JP4940626B2 - Compound having alkyl group in benzene ring, liquid crystal composition containing this compound, and liquid crystal display device containing this liquid crystal composition - Google Patents

Description

  The present invention relates to a liquid crystal compound, a liquid crystal composition, and a liquid crystal display element. More particularly, the present invention relates to a styrene compound, a liquid crystal composition containing the styrene compound and having a nematic phase, and a liquid crystal display device containing the 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) and MIM (metal insulator metal).

  These devices contain a composition having appropriate physical properties. In order to improve the characteristics of the device, the composition preferably has appropriate physical properties. The general physical properties necessary for the compound that is a component of the 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 composition is prepared by mixing many compounds. Therefore, the compound is preferably miscible with other compounds. Since the device may be used at a temperature below freezing point, a compound having good compatibility at a low temperature is preferable. A 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 composition. Preferred compositions have low viscosity and optical anisotropy suitable for the device mode. The large dielectric anisotropy of the compound contributes to the low threshold voltage of the composition. With such a composition, an element having characteristics such as a wide usable temperature range, a short response time, a large contrast ratio, a small driving voltage, a small power consumption, and a large voltage holding ratio can be obtained. .

Conventionally, as a compound having an alkyl group on a benzene ring, for example, the following compound (A) has been reported. However, these compounds have poor liquid crystallinity (for example, see Patent Document 1).

  The conventional techniques are as follows. Further preferred liquid crystalline compounds, liquid crystal compositions and liquid crystal display elements are desired.

JP-A-10-291945

  The first object of the present invention is to provide general physical properties necessary for a compound, stability to heat, light, etc., small viscosity, appropriate optical anisotropy, appropriate dielectric anisotropy, and a wide temperature range of a nematic phase. And a liquid crystal compound having excellent compatibility with other liquid crystal compounds, and particularly to provide a liquid crystal compound having a wide temperature range of a nematic phase. The second object is a liquid crystal composition containing this compound and having a high maximum temperature of the nematic phase, a low minimum temperature of the nematic phase, a small viscosity, a suitable 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 device 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 particularly. A liquid crystal display device having a wide temperature range is provided.

式（１）において、ＲａおよびＲｂは独立して水素または炭素数１〜２０のアルキルであり、このアルキルにおいて任意の−ＣＨ_２−は、−Ｏ−、−Ｓ−、−ＣＯ−、または−ＳｉＨ_２−で置き換えられてもよく、任意の−（ＣＨ_２）_２−は−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、そして任意の水素はハロゲンで置き換えられてもよい。 The present invention includes the following items. Preferred examples of the terminal group, ring and bonding group in compound (1) are also described.
1. A compound represented by the following formula (1).

In Formula (1), Ra and Rb are each independently hydrogen or alkyl having 1 to 20 carbons, and in this alkyl, any —CH ₂ — is —O—, —S—, —CO—, or — SiH ₂ — may be replaced, any — (CH ₂ ) ₂ — may be replaced with —CH═CH— or —C≡C—, and any hydrogen may be replaced with halogen. .

The meaning of the phrase “any —CH ₂ — in alkyl may be replaced by —O—, etc., and any — (CH ₂ ) ₂ — may be replaced by —CH═CH—, etc.” is shown by way of example. An example of a group in which any —CH ₂ — in CH ₃ (CH ₂ ) ₃ — is replaced with —O— or any — (CH ₂ ) ₂ — with —CH═CH— is CH ₃ (CH ₂ ) ₂ O—, CH ₃ —O— (CH ₂ ) ₂ —, CH ₃ —O—CH ₂ —O—, H ₂ C═CH— (CH ₂ ) ₂ —, CH ₃ —CH═CH—CH _{2 -, CH 3 -CH = CH-} O- , and the like. Thus, the term “arbitrary” means “at least one selected without distinction”. Considering the stability of the compound, CH ₃ —O—CH ₂ —O— in which oxygen and oxygen are not adjacent to each other is preferable to CH ₃ —O—O—CH ₂ — in which oxygen and oxygen are adjacent to each other. .

  Examples of Ra or Rb are hydrogen, alkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, alkylthio, alkylthioalkoxy, acyl, acylalkyl, acyloxy, acyloxyalkyl, alkoxycarbonyl, alkoxycarbonylalkyl, alkenyl, alkenyloxy, alkenyloxyalkyl, Alkoxyalkenyl, alkynyl, alkynyloxy, silaalkyl, and disilaalkyl. Also preferred are those groups in which at least one hydrogen has been 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. Even when Ra and Rb are branched groups, it is preferable when they are optically active.

Preferred Ra or Rb are alkyl, alkoxy, alkoxyalkyl, alkenyl, polyfluoroalkyl, and polyfluoroalkoxy.
More preferred Ra or Rb is alkyl, alkoxy, alkoxyalkyl, alkenyl, —CH ₂ F, and —OCH ₂ F.
Most preferred Ra or Rb is alkyl, alkoxy, alkoxyalkyl, and alkenyl.

The preferred configuration of —CH═CH— in alkenyl depends on the position of the double bond. _{-CH = CHCH 3, -CH = CHC} 2 H 5, -CH = CHC 3 H 7, -CH = CHC 4 H 9, -C 2 H 4 CH = CHCH 3, and _{-C 2 H} 4 CH = CHC 2 In alkenyl having a double bond at odd positions such as H ₅ , the trans configuration is preferable. -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 _{alkyl, -CH 3, -C 2 H 5} , -C 3 H 7, -C 4 H 9, -C 5 H 10, -C 6 H 13, -C 7 H 15 , and - it is a C ₈ H _17. Specific examples of the _{alkoxy, -OCH 3, -OC 2 H 5} , -OC 3 H 7, -OC 4 H 9, -OC 5 H 10, -OC 6 H 13, and _-OC 7 _{H 15} in, is there. Specific examples of alkoxyalkyl _{include, -CH 2 OCH 3, -CH 2} OC 2 H 5, -CH 2 OC 3 H 7, - (CH 2) 2 OCH 3, - (CH 2) 2 OC 2 H 5 _{, - (CH 2) 2 OC} 3 H 7, - (CH 2) 3 OCH 3, - (CH 2) 4 OCH 3, and _- a _(CH 2) 5 OCH _3.

Specific examples of alkenyl _{include, -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 _{alkenyloxy, -OCH 2 CH = CH 2,} -OCH 2 CH = CHCH 3, and a _{-OCH 2 CH = CHC 2 H 5} . Specific examples of alkynyl are —C≡CCH ₃ and —C≡CC ₃ H ₇ .

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, and a -CHFCF ₂ CF _3. Specific examples of the at least one hydrogen is replaced by halogen _{alkoxy, -OCF 3, -OCHF 2, -OCH} 2 F, -OCF 2 CF 3, -OCF 2 CHF 2, -OCF 2 CH 2 F, _{-OCF 2 CF 2 CF 3, -OCF} 2 CHFCF 3, and a -OCHFCF ₂ CF _3. Specific examples of at least alkenyl one hydrogen is replaced by _{halogen, -CH = CHF, -CH = CF} 2, -CF = CHF, -CH = CHCH 2 F, -CH = CHCF 3, and - ( CH ₂₎ a ₂ CH = CF _2.

Specific examples of preferred Ra or Rb _{is, -CH 3, -C 2 H 5} , -C 3 H 7, -C 4 H 9, -C 5 H 10, -OCH 3, -OC 2 H 5, - _{OC 3 H 7, -OC 4 H} 9, -OC 5 H 10, -CH 2 OCH 3, - (CH 2) 2 OCH 3, - (CH 2) 3 OCH 3, -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, - (CH 2) 3 CH = CH 2, -OCH 2 CH = CH 2, -OCH 2 CH = CHCH 3, -OCH 2 CH = CHC _{2 H 5, -CF 3, -CHF} 2, -CH 2 _{F, -OCF 3, -OCHF 2,} -OCH 2 F, -OCF 2 CF 3, -OCF 2 CHF 2, -OCF 2 CH 2 F, -OCF 2 CF 2 CF 3, -OCF 2 CHFCF 3, and - OCFCCF ₂ CF ₃ .

More preferably Ra or specific examples of Rb _{is, -CH 3, -C 2 H 5} , -C 3 H 7, -C 4 H 9, -C 5 H 10, -OCH 3, -OC 2 H 5, _{-OC 3 H 7, -OC 4 H} 9, -OC 5 H 10, -CH 2 OCH 3, -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, _{- (CH 2) 3 CH =} CH 2, a _-CH 2 F, and -OCH ₂ F.

Specific examples of the most preferred Ra or Rb _{is, -CH 3, -C 2 H 5} , -C 3 H 7, -C 4 H 9, -C 5 H 10, -OCH 3, -OC 2 H 5, _{-OC 3 H 7, -CH 2 OCH} 3, -CH = CH 2, -CH = CHCH 3, - (CH 2) 2 CH = CH 2, and _{- (CH} 2) a 2 CH = CHCH _3.

Ring A ¹ is independently 1,4-cyclohexylene, 1,4-phenylene, pyridine-2,5-diyl, pyridazine-3,6-diyl, decahydronaphthalene-2,6-diyl, 1,2, 3,4-tetrahydronaphthalene-2,6-diyl, or naphthalene-2,6-diyl, and in these rings, any —CH ₂ — represents —O—, —S—, —CO—, or — SiH ₂ — may be replaced, any — (CH ₂ ) ₂ — may be replaced with —CH═CH—, and any hydrogen in these rings is halogen, —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₃ , —OCHF ₂ , or —OCH ₂ F may be substituted.

“Any —CH ₂ — in these rings may be replaced by —O—, —S—, —CO—, or —SiH ₂ —, where any — (CH ₂ ) ₂ — is —CH═ Examples of the ring to which “which may be replaced by CH—” are the following rings (15-1) to (15-48). Preferred examples include rings (15-1), (15-2), (15-3), (15-4), (15-15), (15-23), (15-31), (15- 32), (15-33), (15-40), (15-43), and (15-48).

Examples of rings applying “any hydrogen in these rings may be replaced by halogen, —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₃ , —OCHF ₂ , or —OCH ₂ F” Are the following rings (16-1) to (16-71). Preferred examples include rings (16-1), (16-2), (16-3), (16-4), (16-6), (16-10), (16-11), (16- 12), (16-13), (16-14), (16-15), (16-54), (16-55), (16-56), (16-57), (16-58) And (16-59).

Examples of ring A ¹ 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, 6-fluoropyridine-2,5-diyl, pyridazine-2,5-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2 , 6-diyl and naphthalene-2,6-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 also applies to 2-fluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, and the like.

Preferred ring A ¹ is 1,4-cyclohexylene, 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, pyridine-2,5-diyl, 6-fluoropyridine-2,5-diyl, and pyridazine-2 , 5-diyl.

More preferred ring A ¹ is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1, 4-phenylene and 2,6-difluoro-1,4-phenylene.

Most preferred ring A ¹ is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, and 2,3-difluoro-1,4-phenylene.

Z ¹ is independently a single bond or alkylene having 1 to 4 carbon atoms, and in the alkylene, any —CH ₂ — may be replaced by —O—, —S—, —CO—, or —SiH ₂ —. Well, any — (CH ₂ ) ₂ — may be replaced with —CH═CH—, or —C≡C—, and any hydrogen may be replaced with a halogen.

Examples of Z ¹ are a single bond, — (CH ₂ ) ₂ —, —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH═. CH -, - CH = CF - , - CF = CH -, - CF = CF -, - C≡C -, - CH 2 CO -, - COCH 2 -, - CH 2 SiH 2 -, - SiH 2 CH 2 _{-, - (CH 2) 4} -, - (CH 2) 2 COO -, - OCO (CH 2) 2 -, - (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—, and —OCH ₂ —CH═CH—. The configuration of the linking group such as —CH═CH—, —CF═CF—, —CH═CH—CH ₂ O—, and —OCH ₂ —CH═CH— is preferably trans rather than cis. .

Preferred Z ¹ is a single bond, — (CH ₂ ) ₂ —, —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH═CH. -, - CF = CF -, - C≡C -, - CH 2 CO -, - COCH 2 -, - CH 2 SiH 2 -, - SiH 2 CH 2 -, and - _{(CH 2) 4} - a.
More preferable Z ¹ is a single bond, — (CH ₂ ) ₂ —, —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH═. CH— and —C≡C—.
Z ¹ is most preferably a single bond and — (CH ₂ ) ₂ —.

W is alkylene having 2 to 4 carbon atoms, and in the alkylene, any —CH ₂ — may be replaced by —O—, —S—, —CO—, or —SiH ₂ —, and any — (CH ₂ ) ₂ — may be replaced with —CH═CH—, or —C≡C—, and any hydrogen may be replaced with halogen.

Examples of W are — (CH ₂ ) ₂ —, —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH═CH—, —CH. = CF -, - CF = CH -, - CF = CF -, - C≡C -, - CH 2 CO -, - COCH 2 -, - CH 2 SiH 2 -, - SiH 2 CH 2 -, - (CH ₂ ) ₄ −, — (CH ₂ ) ₂ COO—, —OCO (CH ₂ ) ₂ —, — (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-, and -OCH ₂ -CH = a CH-. The configuration of the linking group such as —CH═CH—, —CF═CF—, —CH═CH—CH ₂ O—, and —OCH ₂ —CH═CH— is preferably trans rather than cis. .

Preferred W is — (CH ₂ ) ₂ —, —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH═CH—, —CF. ═CF—, —C≡C—, —CH ₂ CO—, —COCH ₂ —, — (CH ₂ ) ₂ CF ₂ O—, —OCF ₂ (CH ₂ ) ₂ —, and — (CH ₂ ) ₄ —. It is.
Further preferred W is — (CH ₂ ) ₂ —, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, — (CH ₂ ) ₂ CF ₂ O—, —OCF ₂ ( CH _{2) 2,} and -CH = a CH-.
Most preferred W is — (CH ₂ ) ₂ — and —CH ₂ O—.

Y ¹ is independently hydrogen, halogen, —CN, —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₃ , —OCHF ₂ , or —OCH ₂ F, where ^one of Y ¹ is halogen, _{-CF 3, -CHF 2, -CH 2} F, -OCF 3, -OCHF 2, or -OCH ₂ F. Preferred halogens are fluorine and chlorine. The most preferred halogen is fluorine. Preferred Y ¹ is hydrogen, fluorine, chlorine, —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₃ , —OCHF ₂ , and —OCH ₂ F. More desirable Y ¹ is hydrogen, fluorine, chlorine, —CF ₃ , —CHF ₂ , —OCF ₃ , and —OCHF ₂ . Most preferred Y ¹ is hydrogen, fluorine and —CF ₃ .

In Formula (17) which is a partial structure of Formula (1), preferred examples of the combination of Y ¹ are (17-1) to (17-41). Further preferred examples are (17-1) to (17-8), (17-18) to (17-26), and (17-32) to (17-41). Most preferred examples are (17-1) to (17-3).

Rc is alkyl having 1 to 4 carbons, and in this alkyl, arbitrary —CH ₂ — may be replaced by —O—, —S—, —CO—, or —SiH ₂ —, and any — (CH ₂ ) ₂ — may be replaced by —CH═CH— or —C≡C—.

  Examples of Rc are hydrogen, alkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, alkylthio, alkylthioalkoxy, acyl, acylalkyl, acyloxy, acyloxyalkyl, alkoxycarbonyl, alkoxycarbonylalkyl, alkenyl, alkenyloxy, alkenyloxyalkyl, alkoxyalkenyl , Alkynyl, alkynyloxy, silaalkyl, and disilaalkyl. In these groups, straight chain is preferable to branch.

  Preferred Rc is alkyl, alkoxy, alkoxyalkyl, and alkenyl. More preferred Rc is alkyl, alkoxy, and alkenyl. Most preferred Rc is alkyl.

Specific examples of _{alkyl, -CH 3, -C 2 H 5} , -C 3 H 7, and _-C a 4 _{H 9.} Specific examples of alkoxy are —OCH ₃ , —OC ₂ H ₅ and —OC ₃ H ₇ . Specific examples of alkoxyalkyl are —CH ₂ OCH ₃ , —CH ₂ OC ₂ H ₅ and — (CH ₂ ) ₂ OCH ₃ .

Specific examples of alkenyl _{include, -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, and a -CH = CHCH = CH _2. Specific examples of alkenyloxy are —OCH═CH ₂ and —OCH ₂ CH═CH ₂ . A specific example of alkynyl is —C≡CH.

Specific examples of preferred Rc _{is, -CH 3, -C 2 H 5} , -C 3 H 7, -C 4 H 9, -OCH 3, -OC 2 H 5, -OC 3 H 7, -CH 2 OCH ₃ , —CH ₂ OC ₂ H ₅ , — (CH ₂ ) ₂ OCH ₃ , —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 , —OCH═CH ₂ , and —OCH ₂ CH═CH ₂ .

Specific examples of more preferable Rc are —CH ₃ , —C ₂ H ₅ , —OCH ₃ , and —CH═CH ₂ . A specific example of the most preferred Rc is —CH ₃ .

m is independently 0, 1 or 2, and the sum of m is 0, 1 or 2. Since there is no great difference in the physical properties of the compound, the compound (1) may contain an isotope such as ² H (deuterium) and ¹³ C in an amount larger than the natural abundance.

2. In Formula (1), Ra and Rb are independently alkyl having 1 to 20 carbon atoms, alkoxy having 1 to 19 carbon atoms, alkoxyalkyl having 2 to 19 carbon atoms, alkenyl having 2 to 20 carbon atoms, and 1 to 1 carbon atoms. 20 polyfluoroalkyl, or polyfluoroalkoxy having 1 to 19 carbon atoms; ring A ¹ is independently 1,4-cyclohexylene, 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, pyridine-2 , 5-diyl, 6-fluoropyridine-2,5-diyl or be 3,6-diyl,; ^{Z 1} is independently a single _{bond, - (CH 2) 2 -} , - COO -, - O _{O -, - CH 2 O -} , - OCH 2 -, - CF 2 O -, - OCF 2 -, - CH = CH -, - CF = CF -, - C≡C -, - CH 2 CO -, - _{COCH 2 -, - CH 2 SiH} 2 -, - SiH 2 CH 2 -, - (CH 2) 2 COO -, - OCO (CH 2) 2 -, - (CH 2) 2 CF 2 O -, - OCF 2 (CH ₂ ) ₂ —, — (CH ₂ ) ₃ O—, —O (CH ₂ ) ₃ — or — (CH ₂ ) ₄ —; W represents —COO—, —OCO—, —CH ₂ O—. , —OCH ₂ —, —CH═CH—, —CF═CF—, —C≡C—, —CF ₂ O—, —OCF ₂ —, — (CH ₂ ) ₂ COO—, —OCO (CH ₂ ) _2- , — (CH ₂ ) ₃ O—, —O (CH ₂ ) ₃ —, — (CH ₂ ) ₂ CF ₂ O—, —OCF ₂ (CH ₂ ) _2- or — (CH ₂ ) ₄ —; Y ¹ is independently hydrogen, fluorine, chlorine, —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₃ , —OCHF ₂ , or —OCH ₂ F and ^one of Y ¹ is fluorine, chlorine, —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₃ , —OCHF ₂ , or —OCH ₂ F; and Rc is 2 carbon atoms Item 4. The compound according to Item 1, wherein the compound is -4 alkyl, C2-C3 alkoxy, C2-C3 alkoxyalkyl, or C2-C4 alkenyl.

3. In Formula (1), Ra and Rb are independently alkyl having 1 to 20 carbon atoms, alkoxy having 1 to 19 carbon atoms, alkoxyalkyl having 2 to 19 carbon atoms, alkenyl having 2 to 20 carbon atoms, and 1 to 1 carbon atoms. 20 polyfluoroalkyl, or polyfluoroalkoxy having 1 to 19 carbon atoms; ring A ¹ is independently 1,4-cyclohexylene, 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, pyridine-2 , 5-diyl 6- fluoro-2,5-diyl or be 3,6-diyl,; ^{Z 1} is independently a single _{bond, - (CH 2) 2 -} , - COO -, - O _{O -, - CH 2 O -} , - OCH 2 -, - CF 2 O -, - OCF 2 -, - CH = CH -, - CF = CF -, - C≡C -, - CH 2 CO -, - _{COCH 2 -, - CH 2 SiH} 2 -, - SiH 2 CH 2 -, - (CH 2) 2 COO -, - OCO (CH 2) 2 -, - (CH 2) 2 CF 2 O -, - OCF 2 (CH ₂ ) ₂ —, — (CH ₂ ) ₃ O—, —O (CH ₂ ) ₃ — or — (CH ₂ ) ₄ —; W is — (CH ₂ ) ₂ —; Y ¹ is Independently hydrogen, fluorine, chlorine, —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₃ , —OCHF ₂ , or —OCH ₂ F, and ^one of Y ¹ is chlorine, —CF _{3 , -CHF 2, -CH 2 F,} -OCF 3, -OCHF 2, or be a -OCH ₂ F; and Rc is alkyl of 2 to 4 carbon atoms, alkoxy of 2-3 carbon atoms, alkoxyalkyl or alkenyl having 2 to 4 carbon atoms, 2 to 3 carbon atoms, A compound according to claim 1.

4). In formula (1), Ra and Rb are each independently alkyl having 1 to 8 carbons, alkoxy having 1 to 7 carbons, alkoxyalkyl having 2 to 7 carbons, or alkenyl having 2 to 8 carbons; A ¹ is independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,3-difluoro-1,4-phenylene; Z ¹ is independently A single bond or — (CH ₂ ) ₂ —; W is — (CH ₂ ) ₄ —, —CH ₂ O—, —OCH ₂ —, —CH═CH— or —C≡C—; Y ¹ There independently hydrogen, fluorine, -CF ₂ H or -CF _3, and one of ^{Y 1} is fluorine, -CH ₂ F or -CF _3; Rc is as defined in claim 1 is -CH ₃ Compound.

5. In formula (1), Ra and Rb are each independently alkyl having 1 to 8 carbons, alkoxy having 1 to 7 carbons, alkoxyalkyl having 2 to 7 carbons, or alkenyl having 2 to 8 carbons; A ¹ is independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,3-difluoro-1,4-phenylene; Z ¹ is independently A single bond or — (CH ₂ ) ₂ —; W is — (CH ₂ ) ₂ —; Y ¹ is independently hydrogen, fluorine, —CF ₂ H or —CF ₃ , and Y ¹ Item 2. The compound according to Item 1, wherein one is —CF ₂ H or —CF ₃ ; and Rc is —CH ₃ .

式（１−１）から式（１−６）において、ＲａおよびＲｂは独立して水素または炭素数１〜１０のアルキルであり、このアルキルにおいて任意の−ＣＨ_２−は、−Ｏ−で置き換えられてもよく、任意の−（ＣＨ_２）_２−は−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、そして任意の水素はハロゲンで置き換えられてもよく；環Ａ１は独立して１，４−シクロヘキシレン、１，４−フェニレン、デカヒドロナフタレン−２，６−ジイル、１，２，３，４−テトラヒドロナフタレン−２，６−ジイル、またはナフタレン−２，６−ジイルであり、これらの環において任意の−ＣＨ_２−は、−Ｏ−で置き換えられてもよく、任意の−（ＣＨ_２）_２−は−ＣＨ＝ＣＨ−で置き換えられてもよく、そしてこれらの環において任意の水素はハロゲン、−ＣＦ_３、−ＣＨＦ_２、または−ＣＨ_２Ｆで置き換えられてもよく；Ｚ１は独立して単結合または炭素数１〜４のアルキレンであり、アルキレンにおいて任意の−ＣＨ_２−は−Ｏ−または−ＣＯ−で置き換えられてもよく、任意の−（ＣＨ_２）_２−は−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、そして任意の水素はハロゲンで置き換えられてもよく；Ｗは−（ＣＨ_２）_２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−Ｃ≡Ｃ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−（ＣＨ_２）_２ＣＯＯ−、−ＯＣＯ（ＣＨ_２）_２−、−（ＣＨ_２）_３Ｏ−、−Ｏ（ＣＨ_２）_３−、−（ＣＨ_２）_２ＣＦ_２Ｏ−、−ＯＣＦ_２（ＣＨ_２）_２−または−（ＣＨ_２）_４−、であり；Ｙ^１は独立して水素、ハロゲン、−ＣＦ_３、−ＣＨＦ_２、または−ＣＨ_２Ｆであり；Ｒｃは炭素数１〜４のアルキルであり、このアルキルにおいて任意の−ＣＨ_２−は、−Ｏ−で置き換えられてもよく、任意の−（ＣＨ_２）_２−は−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよい。 6). A compound represented by any one of the following formulas (1-1) to (1-6).

In formulas (1-1) to (1-6), Ra and Rb are independently hydrogen or alkyl having 1 to 10 carbons, and in this alkyl, arbitrary —CH ₂ — is replaced by —O—. Any — (CH ₂ ) ₂ — may be replaced by —CH═CH— or —C≡C— and any hydrogen may be replaced by halogen; ring A1 is independently 1,4-cyclohexylene, 1,4-phenylene, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, or naphthalene-2,6-diyl And in these rings any —CH ₂ — may be replaced by —O—, any — (CH ₂ ) ₂ — may be replaced by —CH═CH—, and Any in the ring Containing _halogen, -CF 3, -CHF _2, or may be replaced by -CH ₂ F; Z1 is independently a single bond or alkylene having 1 to 4 carbon atoms, arbitrary -CH at alkylene ₂ - May be replaced with —O— or —CO—, any — (CH ₂ ) ₂ — may be replaced with —CH═CH— or —C≡C—, and any hydrogen with a halogen W may be substituted; W represents — (CH ₂ ) ₂ —, —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, —CH═CH—, —CF═CF—, —C≡. C—, —CF ₂ O—, —OCF ₂ —, — (CH ₂ ) ₂ COO—, —OCO (CH ₂ ) ₂ —, — (CH ₂ ) ₃ O—, —O (CH ₂ ) ₃ —, _{- (CH 2) 2 CF 2} O -, - OCF 2 (CH 2) 2 - The - _{(CH 2) 4} -, a and; ^{Y 1} is independently hydrogen, _halogen, -CF 3, -CHF _2, or be a -CH ₂ F; Rc is alkyl of 1 to 4 carbon atoms, the In alkyl, any —CH ₂ — may be replaced by —O—, and any — (CH ₂ ) ₂ — may be replaced by —CH═CH— or —C≡C—.

7). In Formula (1-1) to Formula (1-6), Ra and Rb are each independently alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, alkoxyalkyl having 2 to 9 carbons, or carbon 2 -10 alkenyl, C 1-10 polyfluoroalkyl, or C 2-10 polyfluoroalkoxy; ring A ¹ is independently 1,4-cyclohexylene, 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; Z ¹ is independently a single bond, — (CH ₂ ) ₂ —, —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, -OCF ₂ -, - CH = CH , -CF = CF -, - C≡C -, - (CH 2) 2 COO -, - OCO (CH 2) 2 -, - (CH 2) 2 CF 2 O -, - OCF 2 (CH 2) 2 —, — (CH ₂ ) ₃ O—, —O (CH ₂ ) ₃ — or — (CH ₂ ) ₄ —; W represents —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —. , —CH═CH—, —CF═CF—, —C≡C—, —CF ₂ O—, —OCF ₂ —, — (CH ₂ ) ₂ COO—, —OCO (CH ₂ ) ₂ —, — ( CH ₂ ) ₃ O—, —O (CH ₂ ) ₃ —, — (CH ₂ ) ₂ CF ₂ O—, —OCF ₂ (CH ₂ ) ₂ — or — (CH ₂ ) ₄ —; Y ¹ There independently hydrogen, fluorine, _chlorine, -CF 3, -CHF ₂ or a -CH ₂ F, and ^{Y 1} on one chlorine, _-CF 3,, CHF _2, or be a -CH ₂ F; and an Rc is alkyl having 1 to 4 carbon atoms, C2-4 alkoxy, alkoxyalkyl having 2 to 4 carbon atoms or alkenyl having 2 to 4 carbon atoms, Item 7. The compound according to Item 6.

8). In Formula (1-1) to Formula (1-6), Ra and Rb are each independently alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, alkoxyalkyl having 2 to 9 carbons, or carbon 2 -10 alkenyl, C 1-10 polyfluoroalkyl, or C 2-10 polyfluoroalkoxy; ring A ¹ is independently 1,4-cyclohexylene, 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; Z ¹ is independently a single bond, — (CH ₂ ) ₂ —, —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, -OCF ₂ -, - CH = CH , -CF = CF -, - C≡C -, - (CH 2) 2 COO -, - OCO (CH 2) 2 -, - (CH 2) 2 CF 2 O -, - OCF 2 (CH 2) 2 —, — (CH ₂ ) ₃ O—, —O (CH ₂ ) ₃ — or — (CH ₂ ) ₄ —; W is — (CH ₂ ) ₂ —; Y ¹ is independently hydrogen; Fluorine, chlorine, —CF ₃ , —CHF ₂ , or —CH ₂ F, ^one of Y ¹ is chlorine, —CF ₃ , —CHF _2, or —CH ₂ F; and Rc has 1 to 4 carbon atoms Item 7. The compound according to Item 6, wherein the compound is alkyl having 2 to 4 carbon atoms, alkoxy having 2 to 4 carbon atoms, alkoxyalkyl having 2 to 4 carbon atoms or alkenyl having 2 to 4 carbon atoms.

9. In Formula (1-1) to Formula (1-6), Ra and Rb are each independently alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, alkoxyalkyl having 2 to 9 carbons, or carbon 2 -10 alkenyl, -CH ₂ F, or -OCH ₂ F; ring A ¹ is independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2, 3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, or 2,6-difluoro-1,4-phenylene; Z ¹ is independently a single bond, — (CH ₂ ) ₂ —, —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH═CH— or —C≡C—; _{-COO -, - OCO -, -} CH 2 O -, - OCH 2 -, - CH = CH -, - CF = CF -, - C≡C -, - (CH 2) 2 COO -, - OCO (CH 2) 2 -, - (CH 2) 3 O -, - O ( CH ₂ ) ₃ — or — (CH ₂ ) ₄ —; independently Y ¹ is fluorine, chlorine, —CF ₃ , or —CHF ₂ , and ^one of Y ¹ is chlorine, —CF ₃ , or Item 8. The compound according to Item 7, which is —CHF ₂ ; and Rc is alkyl having 1 to 4 carbons.

10. In Formula (1-1) to Formula (1-6), they are alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, alkoxyalkyl having 2 to 9 carbons, or alkenyl having 2 to 10 carbons. Ra and Rb are each independently alkyl, alkoxy, alkoxyalkyl or alkenyl having 1 to 8 carbon atoms; ring A ¹ is independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-; 1,4-phenylene, or 2,3-difluoro-1,4-phenylene; Z ¹ is independently a single bond or — (CH ₂ ) ₂ —; W is — (CH ₂ ) ₄ —, —CH ₂ O—, —OCH ₂ —, —CH═CH— or —C≡C—; Y ¹ is independently fluorine, hydrogen, —CF ₂ H or —CF ₃ , ^one of Y ¹ There fluorine, -CF ₂ H or - It is F _3; Rc compounds described in claim 7 is -CH _3.

11. Item 8. The compound according to Item 7, wherein in Formula (1-1) to Formula (1-6), W is —CH ₂ O—; Y ¹ is independently fluorine, —CF ₃ , or —CF ₂ H. .

12 Item 8. The compound according to Item 7, wherein in Formula (1-1) to Formula (1-6), W is —CH ₂ O—; and Y ¹ is both fluorine.

13. In Formula (1-1) to Formula (1-6), Ra and Rb are each independently alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, alkoxyalkyl having 2 to 9 carbons, or carbon 2 -10 alkenyl, -CH ₂ F, or -OCH ₂ F; ring A ¹ is independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2, 3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, or 2,6-difluoro-1,4-phenylene; Z ¹ is independently a single bond, — (CH ₂ ) ₂ —, —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH═CH— or —C≡C—; Y ¹ There fluorine independently chlorine, -CF ₃ or -CHF, _2, one is chlorine ^{Y 1,} be -CF ₃ or -CHF _2,; Rc compounds described in claim 8 is alkyl.

14 In Formula (1-1) to Formula (1-6), Ra and Rb are independently alkyl having 1 to 8 carbons, alkoxy having 1 to 7 carbons, alkoxyalkyl having 2 to 7 carbons, or carbon number 2-8 alkenyl; ring A ¹ is independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,3-difluoro-1,4-phenylene Z ¹ is independently a single bond or — (CH ₂ ) ₂ —; Y ¹ is independently hydrogen, fluorine or —CF ₃ , and ^one of Y ¹ is —CF ₃ ; Rc Item 9. The compound according to Item 8, wherein is —CH ₃ .

式（Ｉ）から式（ＩＸ）において、ＲａおよびＲｂは独立して水素または炭素数１〜１０のアルキルであり、このアルキルにおいて任意の−ＣＨ_２−は、−Ｏ−で置き換えられてもよく、任意の−（ＣＨ_２）_２−は−ＣＨ＝ＣＨ−で置き換えられてもよく；Ｚ^１が独立して単結合、−（ＣＨ_２）_２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−Ｃ≡Ｃ−、−（ＣＨ_２）_２ＣＯＯ−、−ＯＣＯ（ＣＨ_２）_２−、−（ＣＨ_２）_２ＣＦ_２Ｏ−、−（ＣＨ_２）_３Ｏ−、−Ｏ（ＣＨ_２）_３−または−（ＣＨ_２）_４−であり；Ｗは−（ＣＨ_２）_２−、−（ＣＨ_２）_４−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−であり；Ｙ^１は独立して水素、フッ素、塩素、−ＣＦ_３、または−ＣＦ_２Ｈである。 15. A compound represented by any one of the following formulas (I) to (IX):

In Formula (I) to Formula (IX), Ra and Rb are independently hydrogen or alkyl having 1 to 10 carbons, and in this alkyl, arbitrary —CH ₂ — may be replaced by —O—. Any — (CH ₂ ) ₂ — may be replaced by —CH═CH—; Z ¹ is independently a single bond, — (CH ₂ ) ₂ —, —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH═CH—, —CF═CF—, —C≡C—, — (CH ₂ ) ₂ COO—, —OCO ( CH ₂ ) ₂ —, — (CH ₂ ) ₂ CF ₂ O—, — (CH ₂ ) ₃ O—, —O (CH ₂ ) ₃ — or — (CH ₂ ) ₄ —; W is — (CH _{2) 2 -, - (CH} 2) 4 -, - CH 2 O -, - OCH 2 -, - CH = CH- or -C C- a and; ^{Y 1} is independently hydrogen, fluorine, chlorine, -CF _3, or -CF ₂ H.

16. In formula (I) to formula (IX), Ra and Rb are independently alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons or alkenyl having 2 to 10 carbons; Z ¹ is independently A single bond, — (CH ₂ ) ₂ —, —CH═CH—, or — (CH ₂ ) ₄ —; W is —CH ₂ O— or —CH═CH—; Y ¹ is independently Item 16. The compound according to Item 15, wherein the compound is hydrogen, fluorine, chlorine, —CF ₃ or —CHF ₂ , and ^one of Y ¹ is fluorine, chlorine, —CF ₃ or —CHF ₂ .

17. In formula (I) to formula (IX), Ra and Rb are independently alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons or alkenyl having 2 to 10 carbons; Z ¹ is independently A single bond, — (CH ₂ ) ₂ —, —CH═CH—, or — (CH ₂ ) ₄ —; W is — (CH ₂ ) ₂ —; Y ¹ is independently hydrogen, fluorine, Item 16. The compound according to Item 15, wherein the compound is —CF ₃ or —CF ₂ H, and ^one of Y ¹ is —CF ₃ or —CF ₂ H.

18. In formulas (I) to (IX), Z ¹ is independently a single bond or —CH═CH—; W is —CH ₂ O—; Y ¹ is independently hydrogen, fluorine or —CF it is _3, and which is one is fluorine or -CF ₃ of ^{Y 1,} a compound according to claim 16.

19. Item 17. The compound according to Item 16, wherein in Formula (I) to Formula (IX); Z ¹ is a single bond; Y ¹ is independently fluorine or —CF ₃ .

20. Item 17. The compound according to Item 16, wherein in Formula (I) to Formula (IX), Z ¹ is a single bond; and Y ¹ is both fluorine.

21. Item 17. The compound according to Item 16, wherein in Formula (I) to Formula (IX), Z ¹ is a single bond; and Y ¹ is both —CF ₃ .

22. In Formula (I) and Formula (III), Ra is alkyl or alkenyl having 1 to 6 carbons, Rb is alkoxy having 1 to 4 carbons; Z ¹ is a single bond; W is —CH ₂ an O-; Y ¹ are both fluorine, compounds described in paragraph 16.

  23. Item 23. A liquid crystal composition containing at least one compound selected from the group of compounds described in any one of items 1 to 22.

式中、Ｒ^１は炭素数１〜１０のアルキルであり、このアルキルにおいて任意の−ＣＨ_２−は−Ｏ−または−ＣＨ＝ＣＨ−で置き換えられてもよく、そして任意の水素はフッ素で置き換えられてもよく；Ｘ^１はフッ素、塩素、−ＯＣＦ_３、−ＯＣＨＦ_２、−ＣＦ_３、−ＣＨＦ_２、−ＣＨ_２Ｆ、−ＯＣＦ_２ＣＨＦ_２、または−ＯＣＦ_２ＣＨＦＣＦ_３であり；環Ｂは独立して１，４−シクロヘキシレン、１，３−ジオキサン−２，５−ジイルまたは任意の水素がフッ素で置き換えられてもよい１，４−フェニレンであり、環Ｅは１，４−シクロヘキシレンまたは任意の水素がフッ素で置き換えられてもよい１，４−フェニレンであり；Ｚ^４は独立して−（ＣＨ_２)_２−、−（ＣＨ_２)_４−、−ＣＯＯ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＨ＝ＣＨ−、または単結合であり；そしてＬ^１は独立して水素またはフッ素である。 24. Item 24. The liquid crystal composition according to item 23, further comprising at least one compound selected from the group of compounds represented by the following formulas (2), (3), and (4).

In the formula, R ¹ is alkyl having 1 to 10 carbons, in which arbitrary —CH ₂ — may be replaced by —O— or —CH═CH—, and arbitrary hydrogen is replaced by fluorine. X ¹ 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 Is independently 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl or 1,4-phenylene in which any hydrogen may be replaced by fluorine, and ring E is 1,4-cyclohexyl. Silene or 1,4-phenylene in which any hydrogen may be replaced by fluorine; Z ⁴ is independently — (CH ₂ ) ₂ —, — (CH ₂ ) ₄ —, —COO—, —CF _2. O-, -OCF _2- , -CH = CH-, or a single bond; and L ¹ is independently hydrogen or fluorine.

式中、Ｒ^１は独立して炭素数１〜１０のアルキルであり、このアルキルにおいて任意の−ＣＨ_２−は−Ｏ−または−ＣＨ＝ＣＨ−で置き換えられてもよく、そして任意の水素はフッ素で置き換えられてもよく；Ｘ^２は−ＣＮまたは−Ｃ≡Ｃ−ＣＮであり；環Ｇは１，４−シクロヘキシレン、１，４−フェニレン、１，３−ジオキサン−２，５−ジイル、またはピリミジン−２，５−ジイルであり；環Ｊは１，４−シクロヘキシレン、ピリミジン−２,５−ジイル、または任意の水素がフッ素で置き換えられてもよい１，４−フェニレンであり；環Ｋは１，４−シクロヘキシレンまたは１，４−フェニレンであり；Ｚ^５は−（ＣＨ_２）_２−、−ＣＯＯ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、または単結合であり；Ｌ^１は独立して水素またはフッ素であり；そしてｂは独立して０または１である。 25. Item 24. The liquid crystal composition according to item 23, further comprising at least one compound selected from the group of compounds represented by formulas (5) and (6) below:

In the formula, R ¹ is independently alkyl having 1 to 10 carbons, in which arbitrary —CH ₂ — may be replaced by —O— or —CH═CH—, and any hydrogen is X ² is —CN or —C≡C—CN; ring G is 1,4-cyclohexylene, 1,4-phenylene, 1,3-dioxane-2,5-diyl Or ring J is 1,4-cyclohexylene, pyrimidine-2,5-diyl, or 1,4-phenylene in which any hydrogen may be replaced by fluorine; Ring K is 1,4-cyclohexylene or 1,4-phenylene; Z ⁵ is — (CH ₂ ) ₂ —, —COO—, —CF ₂ O—, —OCF ₂ —, or a single bond; L ¹ is independently hydrogen or Be Tsu containing; and b are independently 0 or 1.

式中、Ｒ^１は炭素数１〜１０のアルキルであり、このアルキルにおいて任意の−ＣＨ_２−は−Ｏ−または−ＣＨ＝ＣＨ−で置き換えられてもよく、そして任意の水素はフッ素で置き換えられてもよく；Ｒ^２はフッ素または炭素数１〜１０のアルキルであり、このアルキルにおいて任意の−ＣＨ_２−は−Ｏ−または−ＣＨ＝ＣＨ−で置き換えられてもよく、そして任意の水素はフッ素で置き換えられてもよく；環Ｍは独立して１，４−シクロヘキシレン、１，４−フェニレンまたはデカヒドロ−２，６−ナフタレンであり；Ｚ^６は独立して−（ＣＨ_２）_２−、−ＣＯＯ−または単結合であり；そしてＬ^２は独立して水素またはフッ素であり、Ｌ^２の少なくとも一つはフッ素である。 26. Item 24. The liquid crystal composition according to item 23, further comprising at least one compound selected from the group of compounds represented by formulas (7), (8), (9), (10), and (11): .

In the formula, R ¹ is alkyl having 1 to 10 carbons, in which arbitrary —CH ₂ — may be replaced by —O— or —CH═CH—, and arbitrary hydrogen is replaced by fluorine. R ² is fluorine or alkyl having 1 to 10 carbons, in which any —CH ₂ — may be replaced by —O— or —CH═CH—, and any hydrogen May be replaced by fluorine; ring M is independently 1,4-cyclohexylene, 1,4-phenylene or decahydro-2,6-naphthalene; Z ⁶ is independently — (CH ₂ ) ₂ -, -COO- or a single bond; and L ² is independently hydrogen or fluorine, and at least one of L ² is fluorine.

式中、Ｒ^１は独立して炭素数１〜１０のアルキルであり、このアルキルにおいて任意の−ＣＨ_２−は−Ｏ−または−ＣＨ＝ＣＨ−で置き換えられてもよく、そして任意の水素はフッ素で置き換えられてもよく；環Ｊは独立して１，４−シクロヘキシレン、ピリミジン−２，５−ジイル、または任意の水素がフッ素で置き換えられてもよい１，４−フェニレンであり；そしてＺ^７は独立して−Ｃ≡Ｃ−、−ＣＯＯ−、−（ＣＨ_２）_２−、−ＣＨ＝ＣＨ−、または単結合である。 27. Item 24. The liquid crystal composition according to item 23, further comprising at least one compound selected from the group of compounds represented by the following formulas (12), (13), and (14).

In the formula, R ¹ is independently alkyl having 1 to 10 carbons, in which arbitrary —CH ₂ — may be replaced by —O— or —CH═CH—, and any hydrogen is Ring J is independently 1,4-cyclohexylene, pyrimidine-2,5-diyl, or 1,4-phenylene in which any hydrogen may be replaced with fluorine; and Z ⁷ is independently —C≡C—, —COO—, — (CH ₂ ) ₂ —, —CH═CH—, or a single bond.

  28. Item 25. The composition according to item 24, further comprising at least one compound selected from the group of compounds represented by formulas (5) and (6) according to item 25.

  29. Item 25. The composition according to item 24, further comprising at least one compound selected from the group of compounds represented by formulas (12), (13) and (14) according to item 27.

  30. Item 26. The composition according to item 25, further comprising at least one compound selected from the group of compounds represented by formulas (12), (13) and (14) according to item 27.

  31. Item 27. The composition according to item 26, further comprising at least one compound selected from the group of compounds represented by formulas (12), (13) and (14) according to item 27.

  32. Item 32. The liquid crystal composition according to any one of items 23 to 31, further comprising at least one optically active compound.

  33. Item 33. A liquid crystal display device comprising the liquid crystal composition according to any one of items 23 to 32.

  The compounds of the present invention have general physical properties required for the compounds, stability to heat, light, etc., small year, appropriate optical anisotropy, appropriate dielectric anisotropy, wide temperature range of nematic phase, and other Excellent compatibility with liquid crystal compounds. In particular, it has a wide temperature range of the nematic phase. 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 appropriate optical anisotropy, and a low threshold voltage. Have. In particular, it has a high maximum temperature of the nematic phase and a low minimum temperature of the nematic phase. 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 formulas (1) to (14), symbols such as A ¹ , B, and E surrounded by hexagons correspond to ring A ¹ , ring B, and ring E, respectively. The amount of the compound expressed as a percentage is a weight percentage (% by weight) based on the total weight of the composition. A plurality of the same symbols such as A ¹ , Y ¹ , and B are described in the same formula or different formulas, but these may be the same or different. The present invention is further described below.

  First, the compound (1) of the present invention will be further described. A condensed ring such as a naphthalene ring is counted as one part. Compound (1) is a bicyclic, tricyclic or tetracyclic compound having an alkyl group having 2 or more carbon atoms. 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 and bonding group of compound (1). The effects of the types of the terminal groups Ra and Rb, the ring A ¹ , and the bonding group Z ^{1 on} the physical properties of the compound (1) will be described below.

Compound (1) has a large negative dielectric anisotropy. A compound having a large negative dielectric anisotropy is a component for lowering the threshold voltage of the composition. When Ra and Rb are hydrogen, alkyl, alkoxy or the like and Y ¹ is halogen or the like, the dielectric anisotropy of this compound is negative and large.

  When Ra or Rb is linear, the temperature range of the liquid crystal phase is wide and the viscosity is small. When Ra or Rb is a branched chain, the compatibility with other liquid crystal compounds is good. A compound in which Ra or Rb 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 Ra or Rb is not an optically active group is useful as a component of the composition. When Ra or Rb 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. Mol. Cryst. Liq. Cryst., 1985, 131, 109 and Mol. Cryst. Liq. Cryst., 1985, 131, 327 have detailed descriptions.

When the ring A ¹ is 1,4-phenylene in which the hydrogens at the 2nd and 3rd positions are replaced by halogen or the like, the ring A ¹ is negative and has a large dielectric anisotropy. When ring A ¹ is 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, or pyridazine-3,6-diyl in which any hydrogen may be replaced by halogen High optical anisotropy. When ring A ¹ is 1,4-cyclohexylene, 1,4-cyclohexenylene or 1,3-dioxane-2,5-diyl, the optical anisotropy 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.

The bonding group Z ¹ is a single bond, — (CH ₂ ) ₂ —, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH═CH—, —CF═CF—, or - (CH _{2) 4} - is when the viscosity is small at. When the bonding group is a single bond, — (CH ₂ ) ₂ —, —CF ₂ O—, —OCF ₂ —, or —CH═CH—, the viscosity is smaller. When the bonding group is —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 large. When the bonding group is —C≡C—, the optical anisotropy is large.

The bonding group W is — (CH ₂ ) ₂ —, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH═CH—, —CF═CF—, or — (CH ₂₎ 4 _- when the viscosity is small at. When the bonding group W is — (CH ₂ ) ₂ —, —CF ₂ O—, —OCF ₂ —, or —CH═CH—, the viscosity is smaller. When the bonding group W is —CH═CH—, the temperature range of the liquid crystal phase is wider, its clearing point is high, negative Δε is large, the viscosity is small, and the elastic constant ratio K ₃₃ / K ₁₁ (K ₃₃ : Bend elastic constant, K ₁₁ : Spray elastic constant) is large. When the bonding group W is — (CH ₂ ) ₂ —, the temperature range of the liquid crystal phase is wide, the clearing point is high, negative Δε is large, and the viscosity is small. When the bonding group W is —CH ₂ O—, the temperature range of the liquid crystal phase is wider, the clearing point is high, negative Δε is large, and the viscosity is smaller.

When one of the substituents Y ¹ is hydrogen and ^one of Y ¹ is halogen, —CN, —CF ₃ , —CF ₂ H, —OCF ₃ , or —OCF ₂ H, the dielectric anisotropy value is Negatively big. When both substituents Y ₁ are halogen, —CN, —CF ₃ , —CF ₂ H, —OCF ₃ , or —OCF ₂ H, the dielectric anisotropy value is even more negative. When Y ¹ is halogen, —CF ₃ or —CF ₂ H, the temperature range of the liquid crystal phase is wide.

  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 types of terminal groups, rings and bonding groups, 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 (1-1) to (1-6) described in item 6 of the present invention. More specific examples are the following compounds (1-1-1) to (1-6-3). The meanings of the symbols Ra, Rb, A ¹ , and Z ¹ in these compounds are the same as the symbols described in item 6. Y ¹ is halogen, —CN, —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₃ , —OCHF ₂ , or —OCH ₂ F. Re is alkyl having 1 to 4 carbon atoms, and in this alkyl, arbitrary —CH ₂ — may be replaced by —O—, —S—, —CO—, or —SiH ₂ —, and any — (CH ₂ ) ₂ — may be replaced by —CH═CH— or —C≡C—.

  Compound (1) is synthesized by appropriately combining techniques in organic synthetic chemistry. Methods for introducing the desired end groups, rings and linking groups into the starting materials are Organic Syntheses (John Wiley & Sons, Inc), Organic Reactions (John Wiley & Sons, Inc), Comprehensive・ It is described in books such as Organic Synthesis (Pergamon Press) and New Experimental Chemistry Course (Maruzen).

Regarding an example of a method for generating the linking group Z ¹ , 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 M. Kuroboshi et al., Chem. Lett., 1992, 827. Compound (1C) can also be synthesized by fluorinating compound (26) with (diethylamino) sulfur trifluoride (DAST). See 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 t-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 (1E) 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 obtained 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.

Formation of (XI)-(CF ₂ ) _2-
According to the method described in J. Am. Chem. Soc., 2001, 123, 5414., a diketone (—COCO—) is fluorinated with sulfur tetrafluoride in the presence of a hydrogen fluoride catalyst to produce — (CF ₂ ). A compound having _2- is obtained.

  Secondly, the composition of the present invention will be further described. The component of this composition may be only a plurality of compounds selected from the compound (1). A preferred composition contains 1 to 99% of at least one compound selected from the compound (1). This composition mainly contains 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 positive and large 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 large negative dielectric anisotropy is as follows. A 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.

  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). This composition may further contain at least one compound selected from the group of compounds (2) to (6). This composition may further contain compounds such as other liquid crystal compounds and additives.

  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 positive and large 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 positive dielectric anisotropy and are very large, 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.

Desirable compounds (2) to (14) are respectively the compounds (2-1) to (2-9), the compounds (3-1) to (3-97), and the compounds (4-1) to (4-33). , 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 ¹ , R ² , X ¹ , and X ² are the same as those in the compounds (2) to (14).

  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 the 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.

A stabilizer may be added for the purpose of preventing deterioration of the composition due to ultraviolet rays or oxidation. Examples of the stabilizer are stabilizers (Sb-1) to (Sb-32).

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.

  Thirdly, the present invention will be described in more detail with reference to examples. The present invention is not limited by these examples. No. Compound numbers such as 1 correspond to those of the compound shown in Example 14. The obtained compound is identified by a nuclear magnetic resonance spectrum, a mass spectrum or the like. In the nuclear magnetic resonance spectrum, s is a singlet, d is a doublet, t is a triplet, q is a quartet, and m is a multiplet.

  The ratio (percentage) of the component or the liquid crystal compound is a weight percentage (% by weight) based on the total weight of the liquid crystal compound. The composition is prepared by measuring the weight of components such as a liquid crystal compound and then mixing them. Therefore, it is easy to calculate the weight percentage of the component. However, it is not easy to accurately calculate the ratio of components by gas chromatographic analysis of the composition. This is because the correction coefficient depends on the type of liquid crystal compound. Fortunately, the correction factor is approximately 1. Furthermore, the influence of the 1% by weight difference in the component compounds on the properties of the composition is small. Therefore, in the present invention, the area ratio of the component peak in the gas chromatograph can be regarded as the weight percent of the component compound. In other words, the result of gas chromatographic analysis (peak area ratio) can be considered to be equivalent to the weight percent of the liquid crystal compound without correction.

  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 wt% compound and 85 wt% mother liquid crystals. The characteristic value of the compound was calculated by extrapolation from the value obtained by the measurement. Extrapolated value = (measured value of sample−0.85 × measured value of mother liquid crystal) /0.15. When the smectic phase (or crystal) is precipitated at 25 ° C. at this ratio, the ratio of the compound and the mother liquid crystal is 10% by weight: 90% by weight, 5% by weight: 95% by weight, 1% by weight: 99% by weight 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.

  When a compound is mixed with mother liquid crystals and used as a sample, there are a plurality of mother liquid crystals. When the compound has a positive dielectric anisotropy, an example of the mother liquid crystal is the mother liquid crystal A. When the compound has a negative dielectric anisotropy, an example of the mother liquid crystal is the mother liquid crystal B. The compositions of the mother liquid crystals A and B are as follows.

Mother liquid crystal A:

Mother liquid crystal B:

  The characteristic values were 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 element or VA element used for the 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 and a Diamond DSC system manufactured by PerkinElmer Co., Ltd., the measurement was performed at a rate of 3 ° C./min.

The crystal was represented as C. If a crystal is distinguished into two crystals, it is denoted 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”.

  Low temperature compatibility (TC;% by weight): A sample obtained by mixing 20% by weight, 15% by weight, 10% by weight, 5% by weight, 3% by weight and 1% by weight of a compound with a mother liquid crystal is put in a glass bottle, and the temperature is set to −20 ° C. After storage in a freezer for 30 days, the liquid crystal phase was observed. For example, TC = 15% by weight was described when the sample when mixed by 20% by weight was a crystal or smectic and the sample when mixed by 15% by weight was a nematic phase.

  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 having positive 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 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 polarization direction was parallel to the rubbing direction. The refractive index n⊥ was measured when the polarization direction was perpendicular to the rubbing direction. The value of optical anisotropy was calculated from the equation: Δn = n∥−n⊥.

Dielectric anisotropy (Δε; measured at 25 ° C.):
1) Sample with positive dielectric anisotropy: A sample was put in a TN device in which the distance between two glass substrates (cell gap) was 9 μm and the twist angle was 80 degrees. Sine waves (10 V, 1 kHz) were applied to the device, and after 2 seconds, the dielectric constant (ε‖) in the major axis direction of the liquid crystal molecules was measured. Sine waves (0.5 V, 1 kHz) were applied to the device, and after 2 seconds, 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) Sample with negative dielectric anisotropy: A sample was placed in a VA device in which the distance between two glass substrates (cell gap) was 20 μm. Sine waves (0.5 V, 1 kHz) were applied to the device, and after 2 seconds, the dielectric constant (ε‖) in the major axis direction of the liquid crystal molecules was measured. A sample was put in a TN device in which the distance between two glass substrates (cell gap) was 9 μm and the twist angle was 80 degrees. Sine waves (0.5 V, 1 kHz) were applied to the device, and after 2 seconds, 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⊥.

  Threshold voltage (Vth; measured at 25 ° C .; V): In this item, only a sample having a positive dielectric anisotropy was measured. An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source is a halogen lamp. A sample was put in a normally white mode TN device in which the distance between two glass substrates (cell gap) was 9.0 μm and the twist angle was 80 degrees. The voltage (32 Hz, rectangular wave) applied to this element was increased stepwise from 0V to 10V by 0.02V. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. A voltage-transmittance curve was created in which the transmittance was 100% when the light amount reached the maximum and the transmittance was 0% when the light amount was the minimum. The threshold voltage is a voltage when the transmittance reaches 90%.

  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.

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 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 200 ° 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 weight), 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.

  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 weight percentage of the component compounds is not completely the same as the area ratio of each peak. However, in the present invention, when these capillary columns are used, the weight percentage of the component compounds may be considered to be 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.

Example 1
Synthesis of 1-ethoxy-2,3-difluoro-4- (2- (4-propylcyclohexyl) ethyl) -5-methylbenzene (compound 1-1-3-4)

First Step Under a nitrogen atmosphere, 82.5 g of 3,4-difluorobromobenzene (1) dissolved in 150 mL of tetrahydrofuran (THF) was added dropwise to 12.5 g of dried magnesium, and the mixture was heated to reflux for 1 hour after completion of the addition. . This solution was added dropwise to 15 mL of THF containing 91.5 g of methyl iodide and 12.3 g of copper (I) iodide while cooling in an ice bath. After stirring overnight, a saturated aqueous solution of ammonium chloride was added to stop the reaction, and the aqueous layer was combined with the extracted organic layer with diethyl ether, washed with saturated brine, and dried over anhydrous magnesium sulfate. Thereafter, distillation was performed to obtain 37.6 g of 2,3-difluorotoluene (2).

Second Step Under a nitrogen atmosphere, 30 g of (2) dissolved in 240 mL of THF was cooled to −78 ° C., 284 mL of sec-BuLi (1 M / L) was added thereto, and the mixture was stirred at the same temperature for 2 hours. Further, 48.7 g of trimethyl borate dissolved in 120 mL of THF at the same temperature was added dropwise, stirred at the same temperature for 1 hour, warmed to room temperature, and stirred overnight. While cooling in an ice bath, 200 mL of 3N hydrochloric acid was added, the aqueous layer was extracted with diethyl ether, the organic layers were combined, washed with saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and 48.8 g of 2,3-difluoro-5-methylphenylboric acid (3) was used for the next step without purification.

Third step
While cooling in an ice bath, 53.1 g of hydrogen peroxide was slowly added dropwise to (3) dissolved in 300 mL of THF, and then stirred at room temperature for 3 hours. While cooling in an ice bath, 100 mL of saturated aqueous sodium hydrogen sulfite solution was added dropwise to stop the reaction, the aqueous layer was extracted with diethyl ether, the organic layers were combined, washed with saturated aqueous sodium hydrogen sulfite solution and saturated brine, and anhydrous magnesium sulfate. Dried. The solvent was distilled off under reduced pressure to obtain 22.7 g of 2,3-difluoro-5-methylphenol (4).

Fourth Step 21.7 g of potassium carbonate and 36.6 g of ethyl iodide dissolved in 100 mL of MEK were added to (4) dissolved in 200 mL of methyl ethyl ketone (MEK), and the mixture was heated to reflux for 3 hours. Water was added to stop the reaction, and the aqueous layer was extracted with diethyl ether, washed with 2N aqueous sodium hydroxide solution and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 19.2 g of 2,3-difluoro-5-methylethoxybenzene (5).

Fifth Step Under nitrogen atmosphere, 10.0 g of (5) dissolved in 100 mL of THF was cooled to −78 ° C., and 72.6 mL of sec-BuLi (1 M / L) was added thereto, followed by stirring at the same temperature for 2 hours. Thereafter, 11.7 g of 2- (4-propylcyclohexyl) acetaldehyde dissolved in 10 mL of THF at the same temperature was dropped, and the mixture was heated to room temperature for 1 hour at the same temperature and stirred overnight. Saturated aqueous ammonium chloride solution was added to stop the reaction, the aqueous layer was extracted with ethyl acetate, the organic layers were combined, washed with saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off and 1- (2,3-difluoro-4-ethoxy-6-methylphenyl) -2- (4-propylcyclohexyl) ethanol (6) was used in the next step without purification.

Sixth Step 0.55 g of p-toluenesulfonic acid monohydrate was added to (6) dissolved in 120 mL of toluene, and the mixture was heated and stirred using a Dean-Stork trap until water no longer azeotroped. Water was added to stop the reaction, and the aqueous layer was extracted with toluene, washed with saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography, followed by recrystallization, and 2.01 g of 1- (2,3-difluoro-4-ethoxy-6-methylphenyl) -2- (4-Propylcyclohexyl) ethene (Compound 1-1-3-17) was obtained as colorless crystals.

¹ H-NMR (CDCl ₃ ): δ (ppm); 6.51 (d, 1H), 6.15 (d, 1H), 6.08 (dd, 1H), 4.08 (q, 2H), 2.25 (s, 3H), 2.09-2.03 (m, 1H), 1.85-1.78 (m, 4H), 1.43 (t, 3H), 1.36-1. 29 (m, 2H), 1.25-1.16 (m, 5H), 0.957 (q, 2H), 0.886 (t, 3H).

Step 7 0.1 g of Pd / C was added to the compound (1-1-3-17) dissolved in 20 mL of toluene and 20 mL of Solmix, and the mixture was stirred at room temperature under a hydrogen atmosphere until it did not absorb hydrogen. Pd / C was removed, the solvent was distilled off, the residue was purified by silica gel column chromatography and recrystallization, and 2.01 g of 1- (2,3-difluoro-4-ethoxy-6-methylphenyl) -2- (4 -Propylcyclohexyl) ethane (compound 1-2-3-4) was obtained as colorless crystals. Phase transition point (° C) C 34.4 Iso

¹ H-NMR (CDCl ₃ ): δ (ppm); 6.51 (d, 1H), 4.07 (q, 2H), 2.58-2.54 (m, 2H), 2.23 (s , 3H), 1.82-1.73 (m, 4H), 1.42 (t, 3H), 1.36-1.29 (m, 4H), 1.27-1.13 (m, 4H) ), 0.957-0.950 (m, 7H).

Example 2
Synthesis of 1-ethoxy-2,3-difluoro-4- (2- (4-pentylcyclohexyl) ethyl) -5-methylbenzene (compound 1-1-3-5)

First Step Under nitrogen atmosphere, 10.0 g of (5) dissolved in 100 mL of THF was cooled to −78 ° C., 72.6 mL of sec-BuLi (1 M / L) was added thereto, and the mixture was stirred at the same temperature for 2 hours. Thereafter, 13.3 g of 2- (4-pentylcyclohexyl) acetaldehyde dissolved in 13.3 mL of THF at the same temperature was added dropwise, and the mixture was heated to room temperature for 1 hour at the same temperature and stirred overnight. Saturated aqueous ammonium chloride solution was added to stop the reaction, the aqueous layer was extracted with ethyl acetate, the organic layers were combined, washed with saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off and 1- (2,3-difluoro-4-ethoxy-6-methylphenyl) -2- (4-pentylcyclohexyl) ethanol (7) was used in the next step without purification.

Second Step 0.55 g of p-toluenesulfonic acid monohydrate was added to (7) dissolved in 120 mL of toluene, and the mixture was heated and stirred using a Dean-Stork trap until water no longer azeotroped. Water was added to stop the reaction, and the aqueous layer was extracted with toluene, washed with saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography and then recrystallized to give 6.53 g of 1- (2,3-difluoro-4-ethoxy-6-methylphenyl) -2- (4-Pentylcyclohexyl) ethene (Compound 1-1-3-18) was obtained as colorless crystals.

¹ H-NMR (CDCl ₃ ): δ (ppm); 6.51 (d, 1H), 6.15 (d, 1H), 6.08 (dd, 1H), 4.08 (q, 2H), 2.25 (s, 3H), 2.09-2.03 (m, 1H), 1.85-1.78 (m, 4H), 1.43 (t, 3H), 1.36-1. 29 (m, 2H), 1.25-1.16 (m, 7H), 0.957-0.950 (m, 7H).

Third Step 0.27 g of Pd / C was added to 6.53 g of the compound (1-1-3-18) dissolved in 50 mL of toluene and 50 mL of Solmix, and at room temperature until hydrogen could not be absorbed in a hydrogen atmosphere. Stir. Pd / C was removed, the solvent was distilled off, the residue was purified by silica gel column chromatography and recrystallization, and 1.8 g of 1- (2,3-difluoro-4-ethoxy-6-methylphenyl) -2- (4 -Pentylcyclohexyl) ethane (compound 1-1-3-5) was obtained as colorless crystals. Phase transition point (° C) C 41.8 Iso

¹ H-NMR (CDCl ₃ ): δ (ppm); 6.51 (d, 1H), 4.07 (q, 2H), 2.57-2.54 (m, 2H), 2.23 (s , 3H), 1.82-1.73 (m, 4H), 1.42 (t, 3H), 1.36-1.23 (m, 8H), 1.17-1.15 (m, 4H) ), 0.957-0.950 (m, 7H).

Example 3
Synthesis of 1-ethoxy-2,3-difluoro-4- (2- (4- (4-propylcyclohexyl) cyclohexyl) ethyl) -5-methylbenzene (Compound 1-3-3-1)

First Step Under nitrogen atmosphere, 10.0 g of (5) dissolved in 100 mL of THF was cooled to −78 ° C., 72.6 mL of sec-BuLi (1 M / L) was added thereto, and the mixture was stirred at the same temperature for 2 hours. Thereafter, 17.5 g of 2- (4- (4-propylcyclohexyl) cyclohexyl) acetaldehyde dissolved in 18 mL of THF at the same temperature was added dropwise, and the mixture was heated to room temperature for 1 hour at the same temperature and stirred overnight. Saturated aqueous ammonium chloride solution was added to stop the reaction, the aqueous layer was extracted with ethyl acetate, the organic layers were combined, washed with saturated brine, and dried over anhydrous magnesium sulfate. The next step without purifying 1- (2,3-difluoro-4-ethoxy-6-methylphenyl) -2- (4- (4-propylcyclohexyl) cyclohexyl) ethanol (8) by distilling off the solvent. Used for.

Second Step 0.55 g of p-toluenesulfonic acid monohydrate was added to (8) dissolved in 120 mL of toluene, and the mixture was heated and stirred using a Dean-Stork trap until water no longer azeotroped. Water was added to stop the reaction, and the aqueous layer was extracted with toluene, washed with saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography, followed by recrystallization, and 11.2 g of 1- (2,3-difluoro-4-ethoxy-6-methylphenyl) -2- (4- (4-Propylcyclohexyl) cyclohexyl) ethene (Compound 1-3-3-9) was obtained as colorless crystals.
Phase transition temperature C 92.9 N 196.9 Iso

¹ H-NMR (CDCl ₃ ): δ (ppm); 6.51 (d, 1H), 6.15 (d, 1H), 6.07 (dd, 1H), 4.08 (q, 2H), 2.26 (s, 3H), 2.09-2.02 (m, 1H), 1.85 (d, 2H), 1.79-1.70 (m, 4H), 1.43 (t, 3H), 1.34-1.27 (m, 2H), 1.21-0.94 (m, 11H), 0.957 (q, 2H), 0.871 (t, 3H), 0.886 -0.811 (m, 2H).

Third step: 0.31 g of Pd / C was added to 6.20 g of compound (1-3-9-9) dissolved in 50 mL of toluene and 50 mL of Solmix, and the mixture was stirred at room temperature in a hydrogen atmosphere until no hydrogen was absorbed. Pd / C was removed, the solvent was distilled off, the residue was purified by silica gel column chromatography and recrystallization, and 5.03 g of 1- (2,3-difluoro-4-ethoxy-6-methylphenyl) -2- (4 -(4-Propylcyclohexyl) cyclohexyl) ethane (Compound 1-3-3-1) was obtained as colorless crystals.
Phase transition point (° C.) C ₁ 68.6 C ₂ 87.1 N 127.4 Iso

¹ H-NMR (CDCl ₃ ): δ (ppm); 6.51 (d, 1H), 4.07 (q, 2H), 2.57-2.54 (m, 2H), 2.22 (s , 3H), 1.83 (d, 2H), 1.75-1.68 (m, 6H), 1.42 (t, 3H), 1.35 to 1.26 (m, 4H), 22-1.12 (m, 4H), 1.01-0.903 (m, 8H), 0.881-0.801 (m, 5H).

Example 4
Synthesis of 1-ethoxy-2,3-difluoro-4- (2- (4- (4-pentylcyclohexyl) cyclohexyl) ethyl) -5-methylbenzene (compound 1-3-3-2)

First Step Under a nitrogen atmosphere, 7.0 g of (5) dissolved in 70 mL of THF was cooled to −78 ° C., 48.8 mL of sec-BuLi (1 M / L) was added thereto, and the mixture was stirred at the same temperature for 2 hours. Thereafter, 13.6 g of 2- (4- (4-pentylcyclohexyl) cyclohexyl) acetaldehyde dissolved in 13 mL of THF at the same temperature was added dropwise, and the mixture was heated to room temperature for 1 hour at the same temperature and stirred overnight. Saturated aqueous ammonium chloride solution was added to stop the reaction, the aqueous layer was extracted with ethyl acetate, the organic layers were combined, washed with saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off and 1- (2,3-difluoro-4-ethoxy-6-methylphenyl) -2- (4- (4-pentylcyclohexyl) cyclohexyl) ethanol (9) was purified without purification. Used for.

Second Step 0.16 g of p-toluenesulfonic acid monohydrate was added to (9) dissolved in 60 mL of toluene, and the mixture was heated and stirred using a Dean-Stork trap until water no longer azeotroped. Water was added to stop the reaction, and the aqueous layer was extracted with toluene, washed with saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography, followed by recrystallization, and 11.2 g of 1- (2,3-difluoro-4-ethoxy-6-methylphenyl) -2- (4- (4-Pentylcyclohexyl) cyclohexyl) ethene (Compound 1-3-3-10) was obtained as colorless crystals.

Step 3 0.08 g of Pd / C is added to 1.65 g of the compound (1-3-3-10) dissolved in 12.5 mL of toluene and 12.5 mL of Solmix, and the mixture is brought to room temperature under a hydrogen atmosphere until it does not absorb hydrogen. And stirred. Pd / C was removed, the solvent was distilled off, the residue was purified by silica gel column chromatography and recrystallization, and 0.83 g of 1- (2,3-difluoro-4-ethoxy-6-methylphenyl) -2- (4 -(4-Pentylcyclohexyl) cyclohexyl) ethane (Compound 1-3-3-2) was obtained as colorless crystals.
Phase transition point (° C.) C 63.93 (SmB 63.3) N 131.8 Iso

¹ H-NMR (CDCl ₃ ): δ (ppm); 6.51 (d, 1H), 4.07 (q, 2H), 2.57-2.54 (m, 2H), 2.22 (s , 3H), 1.83 (d, 2H), 1.76-1.68 (m, 6H), 1.42 (t, 3H), 1.35-1.18 (m, 8H), 16-1.07 (m, 4H), 1.01-0.924 (m, 8H), 0.881-0.801 (m, 5H).

Example 5
Synthesis of 1-ethoxy-2,3-difluoro-4- (2- (4- (4-propylcyclohexyl) cyclohexyl) methoxy) -5-methylbenzene (compound 1-3-3-5)

First Step Under a nitrogen atmosphere, 5.0 g of (5) dissolved in 30 mL of THF was cooled to −78 ° C., and 35.2 mL of sec-BuLi (1 M / L) was added thereto and stirred at the same temperature for 2 hours. . Further, 6.03 g of trimethyl borate dissolved in 15 mL of THF at the same temperature was added dropwise, stirred at the same temperature for 1 hour, warmed to room temperature, and stirred overnight. While cooling in an ice bath, 25 mL of 3N hydrochloric acid was added, the aqueous layer was extracted with diethyl ether, the organic layers were combined, washed with saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off and 6.19 g of 2,3-difluoro-4-ethoxy-6-methylphenylboric acid (10) was used for the next step without purification.

Second Step While cooling in an ice bath, 6.57 g of hydrogen peroxide solution was slowly added dropwise to (10) dissolved in 37 mL of THF, and then stirred at room temperature for 3 hours. While cooling in an ice bath, 20 mL of a saturated aqueous sodium hydrogen sulfite solution was added dropwise to stop the reaction, the aqueous layer was extracted with diethyl ether, the organic layers were combined, washed with a saturated aqueous sodium hydrogen sulfite solution and saturated brine, and anhydrous magnesium sulfate. Dried. The solvent was distilled off under reduced pressure to obtain 3.84 g of 2,3-difluoro-5-methylphenol (11).

Third Step 1- (4- (4-Propylcyclohexyl) cyclohexyl) -4-bromomethane (5.0 g), compound (11) 2.5 g, tetrabutylammonium bromide (TBAB) 0.22 g was added to N, N-dimethylformamide ( (DMF) was dissolved in 70 mL, 2.3 g of potassium carbonate was added, and the mixture was heated to reflux for 3 hours. Water was added to stop the reaction, the aqueous layer was extracted with toluene, the organic layers were combined, washed with saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography and recrystallization. 3.78 g of 1-ethoxy-2,3-difluoro-4- (2- (4- (4-propylcyclohexyl) cyclohexyl) methoxy ) -5-methylbenzene (compound 1-3-3-5) was obtained as colorless crystals.
Phase transition point (° C.) C ₁ 33.0 C ₂ 61.7 N 128.9 Iso

¹ H-NMR (CDCl ₃ ): δ (ppm); 6.49 (dd, 1H), 4.05 (q, 2H), 3.73 (d, 2H), 2.20 (s, 3H), 1.94 (d, 2H), 1.78-1.70 (m, 8H), 1.41 (t, 3H), 1.32-1.27 (m, 2H), 1.15-1. 13 (m, 2H), 1.04-0.936 (m, 8H), 0.869 (t, 3H) 0.854-0.808 (m, 2H).

Example 6
Synthesis of 1-ethoxy-2,3-difluoro-4- (2- (4- (4-pentylcyclohexyl) cyclohexyl) methoxy) -5-methylbenzene (compound 1-3-3-6)

First Step 1- (4- (4-Pentylcyclohexyl) cyclohexyl) -4-bromomethane (10.9 g), Compound (11) (5.0 g) and tetrabutylammonium bromide (TBAB) (0.44 g) were added to N, N-dimethylformamide ( DMF) was dissolved in 140 mL, 4.6 g of potassium carbonate was added, and the mixture was heated to reflux for 3 hours. Water was added to stop the reaction, the aqueous layer was extracted with toluene, the organic layers were combined, washed with saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography and recrystallization. 4.43 g of 1-ethoxy-2,3-difluoro-4- (2- (4- (4-pentylcyclohexyl) cyclohexyl) methoxy ) -5-methylbenzene (compound 1-3-3-6) was obtained as colorless crystals.
Phase transition point (° C.) C 63.1 N 130.0 Iso

¹ H-NMR (CDCl ₃ ): δ (ppm); 6.49 (dd, 1H), 4.05 (q, 2H), 3.73 (d, 2H), 2.20 (s, 3H), 1.94 (d, 2H), 1.78-1.70 (m, 8H), 1.41 (t, 3H), 1.31-1.23 (m, 6H), 1.15-1. 13 (m, 2H), 1.04-0.936 (m, 8H), 0.869 (t, 3H) 0.854-0.808 (m, 2H).

Example 7
1-ethoxy-2,3-difluoro-4- (2- (4- (4-propylcyclohexyl) cyclohexyl) -1,1-difluoromethoxy) -5-methylbenzene (compound 1-3-3-7) Composition

Step 1 Under a nitrogen atmosphere, 25.6 g of (12) dissolved in 180 mL of chloroform was cooled to −30 ° C., and 16.7 g of bromine dissolved in 18 mL of chloroform was added dropwise thereto and stirred at the same temperature for 30 minutes. did. Water was added and the aqueous layer was extracted with heptane. The organic layers were combined, washed with a saturated aqueous sodium hydrogensulfite solution and water, and dried over anhydrous magnesium sulfate. The solvent was distilled off to obtain 37.5 g of 1-bromo-1-bromodifluoromethyl-4- (4-propylcyclohexyl) cyclohexane (13).

Second step
Compound (11) (5.0 g), potassium carbonate (7.73 g), and TBAB (0.43 g) were dissolved in DMF (35 mL). After heating up to 110 degreeC, the compound (13) dissolved in DMF30mL at the same temperature was dripped, and it heated and stirred at the same temperature for 4 hours. After cooling to room temperature, water was added to stop the reaction, and the mixture was extracted with toluene. The organic layers were combined, washed with a saturated aqueous sodium hydrogen carbonate solution and saturated brine, and then dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 6.22 g of 5-ethoxy-3,4-difluoro-1-methyl-2- (4- (4-propylcyclohexyl) cyclohexenyl) difluoromethoxybenzene (14).

Third Step 0.31 g of Pd / C was added to 6.22 g of Compound (14) dissolved in 50 mL of toluene and 50 mL of Solmix, and the mixture was stirred at room temperature under a hydrogen atmosphere until it did not absorb hydrogen. Pd / C was filtered off and the solvent was distilled off. The residue was purified by silica gel column chromatography and recrystallization, and 1.75 g of 1-ethoxy-2,3-difluoro-4- (2- (4- (4-propylcyclohexyl) cyclohexyl) difluoromethoxy) -5-methyl Benzene (Compound 1-3-3-7) was obtained as colorless crystals.
Phase transition point (° C) C 92.5 N 143.9 Iso

¹ H-NMR (CDCl ₃ ): δ (ppm); 6.58 (dd, 1H), 4.08 (q, 2H), 2.21 (s, 3H), 2.11-1.03 (m , 3H), 1.85 (d, 2H), 1.77-1.70 (m, 4H), 1.43 (t, 3H), 1.46-1.38 (m, 2H), 34-1.27 (m, 2H), 1.14 (t, 3H), 1.09-0.94 (m, 6H), 0.872 (t, 3H) 0.886-0.815 (m , 2H).

Example 8
1- (1,1-difluoro-1- (2,3-difluoro-4-ethoxy-6-methylphenyl) methoxy) -4- (4-propylcyclohexyl) benzene (compound 1-3-3-15) Composition

First Step Under a nitrogen atmosphere, 20.0 g of (5) dissolved in 280 mL of THF was cooled to −78 ° C., 140.0 mL of sec-BuLi (1 M / L) was added, and the mixture was stirred at the same temperature for 2 hours. The dry ice lump was added there, and it stirred at -78 degreeC for 1 hour, Then, after heating up to room temperature, it stirred all night. 3N hydrochloric acid (100 mL) was added, and the aqueous layer was extracted with ether. The organic layers were combined, washed with saturated brine, and dried over anhydrous magnesium sulfate. After distilling off the solvent, recrystallization was performed with acetone to obtain 12.7 g of 2,3-difluoro-4-ethoxy-6-methylbenzoic acid (15).

Second step
10.0 g of compound (15) and 10.1 g of 4- (4-propylcyclohexyl) phenol are dissolved in 500 mL of dichloromethane, and 6.2 g of 4-dimethylaminopyridine (DMAP) is added thereto, and the mixture is stirred at room temperature for 1 hour. Stir. Thereto was added 10.5 g of N, N-dicyclohexylcarbodiimide (DCC) dissolved in 200 mL of dichloromethane at room temperature, and the mixture was stirred at room temperature overnight. 100 mL of ether was added to the reaction solution, and the precipitated urea was filtered off, and 500 mL of saturated brine was added to the filtrate, and the mixture was stirred for 3 hours. The organic layer was separated, washed with 3N hydrochloric acid and saturated aqueous sodium hydrogen carbonate solution, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 19.9 g of 2,3-difluoro-4-ethoxy-6-methylbenzoic acid 4- (4-propylcyclohexyl) (16).

Third Step 34.8 g of Lawesson's reagent was added to 17.9 g of the compound (16) dissolved in 180 mL of mesitylene, and the mixture was stirred for 4 hours with heating under reflux. The reaction solution was returned to room temperature, water was added, the aqueous layer was extracted with toluene, the organic layers were combined, washed with a saturated aqueous sodium hydrogen carbonate solution, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain 2.34 g of 2,3-difluoro-4-ethoxy-6-methylthiobenzoic acid O-4- (4-propylcyclohexyl) (17). It was.

Fourth Step 2.32 g of hydrogen fluoride pyridine was added dropwise to 1.93 g of N-bromosuccinimide (NBS) dissolved in 20 mL of dichloromethane at −78 ° C., followed by stirring at the same temperature for 20 minutes. To the reaction solution at −78 ° C., 2.34 g of Compound (17) dissolved in 10 mL of dichloromethane was added dropwise, and stirred at the same temperature for 3 hours. The reaction solution was poured into a saturated aqueous solution of sodium bicarbonate and stirred at room temperature overnight. The aqueous layer was extracted with dichloromethane, and the organic layers were combined, washed with a saturated aqueous sodium hydrogensulfite solution, 3N hydrochloric acid, and a saturated aqueous sodium hydrogencarbonate solution, and then dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography and recrystallization. 1.86 g of 1- (1,1-difluoro-1- (2,3-difluoro-4-ethoxy-6-methylphenyl) Methoxy) -4- (4-propylcyclohexyl) benzene (Compound 1-3-3-15) was obtained as colorless crystals.
Phase transition point (° C) C 78.1 Iso

¹ H-NMR (CDCl ₃ ): δ (ppm); 7.17 (m, 4H), 6.56 (d, 1H), 4.13 (q, 2H), 2.50 (s, 3H), 2.48-1.42 (m, 1H) 1.89-1.84 (m, 4H), 1.45 (t, 3H), 1.46-1.18 (m, 7H), 1.07 -0.99 (m, 2H), 0.899 (t, 3H).

Example 9
Synthesis of 1-ethoxy-2,3-difluoro-4- (2- (4-propylcyclohexyl) methoxy) -5-methylbenzene (compound 1-1-3-11)

First step 5.14 g of 1- (4-propylcyclohexyl) -4-bromomethane, 4.0 g of compound (11), and 0.34 g of TBAB were dissolved in 140 mL of DMF, and 3.24 g of potassium carbonate was added thereto, followed by heating under reflux for 3 hours. . Water was added to stop the reaction, the aqueous layer was extracted with toluene, the organic layers were combined, washed with saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, the residue was purified by silica gel column chromatography and recrystallization, and 4.39 g of 1-ethoxy-2,3-difluoro-4- (2- (4-propylcyclohexyl) methoxy) -5-methyl Benzene (Compound 1-1-3-11) was obtained as colorless crystals.
Phase transition point (° C) C 29.9 Iso

¹ H-NMR (CDCl ₃ ): δ (ppm); 6.49 (dd, 1H), 4.04 (q, 2H), 3.74 (d, 2H), 2.20 (s, 3H), 1.93-1.79 (m, 4H), 1.76-1.68 (m, 1H), 1.41 (t, 3H), 1.36-1.28 (m, 2H), 25-1.15 (m, 3H), 1.11-1.03 (m, 2H), 0.976-0.922 (m, 2H) 0.882 (t, 3H).

第１工程
１−（４−ペンチルシクロヘキシル）−４−ブロモメタン５．７８ｇ、化合物（１１）４．０ｇ、ＴＢＡＢ０．３４ｇをＤＭＦ１４０ｍＬに溶解させ、炭酸カリウム３．２４ｇを加え３時間加熱還流を行った。水を加え反応を停止させ、水層をトルエンで抽出し有機層を合わせ、飽和食塩水で洗浄した後、無水硫酸マグネシウムで乾燥した。溶媒を留去し、残渣をシリカゲルカラムクロマトグラフィー、再結晶で精製し、５．８９ｇの１−エトキシ−２，３−ジフルオロ−４−（２−（４−ペンチルシクロヘキシル）メトキシ）−５−メチルベンゼン（化合物１−１−３−１２）を無色結晶として得た。
相転移点（℃）Ｃ ３１．６ Ｉｓｏ Example 10
Synthesis of 1-ethoxy-2,3-difluoro-4- (2- (4-pentylcyclohexyl) methoxy) -5-methylbenzene (compound 1-1-3-12)

First Step 5.78 g of 1- (4-pentylcyclohexyl) -4-bromomethane, 4.0 g of compound (11), 0.34 g of TBAB were dissolved in 140 mL of DMF, added with 3.24 g of potassium carbonate, and heated to reflux for 3 hours. . Water was added to stop the reaction, the aqueous layer was extracted with toluene, the organic layers were combined, washed with saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, the residue was purified by silica gel column chromatography and recrystallization, and 5.89 g of 1-ethoxy-2,3-difluoro-4- (2- (4-pentylcyclohexyl) methoxy) -5-methyl. Benzene (Compound 1-1-3-12) was obtained as colorless crystals.
Phase transition point (° C) C 31.6 Iso

¹ H-NMR (CDCl ₃ ): δ (ppm); 6.49 (dd, 1H), 4.05 (q, 2H), 3.74 (d, 2H), 2.20 (s, 3H), 1.93-1.79 (m, 4H), 1.76-1.68 (m, 1H), 1.41 (t, 3H), 1.34-1.17 (m, 9H), 1. 11-1.03 (m, 2H), 0.974-0.922 (m, 2H) 0.885 (q, 3H).

Example 11
Synthesis of 2- (2- (4- (4-propylcyclohexyl) phenyl) ethyl) -2,3-difluoro-4-ethoxytoluene (Compound 1-3-3-12)

First Step Under a nitrogen atmosphere, 15.0 g of (5) dissolved in 180 mL of THF was cooled to −78 ° C., 105.0 mL of sec-BuLi (1 M / L) was added, and the mixture was stirred at the same temperature for 2 hours. Thereto was added 8.28 g of DMF dissolved in 120 mL of THF, and the mixture was stirred at −78 ° C. for 1 hour, then warmed to room temperature, and stirred overnight. After adding 80 mL of 3N hydrochloric acid and extracting the aqueous layer with toluene, the organic layers were combined, washed with saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off to obtain 12.0 g of 2,3-difluoro-4-ethoxy-6-methylbenzaldehyde (18).

Second step
60 mL of THF was added to 18.7 g of dried 1- (4- (4-propylcyclohexyl) phenyl) methyltriphenylphosphonium bromide, and the mixture was cooled to −60 ° C. in a nitrogen atmosphere. To the suspension, 3.70 g of potassium t-butoxide was added and stirred for 1 hour. Further, 6.0 g of the compound (18) dissolved in 60 mL of THF was added dropwise to the suspension, and the mixture was stirred at the same temperature for 1 hour, and then stirred at room temperature overnight. The reaction solution was passed through a silica gel layer, the solvent of the filtrate was distilled off under reduced pressure, the residue was purified by silica gel column chromatography, and 10.6 g of 2- (2- (4- (4-propylcyclohexyl) phenyl) ethenyl. ) -2,3-difluoro-4-ethoxytoluene (19) was obtained.

Third Step 0.53 g of Pd / C was added to 10.6 g of Compound (19) dissolved in 100 mL of toluene and 100 mL of Solmix, and the mixture was stirred at room temperature under a hydrogen atmosphere until it did not absorb hydrogen. Pd / C was filtered off and the solvent was distilled off. The residue was purified by silica gel column chromatography and recrystallization, and 6.90 g of 2- (2- (4- (4-propylcyclohexyl) phenyl) ethyl) -2,3-difluoro-4-ethoxytoluene (Compound 1- 3-3-12) was obtained as colorless crystals.
Phase transition point (° C) C 82.4 Iso

¹ H-NMR (CDCl ₃ ): δ (ppm); 7.14-7.10 (m, 4H), 6.51 (dd, 1H), 4.08 (q, 2H), 2.86-2 .83 (m, 2H), 2.75-2.71 (m, 2H), 2.47-2.41 (m, 1H), 2.15 (s, 3H), 1.89-1.84 (M, 4H), 1.48-1.19 (m, 1H), 1.43 (t, 3H), 1.08-1.00 (m, 2H), 0.901 (t, 3H).

Example 12
Synthesis of 2- (2- (4- (4-propylphenyl) phenyl) ethyl) -2,3-difluoro-4-ethoxytoluene (Compound 1-3-3-22)

First step
To 12.1 g of the dried 1- (4- (4-propylphenyl) phenyl) methyltriphenylphosphonium bromide, 40 mL of THF was added and cooled to −60 ° C. in a nitrogen atmosphere. To the suspension, 2.47 g of potassium t-butoxide was added and stirred for 1 hour. Further, 4.0 g of the compound (18) dissolved in 40 mL of THF was added dropwise to the suspension, and the mixture was stirred at the same temperature for 1 hour and then stirred at room temperature overnight. The reaction solution was passed through a silica gel layer, the solvent of the filtrate was distilled off under reduced pressure, the residue was purified by silica gel column chromatography, and 7.29 g of 2- (2- (4- (4-propylphenyl) phenyl) ethenyl. ) -2,3-difluoro-4-ethoxytoluene (20) was obtained.

Second Step 0.36 g of Pd / C was added to 7.29 g of Compound (20) dissolved in 100 mL of toluene and 100 mL of Solmix, and the mixture was stirred at room temperature under a hydrogen atmosphere until it did not absorb hydrogen. Pd / C was filtered off and the solvent was distilled off. The residue was purified by silica gel column chromatography and recrystallization, and 6.00 g of 2- (2- (4- (4-propylphenyl) phenyl) ethyl) -2,3-difluoro-4-ethoxytoluene (Compound 1- 3-3-22) was obtained as colorless crystals.
Phase transition point (° C) C 80.8 Iso

¹ H-NMR (CDCl ₃ ): δ (ppm); 7.50 (d, 4H) 7.24-7.21 (m, 4H), 6.50 (dd, 1H), 4.07 (q, 2H), 2.90-2.86 (m, 2H), 2.82-2.79 (m, 2H), 2.62 (t, 2H), 2.15 (s, 3H), 1.71 -1.63 (m, 2H), 1.42 (t, 3H), 0.968 (t, 3H).

Example 13
Synthesis of 2- (4-propylphenyl) ethyl-2,3-difluoro-4- (4-pentylphenyl) toluene (Compound 1-2-3-3)

First Step Under a nitrogen atmosphere, 10.0 g of (2) dissolved in 70 mL of THF was cooled to −78 ° C., 85.0 mL of sec-BuLi (1 M / L) was added, and the mixture was stirred at the same temperature for 2 hours. Thereto was added 23.8 g of iodine dissolved in 35 mL of THF, and the mixture was stirred at −78 ° C. for 1 hour, then warmed to room temperature, and stirred overnight. After adding 40 mL of water and extracting the aqueous layer with ether, the organic layers were combined, washed with a saturated aqueous sodium hydrogensulfite solution and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off to obtain 20.0 g of 3-iodo-4,5-difluorotoluene (21).

Second Step 9.04 g of Compound (21) dissolved in a mixed solvent of 50 mL of toluene and 50 mL of Solmix, 6.84 g of 4-pentylphenylboric acid, 5.74 g of TBAB, 9.84 g of potassium carbonate, 0 .76 g of Pd / C was added, and the mixture was stirred for 4 hours with heating under reflux. After removing Pd / C by filtration, the filtrate was separated, the aqueous layer was extracted with toluene, the organic layers were combined, washed with a saturated aqueous sodium hydrogen carbonate solution and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain 8.93 g of 3,4-difluoro-5- (4-pentylphenyl) toluene (22).

Third Step Under a nitrogen atmosphere, 8.93 g of (22) dissolved in 66 mL of THF was cooled to −78 ° C., 39.0 mL of sec-BuLi (1 M / L) was added, and the mixture was stirred at the same temperature for 2 hours. Thereto was added 3.56 g of DMF dissolved in 44 mL of THF, and the mixture was stirred at −78 ° C. for 1 hour, then warmed to room temperature, and stirred overnight. After adding 20 mL of 3N hydrochloric acid and extracting the aqueous layer with toluene, the organic layers were combined, washed with saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off to obtain 7.61 g of 2,3-difluoro-4- (4-pentylphenyl) -6-methylbenzaldehyde (23).

Fourth Step 40 mL of THF was added to 10.5 g of dried 1 (4-propylphenyl) methyltriphenylphosphonium bromide and cooled to −60 ° C. in a nitrogen atmosphere. To the suspension, 2.47 g of potassium t-butoxide was added and stirred for 1 hour. Further, 6.0 g of the compound (23) dissolved in 40 mL of THF was added dropwise to the suspension, and the mixture was stirred at the same temperature for 1 hour and then stirred at room temperature overnight. The reaction solution was passed through a silica gel layer, the solvent of the filtrate was distilled off under reduced pressure, the residue was purified by silica gel column chromatography, and 6.50 g of 2- (4-propylphenyl) ethenyl-2,3-difluoro-4. -(4-Pentylphenyl) toluene (24) was obtained.

Fifth Step 0.33 g of Pd / C was added to 6.50 g of the compound (24) dissolved in 100 mL of toluene and 100 mL of Solmix, and the mixture was stirred at room temperature in a hydrogen atmosphere until no hydrogen was absorbed. Pd / C was filtered off and the solvent was distilled off. The residue was purified by silica gel column chromatography and recrystallization, and 3.94 g of 2- (4-propylphenyl) ethyl-2,3-difluoro-4- (4-pentylphenyl) toluene (Compound 1-2-3- 3) was obtained as colorless crystals.
Phase transition point (° C) C 47.1 Iso

¹ H-NMR (CDCl ₃ ): δ (ppm); 7.45-7.23 (m, 4H), 7.14-7.10 (m, 4H), 6.95 (d, 1H), 2 95-2.92 (m, 2H), 2.82-2.79 (m, 2H), 2.64 (t, 2H), 2.56 (t, 2H), 2.22 (s, 3H) ), 1.68-1.59 (m, 4H), 1.36-1.33 (m, 4H), 0.935 (t, 3H), 0.905 (t, 3H).

Example 14
The following compounds 1-1-1-1 to 1-9-3-10 are synthesized based on Examples 1 to 13 and the synthesis methods described further. Compounds obtained in Example 1 to Example 13 (1-1-3-4, 1-1-3-5, 1-1-3-11, 1-1-3-12, 1-2-3- 3, 1-3-3-1, 1-3-3-2, 1-3-3-5, 1-3-3-6, 1-3-3-7, 1-3-3-9, 1-3-3-12, 1-3-3-15, and 1-3-3-22) are also shown again. The measurement procedures for the maximum temperature, viscosity, optical anisotropy and dielectric anisotropy are described in Example 15.

Example 15
Five compounds were mixed to prepare a composition A (mother liquid crystal B) having a nematic phase. The five compounds are 4-ethoxyphenyl 4-propylcyclohexanecarboxylate (17.2%), 4-butoxyphenyl 4-propylcyclohexanecarboxylate (27.6%), 4-ethoxyphenyl 4-butylcyclohexane. Carboxylate (20.7%), 4-methoxyphenyl 4-pentylcyclohexanecarboxylate (20.7%), and 4-ethoxyphenyl 4-pentylcyclohexanecarboxylate (13.8%). The physical properties of Composition A were as follows. Maximum temperature (NI) = 74.0 ° C .; viscosity (η ₂₀ ) = 18.9 mPa · s; optical anisotropy (Δn) = 0.087; dielectric anisotropy (Δε) = − 1.3.

  85% of this composition A and 1-ethoxy-2,3-difluoro-4- (2- (4- (4-propylcyclohexyl) cyclohexyl) ethyl) -5-methylbenzene obtained in Example 3 (Compound No. A composition B consisting of 15% of 1-3-3-1) was prepared. The physical properties of composition B are as follows. Optical anisotropy (Δn) = 0.088; dielectric anisotropy (Δε) = − 1.93. Compound No. It has been found that by adding 1-3-3-1, the dielectric anisotropy becomes negatively large and has a low driving voltage when a liquid crystal display element is formed.

Example 16
85% of Composition A described in Example 15 and 1-ethoxy-2,3-difluoro-4- (2- (4- (4-propylcyclohexyl) cyclohexyl) methoxy) -5- obtained in Example 6 A composition C consisting of 15% of methylbenzene (Compound No. 1-3-3-5) was prepared. The physical properties of Composition C are as follows. Optical anisotropy (Δn) = 0.087; dielectric anisotropy (Δε) = − 1.83. Compound No. It has been found that by adding 1-3-3-5, the dielectric anisotropy becomes negatively large, and the liquid crystal display element has a low driving voltage.

Comparative Example 1
Example 5 (Compound 1-3-3-5) and Example 6 which are similar to the physical property values of the compound having an alkyl group on the benzene ring reported in Patent Document 1 (Japanese Patent Laid-Open No. 10-291945). The physical property values of the compounds synthesized in (Compound 1-3-3-6) were compared. As a result, the conventionally reported compounds having an alkyl group on the benzene ring do not exhibit a liquid crystal phase or are very narrow at about 2.5 ° C. even if a liquid crystal phase is exhibited. In comparison, it was confirmed by comparison that the compound of the present application developed a liquid crystal phase (nematic phase) and its temperature range was as wide as about 60 ° C.

Comparative Example 2
Example 3 (Compound 1-3-3-1) and Example 4 which are similar to the physical property values of the compound having an alkyl group on the benzene ring reported in Patent Document 1 (Japanese Patent Laid-Open No. 10-291945). The physical property values of the compounds synthesized in (Compound 1-3-3-2) were compared. As a result, the conventionally reported compounds having an alkyl group on the benzene ring do not exhibit a liquid crystal phase or are very narrow at about 2.5 ° C. even if a liquid crystal phase is exhibited. In comparison, it was confirmed by comparison that the compound of the present application developed a liquid crystal phase (nematic phase) and its temperature range was as wide as 40 ° C to 60 ° C.

Comparative Example 3
Example 5 (Compound 1-3-3-5) and Example 6 which are similar to the physical property values of the compound having an alkyl group on the benzene ring reported in Patent Document 1 (Japanese Patent Laid-Open No. 10-291945). The compatibility of the compound synthesized in (Compound 1-3-3-6) with respect to the mother liquid crystal B at room temperature was compared. As a result, conventionally reported compounds having an alkyl group on the benzene ring dissolved only 5% or 10% in the mother liquid crystal. On the other hand, at least 15% of the compound of the present invention was dissolved in the mother liquid crystal, and it was confirmed by comparison that it was excellent in compatibility.

Comparative Example 4
Example 3 (Compound 1-3-3-1) and Example 4 which are similar to the physical property values of the compound having an alkyl group on the benzene ring reported in Patent Document 1 (Japanese Patent Laid-Open No. 10-291945). The compatibility of the compound synthesized in (Compound 1-3-3-2) with respect to the mother liquid crystal B at room temperature was compared. As a result, conventionally reported compounds having an alkyl group on the benzene ring dissolved only 5% or 10% of the mother liquid crystal. On the other hand, at least 15% of the compound of the present invention was dissolved in the mother liquid crystal, and it was confirmed by comparison that it was excellent in compatibility.

Claims (26)

A compound represented by the following formula (1).

In the formula (1), Ra and Rb are alkyl of 1 to 20 carbon atoms independently, any -CH ₂ - in the alkyl can be replaced by -O- well, any - (CH ₂ ) ₂ — may be replaced by —CH═CH— or —C≡C—, and any hydrogen may be replaced by halogen; ring A ¹ is independently 1,4-cyclohexylene, 1 , 4-phenylene , decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, or naphthalene-2,6-diyl, any- CH ₂ — may be replaced with —O—, any — (CH ₂ ) ₂ — may be replaced with —CH═CH—, and any hydrogen in these rings is halogen, —CF _3, - _{HF 2, -CH 2 F, -OCF} 3, -OCHF 2, or may be replaced by -OCH ₂ F; ^{Z 1} is independently a single _{bond, - (CH 2) 2 -} , - COO -, - OCO—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH═CH—, —CF═CF— , —C≡C—, —CH ₂ CO—, — _{COCH 2 -, - (CH 2} ) 2 COO -, - OCO (CH 2) 2 -, - (CH 2) 2 CF 2 O -, - OCF 2 (CH 2) 2 -, - (CH 2) 3 O —, —O (CH ₂ ) ₃ — or — (CH ₂ ) ₄ — ; W represents —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, —CH═CH— , —CF ═CF—, —C≡C—, —CF ₂ O—, —OCF ₂ —, — (CH ₂ ) ₂ COO—, —OCO (CH _{2) 2 -, - (CH} 2) 3 O -, - O (CH 2) 3 -, - (CH 2) 2 CF 2 O -, - OCF 2 (CH 2) 2 - or - _{(CH 2) 4} -, and; ^{Y 1} is independently hydrogen, _{halogen, -CN, -CF 3, -CHF 2} , -CH 2 F, -OCF 3, -OCHF 2, or a -OCH ₂ F, and the ^{Y 1} one _{halogen, -CF 3, -CHF 2, -CH} 2 F, -OCF 3, -OCHF 2, or be a -OCH ₂ F; Rc is Ri alkyl der of 1 to 4 carbon atoms; and, m is It is independently 0, 1 or 2, and the sum of a plurality of m is 0, 1 or 2. In Formula (1), Ra and Rb are independently alkyl having 1 to 20 carbon atoms, alkoxy having 1 to 19 carbon atoms, alkoxyalkyl having 2 to 19 carbon atoms, alkenyl having 2 to 20 carbon atoms, and 1 to 1 carbon atoms. 20 polyfluoroalkyl, or polyfluoroalkoxy having 1 to 19 carbon atoms; ring A ¹ is independently 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1,4-phenylene , it is a 2-fluoro 1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene or 2,6-difluoro-1,4-phenylene; Z ¹ is independently a single bond, — (CH ₂ ) ₂ —, —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH═ CH-, -CF _{CF -, - C≡C -, -} CH 2 CO -, - COCH 2 -, - CH 2 SiH 2 -, - SiH 2 CH 2 -, - (CH 2) 2 COO -, - OCO (CH 2) 2 _{-, - (CH 2) 2} CF 2 O -, - OCF 2 (CH 2) 2 -, - (CH 2) 3 O -, - O (CH 2) 3 - or - _{(CH 2) 4} - a and W represents —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, —CH═CH—, —CF═CF—, —C≡C—, —CF ₂ O—, —OCF ₂ —; , — (CH ₂ ) ₂ COO—, —OCO (CH ₂ ) ₂ —, — (CH ₂ ) ₃ O—, —O (CH ₂ ) ₃ —, — (CH ₂ ) ₂ CF ₂ O—, —OCF ₂ (CH ₂ ) ₂ — or — (CH ₂ ) ₄ —, Y ¹ is independently hydrogen, fluorine, chlorine, —CF ₃ , —CH F ₂ , —CH ₂ F, —OCF ₃ , —OCHF ₂ , or —OCH ₂ F, and ^one of Y ¹ is fluorine, chlorine, —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₃ , -OCHF _2, or be a -OCH ₂ F; and Rc is alkyl having 2 to 4 carbon atoms, a compound according to claim 1. In formula (1), Ra and Rb are each independently alkyl having 1 to 8 carbons, alkoxy having 1 to 7 carbons, alkoxyalkyl having 2 to 7 carbons, or alkenyl having 2 to 8 carbons; A ¹ is independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,3-difluoro-1,4-phenylene; Z ¹ is independently A single bond or — (CH ₂ ) ₂ —; W is — (CH ₂ ) ₄ —, —CH ₂ O—, —OCH ₂ —, —CH═CH— or —C≡C—; Y ¹ 2 is independently hydrogen, fluorine, —CF ₂ H or —CF ₃ , and ^one of Y ¹ is fluorine, —CH ₂ F or —CF ₃ ; and Rc is —CH _3. Compound. A compound represented by any one of the following formulas (1-1) to (1-6).

In the formula (1-6) from the equation (1-1), Ra and Rb are alkyl of 1 to 10 carbon atoms independently, any -CH ₂ - in the alkyl can be replaced by -O- Any — (CH ₂ ) ₂ — may be replaced by —CH═CH— or —C≡C— and any hydrogen may be replaced by halogen; ring A ¹ is independently 1,4-cyclohexylene, 1,4-phenylene, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, or naphthalene-2,6-diyl And in these rings any —CH ₂ — may be replaced by —O—, any — (CH ₂ ) ₂ — may be replaced by —CH═CH—, and these rings Any hydrogen in halo _Gen, -CF 3, -CHF _2, or may be replaced by -CH ₂ F; ^{Z 1} is independently a single _{bond, - (CH 2) 2 -} , - COO -, - OCO -, - CH 2 O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH═CH—, —CF═CF— , —C≡C—, —CH ₂ CO—, —COCH ₂ —, — ( _{CH 2) 2 COO -, -} OCO (CH 2) 2 -, - (CH 2) 2 CF 2 O -, - OCF 2 (CH 2) 2 -, - (CH 2) 3 O -, - O (CH ₂ ) ₃ — or — (CH ₂ ) ₄ — ; W is —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, —CH═CH—, —CF═CF—, —C ≡C—, —CF ₂ O—, —OCF ₂ —, — (CH ₂ ) ₂ COO—, —OCO (CH ₂ ) ₂ —, — (CH ₂ ) ₃ O—, —O (CH ₂ ) ₃ —, — (CH ₂ ) ₂ CF ₂ O—, —OCF ₂ (CH ₂ ) ₂ — or — (CH ₂ ) ₄ —; Y ¹ is independent Hydrogen, halogen, —CF ₃ , —CHF ₂ , or —CH ₂ F, and ^one of Y ¹ is halogen, —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₃ , —OCHF ₂ , or a -OCH ₂ F; Rc is Ru alkyl der 1 to 4 carbon atoms.

In Formula (1-1) to Formula (1-6), Ra and Rb are each independently alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, alkoxyalkyl having 2 to 9 carbons, or carbon 2 -10 alkenyl, C 1-10 polyfluoroalkyl, or C 2-10 polyfluoroalkoxy; ring A ¹ is independently 1,4-cyclohexylene, 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; Z ¹ is independently a single bond, — (CH ₂ ) ₂ —, —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, -OCF ₂ -, - CH = CH , -CF = CF -, - C≡C -, - (CH 2) 2 COO -, - OCO (CH 2) 2 -, - (CH 2) 2 CF 2 O -, - OCF 2 (CH 2) 2 —, — (CH ₂ ) ₃ O—, —O (CH ₂ ) ₃ — or — (CH ₂ ) ₄ —; W represents —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —. , —CH═CH—, —CF═CF—, —C≡C—, —CF ₂ O—, —OCF ₂ —, — (CH ₂ ) ₂ COO—, —OCO (CH ₂ ) ₂ —, — ( CH ₂ ) ₃ O—, —O (CH ₂ ) ₃ —, — (CH ₂ ) ₂ CF ₂ O—, —OCF ₂ (CH ₂ ) ₂ — or — (CH ₂ ) ₄ —; Y ¹ There independently hydrogen, fluorine, _chlorine, -CF 3, -CHF ₂ or a -CH ₂ F, and ^{Y 1} on one chlorine, _-CF 3,, CHF _2, or be a -CH ₂ F; and Rc is alkyl having 1 to 4 carbon atoms, A compound according to claim 4. In Formula (1-1) to Formula (1-6), Ra and Rb are each independently alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, alkoxyalkyl having 2 to 9 carbons, or carbon 2 -10 alkenyl, -CH ₂ F, or -OCH ₂ F; ring A ¹ is independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2, 3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, or 2,6-difluoro-1,4-phenylene; Z ¹ is independently a single bond, — (CH ₂ ) ₂ —, —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH═CH— or —C≡C—; _{-COO -, - OCO -, -} CH 2 O -, - OCH 2 -, - CH = CH -, - CF = CF -, - C≡C -, - (CH 2) 2 COO -, - OCO (CH 2) 2 -, - (CH 2) 3 O -, - O ( CH ₂ ) ₃ — or — (CH ₂ ) ₄ —; independently Y ¹ is fluorine, chlorine, —CF ₃ , or —CHF ₂ , and ^one of Y ¹ is chlorine, —CF ₃ , or be -CHF _2; Rc is a compound according to claim 5 is alkyl of 1 to 4 carbon atoms. In Formula (1-1) to Formula (1-6), Ra and Rb are each independently alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, alkoxyalkyl having 2 to 9 carbons, or carbon number 2-10 alkenyl; ring A ¹ is independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,3-difluoro-1,4- Z ¹ is independently a single bond or — (CH ₂ ) ₂ —; W is — (CH ₂ ) ₄ —, —CH ₂ O—, —OCH ₂ —, —CH═CH— or —C≡C—; Y ¹ is independently fluorine, hydrogen, —CF ₂ H or —CF ₃ , ^one of Y ¹ is —CF ₂ H or —CF ₃ ; Rc is —CH ₃ The compound according to claim 5 , wherein In the formula (1-6) from the equation (1-1), W is _-CH 2 O-; ^{Y 1} is independently fluorine, according to claim 5 -CF _3, or -CF ₂ H Compound. A compound represented by any one of the following formulas (I) to (IX):

In formula (IX) from the formula (I), Ra and Rb are independently alkyl having 1 to 10 carbon atoms, any -CH ₂ - in the alkyl may be replaced by -O-, optionally — (CH ₂ ) ₂ — may be replaced by —CH═CH—; Z ¹ is independently a single bond, — (CH ₂ ) ₂ —, —COO—, —OCO—, —CH ₂ O _{-, - OCH 2 -, -} CF 2 O -, - OCF 2 -, - CH = CH -, - CF = CF -, - C≡C -, - (CH 2) 2 COO -, - OCO (CH 2 ) ₂₋ , — (CH ₂ ) ₂ CF ₂ O—, — (CH ₂ ) ₃ O—, —O (CH ₂ ) ₃ — or — (CH ₂ ) ₄ —; W is — (CH ₂ ) _{4 -, - CH 2 O -} , - OCH 2 -, - CH = CH- or a -C≡C-; ^{Y 1} is independently water , Fluorine, chlorine, -CF ₃ or Ri -CF ₂ H Der, and one is chlorine ^{Y 1,} _fluorine, -CF 3, -CHF _2, or Ru -CH ₂ F der. In formula (I) to formula (IX), Ra and Rb are independently alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons or alkenyl having 2 to 10 carbons; Z ¹ is independently A single bond, — (CH ₂ ) ₂ —, —CH═CH—, or — (CH ₂ ) ₄ —; W is —CH ₂ O— or —CH═CH—; Y ¹ is independently hydrogen, fluorine, chlorine, -CF ₃ or -CHF _2, and one of ^{Y 1} is fluorine, chlorine, -CF ₃ or -CHF _2, a compound according to claim 9. In formulas (I) to (IX), Z ¹ is independently a single bond or —CH═CH—; W is —CH ₂ O—; Y ¹ is independently hydrogen, fluorine or —CF is ₃ and one of ^{Y 1} is fluorine or -CF _3, a compound according to claim 10. In formula (IX) from the formula (I),; ^{Z 1} represents a single bond; ^{Y 1} is independently fluorine or -CF _3, A compound according to claim 10. The compound according to claim 10 , wherein in formula (I) to formula (IX), Z ¹ is a single bond; and Y ¹ are both fluorine. The compound according to claim 10 , wherein in formula (I) to formula (IX), Z ¹ is a single bond; and Y ¹ are both -CF ₃ . In Formula (I) and Formula (III), Ra is alkyl or alkenyl having 1 to 6 carbons, Rb is alkoxy having 1 to 4 carbons; Z ¹ is a single bond; W is —CH ₂ an O-; ^{Y 1} are both fluorine, compounds described in claim 10. A liquid crystal composition comprising at least one compound selected from the group of compounds described in any one of claims 1 to 15 . The liquid crystal composition according to claim 16 , further comprising at least one compound selected from the group of compounds represented by the following formulas (2), (3) and (4).

In the formula, R ¹ is alkyl having 1 to 10 carbons, in which arbitrary —CH ₂ — may be replaced by —O— or —CH═CH—, and arbitrary hydrogen is replaced by fluorine. X ¹ 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 Is independently 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl or 1,4-phenylene in which any hydrogen may be replaced by fluorine, and ring E is 1,4-cyclohexyl. Silene or 1,4-phenylene in which any hydrogen may be replaced by fluorine; Z ⁴ is independently — (CH ₂ ) ₂ —, — (CH ₂ ) ₄ —, —COO—, —CF _2. O-, -OCF _2- , -CH = CH-, or a single bond; and L ¹ is independently hydrogen or fluorine. The liquid crystal composition according to claim 16 , further comprising at least one compound selected from the group of compounds represented by the following formulas (5) and (6).

In the formula, R ¹ is independently alkyl having 1 to 10 carbons, in which arbitrary —CH ₂ — may be replaced by —O— or —CH═CH—, and any hydrogen is X ² is —CN or —C≡C—CN; ring G is 1,4-cyclohexylene, 1,4-phenylene, 1,3-dioxane-2,5-diyl Or ring J is 1,4-cyclohexylene, pyrimidine-2,5-diyl, or 1,4-phenylene in which any hydrogen may be replaced by fluorine; Ring K is 1,4-cyclohexylene or 1,4-phenylene; Z ⁵ is — (CH ₂ ) ₂ —, —COO—, —CF ₂ O—, —OCF ₂ —, or a single bond; L ¹ is independently hydrogen or Be Tsu containing; and b are independently 0 or 1. The liquid crystal composition according to claim 16 , further comprising at least one compound selected from the group of compounds represented by the following formulas (7), (8), (9), (10), and (11): object.

In the formula, R ¹ is alkyl having 1 to 10 carbons, in which arbitrary —CH ₂ — may be replaced by —O— or —CH═CH—, and arbitrary hydrogen is replaced by fluorine. R ² is fluorine or alkyl having 1 to 10 carbons, in which any —CH ₂ — may be replaced by —O— or —CH═CH—, and any hydrogen May be replaced by fluorine; ring M is independently 1,4-cyclohexylene, 1,4-phenylene or decahydro-2,6-naphthalene; Z ⁶ is independently — (CH ₂ ) ₂ -, -COO- or a single bond; and L ² is independently hydrogen or fluorine, and at least one of L ² is fluorine. The liquid crystal composition according to claim 16 , further comprising at least one compound selected from the group of compounds represented by the following formulas (12), (13) and (14).

In the formula, R ¹ is independently alkyl having 1 to 10 carbons, in which arbitrary —CH ₂ — may be replaced by —O— or —CH═CH—, and any hydrogen is Ring J is independently 1,4-cyclohexylene, pyrimidine-2,5-diyl, or 1,4-phenylene in which any hydrogen may be replaced with fluorine; and Z ⁷ is independently —C≡C—, —COO—, — (CH ₂ ) ₂ —, —CH═CH—, or a single bond. At least one compound further composition according to claim 17 containing selected from the group of compounds represented by formula (5) and (6) according to claim 18. Formula according to claim 20 (12), (13) and (14) The composition of claim 17, further comprising at least one compound selected from the group of compounds represented by. Formula according to claim 20 (12), (13) and (14) The composition according to claim 18, further comprising at least one compound selected from the group of compounds represented by. 20. the formulas described (12), (13) and (14) at least one compound further composition of claim 19 containing selected from the group of compounds represented by. The liquid crystal composition according to any one of claims 16 to 24 , further comprising at least one optically active compound. A liquid crystal display device containing the liquid crystal composition according to any one of claims 16-25.