JP5140983B2 - Compound having alkadienyl group as side chain and liquid crystal composition using the same - Google Patents

Description

  The present invention relates to a novel liquid crystal compound useful as a material for a liquid crystal display device and a liquid crystal composition containing the compound. Specifically, it has low viscosity, good compatibility with other liquid crystal compounds, and has appropriate refractive index anisotropy value and dielectric anisotropy value when used in liquid crystal display elements. Relates to a novel liquid crystal compound capable of obtaining steep electro-optical characteristics, a liquid crystal composition containing the compound, and a liquid crystal display device containing the liquid crystal composition.

In the liquid crystal display element, the classification based on the operation mode of the liquid crystal includes PC (phase change), TN (twisted nematic), STN (super twisted nematic), BTN (Bistable twisted nematic), ECB (electrically controlled birefringence), OCB ( optically compensated bend), IPS (in-plane switching), VA (vertical alignment), and the like. The classification based on the element driving method is PM (passive matrix) and AM (active matrix). PM (passive matrix) is classified into static and multiplex, and AM is classified into TFT (thin film transistor), MIM (metalinsulator metal), and the like.

These liquid crystal display elements contain a liquid crystal composition having appropriate physical properties. In order to improve the characteristics of the liquid crystal display element, the liquid crystal composition preferably has appropriate physical properties. General physical properties necessary for the liquid crystal compound that is a component of the liquid crystal composition are as follows.
(1) Chemical stability and physical stability.
(2) High clearing point. The clearing point is a liquid crystal phase-isotropic phase transition temperature.
(3) Low minimum temperature of the liquid crystal phase. The liquid crystal phase means a nematic phase, a smectic phase, or the like.
(4) Small viscosity.
(5) Appropriate optical anisotropy.
(6) Appropriate dielectric anisotropy. A compound having a large dielectric anisotropy often has a large viscosity.
(7) Large specific resistance.

  The liquid crystal composition is prepared by mixing many liquid crystal compounds. Therefore, it is preferable that the liquid crystal compound is well mixed with other liquid crystal compounds. Since the liquid crystal display element may be used at a temperature below freezing point, a liquid crystalline compound having good compatibility at a low temperature is preferable. A liquid crystalline compound having a high clearing point or a low minimum temperature of the liquid crystal phase contributes to a wide temperature range of the nematic phase in the liquid crystal composition. Preferred liquid crystal compositions have a small viscosity and optical anisotropy suitable for the mode of the liquid crystal display element. The large dielectric anisotropy of the liquid crystal compound contributes to the low threshold voltage of the liquid crystal composition. With such a liquid crystal composition, a liquid crystal display element having characteristics such as a wide usable temperature range, a short response time, a high contrast ratio, a low driving voltage, a low power consumption, and a high voltage holding ratio is obtained. be able to.

Conventionally, various compounds having an alkenyl group in the side chain have been synthesized as liquid crystalline compounds that can be suitably used for liquid crystal display elements such as TN, STN, and TFT, and some of them are practically used. . For example, the compounds represented by the following formulas (s-1) to (s-3) in Non-Patent Document 1 and Patent Document 1 are represented by the following formulas (s-4) and (s-5) in Patent Document 2. Patent documents 3 disclose compounds represented by the following formulas (s-6) and (s-7). Patent Documents 4 to 6 disclose compounds and compositions represented by the formulas (s-8) and (s-9). Further, compounds represented by the following formulas (s-10) and (s-11) in which fluorine is directly bonded to a double bond are disclosed in Patent Document 7, and compounds represented by the following formula (s-12) are disclosed in Patent Document 8. It is disclosed.

  However, the compounds represented by the formulas (s-1) to (s-7) are all highly smectic and cannot be used in a large amount in the composition. Furthermore, the compounds represented by the formulas (s-4) to (s-7) are highly viscous, and the compounds represented by the formulas (s-8) to (s-12) are insufficient in optical stability and thermal stability. There is.

  As other compounds having an alkadienyl group in the side chain, Patent Document 9 discloses a compound represented by the formula (s-13), and Patent Document 10 discloses a compound represented by the formula (s-14).

  Patent Document 11 discloses that the terminal group represented by the formula (s-15) is a polar group such as halogen, but does not disclose a compound having an alkadienyl group at the same time.

All of the compounds represented by the formulas (s-13) and (s-14) have a small dielectric anisotropy value, and a liquid crystal composition containing them cannot lower the driving voltage. Furthermore, the compound represented by the formula (s-13) has high viscosity and a small refractive index anisotropy value, and the compound represented by the formula (s-14) has extremely poor stability. Further, the compound represented by the formula (s-15) is required to be further improved such as a small elastic constant ratio (K ₃₃ / K ₁₁ ), insufficient compatibility, and a low maximum temperature of the nematic phase. Further preferred liquid crystal compounds, liquid crystal compositions and liquid crystal display elements are still desired.

Japanese Patent Laid-Open No. 61-83136 Japanese Patent Application No. 6-92740 German Patent Application Publication No. 19520246 JP 2002-294237 A Japanese Patent Laid-Open No. 10-102060 JP 2005-132998 A JP-T 6-500343 Publication Japanese National Patent Publication No. 4-502627 International Publication No. 96/022261 Pamphlet Special table 2001-500894 gazette International Publication No. 2002/093244 Pamphlet Mol. Cryst. Liq. Cryst., 122, 241 (1885)

  The first object of the present invention is to provide general physical properties necessary for a liquid crystal compound, that is, stability to heat, light, etc., small viscosity, appropriate refractive index anisotropy value, appropriate dielectric constant. It is to provide a liquid crystalline compound having anisotropy value and steep electro-optical characteristics, a wide temperature range of the nematic phase, and excellent compatibility with other liquid crystalline compounds, and in particular, a wide temperature range of the nematic phase. It is providing the liquid crystalline compound which has. The second object is to provide a liquid crystal composition containing this liquid crystalline compound and having a high upper limit temperature of the nematic phase, a lower lower limit temperature of the nematic phase, a small viscosity, an appropriate optical anisotropy, and a low threshold voltage. In particular, it is to provide a liquid crystal composition having a high maximum temperature of the nematic phase and a low minimum temperature of the nematic phase. A third object is to provide a liquid crystal display element containing this composition and having a wide temperature range that can be used, a short response time, a small power consumption, a large contrast, and a low driving voltage, and can be used in particular. A liquid crystal display device having a wide temperature range is provided.

As a result of intensive studies to solve the above problems, the present inventors have found that a compound having an alkadienyl group at one end of the molecule and a polar group such as halogen at the other end has a very large elastic constant ratio (K ₃₃ / K ₁₁ ), found to have very low viscosity, high chemical stability, wide nematic phase temperature range, large refractive index anisotropy value and dielectric anisotropy value. Furthermore, it has been found that when a liquid crystal composition containing the above compound is used, a liquid crystal display element having steep electro-optical characteristics, a short response time, a wide operating temperature range, and a small driving power can be produced. Therefore, the present inventors have found that the above compounds are suitable for liquid crystal display elements, particularly liquid crystal display elements such as TN, STN, and TFT, which are currently widely used, and have completed the present invention.

The gist of the present invention is as described in items 1 to 31 below.
1. The compound represented by General formula (1).

[Wherein R ¹ is hydrogen, alkyl having 1 to 5 carbons, or alkenyl having 2 to 5 carbons;
Ring A ¹ is 1,4-phenylene, in which any hydrogen may be replaced by halogen, and ring A ² and ring A ³ are independently 1,4-cyclohexylene, 1,4- Phenylene, 1,4-cyclohexenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, or 1,2,3,4-tetrahydronaphthalene-2,6-diyl, these Any —CH ₂ — in the ring may be replaced by —O— or —S—, and any —CH═ may be replaced by —N═, and any hydrogen in these rings May be replaced by halogen;
Z ¹ , Z ² and Z ³ are each independently a single bond, —CH ₂ CH ₂ —, —CH═CH—, —C≡C—, —COO—, —OCO—, —CF ₂ O—, — _{OCF 2 -, - CH 2 O} -, - OCH 2 -, - CF = CF -, - (CH 2) 4 -, - O (CH 2) 2 O -, - (CH 2) 2 CF 2 O-, _{- (CH 2) 2 OCF 2} -, - CF 2 O (CH 2) 2 -, - OCF 2 (CH 2) 2 -, - CH = CH-CH 2 O-, or -OCH ₂ -CH = CH- Is;
L ¹ and L ² are independently hydrogen or fluorine;
X ¹ is a group represented by hydrogen, fluorine, chlorine, —C≡N, —N═C═S, —SF ₅ , or —Q—W, Q is a single bond, oxygen, or sulfur; Is a C 1-5 alkyl in which at least one hydrogen is replaced by a halogen;
n and m are each independently 0 or 1, and p is an integer of 1 to 4. ]
2. Item 2. The compound according to Item ¹ , wherein Ring A ¹ , Ring A ² and Ring A ³ are independently 1,4-phenylene or halogenated 1,4-phenylene.
3. At least one of ring A ¹ , ring A ² and ring A ³ is halogenated 1,4-phenylene, and halogenated 1,4-phenylene is fluorinated 1,4-phenylene. Item 3. The compound according to Item 2.
4). Item 4. The compound according to Item 3, wherein the fluorinated 1,4-phenylene is 2-fluoro-1,4-phenylene or 2,6-difluoro-1,4-phenylene.
5). Item 2. The compound according to Item 1, wherein at least one of Ring A ¹ , Ring A ² and Ring A ³ is pyrimidine-2,5-diyl.
6). Item 6. The compound according to any one of Items 1 to 5, wherein at least one of Z ¹ , Z ² and Z ³ is a single bond.
7). Any one of Z ¹ , Z ² and Z ³ is —CH ₂ CH ₂ —, —CH═CH—, —C≡C—, —COO—, —OCO—, —CF ₂ O—, —OCF _{2 -, - CH 2 O -,} - OCH 2 -
Or the compound according to item 6, wherein -CF = CF-.
8). Item 7. The compound according to Item 6, wherein Z ¹ , Z ² and Z ³ are all single bonds.
9. Item 9. The compound according to any one of Items 1 to 8, wherein at least one of L ¹ , L ² and X ¹ is halogen.
10. Item 2. The compound according to item 1, represented by any one of the following general formulas.
A compound represented by the following general formula (1-a) in which p = 1 and n = m = 0 in the general formula (1),
A compound represented by the following general formula (1-b) in which p = 1, n = 0, m = 1 in the general formula (1), or
A compound represented by the following general formula (1-c), wherein p = 1 and n = m = 1 in the general formula (1).

[Wherein R ¹ is hydrogen, alkyl having 1 to 5 carbons, or alkenyl having 2 to 5 carbons;
Ring A ¹ is 1,4-phenylene, in which any hydrogen may be replaced by halogen, and ring A ² and ring A ³ are independently 1,4-phenylene, 1,4-cyclohexyl. Senylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, or 1,2,3,4-tetrahydronaphthalene-2,6-diyl, and any-in 1,4-phenylene CH = may be replaced by -N = and any hydrogen in these rings may be replaced by halogen;
Z ¹ , Z ² and Z ³ are each independently a single bond, —CH ₂ CH ₂ —, —CH═CH—, —C≡C—, —COO—, —OCO—, —CF ₂ O—, — _{OCF 2 -, - CH 2 O} -, - OCH 2 -, or a -CF = CF-;
L ¹ and L ² are independently hydrogen or fluorine;
X ¹ is fluorine, chlorine, —C≡N, —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₃ , —OCHF ₂ , or —OCH ₂ F. ]
11. Item 11. The compound according to Item 10, wherein Ring A ¹ , Ring A ² and Ring A ³ are independently 1,4-phenylene or halogenated 1,4-phenylene.
12 At least one of ring A ¹ , ring A ² and ring A ³ is halogenated 1,4-phenylene, and halogenated 1,4-phenylene is fluorinated 1,4-phenylene. Item 12. The compound according to Item 11.
13. Item 13. The compound according to Item 12, wherein the fluorinated 1,4-phenylene is 2-fluoro-1,4-phenylene or 2,6-difluoro-1,4-phenylene.
14 Item 11. The compound according to Item 10, wherein at least one of Ring A ¹ , Ring A ² and Ring A ³ is pyrimidine-2,5-diyl.
15. Item 15. The compound according to any one of Items 10 to 14, wherein at least one of Z ¹ , Z ² and Z ³ is a single bond.
16. Any one of Z ¹ , Z ² and Z ³ is —CH ₂ CH ₂ —, —CH═CH—, —C≡C—, —COO—, —OCO—, —CF ₂ O—, —OCF ₂ Item 16. The compound according to Item 15, which is —, —CH ₂ O—, or —OCH ₂ —.
17. Item 16. The compound according to Item 15, wherein Z ¹ , Z ² and Z ³ are all a single bond.
18. Item 18. The compound according to any one of Items 10 to 17, wherein at least one of L ¹ , L ² and X ¹ is halogen.
19. Item 5. The compound according to item 1, represented by any one of the following formulas (1-1) to (1-48).

[Wherein R ¹ is hydrogen, alkyl having 1 to 5 carbons, or alkenyl having 2 to 5 carbons;
L ¹ , L ² and Y ^{1 to} Y ⁶ are independently hydrogen or fluorine;
X ¹ is fluorine, chlorine, —C≡N, —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₃ , —OCHF ₂ , or —OCH ₂ F. ]
20. Item 5. The compound according to item 1, represented by any one of the following formulas (1-49) to (1-51):

[Wherein L ¹ , L ² and Y ^{1 to} Y ³ are independently hydrogen or fluorine;
X ¹ is fluorine or chlorine. ]
21. Item 21. A liquid crystal composition comprising two or more components, comprising at least one compound according to any one of items 1 to 20.
22. Item 22. The liquid crystal composition according to item 21, further comprising at least one compound selected from the group of compounds represented by each of the general formulas (2), (3), and (4).

[Wherein, R ² is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and any hydrogen may be replaced by fluorine, and in alkyl, any —CH ₂ — represents —O— May be replaced by;
X ² is fluorine, chlorine, —OCF ₃ , —OCHF ₂ , —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₂ CHF ₂ , or —OCF ₂ CHFCF ₃ ;
Ring B and Ring D are independently 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, or 1,4-phenylene in which any hydrogen may be replaced by fluorine, E is 1,4-cyclohexylene or 1,4-phenylene in which any hydrogen may be replaced by fluorine;
Z ⁴ and Z ⁵ are independently — (CH ₂ ) ₂ —, — (CH ₂ ) ₄ —, —COO—, —CF ₂ O—, —OCF ₂ —, —CH═CH—, or a single bond Is;
L ³ and L ⁴ are independently hydrogen or fluorine. ]
23. Item 22. The liquid crystal composition according to item 21, further comprising at least one compound selected from the group of compounds represented by each of the general formulas (5) and (6).

[Wherein R ³ and R ⁴ are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and any hydrogen may be replaced by fluorine, and any —CH ₂ -may be replaced by -O-;
X ³ is —C≡N or —C≡C—C≡N;
Ring G is 1,4-cyclohexylene, 1,4-phenylene, 1,3-dioxane-2,5-diyl, or pyrimidine-2,5-diyl, and ring J is 1,4-cyclohexylene. , Pyrimidine-2,5-diyl, or 1,4-phenylene in which any hydrogen may be replaced by fluorine, and ring K is 1,4-cyclohexylene or 1,4-phenylene;
Z ⁶ is — (CH ₂ ) ₂ —, —COO—, —CF ₂ O—, —OCF ₂ —, or a single bond;
L ⁵ , L ⁶ and L ⁷ are independently hydrogen or fluorine;
b, c and d are each independently 0 or 1. ]
24. Item 22. The liquid crystal composition according to item 21, further comprising at least one compound selected from the group of compounds represented by each of general formulas (7), (8), (9), (10), and (11): object.

[Wherein, R ⁵ is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and any hydrogen may be replaced by fluorine, and in alkyl, any —CH ₂ — represents —O— May be replaced by;
R ⁶ is fluorine, alkyl having 1 to 10 carbons, or alkenyl having 2 to 10 carbons, and any hydrogen may be replaced by fluorine, and in this alkyl, any —CH ₂ — represents —O— May be replaced by;
Ring M and Ring P are independently 1,4-cyclohexylene, 1,4-phenylene, or decahydro-2,6-naphthylene;
Z ⁷ and Z ⁸ are independently — (CH ₂ ) ₂ —, —COO—, or a single bond;
L ⁸ , L ⁹ , L ¹⁰ and L ¹¹ are independently hydrogen or fluorine, and at least one of L ⁸ , L ⁹ , L ¹⁰ and L ¹¹ is fluorine. ]
25. Item 22. The liquid crystal composition according to item 21, further comprising at least one compound selected from the group of compounds represented by general formulas (12), (13), and (14).

[Wherein, R ⁷ and R ⁸ are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and any hydrogen may be replaced by fluorine, and any — CH ₂ — may be replaced by —O—;
Ring J, Ring T and Ring U are independently 1,4-cyclohexylene, pyrimidine-2,5-diyl, or 1,4-phenylene in which any hydrogen may be replaced by fluorine;
Z ⁹ and Z ¹⁰ are independently —C≡C—, —COO—, — (CH ₂ ) ₂ —, —CH═CH—, or a single bond. ]
26. Item 23. The liquid crystal composition according to item 22, further containing at least one compound selected from the group of compounds represented by formulas (5) and (6).
27. Item 23. The liquid crystal composition according to item 22, further containing at least one compound selected from the group of compounds represented by formulas (12), (13), and (14).
28. Item 24. The liquid crystal composition according to item 23, further comprising at least one compound selected from the group of compounds represented by general formulas (12), (13), and (14).
29. Item 25. The liquid crystal composition according to item 24, further comprising at least one compound selected from the group of compounds represented by each of general formulas (12), (13), and (14).
30. Item 30. The liquid crystal composition according to any one of items 21 to 29, further containing at least one optically active compound.
31. Item 31. A liquid crystal display device comprising the liquid crystal composition according to any one of items 21 to 30.

  The compounds of the present invention have general physical properties necessary for liquid crystal compounds, stability to heat, light, etc., small viscosity, appropriate optical anisotropy, appropriate dielectric anisotropy and other Excellent compatibility with liquid crystal compounds. The liquid crystal composition of the present invention contains at least one of these compounds, and has a high maximum temperature of the nematic phase, a low minimum temperature of the nematic phase, a small viscosity, an optical anisotropy of an appropriate size, a low threshold. Has a value voltage. The liquid crystal display element of the present invention contains this composition and has a wide temperature range that can be used, a short response time, a small power consumption, a large contrast ratio, and a low driving voltage.

Terms used in this specification are as follows. A liquid crystal compound is a generic term for a compound having a liquid crystal phase such as a nematic phase or a smectic phase and a compound having no liquid crystal phase but useful as a component of a liquid crystal composition. A liquid crystal compound, a liquid crystal composition, and a liquid crystal display element may be abbreviated as a compound, a composition, and an element, respectively. A liquid crystal display element is a general term for a liquid crystal display panel and a liquid crystal display module. The upper limit temperature of the nematic phase is the phase transition temperature of the nematic phase-isotropic phase, and may simply be abbreviated as the upper limit temperature. The lower limit temperature of the nematic phase may simply be abbreviated as the lower limit temperature. The compound represented by formula (1) may be abbreviated as compound (1). This abbreviation may also apply to compounds represented by formula (2) and the like. In the formulas (1) to (14), symbols such as A ¹ , B, D, and E surrounded by hexagons correspond to the ring A ¹ , the ring B, the ring D, and the ring E, respectively. The amount of the compound expressed as a percentage is a mass percentage (% by mass) based on the total mass of the composition. The present invention is further described below.

  First, the compound (1) of the present invention will be further described. As described in Table 25 for compound (1), each structure will be described by dividing it into a left terminal group, a linking group, a ring structure, and a right terminal group. Compound (1) is a bicyclic, tricyclic or tetracyclic compound having alkenyl. A condensed ring such as a naphthalene ring is counted as one part. This compound is extremely physically and chemically stable under the conditions under which the device is normally used, and has good compatibility with other liquid crystal compounds. A composition containing this compound is stable under conditions in which the device is normally used. Even when the composition is stored at a low temperature, the compound does not precipitate as crystals (or a smectic phase). This compound has general physical properties necessary for the compound, appropriate optical anisotropy, and appropriate dielectric anisotropy.

It is possible to arbitrarily adjust physical properties such as optical anisotropy and dielectric anisotropy by appropriately selecting the terminal group, ring structure and bonding group of compound (1). The effects of preferred terminal groups in the compound (1), rings A ¹ , A ² and A ³ , bonding groups Z ¹ , Z ² and Z ³ and their types on the physical properties of the compound (1) will be described below.

In the left terminal group in the compound (1), when R ¹ is linear, the temperature range of the liquid crystal phase is wide and the viscosity is small. When R ¹ is a branched chain, the compatibility with other liquid crystal compounds is good. A compound in which R ¹ is an optically active group is useful as a chiral dopant. By adding this compound to the composition, a reverse twisted domain generated in the device can be prevented. A compound in which R ¹ is not an optically active group is useful as a component of the composition. When R ¹ is alkenyl, the preferred configuration depends on the position of the double bond. An alkenyl compound having a preferred configuration has a high maximum temperature or a wide temperature range of the liquid crystal phase. Regarding the relationship between the preferred configuration of alkenyl and the maximum temperature or temperature range of the liquid crystal phase, see Mol. Cryst. Liq. Cryst., 1985, 131, 109 and Mol. Cryst. Liq. Cryst., 1985, 131, 327. There is a detailed explanation.

In the left terminal group, R ¹ is hydrogen, alkyl having 1 to 5 carbons, or alkenyl having 2 to 5 carbons. Here, alkenyl is a group in which any — (CH ₂ ) ₂ — in alkyl is replaced by —CH═CH— or the like, and is shown as an example. Examples of groups in which any — (CH ₂ ) ₂ — in CH ₃ (CH ₂ ) ₃ — is replaced by —CH═CH— are H ₂ C═CH— (CH ₂ ) ₂ —, CH ₃ —CH═. CH—CH ₂ — and the like. Thus, the term “arbitrary” means “at least one selected without distinction”. In consideration of the stability of the compound, the double bond is adjacent _{CH 2 = CH-CH = CH} -CH 2 -CH 2 - than even the double bond is not adjacent _{CH 2 = CH-CH 2 -CH} 2 - CH = CH- is preferred.

When R ¹ is alkyl or alkenyl, straight chain is preferred over branch. Even when R ¹ is a branched group, it is preferable when it is optically active.

The preferred configuration of —CH═CH— in alkenyl depends on the position of the double bond. In alkenyl having a double bond at odd positions such as —CH═CHCH ₃ , —CH═CHC ₂ H ₅ , —CH═CHC ₃ H ₇ and —CH═CHC ₄ H ₉ , the trans configuration is preferred. -CH ₂ CH = CHCH _3, cis configuration in the alkenyl having an even position to the double bond, such as _{-CH 2 CH = CHC 2 H 5} , and -CH ₂ CH = CHC ₃ H ₇ are preferred.

Specific examples of preferable R ¹ are —H, —CH ₃ , —C ₂ H ₅ , —C ₃ H ₇ , —C ₄ H ₉ , —C ₅ H ₁₁ , —CH═CH ₂ , —CH═. CHCH ₃ , —CH ₂ CH═CH ₂ , —CH═CHC ₂ H ₅ , —CH ₂ CH═CHCH ₃ , — (CH ₂ ) ₂ CH═CH ₂ , —CH═CHC ₃ H ₇ , —CH ₂ CH _{= CHC 2 H 5, - (} CH 2) 2 CH = CHCH 3 and - a _{(CH 2) 3 CH = CH} 2.

Specific examples of more preferable R ¹ are —H, —CH ₃ , —C ₂ H ₅ , —C ₃ H ₇ , —C ₄ H ₉ , —C ₅ H ₁₁ , —CH ₂ CH═CH ₂ , _{-CH 2 CH = CHCH 3, -} (CH 2) 2 CH = CH 2, -CH 2 CH = CHC 2 H 5, - (CH 2) 2 CH = CHCH 3 and _{- (CH 2) 3 CH =} CH 2 It is.

Specific examples of most preferred R ¹ are —H, —CH ₃ , —C ₂ H ₅ , —C ₃ H ₇ , —C ₄ H ₉ , —C ₅ H ₁₁ , — (CH ₂ ) ₂ CH═ CH _2, and - (CH ₂₎ a ₂ CH = CHCH _3.

  In the left terminal group, p represents an integer of 1 to 4, and p is preferably 1.

In the right terminal group in the compound (1), X ¹ is a group represented by hydrogen, fluorine, chlorine, —C≡N, —N═C═S, —SF ₅ , or —Q—W, and Q is a single group. A bond, oxygen, or sulfur, and W is an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is replaced by a halogen. The right terminal group can be selected with reference to the following specific examples depending on the use of the compound.

Preferred X ¹ is a group represented by hydrogen, fluorine, chlorine, —C≡N, or —Q—W, Q is a single bond, oxygen, sulfur, and W is at least one hydrogen is replaced by a halogen. It is C1-C5 alkyl.

Further preferred X ¹ is a group represented by fluorine, chlorine, —C≡N, or —Q—W, Q is a single bond, oxygen, and W is carbon number 1 in which at least one hydrogen is replaced by halogen. ~ 5 alkyl.

More preferable X ¹ is fluorine, chlorine, —C≡N, —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₃ , —OCHF ₂ , or —OCH ₂ F.

Further preferred X ¹ is fluorine, chlorine, —C≡N, —OCF ₃ , or —OCHF ₂ .

Most preferred X ¹ is fluorine or chlorine.

  W is an alkyl having 1 to 5 carbon atoms in which at least one hydrogen is replaced by a halogen. Preferred halogens are fluorine and chlorine. A more preferred halogen is fluorine. In these groups, straight chain is preferable to branch.

Specific examples of alkyl in which at least one hydrogen is replaced by halogen include —CH ₂ F, —CHF ₂ , —CF ₃ , — (CH ₂ ) ₂ F, —CF ₂ CH ₂ F, —CF ₂ CHF. ₂ , —CH ₂ CF ₃ , —CF ₂ CF ₃ , — (CH ₂ ) ₃ F, — (CF ₂ ) ₂ CF ₃ , —CF ₂ CHFCF ₃ , —CHFCF ₂ CF ₃ , — (CH ₂ ) ₄ F _{, - (CF 2) 3 CF} 3, - (CH 2) 5 F and - the like (CF _{2) 4} CF _3.

Specific examples of preferred W _{is, -CF 3, -CHF 2, -CH} 2 F, - (CH 2) 2 F, -CF 2 CH 2 F, -CF 2 CHF 2, -CH 2 CF 3, - _{CF 2 CF 3, - (CH} 2) 3 F, - (CF 2) 2 CF 3, -CF 2 CHFCF 3, -CHFCF 2 CF 3, - (CH 2) 4 F, - (CF 2) 3 CF 3 , - (CH _{2) 5} F and - a (CF _{2) 4} CF _3.

Specific examples of more preferred W _{is, -CF 3, -CHF 2, -CH} 2 F, - (CH 2) 2 F, -CF 2 CH 2 F, -CF 2 CHF 2, -CH 2 CF 3, _{-CF 2 CF 3, - (CH} 2) 3 F, - (CF 2) 2 CF 3, -CF 2 CHFCF 3, -CHFCF 2 CF 3, - (CH 2) 4 F, - (CF 2) 3 CF ₃ and _{- (CH 2) 5 F,} - is (CF _{2) 4} CF _3.

The most preferred specific examples of W _{are, -CF 3, -CHF 2, -CH} 2 F, - (CH 2) 2 F, -CF 2 CH 2 F, -CF 2 CHF 2, -CH 2 CF 3, _{-CF 2 CF 3, - (CH} 2) 3 F, - (CF 2) 2 CF 3, a -CF ₂ CHFCF ₃ and -CHFCF ₂ CF _3.

In the ring structure to which the right terminal group is bonded, L ¹ and L ² are independently hydrogen or fluorine.

Compound (1) has a large positive dielectric anisotropy. A compound having a large dielectric anisotropy is
It is useful as a component for lowering the threshold voltage of the composition.

As the ring structure in the compound (1), ring A ¹ is 1,4-phenylene, and in this ring, any hydrogen may be replaced by halogen, and ring A ² and ring A ³ are independently 1 , 4-cyclohexylene, 1,4-phenylene, 1,4-cyclohexenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl and 1,2,3,4-tetrahydronaphthalene-2 , 6-diyl, in which any —CH ₂ — may be replaced by —O— and —S—, and any —CH═ may be replaced by —N═. Also good. Any hydrogen in these rings may be replaced with a halogen.

“Any —CH ₂ — in these rings may be replaced by —O— and —S—, and any —CH═ may be replaced by —N═” Examples are the following rings (15-1) to (15-31). Further preferred examples include rings (15-1), (15-2), (15-3), (15-4), (15-9), (15-10), (15-11) and (15 -12).

  Examples of the ring “any hydrogen in these rings may be replaced by halogen” include the following rings (16-1) to (16-30). Preferred examples are rings (16-1), (16-2), (16-3) and (16-4).

Examples of preferred rings A ² and A ³ are 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,3-dioxane-2,5-diyl, 1,4-phenylene, 2-fluoro-1, 4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, 2,3,5-trifluoro-1 , 4-phenylene, pyridine-2,5-diyl, 3-fluoropyridine-2,5-diyl, pyrimidine-2,5-diyl and pyridazine-3,6-diyl. The configuration of 1,4-cyclohexylene and 1,3-dioxane-2,5-diyl is preferably trans rather than cis. Since 1,3-dioxane-2,5-diyl is structurally identical to 4,6-dioxane-2,5-diyl, the latter was not exemplified. This rule is the relationship between 2-fluoro-1,4-phenylene and 3-fluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene and 3,5-difluoro-1,4-phenylene, etc. Also applies.

More preferred examples of the rings A ² and A ³ are 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5 -Difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyridine-2,5-diyl and pyrimidine-2,5-diyl.

Examples of the most preferred rings A ¹ , A ² and A ³ are 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene.

Any or all of the rings A ¹ , A ² and A ³ are 1,4-phenylene, pyridine-2,5-diyl or 1,3-dioxane-2,5- in which any hydrogen is replaced by halogen. When it is diyl, the dielectric anisotropy is large.

When any or all of the rings A ¹ , A ² and A ³ are 1,4-phenylene or pyridine-2,5-diyl in which any hydrogen may be replaced by halogen, the optical anisotropy is large. . When any or all of the rings A ¹ , A ² and A ³ are 1,4-cyclohexylene, 1,4-cyclohexenylene, or 1,3-dioxane-2,5-diyl, optically anisotropic The nature is small.

  When at least two rings are 1,4-cyclohexylene, the maximum temperature is high, the optical anisotropy is small, and the viscosity is small. When at least one ring is 1,4-phenylene, the optical anisotropy is relatively large and the orientational order parameter is large. When at least two rings are 1,4-phenylene, the optical anisotropy is large, the temperature range of the liquid crystal phase is wide, and the maximum temperature is high.

Z ¹ , Z ² and Z ³ which are bonding groups in the compound (1) are independently a single bond, —CH ₂ CH ₂ —, —CH═CH—, —C≡C—, —COO—, — _{OCO -, - CF 2 O -} , - OCF 2 -, - CH 2 O -, - OCH 2 -, - CF = CF -, - (CH 2) 4 -, - O (CH 2) 2 O -, - _{(CH 2) 2 CF 2 O} -, - (CH 2) 2 OCF 2 -, - CF 2 O (CH 2) 2 -, - OCF 2 (CH 2) 2 -, - CH = CH-CH 2 O- Or —OCH ₂ —CH═CH—. Trans is preferable to cis for the configuration of the double bond of the bonding group such as —CH═CH—.

Preferred Z ¹ , Z ² and Z ³ are a single bond, —CH ₂ CH ₂ —, —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —. , -CH = CH-, -CF = CF-, and -C≡C-.

More preferred Z ¹ , Z ² and Z ³ are a single bond, —CH ₂ CH ₂ —, —COO—, —OCO—, —CF ₂ O—, —OCF ₂ —, —CH═CH—, and —C. ≡C-.

Most preferred Z ¹ , Z ² and Z ³ are single bonds.

Any or all of the bonding groups Z ¹ , Z ² , or Z ³ are a single bond, — (CH ₂ ) ₂ —, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, -CH = CH -, - CF = CF -, - (CH 2) 2 CF 2 O -, - OCF 2 (CH 2) 2 -, or - (CH _{2) 4} - is when the viscosity is small at. When any or all of the bonding groups are a single bond, — (CH ₂ ) ₂ —, —CF ₂ O—, —OCF ₂ —, or —CH═CH—, the viscosity is smaller. When any or all of the bonding groups are —CH═CH—, the temperature range of the liquid crystal phase is wide, and the elastic constant ratio K ₃₃ / K ₁₁ (K ₃₃ : bend elastic constant, K ₁₁ : spray elastic constant) Is big. When any or all of the bonding groups are —C≡C—, the optical anisotropy is large.

  When compound (1) has two or three rings, the viscosity is small. When compound (1) has a tricyclic or tetracyclic ring, the maximum temperature is high. As described above, a compound having desired physical properties can be obtained by appropriately selecting the type of terminal group, ring structure and bonding group, and the number of rings. Therefore, the compound (1) is useful as a component of a composition used for devices such as PC, TN, STN, ECB, OCB, IPS, and VA.

Preferred examples of compound (1) are compounds (1-a) to (1-c) described in item 10 of the present invention. More specific examples are the following compounds (1-ai) to (1-ci). The meanings of the symbols R ¹ , L ¹ , L ² , X ¹ , Z ¹ , Z ² and Z ³ in these compounds are the same as the meanings of the symbols described in Item 10. Y ^{1 to} Y ⁶ are independently hydrogen or fluorine.

More specific examples include the following compounds (1-a-1) to (1-a-3), (1-b-1) to (1-b-6) and (1-c-1) to (1-c-8). The meanings of the symbols R ¹ , L ¹ , L ² , X ¹ , Z ¹ , Z ² and Z ³ in these compounds are the same as the meanings of the symbols described in Item 10.

Other specific examples are the following compounds (1-1) to (1-48). The meanings of the symbols R ¹ , L ¹ , L ² , X ¹ , and Y ^{1 to} Y ⁶ in these compounds are the same as the meanings of the symbols described in Item 19.

Preferred examples are the following compounds (1-49) to (1-51). The meanings of the symbols L ¹ , L ² , X ¹ , Y ^{1 to} Y ³ in these compounds are the same as the meanings of the symbols described in item 20.

  The compound (1) whose structure has been clarified in this specification can be synthesized by appropriately combining techniques in organic synthetic chemistry. Methods for introducing the desired end groups, ring structures, and linking groups into the starting materials are as follows: Organic Syntheses (John Wiley & Sons, Inc), Organic Reactions (Organic Reactions, John Wiley & Sons, Inc), Complement. It is described in books such as Shibu Organic Synthesis (Pergamon Press) and New Experimental Chemistry Course (Maruzen).

With respect to an example of a method for generating a linking group Z ¹ , Z ² , or Z ³ , a scheme is first shown, and then the scheme is described in terms (I) to (XI). In this scheme, MSG ¹ or MSG ² is a monovalent organic group having at least one ring. A plurality of MSG ¹ (or MSG ² ) used in the scheme may be the same or different. Compounds (1A) to (1K) correspond to compound (1).

(I) Formation of Single Bond A compound obtained by reacting arylboric acid (21) with compound (22) synthesized by a known method in the presence of a carbonate aqueous solution and a catalyst such as tetrakis (triphenylphosphine) palladium. Synthesize (1A). This compound (1A) is obtained by reacting compound (23) synthesized by a known method with n-butyllithium and then with zinc chloride, and in the presence of a catalyst such as dichlorobis (triphenylphosphine) palladium. ) Is also reacted.

(II) Formation of —COO— and —OCO— The compound (23) is reacted with n-butyllithium and subsequently with carbon dioxide to obtain a carboxylic acid (24). Compound having —COO— by dehydrating compound (24) and phenol (25) synthesized by a known method in the presence of DDC (1,3-dicyclohexylcarbodiimide) and DMAP (4-dimethylaminopyridine) Synthesize (1B). A compound having —OCO— is also synthesized by this method.

(III) Formation of —CF ₂ O— and —OCF ₂ — Compound (1B) is treated with a sulfurizing agent such as Lawesson's reagent to obtain compound (26). The compound (26) is fluorinated with a hydrogen fluoride pyridine complex and NBS (N-bromosuccinimide) to synthesize a compound (1C) having —CF ₂ O—. See also M. Kuroboshi et al., Chem. Lett., 1992, 827. Compound (1C) can also be synthesized by fluorinating compound (26) with (diethylamino) sulfur trifluoride (DAST). See also WH Bunnelle et al., J. Org. Chem. 1990, 55, 768. A compound having —OCF ₂ — is also synthesized by this method. These linking groups can also be generated by the method described in Peer. Kirsch et al., Anbew. Chem. Int. Ed. 2001, 40, 1480.

(IV) Formation of —CH═CH— The compound (23) is treated with n-butyllithium and then reacted with formamide such as N, N-dimethylformamide (DMF) to obtain the aldehyde (28). A phosphoryl ylide generated by treating a phosphonium salt (27) synthesized by a known method with a base such as potassium tert-butoxide is reacted with an aldehyde (28) to synthesize a compound (1D). Since a cis isomer is generated depending on the reaction conditions, the cis isomer is isomerized to a trans isomer by a known method as necessary.

(V) Formation of — (CH ₂ ) ₂ — Compound (1D) is synthesized by hydrogenating compound (1D) in the presence of a catalyst such as palladium carbon.

(VI) Formation of — (CH ₂ ) ₄ — A compound having — (CH ₂ ) ₂ —CH═CH— is prepared by using the phosphonium salt (29) instead of the phosphonium salt (27) and according to the method of the item (IV) obtain. This is catalytically hydrogenated to synthesize compound (1F).

(VII) Formation of -C≡C- After reacting compound (23) with 2-methyl-3-butyn-2-ol in the presence of a catalyst of dichloropalladium and copper halide, under basic conditions Deprotection yields compound (30). Compound (1G) is synthesized by reacting compound (30) with compound (22) in the presence of a catalyst of dichloropalladium and copper halide.

(VIII) Formation of —CF═CF— The compound (23) is treated with n-butyllithium and then reacted with tetrafluoroethylene to obtain the compound (31). Compound (22) is treated with n-butyllithium and then reacted with compound (31) to synthesize compound (1H).

(IX) Formation of —CH ₂ O— or —OCH ₂ — Compound (32) is obtained by reducing compound (28) with a reducing agent such as sodium borohydride. This is halogenated with hydrobromic acid or the like to obtain compound (33). Compound (1J) is synthesized by reacting compound (33) with compound (25) in the presence of potassium carbonate or the like.

Formation of (X)-(CH ₂ ) ₃ O— or —O (CH ₂ ) ₃ — Compound (1K) was synthesized according to the method of Item (IX) using Compound (34) instead of Compound (28). To do.

Next, specific examples of the method for introducing an alkadienyl group into the compound represented by the formula (T-1) are shown in the following scheme. However, in the following reaction route, R ¹ , A ¹ , A ² , A ³ , Z ¹ , Z ² , Z ³ , L ¹ , L ² , X ¹ , n, m, and p have the same meaning as described above.

  An aldehyde (T-1) produced according to the methods of Japanese Patent Publication No. 7-2653, Japanese Patent Publication No. 7-2654, Japanese Patent Application Laid-Open No. 5-286873 and Japanese Patent Application No. 7-310039 is produced. Then, the aldehyde (T-1) produced is reacted with an ylide prepared from a phosphonium salt of alkenyl halide (T-5) and potassium t-butoxide to produce a cisolefin (T-2).

  After metachloroperbenzoic acid (T-6) is allowed to act on cis-olefin (T-2) to be converted to epoxide (T-3), dibromotriphenylphosphorane (T-7) is converted to epoxide (T-3). To give anti-dibromide (T-4), and then reductively debrominated to produce compound (1) of the present invention.

  Secondly, the composition of the present invention will be further described. The component of the composition may be only two or more kinds of compounds selected from the compound (1). A preferred composition contains 1 to 99% of at least one compound selected from the compound (1). The composition can further contain a component selected from the group of compounds (2) to (14). When preparing the composition, the components are selected in consideration of the dielectric anisotropy of the compound (1).

  A preferred composition containing the compound (1) having a large positive dielectric anisotropy is as follows. This preferred composition contains at least one compound selected from the group of compounds (2), (3) and (4). Another preferred composition contains at least one compound selected from the group of compounds (5) and (6). Another preferred composition contains at least two compounds selected from each of these two groups. These compositions are a group of compounds (12), (13) and (14) for the purpose of adjusting the temperature range, viscosity, optical anisotropy, dielectric anisotropy, threshold voltage and the like of the liquid crystal phase. It may further contain at least one compound selected from These compositions may further contain at least one compound selected from the group of the compounds (7) to (11) for the purpose of further adjusting the physical properties. These compositions may further contain compounds such as other liquid crystal compounds and additives for the purpose of adapting to AM-TN devices, STN devices and the like.

  Another preferred composition contains at least one compound selected from the group of compounds (12), (13) and (14). This composition may further contain at least one compound selected from the group of the compounds (7) to (11) for the purpose of further adjusting the physical properties. This composition may further contain compounds such as other liquid crystalline compounds and additives for the purpose of adapting to AM-TN devices, STN devices and the like.

  A preferred composition containing the compound (1) having a small dielectric anisotropy is as follows. Preferred compositions contain at least one compound selected from the group of compounds (2), (3) and (4). Another preferred composition contains at least one compound selected from the group of compounds (5) and (6). Another preferred composition contains at least two compounds selected from each of these two groups. These compositions are a group of compounds (12), (13) and (14) for the purpose of adjusting the temperature range, viscosity, optical anisotropy, dielectric anisotropy, threshold voltage and the like of the liquid crystal phase. It may further contain at least one compound selected from This composition may further contain at least one compound selected from the group of the compounds (7) to (11) for the purpose of further adjusting the physical properties. This composition may further contain compounds such as other liquid crystalline compounds and additives for the purpose of adapting to AM-TN devices, STN devices and the like.

  Another preferred composition contains at least one compound selected from the group of compounds (7) to (11). This composition may further contain at least one compound selected from the group of compounds (12), (13) and (14). This composition may further contain at least one compound selected from the group of the compounds (2) to (6) for the purpose of further adjusting the physical properties. This composition may further contain compounds such as other liquid crystal compounds and additives for the purpose of adapting to VA devices and the like.

Compounds (2), (3), and (4) have a large positive dielectric anisotropy, and are therefore mainly used in compositions for AM-TN devices. In this composition, the amount of these compounds is 1-99%. A preferred amount is 10-97%. A more preferred amount is 40 to 95%. When compound (12), (13) or (14) is further added to this composition, the preferred amount of this compound is 60% or less. A more preferred amount is 40% or less.

  Since the compounds (5) and (6) have a very large dielectric anisotropy, they are mainly used in compositions for STN devices. In this composition, the amount of these compounds is 1-99%. A preferred amount is 10-97%. A more preferred amount is 40 to 95%. When compound (12), (13) or (14) is further added to this composition, the preferred amount of this compound is 60% or less. A more preferred amount is 40% or less.

  Since the compounds (7), (8), (9), (10), and (11) have a negative dielectric anisotropy, they are mainly used in compositions for VA devices. The preferred amount of these compounds is 80% or less. A more preferred amount is 40 to 80%. When compound (12), (13) or (14) is further added to this composition, the preferred amount of this compound is 60% or less. A more preferred amount is 40% or less.

  The dielectric anisotropy of the compounds (12), (13) and (14) is small. The compound (12) is mainly used for the purpose of adjusting viscosity or optical anisotropy. Compounds (13) and (14) are used for the purpose of increasing the maximum temperature to widen the temperature range of the liquid crystal phase or adjusting the optical anisotropy. Increasing the amount of compounds (12), (13) and (14) increases the threshold voltage of the composition and decreases the viscosity. Accordingly, a large amount may be used as long as the threshold voltage requirement of the composition is satisfied.

Preferred compounds (2) to (14) are, for example, compounds (2-1) to (2-9), compounds (3-1) to (3-97), and compounds (4-1) to (4-), respectively. 33), compounds (5-1) to (5-56), compounds (6-1) to (6-3), compounds (7-1) to (7-4), compounds (8-1) to ( 8-6), compounds (9-1) to (9-4), compound (10-1), compound (11-1), compounds (12-1) to (12-11), compound (13-1) ) To (13-21) and compounds (14-1) to (14-6). In these compounds, the meanings of the symbols R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , X ² , and X ³ are the same as those in the compounds (2) to (14). Is the same as

  The composition of the present invention is prepared by a known method. For example, the component compounds are mixed and dissolved in each other by heating. Appropriate additives may be added to the composition to adjust the physical properties of the composition. Such additives are well known to those skilled in the art. A composition for a GH device may be prepared by adding a dichroic dye which is a compound such as merocyanine, styryl, azo, azomethine, azoxy, quinophthalone, anthraquinone, and tetrazine. On the other hand, a chiral dopant is added for the purpose of inducing a helical structure of the liquid crystal to give a necessary twist angle. Examples of the chiral dopant are, for example, the following optically active compounds (Op-1) to (Op-13).

A chiral dopant is added to the composition to adjust the twist pitch. A preferred pitch for TN elements and TN-TFT elements is in the range of 40-200 μm. A preferred pitch for STN elements is in the range of 6-20 μm. A preferred pitch for the BTN device is in the range of 1.5-4 μm. A relatively large amount of chiral dopant is added to the composition for the PC element. At least two chiral dopants may be added for the purpose of adjusting the temperature dependence of the pitch.

  The composition of the present invention can be used for devices such as PC, TN, STN, BTN, ECB, OCB, IPS, and VA. These elements may be driven by PM or AM. NCAP (nematic curvilinear aligned phase) elements produced by microencapsulating this composition, and PD (polymer dispersed) elements in which a three-dimensional network polymer is formed in the composition, for example, PN (polymer network) elements Can also be used.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the invention is not limited by these examples. The structure of the obtained compound was identified by NMR spectrum, mass spectrum and the like. The measuring method by these followed the method mentioned later.

¹ H-NMR analysis: DRX-500 (Bruker Biospin Co., Ltd.) was used for measurement. A solution in which a deuterated sample such as CDCl ₃ was dissolved in a soluble solvent was measured using a nuclear magnetic resonance apparatus at room temperature. Tetramethylsilane (TMS) was used as a reference material for the zero point of the δ value.

  Gas chromatographic analysis: A GC-14B gas chromatograph manufactured by Shimadzu Corporation was used for measurement. The carrier gas is helium (2 ml / min). The sample vaporization chamber was set at 280 ° C, and the detector (FID) was set at 300 ° C. For separation of the component compounds, capillary column DB-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm; stationary liquid phase is dimethylpolysiloxane; nonpolar) manufactured by Agilent Technologies Inc. was used. The column was held at 180 ° C. for 2 minutes and then heated to 280 ° C. at a rate of 5 ° C./min. A sample was prepared in an acetone solution (0.1% by mass), and 1 μl thereof was injected into the sample vaporization chamber. The recorder is a C-R5A type Chromatopac manufactured by Shimadzu Corporation or an equivalent thereof. The obtained gas chromatogram showed the peak retention time and peak area corresponding to the component compounds.

[Example 1]
3,4,5,2'-tetrafluoro-4 "-octa-3,7-dienyl- [1,1 ', 4', 1"] terphenyl (1-b-2-2) is shown below Synthesized according to the synthesis scheme.

Synthesis of 3'-fluoro-biphenyl-4-carbaldehyde (T-8) 4-Bromobenzaldehyde (32.0 g), 3-fluorophenylboronic acid (25.4 g), potassium carbonate (47.7 g) and Pd ( PPh ₃ ) ₂ Cl ₂ (1.21 g) was dissolved in Solmix (400 ml) and heated to reflux for 4 hours under a nitrogen atmosphere. After completion of the reaction, the mixture was filtered through Celite, and the filtrate was extracted with toluene. The organic layer was washed with 2N aqueous sodium hydroxide, saturated aqueous sodium bicarbonate, water and saturated aqueous sodium chloride, then dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give a black oil. This was recrystallized from heptane-toluene to obtain 3'-fluoro-biphenyl-4-carbaldehyde (T-8) as a pale yellow powder (25.3 g).

Synthesis of (T-10) Phosphonium salt dried in vacuum for 1 hour (T-9) (51.4 g) was added dry tetrahydrofuran (THF) (200 ml) and cooled to -70 ° C. Under a nitrogen atmosphere, potassium-t-butoxide (13.4 g) was added in small portions and stirred for 1 hour. Thereafter, a dry THF solution of 3′-fluoro-biphenyl-4-carbaldehyde (20.0 g) was slowly added dropwise at −70 ° C., and the mixture was warmed to room temperature and stirred for 4 hours. After completion of the reaction, the mixture was extracted with toluene, washed with water and saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a pale yellow solid. This was recrystallized from silica gel column chromatography (heptane: ethyl acetate = 20: 1 (volume ratio)) and heptane to obtain (T-10) as a white powder (16.9 g).

Synthesis of (T-11) Compound (T-10) (16.3 g) obtained by the above operation was dissolved in toluene (100 ml) and isopropyl alcohol (IPA) (100 ml), and Pd-C (NX Type) (0.50 g) was added, and the reaction system was purged with hydrogen and stirred at room temperature for 14 hours. After completion of the reaction, Pd—C was separated by filtration and concentrated under reduced pressure to obtain a light black solid. This was recrystallized from heptane to obtain (T-11) as a white powder (15.2 g).

Synthesis of (T-12) Compound (T-11) (30.0 g) obtained by the above operation was dissolved in dryTHF (400 ml), cooled to -70 ° C, and then sec-BuLi (219 ml) was slowly added. The solution was added dropwise and stirred as it was for 1 hour. Thereafter, a solution of iodine (14.0 g) in dryTHF (140 ml) was slowly added dropwise, and the mixture was warmed to room temperature and stirred for 3 hours. After completion of the reaction, a saturated aqueous sodium thiosulfate solution was added and extracted with toluene. The organic layer was washed with water and a saturated aqueous sodium chloride solution, then dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a pale yellow solid. This was subjected to silica gel column chromatography (heptane: ethyl acetate = 4: 1 (volume ratio)) and recrystallization (heptane: toluene = 4: 1 (volume ratio)) to obtain (T-12) as a white powder. As (30.0 g).

Synthesis of (T-13) Compound (T-12) (15.0 g), 3,4,5-trifluorophenylboronic acid (7.96 g), Pd-C (NX type) obtained by the above operation ( Toluene (75 ml), Solmix (75 ml) and water (3.8 ml) were added to 0.16 g) and potassium carbonate (10.4 g), and the mixture was heated to reflux for 5 hours under a nitrogen atmosphere. After completion of the reaction, Pd—C was filtered off, and the filtrate was washed with saturated aqueous sodium hydrogen carbonate solution, water and saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give a pale yellow solid. This was subjected to silica gel column chromatography (heptane: ethyl acetate = 4: 1 (volume ratio)) and recrystallized (heptane: toluene = 4: 1 (volume ratio)) to obtain (T-13) as a white powder. As (13.9 g).

Synthesis of (T-14) The compound (T-13) (13.9 g) obtained by the above operation was dissolved in formic acid (2.25 ml) and 140 ml of toluene and heated to reflux for 6 hours in a nitrogen atmosphere. Since the progress of the reaction was slow, formic acid (2.25 ml) was added six times along the way. After completion of the reaction, a saturated aqueous sodium hydrogen carbonate solution was added little by little with stirring and extracted with toluene. The organic layer was washed with water and a saturated aqueous sodium chloride solution, then dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a pale yellow solid. This was recrystallized (heptane: toluene = 4: 1 (volume ratio)) to obtain (T-14) as a white powder (10.7 g).

Synthesis of (T-16) 200 ml of dryTHF was added to a phosphonium salt (T-15) (14.8 g) that had been vacuum-dried for 1 hour, and cooled to -70 ° C. Under a nitrogen atmosphere, potassium-t-butoxide (4.03 g) was added in small portions and stirred for 1 hour. Thereafter, a dry THF solution of the compound (T-14) (10.7 g) obtained by the above operation was slowly added dropwise, and the mixture was warmed to room temperature and stirred for 4 hours. After completion of the reaction, the mixture was ice-cooled, water was added with stirring, and the mixture was extracted with toluene. The organic layer was washed with water and a saturated aqueous sodium chloride solution, then dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a pale yellow solid. This was recrystallized from silica gel column chromatography (heptane: ethyl acetate = 20: 1 (volume ratio)) and heptane to obtain (T-16) as a white powder (10.5 g).

Synthesis of (T-17) Potassium carbonate (8.83 g) and dichloromethane (200 ml) were added to the compound (T-16) (10.5 g) obtained by the above operation, and the mixture was cooled with ice, and then metachloroperbenzoic acid ( mCPBA) (4.86 g) was added, and the mixture was stirred at room temperature for 14 hours under a nitrogen atmosphere. Since the progress of the reaction was slow, mCPBA (2.43 g) was added six times along the way. After completion of the reaction, a saturated aqueous sodium thiosulfate solution was added and extracted with dichloromethane. The organic layer was washed with saturated aqueous sodium hydrogen carbonate solution, water and saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give (T-17) as a black oil (10.8 g).

Synthesis of (T-18) Triphenylphosphine dibromide (16.0 g) and toluene (200 ml) were added to the compound (T-17) (10.8 g) obtained by the above operation, and heated for 8 hours under a nitrogen atmosphere. Refluxed. After completion of the reaction, the mixture was extracted with toluene, washed with water and saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a black yellow oil. This was purified by silica gel column chromatography (heptane: ethyl acetate = 4: 1 (volume ratio)) to obtain (T-18) as a yellow oil (9.94 g).

Synthesis of 3,4,5,2′-tetrafluoro-4 ″ -octa-3,7-dienyl- [1,1 ′, 4 ′, 1 ″] terphenyl Compound obtained by the above operation (T-18 ) (9.94 g) was dissolved in acetic acid (100 ml), and zinc powder (5.70 g) was added in small portions and then stirred at room temperature for 3 hours under a nitrogen atmosphere. After completion of the reaction, insoluble matters were filtered off and extracted with heptane. The organic layer was washed with a saturated aqueous solution of sodium bicarbonate, water, and a saturated aqueous solution of sodium chloride, then dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give a black brown oil. This was recrystallized from silica gel column chromatography (heptane: toluene = 40: 1 (volume ratio)) and heptane to give the title compound (1-b-2-2) as a white powder (3.1 g )Obtained.

The physical property values were calculated by extrapolation from the values obtained by preparing a sample by mixing 15% by mass of a compound and 85% by mass of a mother liquid crystal as described in the section of the following composition example. Extrapolated value = (measured value of sample−0.85 × measured value of mother liquid crystal) /0.15. The physical properties are Δε = 12.3, Δn = 0.250, η = 44.6 mPa · s, C 33.3 S _A 78.9 N 118.5 I.

[Example 2]
4-Chloro-3,2′-difluoro-4 ″ -octa-3,7-dienyl- [1,1 ′, 4 ′, 1 ″] terphenyl (1-b-2-1) in Example 1 In the same manner as described above, from the compound (T-12) (21.0 g) obtained by the above operation and 3-chloro-4-fluorophenylboronic acid (10.5 g), white powder (3.0 g) was obtained. )Obtained.

  The physical property values were calculated by extrapolation from the values obtained by preparing a sample by mixing 15% by mass of a compound and 85% by mass of a mother liquid crystal as described in the section of the following composition example. Extrapolated value = (measured value of sample−0.85 × measured value of mother liquid crystal) /0.15. The physical properties are Δε = 17.4, Δn = 0.197, η = 46.3 mPa · s, C 37.0 N 55.8 I.

[Example 3]
4′-fluoro-4-octa-3,7-dienyl-biphenyl (1-a-1-1) was synthesized according to the synthesis scheme shown below.

Synthesis of 4'-fluoro-biphenyl-4-carbaldehyde (T-19) 4-Bromobenzaldehyde (37.0 g), 4-fluorophenylboronic acid (29.4 g), potassium carbonate (41.4 g) and Pd ( PPh ₃ ) ₂ Cl ₂ (1.40 g) was dissolved in Solmix (400 ml) and heated to reflux for 4 hours under a nitrogen atmosphere. After completion of the reaction, the mixture was filtered through Celite, and the filtrate was extracted with toluene. The organic layer was washed with 2N aqueous sodium hydroxide, saturated aqueous sodium bicarbonate, water and saturated aqueous sodium chloride, then dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give a black oil. This was recrystallized from heptane-toluene to obtain 4'-fluoro-biphenyl-4-carbaldehyde (T-19) as a pale yellow powder (25.3 g).

Synthesis of (T-21) Phosphonium salt (T-20) (65.4 g) dried in vacuo for 1 hour was added dry tetrahydrofuran (THF) (300 ml) and cooled to -70 ° C. Under a nitrogen atmosphere, potassium-t-butoxide (25.3 g) was added in small portions and stirred for 1 hour. Thereafter, a dry THF solution of 4′-fluoro-biphenyl-4-carbaldehyde (T-19) (25.3 g) was slowly added dropwise at −70 ° C., and the mixture was warmed to room temperature and stirred for 4 hours. After completion of the reaction, the mixture was extracted with toluene, washed with water and saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a pale yellow solid. This was recrystallized from silica gel column chromatography (heptane: ethyl acetate = 20: 1 (volume ratio)) and heptane to obtain (T-21) as a white powder (27.5 g).

Synthesis of (T-22) Compound (T-21) (27.5 g) obtained by the above operation was dissolved in toluene (150 ml) and isopropyl alcohol (IPA) (150 ml), and Pd-C (NX Type) (0.83 g) was added, and the reaction system was purged with hydrogen and stirred at room temperature for 14 hours. After completion of the reaction, Pd—C was separated by filtration and concentrated under reduced pressure to obtain a light black solid. By recrystallizing this with heptane, (T-22) was obtained as a white powder (27.3 g).

Synthesis of (T-23) The compound (T-22) (27.3 g) obtained by the above operation was dissolved in formic acid (16.0 ml) and 200 ml of toluene and heated to reflux for 6 hours under a nitrogen atmosphere. Since the progress of the reaction was slow, formic acid (8.0 ml) was added twice on the way. After completion of the reaction, a saturated aqueous sodium hydrogen carbonate solution was added little by little with stirring and extracted with toluene. The organic layer was washed with water and a saturated aqueous sodium chloride solution, then dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a pale yellow solid. This was recrystallized (heptane: toluene = 4: 1) to obtain (T-23) as a white powder (21.6 g).

Synthesis of (T-25) 300 ml of dryTHF was added to phosphonium salt (T-24) (46.6 g) which was vacuum-dried for 1 hour, and cooled to -70 ° C. Under a nitrogen atmosphere, potassium tert-butoxide (13.5 g) was added in small portions and stirred for 1 hour. Thereafter, a dry THF solution of the compound (T-14) (21.6 g) obtained by the above operation was slowly added dropwise, and the mixture was warmed to room temperature and stirred for 4 hours. After completion of the reaction, the mixture was ice-cooled, water was added with stirring, and the mixture was extracted with toluene. The organic layer was washed with water and a saturated aqueous sodium chloride solution, then dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a pale yellow solid. This was recrystallized from silica gel column chromatography (heptane: ethyl acetate = 20: 1 (volume ratio)) and heptane to obtain (T-25) as a white powder (23.5 g).

Synthesis of (T-26) Potassium carbonate (28.9 g) and dichloromethane (300 ml) were added to the compound (T-25) (23.5 g) obtained by the above operation, and the mixture was cooled with ice, and then metachloroperbenzoic acid ( mCPBA) (21.7 g) was added, and the mixture was stirred at room temperature for 14 hours under a nitrogen atmosphere. Since the progress of the reaction was slow, mCPBA (10.9 g) was added three times along the way. After completion of the reaction, a saturated aqueous sodium thiosulfate solution was added and extracted with dichloromethane. The organic layer was washed with saturated aqueous sodium hydrogen carbonate solution, water and saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give (T-26) as a black oil (16.8 g).

Synthesis of (T-27) To the compound (T-26) (16.8 g) obtained by the above operation, triphenylphosphine dibromide (35.8 g) and toluene (300 ml) were added, and heated in a nitrogen atmosphere for 8 hours. Refluxed. After completion of the reaction, the mixture was extracted with toluene, washed with water and saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a black yellow oil. This was purified by silica gel column chromatography (heptane: toluene = 20: 1 (volume ratio)) to obtain (T-27) as a yellow oil (7.47 g).

Synthesis of 4′-fluoro-4-octa-3,7-dienyl-biphenyl (1-a-1-1) Compound (T-27) (7.47 g) obtained by the above operation was converted to acetic acid (100 ml). After dissolving and adding zinc powder (5.56 g) in small portions, the mixture was stirred at room temperature for 3 hours under a nitrogen atmosphere. After completion of the reaction, insoluble matters were filtered off and extracted with heptane. The organic layer was washed with a saturated aqueous solution of sodium bicarbonate, water, and a saturated aqueous solution of sodium chloride, then dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give a black brown oil. This was purified by silica gel column chromatography (heptane: toluene = 40: 1 (volume ratio)) to obtain the title compound as a colorless viscous liquid (1.5 g).

  The physical property values of the compounds are shown in Table 1. The physical property values were measured in the same manner as in Examples 1 and 2 above.

[Example 4]
4'-Chloro-4-octa-3,7-dienyl-biphenyl (1-a-1-2) was prepared in the same manner as described in Example 3 using 4-bromobenzaldehyde (37.0 g) and 4- From a chlorophenyl boronic acid (32.8g), it obtained as a white powder (1.1g).

  The physical property values of the compounds are shown in Table 1. The physical property values were measured in the same manner as in Examples 1 and 2 above.

[Example 5]
3,4,5,2'-tetrafluoro-4'-octa-3,7-dienyl-biphenyl (1-a-2-2) was synthesized according to the synthesis scheme shown below.

Synthesis of (T-28) Dry tetrahydrofuran (THF) (300 ml) was added to phosphonium salt (T-9) (65.4 g) which was vacuum-dried for 1 hour, and the mixture was cooled to -70 ° C. Under a nitrogen atmosphere, potassium-t-butoxide (25.3 g) was added in small portions and stirred for 1 hour. Thereafter, a dry THF solution of 3-fluorobenzaldehyde (17.8 g) was slowly added dropwise at −70 ° C., and the mixture was warmed to room temperature and stirred for 4 hours. After completion of the reaction, the mixture was extracted with toluene, washed with water and saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a pale yellow solid. This was recrystallized from silica gel column chromatography (heptane: ethyl acetate = 20: 1 (volume ratio)) and heptane to obtain (T-28) as a white powder (19.8 g).

Synthesis of (T-29) Compound (T-28) (19.8 g) obtained by the above operation was dissolved in toluene (150 ml) and isopropyl alcohol (IPA) (150 ml), and Pd-C (NX Type) (0.89 g) was added, and the reaction system was purged with hydrogen and stirred at room temperature for 14 hours. After completion of the reaction, Pd—C was separated by filtration and concentrated under reduced pressure to obtain a light black solid. This was recrystallized from heptane to obtain (T-29) as a white powder (19.6 g).

Synthesis of (T-30) Compound (T-29) (19.6 g) obtained by the above operation was dissolved in dryTHF (400 ml), cooled to -70 ° C, and then sec-BuLi (119 ml) was slowly added. The solution was added dropwise and stirred as it was for 1 hour. Thereafter, a dry THF (150 ml) solution of iodine (15.2 g) was slowly added dropwise, and the mixture was warmed to room temperature and stirred for 3 hours. After completion of the reaction, a saturated aqueous sodium thiosulfate solution was added and extracted with toluene. The organic layer was washed with water and a saturated aqueous sodium chloride solution, then dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a pale yellow solid. This was recrystallized with silica gel column chromatography (heptane: ethyl acetate = 4: 1 (volume ratio)) and a mixed solvent of heptane / toluene = 4/1 (volume ratio) to obtain (T-30). Obtained as a white powder (21.9 g).

Synthesis of (T-31) Compound (T-30) (21.9 g), 3,4,5-trifluorophenylboronic acid (14.4 g), Pd-C (NX type) ( Toluene (100 ml), Solmix (100 ml) and water (5.0 ml) were added to 0.15 g) and potassium carbonate (18.8 g), and the mixture was heated to reflux for 5 hours under a nitrogen atmosphere. After completion of the reaction, Pd—C was filtered off, and the filtrate was washed with saturated aqueous sodium hydrogen carbonate solution, water and saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give a pale yellow solid. This was recrystallized from silica gel column chromatography (heptane: ethyl acetate = 4: 1 (volume ratio)) and a mixed solvent of heptane / toluene = 4/1 (volume ratio) to obtain (T-31). Obtained (19.1 g) as a white powder.

Synthesis of (T-32) Compound (T-31) (19.1 g) obtained by the above operation was dissolved in formic acid (16.0 ml) and 200 ml of toluene, and the mixture was heated to reflux for 6 hours in a nitrogen atmosphere. Since the progress of the reaction was slow, formic acid (8.0 ml) was added three times along the way. After completion of the reaction, a saturated aqueous sodium hydrogen carbonate solution was added little by little with stirring and extracted with toluene. The organic layer was washed with water and a saturated aqueous sodium chloride solution, then dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a pale yellow solid. This was recrystallized with a mixed solvent of heptane / toluene = 4/1 (volume ratio) to give (T-31) as a white powder (14.4 g).

Synthesis of (T-34) Phosphonium salt (T-33) (25.0 g) vacuum-dried for 1 hour was added to dryTHF200.
ml was added and cooled to -70 ° C. Under a nitrogen atmosphere, potassium-t-butoxide (6.84 g) was added in small portions and stirred for 1 hour. Thereafter, a dry THF solution of the compound (T-32) (14.4 g) obtained by the above operation was slowly added dropwise, and the mixture was warmed to room temperature and stirred for 4 hours. After completion of the reaction, the mixture was ice-cooled, water was added with stirring, and the mixture was extracted with toluene. The organic layer was washed with water and a saturated aqueous sodium chloride solution, then dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a pale yellow solid. This was recrystallized from silica gel column chromatography (heptane: ethyl acetate = 20: 1 (volume ratio)) and heptane to obtain (T-34) as a white powder (14.5 g).

Synthesis of (T-35) Potassium carbonate (14.9 g) and dichloromethane (200 ml) were added to the compound (T-34) (14.5 g) obtained by the above operation, and the mixture was cooled with ice, and then metachloroperbenzoic acid ( mCPBA) (8.22 g) was added, and the mixture was stirred at room temperature under a nitrogen atmosphere for 14 hours. Since the progress of the reaction was slow, mCPBA (4.11 g) was added twice in the middle. After completion of the reaction, a saturated aqueous sodium thiosulfate solution was added and extracted with dichloromethane. The organic layer was washed with a saturated aqueous sodium bicarbonate solution, water, and a saturated aqueous sodium chloride solution, then dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give (T-35) as a black oil (10.1 g).

Synthesis of (T-36) To the compound (T-35) (10.1 g) obtained by the above operation, triphenylphosphine dibromide (18.2 g) and toluene (200 ml) were added, and heated in a nitrogen atmosphere for 8 hours. Refluxed. After completion of the reaction, the mixture was extracted with toluene, washed with water and saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a black yellow oil. This was purified by silica gel column chromatography (heptane: toluene = 20: 1 (volume ratio)) to give (T-36) as a yellow oil (4.27 g).

Synthesis of 3,4,5,2'-tetrafluoro-4'-octa-3,7-dienyl-biphenyl (1-a-2-2) Compound (T-36) (4. 27 g) was dissolved in acetic acid (100 ml), and zinc powder (0.85 g) was added in small portions and then stirred at room temperature for 3 hours under a nitrogen atmosphere. After completion of the reaction, insoluble matters were filtered off and extracted with heptane. The organic layer was washed with a saturated aqueous solution of sodium bicarbonate, water, and a saturated aqueous solution of sodium chloride, then dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give a black brown oil. This was purified by silica gel column chromatography (heptane: toluene = 40: 1 (volume ratio)) to obtain the title compound as a colorless viscous liquid (1.2 g).

  Table 2 shows the physical property values of the compounds. The physical property values were measured in the same manner as in Examples 1 and 2 above.

[Example 6]
4-Chloro-3,2′-difluoro-4′-octa-3,7-dienyl-biphenyl (1-a-2-1) was obtained by the above procedure in the same manner as described in Example 5. Compound (T-30) (21.9 g) and 3-chloro-4-fluorophenylboronic acid (14.2 g) were obtained as a colorless viscous liquid (1.4 g).

  Table 2 shows the physical property values of the compounds. The physical property values were measured in the same manner as in Examples 1 and 2 above.

[Example 7]
4,2 ′, 6′-Trifluoro-4 ″ -octa-3,7-dienyl- [1,1 ′, 4 ′, 1 ″] terphenyl (1-b-3-1) in Example 1 In the same manner as shown, 4-bromobenzaldehyde (38.5 g), 4-fluorophenylboronic acid (21.0 g)
And 3,5-difluorophenylboronic acid (39.5 g) was obtained as a white powder (1.8 g).

[Example 8]
4-Chloro-2 ', 6'-difluoro-4 "-octa-3,7-dienyl- [1,1', 4 ', 1"] terphenyl (1-b-3-2) In the same manner as described in 1), 4-bromobenzaldehyde (30.8 g), 4-chlorophenylboronic acid (23.4 g) and 3,5-difluorophenylboronic acid (31.6 g) were used as a white powder (1 0.5 g) was obtained.

[Example 9]
3,4,5,2 ', 6'-pentafluoro-4 "-octa-3,7-dienyl- [1,1', 4 ', 1"] terphenyl (1-b-3-5) In a manner similar to that shown in Example 1, 4-bromobenzaldehyde (30.8 g), 3,4,5-trifluorophenylboronic acid (17.6 g) and 3,5-difluorophenylboronic acid (31. 6g) was obtained as a white powder (1.7g).

[Example 10]
4-Chloro-3,5,2 ', 6'-tetrafluoro-4 "-octa-3,7-dienyl- [1,1', 4 ', 1"] terphenyl (1-b-3-6 ) In the same manner as described in Example 1 and the synthesis method described, 4-bromobenzaldehyde (30.8 g), 4-chloro-3,5-difluorophenylboronic acid (19.2 g) and 3,5 -Difluorophenylboronic acid (31.6 g) was obtained as a white powder (1.4 g).

[Example 11]
3,4,5-Trifluoro-4 ″ -octa-3,7-dienyl- [1,1 ′, 4 ′, 1 ″] terphenyl (1-b-1-3) is shown in Example 1. In the same manner as in the method and the synthesis method described, from 4-bromobenzaldehyde (19.3 g), 3,4,5-trifluorophenylboronic acid (17.6 g) and 4-chlorophenylboronic acid (23.4 g), Obtained as a white powder (1.7 g).

[Example 12]
Example 1 3-Fluoro-4'-octa-3,7-dienyl-4- [2- (3,4,5-trifluoro-phenyl) -ethyl] -biphenyl (1-b-2-7) And 4-bromobenzaldehyde (38.5 g), 3,4,5-trifluorophenylboronic acid (26.4 g) and 3-fluorophenylboronic acid (35. 0g), (1.4g) was obtained as a white powder.

[Example 13]
Example of 4- [2- (4-Chloro-3,5-difluoro-phenyl) -ethyl] -3-fluoro-4'-octa-3,7-dienyl-biphenyl (1-b-2-6) 4-bromobenzaldehyde (30.8 g), 3,4,5-trifluorophenylboronic acid (26.4 g) and 3-fluorophenylboronic acid (28 0.0g), (1.2g) was obtained as a white powder.

[Example 14]
3,4,5,2'-tetrafluoro-4 "-nona-3,7-dienyl- [1,1 ', 4', 1"] terphenyl (1-b-2-41) 4-Bromobenzaldehyde (23.1 g), 3,4,5-trifluorophenylboronic acid (17.6 g) and 3-fluorophenylboronic acid (21. 0
From g), white powder (1.3 g) was obtained.

[Example 15]
3,4,5,2'-pentafluoro-4 ""-octa-3,7-dienyl- [1,1 ', 4', 1 ", 4", 1 ""] quaterphenyl (1-c- In the same manner as in Example 1 and the synthesis method described in Example 2-2), 4-bromobenzaldehyde (43.2 g), 4-bromophenylboronic acid (56.3 g), 3,4,5- The title compound was obtained as a white powder (1.9 g) from trifluorophenylboronic acid (17.6 g) and 3-fluorophenylboronic acid (28.0 g).

[Example 16]
3,4,5,2 ', 2 "-pentafluoro-4""-octa-3,7-dienyl-[1,1', 4 ', 1", 4 ", 1""] quaterphenyl (1 -C-4-1) was synthesized according to the synthesis scheme shown below.

Synthesis of (T-37) Compound (T-12) (22.1 g) obtained in Example 1, 3-fluorophenylboronic acid (8.55 g), Pd-C (NX type) (0.66 g) Toluene (100 ml), Solmix (100 ml) and water (5.0 ml) were added to potassium carbonate (15.3 g), and the mixture was heated to reflux for 5 hours under a nitrogen atmosphere. After completion of the reaction, Pd—C was filtered off, and the filtrate was washed with saturated aqueous sodium hydrogen carbonate solution, water and saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give a pale yellow solid. This was subjected to silica gel column chromatography (heptane: ethyl acetate = 4: 1 (volume ratio)) and recrystallized (heptane: toluene = 4: 1 (volume ratio)) to give (T-37) as a white powder. As (14.7 g).

Synthesis of (T-38) Compound (T-37) (29.4 g) obtained by the above operation was dissolved in dryTHF (400 ml), cooled to -70 ° C, and then sec-BuLi (96 ml) was slowly added. The solution was added dropwise and stirred for 3 hours. Thereafter, a dry THF (150 ml) solution of iodine (30.6 g) was slowly added dropwise, and the mixture was warmed to room temperature and stirred for 12 hours. After completion of the reaction, a saturated aqueous sodium thiosulfate solution was added and extracted with toluene. The organic layer was washed with water and a saturated aqueous sodium chloride solution, then dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a pale yellow solid. This was subjected to silica gel column chromatography (heptane: ethyl acetate = 4: 1 (volume ratio)) and recrystallized (heptane: toluene = 4: 1 (volume ratio)) to give (T-38) as a white powder. As (17.2 g).

Synthesis of (T-39) Compound (T-38) (17.2 g), 3,4,5-trifluorophenylboronic acid (6.78 g), Pd-C (NX type) ( Toluene (150 ml), Solmix (150 ml) and water (7.5 ml) were added to 0.52 g) and potassium carbonate (9.66 g), and the mixture was heated to reflux for 6 hours under a nitrogen atmosphere. After completion of the reaction, Pd—C was filtered off, and the filtrate was washed with saturated aqueous sodium hydrogen carbonate solution, water and saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give a pale yellow solid. This was subjected to silica gel column chromatography (heptane: ethyl acetate = 4: 1 (volume ratio)) and recrystallized (heptane: toluene = 4: 1 (volume ratio)) to give (T-39) as a white powder. As (20.2 g).

Synthesis of (T-40) The compound (T-39) (20.2 g) obtained by the above operation was dissolved in formic acid (8.0 ml) and 200 ml of toluene, and heated to reflux for 6 hours in a nitrogen atmosphere. Since the progress of the reaction was slow, formic acid (8 ml) was added twice on the way. After completion of the reaction, a saturated aqueous sodium hydrogen carbonate solution was added little by little with stirring and extracted with toluene. The organic layer was washed with water and a saturated aqueous sodium chloride solution, then dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a pale yellow solid. This was recrystallized (heptane: toluene = 4: 1 (volume ratio)) to give (T-40) as a white powder (16.0 g).

Synthesis of (T-41) 200 ml of dryTHF was added to phosphonium salt (T-15) (15.2 g) which was vacuum-dried for 1 hour, and cooled to -70 ° C. Under a nitrogen atmosphere, potassium tert-butoxide (4.17 g) was added in small portions and stirred for 1 hour. Thereafter, a dry THF solution of the compound (T-40) (14.0 g) obtained by the above operation was slowly added dropwise, and the mixture was warmed to room temperature and stirred for 4 hours. After completion of the reaction, the mixture was ice-cooled, water was added with stirring, and the mixture was extracted with toluene. The organic layer was washed with water and a saturated aqueous sodium chloride solution, then dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a pale yellow solid. This was recrystallized from silica gel column chromatography (heptane: ethyl acetate = 20: 1 (volume ratio)) and heptane to obtain (T-41) as a white powder (10.8 g).

Synthesis of (T-42) To compound (T-41) (10.8 g) obtained by the above operation, potassium carbonate (7.40 g) and dichloromethane (100 ml) were added and ice-cooled, and then metachloroperbenzoic acid ( mCPBA) (11.1 g) was added and stirred at room temperature under a nitrogen atmosphere for 14 hours. Since the progress of the reaction was slow, mCPBA (6.5 g) was added twice on the way. After completion of the reaction, a saturated aqueous sodium thiosulfate solution was added and extracted with dichloromethane. The organic layer was washed with saturated aqueous sodium hydrogen carbonate solution, water and saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give (T-42) as a black oil (10.6 g).

Synthesis of (T-43) To the compound (T-42) (10.6 g) obtained by the above operation, triphenylphosphine dibromide (13.3 g) and toluene (200 ml) were added, and heated under a nitrogen atmosphere for 8 hours. Refluxed. After completion of the reaction, the mixture was extracted with toluene, washed with water and saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a black yellow oil. This was purified by silica gel column chromatography (heptane: ethyl acetate = 4: 1 (volume ratio)) to give (T-43) as a yellow oil (11.2 g).

3,4,5,2 ', 2 "-pentafluoro-4""-octa-3,7-dienyl-[1,1', 4 ', 1", 4 ", 1""] quaterphenyl (1 -C-4-1) Synthesis Compound (T-43) (11.2 g) obtained by the above operation was dissolved in acetic acid (100 ml), and zinc powder (4.41 g) was added in small portions. Thereafter, the mixture was stirred at room temperature for 3 hours under a nitrogen atmosphere, and after completion of the reaction, the insoluble material was filtered off and extracted with heptane. It was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain a black brown oily substance, which was recrystallized with silica gel column chromatography (heptane: toluene = 40: 1 (volume ratio)) and heptane, Title compound (1-c-4- 1) was obtained as a white powder (1.0 g).

  Table 22 shows the physical property values of the compounds. The physical property values were measured in the same manner as in Examples 1 and 2 above.

[Example 17]
4-chloro-3,2 ′, 2 ″ -trifluoro-4 ″ ″-octa-3,7-dienyl- [1,1 ′, 4 ′, 1 ″, 4 ″, 1 ″ ′] quarterphenyl (1 -C-4-7) in the same manner as in Example 16, compound (T-38) (20.0 g) obtained by the above operation and 3-chloro-4-fluorophenylboronic acid (7 .42 g) was obtained as a white powder (0.14 g).

  Table 22 shows the physical property values of the compounds. The physical property values were measured in the same manner as in Examples 1 and 2 above.

  The following compounds are synthesized based on the synthesis methods described in Examples 1 to 17. Of the compounds represented by the general formula (1), compounds with p = 1 and m = n = 0 are shown in Tables 1 to 4. Of the compounds represented by the general formula (1), compounds having p = 1, m = 0, and n = 1 are shown in Tables 5 to 15. Of the compounds represented by the general formula (1), compounds having p = 1 and m = n = 1 are shown in Tables 16 to 24. Compounds obtained in Examples 1 to 17 (1-a-1-1, 1-a-1-2, 1-a-2-1, 1-a-2-2, 1-b-1-- 3, 1-b-2-1, 1-b-2-2, 1-b-2-6, 1-b-2-7, 1-b-2-41, 1-b-3-1, 1-b-3-2, 1-b-3-5, 1-b-3-6, 1-c-2-2, 1-c-4-1 and 1-c-4-7) are also reprinted did.

  An example of a typical composition of the present invention is shown below. The physical property values were measured according to the methods described later.

[Composition Example 1]
Four compounds were mixed to prepare a composition A (mother liquid crystal) having a nematic phase. The four compounds are 4- (4-propylcyclohexyl) benzonitrile (24%), 4- (4
-Pentylcyclohexyl) benzonitrile (36%), 4- (4-heptylcyclohexyl) benzonitrile (25%), 4- (4-pentylcyclohexyl) -4'-cyanobiphenyl (15%).

The physical properties of composition A were as follows. Maximum temperature (NI) = 71.7 ° C .; viscosity (η ₂₀ ) = 27.0 mPa · s; optical anisotropy (Δn) = 0.137; dielectric anisotropy (Δε) = 11.0.

  15% of this composition A was mixed with 3,4,5,2′-tetrafluoro-4 ″ -octa-3,7-dienyl- [1,1 ′, 4 ′, 1 ″] terphenyl described in Example 1. The physical properties were measured by adding mass%. As a result, the maximum temperature (NI) was 58.4 ° C .; the optical anisotropy (Δn) = 0.197; and the dielectric anisotropy (Δε) = 17.4.

[Comparative Example 1]
A composition comprising 85% of Composition A described in Composition Example 1 and 15% of 4 "-fluoro-4-hexa-1,5-dienyl- [1,1 ', 4', 1"] terphenyl. Was prepared, and physical property values were measured. However, this compound did not dissolve in the mother liquid crystal at all, and the physical property values could not be measured. Since this compound has a structure in which a double bond is directly bonded to phenylene, the stability is extremely poor, and it is expected that a polymerization reaction has occurred. Therefore, the same thing is expected to occur in other compounds having such a structure.

  Further, representative compositions of the present invention are summarized in Composition Examples 2-14. Initially, the compound which is a component of a composition, and its quantity (mass%) were shown. The compounds were indicated by the symbols of the left terminal group, linking group, ring structure, and right terminal group according to the conventions in Table 25. The configuration of 1,4-cyclohexylene and 1,3-dioxane-2,5-diyl is trans. If there is no end group symbol, it means that the end group is hydrogen. Next, physical property values of the composition are shown.

  The characteristic value can be measured according to the following method. Many of them are the method described in the Standard of Electric Industries Association of Japan EIAJ ED-2521A or a modified method thereof. No TFT was attached to the TN device used for measurement.

Transition temperature (° C.): Measured by one of the following methods. 1) A sample was placed on a hot plate (Mettler FP-52 type hot stage) of a melting point measuring apparatus equipped with a polarizing microscope and heated at a rate of 1 ° C./min. The temperature at which the sample changed phase was measured. 2) Using a scanning calorimeter DSC-7 system manufactured by PerkinElmer Co., Ltd., it was measured at a rate of 3 ° C./min.

The crystal was represented as C. When the crystal could be distinguished, it was expressed as C ₁ or C ₂ respectively. The smectic phase was represented as S. The liquid (isotropic) was expressed as Iso. The nematic phase was represented as N. In the smectic phase, when a smectic B phase, a smectic C phase or a smectic A phase can be distinguished, they are represented as S _B , S _C or S _A , respectively. As a notation of transition temperature, “C 92.9 N 196.9 Iso” means that the transition temperature (CN) from the crystal to the nematic phase is 92.9 ° C., and the transition temperature from the nematic phase to the liquid (NI). Is 196.9 ° C. The same applies to other notations.

  Maximum temperature of nematic phase (NI; ° C.): A sample was placed on a hot plate of a melting point measuring apparatus equipped with a polarizing microscope and heated at a rate of 1 ° C./min. The temperature was measured when a part of the sample changed from a nematic phase to an isotropic liquid. The upper limit temperature of the nematic phase may be abbreviated as “upper limit temperature”.

Minimum temperature of nematic phase (T _C ; ° C.): A sample having a nematic phase is stored in a freezer at 0 ° C., −10 ° C., −20 ° C., −30 ° C., and −40 ° C. Observed. For example, when the sample remains in a nematic phase at −20 ° C. and changes to a crystal (or smectic phase) at −30 ° C., T _C is described as ≦ −20 ° C. The lower limit temperature of the nematic phase may be abbreviated as “lower limit temperature”.

  Compound compatibility: A mother liquid crystal having a nematic phase was prepared by mixing several compounds having a similar structure. A composition in which the compound to be measured and this mother liquid crystal were mixed was obtained. An example of the mixing ratio is 15% compound and 85% mother liquid crystal. This composition was stored at a low temperature such as −20 ° C. and −30 ° C. for 30 days. It was observed whether a part of this composition was changed to a crystal (or smectic phase). The mixing ratio and storage temperature were changed as necessary. From the measurement results, the conditions under which crystals (or smectic phases) precipitate and the conditions under which crystals (or smectic phases) do not precipitate were determined. These conditions are a measure of compatibility.

  Viscosity (η; measured at 20 ° C .; mPa · s): An E-type viscometer was used for measurement.

  Rotational viscosity (γ1; measured at 25 ° C .; mPa · s): 1) Sample with positive dielectric anisotropy: measured by M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995) ) Was followed. A sample was put in a TN device having a twist angle of 0 ° and a distance (cell gap) between two glass substrates of 5 μm. The voltage was applied to the TN device stepwise in the range of 16 to 19.5 volts every 0.5 volts. After no application for 0.2 seconds, the application was repeated under the condition of only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds). The peak current and peak time of the transient current generated by this application were measured. The value of rotational viscosity was obtained from these measured values and the paper by M. Imai et al., Formula (8) on page 40. The value of dielectric anisotropy necessary for this calculation was obtained by the following dielectric anisotropy measurement method using the element used for the measurement of the rotational viscosity.

2) Sample with negative dielectric anisotropy: Measurement was performed according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). A sample was put in a VA device having a distance (cell gap) between two glass substrates of 20 μm. This element was applied stepwise in increments of 1 volt in the range of 30 to 50 volts. After no application for 0.2 seconds, the application was repeated under the condition of only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds). The peak current and peak time of the transient current generated by this application were measured. The value of rotational viscosity was obtained from these measured values and the paper by M. Imai et al., Formula (8) on page 40. As the dielectric anisotropy necessary for this calculation, a value measured by the following dielectric anisotropy was used.

  Optical anisotropy (refractive index anisotropy; Δn; measured at 25 ° C.): Measurement was performed with an Abbe refractometer using a light having a wavelength of 589 nm and a polarizing plate attached to an eyepiece. After rubbing the surface of the main prism in one direction, the sample was dropped on the main prism. The refractive index (n‖) was measured when the direction of polarized light was parallel to the direction of rubbing. The refractive index (n⊥) was measured when the direction of polarized light was perpendicular to the direction of rubbing. The value of optical anisotropy was calculated from the equation: Δn = n∥−n⊥. When the sample was a composition, the optical anisotropy was measured by this method. When the sample was a compound, the optical anisotropy was measured after mixing the compound with an appropriate composition. The optical anisotropy of the compound is an extrapolated value.

  Dielectric Anisotropy (Δε; measured at 25 ° C.): When the sample was a compound, the compound was mixed with an appropriate composition, and then the dielectric anisotropy was measured. The dielectric anisotropy of the compound is an extrapolated value. 1) Composition having a positive dielectric anisotropy: A sample was placed in a liquid crystal cell in which the distance (gap) between two glass substrates was about 9 μm and the twist angle was 80 degrees. 20 volts was applied to the cell, and the dielectric constant (ε 率) in the major axis direction of the liquid crystal molecules was measured. 0.5 V was applied, and the dielectric constant (ε⊥) in the minor axis direction of the liquid crystal molecules was measured. The value of dielectric anisotropy was calculated from the equation: Δε = ε∥−ε⊥.

2) Composition having a negative dielectric anisotropy: A sample was placed in a liquid crystal cell treated in a homeotropic alignment, and 0.5 volt was applied to measure the dielectric constant (ε ボ ル ト). A sample was put in a liquid crystal cell treated to homogeneous alignment, and a dielectric constant (ε⊥) was measured by applying 0.5 volts. The value of dielectric anisotropy was calculated from the equation: Δε = ε∥−ε⊥.

  Threshold voltage (Vth; measured at 25 ° C .; V): When the sample was a compound, the threshold voltage was measured after mixing the compound with an appropriate composition. The threshold voltage of the compound is an extrapolated value. 1) A composition having a positive dielectric anisotropy: a normally white mode (normally white mode) in which a distance (gap) between two glass substrates is (0.5 / Δn) μm and a twist angle is 80 degrees. A sample was put in a liquid crystal display element in white mode). Δn is a value of optical anisotropy measured by the above method. A rectangular wave having a frequency of 32 Hz was applied to this element. The voltage of the rectangular wave was increased and the value of the voltage when the transmittance of light passing through the element reached 90% was measured.

2) Composition having a negative dielectric anisotropy: For a normally black mode liquid crystal display element in which the distance (gap) between two glass substrates is about 9 μm and is processed in a homeotropic alignment. A sample was placed. A rectangular wave having a frequency of 32 Hz was applied to this element. The voltage of the rectangular wave was raised, and the value of the voltage when the transmittance of light passing through the element reached 10% was measured.

  Voltage holding ratio (VHR; measured at 25 ° C .;%): The TN device used for measurement has a polyimide alignment film, and the distance between two glass substrates (cell gap) is 6 μm. This element was sealed with an adhesive polymerized by ultraviolet rays after putting a sample. The TN device was charged by applying a pulse voltage (60 microseconds at 5 V). The decaying voltage was measured for 16.7 milliseconds with a high-speed voltmeter, and the area A between the voltage curve and the horizontal axis in a unit cycle was determined. The area B is an area when it is not attenuated. The voltage holding ratio is a percentage of the area A with respect to the area B.

Helical pitch (measured at 20 ° C .; μm): Kano's wedge cell method was used to measure the helical pitch. A sample was injected into a Kano wedge-shaped cell, and the distance (a; unit: μm) between disclination lines observed from the cell was measured. The helical pitch (P) is given by the formula P = 2 · a
Calculated from tan θ. θ is the angle between the two glass plates in the wedge-shaped cell.

  The ratio (percentage) of the component or the liquid crystal compound is a mass percentage (% by mass) based on the total mass of the liquid crystal compound. The composition is prepared by measuring the mass of a component such as a liquid crystal compound and then mixing them. Therefore, it is easy to calculate the mass% of the component.

  In the measurement of characteristic values, there are three methods: when a single compound is used as it is as a sample, when a compound is mixed with mother liquid crystals and used as a sample, and when a composition is used as a sample as it is. When the compound is mixed with the mother liquid crystal, the following method is taken. Samples were prepared by mixing 15% by weight compound and 85% by weight mother liquid crystals. The characteristic value of the compound was calculated from the value obtained by the measurement by extrapolation. Extrapolated value = (measured value of sample−0.85 × measured value of mother liquid crystal) /0.15. When the smectic phase (or crystal) precipitates at 25 ° C. at this ratio, the ratio of the compound and the mother liquid crystal is 10% by mass: 90% by mass, 5% by mass: 95% by mass, and 1% by mass: 99% by mass in this order. changed.

  Of the values obtained by measurement, the values obtained using the compound alone as a sample and the values obtained using the composition as a sample are described as experimental data. Values obtained by mixing a compound with mother liquid crystals and used as a sample may be described as experimental data as they are, or may be described as values obtained by extrapolation.

  As a solvent for diluting the sample, chloroform, hexane or the like may be used. In order to separate the component compounds, the following capillary column may be used. HP-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by Agilent Technologies Inc., Rtx-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by Restek Corporation, BP-1 made by SGE International Pty. Ltd (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm). In order to prevent compound peaks from overlapping, a capillary column CBP1-M50-025 (length 50 m, inner diameter 0.25 mm, film thickness 0.25 μm) manufactured by Shimadzu Corporation may be used. The area ratio of peaks in the gas chromatogram corresponds to the ratio of component compounds. The mass% of the component compound is not completely the same as the area ratio of each peak. However, in the present invention, when using these capillary columns, the mass% of the component compounds may be regarded as the same as the area ratio of each peak. This is because there is no significant difference in the correction coefficients of the component compounds.

[Composition Example 2]
V2V2-BB (F) B (F, F) -F 5%
V2V2-BB (F) B (F) -CL 5%
2-BEB (F) -C 5%
3-BEB (F) -C 4%
4-BEB (F) -C 12%
1V2-BEB (F, F) -C 14%
3-HB-O2 8%
3-HH-4 3%
3-HHB-F 3%
3-HHB-1 4%
3-HHB-O1 4%
3-HBEB-F 4%
3-HHEB-F 6%
5-HHEB-F 6%
3-H2BTB-2 4%
3-H2BTB-3 4%
3-H2BTB-4 4%
3-HB (F) TB-2 5%
NI = 84.1 ° C .; Δn = 0.145; Δε = 27.2; Vth = 1.17 V.

[Composition Example 3]
V2V2-BB-F 5%
V2V2-BB-CL 4%
2-HB-C 5%
3-HB-C 12%
3-HB-O2 15%
2-BTB-1 3%
3-HHB-F 4%
3-HHB-1 8%
3-HHB-O1 5%
3-HHB-3 13%
3-HHEB-F 4%
5-HHEB-F 4%
2-HHB (F) -F 4%
3-HHB (F) -F 4%
5-HHB (F) -F 5%
3-HHB (F, F) -F 5%

[Composition Example 4]
V2V2-B (F) B (F, F) -F 5%
V2V2-B (F) B (F) -CL 3%
3-BEB (F) -C 8%
3-HB-C 8%
V-HB-C 8%
1V-HB-C 8%
3-HB-O2 3%
3-HH-2V 11%
3-HH-2V1 7%
V2-HHB-1 10%
3-HHB-1 5%
3-HHEB-F 7%
3-H2BTB-2 6%
3-H2BTB-3 6%
3-H2BTB-4 5%

[Composition Example 5]
V2V2-BBB (F, F) -F 3%
1V2V2-BB (F) B (F, F) -F 4%
V2V2-BB (F) 2B (F, F) -F 4%
5-BEB (F) -C 5%
V-HB-C 8%
5-PyB-C 6%
4-BB-3 8%
3-HH-2V 10%
5-HH-V 11%
V-HHB-1 7%
V2-HHB-1 10%
3-HHB-1 9%
1V2-HBB-2 10%
3-HHEBH-3 5%

[Composition Example 6]
V2V2-BB (F) 2B (F) -CL 4%
V2V2-BB (F, F) B-F 4%
1V2-BEB (F, F) -C 6%
3-HB-C 18%
2-BTB-1 10%
5-HH-VFF 22%
3-HHB-1 4%
VFF-HHB-1 8%
VFF2-HHB-1 11%
3-H2BTB-2 5%
3-H2BTB-3 4%
3-H2BTB-4 4%

[Composition Example 7]
V2V2-BB (F) B (F, F) -F 4%
V2V2-BB (F) B (F) -CL 4%
5-HB-CL 16%
3-HH-4 12%
3-HH-5 4%
3-HHB-F 4%
3-HHB-CL 3%
4-HHB-CL 4%
3-HHB (F) -F 8%
4-HHB (F) -F 7%
5-HHB (F) -F 7%
7-HHB (F) -F 6%
5-HBB (F) -F 4%
1O1-HBBH-5 3%
3-HHBB (F, F) -F 2%
4-HHBB (F, F) -F 3%
5-HHBB (F, F) -F 3%
3-HH2BB (F, F) -F 3%
4-HH2BB (F, F) -F 3%
NI = 110.5 ° C .; Δn = 0.095; Δε = 3.8; Vth = 2.62V.

  When 0.25 part of Op-05 was added to 100 parts of the composition, the helical pitch was 61.0 μm.

[Composition Example 8]
V2V2-BB (F, F) B-CL 4%
V2V2-BB (F, F) B (F, F) -F 3%
3-HHB (F, F) -F 9%
3-H2HB (F, F) -F 8%
4-H2HB (F, F) -F 8%
5-H2HB (F, F) -F 8%
3-HBB (F, F) -F 18%
5-HBB (F, F) -F 16%
3-H2BB (F, F) -F 10%
5-HHBB (F, F) -F 3%
5-HHEBB-F 3%
3-HH2BB (F, F) -F 2%
1O1-HBBH-4 4%
1O1-HBBH-5 4%

[Composition Example 9]
V2V2-BB (F, F) B (F, F) -CL 5%
V2V2-BBB (F) B (F, F) -F 3%
5-HB-F 12%
6-HB-F 9%
7-HB-F 7%
2-HHB-OCF3 7%
3-HHB-OCF3 7%
4-HHB-OCF3 7%
5-HHB-OCF3 5%
3-HH2B-OCF3 4%
5-HH2B-OCF3 4%
3-HHB (F, F) -OCHF2 4%
3-HHB (F, F) -OCF3 5%
3-HH2B (F) -F 3%
3-HBB (F) -F 6%
5-HBB (F) -F 6%
5-HBBH-3 3%
3-HB (F) BH-3 3%

[Composition Example 10]
V2V2-BB-F 6%
V2V2-BBB (F, F) -F 4%
5-HB-CL 11%
3-HH-4 8%
3-HHB-1 5%
3-HHB (F, F) -F 8%
3-HBB (F, F) -F 15%
5-HBB (F, F) -F 10%
3-HHEB (F, F) -F 10%
4-HHEB (F, F) -F 3%
5-HHEB (F, F) -F 3%
2-HBEB (F, F) -F 3%
3-HBEB (F, F) -F 5%
5-HBEB (F, F) -F 3%
3-HHBB (F, F) -F 6%

[Composition Example 11]
V2V2-BB-CL 3%
V2V2-B (F) B (F) -CL 3%
3-HB-CL 6%
5-HB-CL 4%
3-HHB-OCF3 5%
3-H2HB-OCF3 5%
5-H4HB-OCF3 15%
V-HHB (F) -F 5%
3-HHB (F) -F 4%
5-HHB (F) -F 4%
3-H4HB (F, F) -CF3 8%
5-H4HB (F, F) -CF3 10%
5-H2HB (F, F) -F 5%
5-H4HB (F, F) -F 7%
2-H2BB (F) -F 3%
3-H2BB (F) -F 8%
3-HBEB (F, F) -F 5%

[Composition Example 12]
V2V2-BB (F) 2B (F, F) -F 5%
V2V2-BB (F) 2B (F) -CL 4%
5-HB-CL 17%
7-HB (F, F) -F 3%
3-HH-4 10%
3-HH-5 5%
3-HB-O2 10%
3-HHB-1 8%
3-HHB-O1 5%
2-HHB (F) -F 5%
3-HHB (F) -F 7%
5-HHB (F) -F 5%
3-HHB (F, F) -F 6%
3-H2HB (F, F) -F 5%
4-H2HB (F, F) -F 5%

[Composition Example 13]
V2V2-B (F) B (F, F) -F 4%
V2V2-BB (F, F) B (F, F) -F 4%
5-HB-CL 3%
7-HB (F) -F 7%
3-HH-4 9%
3-HH-EMe 15%
3-HHEB-F 8%
5-HHEB-F 8%
3-HHEB (F, F) -F 10%
4-HHEB (F, F) -F 5%
4-HGB (F, F) -F 5%
5-HGB (F, F) -F 6%
2-H2GB (F, F) -F 4%
3-H2GB (F, F) -F 5%
5-GHB (F, F) -F 7%

[Composition Example 14]
V2V2-BB (F, F) B-F 3%
V2V2-BB (F, F) B-CL 3%
V2V2-BBB (F) B (F, F) -F 3%
3-HH-4 8%
3-HHB-1 6%
3-HHB (F, F) -F 10%
3-H2HB (F, F) -F 9%
3-HBB (F, F) -F 15%
3-BB (F, F) XB (F, F) -F 26%
1O1-HBBH-5 7%
2-HHBB (F, F) -F 3%
3-HHBB (F, F) -F 3%
3-HH2BB (F, F) -F 4%

Claims (31)

The compound represented by General formula (1).

[Wherein R ¹ is hydrogen, alkyl having 1 to 5 carbons, or alkenyl having 2 to 5 carbons;
Ring A ¹ is 1,4-phenylene, in which any hydrogen may be replaced by halogen, and ring A ² and ring A ³ are independently 1,4-cyclohexylene, 1,4- Phenylene, 1,4-cyclohexenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, or 1,2,3,4-tetrahydronaphthalene-2,6-diyl, these Any —CH ₂ — in the ring may be replaced by —O— or —S—, and any —CH═ may be replaced by —N═, and any hydrogen in these rings May be replaced by halogen;
Z ¹ , Z ² and Z ³ are each independently a single bond, —CH ₂ CH ₂ —, —CH═CH—, —C≡C—, —COO—, —OCO—, —CF ₂ O—, — _{OCF 2 -, - CH 2 O} -, - OCH 2 -, - CF = CF -, - (CH 2) 4 -, - O (CH 2) 2 O -, - (CH 2) 2 CF 2 O-, _{- (CH 2) 2 OCF 2} -, - CF 2 O (CH 2) 2 -, - OCF 2 (CH 2) 2 -, - CH = CH-CH 2 O-, or -OCH ₂ -CH = CH- Is;
L ¹ and L ² are independently hydrogen or fluorine;
X ¹ is a group represented by hydrogen, fluorine, chlorine, —C≡N, —N═C═S, —SF ₅ , or —Q—W, Q is a single bond, oxygen, or sulfur; Is a C 1-5 alkyl in which at least one hydrogen is replaced by a halogen;
n and m are each independently 0 or 1, and p is an integer of 1 to 4. ] The compound according to claim ¹ , wherein ring A ¹ , ring A ² and ring A ³ are independently 1,4-phenylene or halogenated 1,4-phenylene. At least one of ring A ¹ , ring A ² and ring A ³ is halogenated 1,4-phenylene, and halogenated 1,4-phenylene is fluorinated 1,4-phenylene. The compound according to claim 2.   The compound according to claim 3, wherein the fluorinated 1,4-phenylene is 2-fluoro-1,4-phenylene or 2,6-difluoro-1,4-phenylene. The compound according to claim ¹ , wherein at least one of ring A ¹ , ring A ² and ring A ³ is pyrimidine-2,5-diyl. The compound according to any one of claims 1 to 5, wherein at least one of Z ¹ , Z ² and Z ³ is a single bond. Any one of Z ¹ , Z ² and Z ³ is —CH ₂ CH ₂ —, —CH═CH—, —C≡C—, —COO—, —OCO—, —CF ₂ O—, —OCF _{2 -, - CH 2 O -,} - OCH 2 -, or -CF = CF-, a compound according to claim 6. The compound according to claim 6, wherein Z ¹ , Z ² and Z ³ are all a single bond. The compound according to any one of claims 1 to 8, wherein at least one of L ¹ , L ² and X ¹ is halogen. The compound of Claim 1 represented by any one of the following general formulas.
A compound represented by the following general formula (1-a) in which p = 1 and n = m = 0 in the general formula (1),
A compound represented by the following general formula (1-b) in which p = 1, n = 0, m = 1 in the general formula (1), or
A compound represented by the following general formula (1-c), wherein p = 1 and n = m = 1 in the general formula (1).

[Wherein R ¹ is hydrogen, alkyl having 1 to 5 carbons, or alkenyl having 2 to 5 carbons;
Ring A ¹ is 1,4-phenylene, in which any hydrogen may be replaced by halogen, and ring A ² and ring A ³ are independently 1,4-phenylene, 1,4-cyclohexyl. Senylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, or 1,2,3,4-tetrahydronaphthalene-2,6-diyl, and any-in 1,4-phenylene CH = may be replaced by -N = and any hydrogen in these rings may be replaced by halogen;
Z ¹ , Z ² and Z ³ are each independently a single bond, —CH ₂ CH ₂ —, —CH═CH—, —C≡C—, —COO—, —OCO—, —CF ₂ O—, — _{OCF 2 -, - CH 2 O} -, - OCH 2 -, or a -CF = CF-;
L ¹ and L ² are independently hydrogen or fluorine;
X ¹ is fluorine, chlorine, —C≡N, —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₃ , —OCHF ₂ , or —OCH ₂ F. ] Ring A ^1, ring A ² and ring A ³ are independently 1,4-phenylene or halogenated 1,4-phenylene, A compound according to claim 10. At least one of ring A ¹ , ring A ² and ring A ³ is halogenated 1,4-phenylene, and halogenated 1,4-phenylene is fluorinated 1,4-phenylene. 12. A compound according to claim 11.   The compound according to claim 12, wherein the fluorinated 1,4-phenylene is 2-fluoro-1,4-phenylene or 2,6-difluoro-1,4-phenylene. Ring A ^1, at least one of ring A ² and ring A ³ is a pyrimidine-2,5-diyl, A compound according to claim 10. The compound according to any one of claims 10 to 14, wherein at least one of Z ¹ , Z ² and Z ³ is a single bond. Any one of Z ¹ , Z ² and Z ³ is —CH ₂ CH ₂ —, —CH═CH—, —C≡C—, —COO—, —OCO—, —CF ₂ O—, —OCF ₂ -, - CH ₂ O-, or -OCH ₂ - the compound according to claim 15. The compound according to claim 15, wherein Z ¹ , Z ² and Z ³ are all a single bond. The compound according to any one of claims 10 to 17, wherein at least one of L ¹ , L ² and X ¹ is halogen. The compound according to claim 1, which is represented by any one of the following general formulas (1-1) to (1-48).

[Wherein R ¹ is hydrogen, alkyl having 1 to 5 carbons, or alkenyl having 2 to 5 carbons;
L ¹ , L ² and Y ^{1 to} Y ⁶ are independently hydrogen or fluorine;
X ¹ is fluorine, chlorine, —C≡N, —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₃ , —OCHF ₂ , or —OCH ₂ F. ] The compound according to claim 1, which is represented by any one of the following general formulas (1-49) to (1-51).

[Wherein L ¹ , L ² and Y ^{1 to} Y ³ are independently hydrogen or fluorine;
X ¹ is fluorine or chlorine. ]   A liquid crystal composition comprising two or more components, comprising at least one compound according to any one of claims 1 to 20. The liquid crystal composition according to claim 21, further comprising at least one compound selected from the group of compounds represented by formulas (2), (3), and (4).

[Wherein, R ² is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and any hydrogen may be replaced by fluorine, and in alkyl, any —CH ₂ — represents —O— May be replaced by;
X ² is fluorine, chlorine, —OCF ₃ , —OCHF ₂ , —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₂ CHF ₂ , or —OCF ₂ CHFCF ₃ ;
Ring B and Ring D are independently 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, or 1,4-phenylene in which any hydrogen may be replaced by fluorine, E is 1,4-cyclohexylene or 1,4-phenylene in which any hydrogen may be replaced by fluorine;
Z ⁴ and Z ⁵ are independently — (CH ₂ ) ₂ —, — (CH ₂ ) ₄ —, —COO—, —CF ₂ O—, —OCF ₂ —, —CH═CH—, or a single bond Is;
L ³ and L ⁴ are independently hydrogen or fluorine. ] The liquid crystal composition according to claim 21, further comprising at least one compound selected from the group of compounds represented by each of the general formulas (5) and (6).

[Wherein R ³ and R ⁴ are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and any hydrogen may be replaced by fluorine, and any —CH ₂ -may be replaced by -O-;
X ³ is —C≡N or —C≡C—C≡N;
Ring G is 1,4-cyclohexylene, 1,4-phenylene, 1,3-dioxane-2,5-diyl, or pyrimidine-2,5-diyl, and ring J is 1,4-cyclohexylene. , Pyrimidine-2,5-diyl, or 1,4-phenylene in which any hydrogen may be replaced by fluorine, and ring K is 1,4-cyclohexylene or 1,4-phenylene;
Z ⁶ is — (CH ₂ ) ₂ —, —COO—, —CF ₂ O—, —OCF ₂ —, or a single bond;
L ⁵ , L ⁶ and L ⁷ are independently hydrogen or fluorine;
b, c and d are each independently 0 or 1. ] The liquid crystal according to claim 21, further comprising at least one compound selected from the group of compounds represented by each of the general formulas (7), (8), (9), (10) and (11). Composition.

[Wherein, R ⁵ is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and any hydrogen may be replaced by fluorine, and in alkyl, any —CH ₂ — represents —O— May be replaced by;
R ⁶ is fluorine, alkyl having 1 to 10 carbons, or alkenyl having 2 to 10 carbons, and any hydrogen may be replaced by fluorine, in which any —CH ₂ — represents —O May be replaced by-;
Ring M and Ring P are independently 1,4-cyclohexylene, 1,4-phenylene, or decahydro-2,6-naphthylene;
Z ⁷ and Z ⁸ are independently — (CH ₂ ) ₂ —, —COO—, or a single bond;
L ⁸ , L ⁹ , L ¹⁰ and L ¹¹ are independently hydrogen or fluorine, and at least one of L ⁸ , L ⁹ , L ¹⁰ and L ¹¹ is fluorine. ] The liquid crystal composition according to claim 21, further comprising at least one compound selected from the group of compounds represented by formulas (12), (13), and (14).

[Wherein, R ⁷ and R ⁸ are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and any hydrogen may be replaced by fluorine, and any — CH ₂ — may be replaced by —O—;
Ring J, Ring T and Ring U are independently 1,4-cyclohexylene, pyrimidine-2,5-diyl, or 1,4-phenylene in which any hydrogen may be replaced by fluorine;
Z ⁹ and Z ¹⁰ are independently —C≡C—, —COO—, — (CH ₂ ) ₂ —, —CH═CH.
-Or a single bond. ]   The liquid crystal composition according to claim 22, further comprising at least one compound selected from the group of compounds represented by each of the general formulas (5) and (6).   The liquid crystal composition according to claim 22, further comprising at least one compound selected from the group of compounds represented by general formulas (12), (13), and (14).   The liquid crystal composition according to claim 23, further comprising at least one compound selected from the group of compounds represented by general formulas (12), (13), and (14).   The liquid crystal composition according to claim 24, further comprising at least one compound selected from the group of compounds represented by each of the general formulas (12), (13), and (14).   30. The liquid crystal composition according to any one of claims 21 to 29, further comprising at least one optically active compound.   The liquid crystal display element containing the liquid-crystal composition of any one of Claims 21-30.