural number of 1 to 6, and the carbon chain is linear), Ot-C ₄ H ₉ or The polymerizable compound according to claim 1, which represents Os—C ₃ H ₇ . In the general formula (II), Z ² is OH, Cl, OC _c H _{2c + 1} (c represents a natural number of 1 to 6, and the carbon chain is linear), Ot—C ₄ H ₉ or _O-s-C 3 aromatic compound having a hydroxyl group according to claim 2 or 4, wherein represents a _{H 7.} The polymerizable compound according to claim ¹ , wherein R ¹ in formula (I) represents formula (R-1) or formula (R-2). A liquid crystal composition containing the polymerizable compound according to claim 1, 3, 5 or 7. An optical anisotropic body composed of a polymer of a liquid crystal composition containing the polymerizable compound according to claim 8. A liquid crystal display element comprising the optical anisotropic body according to claim 9.