JP5098142B2 - Method for producing polymerizable compound - Google Patents

Description

  The present invention relates to a method for producing a novel polymerizable compound, and more specifically, a polymerizable compound that can be suitably used as a light control layer forming material for a light-scattering liquid crystal device that can be driven at a low voltage in a wide temperature range and has excellent electro-optical characteristics. It relates to the manufacturing method.

  With the development of the information society, the demand for information and communication materials is increasing. In particular, light-scattering liquid crystal devices do not require polarizing plates and have little viewing angle dependency, so advertising boards, decorative display boards, watches, computers, projections, digital paper, portable information terminals, optical shutters, It is highly expected as a liquid crystal display element or an optical element used for the above.

A liquid crystal device having a light control layer comprising a polymer matrix and a liquid crystal composition, which is obtained by irradiating or heating a light control layer forming material comprising a radical polymerizable composition and a liquid crystal composition as a light scattering liquid crystal device. It has been known.
The device does not depend on the type of liquid crystal compound used, and the change in drive voltage is small in a wide temperature range of about -20 ° C to 70 ° C, and the absolute value of the drive voltage is 20 V or less. Is required. In particular, when the liquid crystal driving method is TFT driving, it is indispensable to lower the voltage to 10 V or less and to remove impurities, and the development of a polymerizable compound that satisfies these characteristics is in progress, and the following general formula (E Side-chain type radically polymerizable compounds as schematically represented by) have been developed.

（式中、Mcは主鎖を表し、Sc¹は側鎖1を表し、Sc²は側鎖2を表すが、Sc¹＞Sc²であり、Mc及びScは主に炭素原子により構成される。）

(In the formula, Mc represents a main chain, Sc ¹ represents a side chain 1, Sc ² represents a side chain 2, Sc ¹ > Sc ² , and Mc and Sc are mainly composed of carbon atoms. .)

  For the production of the side chain radically polymerizable compound, conventionally, a production method by simultaneously mixing a polyhydric hydroxyl compound, a fatty acid, and acrylic acid and carrying out an esterification reaction has been disclosed (see Patent Document 1). . However, in the production method described in the cited document, a large amount of impurities having a structure similar to the target product is generated. For this reason, the properties required for the polymerizable liquid crystal composition cannot be obtained due to the influence of impurities mixed into the final product, and there is a problem that the quality of the liquid crystal device varies greatly. . In particular, in a light-scattering liquid crystal device for driving a TFT, it is necessary to minimize the mixing of impurities, and it is necessary to remove similar structures other than the target compound, polar impurities, and the like in the manufacturing process. However, it is difficult to efficiently extract only the target compound from the mixture obtained by the production method described in the cited document, and there is a problem that production efficiency is greatly reduced. This is performed by a method using an oxetane derivative (see Patent Document 2).

（式中、Ｒ^１は一般式（１）と同じ意味を表す。）しかしながら、当該方法を用いても目的物の純度は必ずしも十分ではなく、側鎖型ラジカル重合性化合物を効率的に製造する方法としてより効率的な方法の開発が求められていた。

(In the formula, R ¹ has the same meaning as in the general formula (1).) However, even if this method is used, the purity of the target product is not always sufficient, and a side chain type radical polymerizable compound is efficiently produced. The development of more efficient methods has been demanded.

JP 2004-352851 A JP 2005-225831 A

  The problem to be solved by the present invention is to provide an efficient method for producing a side chain type radically polymerizable compound, and also to provide a polymerizable compound useful as a component of a light scattering type liquid crystal device.

As a result of studying various polymerizable compounds, the present inventors have found that the above-mentioned problems can be solved by using a polymerizable compound having a specific structure as an intermediate, and have completed the present invention.
The present invention provides a general formula (1)

（式中、Ｒ^１は、炭素原子数１〜１５のアルキル基を表わす。）で表される化合物に、

(Wherein R ¹ represents an alkyl group having 1 to 15 carbon atoms),

（式中、Ｒ^２は炭素原子数１〜２０の直鎖又は分岐アルキル基を表し、基中に存在する１個又は２個以上の炭素原子は、酸素原子が相互に直接に結合しないものとして酸素原子により置き換えられていても良く、基中に存在する１個又は２個以上の炭素間の単結合は、二重結合又は三重結合により置き換えられていても良く、基中に存在する水素原子はハロゲンによって置換されていても良く、Ｙ^１はカルボニル基又は単結合を表し、Ｘ^１は水酸基、置換スルホニルオキシ基又はハロゲンを表すが、Ｙ^１がカルボニル基を表し、Ｘ^１が水酸基を表す場合、当該化合物の酸無水物であっても良い。）で表される化合物、一般式（３）

(In the formula, R ² represents a linear or branched alkyl group having 1 to 20 carbon atoms, and one or two or more carbon atoms present in the group are such that oxygen atoms are not directly bonded to each other. A single bond between one or more carbons which may be replaced by an oxygen atom and which is present in the group may be replaced by a double bond or a triple bond, and a hydrogen atom present in the group May be substituted by halogen, Y ¹ represents a carbonyl group or a single bond, X ¹ represents a hydroxyl group, a substituted sulfonyloxy group or a halogen, Y ¹ represents a carbonyl group, and X ¹ represents a hydroxyl group. In this case, it may be an acid anhydride of the compound.), A compound represented by the general formula (3)

（式中、Ｒ^３は水素原子又はメチル基を表し、Ｒ^４は炭素原子数１〜６の直鎖又は分岐アルキレン基又は単結合を表すが、基中に存在する１個又は２個以上の炭素原子は、酸素原子が相互に直接に結合しないものとして酸素原子により置き換えられていても良く、基中に存在する１個又は２個以上の炭素間の単結合は、二重結合又は三重結合により置き換えられていても良く、基中に存在する水素原子はハロゲンによって置換されていても良く、Ｙ^２は単結合又は酸素原子を表し、Ｙ^３はカルボニル基又は単結合を表し、を表し、Ｘ^２は水酸基、置換スルホニルオキシ基又はハロゲンを表すが、Ｙ^３がカルボニル基を表し、Ｘ^２が水酸基を表す場合、当該化合物の酸無水物であっても良い。）で表される化合物及び一般式（４）

(In the formula, R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a linear or branched alkylene group having 1 to 6 carbon atoms or a single bond, but one or two or more present in the group. Carbon atoms may be replaced by oxygen atoms as if the oxygen atoms are not directly bonded to each other, and single bonds between one or more carbons present in the group may be double bonds or triple bonds The hydrogen atom present in the group may be substituted by a halogen, Y ² represents a single bond or an oxygen atom, Y ³ represents a carbonyl group or a single bond, and X ² represents a hydroxyl group, a substituted sulfonyloxy group or a halogen, and when Y ³ represents a carbonyl group and X ² represents a hydroxyl group, the compound may be an acid anhydride of the compound. General formula (4)

（式中、Ｒ^５は直鎖であっても分岐していていても良い炭素原子数５〜２５のアルキレン基又はアルカントリイル基を表し、基中に存在する１個又は２個以上の炭素原子は、酸素原子が相互に直接に結合しないものとして酸素原子により置き換えられていても良く、基中に存在する１個又は２個以上の炭素間の単結合は、二重結合又は三重結合により置き換えられていても良く、ｎは２又は３を表し、Ｘ^３は水酸基、置換スルホニルオキシ基又はハロゲンを表す。）で表される化合物を反応させることによる一般式（５）

(In the formula, R ⁵ represents a linear or branched alkylene group having 5 to 25 carbon atoms or alkanetriyl group, and one or more carbon atoms present in the group. An atom may be replaced by an oxygen atom as if the oxygen atoms are not directly bonded to each other, and a single bond between one or more carbons present in the group may be a double bond or a triple bond. May be substituted, n represents 2 or 3, and X ³ represents a hydroxyl group, a substituted sulfonyloxy group or a halogen).

（式中、Ｒ^１は、炭素原子数１〜１５のアルキル基を表し、Ｒ^２は炭素原子数１〜２０の直鎖又は分岐アルキル基を表し、基中に存在する１個又は２個以上の炭素原子は、酸素原子が相互に直接に結合しないものとして酸素原子により置き換えられていても良く、基中に存在する１個又は２個以上の炭素間の単結合は、二重結合又は三重結合により置き換えられていても良く、基中に存在する水素原子はハロゲンによって置換されていても良く、Ｒ^３は水素原子又はメチル基を表し、Ｒ^４は炭素原子数１〜６の直鎖又は分岐アルキレン基又は単結合を表すが、基中に存在する１個又は２個以上の炭素原子は、酸素原子が相互に直接に結合しないものとして酸素原子により置き換えられていても良く、基中に存在する１個又は２個以上の炭素間の単結合は、二重結合又は三重結合により置き換えられていても良く、基中に存在する水素原子はハロゲンによって置換されていても良く、Ｒ^５は直鎖であっても分岐していていても良い炭素原子数５〜２５のアルキレン基又はアルカントリイル基を表し、基中に存在する１個又は２個以上の炭素原子は、酸素原子が相互に直接に結合しないものとして酸素原子により置き換えられていても良く、基中に存在する１個又は２個以上の炭素間の単結合は、二重結合又は三重結合により置き換えられていても良く、
ｎは２又は３を表し、
Ｙ^１及びＹ^３はそれぞれ独立してカルボニル基又は単結合を表し、Ｙ^２は単結合又は酸素原子を表す。）で表される重合性化合物の製造方法及び当該一般式（５）で表される重合性化合物を提供する。

(In the formula, R ¹ represents an alkyl group having 1 to 15 carbon atoms, R ² represents a linear or branched alkyl group having 1 to 20 carbon atoms, and one or two or more existing in the group) Carbon atoms may be replaced by oxygen atoms so that the oxygen atoms are not directly bonded to each other, and a single bond between one or more carbons present in the group may be a double bond or a triple bond. May be replaced by a bond, a hydrogen atom present in the group may be replaced by a halogen, R ³ represents a hydrogen atom or a methyl group, and R ⁴ is a straight chain having 1 to 6 carbon atoms or Represents a branched alkylene group or a single bond, wherein one or more carbon atoms present in the group may be replaced by oxygen atoms as those in which the oxygen atoms are not directly bonded to each other; One or more carbons present The single bond between them may be replaced by a double bond or a triple bond, a hydrogen atom present in the group may be replaced by a halogen, and R ⁵ may be linear or branched. Represents an alkylene group having 5 to 25 carbon atoms or an alkanetriyl group, and one or two or more carbon atoms present in the group are represented by oxygen atoms as oxygen atoms are not directly bonded to each other. A single bond between one or more carbons present in the group may be replaced by a double or triple bond;
n represents 2 or 3,
Y ¹ and Y ³ each independently represent a carbonyl group or a single bond, and Y ² represents a single bond or an oxygen atom. And a polymerizable compound represented by the general formula (5).

  By producing a polymerizable compound at a low cost by the production method of the present invention, a light scattering liquid crystal device having a light control layer comprising a polymer matrix and a liquid crystal composition, which can be driven at a low voltage even in a wide temperature range, is inexpensive. Obtainable.

  The production method of the present invention is characterized in that the compound represented by the general formula (1) is reacted with the compound represented by the general formula (2), the general formula (3) and the general formula (3). It is. The order of reaction of the compounds represented by the general formula (2), the general formula (3), and the general formula (3) can be started from any compound. However, from the viewpoint of ease of purification of the intermediate, the compound represented by the general formula (1) is generally reacted with the halogen compound represented by the general formula (2), a carboxylic acid or a derivative thereof. Formula (6)

（式中、Ｒ^１は一般式（１）と同じ意味を表し、Ｒ^２及びＹ^１は一般式（２）と同じ意味を表す。）で表される化合物とした後、一般式（３）で表される化合物を反応させることにより、一般式（７）

(Wherein R ¹ represents the same meaning as in general formula (1), and R ² and Y ¹ represent the same meaning as in general formula (2)), and then the general formula (3) By reacting the compound represented by general formula (7)

（式中、Ｒ^１は一般式（１）と同じ意味を表し、Ｒ^２及びＹ^１は一般式（２）と同じ意味を表し、Ｒ^３、Ｒ^４、Ｙ^２及びＹ^３は一般式（３）と同じ意味を表す。）で表される化合物とした後、一般式（４）で表される化合物を反応させることが好ましい。

(In the formula, R ¹ represents the same meaning as in general formula (1), R ² and Y ¹ represent the same meaning as in general formula (2), and R ³ , R ⁴ , Y ² and Y ³ represent the general formula ( It is preferable to react the compound represented by the general formula (4) after the compound represented by the same meaning as 3).

The reaction for producing the compound represented by the general formula (6) from the diol derivative represented by the general formula (1) and the compound represented by the general formula (2) is performed in the presence of a basic compound such as triethylamine or pyridine. It is preferable. A solvent having high solubility with the raw material alcohol is selected as the reaction solvent. It is not preferable to carry out the reaction in a state in which the raw material alcohol is dispersed using a solvent having low solubility because a large amount of dialkyl and trialkyl forms are generated. The reaction temperature is preferably about room temperature, and it is preferable to suppress the dropping rate of the compound represented by the general formula (2).
Dialkyl and trialkyl compounds by-produced in the reaction are polar solvents such as hexane, heptane and other hydrocarbon solvents, dimethyl sulfoxide (hereinafter abbreviated as DMSO), N, N-dimethylformamide (hereinafter abbreviated as DMF), methanol, and the like. Since it moves to the hydrocarbon solvent side by two-liquid separation with a solvent, the target product can be easily removed (transfer to a polar solvent). Thereafter, the target product is extracted from the polar solvent. Furthermore, the hydroxycarboxylic acid derivative represented by the general formula (6) with high purity can be obtained by recrystallization or distillation.
In particular, a combination of hexane or heptane and methanol or a methanol / water mixed solvent is preferable because it not only has a high resolution, but also facilitates removal of the solvent after the separation.

The compound represented by the general formula (6) is sequentially reacted with the compound represented by the general formula (3) and the compound represented by the general formula (4). In consideration of the efficiency of the reaction, the general formula (3) It is preferable to react the compound represented by General Formula (4) after reacting the compound represented by General Formula (7).
The compound represented by the general formula (7) is produced by esterifying the compound represented by the general formula (6) and the general formula (3) with an acid catalyst or 1,3-dicyclohexylcarbodiimide (DCC), N-ethyl. Although it can be performed by esterification with a dehydrating condensing agent such as —N ′-(3-dimethylaminopropyl) carbodiimide (WSC), it is preferable to use a dehydrating condensing agent in terms of reaction yield.
An acrylic acid chloride (when X ² represents halogen in the general formula (3)) can be reacted in the presence of an amine catalyst instead of the acrylic acid derivative, but the acrylic acid derivative is more often used. It is preferable because the production of diacrylic body can be suppressed.
The reaction product thus synthesized can be easily purified by the same polar-nonpolar two-liquid separation as described above, or a silica gel column.

The compound represented by general formula (7) is reacted with the compound represented by general formula (4) for esterification to produce final formula (5). The esterification may be performed by esterification with an acid catalyst or esterification with a dehydration condensing agent such as 1,3-dicyclohexylcarbodiimide (DCC) or N-ethyl-N ′-(3-dimethylaminopropyl) carbodiimide (WSC). However, it is preferable to use a dehydrating condensing agent in terms of reaction yield.
It is also possible to carry out esterification after converting the compound represented by the general formula (7) into acid chloride.
Furthermore, by two-liquid separation using a hydrocarbon solvent such as hexane and heptane and a polar solvent such as DMSO, DMF, and methanol, the target product is transferred to the hydrocarbon solvent side, and raw materials, carbodiimide, and by-product urea compounds are easily obtained. Can be removed. In particular, a combination of hexane or heptane and methanol or a methanol / water mixed solvent is preferable because it not only has a high resolution, but also facilitates removal of the solvent after the separation.

In the general formula (1), R ¹ is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably a linear alkyl group having 1 to 4 carbon atoms.
In the general formula (2), R ² is preferably a linear or branched alkyl group having 5 to 20 carbon atoms, more preferably a linear alkyl group having 5 to 14 carbon atoms, or a branched alkyl group having 8 to 18 carbon atoms. preferable. Specifically, n-hexyl group, 2-ethylhexyl group, n-octyl group, n-undecyl group, n-tridecyl group, n-tetradecyl group, n-octadecyl group, 2-n-heptylnonyl group, isomyristyl group 2-ethylhexyl group, butoxyethyl group, hexyloxyethyl group, n-butoxyethoxymethyl group, cyclohexyl group, polyethylene glycol monoether group, 4-octylcyclohexyl group and the like.
In General Formula (2), Y ¹ represents a carbonyl group or a single bond, X ¹ represents a hydroxyl group, a substituted sulfonyloxy group, or a halogen, Y ¹ is a carbonyl group, and X ¹ is a halogen, or A production method using a compound in which Y ¹ is a single bond and X ¹ is halogen is preferable from the viewpoint of cost reduction.

In the general formula (3), R ³ represents hydrogen or a methyl group, and hydrogen is more preferable because of high reactivity. In the general formula (3), R ⁴ preferably has 0 to 2 carbon atoms, Y ² is an oxygen atom, Y ³ is a single bond or a carbonyl group, and X ³ is preferably a hydroxyl group. Specific compounds include acrylic acid, acrylic acid dimer, or hydroxyethyl acrylate.
In the general formula (4), R ⁵ is preferably an alkylene group having ^{5 to} 26 carbon atoms or an alkanetriyl group, more preferably an alkylene group having 5 to 22 carbon atoms, and X ³ is preferably a hydroxyl group or halogen. Specific compounds include 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol. Linear diols such as 1,12-dodecane diol, branched diols such as dimethylol heptane, neopentyl glycol, etc., and preferably linear and branched compounds having 6 to 10 carbon atoms. preferable.

The composition of the polymerizable compound represented by the general formula (5) and the liquid crystal composition thus obtained is particularly useful as a light control layer forming material for a light scattering liquid crystal device.
The light-scattering liquid crystal device has, for example, a transparent electrode layer and at least one of the transparent liquid crystal devices is transparent. Between the two substrates that are spaced apart by using a spacer or the like with the transparent electrode layer facing each other, It can be obtained by sandwiching a composition of a polymerizable compound, light or thermal polymerization initiator and a liquid crystal composition and irradiating with light or heating.

The liquid crystal composition is a composition that exhibits a phase that is generally recognized as a liquid crystal phase in this technical field. Among them, a liquid crystal phase that exhibits a nematic liquid crystal, a smectic liquid crystal, a cholesteric liquid crystal, a chiral nematic liquid crystal, or a chiral smectic liquid crystal. Is preferred. Specifically, it is a composition composed of the following compound group, and the characteristics of the liquid crystal material, that is, the phase transition temperature, melting point, viscosity, birefringence, dielectric anisotropy of isotropic liquid and liquid crystal In consideration of the positive / negative of the property (Δε), or for the purpose of adjusting the solubility with the polymerizable composition or the like, it can be appropriately selected, blended and used.
Liquid crystal materials include benzoic acid ester, cyclohexanecarboxylic acid ester, biphenyl, terphenyl, phenylcyclohexane, pyrimidine, pyridine, dioxane, cyclohexylcyclohexane ester, tolan, alkenyl, and fluorobenzene. , Cyano, naphthalene, etc., general formula (8)

（式中、Ａ、Ｂ及びＣは、それぞれ独立に、下記の環のいずれかを表し、

(In the formula, A, B and C each independently represent any of the following rings:

p represents an integer of 0 to 2, n ′ represents an integer of 1 to 4, and Y _a and Y _b each independently represent a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —OCF 2 —, —CF 2 O—, —CO—O—, —OCO—, —C≡C—, —CH═CH—, —CF═CF—, — (CH ₂ ) ₄ —, — (CH ₂ ) ₃ O— or —CH ₂ ═CHCH ₂ CH ₂ , Y _c represents a single bond, —CO—O—, or —OCO—, and R _a and R _b each independently represent a hydrogen atom or a halogen atom. , A cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an alkenyl group, an alkenyloxy group, a fluoroalkyl group, or a fluoroalkoxy group. ) Can be used alone or in a composition in which a plurality of liquid crystal compounds are blended.

Examples of the present invention will be shown below, and the present invention will be described more specifically. However, the present invention is not limited to these examples. In the following examples, “%” represents “% by mass” unless otherwise specified.
(Example 1 Production of polymerizable compound (M-1))
(Example 1-1)
A reaction vessel equipped with a stirrer and a thermometer was charged with 100 g (0.67 mol) of 2,2-bis (hydroxymethyl) -n-butyric acid, 54 g (0.53 mol) of triethylamine, and 800 ml of THF. The reaction vessel was kept at 5 ° C. or lower, and 135 g (0.44 mol) of n-stearoyl chloride was slowly dropped with a dropping funnel. After completion of dropping, the mixture was stirred at room temperature for 3 hours and then stirred at 40 ° C. for 1 hour to complete the reaction. The reaction solution was washed with 800 ml of ethyl acetate, 200 ml of n-hexane, and 1 L of a 10% aqueous hydrochloric acid solution, followed by washing with water and saturated brine. The organic layer was concentrated, dissolved in 1.2 L of n-hexane, and extracted with 1.2 L of methanol. Methanol is distilled off from the methanol / water layer, and 1 L of ethyl acetate, 200 ml of n-hexane and 1 L of pure water are added and washed. The organic layer was dried over anhydrous sodium sulfate and the solvent was distilled off to obtain 135 g of a crude product. Recrystallization was performed twice with 400 ml of an n-hexane / ethanol mixed solution 4/1 (volume ratio) to obtain 120 g of a compound represented by the formula (10).

（物性値）
¹Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：１２．３（ｓ，１Ｈ），４．３２（ｓ，２Ｈ），３．６２（ｍ，２Ｈ），２．８０（ｍ，１Ｈ），２．４２（ｔ，２H），１．６９（ｍ，２Ｈ），１．４４−１．２６（ｍ，３０Ｈ），０．９２−０．８０（ｍ，６Ｈ）
^１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：１７３．５，６５．９，６４．１，４２．９，３４．３，３１．８，２９．９−２９．０，２５．１，２２．６，２２．５，１４．０，７．３
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：２９００−３５００ｃｍ^−１

(Physical property value)
¹ H-NMR (solvent: deuterated chloroform): δ: 12.3 (s, 1H), 4.32 (s, 2H), 3.62 (m, 2H), 2.80 (m, 1H), 2 .42 (t, 2H), 1.69 (m, 2H), 1.44-1.26 (m, 30H), 0.92-0.80 (m, 6H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 173.5, 65.9, 64.1, 42.9, 34.3, 31.8, 29.9-29.0, 25.1, 22 .6, 22.5, 14.0, 7.3
Infrared absorption spectrum (IR) (KBr): 2900-3500 cm ⁻¹

(Example 1-2)
Next, 120 g (0.29 mol) of the compound represented by the formula (10) synthesized above, 35 g (0.35 mol) of triethylamine, and 800 ml of THF were charged into a reaction vessel equipped with a stirrer and a thermometer. . The reaction vessel was kept at 5 ° C. or lower, and 26.3 g (0.29 mol) of acrylic acid chloride was slowly dropped with a dropping funnel. After completion of dropping, the mixture was stirred at room temperature for 3 hours and then stirred at 40 ° C. for 1 hour to complete the reaction. The reaction solution was washed with 800 ml of ethyl acetate, 200 ml of n-hexane, and 1 L of a 10% aqueous hydrochloric acid solution, followed by washing with water and saturated brine. The organic layer was purified by a 5-fold amount (weight ratio) silica gel column after distilling off the dry solvent with anhydrous sodium sulfate to obtain 108 g of a compound represented by the formula (11).

（物性値）
^１Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：１２．３（ｓ，１Ｈ），６．５５（ｄ，１Ｈ），６．２１（ｑ，１Ｈ），５．９４（ｄ，１Ｈ），４．２２（ｓ，２Ｈ），４．１５（ｓ，２Ｈ），２．８０（ｓ，１Ｈ），２．４２（ｔ，２H），１．６９（ｍ，２Ｈ），１．４４−１．２６（ｍ，３０Ｈ），０．９２−０．８０（ｍ，６Ｈ）
^１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：１７４．１，１７３．５，１６６．３，１３１．１，１２８．２，１２７．９，６３．９，６３．７，６２．２，４２．６，３４．２，３１．７，３１．５，２９．９−２９．０，２４．９，２２．６，１４．０，７．３
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：２９００−３５００ｃｍ^−１

(Physical property value)
¹ H-NMR (solvent: deuterated chloroform): δ: 12.3 (s, 1H), 6.55 (d, 1H), 6.21 (q, 1H), 5.94 (d, 1H), 4 .22 (s, 2H), 4.15 (s, 2H), 2.80 (s, 1H), 2.42 (t, 2H), 1.69 (m, 2H), 1.44-1. 26 (m, 30H), 0.92-0.80 (m, 6H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 174.1, 173.5, 166.3, 131.1, 128.2, 127.9, 63.9, 63.7, 62.2, 42 6, 34.2, 31.7, 31.5, 29.9-29.0, 24.9, 22.6, 14.0, 7.3
Infrared absorption spectrum (IR) (KBr): 2900-3500 cm ⁻¹

(Example 1-3)
Furthermore, 108 g (0.23 mol) of the compound represented by the formula (11) synthesized above in a reaction vessel equipped with a stirrer and a thermometer, 20 g (0.115 mol) of 1,10-decanediol, 2 g of dinopyridine and 1 L of methylene chloride were charged. Under a nitrogen gas atmosphere, the reaction vessel was cooled to 0 to 5 ° C., and 34.7 g (0.27 mol) of diisopropylcarbodiimide was slowly added dropwise. After completion of dropping, the reaction was allowed to proceed at room temperature for 4 hours. The reaction solution was washed with 200 ml of methylene chloride and 700 ml of a 10% aqueous hydrochloric acid solution, further washed with saturated saline, and the solvent of the organic layer was distilled off. Then, 1 L of n-hexane was added, and 4/1 (volume by volume of methanol / water). Ratio) Washed twice with 600 ml of the mixed solution. Further, the organic layer was washed with pure water and saturated brine, the organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and further purified with a 5-fold amount (weight ratio) silica gel column to obtain the target compound (M-1 ) Was obtained.

（物性値）
^１Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：６．４３（ｄ，２Ｈ），６．１１（ｑ，２Ｈ），５．８４（ｄ，２Ｈ），４．１２（ｓ，４Ｈ），４．０５（ｓ，８Ｈ），２．３４（ｔ，４Ｈ），１．６４（ｍ，８Ｈ），１．５９（ｍ，４Ｈ），１．３８−１．２５（ｍ，６８Ｈ），０．９１−８０（ｍ，１８Ｈ）
^１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：１７３．４，１６５．７，１３１．０，１２７．９，６４．１，６３．６，４０．６，３４．２，３１．８，２９．８−２９．０，２６．８，２４．９，２３．０，２２．６，１４．０，１０．７，７．３
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：２９２５，２８５５，１７３３，１６５２−１６２２，１１９０，８０８．９
当該化合物は、重合性液晶組成物の構成部材として好適に使用できる。
（比較例）
これに対して、主鎖に連結する置換基としてカルボニル基を有さない化合物である式（Ｒ−１）

(Physical property value)
¹ H-NMR (solvent: deuterated chloroform): δ: 6.43 (d, 2H), 6.11 (q, 2H), 5.84 (d, 2H), 4.12 (s, 4H), 4 .05 (s, 8H), 2.34 (t, 4H), 1.64 (m, 8H), 1.59 (m, 4H), 1.38-1.25 (m, 68H),. 91-80 (m, 18H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 173.4, 165.7, 131.0, 127.9, 64.1, 63.6, 40.6, 34.2, 31.8, 29 .8-29.0, 26.8, 24.9, 23.0, 22.6, 14.0, 10.7, 7.3
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1733, 1652-1622, 1190, 808.9
The said compound can be conveniently used as a structural member of a polymeric liquid crystal composition.
(Comparative example)
On the other hand, a compound having no carbonyl group as a substituent linked to the main chain (R-1)

は、高分子分散型表示素子として構成した場合の閾値電圧、閾値電圧の温度特性、応答速度等は優れているが、主鎖との連結がエーテル化によるものであるため、エステル化により極めて簡便に製造可能な本願発明の化合物に製造効率の点では劣っていた。
（実施例２ 重合性化合物（Ｍ−２）の製造）
（実施例２−１）
１，１−ジヒドロキシメチルプロピオン酸（２．５モル）及びウンデシルクロリド（１モル）を用い、実施例１−１と同様にして式（１２）で表される化合物を得た。

Is superior in threshold voltage, temperature characteristics of threshold voltage, response speed, etc. when configured as a polymer dispersion type display device, but it is very easy to make by esterification because the connection with the main chain is due to etherification. It was inferior in terms of production efficiency to the compound of the present invention that can be produced easily.
(Example 2 Production of polymerizable compound (M-2))
(Example 2-1)
A compound represented by the formula (12) was obtained in the same manner as in Example 1-1 using 1,1-dihydroxymethylpropionic acid (2.5 mol) and undecyl chloride (1 mol).

（物性値）
¹Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：１２．３（ｓ，１Ｈ），４．３２（ｓ，２Ｈ），３．６２（ｍ，２Ｈ），２．８０（ｍ，１Ｈ），２．４２（ｔ，２H），１．６９（ｍ，２Ｈ），１．４４−１．２６（ｍ，１６Ｈ），０．９２−０．８０（ｍ，６Ｈ）
^１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：１７３．５，６５．９，６４．１，４２．９，３４．３，３１．８，２９．９−２９．０，２５．１，２２．６，２２．５，１４．０，７．３
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：２９００−３５００ｃｍ^−１
（実施例２−２）
式（１２）で表される化合物（１モル）とアクリル酸クロリド（１．２モル）を用い、実施例１−２と同様にして式（１３）で表される化合物を得た。

(Physical property value)
¹ H-NMR (solvent: deuterated chloroform): δ: 12.3 (s, 1H), 4.32 (s, 2H), 3.62 (m, 2H), 2.80 (m, 1H), 2 .42 (t, 2H), 1.69 (m, 2H), 1.44-1.26 (m, 16H), 0.92-0.80 (m, 6H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 173.5, 65.9, 64.1, 42.9, 34.3, 31.8, 29.9-29.0, 25.1, 22 .6, 22.5, 14.0, 7.3
Infrared absorption spectrum (IR) (KBr): 2900-3500 cm ⁻¹
(Example 2-2)
A compound represented by the formula (13) was obtained in the same manner as in Example 1-2 using the compound represented by the formula (12) (1 mol) and acrylic acid chloride (1.2 mol).

（物性値）
^１Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：１２．３（ｓ，１Ｈ），６．５５（ｄ，１Ｈ），６．２１（ｑ，１Ｈ），５．９４（ｄ，１Ｈ），４．２２（ｓ，２Ｈ），４．１５（ｓ，２Ｈ），２．８０（ｓ，１Ｈ），２．４２（ｔ，２H），１．６９（ｍ，２Ｈ），１．４４−１．２６（ｍ，１６Ｈ），０．９２−０．８０（ｍ，６Ｈ）
^１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：１７４．１，１７３．５，１６６．３，１３１．１，１２８．２，１２７．９，６３．９，６３．７，６２．２，４２．６，３４．２，３１．７，３１．５，２９．９−２９．０，２４．９，２２．６，１４．０，７．３
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：２９００−３５００ｃｍ^−１
（実施例２−２）
式（１３）で表される化合物及び１，１０−デカンジオールを用い、実施例１−３と同様にして式（Ｍ−２）で表される重合性化合物を得た。

(Physical property value)
¹ H-NMR (solvent: deuterated chloroform): δ: 12.3 (s, 1H), 6.55 (d, 1H), 6.21 (q, 1H), 5.94 (d, 1H), 4 .22 (s, 2H), 4.15 (s, 2H), 2.80 (s, 1H), 2.42 (t, 2H), 1.69 (m, 2H), 1.44-1. 26 (m, 16H), 0.92-0.80 (m, 6H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 174.1, 173.5, 166.3, 131.1, 128.2, 127.9, 63.9, 63.7, 62.2, 42 6, 34.2, 31.7, 31.5, 29.9-29.0, 24.9, 22.6, 14.0, 7.3
Infrared absorption spectrum (IR) (KBr): 2900-3500 cm ⁻¹
(Example 2-2)
A polymerizable compound represented by the formula (M-2) was obtained in the same manner as in Example 1-3 using the compound represented by the formula (13) and 1,10-decanediol.

（物性値）
^１Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：６．４３（ｄ，２Ｈ），６．１１（ｑ，２Ｈ），５．８４（ｄ，２Ｈ），４．１２（ｓ，４Ｈ），４．０５（ｓ，８Ｈ），２．３４（ｔ，４Ｈ），１．６４（ｍ，８Ｈ），１．５９（ｍ，４Ｈ），１．３８−１．２５（ｍ，４０Ｈ），０．９１−８０（ｍ，１８Ｈ）
^１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：１７３．４，１６５．７，１３１．０，１２７．９，６４．１，６３．６，４０．６，３４．２，３１．８，２９．８−２９．０，２６．８，２４．９，２３．０，２２．６，１４．０，１０．７，７．３
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：２９２５，２８５５，１７３３，１６５２−１６２２，１１９０，８０８．９
（実施例３ 重合性化合物（Ｍ−３）の製造）
（実施例３−１）
１，１−ジヒドロキシメチルプロピオン酸（１モル）と１−ブロモデカン（１．５モル）を用い、実施例１−１と同様にして式（１４）で表される化合物を得た。

(Physical property value)
¹ H-NMR (solvent: deuterated chloroform): δ: 6.43 (d, 2H), 6.11 (q, 2H), 5.84 (d, 2H), 4.12 (s, 4H), 4 .05 (s, 8H), 2.34 (t, 4H), 1.64 (m, 8H), 1.59 (m, 4H), 1.38-1.25 (m, 40H), 0. 91-80 (m, 18H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 173.4, 165.7, 131.0, 127.9, 64.1, 63.6, 40.6, 34.2, 31.8, 29 .8-29.0, 26.8, 24.9, 23.0, 22.6, 14.0, 10.7, 7.3
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1733, 1652-1622, 1190, 808.9
(Example 3 Production of polymerizable compound (M-3))
(Example 3-1)
A compound represented by the formula (14) was obtained in the same manner as in Example 1-1, using 1,1-dihydroxymethylpropionic acid (1 mol) and 1-bromodecane (1.5 mol).

物性値）
¹Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：１２．３（ｓ，１Ｈ），３．８０（ｓ，２Ｈ），３．４２（ｓ，２Ｈ），３．４０（s，２Ｈ），２．８０（ｍ，１Ｈ），１．６０（ｍ，２Ｈ），１．４４−１．２６（ｍ，８Ｈ），０．９２−０．８０（ｍ，６Ｈ）
^１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：１７３．５，６７．５，６５．９，６４．１，３１．５，２９．９−２９．０，２５．１，２２．５，１４．０，７．３
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：２９００−３５００ｃｍ^−１
（実施例３−２）
式（１４）で表される化合物（１モル）とアクリル酸クロリド（１．２モル）を用い、実施例１−２と同様にして式（１５）で表される化合物を得た。

Physical property value)
¹ H-NMR (solvent: deuterated chloroform): δ: 12.3 (s, 1H), 3.80 (s, 2H), 3.42 (s, 2H), 3.40 (s, 2H), 2 .80 (m, 1H), 1.60 (m, 2H), 1.44-1.26 (m, 8H), 0.92-0.80 (m, 6H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 173.5, 67.5, 65.9, 64.1, 31.5, 29.9-29.0, 25.1, 22.5, 14 0.0, 7.3
Infrared absorption spectrum (IR) (KBr): 2900-3500 cm ⁻¹
(Example 3-2)
A compound represented by the formula (15) was obtained in the same manner as in Example 1-2 using the compound represented by the formula (14) (1 mol) and acrylic acid chloride (1.2 mol).

（物性値）
¹Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：１２．３（ｓ，１Ｈ），δ：１２．３（ｓ，１Ｈ），６．５５（ｄ，１Ｈ），６．２１（ｑ，１Ｈ），５．９４（ｄ，１Ｈ），４．２２（ｓ，２Ｈ），３．８０（ｓ，２Ｈ），３．４２（ｓ，２Ｈ），１．６０（ｍ，２Ｈ），１．４４−１．２６（ｍ，８Ｈ），０．９２−０．８０（ｍ，６Ｈ）
^１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：１７３．５，１７４．１，１７３．５，１６６．３，１３１．１，１２８．２，１２７．９，６７．５，６５．９，６４．１，３１．５，２９．９−２９．０，２５．１，２２．５，１４．０，７．３
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：２９００−３５００ｃｍ^−１
（実施例３−２）
式（１５）で表される化合物及び１，１０−デカンジオールを用い、実施例１−３と同様にして式（Ｍ−３）で表される重合性化合物を得た。

(Physical property value)
¹ H-NMR (solvent: deuterated chloroform): δ: 12.3 (s, 1H), δ: 12.3 (s, 1H), 6.55 (d, 1H), 6.21 (q, 1H) , 5.94 (d, 1H), 4.22 (s, 2H), 3.80 (s, 2H), 3.42 (s, 2H), 1.60 (m, 2H), 1.44 1.26 (m, 8H), 0.92-0.80 (m, 6H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 173.5, 174.1, 173.5, 166.3, 131.1, 128.2, 127.9, 67.5, 65.9, 64 1, 31.5, 29.9-29.0, 25.1, 22.5, 14.0, 7.3
Infrared absorption spectrum (IR) (KBr): 2900-3500 cm ⁻¹
(Example 3-2)
A polymerizable compound represented by the formula (M-3) was obtained in the same manner as in Example 1-3 using the compound represented by the formula (15) and 1,10-decanediol.

（物性値）
^１Ｈ−ＮＭＲ（溶媒：重クロロホルム）：δ：６．４３（ｄ，２Ｈ），６．１１（ｑ，２Ｈ），５．８４（ｄ，２Ｈ），４．１２（ｓ，４Ｈ），４．０５（ｓ，４Ｈ），３．８０（ｓ，４Ｈ），３．４２（ｓ，４Ｈ），１．６４（ｍ，４Ｈ），１．５９（ｍ，４Ｈ），１．４４（４Ｈ），１．３８−１．２５（ｍ，２４Ｈ），０．９１−８０（ｍ，１８Ｈ）
^１３Ｃ−ＮＭＲ（溶媒：重クロロホルム）：δ：１７３．４，１６５．７，１３１．０，１２７．９，７１．２，６８．０，６３．６，４０．６，３４．２，２９．８−２９．０，２６．８，２３．０，２２．６，１４．０，１０．７，７．３
赤外吸収スペクトル（ＩＲ）（ＫＢｒ）：２９２５，２８５５，１７３３，１６５２−１６２２，１１９０，８０８．９

(Physical property value)
¹ H-NMR (solvent: deuterated chloroform): δ: 6.43 (d, 2H), 6.11 (q, 2H), 5.84 (d, 2H), 4.12 (s, 4H), 4 .05 (s, 4H), 3.80 (s, 4H), 3.42 (s, 4H), 1.64 (m, 4H), 1.59 (m, 4H), 1.44 (4H) 1.38-1.25 (m, 24H), 0.91-80 (m, 18H)
¹³ C-NMR (solvent: deuterated chloroform): δ: 173.4, 165.7, 131.0, 127.9, 71.2, 68.0, 63.6, 40.6, 34.2, 29 .8-29.0, 26.8, 23.0, 22.6, 14.0, 10.7, 7.3
Infrared absorption spectrum (IR) (KBr): 2925, 2855, 1733, 1652-1622, 1190, 808.9

Claims (4)

General formula (1)

(Wherein R ¹ represents an alkyl group having 1 to 15 carbon atoms), and the compound represented by the general formula (2)

(In the formula, R ² represents a linear or branched alkyl group having 1 to 20 carbon atoms, and one or two or more carbon atoms present in the group are such that oxygen atoms are not directly bonded to each other. A single bond between one or more carbons which may be replaced by an oxygen atom and which is present in the group may be replaced by a double bond or a triple bond, and a hydrogen atom present in the group May be substituted by halogen, Y ¹ represents a carbonyl group , X ¹ represents a hydroxyl group, a substituted sulfonyloxy group or halogen, but when Y ¹ represents a carbonyl group and X ¹ represents a hydroxyl group, It may be an acid anhydride of the compound.) By reacting the compound represented by the general formula (6)

(Wherein R ¹ represents the same meaning as in general formula (1), and R ² and Y ¹ represent the same meaning as in general formula (2)), and then the general formula (3)

(In the formula, R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a single bond , Y ² represents a single bond , Y ³ represents a single bond , and X ² represents a hydroxyl group, a substituted sulfonyloxy group or a halogen. By reacting the compound represented by formula (7)

(In the formula, R ¹ represents the same meaning as in general formula (1), R ² and Y ¹ represent the same meaning as in general formula (2), and R ³ , R ⁴ , Y ² and Y ³ represent the general formula ( The same meaning as 3) is obtained, and then the compound represented by formula (4) is obtained.

(In the formula, R ⁵ represents a linear or branched alkylene group having 5 to 25 carbon atoms or alkanetriyl group, and one or more carbon atoms present in the group. An atom may be replaced by an oxygen atom as if the oxygen atoms are not directly bonded to each other, and a single bond between one or more carbons present in the group may be a double bond or a triple bond. May be substituted, n represents 2 or 3, and X ³ represents a hydroxyl group, a substituted sulfonyloxy group or a halogen).

(Wherein R ⁵ and n represent the same meaning as in general formula (4), R ¹ represents the same meaning as in general formula (1), and R ² and Y ¹ represent the same meaning as in general formula (2). , R ³ , R ⁴ , Y ² and Y ³ represent the same meaning as in general formula (3)). In the general formula (2) The method according to claim 1, wherein R ² represents a linear or branched alkyl group having 5 to 20 carbon atoms. General formula (5)

(In the formula, R ¹ represents an alkyl group having 1 to 15 carbon atoms, R ² represents a linear or branched alkyl group having 1 to 20 carbon atoms, and one or two or more existing in the group) Carbon atoms may be replaced by oxygen atoms so that the oxygen atoms are not directly bonded to each other, and a single bond between one or more carbons present in the group may be a double bond or a triple bond. ^{May be} replaced by a bond, a hydrogen atom present in the group may be replaced by a halogen, R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a single bond , and R ⁵ represents a straight chain Represents an alkylene group or alkanetriyl group having 5 to 25 carbon atoms which may be branched or branched, and one or two or more carbon atoms present in the group are oxygen atoms directly to each other Placed by oxygen atoms as not bound to May also be gills, single bond between one or more carbons present in the group may be replaced by a double bond or triple bond,
n represents 2 or 3,
Y ¹ represents a carbonyl group , Y ³ represents a single bond, and Y ² represents a single bond . ) A polymerizable compound represented by: The polymerizable compound according to claim 3, wherein, in the general formula (5), R ² represents a linear or branched alkyl group having 5 to 20 carbon atoms.