JP6365002B2 - Novel liquid crystalline compound and liquid crystal composition using the same - Google Patents

Description

  The present invention relates to a novel liquid crystal compound, a liquid crystal composition containing the compound, and a liquid crystal display element containing the liquid crystal composition.

  Liquid crystal display elements are used in various measuring instruments, automobile panels, word processors, electronic notebooks, printers, computers, televisions, watches, advertisement display boards, as well as watches and calculators. Typical liquid crystal display methods include TN (twisted nematic) type, STN (super twisted nematic) type, vertical alignment type using TFT (thin film transistor), and IPS (in-plane switching) type. Alternatively, there are FFS (fringe field switching) type and the like. The main characteristics required of the liquid crystal composition are (1) being stable against external stimuli such as moisture, air, heat, and light, and (2) the liquid crystal phase in the widest possible temperature range centering on room temperature. And (4) low viscosity and (4) low driving voltage. For each display element, dielectric anisotropy (Δε) and refractive index anisotropy (Δn) In general, the liquid crystal composition is composed of several to several tens of kinds of compounds in order to obtain an optimal value.

  At present, improvement in response speed is required in all driving systems, and in order to solve this problem, a liquid crystal composition having a viscosity lower than that of the current one is required. One effective method for obtaining a low-viscosity liquid crystal composition is to use a nonpolar liquid crystal compound having a higher Δn than before in order to increase the content of the viscosity reducing component in the system. is there. Patent document 1 is mentioned as this prior art. Patent Document 1 discloses a composition having an extremely low rotational viscosity γ1 and a relatively high optical anisotropy value Δn by using a compound having a terphenyl skeleton represented by general formula (I). . Also, in Patent Document 2, which is another prior art, by using the same terphenyl skeleton compound as in Patent Document 1, a high maximum temperature of the nematic phase, a low minimum temperature of the nematic phase, a low viscosity, an appropriate optical property, and the like. There is a description that a composition satisfying a plurality of characteristics such as anisotropy, a low threshold voltage, and a large specific resistance can be provided.

International Publication No. 2005/007775 Pamphlet International Publication No. 2006/038443 Pamphlet

  As shown in the Examples of Patent Document 1 and Patent Document 2 described above, the conventional compound (D) having the terphenyl skeleton as shown below, and the following formula (B) or the following formula (C In combination with a compound represented by (), the entire liquid crystal composition has been increased in Δn.

  However, the compound of the formula (B) has a transition temperature of around 0 ° C., and the compound of the formula (C) has a drawback that it has a relatively high transition temperature of around 160 ° C. but has a low compatibility with other liquid crystal compositions. is there. In addition, although Δn of the compound of the formula (D), which is an essential component of the above-mentioned patent documents (1) and (2), is as large as about 0.24, and the transition temperature is also around 120 ° C., a wide nematic temperature range. The physical properties of the liquid crystal compound having the above were not sufficient.

  Therefore, the combination of the conventional liquid crystal compounds cannot simultaneously satisfy the characteristics, low viscosity, compatibility, high transition temperature, and high Δn necessary for achieving high-speed response and a wide operating temperature range at the same time.

  Therefore, an object of the present invention is to provide a compound that can guarantee the low viscosity and compatibility of characteristics required for high-speed response and contribute to the improvement of Tni and Δn values.

  In order to solve the above problems, the present inventors provide a naphthalene derivative represented by the general formula (1) and a liquid crystal composition containing the naphthalene derivative.

  The liquid crystal compound according to the present invention has a low viscosity, a high isotropic transition temperature, a high compatibility, a high refractive index anisotropy, and is hardly deteriorated by heat or light. When the liquid crystal composition using the liquid crystal compound according to the present invention is used, a high-speed response liquid crystal display element can be provided.

FIG. 1 is a diagram schematically showing an example of the configuration of a liquid crystal display element according to the present invention. FIG. 2 is a diagram schematically showing an example of the configuration of the liquid crystal display element according to the present invention.

  The first of the present invention is the general formula (1)

(In the general formula (1), R and R ′ each independently represents an alkyl group having 1 to 15 carbon atoms or an alkenyl group having 2 to 15 carbon atoms, and one existing in these groups. or nonadjacent two or more -CH ₂ - - is -O - -CH ₂ of, - S -, - COO - , - OCO- or may be replaced by -CO-,
The naphthalene ring may be substituted with a hydrogen atom or a fluorine atom,
Ring A ¹ , Ring A ² , Ring A ³ , Ring A ⁴ , Ring A ⁵ , Ring A ⁶ , Ring A ⁷ and Ring A ⁸ are each independently the following (a), (b) and (c) A group selected from the group consisting of:
(A) 1,4-cyclohexylene group (the one present in the group -CH ₂ - or nonadjacent two or more -CH ₂ - is replaced by -O- or -S- Is also good.)
(B) 1,4-phenylene group (one —CH═ present in this group or two or more non-adjacent —CH═ may be replaced by —N═ and present in this group) The hydrogen atom to be substituted may be replaced by a fluorine atom.)
(C) Naphthalene-2,6-diyl group (the hydrogen atom present in this group may be substituted with a fluorine atom)
Said group (a)-group (c) may each independently be substituted with a cyano group, a fluorine atom or a chlorine atom,
Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ , Z ⁶ , Z ⁷ and Z ⁸ are each independently —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —. , —CH ₂ CH ₂ —, —CF ₂ CF ₂ —, —CH═CH—, —CF═CF—, —C≡C— or a single bond, m, n, p, r, s, t, u and v each independently represent 0 or 1, but m + n + p + r + s + t + u + v is 0, 1, 2, 3 or 4. ).

  The naphthalene derivative represented by the general formula (1) can provide a liquid crystal composition excellent in low viscosity, high isotropic transition temperature, high compatibility, high refractive index anisotropy, heat resistance and light resistance. .

In the general formula (1), ring A ¹ , ring A ² , ring A ³ , ring A ⁴ , ring A ⁵ , ring A ⁶ , ring A ⁷ and ring A ⁸ are each independently represented by the following formula (1) It is preferably represented by at least one selected from the group consisting of -1) to (1-37).

In the compound represented by the general formula (1) according to the present invention, a group consisting of ring A ¹ , ring A ² , ring A ³ , ring A ⁴ , ring A ⁵ , ring A ⁶ , ring A ⁷ and ring A ^8. At least one selected from benzene is preferably benzene (formula (1-1)) when importance is placed on Δn and Tni, and monofluorinated benzene (formula (1-2) to formula is preferred when compatibility is emphasized. (1-3)) is preferable. Further, when importance is placed on Δn and Tni, naphthalene series (formula (1-9) to formula (1-29)) is preferable, and when importance is placed on Δε, pyran, dioxane, pyrimidine (formula (1-30)) To formula (1-36)), and when importance is attached to compatibility and viscosity, a cyclohexane ring (formula (1-37)) is preferable. When importance is placed on Δn, Tni, compatibility, viscosity, etc., a benzene ring (formula (1-1) to formula (1-8)) and a naphthalene ring (formula (1-9) to formula (1-29)) Is preferably a partial structure in which a benzene ring (formula (1-1) to formula (1-3)) and a naphthalene ring (formula (1-9)) are joined by a single bond. More preferred. When importance is attached to compatibility and viscosity, a partial structure in which a cyclohexane ring (formula (1-387) and a benzene ring (formula (1-1) to formula (1-8)) are connected by a single bond is preferable. A partial structure in which a cyclohexane ring (formula (1-37)) and a benzene ring (formula (1-1) to formula (1-3)) are connected by a single bond is more preferable.

Among these, at least one selected from the group consisting of formulas (1-1) to (1-4), formulas (1-9) to (1-15) and formula (1-39) is preferable. (1-1), Formula (1-2), Formula (1-3), Formula (1-9), and Formula (1-37) are more preferable, and Formula (1-2) and Formula (1-3) are more preferable. ), Formula (1-9) and formula (1-37) are particularly preferred.
Further, it is considered that if the direction of fluorine in the ring structure of another p-type liquid crystal compound or other n-type liquid crystal compound to be used is the same, it contributes to Δε.

  In the present specification, examples of the alkenyl group having 2 to 15 carbon atoms include vinyl group, allyl group, 1-propenyl group, isopropenyl group, 2-butenyl group, 3-butenyl group, 1,3-butadienyl group, A 2-pentenyl group, a 3-pentenyl group, a 2-hexenyl group and the like can be mentioned, and a straight chain or branched chain is preferable, and a straight chain is more preferable.

  More preferable alkenyl groups according to the present invention include the following formula (xi) (vinyl group), formula (xii) (1-propenyl group), formula (xiii) (3-butenyl group) and formula (xiv) ( 3-pentenyl group):

(In the above formulas (i) to (iv), * represents a binding site to the ring structure.)
It is represented by

  Examples of the “alkyl group having 1 to 15 carbon atoms” according to the present invention include methyl, ethyl, propyl, butyl, isopropyl, isobutyl, t-butyl, 3-pentyl, and isopentyl. Group, neopentyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, pentadecyl group and the like. In the present specification, examples of the alkyl group are common, and are appropriately selected from the above examples depending on the number of carbon atoms of each alkyl group.

  Moreover, the example of the alkoxy group based on this invention has the preferable alkoxy group which the oxygen atom couple | bonded with the said alkyl group.

In the general formula (1), R ¹ and R ² are each independently more preferably an alkenyl group having 2 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms. It is preferable from the viewpoint of solubility and nematic phase formation that the number of carbon atoms of the substituents at both ends of the compound represented by the general formula (1) is 5 or less.

  In the compound represented by the general formula (1) according to the present invention, the number of rings is preferably 1 to 5, more preferably 2 to 4, and the number of rings 3 to 3. Four is more preferable. For example, when selecting a compound with high Δn and compatibility and low viscosity, select two rings, when selecting a compound with high compatibility and Tni and low viscosity, select a compound with three rings and high Δn and Tni. Is a four ring. The number of rings here is one for a condensed ring such as a naphthalene ring.

  In the general formula (1), m + n + p + r + s + t + u + v is preferably 1, 2, or 3, and m + n + p + r + s + t + u + v is more preferably 1 or 2.

  In the general formula (1), s is preferably 0 or 1, and more preferably 0. In the general formula (1), t is preferably 0 or 1, more preferably 0. In the general formula (1), u is preferably 0 or 1, and more preferably 0. In the general formula (1), v is preferably 0 or 1, and more preferably 0.

  In the general formula (1), either m + n + p + r or s + t + u + v is preferably 0.

In the general formula (1), Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ , Z ⁶ , Z ⁷ and Z ⁸ are each independently —CH ₂ O—, —OCH ₂ —, —CF. ₂ O—, —OCF ₂ —, —CH═CH—, —CF═CF—, —C≡C— or a single bond is preferable, —CH═CH—, —CF═CF—, —C≡. More preferably, it is C- or a single bond. In the general formula (1), at least one of Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ , Z ⁶ , Z ⁷ and Z ⁸ is preferably a single bond.

  The compound represented by the general formula (1) according to the present invention is preferably a compound represented by the following general formula (N).

  The general formula (N) is

(In the general formula (N), L ¹ , L ² , L ³ , L ⁴ and L ⁵ each independently represent a hydrogen atom, a fluorine atom or a cyano group,
R ¹ and R ² are each independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydrogen atom, a fluorine atom, Represents a cyano group, —CF ₃ or —OCF ₃ ;
Z ¹ and Z ² are each independently —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH ₂ CH ₂ —, —CF ₂ CF ₂ —, —CH═. CH—, —CF═CF—, —C≡C— or a single bond,
Ring A ¹ and Ring A ² are each independently
a) 1,4-cyclohexylene group (the one present in the group -CH ₂ - or nonadjacent two or more -CH ₂ - may be replaced by -O- or -S- good.)
(B) 1,4-phenylene group (one —CH═ present in this group or two or more non-adjacent —CH═ may be replaced by —N═ and present in this group) The hydrogen atom to be substituted may be replaced by a fluorine atom.)
(C) Naphthalene-2,6-diyl group (the hydrogen atom present in this group may be substituted with a fluorine atom)
Each of the groups (a) to (c) may be independently substituted with a cyano group, a fluorine atom or a chlorine atom,
a and b each independently represents 0, 1 or 2; Preferably it is at least one compound.

  The compound represented by the general formula (N) has both a high Δn and a low viscosity because it has a naphthalene ring and a phenyl ring and a naphthalene ring are bonded by a single bond.

In the general formula (N), L ¹ , L ² , L ³ , L ⁴ and L ⁵ are each independently preferably a hydrogen atom or a fluorine atom. Moreover, it is preferable that at least one of L ¹ , L ² , L ³ , L ⁴ and L ⁵ is substituted with a fluorine atom, and either L ¹ or L ^{2 in} the same ring Or any one of L ³ , L ⁴ and L ⁵ is more preferably substituted with a fluorine atom.

  In the general formula (N), a is preferably 1 or 2, b is preferably 0 or 1, a + b is preferably 1, 2 or 3, and a + b is 1 or 2. More preferably, b is even more preferably 0.

In the general formula (N), the ring A ¹ and the ring A ² are each independently preferably a 1,4-cyclohexylene group or a 1,4-phenylene group.

In the general formula (N), Z ¹ and Z ² are each independently, and Z ¹ and Z ² are each independently —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF _2. —, —CH ₂ CH ₂ —, —CF ₂ CF ₂ —, —CH═CH—, —CF═CF—, —C≡C— or a single bond is preferred, —CH═CH—, —CF More preferred is ═CF—, —C≡C— or a single bond.

  Preferred examples of the compound represented by the general formula (1) according to the present invention include at least one selected from the group consisting of compounds represented by the following general formulas (N-1) to (N-7). Are preferred.

(In the above general formulas (N-1) to (N-7), R ¹ and R ² are each independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, Represents an alkoxy group having 1 to 10 carbon atoms or an alkenyloxy group having 2 to 10 carbon atoms.)
Specific examples of the compound represented by the general formula (1) according to the present invention include the following (n.1-1) to (n.7-6).

  By monofluorination of the benzene ring adjacent to the naphthalene ring, it has the feature of suppressing the decrease in solubility and viscosity without impairing the excellent properties such as the high Δn and high Tni inherent in the phenylnaphthalene skeleton.

  In the present invention, the compound represented by the general formula (1) can be produced, for example, according to the following production methods 1 to 3. Of course, the spirit and scope of the present invention are not limited by these production examples.

(Production method 1)
General formula (2)

(In the general formula (2), M represents a boronic acid (—B (OH) ₂ ) or a boronic ester, and R, A ¹ , A ² , A ³ , A ⁴ , Z ¹ , Z ² , Z ^3. , Z ⁴ , m, n, p and r are each independently R, A ¹ , A ² , A ³ , A ⁴ , Z ¹ , Z ² , Z ³ , Z ⁴ , m in the general formula (1). , N, p and r have the same meanings), and a compound represented by the general formula (3)

(In the general formula (3), X represents a chlorine atom, a bromine atom, an iodine atom or a trifluoromethanesulfonyloxy group, and R ′, A ⁵ , A ⁶ , A ⁷ , A ⁸ , Z ⁵ , Z ⁶ , Z ⁷ , Z ⁸ , s, t, u and v are each independently R ′, A ⁵ , A ⁶ , A ⁷ , A ⁸ , Z ⁵ , Z ⁶ , Z ⁷ , Z ⁸ , in general formula (1). A compound represented by the general formula (1) can be obtained by reacting a compound represented by the same meaning as s, t, u and v.

  In the production method 1, an example of the reaction is a method of cross-coupling in the presence of a metal catalyst and a base. Specific examples of metal catalysts include [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride, palladium (II) acetate, tetrakis (triphenylphosphine) palladium (0), bis (triphenylphosphine) Palladium, dichlorobis [di-t-butyl (p-dimethylaminophenyl) phosphino] palladium (II) and the like are preferable. Specific examples of the base are preferably potassium carbonate, potassium phosphate, cesium carbonate and the like. Specific examples of the solvent are preferably tetrahydrofuran, toluene, ethanol, water and the like.

In the present specification, boronic acid (for example, in the above general formula (2)) refers to a compound having a boron-carbon bond, and boronic ester refers to a complex of boronic acid and (polyhydric) alcohol (so-called A boronic acid ester residue, for example, Ph-B (OR) ₂ ), includes the following structures: In addition, * in the following formulas means a bond to a carbon atom.

  The reaction temperature in the reaction of the general formula (2) and the general formula (3) is preferably from room temperature (25 ° C) to 120 ° C, more preferably from 40 to 80 ° C.

  The reaction atmosphere in the reaction of the general formula (2) and the general formula (3) is preferably carried out in an inert atmosphere (nitrogen and / or argon atmosphere) although the reaction proceeds even in the air.

  The reaction time in the reaction of the general formula (2) and the general formula (3) is preferably about 30 minutes to 10 hours.

(Manufacturing method 2)
General formula (4)

(In the general formula (4), X represents a chlorine atom, a bromine atom, an iodine atom or a trifluoromethanesulfonyloxy ^{group, R, A 1, A 2} , A 3, A 4, Z 1, Z 2, Z 3 , Z ⁴ , m, n, p and r are each independently R, A ¹ , A ² , A ³ , A ⁴ , Z ¹ , Z ² , Z ³ , Z ⁴ , m, in the general formula (1). the same meaning as n, p and r.) and a compound represented by the general formula (5)

(In the general formula (5), M represents boric acid or a boric acid ester, and R ′, A ⁵ , A ⁶ , A ⁷ , A ⁸ , Z ⁵ , Z ⁶ , Z ⁷ , Z ⁸ , s, t , U and v are each independently R ′, A ⁵ , A ⁶ , A ⁷ , A ⁸ , Z ⁵ , Z ⁶ , Z ⁷ , Z ⁸ , s, t, u and v in the general formula (1). The compound represented by the general formula (1) can be obtained using the same reaction example as in Production Method 1 by reacting the compound represented by the same meaning.

  The reaction temperature in the reaction of the general formula (4) and the general formula (5) is preferably from room temperature (25 ° C) to 120 ° C, more preferably from 40 to 80 ° C.

  The reaction atmosphere in the reaction of the general formula (2) and the general formula (3) is preferably carried out in an inert atmosphere (nitrogen and / or argon atmosphere) although the reaction proceeds even in the air.

  The reaction time in the reaction of the general formula (2) and the general formula (3) is preferably about 30 minutes to 10 hours.

(Manufacturing method 3)
Of the compounds represented by the general formula (1), the general formula (1-1)

(In the formula, R ¹ and R ² each independently represent an alkyl group having 1 to 15 carbon atoms or an alkenyl group having 2 to 15 carbon atoms, and A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ , Z ¹ , Z ² , Z ³ , Z ⁵ , Z ⁶ , Z ⁷ , m, n, p, r, s, t, u and v are each independently a general formula A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ , Z ¹ , Z ² , Z ³ , Z ⁵ , Z ⁶ , Z ⁷ , m, n in (1) The compounds represented by p, r, s, t, u, and v have the same meanings as in the above production methods 1 and 2, but the step (A1), step (A2), and step (B) described below. ), Step (C) and step (D). That is, the compound represented by the general formula (1-1) according to the present invention is a step (A1) in which the compound represented by the general formula (6) and the compound represented by the general formula (7) are reacted. After obtaining the compound represented by the general formula (1-2) described later by the step (A2) of reacting the compound represented by the general formula (8) with the compound represented by the general formula (9), The compound represented by the general formula (1-2) is reduced to obtain the compound represented by the general formula (1-3) (step (B)), and represented by the general formula (1-3). To obtain a compound represented by the general formula (1-4) (step (C)), and then alkenylate the compound represented by the general formula (1-4). It is preferable to obtain the compound represented by (1-1) (step (D)). Hereinafter, each step will be described.

(Process (A))
General formula (6)

(In the general formula (6), X represents a chlorine atom, a bromine atom, an iodine atom or a trifluoromethanesulfonyloxy group, and R ³ represents a formyl group, a carboxyl group, an ester group or an alkyl group having 1 to 15 carbon atoms. A ¹ , A ² , A ³ , A ⁴ , Z ¹ , Z ² , Z ³ , m, n, p and r are each independently R, A ¹ , A ² , A in the general formula (1). ³ , A ⁴ , Z ¹ , Z ² , Z ³ , m, n, p and r represent the same meanings) and the general formula (7)

(In the general formula (7), M represents boric acid or a boric acid ester, R ⁴ represents a formyl group, a carboxyl group, an ester group, or an alkyl group having 1 to 15 carbon atoms, and A ⁵ , A ⁶ , A ⁷ , A ⁸ , Z ⁵ , Z ⁶ , Z ⁷ , s, t, u and v are each independently R ′, A ⁵ , A ⁶ , A ⁷ , A ⁸ , Z ⁵ in the general formula (1). , Z ⁶ , Z ⁷ , s, t, u and v are represented by the same method) (A1) or general formula (8)

(In the general formula (8), M represents boric acid or a boric acid ester, R ³ represents a formyl group, a carboxyl group, an ester group, or an alkyl group having 1 to 15 carbon atoms, and A ¹ , A ² , A ³ , A ⁴ , Z ¹ , Z ² , Z ³ , m, n, p and r are each independently R, A ¹ , A ² , A ³ , A ⁴ , Z ¹ , R in the general formula (1). Z ² , Z ³ , m, n, p, and r have the same meaning.) And the general formula (9)

(In the general formula (9), X represents a chlorine atom, a bromine atom, an iodine atom or a trifluoromethanesulfonyloxy group, and R ⁴ represents a formyl group, a carboxyl group, an ester group or an alkyl group having 1 to 15 carbon atoms. A ⁵ , A ⁶ , A ⁷ , A ⁸ , Z ⁵ , Z ⁶ , Z ⁷ , s, t, u and v are each independently R ′, A ⁵ , A ⁶ , A ⁷ , A ⁸ , Z ⁵ , Z ⁶ , Z ⁷ , s, t, u and v are represented by the formula (1-2). The compound represented by the following general formula (1-2) can be obtained by using the same reaction conditions as in Production Method 1 or Production Method 2 in the step of reacting the compound (A2).

(In the formula, R ³ and R ⁴ are a formyl group, a carboxyl group, an ester group, or an alkyl group having 1 to 15 carbon atoms (at least one of R ^{3 and} R ⁴ represents a formyl group, a carboxyl group, and an ester group) A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ , Z ¹ , Z ² , Z ³ , Z ⁵ , Z ⁶ , Z ⁷ , m, n, p, r, s, t, u, and v are each independently A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ , Z ¹ , Z in the general formula (1). ² , Z ³ , Z ⁵ , Z ⁶ , Z ⁷ , m, n, p, r, s, t, u and v represent the same meaning.)
(Process (B))
In the step (B), the compound represented by the general formula (1-2) is reduced to reduce the compound represented by the following general formula (1-3).

(In the general formula (1-3), R ⁵ and R ⁶ represent a hydroxymethyl group or an alkyl group having 1 to 15 carbon atoms (at least one of R ^{5 and} R ⁶ represents a hydroxymethyl group). ^{, A 1, A 2, A} 3, A 4, A 5, A 6, A 7, A 8, Z 1, Z 2, Z 3, Z 5, Z 6, Z 7, m, n, p, r , S, t, u and v are each independently A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ , Z ¹ , Z ² , Z in the general formula (1). ³ , Z ⁵ , Z ⁶ , Z ⁷ , m, n, p, r, s, t, u and v have the same meanings)).

  In the step (B), examples of the reducing agent include hydride reducing agents such as lithium aluminum hydride. Specific examples of the solvent include ether solvents such as tetrahydrofuran.

  In the reaction of the above step (B), a catalyst may be used or a known one may be used. Further, the reaction temperature in the reaction is preferably from -40 ° C to 80 ° C, more preferably from 0 to 30 ° C.

In addition, the reaction atmosphere in the reaction of the above step (B) proceeds even under air, but it is preferably performed under an inert atmosphere (nitrogen and / or argon atmosphere).
The reaction time in the reaction in the step (B) is preferably about 30 minutes to 5 hours. Furthermore, the reaction in the above step (B) is preferably performed under water-free conditions from the viewpoint of safety.

(Process (C))
In the step (C), the compound represented by the general formula (1-3) is chlorinated to give a general formula (1-4).

(In the above general formula (1-4), R ⁷ and R ⁸ represent a chloromethyl group or an alkyl group having 1 to 15 carbon atoms (at least one of R ⁷ or R ⁸ represents a chloromethyl group). ^{, A 1, A 2, A} 3, A 4, A 5, A 6, A 7, A 8, Z 1, Z 2, Z 3, Z 5, Z 6, Z 7, m, n, p, r , S, t, u and v are each independently A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ , Z ¹ , Z ² , Z in the general formula (1). ³ , Z ⁵ , Z ⁶ , Z ⁷ , m, n, p, r, s, t, u and v have the same meanings)).

  Examples of the chlorinating reagent in the step (C) include p-toluenesulfonic acid chloride, thionyl chloride, phosphorus oxychloride and the like. Specific examples of the solvent include tetrahydrofuran, N, N-dimethylformamide, dichloromethane and the like. Specific examples of the coexisting base include pyridine, N, N-dimethylaminopyridine, triethylamine, diisopropylethylamine and the like.

  In the reaction of the above step (C), the catalyst may not be used or a known one may be used. Further, the reaction temperature in the reaction is preferably -20 ° C to 80 ° C, more preferably 0 to 30 ° C.

In addition, the reaction atmosphere in the reaction of the above step (C) proceeds even under air, but it is preferably performed under an inert atmosphere (nitrogen and / or argon atmosphere).
The reaction time in the reaction in the step (C) is preferably about 30 minutes to 5 hours. Furthermore, the reaction in the above step (C) is preferably performed under water-free conditions from the viewpoint of safety.

(Process (D))
In the step (D), a compound represented by the general formula (1-1) can be obtained by alkenylating the compound represented by the general formula (1-4).

  Examples of the alkenylating reagent include allylmagnesium chloride, allylmagnesium bromide, crotylmagnesium chloride, crotylmagnesium bromide and the like. Specific examples of the solvent include ether solvents such as tetrahydrofuran.

  In the reaction of the above step (D), the catalyst may not be used or a known one may be used. Moreover, -70 degreeC to 80 degreeC is preferable, and, as for the reaction temperature in the said reaction, -20-50 degreeC is more preferable.

Further, the reaction atmosphere in the reaction of the above step (D) proceeds even under air, but it is preferable to carry out under an inert atmosphere (nitrogen and / or argon atmosphere).
The reaction time in the reaction of the above step (D) is preferably about 30 minutes to 5 hours. Furthermore, the reaction in the above step (D) is preferably performed under water-free conditions from the viewpoint of safety.

  The second of the present invention is a liquid crystal composition containing a compound represented by the general formula (1), and is preferably a nematic liquid crystal composition.

  Since liquid crystal compositions are generally prepared with a value of Δn, the use of a nonpolar liquid crystal compound with a higher Δn can reduce the amount used, resulting in a viscosity that serves as a viscosity reducing component. The content of a low compound can be increased. Thereby, the viscosity of the whole composition can be made low.

  In this case, in order to adjust the physical property value of the liquid crystal composition, a compound other than the compound represented by the general formula (1) may be used. It is also possible to add non-compounds.

  Thus, as a preferable representative example of the compound that can be used by mixing with the compound represented by the general formula (1), in the composition provided by the present invention, the general component (1) At least one compound represented by formula (1), but it is preferable to contain at least one of the following second to seventh components as other components.

  The liquid crystal composition containing the compound represented by the general formula (1) according to the present invention is preferably a nematic liquid crystal composition. When the liquid crystal composition according to the present invention is used as a p-type nematic liquid crystal composition, at least one compound represented by the general formula (1) is used as the first component, and the following general formula (A1) is used as the second component. ) To (A3) at least one selected from the group consisting of compounds and / or at least one selected from the group consisting of compounds represented by the following general formulas (B1) to (B3) as the third component It is preferable that at least one compound selected from the group consisting of the fourth component to the seventh component is included if necessary, and at least one compound represented by the general formula (1) is included as the first component. And at least one selected from the group consisting of compounds represented by the following general formulas (A1) to (A3) as the second component and / or the following general formulas (B1) to (B3) as the third component: At least one selected from the group consisting of the compounds shown, and at least one selected from the group consisting of compounds shown by the compounds represented by the general formulas (C1) to (C3) as the fourth component, More preferably, it contains at least one compound selected from the group consisting of the fifth component to the seventh component as necessary.

  When the liquid crystal composition according to the present invention is used as an n-type nematic liquid crystal composition, at least one compound represented by the general formula (1) is used as the first component, and the following general formula is used as the seventh component. Including at least one compound selected from the group consisting of the compounds represented by (F1) to (F3), and optionally including at least one compound selected from the group consisting of the second component to the sixth component. At least one compound represented by the general formula (1) as the first component and at least selected from the group consisting of compounds represented by the following general formulas (F1) to (F3) as the seventh component 1 type and at least 1 sort (s) selected from the group which consists of a compound shown by the compound shown by general formula (C1)-(C3) as a 4th component, and from the 2nd component-a 6th component as needed Group More preferably contains at least one compound al selected.

  That is, the second component is a so-called fluorine-based (halogen-based) p-type liquid crystal compound, and examples thereof include compounds represented by the following general formulas (A1) to (A3).

In the above formula, R ^b represents an alkyl group having 1 to 12 carbon atoms, which may be linear or branched, and has a 3- to 6-membered cyclic structure. Any —CH ₂ — present in the group may be replaced by —O—, —CH═CH—, —CH═CF—, —CF═CH—, —CF═CF— or —C≡C—. Any hydrogen atom present in the group may be substituted with a fluorine atom or a trifluoromethoxy group, but a linear alkyl group having 1 to 7 carbon atoms, 2 to 2 carbon atoms 7 linear 1-alkenyl groups, linear 4-alkenyl groups having 4 to 7 carbon atoms, and alkyl groups having 1 to 5 carbon atoms substituted at the ends by alkoxy groups having 1 to 3 carbon atoms. preferable. Further, when asymmetric carbon is generated by branching, the compound may be optically active or racemic.

  Ring A, Ring B and Ring C may each independently be substituted with a trans-1,4-cyclohexylene group, a transdecahydronaphthalene-trans-2,6-diyl group, or one or more fluorine atoms. A good 1,4-phenylene group, a naphthalene-2,6-diyl group optionally substituted by one or more fluorine atoms, a tetrahydronaphthalene-2,6-optionally substituted by one or more fluorine atoms Diyl group, 1,4-cyclohexenylene group optionally substituted by a fluorine atom, 1,3-dioxane-trans-2,5-diyl group, pyrimidine-2,5-diyl group or pyridine-2,5 -Represents a diyl group, but is substituted by a trans-1,4-cyclohexylene group, a transdecahydronaphthalene-trans-2,6-diyl group, or a fluorine atom. An optional naphthalene-2,6-diyl group or a 1,4-phenylene group optionally substituted by 1 to 2 fluorine atoms is preferred. In particular, when ring B is a trans-1,4-cyclohexylene group or a transdecahydronaphthalene-trans-2,6-diyl group, ring A may be a trans-1,4-cyclohexylene group. Preferably, when ring C is a trans-1,4-cyclohexylene group or a transdecahydronaphthalene-trans-2,6-diyl group, ring B and ring A are trans-1,4-cyclohexylene groups. Preferably there is. In (A3), ring A is preferably a trans-1,4-cyclohexylene group.

L ^a , L ^b and L ^c are each a linking group and each independently represents a single bond, an ethylene group (—CH ₂ CH ₂ —), a 1,2-propylene group (—CH (CH ₃ ) CH ₂ — and _{-CH 2 CH (CH 3) -} ), 1,4- butylene _{group, -COO -, - OCO -,} - OCF 2 -, - CF 2 O -, - CH = CH -, - CH = CF -, - CF═CH—, —CF═CF—, —C≡C— or —CH═NN═CH—, each represents a single bond, ethylene group, 1,4-butylene group, —COO—, —OCF ₂ —, —CF ₂ O—, —CF═CF— or —C≡C— are preferred, and a single bond or an ethylene group is particularly preferred. Further, it is preferable that at least one of (A2) represents a single bond and at least two of (A3) represent a single bond.

  Ring Z is an aromatic ring and represents any one of the following general formulas (La) to (Lc).

In the formula, Y ^{a to} Y ^j each independently represent a hydrogen atom or a fluorine atom. In (La), at least one of Y ^a and Y ^b is preferably a fluorine atom, and in (Lb), At least one of Y ^{d to} Y ^f is preferably a fluorine atom, particularly preferably Y ^d is a fluorine atom, and in (Lc), at least one of Y ^h and Y ⁱ is a fluorine atom. In particular, Y ^h is more preferably a fluorine atom.

Terminal group P ^a represents a fluorine atom, a chlorine atom, trifluoromethoxy group, difluoromethoxy group, trifluoromethyl group or difluoromethyl group, two or more carbon atoms substituted by fluorine atoms 2 or 3 alkoxy groups, 2 An alkyl group having 2 or 3 carbon atoms substituted by 2 or more fluorine atoms, an alkenyl group having 2 or 3 carbon atoms substituted by 2 or more fluorine atoms, or a carbon substituted by 2 or more fluorine atoms Although an alkenyloxy group having 2 or 3 atoms is represented, a fluorine atom, a trifluoromethoxy group or a difluoromethoxy group is preferable, and a fluorine atom is particularly preferable.

  The third component is a so-called cyano p-type liquid crystal compound, and examples thereof include compounds represented by the following general formulas (B1) to (B3).

In the above formula, R ^c represents an alkyl group having 1 to 12 carbon atoms, which may be linear or branched, and has a 3- to 6-membered cyclic structure. Any —CH ₂ — present in the group may be replaced by —O—, —CH═CH—, —CH═CF—, —CF═CH—, —CF═CF— or —C≡C—. Any hydrogen atom present in the group may be substituted with a fluorine atom or a trifluoromethoxy group, but a linear alkyl group having 1 to 7 carbon atoms, 2 to 2 carbon atoms A linear 1-alkenyl group having 7 carbon atoms, a linear 3-alkenyl group having 4 to 7 carbon atoms, and an alkyl group having 1 to 5 carbon atoms substituted at the terminal by an alkoxy group having 1 to 3 carbon atoms. preferable. Further, when asymmetric carbon is generated by branching, the compound may be optically active or racemic.

  Ring D, Ring E and Ring F may be each independently substituted with a trans-1,4-cyclohexylene group, a transdecahydronaphthalene-trans-2,6-diyl group, or one or more fluorine atoms. A good 1,4-phenylene group, a naphthalene-2,6-diyl group optionally substituted by one or more fluorine atoms, a tetrahydronaphthalene-2,6-optionally substituted by one or more fluorine atoms Diyl group, 1,4-cyclohexenylene group optionally substituted by a fluorine atom, 1,3-dioxane-trans-2,5-diyl group, pyrimidine-2,5-diyl group or pyridine-2,5 -Represents a diyl group, but is substituted by a trans-1,4-cyclohexylene group, a transdecahydronaphthalene-trans-2,6-diyl group, or a fluorine atom. Preferred also good naphthalene-2,6-diyl group or 1-2 by fluorine atoms may be substituted 1,4-phenylene group. In particular, when ring E is a trans-1,4-cyclohexylene group or a transdecahydronaphthalene-trans-2,6-diyl group, ring D may be a trans-1,4-cyclohexylene group. Preferably, when Ring F is a trans-1,4-cyclohexylene group or a transdecahydronaphthalene-trans-2,6-diyl group, Ring D and Ring E are trans-1,4-cyclohexylene groups. Preferably there is. In (B3), ring D is preferably a trans-1,4-cyclohexylene group.

L ^d , ^Le and L ^f are each a linking group and each independently represents a single bond, an ethylene group (—CH ₂ CH ₂ —), a 1,2-propylene group (—CH (CH ₃ ) CH ₂ — and ) —CH ₂ CH (CH ₃ ) —), 1,4-butylene group, —COO—, —OCO—, —OCF ₂ —, —CF ₂ O—, —CH═CH—, —CH═CF—, —CF═CH—, —CF═CF—, —C≡C—, —OCH ₂ —, —CH ₂ O— or —CH═NN═CH— represents a single bond, ethylene group, —COO—, —OCF ₂ —, —CF ₂ O—, —CF═CF— or —C≡C— are preferred, and a single bond, an ethylene group or —COO— is particularly preferred. In the general formula (B2), at least one of them preferably represents a single bond. In the general formula (B3), at least two of them preferably represent a single bond.

P ^b represents a cyano group.

  Ring Y is an aromatic ring and represents any one of the following general formulas (Ld) to (Lf).

In the formula, Y ^{k to} Y ^q each independently represent a hydrogen atom or a fluorine atom. In (Ld), at least one of Y ^k and Y ^l is preferably a fluorine atom, and in (Le) , Y ^{m to} Y ^o are preferably fluorine atoms, particularly Y ^m is more preferably a fluorine atom, and in (Lf), at least one of Y ^p and Y ^q is a fluorine atom. preferably there, it is further preferred, especially Y ^p is a fluorine atom.

  The fourth component is a so-called nonpolar liquid crystal compound having a dielectric anisotropy of about −1 to +5, and examples thereof include compounds represented by the following general formulas (C1) to (C3).

In the above formula, R ^d and ^Pe each independently represent an alkyl group having 1 to 12 carbon atoms, which may be linear or branched, and may be a 3- to 6-membered ring. Any —CH ₂ — that may have a cyclic structure and is present in the group is —O—, —CH═CH—, —CH═CF—, —CF═CH—, —CF═CF— or Any hydrogen atom present in the group may be substituted by —C≡C—, and may be substituted by a fluorine atom or a trifluoromethoxy group, but a linear alkyl having 1 to 7 carbon atoms Group, a linear 1-alkenyl group having 2 to 7 carbon atoms, a linear 3-alkenyl group having 4 to 7 carbon atoms, a linear alkoxy group having 1 to 3 carbon atoms, or a terminal having carbon atoms A linear alkyl group having 1 to 5 carbon atoms substituted by 1 to 3 alkoxy groups is preferred, At least one of them is a linear alkyl group having 1 to 7 carbon atoms, a linear 1-alkenyl group having 2 to 7 carbon atoms, or a linear 3-alkenyl group having 4 to 7 carbon atoms. Particularly preferred.

  Ring G, Ring H, Ring I and Ring J are each independently a trans-1,4-cyclohexylene group, a transdecahydronaphthalene-trans-2,6-diyl group, 1 to 2 fluorine atoms, or 1,4-phenylene group optionally substituted by a methyl group, naphthalene-2,6-diyl group optionally substituted by one or more fluorine atoms, substituted by 1 or 2 fluorine atoms A tetrahydronaphthalene-2,6-diyl group, a 1,4-cyclohexenylene group optionally substituted by 1 to 2 fluorine atoms, a 1,3-dioxane-trans-2,5-diyl group, Represents a pyrimidine-2,5-diyl group or a pyridine-2,5-diyl group, but in each compound, a transdecahydronaphthalene-trans-2,6-diyl group, one or more fluorine groups. A naphthalene-2,6-diyl group optionally substituted by an atom, a tetrahydronaphthalene-2,6-diyl group optionally substituted by one or two fluorine atoms, and may be substituted by a fluorine atom The number of 1,4-cyclohexenylene group, 1,3-dioxane-trans-2,5-diyl group, pyrimidine-2,5-diyl group or pyridine-2,5-diyl group is preferably within one. The other ring is preferably a trans-1,4-cyclohexylene group or a 1,4-phenylene group optionally substituted by 1 to 2 fluorine atoms or a methyl group. The total number of fluorine atoms present in ring G, ring H, ring I and ring J is preferably 2 or less, and preferably 0 or 1.

L ^g , L ^h and ^Li are each a linking group, each independently a single bond, an ethylene group (—CH ₂ CH ₂ —), a 1,2-propylene group (—CH (CH ₃ ) CH ₂ — and ) —CH ₂ CH (CH ₃ ) —), 1,4-butylene group, —COO—, —OCO—, —OCF ₂ —, —CF ₂ O—, —CH═CH—, —CH═CF—, —CF═CH—, —CF═CF—, —C≡C— or —CH═NN═CH—, each represents a single bond, ethylene group, 1,4-butylene group, —COO—, —OCO—, —OCF ₂ —, —CF ₂ O—, —CF═CF—, —C≡C— or —CH═NN═CH— are preferred, and in general formula (C2), at least one of them is represented by general formula (C3 ), At least two of them preferably represent a single bond.

  The compounds represented by the general formulas (C1) to (C3) exclude the compounds represented by the general formulas (A1) to (A3) and the compounds represented by the general formulas (B1) to (B3).

  In the compounds represented by the general formulas (A1) to (A3), the general formulas (B1) to (B3), and the compounds represented by the general formulas (C1) to (C3), heteroatoms are directly bonded to each other. There is no structure. The general formulas (C1) to (C3) are represented by the general formula (LC6-a) to the general formula (LC6-m).

(In the formula, R ^LC61 and R ^LC62 are each independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or 2 to 7 carbon atoms. It is more preferable that it is 1 type, or 2 or more types of compounds chosen from the group which consists of a compound represented by this.

  The fifth component is an optically active compound used to induce a helical structure in the liquid crystal composition. A compound having an asymmetric carbon atom is preferable, and a compound having a 1-methylheptyloxy group is more preferable.

  The sixth component is a compound having a polymerizable functional group that can be polymerized by ultraviolet irradiation or heating, which is added to improve the response speed or improve the orientation of the liquid crystal composition. The polymerizable group is preferably an acryloxy group or a methacryloxy group, and more preferably a methacryloxy group. Moreover, it is preferable to have 1 to 3 polymerizable functional groups, and it is more preferable to have 2 polymerizable functional groups.

  The seventh component is a so-called fluorine-based (halogen-based) n-type liquid crystal compound, and examples thereof include compounds represented by the following general formulas (F1) to (F3).

(In the ^{formula, R LC31, R LC32, R} LC41, R LC42, R LC51 and ^{R LC52} represents an alkyl group of 1-15 carbon atoms each independently one or two or more of the alkyl group The CH ₂ group may be substituted with —O—, —CH═CH—, —CO—, —OCO—, —COO— or —C≡C— so that the oxygen atom is not directly adjacent to the alkyl group. one or more hydrogen atoms in the group may be optionally substituted by a halogen ^{atom, a LC31, a LC32, a} LC41, a LC42, a LC51 and ^{a LC52} each independently any of the following Structure

(In the structure, one or more CH ₂ groups in the cyclohexylene group may be substituted with an oxygen atom, and one or more CH groups in the 1,4-phenylene group are nitrogen atoms. And one or more hydrogen atoms in the structure may be substituted with Cl, CF _3, or OCF ₃ ), Z ^LC31 , Z ^{LC32, Z LC41, Z LC42,} Z LC51 and ^{Z LC51} each independently represent a single bond, -CH = CH -, - C≡C -, - CH 2 CH 2 -, - (CH 2) 4 -, - COO _{-, - OCH 2 -, -} CH 2 O -, - OCF 2 - or _-CF 2 O-a represents, ^{Z 5} represents a CH ₂ group or an oxygen ^{atom, X LC41} represents a hydrogen atom or a fluorine atom, m ^{LC31, m LC32, m LC41,} m L ^{42, m LC51} and ^{m LC52} represent 0-3 ^{independently, m LC31 + m LC32, m} LC41 + m LC42 and ^m LC51 ^{+ m LC52} is 1, 2 or ^{3, A LC31 ~A LC52, Z} LC31 ~ When there are a plurality of Z ^LC52s , they may be the same or different. It is preferable that it is 1 type, or 2 or more types of compounds chosen from the compound group represented by this.

R ^{LC31 to} R ^LC52 are each independently preferably an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms. Most preferably,

(In the formula, it shall be bonded to the ring structure at the right end.)
A ^{LC31 to} A ^LC52 each independently preferably have the following structure:

Z ^{LC31 to} Z ^LC51 are each independently a single bond, —CH ₂ O—, —COO—, ^—OCO— , —CH ₂ CH ₂ —, —CF ₂ O—, —OCF ₂ — or —OCH ₂ —. preferable.

  The general formula (F1) is represented by the following general formula (LC3-a) and general formula (LC3-b).

(Wherein R ^LC31 , R ^LC32 , A ^LC31 and Z ^LC31 each independently represent the same meaning as R ^LC31 , R ^LC32 , A ^LC31 and Z ^LC31 in the general formula (F1), and X ^{LC3b1 to} X ^LC3b6 are Represents a hydrogen atom or a fluorine atom, and at least one of X ^LC3b1 and X ^LC3b2 or X ^LC3b3 and X ^LC3b4 represents a fluorine atom, m ^LC3a1 is 1, 2 or 3, and m ^LC3b1 is 0 or 1 and when there are a plurality of A ^LC31 and Z ^LC31 , they may be the same or different.) Or one or more compounds selected from the group of compounds represented by Is preferred.
R ^LC31 and R ^LC32 are each independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 2 to 7 carbon atoms. Is preferably represented.
A ^LC31 preferably represents a 1,4-phenylene group, a trans-1,4-cyclohexylene group, a tetrahydropyran-2,5-diyl group, or a 1,3-dioxane-2,5-diyl group. , 4-phenylene group and trans-1,4-cyclohexylene group are more preferable.
Z ^LC31 is a single _{bond, -CH 2 O -, - COO} -, - OCO -, - CH 2 CH 2 - is preferred to represent, and more preferably a single bond.
The general formula (LC3-a) preferably represents the following general formula (LC3-a1) to general formula (LC3-a4).

(In the formula, R ^LC31 and R ^LC32 each independently represent the same meaning as R ^LC31 and R ^LC32 in General Formula (LC3).)
R ^LC31 and R ^LC32 are each independently preferably an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms, and R ^LC31 has 1 carbon atom. It is more preferable that R 7 represents an alkyl group having ^˜7 , and R ^LC32 represents an alkoxy group having 1 to 7 carbon atoms.

  As general formula (LC3-b), it is preferable to represent the following general formula (LC3-b1) to general formula (LC3-b12), and general formula (LC3-b1), general formula (LC3-b6), and general formula (LC3-b8) and general formula (LC3-b11) are more preferable, general formula (LC3-b1) and general formula (LC3-b6) are more preferable, and general formula (LC3-b1) is represented. Most preferably it represents.

(In the formula, R ^LC31 and R ^LC32 each independently represent the same meaning as R ^LC31 and R ^LC32 in General Formula (LC3).)
R ^LC31 and R ^LC32 are each independently preferably an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms, and R ^LC31 has 2 carbon atoms. Or an alkyl group having 3 carbon atoms, and more preferably R ^LC32 represents an alkyl group having 2 carbon atoms.

  The general formula (F2) is represented by the following general formula (LC4-a) to general formula (LC4-c), and the general formula (F3) is represented by the following general formula (LC5-a) to general formula (LC5-c):

^{(Wherein, R LC41,} R ^LC42 and ^{X LC41} each independently represent the same meaning as ^{R LC41, R LC42} and ^{X LC41} in the general formula ^{(F2), R LC51} and ^{R LC52} is the general independently It represents the same meaning as ^{R LC51} and ^{R LC52} in formula ^{(LC5), Z LC4a1, Z} LC4b1, Z LC4c1, Z LC5a1, Z LC5b1 and ^{Z LC5c1} each independently represent a single bond, -CH = CH -, - C≡ C—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —COO—, —OCH ₂ —, —CH ₂ O—, —OCF ₂ — or —CF ₂ O—. More preferably, it is one or more compounds selected from the group consisting of the following compounds.

^{R LC41,} R LC42, R ^LC51 and ^{R LC52} each independently represents an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, the number alkenyl group or a carbon atom of 2 to 7 carbon atoms 2 It preferably represents -7 alkenyloxy groups.

Z ^{LC4a1 to} Z ^LC5c1 each independently preferably represents a single bond, —CH ₂ O—, ^{—COO—, —OCO—} , —CH ₂ CH ₂ —, and more preferably represents a single bond.

  3rd of this invention is a liquid crystal display composition provided with the liquid crystal composition containing the compound represented by General formula (1). The liquid crystal display device using the liquid crystal composition containing the compound of the present invention is useful for achieving both high-speed response and suppression of display failure, and is particularly useful for a liquid crystal display device for active matrix driving. It can be applied to liquid crystal display elements for mode, PSVA mode, PSA mode, IPS mode, FFS mode or ECB mode.

  Hereinafter, examples of using the liquid crystal compound (general formula (1)) according to the present invention as a p-type liquid crystal composition in a liquid crystal display element will be described with reference to the drawings. The embodiment will be described in detail. Needless to say, the scope of the present invention is not limited to the drawings, and the liquid crystalline compound according to the present invention can also be used in an n-type liquid crystal composition and a liquid crystal display device including the same.

  FIG. 1 is a cross-sectional view showing a liquid crystal display element including two substrates facing each other, a sealing material provided between the substrates, and liquid crystal sealed in a sealing region surrounded by the sealing material. It is.

Specifically, the TFT layer 102 and the pixel electrode 103 are provided on the substrate a100, the backplane on which the passivation film 104 and the alignment film a105 are provided, and the black matrix 202, the color filter 203, A planarizing film (overcoat layer) 201 and a transparent electrode 204 are provided, an alignment film b205 is provided thereon, a front plane facing the back plane, a sealing material 301 provided between the substrates, and the seal A specific mode of a liquid crystal display element including a liquid crystal layer 303 sealed in a sealing region surrounded by a material and provided with a protrusion 304 on a substrate surface in contact with the sealing material 301 is shown.
The substrate a or the substrate b is not particularly limited as long as it is substantially transparent, and glass, ceramics, plastics, or the like can be used. Examples of plastic substrates include cellulose derivatives such as cellulose, triacetyl cellulose, diacetyl cellulose, polycycloolefin derivatives, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polypropylene, and polyethylene. Polyolefin, polycarbonate, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyamide, polyimide, polyimide amide, polystyrene, polyacrylate, polymethyl methacrylate, polyether sulfone, polyarylate, and glass fiber-epoxy resin Inorganic-organic composite materials such as glass fiber and acrylic resin can be used.

  When a plastic substrate is used, it is preferable to provide a barrier film. The function of the barrier film is to reduce the moisture permeability of the plastic substrate and to improve the reliability of the electrical characteristics of the liquid crystal display element. The barrier film is not particularly limited as long as it has high transparency and low water vapor permeability. Generally, vapor deposition, sputtering, chemical vapor deposition method (CVD method) using an inorganic material such as silicon oxide is used. ) Is used.

  In the present invention, the same material or different materials may be used as the substrate a or the substrate b, and there is no particular limitation. Use of a glass substrate is preferable because a liquid crystal display element having excellent heat resistance and dimensional stability can be produced. In addition, a plastic substrate is preferable because it is suitable for a manufacturing method using a roll-to-roll method and is suitable for weight reduction or flexibility. For the purpose of imparting flatness and heat resistance, good results can be obtained by combining a plastic substrate and a glass substrate.

  In the backplane, a TFT layer 102 and a pixel electrode 103 are provided on a substrate a100. These are manufactured by a normal array process. A backplane is obtained by providing a passivation film 104 and an alignment film a105 thereon.

  A passivation film 104 (also referred to as an inorganic protective film) is a film for protecting the TFT layer. Usually, a nitride film (SiNx), an oxide film (SiOx), or the like is formed by a chemical vapor deposition (CVD) technique or the like.

  The alignment film a105 is a film having a function of aligning liquid crystals, and a polymer material such as polyimide is usually used in many cases. As the coating solution, an alignment agent solution composed of a polymer material and a solvent is used. Since the alignment film may hinder the adhesive force with the sealing material, a pattern is applied in the sealing region. For the application, a printing method such as a flexographic printing method or a droplet discharge method such as an ink jet is used. The applied alignment agent solution is crosslinked and cured by baking after the solvent is evaporated by temporary drying. Thereafter, an alignment process is performed to provide an alignment function.

  The alignment treatment is usually performed by a rubbing method. The polymer film formed as described above is rubbed in one direction using a rubbing cloth made of fibers such as rayon, thereby producing liquid crystal alignment ability.

  Moreover, the photo-alignment method may be used. The photo-alignment method is a method of generating alignment ability by irradiating polarized light on an alignment film containing an organic material having photosensitivity, and does not cause the generation of scratches or dust on the substrate due to the rubbing method. Examples of the organic material in the photo-alignment method include a material containing a dichroic dye. Dichroic dyes include molecular orientation induction or isomerization reaction (eg azobenzene group), dimerization reaction (eg cinnamoyl group), photocrosslinking reaction (eg benzophenone group) due to Weigert effect due to photodichroism. Alternatively, those having a group (hereinafter abbreviated as a photo-alignment group) that causes a photoreaction that causes liquid crystal alignment ability, such as a photolysis reaction (eg, polyimide group), can be used. After the solvent is evaporated by temporary drying, the applied alignment agent solution is irradiated with light having an arbitrary deflection (polarized light), whereby an alignment film having alignment ability in an arbitrary direction can be obtained.

  One front plane is provided with a black matrix 202, a color filter 203, a planarization film 201, a transparent electrode 204, and an alignment film b205 on a substrate b200.

  The black matrix 202 is produced by, for example, a pigment dispersion method. Specifically, a color resin solution in which a black colorant is uniformly dispersed for forming a black matrix is applied on a substrate b200 provided with a barrier film 201, thereby forming a colored layer. Subsequently, the colored layer is baked and cured. A photoresist is applied on this and prebaked. After exposing the photoresist through a mask pattern, development is performed to pattern the colored layer. Thereafter, the photoresist layer is peeled off and the colored layer is baked to complete the black matrix 202.

  Alternatively, a photoresist type pigment dispersion may be used. In this case, a photoresist-type pigment dispersion is applied, pre-baked, exposed through a mask pattern, and then developed to pattern the colored layer. Thereafter, the photoresist layer is peeled off and the colored layer is baked to complete the black matrix 202.

  The color filter 203 is created by a pigment dispersion method, an electrodeposition method, a printing method, a dyeing method, or the like. Taking the pigment dispersion method as an example, a color resin solution in which a pigment (for example, red) is uniformly dispersed is applied onto the substrate b200, and after baking and curing, a photoresist is applied thereon and prebaked. After the photoresist is exposed through a mask pattern, development is performed and patterning is performed. Thereafter, the photoresist layer is peeled off and baked again to complete the (red) color filter 203. There is no particular limitation on the color order to be created. Similarly, a green color filter 203 and a blue color filter 203 are formed.

  The transparent electrode 204 is provided on the color filter 203 (an overcoat layer (201) may be provided on the color filter 203 for planarization as necessary). The transparent electrode 204 preferably has a high transmittance, and preferably has a low electrical resistance. The transparent electrode 204 is formed by sputtering an oxide film such as ITO.

  In addition, a passivation film may be provided on the transparent electrode 204 for the purpose of protecting the transparent electrode 204.

  The alignment film b205 is the same as the alignment film a105 described above.

  Although specific embodiments of the backplane and the front plane used in the present invention have been described above, the present invention is not limited to the specific embodiments, and changes in the embodiments according to the desired liquid crystal display element are possible. Is free.

  The shape of the columnar spacer is not particularly limited, and the horizontal cross section can be various shapes such as a circle and a polygon such as a quadrangle. A polygonal shape is particularly preferable. The protrusion shape is preferably a truncated cone or a truncated pyramid.

  The material of the columnar spacer is not particularly limited as long as it is a sealing material, an organic solvent used for the sealing material, or a material that does not dissolve in liquid crystal, but it may be a synthetic resin (curable resin) in terms of processing and weight reduction. preferable. On the other hand, the protrusion can be provided on the surface of the first substrate in contact with the sealing material by a photolithography method or a droplet discharge method. For these reasons, it is preferable to use a photocurable resin suitable for a photolithography method or a droplet discharge method.

  As an example, a case where the front columnar spacer is obtained by photolithography will be described.

  On the transparent electrode 204 of the front plane, a resin solution for forming columnar spacers (not containing a colorant) is applied. Subsequently, the resin layer is baked and cured. A photoresist is applied on this and prebaked. After exposing the photoresist through a mask pattern, development is performed to pattern the resin layer. Thereafter, the photoresist layer is peeled off, and the resin layer is baked to complete the columnar spacer.

  The formation position of the columnar spacer can be determined at a desired position by a mask pattern. Therefore, both the inside of the sealing region of the liquid crystal display element and the outside of the sealing region (sealing material application portion) can be created at the same time. The columnar spacer is preferably formed so as to be positioned on the black matrix so that the quality of the sealing region does not deteriorate. A columnar spacer manufactured by a photolithography method in this way is sometimes called a column spacer or a photospacer.

  As the material of the spacer, a negative water-soluble resin such as PVA-stilbazo photosensitive resin, a mixture of a polyfunctional acrylic monomer, an acrylic acid copolymer, a triazole initiator, or the like is used. Alternatively, there is a method using a color resin in which a colorant is dispersed in a polyimide resin. In the present invention, there is no particular limitation, and a spacer can be obtained from a known material in accordance with the compatibility with the liquid crystal or the sealing material to be used.

  Thus, after providing a columnar spacer on the surface to be a sealing region on the front plane, a seal material (301 in FIG. 1) is applied to the surface of the back plane that contacts the seal material.

  The material of the sealing material is not particularly limited, and a curable resin composition obtained by adding a polymerization initiator to an epoxy or acrylic photocurable, thermosetting, or photothermal combination curable resin is used. In order to control moisture permeability, elastic modulus, viscosity, etc., fillers made of inorganic or organic substances may be added. The shape of these fillers is not particularly limited, and includes a spherical shape, a fiber shape, and an amorphous shape. Furthermore, in order to control the cell gap satisfactorily, a spherical or fibrous gap material having a monodisperse diameter is mixed, or in order to further strengthen the adhesive force with the substrate, a fibrous substance that is easily entangled with the protrusions on the substrate is used. You may mix. The diameter of the fibrous material used at this time is desirably about 1/5 to 1/10 or less of the cell gap, and the length of the fibrous material is desirably shorter than the seal coating width.

  The material of the fibrous substance is not particularly limited as long as a predetermined shape can be obtained, and synthetic fibers such as cellulose, polyamide and polyester, and inorganic materials such as glass and carbon can be appropriately selected.

  As a method for applying the sealing material, there are a printing method and a dispensing method, but a dispensing method with a small amount of the sealing material used is desirable. The application position of the sealing material is usually on the black matrix so as not to adversely affect the sealing area. In order to form a liquid crystal dropping region in the next step (so that the liquid crystal does not leak), the sealing material application shape is a closed loop shape.

  Liquid crystal is dropped onto the closed loop shape (sealing region) of the front plane to which the sealing material is applied. Usually a dispenser is used. Since the amount of liquid crystal to be dropped coincides with the volume of the liquid crystal cell, the amount is basically the same as the volume obtained by multiplying the height of the column spacer and the seal application area. However, in order to optimize liquid crystal leakage and display characteristics in the cell bonding process, the amount of liquid crystal to be dropped may be adjusted as appropriate, or the liquid crystal dropping position may be dispersed.

  Next, a back plane is bonded to the front plane on which the sealing material is applied and liquid crystal is dropped. Specifically, the front plane and the back plane are adsorbed on a stage having a mechanism for adsorbing a substrate such as an electrostatic chuck, and the alignment film b on the front plane and the alignment film a on the back plane face each other. It is arranged at a position (distance) where the sealing material does not contact the other substrate. In this state, the system is depressurized. After decompression is completed, the positions of both substrates are adjusted while confirming the bonding position between the front plane and the back plane (alignment operation). When the adjustment of the bonding position is completed, the substrate is brought close to a position where the sealing material on the front plane and the back plane are in contact with each other. In this state, the system is filled with an inert gas, and the pressure is gradually returned to normal pressure while releasing the reduced pressure. At this time, the front plane and the back plane are bonded together by atmospheric pressure, and a cell gap is formed at the height of the columnar spacer. In this state, the sealing material is irradiated with ultraviolet rays to cure the sealing material, thereby forming a liquid crystal cell. Thereafter, a heating step is added in some cases to promote curing of the sealing material. A heating process is often added to enhance the adhesive strength of the sealing material and improve the reliability of electrical characteristics.

  EXAMPLES Hereinafter, although an Example is given and this invention is further explained in full detail, this invention is not limited to these Examples.

  The phase transition temperature was measured using a polarizing microscope equipped with a temperature control stage and a differential scanning calorimeter (DSC).

  “%” In the compositions of the following examples and comparative examples means “mass%”.

T _n−i represents a transition temperature between a nematic phase and an isotropic phase.

  The following abbreviations are used in compound descriptions.

THF: tetrahydrofuran, DMF: N, N-dimethylformamide Me: methyl group, Ph: phenyl group, Ts: p-toluenesulfonyl group py: pyridine, Tf: trifluoromethanesulfonyl group PPTS: pyridinium p-toluenesulfonate DHP: 3 , 4-Dihydro-2H-pyran THP: Tetrahydro-2H-pyran-2-yl group dppf: 1,1′-bis (diphenylphosphino) ferrocene amphos: di-t-butyl (p-dimethylaminophenyl) phosphine ( Example 1) Synthesis of 2- (3-buten-1-yl) -6- (4'-ethyl-3-fluoro- [1,1'-biphenyl] -4-yl) naphthalene

(1-1) Under a nitrogen atmosphere, methyl 6-bromo-2-naphthoate (80.0 g), tetrakis (triphenylphosphine) palladium (0) (1.7 g), 2 mol / L aqueous potassium carbonate solution (302 mL) and THF (400 mL) was mixed and heated to 60 ° C. Under heating, a solution of (4′-ethyl-3-fluoro- [1,1′-biphenyl] -4-yl) boric acid (81.1 g) in THF (400 mL) was added dropwise and the mixture was heated at 60 ° C. for 3.5 hours. Stir. The mixture was allowed to cool to room temperature, water and a saturated aqueous ammonium chloride solution were added, the aqueous layer was separated, extracted with a THF / toluene mixed solvent, the organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, the residue was purified by silica gel column chromatography, and suspended and washed with acetone to give 6- (4′-ethyl-3-fluoro- [1,1′-biphenyl] -4-yl). Methyl-2-naphthoate (103.1 g) was obtained.

(1-2) Under a nitrogen atmosphere, to a mixture of lithium aluminum hydride (10.1 g) and THF (100 mL), add 6- (4′-ethyl-3-fluoro- [1,1′-biphenyl] -4- A solution of methyl yl) -2-naphthoate (102.0 g) in THF (500 mL) was added dropwise under ice cooling, and the mixture was stirred at room temperature for 2 hours. Under ice-cooling, water, 10% hydrochloric acid and toluene were added, and the aqueous layer was separated and extracted with a THF / toluene mixed solvent. The organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and 2- (4′-ethyl-3-fluoro- [1,1′-biphenyl] -4-yl) -6-hydroxymethylnaphthalene (91.4 g) was suspended and washed with toluene. )

(1-3) 2- (4′-ethyl-3-fluoro- [1,1′-biphenyl] -4-yl) -6-hydroxymethylnaphthalene (86.3 g), p-toluenesulfonyl under nitrogen atmosphere To a solution of chloride (50.8 g) and DMF (350 mL), pyridine (1.9 g) was added dropwise at room temperature and stirred for 3 hours. Water was added, and the precipitated solid was collected by filtration, washed with methanol, and then suspended and washed with acetone to give 2-chloromethyl-6- (4′-ethyl-3-fluoro- [1,1′-biphenyl]. -4-yl) naphthalene (87.2 g) was obtained.

(1-4) 2-chloromethyl-6- (4′-ethyl-3-fluoro- [1,1′-biphenyl] -4-yl in a 2 mol / L allylmagnesium chloride THF solution (174 mL) under a nitrogen atmosphere ) A solution of naphthalene (87.0 g) in THF (870 mL) was added dropwise at room temperature and stirred for 2 hours. Water and hydrochloric acid were added, and the aqueous layer was separated and extracted with toluene. The organic layers were combined, washed twice with saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, the residue was purified by silica gel column chromatography, and recrystallized twice from acetone and once from a hexane / toluene mixed solvent to give 2- (3-buten-1-yl) -6- ( 4′-Ethyl-3-fluoro- [1,1′-biphenyl] -4-yl) naphthalene (69.2 g) was obtained.
MS m / z: 380 [M ⁺ ]
Phase transition temperature (° C.): Cr 107 N 234 Iso
¹ HNMR (CDCl ₃ , TMS internal standard) δ (ppm) = 1.30 (t, 3H, J = 7.6 Hz), 2.48 (m, 2H), 2.72 (q, 2H, J = 7) .6 Hz), 2.90 (t, 2H, J = 8.0 Hz), 5.05 (m, 2H), 5.90 (m, 1H), 7.39 (m, 5H), 7.64 ( m, 5H), 7.85 (m, 2H), 8.03 (s, 1H)
Example 2 Synthesis of 2- (4′-ethyl-3-fluoro- [1,1′-biphenyl] -4-yl) -6-propylnaphthalene

(2-1) 2-Bromo-6-methoxynaphthalene (100.0 g) and dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloromethane adduct (0.7 g) under nitrogen atmosphere To a THF (2000 mL) solution, 1 mol / L propylmagnesium chloride THF solution (635 mL) was added dropwise at room temperature and stirred for 16 hours. The reaction solution was added to hydrochloric acid at 0 ° C., and the aqueous layer was separated and extracted twice with toluene. The organic layers were combined, washed with a saturated aqueous sodium hydrogen carbonate solution and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 2-methoxy-6-propylnaphthalene (74.2 g).

(2-2) A 1 mol / L boron tribromide dichloromethane solution (550 mL) was added dropwise at 0 ° C. to a dichloromethane solution (550 mL) of 2-methoxy-6-propylnaphthalene (74.2 g) in a nitrogen atmosphere. For 2 hours and at room temperature for 4 hours. The reaction solution was added to ice water, and the aqueous layer was separated and extracted twice with dichloromethane. The organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 6-propylnaphthalen-2-ol (55.1 g).

(2-1) A solution of 6-propylnaphthalen-2-ol (50.0 g) and pyridine (25.5 g) in dichloromethane (200 mL) was added to trifluoromethanesulfonic anhydride (79.7 g) in dichloromethane (150 mL). The solution was added dropwise at 0 ° C. and stirred for 2.5 hours. Hydrochloric acid was added at 0 ° C., and the organic layer was washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 6-propyl-2-naphthyl trifluoromethanesulfonate (79.1 g).

(2-2) 6-propyl-2-naphthyl trifluoromethanesulfonate (31.8 g), tetrakis (triphenylphosphine) palladium (0) (0.6 g), 2 mol / L aqueous potassium carbonate solution (75 mL) under nitrogen atmosphere ) And toluene (80 mL) were mixed and heated to 60 ° C. Under heating, a solution of (4′-ethyl-3-fluoro- [1,1′-biphenyl] -4-yl) boric acid (24.4 g) in ethanol (122 mL) was added dropwise, and the mixture was heated at 60 ° C. for 3.5 hours. Stir. The mixture was allowed to cool to room temperature, water and toluene were added, the aqueous layer was separated, extracted with toluene, the organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, the residue was purified by silica gel column chromatography, and recrystallized twice from an acetone / methanol mixed solvent and once from a hexane / toluene mixed solvent to give 2- (4′-ethyl-3- Fluoro- [1,1′-biphenyl] -4-yl) -6-propylnaphthalene (22.6 g) was obtained.
MS m / z: 368 [M ⁺ ]
Phase transition temperature (° C.): Cr 118 N 232 Iso
¹ HNMR (CDCl ₃ , TMS internal standard) δ (ppm) = 0.99 (t, 3H, J = 7.2 Hz), 1.29 (t, 3H, J = 8.0 Hz), 1.75 (m , 2H), 2.74 (m, 4H), 7.40 (m, 5H), 7.63 (m, 5H), 7.84 (m, 2H), 8.02 (s, 1H)
Example 3 Synthesis of 2- (3-buten-1-yl) -6- [4- (trans-4-ethylcyclohexyl) -2-fluorophenyl] naphthalene

(3-1) Under a nitrogen atmosphere, methyl 6-bromo-2-naphthoate (25.0 g), tetrakis (triphenylphosphine) palladium (0) (5.4 g), 2 mol / L potassium carbonate aqueous solution (95 mL) and THF (125 mL) was mixed and heated to 50 ° C. Under heating, a solution of 4- (trans-4-ethylcyclohexyl) -2-fluorophenylboric acid (25.9 g) in THF (125 mL) was added dropwise, and the mixture was stirred at 50 ° C. for 11.5 hours. The mixture was ice-cooled, water and methanol were added, and the precipitated solid was collected by filtration and washed with water and methanol. Purification by silica gel column chromatography and suspension washing with acetone gave methyl 6- [4- (trans-4-ethylcyclohexyl) -2-fluorophenyl] -2-naphthoate (34.8 g).

(3-2) Under a nitrogen atmosphere, to a mixture of lithium aluminum hydride (3.9 g) and THF (35 mL), 6- [4- (trans-4-ethylcyclohexyl) -2-fluorophenyl] -2-naphtho A solution of methyl acid (34.8 g) in THF (175 mL) was added dropwise under ice cooling, and the mixture was stirred at room temperature for 4 hours. Under ice-cooling, water, 10% hydrochloric acid and toluene were added, and the aqueous layer was separated and extracted with a THF / toluene mixed solvent. The organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and 2- [4- (trans-4-ethylcyclohexyl) -2-fluorophenyl] -6-hydroxymethylnaphthalene (30.5 g) was obtained by suspension washing with toluene.

(3-3) 2- [4- (trans-4-ethylcyclohexyl) -2-fluorophenyl] -6-hydroxymethylnaphthalene (30.5 g), p-toluenesulfonyl chloride (17.6 g) under nitrogen atmosphere And pyridine (0.7g) was dripped at the solution of DMF (120mL) at room temperature, and it stirred for 2 hours. The mixture was ice-cooled, water was added, and the precipitated solid was collected by filtration and washed with water and methanol. By recrystallization from an acetone / methanol mixed solvent, 2-chloromethyl-6- [4- (trans-4-ethylcyclohexyl) -2-fluorophenyl] naphthalene (28.6 g) was obtained.

(3-4) 2 mol / L of 2-chloromethyl-6- [4- (trans-4-ethylcyclohexyl) -2-fluorophenyl] naphthalene (28.6 g) in THF (150 mL) was added under a nitrogen atmosphere. Allylmagnesium chloride THF solution (56 mL) was added dropwise at room temperature and stirred for 1.5 hours. Water, hydrochloric acid and toluene were added, and the organic layer was washed with hydrochloric acid and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, the residue was purified by silica gel column chromatography, and recrystallized once from an acetone / ethanol mixed solvent, once from acetone, and once from a hexane / toluene mixed solvent to give 2- (3-butene -1-yl) -6- [4- (trans-4-ethylcyclohexyl) -2-fluorophenyl] naphthalene (11.0 g) was obtained.
MS m / z: 386 [M ⁺ ]
Phase transition temperature (° C.): Cr 86 N 205 Iso
¹ HNMR (CDCl ₃ , TMS internal standard) δ (ppm) = 0.92 (t, 3H, J = 7.2 Hz), 1.06 (m, 2H), 1.27 (m, 3H), 1. 48 (dq, 2H, J = 2.8 Hz, 12.8 Hz), 1.94 (m, 4H), 2.50 (m, 3H), 2.89 (t, 2H, J = 8.0 Hz), 5.05 (m, 2H), 5.90 (m, 1H), 7.06 (m, 2H), 7.34-7.83 (m, 6H), 7.96 (s, 1H)
Example 4 Synthesis of 2- [4 ′-(3-buten-1-yl) -3-fluoro- [1,1′-biphenyl] -4-yl] -6-propylnaphthalene

(4-1) 3,4-Dihydro-2H-pyran (50.0 g) was added to a mixture of p-bromobenzyl alcohol (75.0 g), pyridinium p-toluenesulfonate (4.0 g) and dichloromethane (250 mL). Added at room temperature and stirred for 9 hours. Saturated aqueous sodium hydrogen carbonate solution was added at room temperature, washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 4-{[(tetrahydro-2H-pyran-2-yl) oxy] methyl} bromobenzene (113.0 g).

(4-2) Under a nitrogen atmosphere, a solution of 4-{[(tetrahydro-2H-pyran-2-yl) oxy] methyl} bromobenzene (113.0 g) in THF (315 mL) was added with 1.6 mol / L normal butyl. The lithium hexane solution was added dropwise at −70 ° C. and stirred for 1 hour, and then trimethyl borate (47.7 g) was added dropwise at −60 ° C. and stirred for 0.5 hour. The mixture was allowed to cool to room temperature, water and a saturated aqueous ammonium chloride solution were added, the aqueous layer was extracted with toluene, washed with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 4-{[(tetrahydro-2H-pyran-2-yl) oxy] methyl} phenyl boric acid (97.6 g).

(4-3) 6-propylnaphthalen-2-yltrifluoromethanesulfonic acid (183.0 g), dichloro [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloromethane adduct (under nitrogen atmosphere) 4.7 g), potassium acetate (180.0 g) and dimethyl sulfoxide (1200 mL) were mixed with bis (pinacolato) diboron (161.0 g) at 85 ° C. and stirred at 85 ° C. for 5 hours. It was ice-cooled, water was added, the aqueous layer was separated, extracted with toluene, the organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 4,4,5,5-tetramethyl-2- (6-propylnaphthalen-2-yl) -1,3,2-dioxaborolane (178.3 g).

(4-4) 4-Bromo-3-fluorophenol (100.0 g), dichlorobis [di-t-butyl (p-dimethylaminophenyl) phosphino] palladium (II) (1.9 g), 2 mol under nitrogen atmosphere / L Aqueous potassium carbonate (520 mL) and THF (500 mL) were mixed and heated to 60 ° C. Under heating, a solution of 4,4,5,5-tetramethyl-2- (6-propylnaphthalen-2-yl) -1,3,2-dioxaborolane (173.5 g) in THF (500 mL) was added dropwise. Stir at 0 ° C. for 3 hours. It was ice-cooled, water was added, the aqueous layer was separated, extracted with toluene, the organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 3-fluoro-4- (6-propylnaphthalen-2-yl) phenol (203.0 g).

(4-5) A solution of 3-fluoro-4- (6-propylnaphthalen-2-yl) phenol (203.0 g) and pyridine (50.0 g) in dichloromethane (400 mL) was added to trifluoromethanesulfonic anhydride ( A solution of 158.1 g) in dichloromethane (400 mL) was added dropwise at 0 ° C. and stirred for 5 hours. Water was added at 0 ° C., and the aqueous layer was separated and extracted with dichloromethane. The organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 3-fluoro-4- (6-propylnaphthalen-2-yl) phenyl trifluoromethanesulfonate (212.1 g).

(4-6) Trifluoromethanesulfonic acid 3-fluoro-4- (6-propylnaphthalen-2-yl) phenyl (127.0 g), dichlorobis [di-t-butyl (p-dimethylaminophenyl) under nitrogen atmosphere Phosphino] palladium (II) (2.0 g), 2 mol / L aqueous potassium carbonate solution (308 mL) and THF (635 mL) were mixed and heated to 60 ° C. Under heating, a solution of 4-{[(tetrahydro-2H-pyran-2-yl) oxy] methyl} phenyl boric acid (80.0 g) in THF (400 mL) was added dropwise and stirred at 60 ° C. for 20 hours. The mixture was cooled on ice, water was added, and the aqueous layer was separated and extracted with toluene. The organic layers were combined, washed with water, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, the residue was purified by column chromatography, and recrystallized from an acetone / methanol mixed solvent to give 2- (3-fluoro-4 ′-{[(tetrahydro-2H-pyran-2-yl )] Oxy] methyl}-[1,1′-biphenyl] -4-yl) -6-propylnaphthalene (109.9 g).

(4-7) 2- (3-fluoro-4 ′-{[(tetrahydro-2H-pyran-2-yl) oxy] methyl}-[1,1′-biphenyl] -4-yl) under nitrogen atmosphere -6-propylnaphthalene (109.9 g), THF (550 mL), methanol (110 mL) and concentrated hydrochloric acid (15 mL) were mixed and stirred at room temperature for 5 hours. The mixture was cooled on ice, water and methanol were added, and the precipitated solid was collected by filtration, washed with methanol, and recrystallized from an acetone / methanol mixed solvent to give 2- (3-fluoro-4′-hydroxymethyl- [1 , 1′-biphenyl] -4-yl) -6-propylnaphthalene (45.6 g).

(4-8) 2- (3-Fluoro-4′-hydroxymethyl- [1,1′-biphenyl] -4-yl) -6-propylnaphthalene (45.0 g), p-toluenesulfonyl under nitrogen atmosphere To a solution of chloride (25.5 g) and DMF (180 mL), pyridine (1.0 g) was added dropwise at room temperature and stirred for 4 hours. Water was added, and the precipitated solid was collected by filtration, washed with methanol, and suspended and washed with acetone to give 2- (3-fluoro-4′-chloromethyl- [1,1′-biphenyl] -4-yl. ) -6-propylnaphthalene (41.4 g) was obtained.

(4-9) 2- (3-Fluoro-4'-chloromethyl- [1,1'-biphenyl] -4-yl) -6-yl in a 2 mol / L allylmagnesium chloride THF solution (79 mL) under a nitrogen atmosphere A solution of propylnaphthalene (41.0 g) in THF (410 mL) was added dropwise at room temperature, and the mixture was stirred for 2 hours. Water and hydrochloric acid were added, and the aqueous layer was separated and extracted with toluene. The organic layers were combined, washed twice with saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, the residue was purified by silica gel column chromatography, and recrystallized from a mixed solvent of acetone and hexane / toluene to give 2- {4 ′-(3-buten-1-yl) -3-fluoro. -[1,1'-biphenyl] -4-yl} -6-propylnaphthalene (16.6 g) was obtained.
MS m / z: 394 [M ⁺ ]
Phase transition temperature (° C.): Cr 101 SmA 104 N 238 Iso
¹ HNMR (CDCl ₃ , TMS internal standard) δ (ppm) = 0.99 (t, 3H, J = 7.2 Hz), 1.76 (m, 2H), 2.43 (m, 2H), 2. 77 (m, 4H), 5.05 (m, 2H), 5.90 (m, 1H), 7.38 (m, 5H), 7.63 (m, 5H), 7.84 (m, 2H) ), 8.02 (s, 1H)
Example 5 Synthesis of 2- (3-buten-1-yl) -6- [4- (trans-4-ethylcyclohexyl) phenyl] naphthalene

(5-1) Under a nitrogen atmosphere, a solution of 4- (trans-4-ethylcyclohexyl) bromobenzene (53.4 g) in THF (150 mL) was added to a mixture of magnesium (5.3 g) and THF (5 mL) at -70. After dropwise addition at 0 ° C. and stirring for 1 hour, a solution of trimethyl borate (23.9 g) in THF (50 mL) was added dropwise at 0 ° C. and stirred for 1.5 hours at room temperature. The mixture was ice-cooled, water, hydrochloric acid and toluene were added, the aqueous layer was separated, extracted with a toluene / THF mixed solvent, the organic layers were combined, washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and 4- (trans-4-ethylcyclohexyl) phenyl boric acid (31.6 g) was obtained by suspension washing with hexane.

(5-2) Implemented except that 4- (trans-4-ethylcyclohexyl) phenyl boric acid was used instead of 4- (trans-4-ethylcyclohexyl) -2-fluorophenyl boric acid used in Example 3. 2- (3-Buten-1-yl) -6- [4- (trans-4-ethylcyclohexyl) phenyl] naphthalene was obtained by the method described in Example 3.
MS m / z: 368 [M ⁺ ]
¹ HNMR (CDCl ₃ , TMS internal standard) δ (ppm) = 0.93 (t, 3H, J = 7.2 Hz), 1.08 (m, 2H), 1.27 (m, 3H), 1. 50 (m, 2H), 1.93 (m, 4H), 2.50 (m, 3H), 2.88 (t, 2H, J = 8.0 Hz), 5.04 (m, 2H), 5 .90 (m, 1H), 7.33 (m, 3H), 7.63-7.84 (m, 6H), 7.9 (s, 1H)
Comparative Example 1 Synthesis of 4- (3-buten-1-yl) -4 ″ -ethyl-2′-fluoro-1,1 ′: 4 ′, 1 ′ ′-terphenyl

4- (3-buten-1-yl) -4 ″ -ethyl-2′-fluoro-1,1 ′: 4 ′, 1 ″ -terphenyl was synthesized by the method described in Japanese Patent No. 507074. .

Example 6 Preparation of Liquid Crystal Composition-1
Host liquid crystal composition (H) having the following composition

Was prepared. Here, the physical property values of (H) are as follows.

Nematic phase upper limit temperature (T _n−i ): 103.4 ° C.
Refractive index anisotropy (Δn): 0.099
80% of the base liquid crystal (H) and 2- (3-buten-1-yl) -6- (4′-ethyl-3-fluoro- [1,1′-biphenyl]-obtained in Example 1 A liquid crystal composition (MA) comprising 20% of 4-yl) naphthalene was prepared. The physical properties of this composition are as follows.

T _n−i : 123.5 ° C.
Δn: 0.1461
The prepared liquid crystal composition (MA) maintained a uniform nematic liquid crystal state for one month or more at room temperature.

(Example 7) Preparation of liquid crystal composition-2
Liquid crystal composed of 80% of the base liquid crystal (H) and 20% of 2- (4′-ethyl-3-fluoro- [1,1′-biphenyl] -4-yl) -6-propylnaphthalene obtained in Example 2 A composition (MB) was prepared. The physical properties of this composition are as follows.

T _n−i : 121.8 ° C.
Δn: 0.1468
The prepared liquid crystal composition (MB) maintained a uniform nematic liquid crystal state for one month or more at room temperature.

Comparative Example 2 Preparation of Liquid Crystal Composition-3
4- (3-buten-1-yl) -4 ″ -ethyl-2′-fluoro-1,1 ′ obtained in 80% of the base liquid crystal (H) and Comparative Example 1: 4 ′, 1 ′ ′ -A liquid crystal composition (MC) comprising 20% terphenyl was prepared. The physical properties of this composition are as follows.

T _n−i : 108.5 ° C.
Δn: 0.1325
The prepared liquid crystal composition (MC) maintained a uniform nematic liquid crystal state for one month or more at room temperature.

By comparing Examples 6 and 7 with Comparative Example 2, it was found that the present compound effectively increased T 1 _{→ i} and Δn.

Claims (8)

General formula (N)

(In the general formula (N), L ¹ , L ³ , L ⁴ and L ⁵ represent a hydrogen atom,
L ² represents a fluorine atom,
R ¹ and R ² each independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a hydrogen atom,
Z ¹ represents —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH ₂ CH ₂ —, —CF ₂ CF ₂ —, —CH═CH—, —CF═CF—. Or a single bond,
Z ² represents —CH ₂ O—, —OCH ₂ —, —CH ₂ CH ₂ —, —CH═CH— , —CF═CF—, —C≡C— or a single bond,
Ring A ¹ and Ring A ² are each independently
(A) 1,4-cyclohexylene group (the one present in the group -CH ₂ - or nonadjacent two or more -CH ₂ - is replaced by -O- or -S- Is also good.)
(B) 1,4-phenylene group (the hydrogen atom present in this group may be substituted with a fluorine atom)
(C) Naphthalene-2,6-diyl group (the hydrogen atom present in this group may be substituted with a fluorine atom)
Each of the groups (a) to (c) may be independently substituted with a cyano group, a fluorine atom or a chlorine atom,
a and b each independently represents 0, 1 or 2; ) A compound represented by In the general formula (1), A ¹ and A ² are each independently represented by at least one selected from the group consisting of the following formulas (1-1) to (1-3 7 ): Item 1. The compound according to Item 1.

The compound according to claim 1 or 2 , wherein a is 1 or 2 in the general formula (1). The compound according to any one of claims 1 to 3, wherein b is 0 in the general formula (1). In the general formula (1), independently ^of R ¹ and R ² are each any one of claims 1 represents an alkyl group or an alkenyl group of 2 to 1 0 carbon atoms having 1 to 10 carbon atoms 4 1 The compound according to item.   A p-type liquid crystal composition containing one or more compounds according to claim 1.   An n-type liquid crystal composition containing one or more compounds according to claim 1.   A liquid crystal display device using the liquid crystal composition according to claim 6.

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