TWI797021B - Liquid crystal compound with negative dielectric anisotropy, liquid crystal composition, liquid crystal display device - Google Patents

Abstract

The invention relates to a liquid crystal compound, a liquid crystal composition and a liquid crystal display device with negative dielectric anisotropy. The liquid crystal compound has a small response index value on the basis of maintaining a certain level of negative dielectric constant and thus has a faster response time.

Description

Liquid crystal compound with negative dielectric anisotropy, liquid crystal composition, liquid crystal display device

The invention relates to the field of liquid crystal display materials, in particular to a liquid crystal compound with negative dielectric anisotropy, a liquid crystal composition and a liquid crystal display device.

At present, the application range of liquid crystal compounds is expanding more and more widely, and it can be applied to various types of displays, electro-optic devices, sensors, and the like. There are various types of liquid crystal compounds used in the above-mentioned display fields, among which nematic liquid crystals are most widely used. Nematic liquid crystals have been used in passive TN, STN matrix displays and systems with TFT active matrix.

For the application field of thin film transistor technology (TFT-LCD), although the market has been huge and the technology has gradually matured in recent years, people's requirements for display technology are also constantly improving. With the continuous development of TFT-LCD, the wide viewing angle mode has become the goal pursued by the industry. At present, the mainstream wide viewing angle technology mainly adopts display types such as VA vertical orientation, IPS in-plane switching and FFS fringe field switching. For these display modes, liquid crystal media with negative dielectric anisotropy are widely used.

)、彈性係數(Kii、pN)、旋轉粘度(Gamma 1, mPa.s)等多個因素的影響，如何獲得這些因素綜合作用下的響應時間提高的液晶化合物是本領域亟待解決的問題之一。 The demands on the response time of the liquid-crystalline media used in these modes are increasingly higher. The response time of the liquid crystal medium is affected by the clearing point T _NI (℃), the refractive index (Δn), the dielectric constant (

), elastic coefficient (Kii, pN), rotational viscosity (Gamma 1, mPa.s) and other factors, how to obtain the liquid crystal compound whose response time is improved under the combined effect of these factors is one of the problems to be solved urgently in this field .

The present invention aims at the problems existing in the above-mentioned prior art. After in-depth research, it is found that the liquid crystal compound shown in the formula I of the present invention can obtain a response time that is improved on the basis of maintaining a certain level of negative dielectric constant. novel liquid crystal compounds, thus completing the present invention.

For liquid crystal media, according to different display modes, the response time of liquid crystal media is related to G1/(K ₁₁ *△n*△n) or G1/(K ₃₃ *△n*△n). Specifically, in VA (vertical alignment, vertical alignment) or PS-VA (Polymer stabilized vertical alignment, polymer stabilized vertical alignment) mode, the response time of the liquid crystal medium is related to that of G1/(K ₃₃ *△n*△n) Value-related, while in FFS (Fringe Field Switching, fringe field switch), IPS (In-Plane Switching, plane conversion), PS-FFS (Polymer stabilized Fringe Field Switching, polymer stabilized fringe field switch), PS-IPS (Polymer Stabilized In-Plane Switching, polymer stabilized plane switching) and other modes, the response time of the liquid crystal medium is related to the value of G1/(K ₁₁ *△n*△n).

In the present application, the values of G1/(K ₃₃ *Δn*Δn) and G1/(K ₁₁ *Δn*Δn) are referred to as response index values. The smaller the aforementioned response index value, the faster the response time of the liquid crystal medium.

The liquid crystal compound with negative dielectric anisotropy of the present invention has a small response index value and thus an improved response time on the basis of maintaining a certain level of negative dielectric constant.

The present invention comprises following technical scheme:

Ⅰ In one aspect, the present invention provides a liquid crystal compound with negative dielectric anisotropy, the compound has the structure shown in the following formula I:

I

In formula I, R ₁ and R ₂ each independently represent a hydrogen atom, a straight-chain alkyl group with 1 to 8 carbon atoms, a straight-chain alkoxy group with 1 to 8 carbon atoms, and a straight chain alkoxy group with 2 to 8 carbon atoms. straight-chain alkenyl, straight-chain alkenyloxy with 2 to 8 carbon atoms, in which one or two non-adjacent -CH ₂ -s are optionally substituted by -O-, and any H is optionally substituted by an F atom;

Ring A1 is selected from the group consisting of 1,4-cyclohexylene, cyclohexene-1,4-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene base, 2,3-difluoro-1,4-phenylene, oxane-2,5-diyl, 1,3-dioxane-2,5-diyl, 1- Methylcyclohexane-1,4-diyl, 2-methylcyclohexane-1,4-diyl, 2-methylbenzene-1,4-diyl;

Z represents a single bond, -C ₂ H ₂ -, -C ₂ H ₄ -, -C ₂ H ₂ CH ₂ O-, -OCH ₂ C ₂ H ₂ -, -CH ₂ O-, -OCH ₂ -, - C ₂ H ₂ CH ₂ S-, -SCH ₂ C ₂ H ₂ -, -CH ₂ S-, -SCH ₂ -, -O-, -S-, -CF ₂ O-, -OCF ₂ -, -C ≡C-, -OOC-, or -COO-, where -CH ₂ O-, -C ₂ H ₂ -, -C ₂ H ₄ -, -C ₂ H ₂ CH ₂ O-, -OCH ₂ C ₂ H Any H in _2- is optionally substituted by F;

X represents -O-, -S-, -SO-, -SOO-, -CF ₂ -, -CO- or -CH ₂ -;

Y ₁ and Y ₂ each independently represent -F-, -CH ₂ F-, -CHF ₂ -, -CF ₃ -, -OCH ₂ F-, -OCHF _2- or -OCF ₃ -;

n represents 0, 1, 2 or 3.

Another aspect of the present invention provides a liquid crystal composition, which contains the aforementioned liquid crystal compound with negative dielectric anisotropy of the present invention.

Still another aspect of the present invention provides a liquid crystal display device, which contains the aforementioned liquid crystal compound with negative dielectric anisotropy of the present invention or the aforementioned liquid crystal composition of the present invention.

Invention effect

Compared with the prior art, the liquid crystal compound with negative dielectric anisotropy of the present invention has a small response index value on the basis of maintaining a certain level of negative dielectric constant and thus has a faster response time. By using the liquid crystal compound with negative dielectric anisotropy of the present invention in the liquid crystal composition of the present invention, and containing the liquid crystal composition using the liquid crystal compound of the present invention in the liquid crystal display device of the present invention, the display device can be made Response time is faster.

The present invention will be described below in combination with specific embodiments. It should be noted that the following examples are examples of the present invention, and are only used to illustrate the present invention, not to limit the present invention. Other combinations and various modifications within the concept of the present invention can be made without departing from the spirit or scope of the present invention.

[Liquid Crystal Compounds with Negative Dielectric Anisotropy]

Ⅰ The liquid crystal compound with negative dielectric anisotropy of the present invention has the structure shown in the following formula I:

I

In formula I, R ₁ and R ₂ each independently represent a hydrogen atom, a straight-chain alkyl group with 1 to 8 carbon atoms, a straight-chain alkoxy group with 1 to 8 carbon atoms, and a straight chain alkoxy group with 2 to 8 carbon atoms. straight-chain alkenyl, or straight-chain alkenyloxy with 2 to 8 carbon atoms, in which one or two non-adjacent -CH ₂ -s are optionally substituted by -O-, and any H is optionally substituted by an F atom .

Ring A1 is selected from the group consisting of 1,4-cyclohexylene, cyclohexene-1,4-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene base, 2,3-difluoro-1,4-phenylene, oxane-2,5-diyl, 1,3-dioxane-2,5-diyl, 1- Methylcyclohexane-1,4-diyl, 2-methylcyclohexane-1,4-diyl, 2-methylbenzene-1,4-diyl.

、

The aforementioned 2-fluoro-1,4-phenylene represents the following two divalent groups, in which the fluorine substituent may be on the left side or on the right side. This rule also applies to other similar groups.

,

Z represents a single bond, -C ₂ H ₂ -, -C ₂ H ₄ -, -C ₂ H ₂ CH ₂ O-, -OCH ₂ C ₂ H ₂ -, -CH ₂ O-, -OCH ₂ -, - C ₂ H ₂ CH ₂ S-, -SCH ₂ C ₂ H ₂ -, -CH ₂ S-, -SCH ₂ -, -O-, -S-, -CF ₂ O-, -OCF ₂ -, -C ≡C-, -OOC- or -COO-, where -CH ₂ O-, -C ₂ H ₂ -, -C ₂ H ₄ -, -C ₂ H ₂ CH ₂ O-, -OCH ₂ C ₂ H ₂ Any H in - is optionally replaced by F;

X represents -O-, -S-, -SO-, -SOO-, -CF ₂ -, -CO- or -CH ₂ -;

Y ₁ and Y ₂ each independently represent -F-, -CH ₂ F-, -CHF ₂ -, -CF ₃ -, -OCH ₂ F-, -OCHF _2- or -OCF ₃ -;

n represents 0, 1, 2 or 3.

Examples of the aforementioned "straight-chain alkyl group having 1 to 8 carbon atoms" include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl Base etc.

Examples of the aforementioned "straight-chain alkoxy group having 1 to 8 carbon atoms" include methoxy, ethoxy, n-propoxy, n-butoxy, n-pentyloxy, and n-hexyloxy. , n-heptyloxy, n-octyloxy, etc.

Examples of the aforementioned "straight-chain alkenyl group having 2 to 8 carbon atoms" include vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, Butenyl, 1-pentenyl, 2-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 1-heptenyl, 2-heptenyl, 3-heptenyl 1-octenyl, 2-octenyl, 3-octenyl.

Examples of the aforementioned "straight-chain alkenyloxy group having 2 to 8 carbon atoms" include ethyleneoxy, 1-propyleneoxy, 2-propyleneoxy, 1-butenyloxy, 2-but Alkenyloxy, 3-butenyloxy, 1-pentenyloxy, 2-pentenyloxy, 1-hexenyloxy, 2-hexenyloxy, 3-hexenyloxy, 1-heptene oxy, 2-heptenyloxy, 3-heptenyloxy, 1-octenyloxy, 2-octenyloxy, 3-octenyloxy and the like.

The aforementioned "one or two non-adjacent -CH ₂ - optionally substituted by -O-" means that the aforementioned straight-chain alkyl group with 1-8 carbon atoms, straight-chain alkyl group with 1-8 carbon atoms Any -CH ₂ - in alkoxy, straight-chain alkenyl with 2 to 8 carbon atoms, and straight-chain alkenyloxy with 2 to 8 carbon atoms is optionally substituted with -O-, but the adjacent The -CH ₂ - is not simultaneously substituted.

The aforementioned "any H is optionally substituted by an F atom" means that there is no limitation on the number of F substitutions, which may be monofluoro, polyfluoro, or perfluoro substituted.

Preferably, the aforementioned _R represents a hydrogen atom, a straight-chain alkyl group with 1 to 5 carbon atoms, a straight-chain alkoxy group with 1 to 5 carbon atoms, a straight-chain alkenyl group with 2 to 5 carbon atoms, or carbon A linear alkenyloxy group with 2 to 5 atoms, in which one or two non-adjacent -CH ₂ -s are optionally substituted by -O-, and any H is optionally substituted by an F atom.

The aforementioned "straight-chain alkyl group having 1 to 5 carbon atoms" includes, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group and the like. Preferred is methyl, ethyl or n-propyl.

Examples of the "straight-chain alkoxy group having 1 to 5 carbon atoms" include methoxy, ethoxy, n-propoxy, n-butoxy, and n-pentoxy. Preference is given to methoxy, ethoxy or n-propoxy.

Examples of the aforementioned "straight-chain alkenyl group having 2 to 5 carbon atoms" include vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl Alkenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl. Preferred is vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl.

Examples of the aforementioned "straight-chain alkenyloxy group having 2 to 5 carbon atoms" include ethyleneoxy, 1-propyleneoxy, 2-propyleneoxy, 1-buteneoxy, 2-butene Oxy, 3-butenyloxy, 1-pentenyloxy, 2-pentenyloxy, 3-pentenyloxy. Preferably, it is ethyleneoxy, 1-propyleneoxy, 3-butenyloxy, or 3-pentenyloxy.

The aforementioned straight-chain alkyl group with 1 to 5 carbon atoms, straight-chain alkoxy group with 1-5 carbon atoms, straight-chain alkenyl group with 2-5 carbon atoms, or straight-chain group with 2-5 carbon atoms In alkenyloxy, one or two non-adjacent -CH ₂ -s are optionally substituted by -O-, and any H is optionally substituted by F atoms.

In some embodiments of the compound represented by formula I of the present invention, the aforementioned R ₁ is preferably a straight-chain alkyl group with 1 to 5 carbon atoms or a straight-chain alkenyl group with 2 to 5 carbon atoms.

In some embodiments of the compound represented by formula I of the present invention, the aforementioned _R2 is preferably a straight-chain alkoxy group with 1 to 5 carbon atoms or a straight-chain alkenyloxy group with 2 to 5 carbon atoms.

In some embodiments of the compound represented by formula I of the present invention, ring A1 is preferably 1,4-cyclohexylene, cyclohexene-1,4-diyl or 1,4-phenylene, more preferably 1 ,4-cyclohexylene.

In some embodiments of the compound represented by formula I of the present invention, Z preferably represents a single bond, -C ₂ H ₂ -, or -C ₂ H ₄ -, more preferably a single bond.

In some embodiments of the compound represented by formula I of the present invention, X is preferably -O- or -S-.

In formula I, n represents 0, 1, 2, or 3, and from aspects such as obtaining a smaller response index value and thus having a faster response time, n is preferably 0, 1 or 2, and is more preferably n=0 or 1.

IA

IB

IC

ID

IE

IF

IG

IH

II

IJ

IK

IL

IM

IN

Ia

Ib

Ic

Id

Ie

If

Ig

Ih

Ii

Ij

Ik

Il

Im

In Among the liquid crystal compounds with negative dielectric anisotropy of the present invention, preferably, they are selected from the compounds represented by the following formulas IA-IN and Ia-In.

IA

IB

IC

ID

IE

IF

IG

IH

II

IJ

IK

IL

IM

IN

Ia

Ib

IC

ID

Ie

If

Ig

Ih

II

Ij

Ik

Il

Im

In

Wherein, the definitions of R ₁ and R ₂ are the same as above.

IA-1

IA-2

IA-3

IA-4

IB-1

IB-2

IB-3

IB-4

IC-1

IC-2

IC-3

IC-4

ID-1

ID-2

ID-3

ID-4

IE-1

IE-2

IE-3

IE-4

IF-1

IF-2

IF-3

IF-4

IG-1

IG-2

IG-3

IG-4

IH-1

IH-2

IH-3

IH-4

II-1

II-2

II-3

II-4

IJ-1

IJ-2

IJ-3

IJ-4

IK-1

IK-2

IK-3

IK-4

IL-1

IL-2

IL-3

IL-4

IM-1

IM-2

IM-3

IM-4

IN-1

IN-2

IN-3

IN-4

Ia-1

Ia-2

Ia-3

Ia-4

Ib-1

Ib-2

Ib-3

Ib-4

Ic-1

Ic-2

Ic-3

Ic-4

Id-1

Id-2

Id-3

Id-4

Ie-1

Ie-2

Ie-3

Ie-4

If-1

If-2

If-3

If-4

Ig-1

Ig-2

Ig-3

Ig-4

Ih-1

Ih-2

Ih-3

Ih-4

Ii-1

Ii-2

Ii-3

Ii-4

Ij-1

Ij-2

Ij-3

Ij-4

Ik-1

Ik-2

Ik-3

Ik-4

Il-1

Il-2

Il-3

Il-4

Im-1

Im-2

Im-3

Im-4

In-1

In-2

In-3

In-4 Further, the liquid crystal compound with negative dielectric anisotropy of the present invention is preferably selected from the group consisting of compounds represented by the following formulas IA-1~IN-4, Ia-1~In-4, wherein each of Alkyl independently represent a straight-chain alkyl group with 1 to 8 carbon atoms, and Alkenyl each independently represent a straight-chain alkenyl group with a carbon number of 2 to 8,

IA-1

IA-2

IA-3

IA-4

IB-1

IB-2

IB-3

IB-4

IC-1

IC-2

IC-3

IC-4

ID-1

ID-2

ID-3

ID-4

IE-1

IE-2

IE-3

IE-4

IF-1

IF-2

IF-3

IF-4

IG-1

IG-2

IG-3

IG-4

IH-1

IH-2

IH-3

IH-4

II-1

II-2

II-3

II-4

IJ-1

IJ-2

IJ-3

IJ-4

IK-1

IK-2

IK-3

IK-4

IL-1

IL-2

IL-3

IL-4

IM-1

IM-2

IM-3

IM-4

IN-1

IN-2

IN-3

IN-4

Ia-1

Ia-2

Ia-3

Ia-4

Ib-1

Ib-2

Ib-3

Ib-4

Ic-1

Ic-2

Ic-3

Ic-4

Id-1

Id-2

Id-3

Id-4

Ie-1

Ie-2

Ie-3

Ie-4

If-1

If-2

If-3

If-4

Ig-1

Ig-2

Ig-3

Ig-4

Ih-1

Ih-2

Ih-3

Ih-4

II-1

II-2

II-3

II-4

Ij-1

Ij-2

Ij-3

Ij-4

Ik-1

Ik-2

Ik-3

Ik-4

Il-1

Il-2

Il-3

Il-4

Im-1

Im-2

Im-3

Im-4

In-1

In-2

In-3

In-4

Examples of straight-chain alkyl groups having 1 to 8 carbon atoms represented by the aforementioned Alkyl include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl. group, preferably methyl, ethyl or n-propyl.

Examples of straight-chain alkenyl groups having 2 to 8 carbon atoms represented by Alkenyl include vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3 -butenyl, 1-pentenyl, 2-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 1-heptenyl, 2-heptenyl, 3-heptenyl Alkenyl, 1-octenyl, 2-octenyl, 3-octenyl and the like are preferably vinyl, 1-propenyl or 2-propenyl.

[Preparation method of liquid crystal compound]

Next, the preparation method of the liquid crystal compound having negative dielectric anisotropy of the present invention will be described.

It should be understood that the preparation method of the liquid crystal compound with negative dielectric anisotropy of the present invention is not limited to the preparation method described below. Those skilled in the art can use other suitable methods for preparation.

In addition, part of the compounds represented by formula I are described in the following descriptions, and other compounds can be obtained by those skilled in the art by referring to the following descriptions in combination with conventional technical means in the field.

式I-1 The liquid crystal compound represented by the following structural formula is prepared by a method comprising the following preparation steps, wherein the definitions of R ₁ , R ₂ , Y ₁ and Y ₂ are the same as above.

Formula I-1

Step A1: Carbo-arylation of benzene substituted by _Y1 and _Y2 with cyclohexanone with _R1 substituent in the presence of a palladium metal catalyst to obtain phenylcyclohexanone compound (A1);

Step A2: further subjecting the aforementioned phenylcyclohexanone compound (A1) to a palladium metal-catalyzed oxygen-arylation reaction to obtain a benzofuran compound (B1);

Step A3: The benzofuran compound (B1) obtained in the aforementioned step A2 is reacted with trimethyl borate under the action of a strong base in turn, followed by hydrolysis and oxidation to generate a benzofuran compound (B1) with an _R1 substituent and a phenolic hydroxyl group. furan compound (C1);

Step A4: Reaction of a benzofuran compound (C1) substituted by unilateral R ₁ with a phenolic hydroxyl group and R ₂ X (X represents bromine or iodine) under basic conditions to form a bilaterally symmetrical or asymmetrical benzofuran compound (I-1).

式I-2 The above-mentioned liquid crystal compound represented by the formula I-2 is prepared by a method comprising the following preparation steps, wherein the definitions of R ₁ , R ₂ , Y ₁ and Y ₂ are the same as above.

Formula I-2

Step B1: Palladium metal carbon-arylation reaction of benzene substituted by _Y1 and _Y2 and cyclohexanone with _R1 substituent to obtain phenylcyclohexanone compound (A2);

Step B2: reacting the aforementioned phenylcyclohexanone compound (A2) with a vulcanizing reagent to generate a phenylcyclohexanone compound (B2) of the corresponding structure;

Step B3: subjecting the phenylthiophene compound (B2) to a palladium metal-catalyzed sulfur-arylation reaction to obtain the benzothiophene compound (C2);

Step B4: react the benzothiophene compound (C2) with _R1 substituent with trimethyl borate in sequence, followed by hydrolysis and oxidation to generate benzene with _R1 substituent and phenolic hydroxyl group Thiophene compound (D2);

Step B5: Reaction of the benzothiophene compound (D2) substituted with a unilateral R ₁ group with a phenolic hydroxyl group and R ₂ X (X represents bromine or iodine) under basic conditions to form a symmetrical or asymmetrical benzothiophene compound (D2) Furan compound (I-2).

The preparation methods of the compounds represented by the aforementioned formula I-1 and formula I-2 are shown above. For the preparation of other compounds, those skilled in the art can refer to the above-mentioned preparation methods, and according to the technical knowledge in the field, change the reaction raw materials in the above-mentioned preparation methods for preparation, without special limitation.

[Liquid Crystal Composition]

The liquid crystal composition of the present invention contains the aforementioned liquid crystal compound with negative dielectric anisotropy of the present invention.

The liquid crystal composition of the present invention may contain one or more liquid crystal compounds with negative dielectric anisotropy of the present invention, and the content thereof is not particularly limited.

In the liquid crystal composition of the present invention, the content of the liquid crystal compound with negative dielectric anisotropy of the present invention may be, for example, 20% or less by weight percentage. From the viewpoint of low-temperature solubility, reliability, etc., it is preferably in the range of 15% or less. When multiple liquid crystal compounds with negative dielectric anisotropy of the present invention are contained, the total content of the liquid crystal compounds with negative dielectric anisotropy of the present invention may be, for example, 50% or less in weight percent.

In the liquid crystal composition of the present invention, in addition to the aforementioned liquid crystal compound with negative dielectric anisotropy, those skilled in the art can also add other liquid crystal compounds on the basis of not destroying the desired properties of the liquid crystal composition.

Optionally, various functional dopants may be added to the liquid crystal composition of the present invention, and these dopants include, for example, antioxidants, ultraviolet absorbers, and chiral agents.

As mentioned above, although the liquid crystal composition of the present invention contains the liquid crystal compound with negative dielectric anisotropy of the present invention, the composition of the present invention does not necessarily have negative dielectric anisotropy, and it can also be Positive dielectric anisotropy. A person skilled in the art can adjust the composition and proportion of each component of the composition as required to obtain a composition with desired anisotropy.

The preparation of the liquid crystal composition of the present invention is not particularly limited. On the basis of containing the liquid crystal compound of the present invention, those skilled in the art can select appropriate other components for preparation as required.

[Liquid crystal display device]

The third aspect of the present invention provides a liquid crystal display device, which is not particularly limited as long as it contains the aforementioned liquid crystal compound with negative dielectric anisotropy of the present invention, or the aforementioned liquid crystal composition. The liquid crystal display device of the present invention may be an active matrix display device or a passive matrix display device. Those skilled in the art can select a suitable liquid crystal display component and structure of the liquid crystal display according to the required performance.

Example

Example 1 LOY-3-O2

synthetic route:

Add 1.13 g cesium carbonate (3.45 mmol), 7.2 mg _Pd2 (dba) ₃ (0.008 mmol) and 11 mg Xantphos (0.019 mmol, 4,5-bisdiphenylphosphine-9,9-dimethyl xanthene), then replace the reaction bottle with nitrogen, add 4 mL of anhydrous dioxane, 0.5 g of 1-bromo-3,4-difluoro-2-iodobenzene (1.57 mmol) and 0.44 g of 3-propyl Cyclohexanone (3.14 mmol). Then react in an oil bath at 80° C. for 24 hours. After the reaction solution was cooled, it was extracted with diethyl ether and water, and the organic layer was collected, and then the organic layer was dehydrated with anhydrous MgSO ₄ and concentrated under reduced pressure. The concentrate was subjected to column chromatography to obtain 0.41 g of product A3.

¹ H-NMR (500MHz, CDCl ₃ , ppm): 7.13 (d, 1H), 6.66 (d, 1H), 3.50 (t, 1H), 2.31 (m, 2H) , 2.21 (m, 2H) , 1.86 ( m, 2H), 1.79 (m, 1H), 1.33-1.25 (m, 4H), 0.96 (t, 3H).

Take 0.5g compound A3 (1.51 mmol), 0.69g cesium carbonate (2.11 mmol), 34.6mg Pd ₂ (dba) ₃ (0.038 mmol) and 40.7mg DPEPhos (0.076 mmol, (2-diphenylphosphine phenyl) ether ) in the reaction bottle, and then replace the reaction bottle gas with nitrogen. After adding 4 mL of anhydrous toluene, react in an oil bath at 100°C for 20 hours. After cooling, filter the reaction solution with diatomaceous earth, concentrate under reduced pressure, and purify the concentrated solution by column chromatography to obtain 0.36 g of product B3.

¹ H-NMR (500MHz, CDCl ₃ , ppm): 7.17(d, 1H), 6.88 (d, 1H), 2.60 (m, 2H), 2.48 (m, 2H), 1.86 (m, 1H), 1.71( m, 2H), 1.33-1.25(m, 4H), 0.96 (t, 3H).

Dissolve 0.5g of compound B3 (2.0 mmol) in 12ml of THF, cool the reaction flask to -78°C, add 1.4ml of hexane solution containing 1.5M n-butyl lithium (2.1 mmol), then cool down to 0°C React for 30 minutes. Then, after adding 0.22 g of trimethyl borate (2.1 mmol) at -78°C, the temperature was raised to room temperature for 1 hour of reaction. After that, 1 ml of acetic acid and 0.25 ml of 30% H ₂ O ₂ were added, and the stirring was continued until the next day. The reaction solution was extracted with ethyl acetate and water, and the organic layer was dehydrated with anhydrous MgSO ₄ and concentrated under reduced pressure. The obtained concentrate was subjected to column chromatography to obtain 0.45 g of product C3.

¹ H-NMR (500MHz, CDCl ₃ , ppm): 6.64(s, 1H), 5.0(s, 1H), 2.60 (m, 2H), 2.48 (m, 2H), 1.86 (m, 1H), 1.71 ( m, 2H), 1.33-1.25 (m, 4H), 0.96 (t, 3H).

Take 0.5g of compound C3 (1.88 mmol), 0.52g of potassium carbonate (3.76 mmol) and 0.35g of iodoethane (2.26 mmol) in a reaction flask, add 6mL of dimethylformamide, and react in an oil bath at 70°C for 3 hours , After the reaction solution cooled down, it was extracted with water and ethyl acetate, and then the organic layer was dehydrated with anhydrous MgSO ₄ and concentrated under reduced pressure. The concentrate was subjected to column chromatography to obtain 0.56 g of product D3.

The mass spectrum and nuclear magnetic resonance spectrum data of the prepared compound D3 (LOY-3-O2) are as follows. According to the test results, compound D3 has the structure shown in LOY-3-O2.

MS (EI, m/z): 206, 265, 294.

¹ H-NMR (500MHz, CDCl ₃ , ppm): 6.68(d, 1H), 3.98 (q, 2H), 2.6 (m, 2H), 2.48 (m, 2H), 1.86(m, 1H), 1.71 ( m, 2H), 1.33-1.25 (m, 7H), 0.96 (t, 3H).

¹³ C-NMR (500 MHz, CDCl ₃ , ppm): 153.6, 150.3, 143.5, 142.8, 129.5, 112.1, 109.6, 93.7, 64.7, 34.3, 32.2, 31.6, 29.9, 20, 17.3, 14.8, 14.4.

Example 2

LSY-3-O2

synthetic route:

Add 1.13 g cesium carbonate (3.45 mmol), 7.2 mg Pd ₂ (dba) ₃ (0.008 mmol) and 11 mg Xantphos (0.019 mmol, 4,5-bisdiphenylphosphine-9,9-dimethyl xanthene), then replace the reaction bottle with nitrogen, add 4 mL of anhydrous dioxane, 0.5 g of 1-bromo-3,4-difluoro-2-iodobenzene (1.57 mmol) and 0.44 g of 3-propane Cyclohexanone (3.14 mmol). Then react in an oil bath at 80° C. for 24 hours. After the reaction solution was cooled, it was extracted with diethyl ether and water, and the organic layer was collected, and then the organic layer was dehydrated with anhydrous MgSO ₄ and concentrated under reduced pressure. The concentrate was subjected to column chromatography to obtain 0.41 g of product A4.

¹ H-NMR (500MHz, CDCl ₃ , ppm): 7.13(d, 1H), 6.66 (d, 1H), 3.50 (t, 1H), 2.31 (m, 2H) , 2.21 (m, 2H) , 1.86 ( m, 2H), 1.79 (m, 1H), 1.33-1.25 (m, 4H), 0.96 (t, 3H).

Take 0.5g of compound A4 (1.51 mmol) and 0.054g of phosphorus pentasulfide (0.38 mmol) in the reaction bottle, then replace the gas in the reaction bottle with nitrogen, then add 6 mL of anhydrous toluene and stir at room temperature for 30 minutes. Next, 0.42 g of hexamethyldisiloxane (2.57 mmol) was added and reacted in an oil bath at 90° C. for 24 hours. After the reaction solution was cooled, the reaction solution was filtered through a short silica gel column and concentrated under reduced pressure to obtain 0.37 g of the product B4.

¹ H-NMR (500MHz, CDCl ₃ , ppm): 7.13 (d, 1H), 6.66 (d, 1H), 2.8 (t, 1H), 1.7 (m, 2H), 1.5 (m, 1H), 1. 40 (m, 2H), 1.38 (m, 2H), 1.33-1.25 (m, 4H), 0.96 (t, 3H).

Take 0.5g compound B4 (1.44 mmol), 0.66g cesium carbonate (2.02 mmol), 33mg Pd ₂ (dba) ₃ (0.036 mmol) and 38.8 mg DPEPhos (0.072 mmol, (2-diphenylphosphine phenyl) ether) In the reaction bottle, the gas in the reaction bottle was replaced with nitrogen. After adding 4 mL of anhydrous toluene, react in an oil bath at 100°C for 20 hours. After cooling, filter the reaction solution with diatomaceous earth, concentrate under reduced pressure, and purify the concentrated solution by column chromatography to obtain 0.36 g of product C4.

¹ H-NMR (500MHz, CDCl ₃ , ppm): 7.61(d, 1H), 7.00 (d, 1H), 2.63 (m, 2H), 2.50 (m, 2H) , 1.86 (m, 1H), 1.71( m, 2H), 1. 33-1.25 (m, 4H), 0.96 (t, 3H).

Dissolve 0.5g of compound C (1.88 mmol) in 13ml of THF, cool the reaction flask to -78°C, add 1.3ml of 1.5M n-butyllithium (1.97 mmol) in hexane, then heat up to 0°C React for 30 minutes. Next, after adding 0.2 g of trimethyl borate (1.97 mmol) at -78°C, the temperature was raised to room temperature for 1 hour of reaction. After that, 1 ml of acetic acid and 0.22 ml of 30% H ₂ O ₂ were added, and the stirring was continued until the next day. The reaction solution was extracted with ethyl acetate and water, and the organic layer was dehydrated with anhydrous MgSO ₄ and concentrated under reduced pressure. The obtained concentrate was subjected to column chromatography to obtain 0.45 g of product D4.

¹ H-NMR (500MHz, CDCl ₃ , ppm): 7.08(s, 1H), 5.0(s, 1H), 2.63 (m, 2H), 2.50 (m, 2H), 1.86 (m, 1H), 1.71 ( m, 2H), 1.33-1.25 (m, 4H), 0.96 (t, 3H).

Take 0.5g of compound D4 (1.77 mmol), 0.49g of potassium carbonate (3.54 mmol) and 0.33g of iodoethane (2.12 mmol) in a reaction flask, add 5mL of dimethylformamide, and react in an oil bath at 70°C for 3 hours , After the reaction solution cooled down, it was extracted with water and ethyl acetate, and then the organic layer was dehydrated with anhydrous MgSO ₄ and concentrated under reduced pressure. The concentrate was subjected to column chromatography to obtain 0.44 g of product E4.

The prepared compound E4 (LSY-3-O2) was tested by mass spectrometry and nuclear magnetic resonance spectrum, and the data obtained by the test are as follows. According to the test results, compound E4 has the structure shown in LSY-3-O2.

MS (EI, m/z): 222, 265, 310.

¹ H-NMR (500MHz, CDCl ₃ , ppm): 7.12(s, 1H), 3.98 (q, 2H), 2.63 (m, 2H), 2.60 (m, 2H), 1.86 (m, 1H), 1.71( m, 2H), 1.33-1.25 (m, 7H), 0.98 (t, 3H).

¹³ C-NMR (500 MHz, CDCl ₃ , ppm): 145.6, 143.1, 141.8, 136, 131.5, 130.6, 121.9, 101, 64.7, 36.7, 34.7, 31.6, 27.7, 22.8, 20.6, 15.1, 14.6.

Example 3

LSP[F,OT]-3-O2

synthetic route:

Add 0.93 g cesium carbonate (2.86 mmol), 5.95 mg Pd ₂ (dba) ₃ (0.065 mmol) and 9.23 mg Xantphos (0.016 mmol, 4,5-bisdiphenylphosphine-9,9-dimethyl oxanthene), then replace the gas in the reaction bottle with nitrogen, add 4 mL of anhydrous dioxane, 0.5 g of 1-bromo-3-fluoro-2-iodo-4-(trifluoromethoxy)benzene (1.30 mmol) and 0.36 g 3-propylcyclohexanone (2.6 mmol). Then react in an oil bath at 80° C. for 24 hours. After the reaction solution was cooled, it was extracted with diethyl ether and water, and the organic layer was collected, and then the organic layer was dehydrated with anhydrous MgSO ₄ and concentrated under reduced pressure. The concentrate was subjected to column chromatography to obtain 0.40 g of product A5.

¹ H-NMR (500MHz, CDCl ₃ , ppm): 7.04(d, 1H), 6.46 (d, 1H), 3.50 (t, 1H), 2.31(m, 2H) , 2.21(m, 2H) , 1.88( m, 2H), 1.79(m, 1H), 1.33-1.25 (m, 4H), 0.96 (t, 3H).

Take 0.5g of compound A5 (1.26 mmol) and 0.045g of phosphorus pentasulfide (0.31 mmol) in the reaction bottle, then replace the gas in the reaction bottle with nitrogen, then add 5mL of anhydrous toluene and stir at room temperature for 30 minutes. Next, 0.35 g of hexamethyldisiloxane (2.14 mmol) was added, and reacted in an oil bath at 90° C. for 24 hours. After the reaction solution was cooled, the reaction solution was filtered through a short silica gel column and concentrated under reduced pressure to obtain 0.36 g of product B5.

¹ H-NMR (500MHz, CDCl ₃ , ppm): 7.04 (d, 1H), 6.46 (d, 1H), 2.8 (t, 1H), 1.7 (m, 2H), 1.5 (m, 1H) , 1.4 ( m, 2H), 1.38(m, 2H), 1.33-1.25 (m, 4H), 0.96 (t, 3H).

Take 0.5g compound B5 (1.21 mmol), 0.55 g cesium carbonate (1.69 mmol), 27.7 mg Pd ₂ (dba) ₃ (0.03 mmol) and 32.6 mg DPEPhos (0.061 mmol, (2-diphenylphosphine phenyl) ether ) in the reaction bottle, and then replace the reaction bottle gas with nitrogen. Then add 4mL of anhydrous toluene, react in an oil bath at 100°C for 20 hours, after cooling, filter the reaction solution with diatomaceous earth, concentrate under reduced pressure, and purify the concentrated solution by column chromatography to obtain 0.38g of product C5.

¹ H-NMR (500MHz, CDCl ₃ , ppm): 7.52 (d, 1H), 6.8 (d, 1H), 2.63 (m, 2H), 2.5 (m, 2H), 1.86 (m, 1H), 1.71 ( m, 2H), 1. 35-1.24 (m, 4H), 0.99 (t, 3H).

Dissolve 0.5g of compound C5 (1.5 mmol) in 10ml of THF, cool the reaction flask to -78°C, add 1.05ml of hexane solution containing 1.5M n-butyllithium (1.58 mmol), and then raise the temperature to 0°C React for 30 minutes. Then, after adding 0.16 g of trimethyl borate (1.58 mmol) at -78°C, the temperature was returned to room temperature for 1 hour of reaction. After that, 1 ml of acetic acid and 0.18 ml of 30% H ₂ O ₂ were added, and the stirring was continued until the next day. The reaction solution was extracted with ethyl acetate and water, and the organic layer was dehydrated with anhydrous MgSO ₄ and concentrated under reduced pressure. The obtained concentrate was subjected to column chromatography to obtain 0.44 g of product D5.

¹ H-NMR (500MHz, CDCl ₃ , ppm): 6.99(s, 1H), 5.0(s, 1H), 2.63 (m, 2H), 2.60 (m, 2H), 1.86 (m, 1H), 1.71 ( m, 2H), 1.33-1.25 (m, 4H), 0.96 (t, 3H).

Take 0.5g of compound D5 (1.44 mmol), 0.4g of potassium carbonate (2.88 mmol) and 0.27g of ethyl iodide (1.73 mmol) in a reaction flask, add 5mL of dimethylformamide, and react in an oil bath at 70°C for 3 hours , After the reaction solution cooled down, it was extracted with water and ethyl acetate, and then the organic layer was dehydrated with anhydrous MgSO ₄ and concentrated under reduced pressure. The concentrate was subjected to column chromatography to obtain 0.43 g of product E5. The prepared compound E (LSP(FOT)-3-O2) was subjected to mass spectrometry and nuclear magnetic resonance spectrometry tests, and the data obtained from the tests were as follows. According to the test results, the compound E5 has the structure shown in LSP(FOT)-3-O2.

MS (EI. m/z): 288, 333, 376.

¹ H-NMR (500MHz, CDCl ₃ , ppm): 7.03(s, 1H), 3.98 (q, 2H), 2.63 (m, 2H), 2.60 (m, 2H), 1.86 (m, 1H), 1.71( m, 2H), 1.35-1.26 (m, 7H), 0.97 (t, 3H).

¹³ C-NMR (500 MHz, CDCl ₃ ): 147.6, 143.6, 141.8, 132.7, 131.8, 130.1, 122.1, 121.3, 101.4, 66.2, 36.7, 34.7, 31.6, 27.7, 22.8, 20.6, 15.2, 14.6.

Example 4

LSP[TO,OT]-3-O2

synthetic route:

Add 0.80 g cesium carbonate (2.44 mmol), 5.08 mg Pd ₂ (dba) ₃ (0.0056 mmol) and 7.7 mg Xantphos (0.133 mmol, 4,5-bisdiphenylphosphine-9,9-dimethyl oxanthene), then replace the reaction bottle gas with nitrogen, add 3 mL of anhydrous dioxane, 0.5 g 1-bromo-2-iodo-3,4-bis(trifluoromethoxy)benzene (1.11 mmol) and 0.31 g 3-propylcyclohexanone (2.22 mmol). Then react in an oil bath at 80° C. for 24 hours. After the reaction solution was cooled, it was extracted with diethyl ether and water, and the organic layer was collected, and then the organic layer was dehydrated with anhydrous MgSO ₄ and concentrated under reduced pressure. The concentrate was subjected to column chromatography to obtain 0.40 g of product A6.

¹ H-NMR (500MHz, CDCl ₃ , ppm): 6.83 (d, 1H), 6.37 (d, 1H), 3.50 (t, 1H), 2.36 (m, 2H), 2.21 (m, 2H), 1.89 ( m, 2H), 1.77 (m, 1H), 1.36-1.24 (m, 4H), 0.97 (t, 3H).

Take 0.5g of compound A6 (1.08mmol) and 0.038g of phosphorus pentasulfide (0.27mmol) in the reaction bottle, then replace the gas in the reaction bottle with nitrogen, then add 5mL of anhydrous toluene and stir at room temperature for 30 minutes. Next, 0.3 g of hexamethyldisiloxane (1.84 mmol) was added, and reacted in an oil bath at 90° C. for 24 hours. After the reaction solution was cooled, the reaction solution was filtered through a short silica gel column and concentrated under reduced pressure to obtain 0.34 g of the product B6.

¹ H-NMR (500MHz, CDCl ₃ , ppm): 6.85 (d, 1H), 6.38 (d, 1H), 2.8 (t, 1H), 1.7 (m, 2H), 1.5 (m, 1H), 1.4 ( m, 2H), 1.38 (m, 2H), 1. 33-1.25 (m, 4H), 0.95 (t, 3H).

Take 0.5g compound 0.5g compound B (1.04 mmol), 0.48g cesium carbonate (1.46 mmol), 24 mg Pd ₂ (dba) ₃ (0.026 mmol) and 28 mg DPEPhos (0.052 mmol, (2-diphenylphosphine phenyl) ether) in the reaction bottle, and then the reaction bottle gas was replaced with nitrogen. After adding 3mL of anhydrous toluene, react in an oil bath at 100°C for 20 hours. After cooling, filter the reaction solution with diatomaceous earth, concentrate under reduced pressure, and purify the concentrated solution by column chromatography to obtain 0.4 g of product C6.

¹ H-NMR (500MHz, CDCl ₃ , ppm): 7.31 (d, 1H), 6.71 (d, 1H), 2.63 (m, 2H), 2.50 (m, 2H), 1.86 (m, 1), 1.7 ( m, 2H), 1.34-1.23 (m, 4H), 0.96 (t, 3H).

Dissolve 0.5g of compound C6 (1.2 6mmol) in 10ml of THF, cool the reaction flask to -78°C, add 1.05ml of butane containing 1.5M n-butyllithium (1.32 mmol), then heat up to 0°C for reaction 30 minutes. Then, after adding 0.14 g of trimethyl borate (1.32 mmol) at -78°C, the temperature was returned to room temperature for 1 hour of reaction. After that, 1 ml of acetic acid and 0.15 ml of 30% H ₂ O ₂ were added, and the stirring was continued until the next day. The reaction solution was extracted with ethyl acetate and water, and the organic layer was dehydrated with anhydrous MgSO ₄ and concentrated under reduced pressure. The obtained concentrate was subjected to column chromatography to obtain 0.45 g of product D6.

¹ H-NMR (500MHz, CDCl ₃ , ppm): 6.78(s, 1H), 5.0(s, 1H), 2.63 (m, 2H), 2.50 (m, 2H), 1.86(m, 1H), 1.7 ( m, 2H), 1.33-1.25 (m, 4H), 0.96 (t, 3H).

Take 0.5g of compound D6 (1.21 mmol), 0.33g of potassium carbonate (2.42 mmol) and 0.23g of ethyl iodide (1.45 mmol) in a reaction flask, add 5mL of dimethylformamide, and react in an oil bath at 70°C for 3 hours , After the reaction solution cooled down, it was extracted with water and ethyl acetate, and then the organic layer was dehydrated with anhydrous MgSO ₄ and concentrated under reduced pressure. The concentrate was subjected to column chromatography to obtain 0.38 g of product E6. The prepared compound was tested by mass spectrometry and nuclear magnetic resonance spectrum, and the data obtained by the test are as follows. According to the test results, the compound E6 has the structure shown in LSP(TOOT)-3-O2.

MS (EI, m/z): 356, 399, 442.

¹ H-NMR (500MHz, CDCl ₃ , ppm): 6.82 (s, 1H), 3.98 (q, 2H), 2.63 (m, 2H), 2.60 (m, 2H), 1.86 (m, 1H), 1.71 ( m, 2H), 1.32-1.23 (m, 7H), 0.98 (t, 3H).

¹³ C-NMR (500 MHz, CDCl ₃ ): 147, 142.5, 140.8, 132.1, 131.1, 129.1, 122.5, 122.4, 119.9, 97.1, 65, 36.7, 34.7, 31.6, 27.2, 22.7, 20.6, 14.6, 13.9.

Example 5

LSP[T,F]-3-O2

synthetic route:

Take 1.0g 3-propylcyclohexan-1-one (7.14 mmol), 1.25g 1-bromo-4-fluoro-2-iodo-3-(trifluoromethyl)benzene (3.39 mmol), 2.33g cesium carbonate (7.14 mmol), 73mg Pd ₂ (dba) ₃ (0.08 mmol) and 14.8mg Xantphos (0.16 mmol, 4,5-bisdiphenylphosphine-9,9-dimethyloxanthene) in the reaction flask, And the gas was replaced with nitrogen. Next, 15 ml of anhydrous dioxane was added and stirred, then heated to 90° C., and reacted for 24 hours. After waiting for the temperature to return to room temperature, the reaction solution was extracted with ethyl acetate and water, and the organic layer was collected. After that, the organic layer was dehydrated with anhydrous MgSO ₄ and concentrated under reduced pressure. The concentrate was subjected to column chromatography to obtain 0.93 g of product A7.

¹ H-NMR (500MHz, CDCl ₃ , ppm): 7.52 (d, 1H), 7.02 (d, 1H), 3.5 (t, 1H), 2.31~2.21 (m, 2H), 2.06~1.96 (m, 2H ), 1.72 (m, 2H), 1.48 (q, 1H), 1.32 (q, 2H), 1.18 (q, 2H), 0.91 (t, 3H).

Take 0.5 g of compound A7 (1.31 mmol) and 73 mg of phosphorus pentasulfide (0.33 mmol) in a reaction flask, then replace the gas with nitrogen, add 8 mL of anhydrous toluene, and stir at room temperature for 30 minutes. Next, 0.36 g of hexamethyldisiloxane (2.23 mmol) was added, and the mixture was moved to 90° C. in an oil bath and stirred for 24 hours. After the reaction solution was cooled, the reaction solution was filtered with a short silica gel column, and then the solution was concentrated under reduced pressure to obtain 0.32 g of product B7.

¹ H-NMR (500MHz, CDCl ₃ , ppm): 7.55 (d, 1H), 7.08 (d, 1H), 2.75 (t, 1H), 1.73 (q, 1H), 1.51 (q, 1H), 1.35~ 1.18 (m, 7H), 1.02 (q, 2H), 0.91 (t, 3H).

Take 0.5g compound B7 (1.26 mmol), 0.61g cesium carbonate (1.89 mmol), 28.8mg Pd ₂ (dba) ₃ (0.031mmol) and 33.9mg DPEPhos (0.063mmol, (2-diphenylphosphine phenyl) ether ) in the reaction flask, then the gas was replaced with nitrogen, 5 mL of anhydrous toluene was added, and the reaction was carried out at 100° C. in an oil bath for 20 hours. After the reaction solution was cooled, the reaction solution was filtered through a diatomaceous earth short column, concentrated under reduced pressure, and then the concentrated solution was purified by column chromatography to obtain 0.3 g of product C7.

¹ H-NMR (500MHz, CDCl ₃ , ppm): 7.98 (d, 1H), 7.15 (d, 1H), 2.88~2.8 (m, 3H), 2.58 (d, 1H), 1.68~1.56 (m, 2H ), 1.35~1.18 (m, 5H), 0.88 (t, 3H).

Get 0.5g of compound C7 (1.58 mmol) and dissolve in 10ml THF, add 1.11ml of butane containing 1.5M n-butyllithium (1.66 mmol) after the reaction bottle is cooled to -78 ° C, then from -78 ° C Raise the temperature to 0°C for 30 minutes. Then, after adding 0.17 g of trimethyl borate (1.32 mmol) at -78 ° C, the temperature was raised to room temperature for 1 hour. After that, 1 ml of acetic acid and 0.2 ml of 30% H ₂ O ₂ were added, and the stirring was continued until the next day. The reaction solution was extracted with ethyl acetate and water, and the organic layer was dehydrated with anhydrous MgSO ₄ and concentrated under reduced pressure. The obtained concentrate was subjected to column chromatography to obtain 0.39 g of product D7.

¹ H-NMR (500MHz, CDCl ₃ , ppm): 8.9 (s, 1H), 7.20 (s, 1H), 2.8~2.81 (m, 3H), 2.62 (d, 1H), 1.70~1.58 (m, 2H ), 1.33~1.20 (m, 5H), 0.89 (t, 3H).

Take 0.5 g of compound D7 (1.50 mmol), 0.196 g of bromoethane (1.80 mmol) and 8 mL of THF in a reaction flask, then add 0.23 g of triethylamine (2.25 mmol) dropwise, and finally heat to reflux for 3 hours. After the reaction solution cooled down, it was extracted with ethyl acetate and water, and then the organic layer was dehydrated with anhydrous MgSO ₄ and concentrated under reduced pressure. Then the concentrate was subjected to column chromatography to obtain 0.47 g of product E7.

The prepared compound E7 was tested by mass spectrometry and nuclear magnetic resonance spectrum, and the data obtained from the test are as follows. According to the test results, the compound E7 has the structure shown in LSP(TF)-3-O2.

MS (EI, m/z): 272, 315, 360.

¹ H-NMR (500MHz, CDCl ₃ , ppm): 7.41 (s, 1H), 4.06 (q, 2H), 2.8~2.82 (m, 3H), 2.62 (d, 1H), 1.69~1.58 (m, 2H ), 1.33~1.20 (m, 8H), 0.88 (t, 3H).

¹³ C-NMR (500 MHz, CDCl ₃ , ppm): 142, 141.7, 140.4, 134.1, 131.7, 115.4, 113.9, 108.6, 64.6, 38.8, 34.6, 32.3, 27.5, 22.6, 20.5, 14.8, 14.2.

Example 6

LSP[T,T]-3-O2

synthetic route:

Take 1.0 g of 3-propylcyclohexan-1-one (7.14 mmol), 1.42 g of 1-bromo-2-iodo-3,4-bis(trifluoromethyl)benzene (3.39 mmol), 2.33 g of cesium carbonate ( 7.14 mmol), 73mg Pd ₂ (dba) ₃ (0.08 mmol) and 14.8mg Xantphos (0.16 mmol, 4,5-bisdiphenylphosphine-9,9-dimethylxanthene) in the reaction flask, and The gas was replaced with nitrogen. Next, 15 ml of anhydrous dioxane was added and stirred, then heated to 90° C., and reacted for 24 hours. After waiting for the temperature to return to room temperature, the reaction solution was extracted with ethyl acetate and water, and the organic layer was collected. After that, the organic layer was dehydrated with anhydrous MgSO ₄ and concentrated under reduced pressure. The concentrate was subjected to column chromatography to obtain 1.08 g of product A8.

¹ H-NMR (500MHz, CDCl ₃ , ppm): 7.51 (d, 1H), 7.30 (d, 1H), 3.52 (t, 1H), 2.32~2.21 (m, 2H), 2.05~1.96 (m, 2H ), 1.73 (m, 2H), 1.51 (q, 1H), 1.32 (q, 2H), 1.21 (q, 2H), 0.90 (t, 3H).

Take 0.5 g of compound A8 (1.16 mmol) and 64.4 mg of phosphorus pentasulfide (0.29 mmol) in a reaction flask, then replace the gas with nitrogen, add 8 mL of anhydrous toluene, and stir at room temperature for 30 minutes. Next, 0.32 g of hexamethyldisiloxane (1.97 mmol) was added, and the mixture was moved to 90° C. in an oil bath and stirred for 24 hours. After the reaction solution was cooled, the reaction solution was filtered with a short silica gel column, and then the solution was concentrated under reduced pressure to obtain 0.36 g of product B8.

¹ H-NMR (500MHz, CDCl ₃ , ppm): 7.49 (d, 1H), 7.29 (d, 1H), 2.72 (t, 1H), 1.71 (q, 1H), 1.55 (q, 1H), 1.32~ 1.18 (m, 7H), 1.04 (m, 2H), 0.89 (t, 3H).

Take 0.5g compound B8 (1.12 mmol), 0.55 g cesium carbonate (1.68 mmol), 25.6 mg Pd ₂ (dba) ₃ (0.028 mmol) and 30.2 mg DPEphos (0.056 mmol, (2-diphenylphosphine phenyl) ether ) in the reaction flask, then the gas was replaced with nitrogen, 5 mL of anhydrous toluene was added, and the reaction was carried out at 100° C. in an oil bath for 20 hours. After the reaction solution was cooled, the reaction solution was filtered through a diatomaceous earth short column, concentrated under reduced pressure, and then the concentrated solution was purified by column chromatography to obtain 0.24 g of the product C8.

¹ H-NMR (500MHz, CDCl ₃ , ppm): 7.76 (d, 1H), 7.51 (d, 1H), 2.90~2.79 (m, 3H), 2.65 (d, 1H), 1.68~1.56 (m, 2H ), 1.33~1.20 (m, 5H), 0.91 (t, 3H).

Get 0.5g of compound C8 (1.36 mmol) and dissolve it in 10ml THF, add 0.95ml of hexane containing 1.5M n-butyllithium (1.43 mmol) after the reaction bottle is cooled to -78 ° C, then from -78 ° C Raise the temperature to 0°C for 30 minutes. Then, after adding 0.16 g of trimethyl borate (1.5 mmol) at -78° C., the temperature was returned to room temperature for 1 hour. After that, 1 ml of acetic acid and 0.15 ml of 30% H ₂ O ₂ were added, and the stirring was continued until the next day. The reaction solution was extracted with ethyl acetate and water, and the organic layer was dehydrated with anhydrous MgSO ₄ and concentrated under reduced pressure. The obtained concentrate was subjected to column chromatography to obtain 0.43 g of product D8.

¹ H-NMR (500MHz, CDCl ₃ , ppm): 9.69 (br, 1H), 7.21 (s, 1H), 2.91~2.80 (m, 3H), 2.63 (d, 1H), 1.68~1.58 (m, 2H ), 1.35~1.19 (m, 5H), 0.91 (t, 3H).

Take 0.5 g of compound D8 (1.31 mmol), 0.17 g of bromoethane (1.57 mmol) and 8 mL of THF in a reaction flask, then add 0.20 g of triethylamine (1.97 mmol) dropwise, and finally heat to reflux for 3 hours. After the reaction solution cooled down, it was extracted with ethyl acetate and water, and then the organic layer was dehydrated with anhydrous MgSO ₄ and concentrated under reduced pressure. Then the concentrate was subjected to column chromatography to obtain 0.43 g of product E8.

The prepared compound E8 was subjected to mass spectrometry and nuclear magnetic resonance spectrometry tests, and the data obtained from the tests are as follows. According to the test results, the compound E8 has the structure shown in LSP(TT)-3-O2.

MS (EI, m/z): 322,381,410.

¹ H-NMR (500MHz, CDCl ₃ , ppm): 7.35 (s, 1H), 4.8 (q, 2H), 2.8~2.83 (m, 3H), 2.61 (d, 1H), 1.69~1.57 (m, 2H ), 1.33~1.20 (m, 8H), 0.89 (t, 3H).

¹³ C-NMR (500 MHz, CDCl ₃ , ppm): 151.8, 143.8, 131.5, 130.4, 123.7, 119.7, 116.1, 109.5, 107.3, 64.9, 38.8, 35.8, 31.5, 27.5, 21.6, 20.5, 14.8, 13.9.

Example 7

CLOY-3-O2

synthetic route:

Take 1.0g 4'-propyl-[1,1'-di(cyclohexane)]-3-one (4.5 mmol), 0.68g 1-bromo-4-fluoro-2-iodo-3-(trifluoro Methyl)benzene (2.14 mmol), 1.46g cesium carbonate (4.49 mmol), 49mg Pd ₂ (dba) ₃ (0.08 mmol) and 62mg Xantphos (0.11 mmol, 4,5-bisdiphenylphosphine-9,9- dimethylxanthene) in the reaction flask, and the gas was replaced with nitrogen. Next, 15 ml of anhydrous dioxane was added and stirred, then heated to 90° C., and reacted for 24 hours. After waiting for the temperature to return to room temperature, the reaction solution was extracted with ethyl acetate and water, and the organic layer was collected. After that, the organic layer was dehydrated with anhydrous MgSO ₄ and concentrated under reduced pressure. The concentrate was subjected to column chromatography to obtain 0.64 g of product A9.

¹ H-NMR (500MHz, CDCl ₃ , ppm): 7.33 (d, 1H), 7.12 (d, 1H), 3.55 (t, 1H), 2.3~2.22 (m, 2H), 2.08~1.98 (m, 2H ), 1.78~1.2 (m, 17H), 0.92 (t, 3H).

Take 0.5g compound A9 (1.21 mmol), 0.59 g cesium carbonate (1.82 mmol), 22.9 mg Pd ₂ (dba) ₃ (0.028 mmol) and 32.6 mg DPEphos (0.061 mmol, (2-diphenylphosphine phenyl) ether ) in the reaction flask, then replace the gas with nitrogen, add 5mL of anhydrous toluene, and react for 20 hours at 100°C in an oil bath. After the reaction solution was cooled, the reaction solution was filtered through a diatomaceous earth short column, concentrated under reduced pressure, and then the concentrated solution was purified by column chromatography to obtain 0.34 g of product B9.

¹ H-NMR (500MHz, CDCl ₃ , ppm): 7.38 (d, 1H), 6.82 (d, 1H), 2.87~2.75 (q, 2H), 2.46 (d, 1H), 2.30 (d, 1H), 1.66~1.21 (m, 17H), 0.91 (t, 3H).

0.5g compound B9 (1.50 mmol) was dissolved in 10ml THF, and the reaction flask was cooled to -78 °C, and 1.05ml of 1.5M n-butyl lithium in hexane (1.58 mmol) was added, and then the temperature was raised from -78 °C to React at 0°C for 30 minutes. Then, after adding 0.17 g of trimethyl borate (1.65 mmol) at -78° C., the temperature was returned to room temperature for 1 hour. After that, 1 ml of acetic acid and 0.17 ml of 30% H ₂ O ₂ were added, and the stirring was continued until the next day. The reaction solution was extracted with ethyl acetate and water, and the organic layer was dehydrated with anhydrous MgSO ₄ and concentrated under reduced pressure. The obtained concentrate was subjected to column chromatography to obtain 0.46 g of product C9.

¹ H-NMR (500MHz, CDCl ₃ , ppm): 9.63 (s, 1H), 7.15 (d, 1H), 2.87~2.74 (m, 2H), 2.48 (d, 1H), 2.23 (d, 1H), 1.72~1.3 (m, 17H), 0.91 (t, 3H).

Take 0.5 g of compound D9 (1.44 mmol), 0.19 g of bromoethane (1.73 mmol) and 8 mL of THF in a reaction flask, then add 0.22 g of triethylamine (2.16 mmol) dropwise, and finally heat to reflux for 3 hours. After the reaction solution cooled down, it was extracted with ethyl acetate and water, and then the organic layer was dehydrated with anhydrous MgSO ₄ and concentrated under reduced pressure. Then the concentrate was subjected to column chromatography to obtain 0.45 g of product D9.

The prepared compound D9 was subjected to mass spectrometry and nuclear magnetic resonance spectrometry tests, and the data obtained from the tests are as follows. According to the test results, the compound has the structure shown in CLOY-3-O2.

MS (EI, m/z): 206, 251, 376.

¹ H-NMR (500MHz, CDCl ₃ , ppm): 7.33 (s, 1H), 4.13 (q, 2H), 2.90~2.78 (q, 2H), 2.47 (d, 1H), 2.23 (d, 1H), 1.71~1.31 (m, 20H), 0.93 (t, 3H).

¹³ C-NMR (500MHz, CDCl ₃ , ppm): 155.4, 150.5, 143.5, 142.8, 129.5, 112.1, 109.6, 93.6, 64.6, 40.1, 37.3, 35.8, 30.3, 29.3, 26.8, 20.5, 17.1, 15.1, 14.4 .

Example 8

CLSY-3-O2

synthetic route:

Take 1.0g 4'-propyl-[1,1'-bis(cyclohexane)]-3-one (2.5 mmol), 0.68g 1-bromo-4-fluoro-2-iodo-3-(trifluoro Methyl)benzene (2.14 mmol), 1.46g cesium carbonate (4.49 mmol), 49mg Pd ₂ (dba) ₃ (0.08 mmol) and 62mg Xantphos (0.11 mmol, 4,5-bisdiphenylphosphine-9,9- dimethylxanthene) in the reaction flask, and the gas was replaced with nitrogen. Next, 15 ml of anhydrous dioxane was added and stirred, then heated to 90° C., and reacted for 24 hours. After waiting for the temperature to return to room temperature, the reaction solution was extracted with ethyl acetate and water, and the organic layer was collected. After that, the organic layer was dehydrated with anhydrous MgSO ₄ and concentrated under reduced pressure. The concentrate was subjected to column chromatography to obtain 0.64 g of product A10.

¹ H-NMR (500MHz, CDCl ₃ , ppm): 7.33 (d, 1H), 7.12 (d, 1H), 3.55 (t, 1H), 2.3~2.22 (m, 2H), 2.08~1.98 (m, 2H ), 1.78~1.2 (m, 17H), 0.92 (t, 3H).

Take 0.5 g of compound A10 (1.21 mmol) and 67.2 mg of phosphorus pentasulfide (0.30 mmol) in a reaction flask, then replace the gas with nitrogen, add 8 mL of anhydrous toluene, and stir at room temperature for 30 minutes. Next, 0.33 g of hexamethyldisiloxane (2.06 mmol) was added, and the mixture was moved to a 90° C. oil bath and stirred for 24 hours. After the reaction solution was cooled, the reaction solution was filtered through a short silica gel column, and then the solution was concentrated under reduced pressure to obtain 0.52 g of the product B10.

¹ H-NMR (500MHz, CDCl ₃ , ppm): 7.33 (d, 1H), 7.11 (d, 1H), 2.76 (t, 1H)), 1.82~1.05 (m, 21H), 0.91 (t, 3H) .

Take 0.5g compound B10 (1.16 mmol), 0.57g cesium carbonate (1.74 mmol), 29 mg Pd ₂ (dba) ₃ (0.029 mmol) and 31.2 mg DPEphos (0.058 mmol, (2-diphenylphosphine phenyl) ether) In the reaction bottle, then the gas was replaced with nitrogen, 5mL of anhydrous toluene was added, and the reaction was carried out at 100°C in an oil bath for 20 hours. After the reaction solution was cooled, the reaction solution was filtered through a diatomaceous earth short column, concentrated under reduced pressure, and then the concentrated solution was purified by column chromatography to obtain 0.27 g of the product C10.

¹ H-NMR (500MHz, CDCl ₃ , ppm): 7.82 (d, 1H), 7.18 (d, 1H), 2.92~2.81 (m, 3H), 2.58 (d, 1H), 1.66~1.17 (m, 17H ), 0.91 (t, 3H).

Get 0.5g of compound C10 (1.43 mmol) and dissolve in 10ml THF, add 1.0ml of hexane containing 1.5M n-butyllithium (1.50 mmol) after the reaction bottle is cooled to -78 °C, then from -78 °C Raise the temperature to 0°C for 30 minutes. Then, after adding 0.16 g of trimethyl borate (1.57 mmol) at -78° C., the temperature was returned to room temperature for 1 hour. After that, 1 ml of acetic acid and 0.18 ml of 30% H ₂ O ₂ were added, and the stirring was continued until the next day. The reaction solution was extracted with ethyl acetate and water, and the organic layer was dehydrated with anhydrous MgSO ₄ and concentrated under reduced pressure. The obtained concentrate was subjected to column chromatography to obtain 0.4 g of product D10.

¹ H-NMR (500MHz, CDCl ₃ , ppm): 9.23 (s, 1H), 7.15 (s, 1H), 2.92~2.83 (m, 3H), 2.60 (d, 1H), 1.66~1.17 (m, 17H ), 0.92 (t, 3H).

Take 0.5 g of compound D10 (1.37 mmol), 0.18 g of bromoethane (1.65 mmol) and 8 mL of THF in a reaction flask, then add 0.21 g of triethylamine (2.06 mmol) dropwise, and finally heat to reflux for 3 hours. After the reaction solution cooled down, it was extracted with ethyl acetate and water, and then the organic layer was dehydrated with anhydrous MgSO ₄ and concentrated under reduced pressure. Then the concentrate was subjected to column chromatography to obtain 0.43 g of product E10.

The prepared compound E10 was tested by mass spectrometry and nuclear magnetic resonance spectrum, and the data obtained from the tests are as follows. According to the test results, the compound has the structure shown in CLSY-3-O2.

MS (EI, m/z): 222, 349, 392.

¹ H-NMR (500MHz, CDCl ₃ , ppm): 7.18 (s, 1H), 4.13 (q, 2H), 2.92~2.81 (m, 3H), 2.63 (d, 1H), 1.66~1.17 (m, 20H ), 0.90 (t, 3H).

¹³ C-NMR (500MHz, CDCl ₃ , ppm): 145.5, 143.3, 141.8, 135.4, 131.5, 129.6, 121.7, 100.9, 64.6, 42.6, 39.7, 37.1, 30.9, 29.3, 26.8, 25.3, 22.6, 20.5, 15.5 , 13.8.

For each compound monomer of the preceding examples and comparative examples shown in the following Table 1, it is mixed and compatible with the following mother liquid crystal by weight percentage according to the ratio of 10% compound monomer and 90% mother liquid crystal , measure T _NI , Δn, Δε, K ₁₁ , K ₃₃ , and G1 under the following conditions, and then use extrapolation to calculate the T _NI , Δn, Δε, K ₁₁ , K ₃₃ , and G1 of the monomer. The results of various physical properties of the body are shown in Table 2 described later.

Each component and its mass percent content in the aforementioned parent liquid crystal are as follows: CCG-2-F 10% CCP-V-1 20% CCP-V2-1 20% CPU-3-F 20% CP-3-O2 15% CP-3-O1 15%

The response index values G1/(K ₁₁ *△n*△n) and G1/(K ₃₃ *△n*△n) calculated according to these test results are shown in Table 3 below. In VA (vertical alignment, vertical orientation) or PS-VA (Polymer stabilized vertical alignment, polymer stabilized vertical alignment) mode, the response time of the liquid crystal medium is related to the index G1/(K ₃₃ *△n*△n), while in FFS (Fringe Field Switching, fringe field switch), IPS (In-Plane Switching, plane switching), PS-FFS (Polymer stabilized Fringe Field Switching, polymer stabilized fringe field switch), PS-IPS (Polymer stabilized In-Plane Switching, polymer stabilized plane switching ) and other modes, the response time of the liquid crystal medium is related to the response index value G1/(K ₁₁ *△n*△n). The smaller the aforementioned response index value, the faster the response time.

T _NI represents the temperature at which the liquid crystal monomer changes from a nematic phase to a clear phase, and its temperature is measured by MP-90 equipment;

Δn represents optical anisotropy, Δn=n _e -n _o , where n _o is the refractive index of ordinary light, and ne _is the refractive index of extraordinary light. Test conditions: 589 nm, 25±0.2°C.

Δε represents dielectric anisotropy, Δε=ε _∥ -ε _⊥ , where ε _∥ is the dielectric constant parallel to the molecular axis, ε _⊥ is the dielectric constant perpendicular to the molecular axis, test conditions: 25°C, INSTEC: ALCT-IR1, 18 micron vertical cell;

K ₁₁ is the torsional elastic constant, K ₃₃ is the splay elastic constant, and the test conditions are: 25°C, INSTEC: ALCT-IR1, 18 micron vertical box.

Gamma1(mPa.s) is the coefficient of rotational viscosity, abbreviated as "G1", and the test conditions are: 25°C, INSTEC: ALCT-IR1, 18 micron vertical box.

對比例 2 CLY-3-O2

實施例1 (IA-1) LOY-3-O2

實施例2 (Ia-1) LSY-3-O2

實施例3 (Ib-1) LSP[F,OT]-3-O2

實施例4 (Id-1) LSP[OT,OT]-3-O2

實施例5 (If-1) LSP[T,F]-3-O2

實施例6 (Ig-1) LSP[T,T]-3-O2

實施例7 (IH-1) CLOY-3-O2

實施例8 (Ih-1) CLSY-3-O2

Table 1: each compound of embodiment and comparative example Comparative example 1 LY-3-O2

Comparative example 2 CLY-3-O2

Example 1 (IA-1) LOY-3-O2

Example 2 (Ia-1) LSY-3-O2

Example 3 (Ib-1) LSP[F,OT]-3-O2

Example 4 (Id-1) LSP[OT,OT]-3-O2

Example 5 (If-1) LSP[T,F]-3-O2

Example 6 (Ig-1) LSP[T,T]-3-O2

Example 7 (IH-1) CLOY-3-O2

Example 8 (Ih-1) CLSY-3-O2

n) 介電常數(

) 彈性係數K ₁₁(pN) 彈性係數K ₃₃(pN) 旋轉粘滯係數 G1(mPa.s) 對比例1 -5.8 0.0895 -6.0 1.8 3.2 49.3 對比例2 172.5 0.1470 -6.5 34.1 38.0 1025.2 實施例1 12.2 0.1195 -5.9 5.2 6.9 66.2 實施例2 52.2 0.1177 -6.0 12.7 15.2 129.2 實施例3 51.2 0.1077 -9.0 14.7 17.2 103.3 實施例4 55.0 0.1027 -11.0 15.7 18.2 90.4 實施例5 42.2 0.0977 -11.0 11.7 14.2 64.6 實施例6 37.2 0.0927 -13.0 10.68 13.23 51.7 實施例7 192.5 0.1770 -6.4 38.8 44.1 1245.6 實施例8 232.5 0.1970 -6.4 46.3 52.4 1532.5 Table 2: The physical property result of each compound of embodiment and comparative example Physical Properties (25℃) Clearing point T _NI (℃) Refractive index (

n) Dielectric constant (

) Elastic coefficient K ₁₁ (pN) Elastic coefficient K ₃₃ (pN) Coefficient of rotational viscosity G1(mPa.s) Comparative example 1 -5.8 0.0895 -6.0 1.8 3.2 49.3 Comparative example 2 172.5 0.1470 -6.5 34.1 38.0 1025.2 Example 1 12.2 0.1195 -5.9 5.2 6.9 66.2 Example 2 52.2 0.1177 -6.0 12.7 15.2 129.2 Example 3 51.2 0.1077 -9.0 14.7 17.2 103.3 Example 4 55.0 0.1027 -11.0 15.7 18.2 90.4 Example 5 42.2 0.0977 -11.0 11.7 14.2 64.6 Example 6 37.2 0.0927 -13.0 10.68 13.23 51.7 Example 7 192.5 0.1770 -6.4 38.8 44.1 1245.6 Example 8 232.5 0.1970 -6.4 46.3 52.4 1532.5

Table 3: The response index value of each compound of embodiment and comparative example Physical Properties (25℃) G1/(K ₁₁ *△n*△n) G1/(K ₃₃ *△n*△n) Comparative example 1 3398.3 1946.5 Comparative example 2 1392.5 1249.1 Example 1 893.3 672.0 Example 2 735.3 612.2 Example 3 606.9 517.1 Example 4 546.7 470.3 Example 5 579.3 475.5 Example 6 563.0 454.5 Example 7 1024.4 900.9 Example 8 852.9 753.3

It can be seen from the comparison of the response indicators of Examples 1-8 and Comparative Examples 1-2 in Table 3 that the response indicators of the liquid crystal compounds of Examples 1-8 are G1/(K ₁₁ *Δn*Δn), G1/(K ₃₃ *Δn*Δn) decreased relative to the comparative example.

The present invention may be embodied in other specific forms without departing from the spirit or main characteristics of the invention. Therefore, no matter from which point of view, the above-mentioned embodiments of the present invention can only be regarded as descriptions of the present invention and cannot limit the present invention, and the claims have pointed out the scope of the present invention, and the above description does not point out the scope of the present invention. Therefore, any changes within the meaning and scope equivalent to the claims of the present invention should be considered to be included in the scope of the claims of the present invention.

Fig. 1 is the ¹ H nuclear magnetic resonance spectrum of the compound LOY-3-O2 prepared in Example 1 of the present invention dissolved in CDCl ₃ . Fig. 2 is a ¹³ C nuclear magnetic resonance spectrum of the compound LOY-3-O2 prepared in Example 1 of the present invention dissolved in CDCl ₃ .

Claims (8)

A liquid crystal compound with negative dielectric anisotropy, which has the structure shown in the following formula I:

I In formula I, R ₁ and R ₂ each independently represent a hydrogen atom, a straight chain alkyl group with 1 to 8 carbon atoms, a straight chain alkoxy group with 1 to 8 carbon atoms, and a straight chain alkoxy group with 2 to 8 carbon atoms. 8 straight-chain alkenyl, or straight-chain alkenyloxy with 2 to 8 carbon atoms, wherein one or two non-adjacent -CH ₂ - are optionally substituted by -O-, and any H is optionally substituted by F Atom substitution; ring A1 is selected from the group consisting of the following groups: 1,4-cyclohexylene, cyclohexene-1,4-diyl, 1,4-phenylene, 2-fluoro-1,4 -phenylene, 2,3-difluoro-1,4-phenylene, oxane-2,5-diyl, 1,3-dioxane-2,5-diyl , 1-methylcyclohexane-1,4-diyl, 2-methylcyclohexane-1,4-diyl, 2-methylbenzene-1,4-diyl; Z represents a single bond, - C ₂ H ₂ -, -C ₂ H ₄ -, -C ₂ H ₂ CH ₂ O-, -OCH ₂ C ₂ H ₂ -, -CH ₂ O-, -OCH ₂ -, -C ₂ H ₂ CH ₂ S-, -SCH ₂ C ₂ H ₂ -, -CH ₂ S-, -SCH ₂ -, -O-, -S-, -CF ₂ O-, -OCF ₂ -, -C≡C-, -OOC -or -COO-, where any H in -CH ₂ O-, -C ₂ H ₂ -, -C ₂ H ₄ -, -C ₂ H ₂ CH ₂ O-, -OCH ₂ C ₂ H ₂ - is optional Substituted by F; X represents -O-, -S-, -SO-, -SOO-, -CF ₂ -, -CO- or -CH ₂ -; Y ₁ and Y ₂ each independently represent -F-, - CH ₂ F-, -CHF ₂ -, -CF ₃ -, -OCH ₂ F-, -OCHF _2- or -OCF ₃ -; n represents 0, 1, 2 or 3. The liquid crystal compound with negative dielectric anisotropy as described in claim item 1, wherein, R ₁ represents a hydrogen atom, a straight-chain alkyl group with 1 to 5 carbon atoms, and a straight-chain alkyl group with 1 to 5 carbon atoms Oxygen, straight-chain alkenyl with 2 to 5 carbon atoms, or straight-chain alkenyloxy with 2 to 5 carbon atoms, in which one or two non-adjacent -CH ₂ - are optionally replaced by -O- Substituted, any H is optionally substituted by an F atom. The liquid crystal compound with negative dielectric anisotropy according to Claim 1 or 2, wherein n represents 0, 1 or 2. The liquid crystal compound with negative dielectric anisotropy as claimed in claim 3, wherein n represents 0 or 1. The liquid crystal compound with negative dielectric anisotropy as described in claim item 1, which is selected from the group consisting of compounds represented by the following formulas IA~IN, Ia~In, wherein R ₁ and R ₂ are as defined in the claim item same as in 1,

IA

IB

IC

ID

IE

IF

IG

IH

II

IJ

IK

IL

IM

IN

Ia

Ib

IC

ID

Ie

If

Ig

Ih

II

Ij

Ik

Il

Im

In. The liquid crystal compound with negative dielectric anisotropy as described in claim 1, which is selected from the group consisting of compounds represented by the following formulas IA-1~IN-4, Ia-1~In-4, wherein , Alkyl each independently represents a straight-chain alkyl group with 1 to 8 carbon atoms, and Alkenyl each independently represents a straight-chain alkenyl group with 2 to 8 carbon atoms,

IA-1

IA-2

IA-3

IA-4

IB-1

IB-2

IB-3

IB-4

IC-1

IC-2

IC-3

IC-4

ID-1

ID-2

ID-3

ID-4

IE-1

IE-2

IE-3

IE-4

IF-1

IF-2

IF-3

IF-4

IG-1

IG-2

IG-3

IG-4

IH-1

IH-2

IH-3

IH-4

II-1

II-2

II-3

II-4

IJ-1

IJ-2

IJ-3

IJ-4

IK-1

IK-2

IK-3

IK-4

IL-1

IL-2

IL-3

IL-4

IM-1

IM-2

IM-3

IM-4

IN-1

IN-2

IN-3

IN-4

Ia-1

Ia-2

Ia-3

Ia-4

Ib-1

Ib-2

Ib-3

Ib-4

Ic-1

Ic-2

Ic-3

Ic-4

Id-1

Id-2

Id-3

Id-4

Ie-1

Ie-2

Ie-3

Ie-4

If-1

If-2

If-3

If-4

Ig-1

Ig-2

Ig-3

Ig-4

Ih-1

Ih-2

Ih-3

Ih-4

II-1

II-2

II-3

II-4

Ij-1

Ij-2

Ij-3

Ij-4

Ik-1

Ik-2

Ik-3

Ik-4

Il-1

Il-2

Il-3

Il-4

Im-1

Im-2

Im-3

Im-4

In-1

In-2

In-3

In-4. A liquid crystal composition, which contains the liquid crystal compound with negative dielectric anisotropy described in any one of claims 1 to 6, and the liquid crystal compound with negative dielectric anisotropy is calculated as 20% or less. When multiple liquid crystal compounds with negative dielectric anisotropy are contained, the sum of the contents of the liquid crystal compounds with negative dielectric anisotropy is 50% or less by weight percentage. A liquid crystal display device, which comprises the liquid crystal compound with negative dielectric anisotropy described in any one of claim items 1 to 6, or comprises the liquid crystal composition described in claim item 7, and the liquid crystal display device is an active Matrix display devices, or passive matrix display devices.

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