JP2002220356A - Methylenecyclohexane derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystal material that is well compatible with a liquid crystal compound or composition and has an effect to reduce Δn, a low Δn nematic liquid crystal composition containing the above liquid crystal material, and a liquid crystal display element made of the above liquid crystal composition. SOLUTION: This liquid crystal material is a compound having an exomethylene group shown by general formula I (wherein, R is hydrogen or the like; A, B and C are each a single bond or the like; L, M and N are each a 1,4 phenylene group (wherein, one, two or three hydrogen atoms may be substituted by fluorine atoms), a 1,4 cyclohexylene group or the like; X is hydrogen, a cyano group or the like).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a liquid crystal compound, a nematic liquid crystal composition useful as an electro-optical liquid crystal display material, and a liquid crystal display device using the same.

[0002]

2. Description of the Related Art Liquid crystal display elements are used in various measuring instruments such as watches and calculators, panels for automobiles, word processors, electronic organizers, mobile phones, computer displays, and televisions. Typical liquid crystal display systems include TN (twisted nematic) type and STN
(Super Twisted Nematic), DS (Dynamic Light Scattering), GH (Guest / Host), FLC (Ferroelectric Liquid Crystal), etc. In general, simple matrix driving, more recently active matrix driving, has been put to practical use.

Various characteristics are required for liquid crystal materials in accordance with these display systems and drive systems. However, in the TN type and STN type which are currently in practical use, the backlight is required with the recent portable use. A reflection-type liquid crystal display element that does not use a liquid crystal has been put to practical use.

In a liquid crystal display device, the product (Δn · d) of the cell thickness (d) and the refractive index anisotropy (Δn) is set to a certain value (0.5, 0.5) in order to prevent coloring and unevenness due to the occurrence of interference fringes. 1.0, 1.6, 2.
2, usually the former two are often used. ), But this is when a backlight is used.In the above-mentioned reflective liquid crystal display element, the value of d is doubled if the cell thickness is the same to see the reflected light. As a result, a value of 1/2 is required as Δn. By reducing the cell thickness, it is possible to prevent coloring and unevenness due to the generation of interference fringes, but there is a limit, and as a result, a liquid crystal material having a small Δn is required.

At present, as a compound having a small Δn, a compound having a trans-1,4-cyclohexylene group is typical. However, a compound having this skeleton alone cannot sufficiently reduce Δn, and there has been a strong demand for a liquid crystal material having a liquid crystal skeleton having a smaller Δn.

[0006]

An object of the present invention is to provide a liquid crystal composition which can effectively reduce Δn of a liquid crystal composition, is chemically stable, and has excellent compatibility with other liquid crystal materials. It is to provide a methylenecyclohexane derivative which can be easily produced. Another object of the present invention is to provide a material that does not improve or impair other liquid crystal characteristics other than the above, such as Δε and viscosity, by improving the above characteristics. Further, a liquid crystal composition using the same, which has a small Δn, is chemically stable, does not improve or deteriorate various liquid crystal properties, and provides a liquid crystal display device having excellent display quality using the same. Is to do.

[0007]

According to the present invention, there is provided a compound represented by the following general formula (I):

[Formula 2]

(Wherein R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 2 to 10 carbon atoms) Represents an alkyl group or an alkenyloxy group having 3 to 10 carbon atoms, wherein A, B and C each independently represent a single bond, -CO-, -COO-, -OCO-, -CH = N-, -N = CH-, -C≡C-,
_{-CH 2 CH 2 -, - CH} 2 CH 2 CH 2 -, - CH 2 CH 2 CH 2 CH 2 -, - CH 2 O -, - OC
H _2- , -CF ₂ O-, -OCF _2- , -CH = NN = CH-, -CF = CF-, -CH
_{= CH -, - CH 2 CH} 2 CH = CH -, - CH = CHCH 2 CH 2 -, - CH 2 CH = CHC
H ₂ - represents, L, M and N are each independently a 1,4-phenylene group (one, two or three hydrogen atoms in the group may be substituted with a fluorine atom), 1, 4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5
-Diyl group, 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6 -Diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,
6-diyl group (1, 2 or 3 hydrogen atoms in this group may be replaced by fluorine atom), 2,6-naphthylene group (1, 2 or 3 hydrogen atoms in this group) May be substituted with a fluorine atom), a phenanthrene-2,7-diyl group (one or two hydrogen atoms in this group may be substituted with a fluorine atom), 9,10-dihydrophenanthrene -2,7-diyl group (in which 1 or 2 hydrogen atoms may be replaced by fluorine atoms), 1,2,3,4,4a, 9,10a-octahydrophenanthrene 2, A 7-diyl group (one, two or three hydrogen atoms in this group may be replaced by a fluorine atom), a fluorene 2,7-diyl group (one or two hydrogen atoms in this group X may be substituted with a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkenyl having 2 to 10 carbon atoms. Group, an alkoxyalkyl group or an alkenyloxy group having 3 to 10 carbon atoms having 2 to 10 carbon atoms, a cyano group, a fluorine atom, a chlorine atom, a trifluoromethoxy group,
Trifluoromethyl group, difluoromethoxy group, 2,2,2-
Represents a trifluoroethoxy group, l and n each independently represent an integer of 0 or 1, provided that R is an alkyl group, l
And n is 0, A is a single bond, N is a 1,4-phenylene group, and when X represents a cyano group, the phenylene group of N has at least one fluorine atom, R is an alkyl group, l and n is
When 0 and A are a single bond, N is a 1,4-phenylene group and X represents an alkoxyl group, R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X is an alkoxyl group having 1 to 5 carbon atoms. Represents ) Have been found as means for solving the above-mentioned problems. In addition, the present invention includes many compounds by selecting a structure other than the exomethylene skeleton, but provides a material having excellent liquid crystal properties other than those described in the subject, such as Δε and viscosity, by selecting these structures. can do. Further, a liquid crystal composition using the compound and a display element using the liquid crystal composition, for example, a super twisted nematic (STN) type, an active matrix (AM)
And a reflection type liquid crystal display device.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

[0010] The present invention is represented by the general formula (I)
In compounds having an exomethylene group, R is a hydrogen atom
, An alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms
Alkoxyl group, alkenyl group having 2 to 10 carbon atoms, carbon
An alkoxyalkyl group having 2 to 10 atoms or carbon atom
Represents an alkenyloxy group having the number of 3 to 10, but includes a hydrogen atom,
A chain alkyl group or alkenyl group is preferable, and a hydrogen atom
And a linear alkyl group having 1 to 5 carbon atoms is more preferable.
Particularly, a hydrogen atom is particularly preferred. A, B and C are
Each independently represents a single bond, -CO-, -COO-, -OCO-, -CH = N
-, -N = CH-, -C≡C-, -CH_TwoCH_Two-, -CH_TwoCH_TwoCH_Two-, -CH_TwoCH_Two
CH_TwoCH_Two-, -CH_TwoO-, -OCH_Two-, -CF_TwoO-, -OCF_Two-, -CH = N-N
= CH-, -CF = CF-, -CH = CH-, -CH_TwoCH_TwoCH = CH-, -CH = CH
CH_TwoCH_Two-, -CH _TwoCH = CHCH_Two-Represents a single bond, -C≡C- or
Or -CH_TwoCH_TwoIs preferred, and a single bond is particularly preferred. L, M
And N are each independently a 1,4-phenylene group (in this group,
One, two or three hydrogen atoms are replaced by fluorine atoms
May be present), 1,4-cyclohexylene group,
Xenyl group, tetrahydropyran-2,5-diyl group, 1,3-
Dioxane-2,5-diyl group, tetrahydrothiopyran-2,
5-diyl group, 1,4-bicyclo (2,2,2) octylene group, deca
Hydronaphthalene-2,6-diyl group, pyridine-2,5-diyl
Group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl
Group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group (this
Replace 1, 2 or 3 hydrogen atoms in the group with a fluorine atom
2,6-naphthylene group (1, 2 in this group)
Or even if three hydrogen atoms are replaced by fluorine atoms
Good), a phenanthrene-2,7-diyl group (one or
May have two hydrogen atoms replaced by fluorine atoms
9,10-dihydrophenanthrene-2,7-diyl group (this
One or two hydrogen atoms in the group are replaced by fluorine atoms
1,2,3,4,4a, 9,10a-octahydrophenane
Tren 2,7-diyl group (one, two or three hydrogen atoms in this group)
May be substituted with a fluorine atom), fluorene
2,7-diyl group (one or two hydrogen atoms in this group
Which may be substituted with an element atom),
By 4-cyclohexylene or one or more fluorine atoms
An optionally substituted 1,4-phenylene group is preferred.
X is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a carbon atom
Alkoxy group having 1 to 10 carbon atoms, alkenyl having 2 to 10 carbon atoms
Group, an alkoxyalkyl group having 2 to 10 carbon atoms or
An alkenyloxy group having 3 to 10 carbon atoms, a cyano group,
Nitrogen atom, chlorine atom, trifluoromethoxy group, trif
Fluoromethyl group, difluoromethoxy group, 2,2,2-trif
Represents a fluoroethoxy group but has a higher nematic phase upper limit
Temperature (T_NI) Is required.
Alkyl group, alkoxyl group having 1 to 10 carbon atoms, carbon
Alkenyl group having 2 to 10 atoms, alcohol having 2 to 10 carbon atoms
A xyalkyl group or an alkenyl group having 3 to 10 carbon atoms
Xyl groups are preferred, and when lower Vth is required
Represents a cyano group, a fluorine atom, a chlorine atom,
Toxic group, trifluoromethyl group, difluoromethoxy
The group 2,2,2-trifluoroethoxy is preferred. Also,
When X represents an alkenyl group, the following structure is more preferable.
No.

[0011]

Embedded image (The structural formula is linked to the ring at the right end.) L and n each independently represent an integer of 0 or 1, but 1 is 1
Or represents 0, and n preferably represents 0, and l and n
More preferably represents 0. In the general formula (I),
The R, ring L, ring M, ring N, A, B, C, l and n include various types of compound groups, and among them, the compounds represented below are particularly preferable.

[0012]

[Formula 4]

(Wherein R has the same meaning as in formula (I),
A hydrogen atom or an alkyl group having 1 to 5 carbon atoms is preferred. )

[Formula 5] (Wherein R and X represent the same meaning as in the general formula (I), but R is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,
X is an alkyl group having 1 to 5 carbon atoms or 1 to 5 carbon atoms
Five alkoxyl groups are preferred. )

[0014]

[Formula 6]

(Wherein R and X have the same meanings as in formula (I), but R is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and X is an alkyl group having 1 to 5 carbon atoms.) Alternatively, an alkoxyl group having 1 to 5 carbon atoms is preferable.) Further, compounds represented by the following abbreviations are also preferred. Abbreviations used in describing the compounds are shown below. R 'hydrogen atom or linear alkyl group having 1 to 5 carbon atoms -CnH2n + 1 X' hydrogen atom or linear alkyl group having 1 to 5 carbon atoms -CnH2n + 1 -mdn:-(CH2) m -1-C = C-CnH2n + 1 -O (dm) n: -O (CH2) m-2-C = C-CnH2n + 1 -On: -OCnH2n + 1 -CN: -C≡N -F: -F -Cl: -Cl -OCFFF: -OCF3 -OCFF: -OCHF2 -OC1CFF: -OCH2CF3 -CFFF: -CF3 -2-: -CH2CH2- -D-: -CH = CH- -G-:-CF = CF- -T-: -C≡C-

[0016]

Embedded image

R'-EX-Cy-X ', R'-EX-2-Cy-X', R'-EX-D-Cy-X ', R'-EX-Cy-1d0, R'-EX -2-Cy-1d0, R'-EX-D-Cy-1d0, R'-EX-Cy-1d1, R'-EX-2-Cy-1d1, R'-EX-D-Cy-1d1, R '-EX-Cy-3d0, R'-EX-2-Cy-3d0, R'-EX-D-Cy-3d0, R'-EX-G-Cy-X', R'-EX-G-Cy -1d0, R'-EX-G-Cy-1d1, R'-EX-G-Cy-3d0 R'-EX-Ph-CN, R'-EX-2-Ph-CN, R'-EX-D -Ph-CN, R'-EX-Ph-F, R'-EX-2-Ph-F, R'-EX-D-Ph-F, R'-EX-Ph-Cl, R'-EX- 2-Ph-Cl, R'-EX-D-Ph-Cl, R'-EX-Ph-OCFFF, R'-EX-2-Ph-OCFFF, R'-EX-D-Ph-OCFFF, R ' -EX-Ph-OCFF, R'-EX-2-Ph-OCFF, R'-EX-D-Ph-OCFF, R'-EX-Ph-OC1CFFF, R'-EX-2-Ph-OC1CFFF, R '-EX-D-Ph-OC1CFFF, R'-EX-Ph-CFFF, R'-EX-2-Ph-CFFF, R'-EX-D-Ph-CFFF, R'-EX-Ph1-CN, R'-EX-2-Ph1-CN, R'-EX-D-Ph1-CN, R'-EX-Ph1-F, R'-EX-2-Ph1-F, R'-EX-D-Ph1 -F, R'-EX-Ph1-Cl, R'-EX-2-Ph1-Cl, R'-EX-D-Ph1-Cl, R'-EX-Ph1-OCFFF, R'-EX-2- Ph1-OCFFF, R'-EX-D-Ph1-OCFFF, R'-EX-Ph1-OCFF, R'-EX-2-Ph1-OCFF, R'-EX-D-Ph1-OCFF, R'-EX -Ph1-OC1CFFF, R'-EX-2-Ph1-OC1CFFF, R'-EX-D-Ph1-OC1CFFF, R'-EX-Ph1-CFFF, R'-EX-2-Ph1-CFFF, R'- EX-D-Ph1-CFFF, R'-EX-Ph1-X ', R'-EX-2-Ph1-X', R'-EX-D-Ph1-X ', R'- EX-Ph1-OX ', R'-EX-2-Ph1-OX', R'-EX-D-Ph1-OX ', R'-EX-Ph1-2d0, R'-EX-2-Ph1-2d0 , R'-EX-D-Ph1-2d0, R'-EX-Ph1-2d1, R'-EX-2-Ph1-2d1, R'-EX-D-Ph1-2d1, R'-EX-Ph1- 2d0, R'-EX-2-Ph1-2d0, R'-EX-D-Ph1-2d0,

R'-EX-Ph4-CN, R'-EX-2-Ph4-CN, R'-EX-D-Ph4-CN, R'-EX-Ph4-F, R'-EX-2- Ph4-F, R'-EX-D-Ph4-F, R'-EX-Ph4-Cl, R'-EX-2-Ph4-Cl, R'-EX-D-Ph4-Cl, R'-EX -Ph4-OCFFF, R'-EX-2-Ph4-OCFFF, R'-EX-D-Ph4-OCFFF, R'-EX-Ph4-OCFF, R'-EX-2-Ph4-OCFF, R'- EX-D-Ph4-OCFF, R'-EX-Ph4-OC1CFFF, R'-EX-2-Ph4-OC1CFFF, R'-EX-D-Ph4-OC1CFFF, R'-EX-Ph4-CFFF, R ' -EX-2-Ph4-CFFF, R'-EX-D-Ph4-CFFF, R'-EX-Ph4-X ', R'-EX-2-Ph4-X', R'-EX-D-Ph4 -X ', R'-EX-Ph4-OX', R'-EX-2-Ph4-OX ', R'-EX-D-Ph4-OX', R'-EX-Ph4-2d0, R'- EX-2-Ph4-2d0, R'-EX-D-Ph4-2d0, R'-EX-Ph4-2d1, R'-EX-2-Ph4-2d1, R'-EX-D-Ph4-2d1, R'-EX-Ph4-2d0, R'-EX-2-Ph4-2d0, R'-EX-D-Ph4-2d0, R'-EX-Ph2-X ', R'-EX-2-Ph2- X ', R'-EX-D-Ph2-X', R'-EX-Ph2-OX ', R'-EX-2-Ph2-OX', R'-EX-D-Ph2-OX ', R '-EX-Ph2-2d0, R'-EX-2-Ph2-2d0, R'-EX-D-Ph2-2d0, R'-EX-Ph2-2d1, R'-EX-2-Ph2-2d1, R'-EX-D-Ph2-2d1, R'-EX-Ph2-2d0, R'-EX-2-Ph2-2d0, R'-EX-D-Ph2-2d0, R'-EX-Ph3-X ', R'-EX-2-Ph3-X', R'-EX-D-Ph3-X ', R'-EX-Ph3-OX', R'-EX-2-Ph3-OX ', R' -EX-D-Ph3-OX ', R'-EX-Ph3-2d0, R'-EX-2-Ph3-2d0, R'-EX-D-Ph3-2d0 , R'-EX-Ph3-2d1, R'-EX-2-Ph3-2d1, R'-EX-D-Ph3-2d1, R'-EX-Ph3-2d0, R'-EX-2-Ph3- 2d0, R'-EX-D-Ph3-2d0, R'-EX-G-Ph-CN, R'-EX-G-Ph-F, R'-EX-G-Ph-Cl, R'-EX -G-Ph-OCFFF, R'-EX-G-Ph-OCFF, R'-EX-G-Ph-OC1CFFF, R'-EX-G-Ph-CFFF, R'-EX-G-Ph1-CN , R'-EX-G-Ph4-CN, R'-EX-G-Ph1-F, R'-EX-G-Ph4-F, R'-EX-G-Ph1-Cl, R'-EX- G-Ph4-Cl, R'-EX-G-Ph1-OCFFF, R'-EX-G-Ph4-OCFFF, R'-EX-G-Ph1-OCFF, R'-EX-G-Ph4-OCFF, R'-EX-G-Ph1-OC1CFFF, R'-EX-G-Ph4-OC1CFFF, R'-EX-G-Ph1-CFFF, R'-EX-G-Ph4-CFFF, R'-EX-G -Ph1-X ', R'-EX-G-Ph4-X', R'-EX-G-Ph1-OX ', R'-EX-G-Ph4-OX', R'-EX-G-Ph1 -2d0, R'-EX-G-Ph4-2d0, R'-EX-G-Ph1-2d1, R'-EX-G-Ph4-2d1, R'-EX-G-Ph1-2d0, R'- EX-G-Ph4-2d0,

R'-EX-G-Ph2-X ', R'-EX-G-Ph3-X', R'-EX-G-Ph2-OX ', R'-EX-G-Ph3-OX' , R'-EX-G-Ph2-2d0, R'-EX-G-Ph3-2d0, R'-EX-G-Ph2-2d1, R'-EX-G-Ph3-2d1, R'-EX- G-Ph2-2d0, R'-EX-G-Ph3-2d0, R'-EX-Cy-Cy-X ', R'-EX-2-Cy-Cy-X', R'-EX-D- Cy-Cy-X ', R'-EX-Cy-Cy-1d0, R'-EX-2-Cy-Cy-1d0, R'-EX-D-Cy-Cy-1d0, R'-EX-Cy -Cy-1d1, R'-EX-2-Cy-Cy-1d1, R'-EX-D-Cy-Cy-1d1, R'-EX-Cy-Cy-3d0 R'-EX-2-Cy- Cy-3d0, R'-EX-D-Cy-Cy-3d0, R'-EX-G-Cy-Cy-X 'R'-EX-Cy-2-Cy-X', R'-EX-Cy -D-Cy-X ', R'-EX-G-Cy-Cy-1d0, R'-EX-Cy-2-Cy-1d0, R'-EX-Cy-D-Cy-1d0, R'- EX-G-Cy-Cy-1d1, R'-EX-Cy-2-Cy-1d1, R'-EX-Cy-D-Cy-1d1, R'-EX-G-Cy-Cy-3d0, R '-EX-Cy-2-Cy-3d0, R'-EX-Cy-D-Cy-3d0, R'-EX-Cy-G-Cy-X', R'-EX-Cy-G-Cy- 1d0, R'-EX-Cy-G-Cy-1d1, R'-EX-Cy-G-Cy-3d0, R'-EX-2-Cy-2-Cy-X ', R'-EX-2 -Cy-D-Cy-X ', R'-EX-2-Cy-G-Cy-X', R'-EX-2-Cy-2-Cy-1d0, R'-EX-2-Cy- D-Cy-1d0, R'-EX-2-Cy-G-Cy-1d0, R'-EX-2-Cy-2-Cy-1d1, R'-EX-2-Cy-D-Cy-1d1 , R'-EX-2-Cy-G-Cy-1d1, R'-EX-2-Cy-2-Cy-3d0, R'-EX-2-Cy-D-Cy-3d0, R'-EX -2-Cy-G-Cy-3d0,

R'-EX-Ph-Cy-X ', R'-EX-Ph1-Cy-X', R'-EX-Ph2-Cy-X ', R'-EX-Ph-Cy-1d0, R'-EX-Ph1-Cy-1d0, R'-EX-Ph2-Cy-1d0, R'-EX-Ph-Cy-1d1, R'-EX-Ph1-Cy-1d1, R'-EX-Ph2 -Cy-1d1, R'-EX-Ph-Cy-3d0, R'-EX-Ph1-Cy-3d0, R'-EX-Ph2-Cy-3d0, R'-EX-Ph3-Cy-X ', R'-EX-Ph4-Cy-X ', R'-EX-2-Ph-Cy-X', R'-EX-Ph3-Cy-1d0, R'-EX-Ph4-Cy-1d0, R ' -EX-2-Ph-Cy-1d0, R'-EX-Ph3-Cy-1d1, R'-EX-Ph4-Cy-1d1, R'-EX-2-Ph-Cy-1d1, R'-EX -Ph3-Cy-3d0, R'-EX-Ph4-Cy-3d0, R'-EX-2-Ph-Cy-3d0, R'-EX-2-Ph1-Cy-X ', R'-EX- 2-Ph2-Cy-X ', R'-EX-2-Ph3-Cy-X', R'-EX-2-Ph1-Cy-1d0, R'-EX-2-Ph2-Cy-1d0, R '-EX-2-Ph3-Cy-1d0, R'-EX-2-Ph1-Cy-1d1, R'-EX-2-Ph2-Cy-1d1, R'-EX-2-Ph3-Cy-1d1 , R'-EX-2-Ph1-Cy-3d0, R'-EX-2-Ph2-Cy-3d0, R'-EX-2-Ph3-Cy-3d0, R'-EX-2-Ph4-Cy -X ', R'-EX-D-Ph-Cy-X', R'-EX-D-Ph1-Cy-X ', R'-EX-2-Ph4-Cy-1d0, R'-EX- D-Ph-Cy-1d0, R'-EX-D-Ph1-Cy-1d0, R'-EX-2-Ph4-Cy-1d1, R'-EX-D-Ph-Cy-1d1, R'- EX-D-Ph1-Cy-1d1, R'-EX-2-Ph4-Cy-3d0, R'-EX-D-Ph-Cy-3d0, R'-EX-D-Ph1-Cy-3d0, R '-EX-D-Ph2-Cy-X', R'-EX-D-Ph3-Cy-X ', R'-EX-D-Ph4-Cy-X', R'-EX-D-Ph2- Cy-1d0, R'-EX-D- Ph3-Cy-1d0, R'-EX-D-Ph4-Cy-1d0, R'-EX-D-Ph2-Cy-1d1, R'-EX-D-Ph3-Cy-1d1, R'-EX- D-Ph4-Cy-1d1, R'-EX-D-Ph2-Cy-3d0, R'-EX-D-Ph3-Cy-3d0, R'-EX-D-Ph4-Cy-3d0,

R'-EX-G-Ph-Cy-X ', R'-EX-G-Ph1-Cy-X', R'-EX-G-Ph2-Cy-X ', R'-EX- G-Ph-Cy-1d0, R'-EX-G-Ph1-Cy-1d0, R'-EX-G-Ph2-Cy-1d0, R'-EX-G-Ph-Cy-1d1, R'- EX-G-Ph1-Cy-1d1, R'-EX-G-Ph2-Cy-1d1, R'-EX-G-Ph-Cy-3d0, R'-EX-G-Ph1-Cy-3d0, R '-EX-G-Ph2-Cy-3d0, R'-EX-G-Ph3-Cy-X', R'-EX-G-Ph4-Cy-X ', R'-EX-Ph-2-Cy -X ', R'-EX-G-Ph3-Cy-1d0, R'-EX-G-Ph4-Cy-1d0, R'-EX-Ph-2-Cy-1d0, R'-EX-G- Ph3-Cy-1d1, R'-EX-G-Ph4-Cy-1d1, R'-EX-Ph-2-Cy-1d1, R'-EX-G-Ph3-Cy-3d0, R'-EX- G-Ph4-Cy-3d0, R'-EX-Ph-2-Cy-3d0, R'-EX-Ph1-2-Cy-X ', R'-EX-Ph2-2-Cy-X', R '-EX-Ph3-2-Cy-X', R'-EX-Ph1-2-Cy-1d0, R'-EX-Ph2-2-Cy-1d0, R'-EX-Ph3-2-Cy- 1d0, R'-EX-Ph1-2-Cy-1d1, R'-EX-Ph2-2-Cy-1d1, R'-EX-Ph3-2-Cy-1d1, R'-EX-Ph1-2- Cy-3d0, R'-EX-Ph2-2-Cy-3d0, R'-EX-Ph3-2-Cy-3d0, R'-EX-Ph4-2-Cy-X ', R'-EX-Ph -D-Cy-X ', R'-EX-Ph1-D-Cy-X', R'-EX-Ph4-2-Cy-1d0, R'-EX-Ph-D-Cy-1d0, R ' -EX-Ph1-D-Cy-1d0, R'-EX-Ph4-2-Cy-1d1, R'-EX-Ph-D-Cy-1d1, R'-EX-Ph1-D-Cy-1d1, R'-EX-Ph4-2-Cy-3d0, R'-EX-Ph-D-Cy-3d0, R'-EX-Ph1-D-Cy-3d0, R'-EX-Ph2-D-Cy- X ', R'-EX-Ph3-D-Cy-X', R'-EX-P h4-D-Cy-X ', R'-EX-Ph2-D-Cy-1d0, R'-EX-Ph3-D-Cy-1d0, R'-EX-Ph4-D-Cy-1d0, R' -EX-Ph2-D-Cy-1d1, R'-EX-Ph3-D-Cy-1d1, R'-EX-Ph4-D-Cy-1d1, R'-EX-Ph2-D-Cy-3d0, R'-EX-Ph3-D-Cy-3d0, R'-EX-Ph4-D-Cy-3d0, R'-EX-Ph-G-Cy-X ', R'-EX-Ph1-G-Cy -X ', R'-EX-Ph2-G-Cy-X', R'-EX-Ph-G-Cy-1d0, R'-EX-Ph1-G-Cy-1d0, R'-EX-Ph2 -G-Cy-1d0, R'-EX-Ph-G-Cy-1d1, R'-EX-Ph1-G-Cy-1d1, R'-EX-Ph2-G-Cy-1d1, R'-EX -Ph-G-Cy-3d0, R'-EX-Ph1-G-Cy-3d0, R'-EX-Ph2-G-Cy-3d0, R'-EX-Ph3-G-Cy-X ', R '-EX-Ph4-G-Cy-X', R'-EX-2-Ph-2-Cy-X ', R'-EX-Ph3-G-Cy-1d0, R'-EX-Ph4-G -Cy-1d0, R'-EX-2-Ph-2-Cy-1d0, R'-EX-Ph3-G-Cy-1d1, R'-EX-Ph4-G-Cy-1d1 R'-EX- 2-Ph-2-Cy-1d1, R'-EX-Ph3-G-Cy-3d0, R'-EX-Ph4-G-Cy-3d0, R'-EX-2-Ph-2-Cy-3d0 R'-EX-2-Ph1-2-Cy-X ', R'-EX-2-Ph2-2-Cy-X', R'-EX-2-Ph3-2-Cy-X ', R' -EX-2-Ph1-2-Cy-1d0, R'-EX-2-Ph2-2-Cy-1d0, R'-EX-2-Ph3-2-Cy-1d0, R'-EX-2- Ph1-2-Cy-1d1, R'-EX-2-Ph2-2-Cy-1d1, R'-EX-2-Ph3-2-Cy-1d1, R'-EX-2-Ph1-2-Cy -3d0, R'-EX-2-Ph2-2-Cy-3d0, R'-EX-2-Ph3-2-Cy-3d0, R'-EX-2-Ph4-2-Cy-X ', R '-EX-2-Ph-D-Cy-X', R'-EX-2-Ph1-D-Cy-X ', R'-EX-2-Ph4-2 -Cy-1d0, R'-EX-2-Ph-D-Cy-1d0, R'-EX-2-Ph1-D-Cy-1d0, R'-EX-2-Ph4-2-Cy-1d1, R'-EX-2-Ph-D-Cy-1d1, R'-EX-2-Ph1-D-Cy-1d1, R'-EX-2-Ph4-2-Cy-3d0, R'-EX- 2-Ph-D-Cy-3d0, R'-EX-2-Ph1-D-Cy-3d0, R'-EX-2-Ph2-D-Cy-X ', R'-EX-2-Ph3- D-Cy-X ', R'-EX-2-Ph4-D-Cy-X', R'-EX-2-Ph2-D-Cy-1d0, R'-EX-2-Ph3-D-Cy -1d0, R'-EX-2-Ph4-D-Cy-1d0, R'-EX-2-Ph2-D-Cy-1d1, R'-EX-2-Ph3-D-Cy-1d1, R ' -EX-2-Ph4-D-Cy-1d1, R'-EX-2-Ph2-D-Cy-3d0, R'-EX-2-Ph3-D-Cy-3d0, R'-EX-2- Ph4-D-Cy-3d0,

R'-EX-2-Ph-G-Cy-X ', R'-EX-2-Ph1-G-Cy-X', R'-EX-2-Ph2-G-Cy-X ' , R'-EX-2-Ph-G-Cy-1d0, R'-EX-2-Ph1-G-Cy-1d0, R'-EX-2-Ph2-G-Cy-1d0, R'-EX -2-Ph-G-Cy-1d1, R'-EX-2-Ph1-G-Cy-1d1, R'-EX-2-Ph2-G-Cy-1d1, R'-EX-2-Ph- G-Cy-3d0, R'-EX-2-Ph1-G-Cy-3d0, R'-EX-2-Ph2-G-Cy-3d0, R'-EX-2-Ph3-G-Cy-X ', R'-EX-2-Ph4-G-Cy-X', R'-EX-D-Ph-2-Cy-X ', R'-EX-2-Ph3-G-Cy-1d0, R '-EX-2-Ph4-G-Cy-1d0, R'-EX-D-Ph-2-Cy-1d0, R'-EX-2-Ph3-G-Cy-1d1, R'-EX-2 -Ph4-G-Cy-1d1 R'-EX-D-Ph-2-Cy-1d1, R'-EX-2-Ph3-G-Cy-3d0, R'-EX-2-Ph4-G-Cy -3d0, R'-EX-D-Ph-2-Cy-3d0, R'-EX-D-Ph1-2-Cy-X ', R'-EX-D-Ph2-2-Cy-X', R'-EX-D-Ph3-2-Cy-X ', R'-EX-D-Ph1-2-Cy-1d0, R'-EX-D-Ph2-2-Cy-1d0, R'-EX -D-Ph3-2-Cy-1d0, R'-EX-D-Ph1-2-Cy-1d1, R'-EX-D-Ph2-2-Cy-1d1, R'-EX-D-Ph3- 2-Cy-1d1, R'-EX-D-Ph1-2-Cy-3d0, R'-EX-D-Ph2-2-Cy-3d0, R'-EX-D-Ph3-2-Cy-3d0 , R'-EX-D-Ph4-2-Cy-X ', R'-EX-D-Ph-D-Cy-X', R'-EX-D-Ph1-D-Cy-X ', R '-EX-D-Ph4-2-Cy-1d0, R'-EX-D-Ph-D-Cy-1d0, R'-EX-D-Ph1-D-Cy-1d0, R'-EX-D -Ph4-2-Cy-1d1, R'-EX-D-Ph-D-Cy-1d1, R'-EX-D-Ph1-D-Cy-1d1, R'-EX-D-Ph4-2- C y-3d0, R'-EX-D-Ph-D-Cy-3d0, R'-EX-D-Ph1-D-Cy-3d0, R'-EX-D-Ph2-D-Cy-X ', R'-EX-D-Ph3-D-Cy-X ', R'-EX-D-Ph4-D-Cy-X', R'-EX-D-Ph2-D-Cy-1d0, R'- EX-D-Ph3-D-Cy-1d0, R'-EX-D-Ph4-D-Cy-1d0, R'-EX-D-Ph2-D-Cy-1d1, R'-EX-D-Ph3 -D-Cy-1d1, R'-EX-D-Ph4-D-Cy-1d1, R'-EX-D-Ph2-D-Cy-3d0, R'-EX-D-Ph3-D-Cy- 3d0, R'-EX-D-Ph4-D-Cy-3d0,

R'-EX-D-Ph-G-Cy-X ', R'-EX-D-Ph1-G-Cy-X', R'-EX-D-Ph2-G-Cy-X ' , R'-EX-D-Ph-G-Cy-1d0, R'-EX-D-Ph1-G-Cy-1d0, R'-EX-D-Ph2-G-Cy-1d0, R'-EX -D-Ph-G-Cy-1d1, R'-EX-D-Ph1-G-Cy-1d1, R'-EX-D-Ph2-G-Cy-1d1, R'-EX-D-Ph- G-Cy-3d0, R'-EX-D-Ph1-G-Cy-3d0, R'-EX-D-Ph2-G-Cy-3d0, R'-EX-D-Ph3-G-Cy-X ', R'-EX-D-Ph4-G-Cy-X', R'-EX-G-Ph-2-Cy-X ', R'-EX-D-Ph3-G-Cy-1d0, R '-EX-D-Ph4-G-Cy-1d0, R'-EX-G-Ph-2-Cy-1d0, R'-EX-D-Ph3-G-Cy-1d1, R'-EX-D -Ph4-G-Cy-1d1, R'-EX-G-Ph-2-Cy-1d1, R'-EX-D-Ph3-G-Cy-3d0, R'-EX-D-Ph4-G- Cy-3d0, R'-EX-G-Ph-2-Cy-3d0, R'-EX-G-Ph1-2-Cy-X ', R'-EX-G-Ph2-2-Cy-X' , R'-EX-G-Ph3-2-Cy-X ', R'-EX-G-Ph1-2-Cy-1d0, R'-EX-G-Ph2-2-Cy-1d0, R'- EX-G-Ph3-2-Cy-1d0, R'-EX-G-Ph1-2-Cy-1d1, R'-EX-G-Ph2-2-Cy-1d1, R'-EX-G-Ph3 -2-Cy-1d1, R'-EX-G-Ph1-2-Cy-3d0, R'-EX-G-Ph2-2-Cy-3d0, R'-EX-G-Ph3-2-Cy- 3d0, R'-EX-G-Ph4-2-Cy-X ', R'-EX-G-Ph-D-Cy-X', R'-EX-G-Ph1-D-Cy-X ', R'-EX-G-Ph4-2-Cy-1d0, R'-EX-G-Ph-D-Cy-1d0, R'-EX-G-Ph1-D-Cy-1d0, R'-EX- G-Ph4-2-Cy-1d1, R'-EX-G-Ph-D-Cy-1d1, R'-EX-G-Ph1-D-Cy-1d1, R'-EX-G-Ph4-2 - Cy-3d0, R'-EX-G-Ph-D-Cy-3d0, R'-EX-G-Ph1-D-Cy-3d0, R'-EX-G-Ph2-D-Cy-X ', R'-EX-G-Ph3-D-Cy-X ', R'-EX-G-Ph4-D-Cy-X', R'-EX-G-Ph2-D-Cy-1d0, R'- EX-G-Ph3-D-Cy-1d0, R'-EX-G-Ph4-D-Cy-1d0, R'-EX-G-Ph2-D-Cy-1d1, R'-EX-G-Ph3 -D-Cy-1d1, R'-EX-G-Ph4-D-Cy-1d1, R'-EX-G-Ph2-D-Cy-3d0, R'-EX-G-Ph3-D-Cy- 3d0, R'-EX-G-Ph4-D-Cy-3d0, R'-EX-G-Ph-G-Cy-X ', R'-EX-G-Ph1-G-Cy-X', R '-EX-G-Ph2-G-Cy-X', R'-EX-G-Ph-G-Cy-1d0, R'-EX-G-Ph1-G-Cy-1d0, R'-EX- G-Ph2-G-Cy-1d0, R'-EX-G-Ph-G-Cy-1d1, R'-EX-G-Ph1-G-Cy-1d1, R'-EX-G-Ph2-G -Cy-1d1, R'-EX-G-Ph-G-Cy-3d0, R'-EX-G-Ph1-G-Cy-3d0, R'-EX-G-Ph2-G-Cy-3d0, R'-EX-G-Ph3-G-Cy-X ', R'-EX-G-Ph4-G-Cy-X', R'-EX-G-Ph3-G-Cy-1d0, R'- EX-G-Ph4-G-Cy-1d0, R'-EX-G-Ph3-G-Cy-1d1, R'-EX-G-Ph4-G-Cy-1d1, R'-EX-G-Ph3 -G-Cy-3d0, R'-EX-G-Ph4-G-Cy-3d0,

R'-EX-Cy-Ph-CN, R'-EX-Cy-Ph-F, R'-EX-Cy-Ph-Cl, R'-EX-Cy-Ph-OCFFF, R'- EX-Cy-Ph-OCFF, R'-EX-Cy-Ph-OC1CFFF, R'-EX-Cy-Ph-CFFF, R'-EX-Cy-Ph1-CN, R'-EX-Cy-Ph4- CN, R'-EX-Cy-Ph1-F, R'-EX-Cy-Ph4-F, R'-EX-Cy-Ph1-Cl, R'-EX-Cy-Ph4-Cl, R'-EX -Cy-Ph1-OCFFF, R'-EX-Cy-Ph4-OCFFF, R'-EX-Cy-Ph1-OCFF, R'-EX-Cy-Ph4-OCFF, R'-EX-Cy-Ph1-OC1CFFF , R'-EX-Cy-Ph4-OC1CFFF, R'-EX-Cy-Ph1-CFFF, R'-EX-Cy-Ph4-CFFF, R'-EX-Cy-Ph1-X ', R'-EX -Cy-Ph4-X ', R'-EX-Cy-Ph1-OX', R'-EX-Cy-Ph4-OX ', R'-EX-Cy-Ph1-2d0, R'-EX-Cy- Ph4-2d0, R'-EX-Cy-Ph1-2d1, R'-EX-Cy-Ph4-2d1, R'-EX-Cy-Ph2-X ', R'-EX-Cy-Ph3-X', R'-EX-Cy-Ph2-OX ', R'-EX-Cy-Ph3-OX', R'-EX-Cy-Ph2-2d0, R'-EX-Cy-Ph3-2d0, R'-EX -Cy-Ph2-2d1, R'-EX-Cy-Ph3-2d1, R'-EX-2-Cy-Ph-CN, R'-EX-2-Cy-Ph-F, R'-EX-2 -Cy-Ph-Cl, R'-EX-2-Cy-Ph-OCFFF, R'-EX-2-Cy-Ph-OCFF, R'-EX-2-Cy-Ph-OC1CFFF, R'-EX -2-Cy-Ph-CFFF, R'-EX-2-Cy-Ph1-CN, R'-EX-2-Cy-Ph4-CN, R'-EX-2-Cy-Ph1-F, R ' -EX-2-Cy-Ph4-F, R'-EX-2-Cy-Ph1-Cl, R'-EX-2-Cy-Ph4-Cl, R'-EX-2-Cy-Ph1-OCFFF, R'-EX-2-Cy-Ph4-OCFFF, R'-EX-2-Cy-Ph1-OCFF, R'-EX-2-Cy-Ph4-OCFF, R'-EX-2-Cy-Ph1-OC1CFFF, R'-EX-2-Cy-Ph4-OC1CFFF, R'-EX-2-Cy-Ph1- CFFF, R'-EX-2-Cy-Ph4-CFFF, R'-EX-2-Cy-Ph1-X ', R'-EX-2-Cy-Ph4-X', R'-EX-2- Cy-Ph1-OX ', R'-EX-2-Cy-Ph4-OX', R'-EX-2-Cy-Ph1-2d0, R'-EX-2-Cy-Ph4-2d0, R'- EX-2-Cy-Ph1-2d1, R'-EX-2-Cy-Ph4-2d1, R'-EX-2-Cy-Ph2-X ', R'-EX-2-Cy-Ph3-X' , R'-EX-2-Cy-Ph2-OX ', R'-EX-2-Cy-Ph3-OX', R'-EX-2-Cy-Ph2-2d0, R'-EX-2-Cy -Ph3-2d0, R'-EX-2-Cy-Ph2-2d1, R'-EX-2-Cy-Ph3-2d1,

R'-EX-D-Cy-Ph-CN, R'-EX-D-Cy-Ph-F, R'-EX-D-Cy-Ph-Cl, R'-EX-D-Cy -Ph-OCFFF, R'-EX-D-Cy-Ph-OCFF, R'-EX-D-Cy-Ph-OC1CFFF, R'-EX-D-Cy-Ph-CFFF, R'-EX-D -Cy-Ph1-CN, R'-EX-D-Cy-Ph4-CN, R'-EX-D-Cy-Ph1-F, R'-EX-D-Cy-Ph4-F, R'-EX -D-Cy-Ph1-Cl, R'-EX-D-Cy-Ph4-Cl, R'-EX-D-Cy-Ph1-OCFFF, R'-EX-D-Cy-Ph4-OCFFF, R ' -EX-D-Cy-Ph1-OCFF, R'-EX-D-Cy-Ph4-OCFF, R'-EX-D-Cy-Ph1-OC1CFFF, R'-EX-D-Cy-Ph4-OC1CFFF, R'-EX-D-Cy-Ph1-CFFF, R'-EX-D-Cy-Ph4-CFFF, R'-EX-D-Cy-Ph1-X ', R'-EX-D-Cy-Ph4 -X ', R'-EX-D-Cy-Ph1-OX', R'-EX-D-Cy-Ph4-OX ', R'-EX-D-Cy-Ph1-2d0, R'-EX- D-Cy-Ph4-2d0, R'-EX-D-Cy-Ph1-2d1, R'-EX-D-Cy-Ph4-2d1, R'-EX-D-Cy-Ph2-X ', R' -EX-D-Cy-Ph3-X ', R'-EX-D-Cy-Ph2-OX', R'-EX-D-Cy-Ph3-OX ', R'-EX-D-Cy-Ph2 -2d0, R'-EX-D-Cy-Ph3-2d0, R'-EX-D-Cy-Ph2-2d1, R'-EX-D-Cy-Ph3-2d1,

R'-EX-G-Cy-Ph-CN, R'-EX-G-Cy-Ph-F, R'-EX-G-Cy-Ph-Cl, R'-EX-G-Cy -Ph-OCFFF, R'-EX-G-Cy-Ph-OCFF, R'-EX-G-Cy-Ph-OC1CFFF, R'-EX-G-Cy-Ph-CFFF, R'-EX-G -Cy-Ph1-CN, R'-EX-G-Cy-Ph4-CN, R'-EX-G-Cy-Ph1-F, R'-EX-G-Cy-Ph4-F, R'-EX -G-Cy-Ph1-Cl, R'-EX-G-Cy-Ph4-Cl, R'-EX-G-Cy-Ph1-OCFFF, R'-EX-G-Cy-Ph4-OCFFF, R ' -EX-G-Cy-Ph1-OCFF, R'-EX-G-Cy-Ph4-OCFF, R'-EX-G-Cy-Ph1-OC1CFFF, R'-EX-G-Cy-Ph4-OC1CFFF, R'-EX-G-Cy-Ph1-CFFF, R'-EX-G-Cy-Ph4-CFFF, R'-EX-G-Cy-Ph1-X ', R'-EX-G-Cy-Ph4 -X ', R'-EX-G-Cy-Ph1-OX', R'-EX-G-Cy-Ph4-OX ', R'-EX-G-Cy-Ph1-2d0, R'-EX- G-Cy-Ph4-2d0, R'-EX-G-Cy-Ph1-2d1, R'-EX-G-Cy-Ph4-2d1, R'-EX-G-Cy-Ph2-X ', R' -EX-G-Cy-Ph3-X ', R'-EX-G-Cy-Ph2-OX', R'-EX-G-Cy-Ph3-OX ', R'-EX-G-Cy-Ph2 -2d0, R'-EX-G-Cy-Ph3-2d0, R'-EX-G-Cy-Ph2-2d1, R'-EX-G-Cy-Ph3-2d1,

R'-EX-Cy-2-Ph-CN, R'-EX-Cy-2-Ph-F, R'-EX-Cy-2-Ph-Cl, R'-EX-Cy-2 -Ph-OCFFF, R'-EX-Cy-2-Ph-OCFF, R'-EX-Cy-2-Ph-OC1CFFF, R'-EX-Cy-2-Ph-CFFF, R'-EX-Cy -2-Ph1-CN, R'-EX-Cy-2-Ph4-CN, R'-EX-Cy-2-Ph1-F, R'-EX-Cy-2-Ph4-F, R'-EX -Cy-2-Ph1-Cl, R'-EX-Cy-2-Ph4-Cl, R'-EX-Cy-2-Ph1-OCFFF, R'-EX-Cy-2-Ph4-OCFFF, R ' -EX-Cy-2-Ph1-OCFF, R'-EX-Cy-2-Ph4-OCFF, R'-EX-Cy-2-Ph1-OC1CFFF, R'-EX-Cy-2-Ph4-OC1CFFF, R'-EX-Cy-2-Ph1-CFFF, R'-EX-Cy-2-Ph4-CFFF, R'-EX-Cy-2-Ph1-X ', R'-EX-Cy-2-Ph4 -X ', R'-EX-Cy-2-Ph1-OX', R'-EX-Cy-2-Ph4-OX ', R'-EX-Cy-2-Ph1-2d0, R'-EX- Cy-2-Ph4-2d0, R'-EX-Cy-2-Ph1-2d1, R'-EX-Cy-2-Ph4-2d1, R'-EX-Cy-2-Ph2-X ', R' -EX-Cy-2-Ph3-X ', R'-EX-Cy-2-Ph2-OX', R'-EX-Cy-2-Ph3-OX ', R'-EX-Cy-2-Ph2 -2d0, R'-EX-Cy-2-Ph3-2d0, R'-EX-Cy-2-Ph2-2d1, R'-EX-Cy-2-Ph3-2d1, R'-EX-Cy-D -Ph-CN, R'-EX-Cy-D-Ph-F, R'-EX-Cy-D-Ph-Cl, R'-EX-Cy-D-Ph-OCFFF, R'-EX-Cy -D-Ph-OCFF, R'-EX-Cy-D-Ph-OC1CFFF, R'-EX-Cy-D-Ph-CFFF, R'-EX-Cy-D-Ph1-CN, R'-EX -Cy-D-Ph4-CN, R'-EX-Cy-D-Ph1-F, R'-EX-Cy-D-Ph4-F, R'-EX-Cy-D-Ph1-Cl, R ' -EX-Cy-D -Ph4-Cl, R'-EX-Cy-D-Ph1-OCFFF, R'-EX-Cy-D-Ph4-OCFFF, R'-EX-Cy-D-Ph1-OCFF, R'-EX-Cy -D-Ph4-OCFF, R'-EX-Cy-D-Ph1-OC1CFFF, R'-EX-Cy-D-Ph4-OC1CFFF, R'-EX-Cy-D-Ph1-CFFF, R'-EX -Cy-D-Ph4-CFFF, R'-EX-Cy-D-Ph1-X ', R'-EX-Cy-D-Ph4-X', R'-EX-Cy-D-Ph1-OX ' , R'-EX-Cy-D-Ph4-OX ', R'-EX-Cy-D-Ph1-2d0, R'-EX-Cy-D-Ph4-2d0, R'-EX-Cy-D- Ph1-2d1, R'-EX-Cy-D-Ph4-2d1, R'-EX-Cy-D-Ph2-X ', R'-EX-Cy-D-Ph3-X', R'-EX- Cy-D-Ph2-OX ', R'-EX-Cy-D-Ph3-OX', R'-EX-Cy-D-Ph2-2d0, R'-EX-Cy-D-Ph3-2d0, R '-EX-Cy-D-Ph2-2d1, R'-EX-Cy-D-Ph3-2d1,

R'-EX-Cy-G-Ph-CN, R'-EX-Cy-G-Ph-F, R'-EX-Cy-G-Ph-Cl, R'-EX-Cy-G -Ph-OCFFF, R'-EX-Cy-G-Ph-OCFF, R'-EX-Cy-G-Ph-OC1CFFF, R'-EX-Cy-G-Ph-CFFF, R'-EX-Cy -G-Ph1-CN, R'-EX-Cy-G-Ph4-CN, R'-EX-Cy-G-Ph1-F, R'-EX-Cy-G-Ph4-F, R'-EX -Cy-G-Ph1-Cl, R'-EX-Cy-G-Ph4-Cl, R'-EX-Cy-G-Ph1-OCFFF, R'-EX-Cy-G-Ph4-OCFFF, R ' -EX-Cy-G-Ph1-OCFF, R'-EX-Cy-G-Ph4-OCFF, R'-EX-Cy-G-Ph1-OC1CFFF, R'-EX-Cy-G-Ph4-OC1CFFF, R'-EX-Cy-G-Ph1-CFFF, R'-EX-Cy-G-Ph4-CFFF, R'-EX-Cy-G-Ph1-X ', R'-EX-Cy-G-Ph4 -X ', R'-EX-Cy-G-Ph1-OX', R'-EX-Cy-G-Ph4-OX ', R'-EX-Cy-G-Ph1-2d0, R'-EX- Cy-G-Ph4-2d0, R'-EX-Cy-G-Ph1-2d1, R'-EX-Cy-G-Ph4-2d1, R'-EX-Cy-G-Ph2-X ', R' -EX-Cy-G-Ph3-X ', R'-EX-Cy-G-Ph2-OX', R'-EX-Cy-G-Ph3-OX ', R'-EX-Cy-G-Ph2 -2d0, R'-EX-Cy-G-Ph3-2d0, R'-EX-Cy-G-Ph2-2d1, R'-EX-Cy-G-Ph3-2d1,

R'-EX-2-Cy-2-Ph-CN, R'-EX-2-Cy-2-Ph-F, R'-EX-2-Cy-2-Ph-Cl, R ' -EX-2-Cy-2-Ph-OCFFF, R'-EX-2-Cy-2-Ph-OCFF, R'-EX-2-Cy-2-Ph-OC1CFFF, R'-EX-2- Cy-2-Ph-CFFF, R'-EX-2-Cy-2-Ph1-CN, R'-EX-2-Cy-2-Ph4-CN, R'-EX-2-Cy-2-Ph1 -F, R'-EX-2-Cy-2-Ph4-F, R'-EX-2-Cy-2-Ph1-Cl, R'-EX-2-Cy-2-Ph4-Cl, R ' -EX-2-Cy-2-Ph1-OCFFF, R'-EX-2-Cy-2-Ph4-OCFFF, R'-EX-2-Cy-2-Ph1-OCFF, R'-EX-2- Cy-2-Ph4-OCFF, R'-EX-2-Cy-2-Ph1-OC1CFFF, R'-EX-2-Cy-2-Ph4-OC1CFFF, R'-EX-2-Cy-2-Ph1 -CFFF, R'-EX-2-Cy-2-Ph4-CFFF, R'-EX-2-Cy-2-Ph1-X ', R'-EX-2-Cy-2-Ph4-X', R'-EX-2-Cy-2-Ph1-OX ', R'-EX-2-Cy-2-Ph4-OX', R'-EX-2-Cy-2-Ph1-2d0, R'- EX-2-Cy-2-Ph4-2d0, R'-EX-2-Cy-2-Ph1-2d1, R'-EX-2-Cy-2-Ph4-2d1, R'-EX-2-Cy -2-Ph2-X ', R'-EX-2-Cy-2-Ph3-X', R'-EX-2-Cy-2-Ph2-OX ', R'-EX-2-Cy-2 -Ph3-OX ', R'-EX-2-Cy-2-Ph2-2d0, R'-EX-2-Cy-2-Ph3-2d0, R'-EX-2-Cy-2-Ph2-2d1 , R'-EX-2-Cy-2-Ph3-2d1,

R'-EX-2-Cy-D-Ph-CN, R'-EX-2-Cy-D-Ph-F, R'-EX-2-Cy-D-Ph-Cl, R ' -EX-2-Cy-D-Ph-OCFFF, R'-EX-2-Cy-D-Ph-OCFF, R'-EX-2-Cy-D-Ph-OC1CFFF, R'-EX-2- Cy-D-Ph-CFFF, R'-EX-2-Cy-D-Ph1-CN, R'-EX-2-Cy-D-Ph4-CN, R'-EX-2-Cy-D-Ph1 -F, R'-EX-2-Cy-D-Ph4-F, R'-EX-2-Cy-D-Ph1-Cl, R'-EX-2-Cy-D-Ph4-Cl, R ' -EX-2-Cy-D-Ph1-OCFFF, R'-EX-2-Cy-D-Ph4-OCFFF, R'-EX-2-Cy-D-Ph1-OCFF, R'-EX-2- Cy-D-Ph4-OCFF, R'-EX-2-Cy-D-Ph1-OC1CFFF, R'-EX-2-Cy-D-Ph4-OC1CFFF, R'-EX-2-Cy-D-Ph1 -CFFF, R'-EX-2-Cy-D-Ph4-CFFF, R'-EX-2-Cy-D-Ph1-X ', R'-EX-2-Cy-D-Ph4-X', R'-EX-2-Cy-D-Ph1-OX ', R'-EX-2-Cy-D-Ph4-OX', R'-EX-2-Cy-D-Ph1-2d0, R'- EX-2-Cy-D-Ph4-2d0, R'-EX-2-Cy-D-Ph1-2d1, R'-EX-2-Cy-D-Ph4-2d1, R'-EX-2-Cy -D-Ph2-X ', R'-EX-2-Cy-D-Ph3-X', R'-EX-2-Cy-D-Ph2-OX ', R'-EX-2-Cy-D -Ph3-OX ', R'-EX-2-Cy-D-Ph2-2d0, R'-EX-2-Cy-D-Ph3-2d0, R'-EX-2-Cy-D-Ph2-2d1 , R'-EX-2-Cy-D-Ph3-2d1,

R'-EX-2-Cy-G-Ph-CN, R'-EX-2-Cy-G-Ph-F, R'-EX-2-Cy-G-Ph-Cl, R ' -EX-2-Cy-G-Ph-OCFFF, R'-EX-2-Cy-G-Ph-OCFF, R'-EX-2-Cy-G-Ph-OC1CFFF, R'-EX-2- Cy-G-Ph-CFFF, R'-EX-2-Cy-G-Ph1-CN, R'-EX-2-Cy-G-Ph4-CN, R'-EX-2-Cy-G-Ph1 -F, R'-EX-2-Cy-G-Ph4-F, R'-EX-2-Cy-G-Ph1-Cl, R'-EX-2-Cy-G-Ph4-Cl, R ' -EX-2-Cy-G-Ph1-OCFFF, R'-EX-2-Cy-G-Ph4-OCFFF, R'-EX-2-Cy-G-Ph1-OCFF, R'-EX-2- Cy-G-Ph4-OCFF, R'-EX-2-Cy-G-Ph1-OC1CFFF, R'-EX-2-Cy-G-Ph4-OC1CFFF, R'-EX-2-Cy-G-Ph1 -CFFF, R'-EX-2-Cy-G-Ph4-CFFF, R'-EX-2-Cy-G-Ph1-X ', R'-EX-2-Cy-G-Ph4-X', R'-EX-2-Cy-G-Ph1-OX ', R'-EX-2-Cy-G-Ph4-OX', R'-EX-2-Cy-G-Ph1-2d0, R'- EX-2-Cy-G-Ph4-2d0, R'-EX-2-Cy-G-Ph1-2d1, R'-EX-2-Cy-G-Ph4-2d1, R'-EX-2-Cy -G-Ph2-X ', R'-EX-2-Cy-G-Ph3-X', R'-EX-2-Cy-G-Ph2-OX ', R'-EX-2-Cy-G -Ph3-OX ', R'-EX-2-Cy-G-Ph2-2d0, R'-EX-2-Cy-G-Ph3-2d0, R'-EX-2-Cy-G-Ph2-2d1 , R'-EX-2-Cy-G-Ph3-2d1, R'-EX-D-Cy-2-Ph-CN, R'-EX-D-Cy-2-Ph-F, R'-EX -D-Cy-2-Ph-Cl, R'-EX-D-Cy-2-Ph-OCFFF, R'-EX-D-Cy-2-Ph-OCFF, R'-EX-D-Cy- 2-Ph-OC1CFFF, R'-EX-D-Cy-2-Ph-CFFF, R'-EX-D-Cy-2-Ph1 -CN, R'-EX-D-Cy-2-Ph4-CN, R'-EX-D-Cy-2-Ph1-F, R'-EX-D-Cy-2-Ph4-F, R ' -EX-D-Cy-2-Ph1-Cl, R'-EX-D-Cy-2-Ph4-Cl, R'-EX-D-Cy-2-Ph1-OCFFF, R'-EX-D- Cy-2-Ph4-OCFFF, R'-EX-D-Cy-2-Ph1-OCFF, R'-EX-D-Cy-2-Ph4-OCFF, R'-EX-D-Cy-2-Ph1 -OC1CFFF, R'-EX-D-Cy-2-Ph4-OC1CFFF, R'-EX-D-Cy-2-Ph1-CFFF, R'-EX-D-Cy-2-Ph4-CFFF, R ' -EX-D-Cy-2-Ph1-X ', R'-EX-D-Cy-2-Ph4-X', R'-EX-D-Cy-2-Ph1-OX ', R'-EX -D-Cy-2-Ph4-OX ', R'-EX-D-Cy-2-Ph1-2d0, R'-EX-D-Cy-2-Ph4-2d0, R'-EX-D-Cy -2-Ph1-2d1, R'-EX-D-Cy-2-Ph4-2d1, R'-EX-D-Cy-2-Ph2-X ', R'-EX-D-Cy-2-Ph3 -X ', R'-EX-D-Cy-2-Ph2-OX', R'-EX-D-Cy-2-Ph3-OX ', R'-EX-D-Cy-2-Ph2-2d0 , R'-EX-D-Cy-2-Ph3-2d0, R'-EX-D-Cy-2-Ph2-2d1, R'-EX-D-Cy-2-Ph3-2d1,

R'-EX-D-Cy-D-Ph-CN, R'-EX-D-Cy-D-Ph-F, R'-EX-D-Cy-D-Ph-Cl, R ' -EX-D-Cy-D-Ph-OCFFF, R'-EX-D-Cy-D-Ph-OCFF, R'-EX-D-Cy-D-Ph-OC1CFFF, R'-EX-D- Cy-D-Ph-CFFF, R'-EX-D-Cy-D-Ph1-CN, R'-EX-D-Cy-D-Ph4-CN, R'-EX-D-Cy-D-Ph1 -F, R'-EX-D-Cy-D-Ph4-F, R'-EX-D-Cy-D-Ph1-Cl, R'-EX-D-Cy-D-Ph4-Cl, R ' -EX-D-Cy-D-Ph1-OCFFF, R'-EX-D-Cy-D-Ph4-OCFFF, R'-EX-D-Cy-D-Ph1-OCFF, R'-EX-D- Cy-D-Ph4-OCFF, R'-EX-D-Cy-D-Ph1-OC1CFFF, R'-EX-D-Cy-D-Ph4-OC1CFFF, R'-EX-D-Cy-D-Ph1 -CFFF, R'-EX-D-Cy-D-Ph4-CFFF, R'-EX-D-Cy-D-Ph1-X ', R'-EX-D-Cy-D-Ph4-X', R'-EX-D-Cy-D-Ph1-OX ', R'-EX-D-Cy-D-Ph4-OX', R'-EX-D-Cy-D-Ph1-2d0, R'- EX-D-Cy-D-Ph4-2d0, R'-EX-D-Cy-D-Ph1-2d1, R'-EX-D-Cy-D-Ph4-2d1, R'-EX-D-Cy -D-Ph2-X ', R'-EX-D-Cy-D-Ph3-X', R'-EX-D-Cy-D-Ph2-OX ', R'-EX-D-Cy-D -Ph3-OX ', R'-EX-D-Cy-D-Ph2-2d0, R'-EX-D-Cy-D-Ph3-2d0, R'-EX-D-Cy-D-Ph2-2d1 , R'-EX-D-Cy-D-Ph3-2d1,

R'-EX-D-Cy-G-Ph-CN, R'-EX-D-Cy-G-Ph-F, R'-EX-D-Cy-G-Ph-Cl, R ' -EX-D-Cy-G-Ph-OCFFF, R'-EX-D-Cy-G-Ph-OCFF, R'-EX-D-Cy-G-Ph-OC1CFFF, R'-EX-D- Cy-G-Ph-CFFF, R'-EX-D-Cy-G-Ph1-CN, R'-EX-D-Cy-G-Ph4-CN, R'-EX-D-Cy-G-Ph1 -F, R'-EX-D-Cy-G-Ph4-F, R'-EX-D-Cy-G-Ph1-Cl, R'-EX-D-Cy-G-Ph4-Cl, R ' -EX-D-Cy-G-Ph1-OCFFF, R'-EX-D-Cy-G-Ph4-OCFFF, R'-EX-D-Cy-G-Ph1-OCFF, R'-EX-D- Cy-G-Ph4-OCFF, R'-EX-D-Cy-G-Ph1-OC1CFFF, R'-EX-D-Cy-G-Ph4-OC1CFFF, R'-EX-D-Cy-G-Ph1 -CFFF, R'-EX-D-Cy-G-Ph4-CFFF, R'-EX-D-Cy-G-Ph1-X ', R'-EX-D-Cy-G-Ph4-X', R'-EX-D-Cy-G-Ph1-OX ', R'-EX-D-Cy-G-Ph4-OX', R'-EX-D-Cy-G-Ph1-2d0, R'- EX-D-Cy-G-Ph4-2d0, R'-EX-D-Cy-G-Ph1-2d1, R'-EX-D-Cy-G-Ph4-2d1, R'-EX-D-Cy -G-Ph2-X ', R'-EX-D-Cy-G-Ph3-X', R'-EX-D-Cy-G-Ph2-OX ', R'-EX-D-Cy-G -Ph3-OX ', R'-EX-D-Cy-G-Ph2-2d0, R'-EX-D-Cy-G-Ph3-2d0, R'-EX-D-Cy-G-Ph2-2d1 , R'-EX-D-Cy-G-Ph3-2d1, R'-EX-G-Cy-2-Ph-CN, R'-EX-G-Cy-2-Ph-F, R'-EX -G-Cy-2-Ph-Cl, R'-EX-G-Cy-2-Ph-OCFFF, R'-EX-G-Cy-2-Ph-OCFF, R'-EX-G-Cy- 2-Ph-OC1CFFF, R'-EX-G-Cy-2-Ph-CFFF,

R'-EX-G-Cy-2-Ph1-CN, R'-EX-G-Cy-2-Ph4-CN, R'-EX-G-Cy-2-Ph1-F, R ' -EX-G-Cy-2-Ph4-F, R'-EX-G-Cy-2-Ph1-Cl, R'-EX-G-Cy-2-Ph4-Cl, R'-EX-G- Cy-2-Ph1-OCFFF, R'-EX-G-Cy-2-Ph4-OCFFF, R'-EX-G-Cy-2-Ph1-OCFF, R'-EX-G-Cy-2-Ph4 -OCFF, R'-EX-G-Cy-2-Ph1-OC1CFFF, R'-EX-G-Cy-2-Ph4-OC1CFFF, R'-EX-G-Cy-2-Ph1-CFFF, R ' -EX-G-Cy-2-Ph4-CFFF, R'-EX-G-Cy-2-Ph1-X ', R'-EX-G-Cy-2-Ph4-X', R'-EX- G-Cy-2-Ph1-OX ', R'-EX-G-Cy-2-Ph4-OX', R'-EX-G-Cy-2-Ph1-2d0, R'-EX-G-Cy -2-Ph4-2d0, R'-EX-G-Cy-2-Ph1-2d1, R'-EX-G-Cy-2-Ph4-2d1, R'-EX-G-Cy-2-Ph2- X ', R'-EX-G-Cy-2-Ph3-OX', R'-EX-G-Cy-2-Ph2-OX ', R'-EX-G-Cy-2-Ph3-OX' , R'-EX-G-Cy-2-Ph2-2d0, R'-EX-G-Cy-2-Ph3-2d0, R'-EX-G-Cy-2-Ph2-2d1, R'-EX -G-Cy-2-Ph3-2d1, R'-EX-G-Cy-D-Ph-CN, R'-EX-G-Cy-D-Ph-F, R'-EX-G-Cy- D-Ph-Cl, R'-EX-G-Cy-D-Ph-OCFFF, R'-EX-G-Cy-D-Ph-OCFF, R'-EX-G-Cy-D-Ph-OC1CFFF , R'-EX-G-Cy-D-Ph-CFFF, R'-EX-G-Cy-D-Ph1-CN, R'-EX-G-Cy-D-Ph4-CN, R'-EX -G-Cy-D-Ph1-F, R'-EX-G-Cy-D-Ph4-F, R'-EX-G-Cy-D-Ph1-Cl, R'-EX-G-Cy- D-Ph4-Cl, R'-EX-G-Cy-D-Ph1-OCFFF, R'-EX-G-Cy-D-Ph4-OC FFF, R'-EX-G-Cy-D-Ph1-OCFF, R'-EX-G-Cy-D-Ph4-OCFF, R'-EX-G-Cy-D-Ph1-OC1CFFF, R'- EX-G-Cy-D-Ph4-OC1CFFF, R'-EX-G-Cy-D-Ph1-CFFF, R'-EX-G-Cy-D-Ph4-CFFF, R'-EX-G-Cy -D-Ph1-X ', R'-EX-G-Cy-D-Ph4-X', R'-EX-G-Cy-D-Ph1-OX ', R'-EX-G-Cy-D -Ph4-OX ', R'-EX-G-Cy-D-Ph1-2d0, R'-EX-G-Cy-D-Ph4-2d0, R'-EX-G-Cy-D-Ph1-2d1 , R'-EX-G-Cy-D-Ph4-2d1, R'-EX-G-Cy-D-Ph2-X ', R'-EX-G-Cy-D-Ph3-X', R ' -EX-G-Cy-D-Ph2-OX ', R'-EX-G-Cy-D-Ph3-OX', R'-EX-G-Cy-D-Ph2-2d0, R'-EX- G-Cy-D-Ph3-2d0, R'-EX-G-Cy-D-Ph2-2d1, R'-EX-G-Cy-D-Ph3-2d1,

R'-EX-G-Cy-G-Ph-CN, R'-EX-G-Cy-G-Ph-F, R'-EX-G-Cy-G-Ph-Cl, R ' -EX-G-Cy-G-Ph-OCFFF, R'-EX-G-Cy-G-Ph-OCFF, R'-EX-G-Cy-G-Ph-OC1CFFF, R'-EX-G- Cy-G-Ph-CFFF, R'-EX-G-Cy-G-Ph1-CN, R'-EX-G-Cy-G-Ph4-CN, R'-EX-G-Cy-G-Ph1 -F, R'-EX-G-Cy-G-Ph4-F, R'-EX-G-Cy-G-Ph1-Cl, R'-EX-G-Cy-G-Ph4-Cl, R ' -EX-G-Cy-G-Ph1-OCFFF, R'-EX-G-Cy-G-Ph4-OCFFF, R'-EX-G-Cy-G-Ph1-OCFF, R'-EX-G- Cy-G-Ph4-OCFF, R'-EX-G-Cy-G-Ph1-OC1CFFF, R'-EX-G-Cy-G-Ph4-OC1CFFF, R'-EX-G-Cy-G-Ph1 -CFFF, R'-EX-G-Cy-G-Ph4-CFFF, R'-EX-G-Cy-G-Ph1-X ', R'-EX-G-Cy-G-Ph4-X', R'-EX-G-Cy-G-Ph1-OX ', R'-EX-G-Cy-G-Ph4-OX', R'-EX-G-Cy-G-Ph1-2d0, R'- EX-G-Cy-G-Ph4-2d0, R'-EX-G-Cy-G-Ph1-2d1, R'-EX-G-Cy-G-Ph4-2d1, R'-EX-G-Cy -G-Ph2-X ', R'-EX-G-Cy-G-Ph3-X', R'-EX-G-Cy-G-Ph2-OX ', R'-EX-G-Cy-G -Ph3-OX ', R'-EX-G-Cy-G-Ph2-2d0, R'-EX-G-Cy-G-Ph3-2d0, R'-EX-G-Cy-G-Ph2-2d1 , R'-EX-G-Cy-G-Ph3-2d1,

R'-EX-Ph-Ph-CN, R'-EX-Ph-Ph-F, R'-EX-Ph-Ph-Cl, R'-EX-Ph-Ph-OCFFF, R'- EX-Ph-Ph-OCFF, R'-EX-Ph-Ph-OC1CFFF, R'-EX-Ph-Ph-CFFF, R'-EX-Ph-Ph1-CN, R'-EX-Ph-Ph4- CN, R'-EX-Ph-Ph1-F, R'-EX-Ph-Ph4-F, R'-EX-Ph-Ph1-Cl, R'-EX-Ph-Ph4-Cl, R'-EX -Ph-Ph1-OCFFF, R'-EX-Ph-Ph4-OCFFF, R'-EX-Ph-Ph1-OCFF, R'-EX-Ph-Ph4-OCFF, R'-EX-Ph-Ph1-OC1CFFF , R'-EX-Ph-Ph4-OC1CFFF, R'-EX-Ph-Ph1-CFFF, R'-EX-Ph-Ph4-CFFF, R'-EX-Ph-Ph1-X ', R'-EX -Ph-Ph4-X ', R'-EX-Ph-Ph1-OX', R'-EX-Ph-Ph4-OX ', R'-EX-Ph-Ph1-2d0, R'-EX-Ph- Ph4-2d0, R'-EX-Ph-Ph1-2d1, R'-EX-Ph-Ph4-2d1, R'-EX-Ph-Ph2-X ', R'-EX-Ph-Ph3-X', R'-EX-Ph-Ph2-OX ', R'-EX-Ph-Ph3-OX', R'-EX-Ph-Ph2-2d0, R'-EX-Ph-Ph3-2d0, R'-EX -Ph-Ph2-2d1, R'-EX-Ph-Ph3-2d1,

R'-EX-2-Ph-Ph-CN, R'-EX-2-Ph-Ph-F, R'-EX-2-Ph-Ph-Cl, R'-EX-2-Ph -Ph-OCFFF, R'-EX-2-Ph-Ph-OCFF, R'-EX-2-Ph-Ph-OC1CFFF, R'-EX-2-Ph-Ph-CFFF, R'-EX-2 -Ph-Ph1-CN, R'-EX-2-Ph-Ph4-CN, R'-EX-2-Ph-Ph1-F, R'-EX-2-Ph-Ph4-F, R'-EX -2-Ph-Ph1-Cl, R'-EX-2-Ph-Ph4-Cl, R'-EX-2-Ph-Ph1-OCFFF, R'-EX-2-Ph-Ph4-OCFFF, R ' -EX-2-Ph-Ph1-OCFF, R'-EX-2-Ph-Ph4-OCFF, R'-EX-2-Ph-Ph1-OC1CFFF, R'-EX-2-Ph-Ph4-OC1CFFF, R'-EX-2-Ph-Ph1-CFFF, R'-EX-2-Ph-Ph4-CFFF, R'-EX-2-Ph-Ph1-X ', R'-EX-2-Ph-Ph4 -X ', R'-EX-2-Ph-Ph1-OX', R'-EX-2-Ph-Ph4-OX ', R'-EX-2-Ph-Ph1-2d0, R'-EX- 2-Ph-Ph4-2d0, R'-EX-2-Ph-Ph1-2d1, R'-EX-2-Ph-Ph4-2d1, R'-EX-2-Ph-Ph2-X ', R' -EX-2-Ph-Ph3-X ', R'-EX-2-Ph-Ph2-OX', R'-EX-2-Ph-Ph3-OX ', R'-EX-2-Ph-Ph2 -2d0, R'-EX-2-Ph-Ph3-2d1, R'-EX-2-Ph-Ph2-2d1, R'-EX-2-Ph-Ph3-2d1,

R'-EX-D-Ph-Ph-CN, R'-EX-D-Ph-Ph-F, R'-EX-D-Ph-Ph-Cl, R'-EX-D-Ph -Ph-OCFFF, R'-EX-D-Ph-Ph-OCFF, R'-EX-D-Ph-Ph-OC1CFFF, R'-EX-D-Ph-Ph-CFFF, R'-EX-D -Ph-Ph1-CN, R'-EX-D-Ph-Ph4-CN, R'-EX-D-Ph-Ph1-F, R'-EX-D-Ph-Ph4-F, R'-EX -D-Ph-Ph1-Cl, R'-EX-D-Ph-Ph4-Cl, R'-EX-D-Ph-Ph1-OCFFF, R'-EX-D-Ph-Ph4-OCFFF, R ' -EX-D-Ph-Ph1-OCFF, R'-EX-D-Ph-Ph4-OCFF, R'-EX-D-Ph-Ph1-OC1CFFF, R'-EX-D-Ph-Ph4-OC1CFFF, R'-EX-D-Ph-Ph1-CFFF, R'-EX-D-Ph-Ph4-CFFF, R'-EX-D-Ph-Ph1-X ', R'-EX-D-Ph-Ph4 -X ', R'-EX-D-Ph-Ph1-OX', R'-EX-D-Ph-Ph4-OX ', R'-EX-D-Ph-Ph1-2d0, R'-EX- D-Ph-Ph4-2d0, R'-EX-D-Ph-Ph1-2d1, R'-EX-D-Ph-Ph4-2d1, R'-EX-D-Ph-Ph2-X ', R' -EX-D-Ph-Ph3-X ', R'-EX-D-Ph-Ph2-OX', R'-EX-D-Ph-Ph3-OX ', R'-EX-D-Ph-Ph2 -2d0, R'-EX-D-Ph-Ph3-2d0, R'-EX-D-Ph-Ph2-2d1, R'-EX-D-Ph-Ph3-2d1, R'-EX-G-Ph -Ph-CN, R'-EX-G-Ph-Ph-F, R'-EX-G-Ph-Ph-Cl, R'-EX-G-Ph-Ph-OCFFF, R'-EX-G -Ph-Ph-OCFF, R'-EX-G-Ph-Ph-OC1CFFF, R'-EX-G-Ph-Ph-CFFF, R'-EX-G-Ph-Ph1-CN, R'-EX -G-Ph-Ph4-CN, R'-EX-G-Ph-Ph1-F, R'-EX-G-Ph-Ph4-F, R'-EX-G-Ph-Ph1-Cl, R ' -EX-G-Ph -Ph4-Cl, R'-EX-G-Ph-Ph1-OCFFF, R'-EX-G-Ph-Ph4-OCFFF, R'-EX-G-Ph-Ph1-OCFF, R'-EX-G -Ph-Ph4-OCFF, R'-EX-G-Ph-Ph1-OC1CFFF, R'-EX-G-Ph-Ph4-OC1CFFF, R'-EX-G-Ph-Ph1-CFFF, R'-EX -G-Ph-Ph4-CFFF, R'-EX-G-Ph-Ph1-X ', R'-EX-G-Ph-Ph4-X', R'-EX-G-Ph-Ph1-OX ' , R'-EX-G-Ph-Ph4-OX ', R'-EX-G-Ph-Ph1-2d0, R'-EX-G-Ph-Ph4-2d0, R'-EX-G-Ph- Ph1-2d1, R'-EX-G-Ph-Ph4-2d1, R'-EX-G-Ph-Ph2-X ', R'-EX-G-Ph-Ph3-X', R'-EX- G-Ph-Ph2-OX ', R'-EX-G-Ph-Ph3-OX', R'-EX-G-Ph-Ph2-2d0, R'-EX-G-Ph-Ph3-2d0, R '-EX-G-Ph-Ph2-2d1, R'-EX-G-Ph-Ph3-2d1,

R'-EX-Ph-2-Ph-CN, R'-EX-Ph-2-Ph-F, R'-EX-Ph-2-Ph-Cl, R'-EX-Ph-2 -Ph-OCFFF, R'-EX-Ph-2-Ph-OCFF, R'-EX-Ph-2-Ph-OC1CFFF, R'-EX-Ph-2-Ph-CFFF, R'-EX-Ph -2-Ph1-CN, R'-EX-Ph-2-Ph4-CN, R'-EX-Ph-2-Ph1-F, R'-EX-Ph-2-Ph4-F, R'-EX -Ph-2-Ph1-Cl, R'-EX-Ph-2-Ph4-Cl, R'-EX-Ph-2-Ph1-OCFFF, R'-EX-Ph-2-Ph4-OCFFF, R ' -EX-Ph-2-Ph1-OCFF, R'-EX-Ph-2-Ph4-OCFF, R'-EX-Ph-2-Ph1-OC1CFFF, R'-EX-Ph-2-Ph4-OC1CFFF, R'-EX-Ph-2-Ph1-CFFF, R'-EX-Ph-2-Ph4-CFFF, R'-EX-Ph-2-Ph1-X ', R'-EX-Ph-2-Ph4 -X ', R'-EX-Ph-2-Ph1-OX', R'-EX-Ph-2-Ph4-OX ', R'-EX-Ph-2-Ph1-2d0, R'-EX- Ph-2-Ph4-2d0, R'-EX-Ph-2-Ph1-2d1, R'-EX-Ph-2-Ph4-2d1, R'-EX-Ph-2-Ph2-X ', R' -EX-Ph-2-Ph3-X ', R'-EX-Ph-2-Ph2-OX', R'-EX-Ph-2-Ph3-OX ', R'-EX-Ph-2-Ph2 -2d0, R'-EX-Ph-2-Ph3-2d1, R'-EX-Ph-2-Ph2-2d1, R'-EX-Ph-2-Ph3-2d1,

R'-EX-Ph-G-Ph-CN, R'-EX-Ph-G-Ph-F, R'-EX-Ph-G-Ph-Cl, R'-EX-Ph-G -Ph-OCFFF, R'-EX-Ph-G-Ph-OCFF, R'-EX-Ph-G-Ph-OC1CFFF, R'-EX-Ph-G-Ph-CFFF, R'-EX-Ph -G-Ph1-CN, R'-EX-Ph-G-Ph4-CN, R'-EX-Ph-G-Ph1-F, R'-EX-Ph-G-Ph4-F, R'-EX -Ph-G-Ph1-Cl, R'-EX-Ph-G-Ph4-Cl, R'-EX-Ph-G-Ph1-OCFFF, R'-EX-Ph-G-Ph4-OCFFF, R ' -EX-Ph-G-Ph1-OCFF, R'-EX-Ph-G-Ph4-OCFF, R'-EX-Ph-G-Ph1-OC1CFFF, R'-EX-Ph-G-Ph4-OC1CFFF, R'-EX-Ph-G-Ph1-CFFF, R'-EX-Ph-G-Ph4-CFFF, R'-EX-Ph-G-Ph1-X ', R'-EX-Ph-G-Ph4 -X ', R'-EX-Ph-G-Ph1-OX', R'-EX-Ph-G-Ph4-OX ', R'-EX-Ph-G-Ph1-2d0, R'-EX- Ph-G-Ph4-2d0, R'-EX-Ph-G-Ph1-2d1, R'-EX-Ph-G-Ph4-2d1, R'-EX-Ph-G-Ph2-X ', R' -EX-Ph-G-Ph3-X ', R'-EX-Ph-G-Ph2-OX', R'-EX-Ph-G-Ph3-OX ', R'-EX-Ph-G-Ph2 -2d0, R'-EX-Ph-G-Ph3-2d1, R'-EX-Ph-G-Ph2-2d1, R'-EX-Ph-G-Ph3-2d1,

R'-EX-Ph-T-Ph-CN, R'-EX-Ph-T-Ph-F, R'-EX-Ph-T-Ph-Cl, R'-EX-Ph-T -Ph-OCFFF, R'-EX-Ph-T-Ph-OCFF, R'-EX-Ph-T-Ph-OC1CFFF, R'-EX-Ph-T-Ph-CFFF, R'-EX-Ph -T-Ph1-CN, R'-EX-Ph-T-Ph4-CN, R'-EX-Ph-T-Ph1-F, R'-EX-Ph-T-Ph4-F, R'-EX -Ph-T-Ph1-Cl, R'-EX-Ph-T-Ph4-Cl, R'-EX-Ph-T-Ph1-OCFFF, R'-EX-Ph-T-Ph4-OCFFF, R ' -EX-Ph-T-Ph1-OCFF, R'-EX-Ph-T-Ph4-OCFF, R'-EX-Ph-T-Ph1-OC1CFFF, R'-EX-Ph-T-Ph4-OC1CFFF, R'-EX-Ph-T-Ph1-CFFF, R'-EX-Ph-T-Ph4-CFFF, R'-EX-Ph-T-Ph1-X ', R'-EX-Ph-T-Ph4 -X ', R'-EX-Ph-T-Ph1-OX', R'-EX-Ph-T-Ph4-OX ', R'-EX-Ph-T-Ph1-2d0, R'-EX- Ph-T-Ph4-2d0, R'-EX-Ph-T-Ph1-2d1, R'-EX-Ph-T-Ph4-2d1, R'-EX-Ph-T-Ph2-X ', R' -EX-Ph-T-Ph3-X ', R'-EX-Ph-T-Ph2-OX', R'-EX-Ph-T-Ph3-OX ', R'-EX-Ph-T-Ph2 -2d0, R'-EX-Ph-T-Ph3-2d0, R'-EX-Ph-T-Ph2-2d1, R'-EX-Ph-T-Ph3-2d1, R'-EX-2-Ph -2-Ph-CN, R'-EX-2-Ph-2-Ph-F, R'-EX-2-Ph-2-Ph-Cl, R'-EX-2-Ph-2-Ph- OCFFF, R'-EX-2-Ph-2-Ph-OCFF, R'-EX-2-Ph-2-Ph-OC1CFFF, R'-EX-2-Ph-2-Ph-CFFF, R'- EX-2-Ph-2-Ph1-CN, R'-EX-2-Ph-2-Ph4-CN, R'-EX-2-Ph-2-Ph1-F, R'-EX-2-Ph -2-Ph4-F, R'-EX-2 -Ph-2-Ph1-Cl, R'-EX-2-Ph-2-Ph4-Cl, R'-EX-2-Ph-2-Ph1-OCFFF, R'-EX-2-Ph-2- Ph4-OCFFF, R'-EX-2-Ph-2-Ph1-OCFF, R'-EX-2-Ph-2-Ph4-OCFF, R'-EX-2-Ph-2-Ph1-OC1CFFF, R '-EX-2-Ph-2-Ph4-OC1CFFF, R'-EX-2-Ph-2-Ph1-CFFF, R'-EX-2-Ph-2-Ph4-CFFF, R'-EX-2 -Ph-2-Ph1-X ', R'-EX-2-Ph-2-Ph4-X', R'-EX-2-Ph-2-Ph1-OX ', R'-EX-2-Ph -2-Ph4-OX ', R'-EX-2-Ph-2-Ph1-2d0, R'-EX-2-Ph-2-Ph4-2d0, R'-EX-2-Ph-2-Ph1 -2d1, R'-EX-2-Ph-2-Ph4-2d1, R'-EX-2-Ph-2-Ph2-X ', R'-EX-2-Ph-2-Ph3-X', R'-EX-2-Ph-2-Ph2-OX ', R'-EX-2-Ph-2-Ph3-OX', R'-EX-2-Ph-2-Ph2-2d0, R'- EX-2-Ph-2-Ph3-2d0, R'-EX-2-Ph-2-Ph2-2d1, R'-EX-2-Ph-2-Ph3-2d1,

R'-EX-2-Ph-G-Ph-CN, R'-EX-2-Ph-G-Ph-F, R'-EX-2-Ph-G-Ph-Cl, R ' -EX-2-Ph-G-Ph-OCFFF, R'-EX-2-Ph-G-Ph-OCFF, R'-EX-2-Ph-G-Ph-OC1CFFF, R'-EX-2- Ph-G-Ph-CFFF, R'-EX-2-Ph-G-Ph1-CN, R'-EX-2-Ph-G-Ph4-CN, R'-EX-2-Ph-G-Ph1 -F, R'-EX-2-Ph-G-Ph4-F, R'-EX-2-Ph-G-Ph1-Cl, R'-EX-2-Ph-G-Ph4-Cl, R ' -EX-2-Ph-G-Ph1-OCFFF, R'-EX-2-Ph-G-Ph4-OCFFF, R'-EX-2-Ph-G-Ph1-OCFF, R'-EX-2- Ph-G-Ph4-OCFF, R'-EX-2-Ph-G-Ph1-OC1CFFF, R'-EX-2-Ph-G-Ph4-OC1CFFF, R'-EX-2-Ph-G-Ph1 -CFFF, R'-EX-2-Ph-G-Ph4-CFFF, R'-EX-2-Ph-G-Ph1-X ', R'-EX-2-Ph-G-Ph4-X', R'-EX-2-Ph-G-Ph1-OX ', R'-EX-2-Ph-G-Ph4-OX', R'-EX-2-Ph-G-Ph1-2d0, R'- EX-2-Ph-G-Ph4-2d0, R'-EX-2-Ph-G-Ph1-2d1, R'-EX-2-Ph-G-Ph4-2d1, R'-EX-2-Ph -G-Ph2-X ', R'-EX-2-Ph-G-Ph3-X', R'-EX-2-Ph-G-Ph2-OX ', R'-EX-2-Ph-G -Ph3-OX ', R'-EX-2-Ph-G-Ph2-2d0, R'-EX-2-Ph-G-Ph3-2d0, R'-EX-2-Ph-G-Ph2-2d1 , R'-EX-2-Ph-G-Ph3-2d1,

R'-EX-2-Ph-T-Ph-CN, R'-EX-2-Ph-T-Ph-F, R'-EX-2-Ph-T-Ph-Cl, R ' -EX-2-Ph-T-Ph-OCFFF, R'-EX-2-Ph-T-Ph-OCFF, R'-EX-2-Ph-T-Ph-OC1CFFF, R'-EX-2- Ph-T-Ph-CFFF, R'-EX-2-Ph-T-Ph1-CN, R'-EX-2-Ph-T-Ph4-CN, R'-EX-2-Ph-T-Ph1 -F, R'-EX-2-Ph-T-Ph4-F, R'-EX-2-Ph-T-Ph1-Cl, R'-EX-2-Ph-T-Ph4-Cl, R ' -EX-2-Ph-T-Ph1-OCFFF, R'-EX-2-Ph-T-Ph4-OCFFF, R'-EX-2-Ph-T-Ph1-OCFF, R'-EX-2- Ph-T-Ph4-OCFF, R'-EX-2-Ph-T-Ph1-OC1CFFF, R'-EX-2-Ph-T-Ph4-OC1CFFF, R'-EX-2-Ph-T-Ph1 -CFFF, R'-EX-2-Ph-T-Ph4-CFFF, R'-EX-2-Ph-T-Ph1-X ', R'-EX-2-Ph-T-Ph4-X', R'-EX-2-Ph-T-Ph1-OX ', R'-EX-2-Ph-T-Ph4-OX', R'-EX-2-Ph-T-Ph1-2d0, R'- EX-2-Ph-T-Ph4-2d0, R'-EX-2-Ph-T-Ph1-2d1, R'-EX-2-Ph-T-Ph4-2d1, R'-EX-2-Ph -T-Ph2-X ', R'-EX-2-Ph-T-Ph3-X', R'-EX-2-Ph-T-Ph2-OX ', R'-EX-2-Ph-T -Ph3-OX ', R'-EX-2-Ph-T-Ph2-2d0, R'-EX-2-Ph-T-Ph3-2d0, R'-EX-2-Ph-T-Ph2-2d1 , R'-EX-2-Ph-T-Ph3-2d1,

R'-EX-D-Ph-2-Ph-CN, R'-EX-D-Ph-2-Ph-F, R'-EX-D-Ph-2-Ph-Cl, R ' -EX-D-Ph-2-Ph-OCFFF, R'-EX-D-Ph-2-Ph-OCFF, R'-EX-D-Ph-2-Ph-OC1CFFF, R'-EX-D- Ph-2-Ph-CFFF, R'-EX-D-Ph-2-Ph1-CN, R'-EX-D-Ph-2-Ph4-CN, R'-EX-D-Ph-2-Ph1 -F, R'-EX-D-Ph-2-Ph4-F, R'-EX-D-Ph-2-Ph1-Cl, R'-EX-D-Ph-2-Ph4-Cl, R ' -EX-D-Ph-2-Ph1-OCFFF, R'-EX-D-Ph-2-Ph4-OCFFF, R'-EX-D-Ph-2-Ph1-OCFF, R'-EX-D- Ph-2-Ph4-OCFF, R'-EX-D-Ph-2-Ph1-OC1CFFF, R'-EX-D-Ph-2-Ph4-OC1CFFF, R'-EX-D-Ph-2-Ph1 -CFFF, R'-EX-D-Ph-2-Ph4-CFFF, R'-EX-D-Ph-2-Ph1-X ', R'-EX-D-Ph-2-Ph4-X', R'-EX-D-Ph-2-Ph1-OX ', R'-EX-D-Ph-2-Ph4-OX', R'-EX-D-Ph-2-Ph1-2d0, R'- EX-D-Ph-2-Ph4-2d0, R'-EX-D-Ph-2-Ph1-2d1, R'-EX-D-Ph-2-Ph4-2d1, R'-EX-D-Ph -2-Ph2-X ', R'-EX-D-Ph-2-Ph3-X', R'-EX-D-Ph-2-Ph2-OX ', R'-EX-D-Ph-2 -Ph3-OX ', R'-EX-D-Ph-2-Ph2-2d0, R'-EX-D-Ph-2-Ph3-2d0, R'-EX-D-Ph-2-Ph2-2d1 , R'-EX-D-Ph-2-Ph3-2d1, R'-EX-D-Ph-G-Ph-CN, R'-EX-D-Ph-G-Ph-F, R'-EX -D-Ph-G-Ph-Cl, R'-EX-D-Ph-G-Ph-OCFFF, R'-EX-D-Ph-G-Ph-OCFF, R'-EX-D-Ph- G-Ph-OC1CFFF, R'-EX-D-Ph-G-Ph-CFFF,

R'-EX-D-Ph-G-Ph1-CN, R'-EX-D-Ph-G-Ph4-CN, R'-EX-D-Ph-G-Ph1-F, R ' -EX-D-Ph-G-Ph4-F, R'-EX-D-Ph-G-Ph1-Cl, R'-EX-D-Ph-G-Ph4-Cl, R'-EX-D- Ph-G-Ph1-OCFFF, R'-EX-D-Ph-G-Ph4-OCFFF, R'-EX-D-Ph-G-Ph1-OCFF, R'-EX-D-Ph-G-Ph4 -OCFF, R'-EX-D-Ph-G-Ph1-OC1CFFF, R'-EX-D-Ph-G-Ph4-OC1CFFF, R'-EX-D-Ph-G-Ph1-CFFF, R ' -EX-D-Ph-G-Ph4-CFFF, R'-EX-D-Ph-G-Ph1-X ', R'-EX-D-Ph-G-Ph4-X', R'-EX- D-Ph-G-Ph1-OX ', R'-EX-D-Ph-G-Ph4-OX', R'-EX-D-Ph-G-Ph1-2d0, R'-EX-D-Ph -G-Ph4-2d0, R'-EX-D-Ph-G-Ph1-2d1, R'-EX-D-Ph-G-Ph4-2d1, R'-EX-D-Ph-G-Ph2- X ', R'-EX-D-Ph-G-Ph3-X', R'-EX-D-Ph-G-Ph2-OX ', R'-EX-D-Ph-G-Ph3-OX' , R'-EX-D-Ph-G-Ph2-2d0, R'-EX-D-Ph-G-Ph3-2d0, R'-EX-D-Ph-G-Ph2-2d1, R'-EX -D-Ph-G-Ph3-2d1,

R'-EX-D-Ph-T-Ph-CN, R'-EX-D-Ph-T-Ph-F, R'-EX-D-Ph-T-Ph-Cl, R ' -EX-D-Ph-T-Ph-OCFFF, R'-EX-D-Ph-T-Ph-OCFF, R'-EX-D-Ph-T-Ph-OC1CFFF, R'-EX-D- Ph-T-Ph-CFFF, R'-EX-D-Ph-T-Ph1-CN, R'-EX-D-Ph-T-Ph4-CN, R'-EX-D-Ph-T-Ph1 -F, R'-EX-D-Ph-T-Ph4-F, R'-EX-D-Ph-T-Ph1-Cl, R'-EX-D-Ph-T-Ph4-Cl, R ' -EX-D-Ph-T-Ph1-OCFFF, R'-EX-D-Ph-T-Ph4-OCFFF, R'-EX-D-Ph-T-Ph1-OCFF, R'-EX-D- Ph-T-Ph4-OCFF, R'-EX-D-Ph-T-Ph1-OC1CFFF, R'-EX-D-Ph-T-Ph4-OC1CFFF, R'-EX-D-Ph-T-Ph1 -CFFF, R'-EX-D-Ph-T-Ph4-CFFF, R'-EX-D-Ph-T-Ph1-X ', R'-EX-D-Ph-T-Ph4-X', R'-EX-D-Ph-T-Ph1-OX ', R'-EX-D-Ph-T-Ph4-OX', R'-EX-D-Ph-T-Ph1-2d0, R'- EX-D-Ph-T-Ph4-2d0, R'-EX-D-Ph-T-Ph1-2d1, R'-EX-D-Ph-T-Ph4-2d1, R'-EX-D-Ph -T-Ph2-X ', R'-EX-D-Ph-T-Ph3-X', R'-EX-D-Ph-T-Ph2-OX ', R'-EX-D-Ph-T -Ph3-OX ', R'-EX-D-Ph-T-Ph2-2d0, R'-EX-D-Ph-T-Ph3-2d0, R'-EX-D-Ph-T-Ph2-2d1 , R'-EX-D-Ph-T-Ph3-2d1,

R'-EX-G-Ph-2-Ph-CN, R'-EX-G-Ph-2-Ph-F, R'-EX-G-Ph-2-Ph-Cl, R ' -EX-G-Ph-2-Ph-OCFFF, R'-EX-G-Ph-2-Ph-OCFF, R'-EX-G-Ph-2-Ph-OC1CFFF, R'-EX-G- Ph-2-Ph-CFFF, R'-EX-G-Ph-2-Ph1-CN, R'-EX-G-Ph-2-Ph4-CN, R'-EX-G-Ph-2-Ph1 -F, R'-EX-G-Ph-2-Ph4-F, R'-EX-G-Ph-2-Ph1-Cl, R'-EX-G-Ph-2-Ph4-Cl, R ' -EX-G-Ph-2-Ph1-OCFFF, R'-EX-G-Ph-2-Ph4-OCFFF, R'-EX-G-Ph-2-Ph1-OCFF, R'-EX-G- Ph-2-Ph4-OCFF, R'-EX-G-Ph-2-Ph1-OC1CFFF, R'-EX-G-Ph-2-Ph4-OC1CFFF, R'-EX-G-Ph-2-Ph1 -CFFF, R'-EX-G-Ph-2-Ph4-CFFF, R'-EX-G-Ph-2-Ph1-X ', R'-EX-G-Ph-2-Ph4-X', R'-EX-G-Ph-2-Ph1-OX ', R'-EX-G-Ph-2-Ph4-OX', R'-EX-G-Ph-2-Ph1-2d0, R'- EX-G-Ph-2-Ph4-2d0, R'-EX-G-Ph-2-Ph1-2d1, R'-EX-G-Ph-2-Ph4-2d1, R'-EX-G-Ph -2-Ph2-X ', R'-EX-G-Ph-2-Ph3-X', R'-EX-G-Ph-2-Ph2-OX ', R'-EX-G-Ph-2 -Ph3-OX ', R'-EX-G-Ph-2-Ph2-2d0, R'-EX-G-Ph-2-Ph3-2d0, R'-EX-G-Ph-2-Ph2-2d1 , R'-EX-G-Ph-2-Ph3-2d1,

R'-EX-G-Ph-G-Ph-CN, R'-EX-G-Ph-G-Ph-F, R'-EX-G-Ph-G-Ph-Cl, R ' -EX-G-Ph-G-Ph-OCFFF, R'-EX-G-Ph-G-Ph-OCFF, R'-EX-G-Ph-G-Ph-OC1CFFF, R'-EX-G- Ph-G-Ph-CFFF, R'-EX-G-Ph-G-Ph1-CN, R'-EX-G-Ph-G-Ph4-CN, R'-EX-G-Ph-G-Ph1 -F, R'-EX-G-Ph-G-Ph4-F, R'-EX-G-Ph-G-Ph1-Cl, R'-EX-G-Ph-G-Ph4-Cl, R ' -EX-G-Ph-G-Ph1-OCFFF, R'-EX-G-Ph-G-Ph4-OCFFF, 1-EX-G-Ph-G-Ph1-OCFFF, R'-EX-G-Ph -G-Ph4-OCFF, 2-EX-G-Ph-G-Ph1-OCFFF, R'-EX-G-Ph-G-Ph4-OC1CFFF, 3-EX-G-Ph-G-Ph1-OCFFF, R'-EX-G-Ph-G-Ph4-CFFF, 4-EX-G-Ph-G-Ph1-OCFFF, R'-EX-G-Ph-G-Ph4-X ', 5-EX-G -Ph-G-Ph1-OCFFF, R'-EX-G-Ph-G-Ph1-OCFF, R'-EX-G-Ph-G-Ph1-OC1CFFF, R'-EX-G-Ph-G- Ph1-CFFF, R'-EX-G-Ph-G-Ph1-X ', R'-EX-G-Ph-G-Ph4-OX', R'-EX-G-Ph-G-Ph1-OX ', R'-EX-G-Ph-G-Ph4-2d0, R'-EX-G-Ph-G-Ph1-2d0, R'-EX-G-Ph-G-Ph4-2d1, R'- EX-G-Ph-G-Ph1-2d1, R'-EX-G-Ph-G-Ph2-X ', R'-EX-G-Ph-G-Ph3-X', R'-EX-G -Ph-G-Ph2-OX ', R'-EX-G-Ph-G-Ph3-OX', R'-EX-G-Ph-G-Ph2-2d0, R'-EX-G-Ph- G-Ph3-2d0, R'-EX-G-Ph-G-Ph2-2d1, R'-EX-G-Ph-G-Ph3-2d1,

R'-EX-G-Ph-T-Ph-CN, R'-EX-G-Ph-T-Ph-F, R'-EX-G-Ph-T-Ph-Cl, R ' -EX-G-Ph-T-Ph-OCFFF, R'-EX-G-Ph-T-Ph-OCFF, R'-EX-G-Ph-T-Ph-OC1CFFF, R'-EX-G- Ph-T-Ph-CFFF, R'-EX-G-Ph-T-Ph1-CN, R'-EX-G-Ph-T-Ph4-CN, R'-EX-G-Ph-T-Ph1 -F, R'-EX-G-Ph-T-Ph4-F, R'-EX-G-Ph-T-Ph1-Cl, R'-EX-G-Ph-T-Ph4-Cl, R ' -EX-G-Ph-T-Ph1-OCFFF, R'-EX-G-Ph-T-Ph4-OCFFF, R'-EX-G-Ph-T-Ph1-OCFF, R'-EX-G- Ph-T-Ph4-OCFF, R'-EX-G-Ph-T-Ph1-OC1CFFF, R'-EX-G-Ph-T-Ph4-OC1CFFF, R'-EX-G-Ph-T-Ph1 -CFFF, R'-EX-G-Ph-T-Ph4-CFFF, R'-EX-G-Ph-T-Ph1-X ', R'-EX-G-Ph-T-Ph4-X', R'-EX-G-Ph-T-Ph1-OX ', R'-EX-G-Ph-T-Ph4-OX', R'-EX-G-Ph-T-Ph1-2d0, R'- EX-G-Ph-T-Ph4-2d0, R'-EX-G-Ph-T-Ph1-2d1, R'-EX-G-Ph-T-Ph4-2d1, R'-EX-G-Ph -T-Ph2-X ', R'-EX-G-Ph-T-Ph3-X', R'-EX-G-Ph-T-Ph2-OX ', R'-EX-G-Ph-T -Ph3-OX ', R'-EX-G-Ph-T-Ph2-2d0, R'-EX-G-Ph-T-Ph3-2d0, R'-EX-G-Ph-T-Ph2-2d1 , R'-EX-G-Ph-T-Ph3-2d1, and the like can be mentioned as practical compounds.

The compound of the general formula (I) of the present invention can be produced as follows. That is, the general formula (II)

[Formula 8]

(Wherein L, A, M, B, X, and n have the same meanings as in the general formula) and a general formula (III)

[Formula 9] (Wherein, R has the same meaning as in the general formula.).
The obtained alkylidenecyclohexane derivative does not have cis and trans isomers as compared with the 4-alkylcyclohexane derivative having a similar skeleton, and thus requires an isomerization step required for the 4-alkylcyclohexane derivative and separation of cis and trans. Since it is not available, it is very advantageous industrially.

The compound represented by the general formula (II) is as follows:

[Formula 10] 1,4-cyclohexanedione monoethylene acetal (IV
a), can be produced from 4,4′-bicyclohexanedione monoethylene acetal (IVb) by a general synthesis method.

Many of the compounds represented by the general formula (I) show excellent compatibility with other liquid crystal materials, and thus are suitably used as a material for a liquid crystal display cell in a mixture with other liquid crystal compounds. be able to. The compound (I) can be used in any of the above-described various display methods, but can be used for a simple matrix drive or active matrix drive TN display element and an STN display element, and is used as a reflection type display element. Can also be used.

Preferred examples of the nematic liquid crystal compound which can be used as a mixture with the compound represented by the general formula (I) include the first component in the composition provided by the present invention. At least one compound represented by the general formula (I), and it is particularly preferable to include at least one compound from the following second to fourth components as other components.

That is, the second component is a so-called fluorine-based (halogen-based) p-type liquid crystal compound and has the following general formula (A1)
It consists of the compound represented by (A3).

Embedded image In the above formula, ^Rb represents an alkyl group having 1 to 12 carbon atoms, which may be linear or have a methyl or ethyl branch and have a 3- to 6-membered ring structure. Any -CH _2- present in the group may be -O-, -CH = CH-, -CH = CF-, -CF = C
H-, may be replaced by -CF = CF- or -C≡C-,
Any hydrogen atom present in the group may be substituted by a fluorine atom or a trifluoromethoxy group, but may be a straight-chain alkyl group having 2 to 7 carbon atoms or a straight-chain alkyl group having 2 to 7 carbon atoms. An alkenyl group, a linear 3-alkenyl group having 4 to 7 carbon atoms, and an alkyl group having 1 to 5 carbon atoms, the terminal of which is substituted by an alkoxyl group having 1 to 3 carbon atoms. When an asymmetric carbon is generated by branching, the compound may be optically active or racemic.

Ring A, ring B and ring C are each independently substituted by a trans-1,4-cyclohexylene group, a transdecahydronaphthalene-trans-2,6-diyl group, and one or more fluorine atoms. 1,4-phenylene group which may be substituted, naphthalene-2,6- which may be substituted by one or more fluorine atoms
Diyl group, tetrahydronaphthalene-2,6-diyl group optionally substituted by one or more fluorine atoms, 1,4-cyclohexenylene group optionally substituted by fluorine atom, 1,3-dioxane- Trans-2,5-diyl group, pyrimidine
Represents a -2,5-diyl group or a pyridine-2,5-diyl group,
Trans-1,4-cyclohexylene group, transdecahydronaphthalene-trans-2,6-diyl group, naphthalene-2,6-diyl group which may be substituted by a fluorine atom or 1
A 1,4-phenylene group which may be substituted by 1 to 2 fluorine atoms is preferred. In particular, when ring B is a trans-1,4-cyclohexylene group or a transdecahydronaphthalene-trans-2,6-diyl group, ring A is trans-1,4-
It is preferably a cyclohexylene group, and when ring C is a trans-1,4-cyclohexylene group or transdecahydronaphthalene-trans-2,6-diyl group, ring B and ring A are trans-1 It is preferably a 4,4-cyclohexylene group. In (A3), ring A is preferably a trans-1,4-cyclohexylene group. L ^a , L ^b and L ^c are linking groups, each independently being a single bond, an ethylene group (-CH ₂ CH _2- ), a 1,2-propylene group (-CH (CH ₃ ) C
H ₂ -and -CH ₂ CH (CH ₃ )-), 1,4-butylene group, -COO-, -OCO-, -O
CF _2- , -CF ₂ O-, -CH = CH-, -CH = CF-, -CF = CH-, -CF = CF-, -C≡C-
Or -CH = NN = CH-, but a single bond, an ethylene group, a 1,4-butylene group, -COO-, -OCF _2- , -CF ₂ O-, -CF = CF- or -C≡C Is preferred, and a single bond or an ethylene group is particularly preferred. In (A2), at least one of them preferably represents a single bond in (A3).

Ring Z is an aromatic ring and has the following general formulas (La) to (L)
It can be represented by c).

Embedded image In the formula, Y ^{a to} Y ^j each independently represent a hydrogen atom or a fluorine atom, but in (La), at least one of ^Ya and Y ^b
Is preferably a fluorine atom, and in (Lb), Y ^d
At least one to Y ^f is preferably a fluorine atom, and further preferably in particular Y ^d is a fluorine atom. Terminal group P ^a represents a fluorine atom, a chlorine atom, trifluoromethoxy group, difluoromethoxy group, trifluoromethyl group or difluoromethyl group or 2 or more fluorine atoms optionally substituted carbon atoms 2 or 3 of the alkoxyl group, an alkyl Represents a group, alkenyl group or alkenyloxy group, preferably a fluorine atom, a trifluoromethoxy group or a difluoromethoxy group, particularly preferably a fluorine atom.
In (A2), the compound of the general formula (I) of the present invention is excluded.

The third component is a so-called cyano-based p-type liquid crystal compound, which is a compound represented by the following general formulas (B1) to (B3).

Embedded image In the above formula, R ^c represents an alkyl group having 1 to 12 carbon atoms, which may have a methyl or ethyl branches may be linear, have a cyclic structure having 3 to 6-membered ring Any -CH _2- present in the group may be -O-, -CH = CH-, -CH = CF-, -CF = C
H-, may be replaced by -CF = CF- or -C≡C-,
Any hydrogen atom present in the group may be substituted by a fluorine atom or a trifluoromethoxy group, but may be a straight-chain alkyl group having 2 to 7 carbon atoms or a straight-chain alkyl group having 2 to 7 carbon atoms. An alkenyl group, a linear 3-alkenyl group having 4 to 7 carbon atoms, and an alkyl group having 1 to 5 carbon atoms, the terminal of which is substituted by an alkoxyl group having 1 to 3 carbon atoms. When an asymmetric carbon is generated by branching, the compound may be optically active or racemic.

Ring D, ring E and ring F are each independently substituted with a trans-1,4-cyclohexylene group, a transdecahydronaphthalene-trans-2,6-diyl group, and one or more fluorine atoms. 1,4-phenylene group which may be substituted, naphthalene-2,6- which may be substituted by one or more fluorine atoms
Diyl group, tetrahydronaphthalene-2,6-diyl group optionally substituted by one or more fluorine atoms, 1,4-cyclohexenylene group optionally substituted by fluorine atom, 1,3-dioxane- Trans-2,5-diyl group, pyrimidine
Represents a -2,5-diyl group or a pyridine-2,5-diyl group,
Trans-1,4-cyclohexylene group, transdecahydronaphthalene-trans-2,6-diyl group, naphthalene-2,6-diyl group which may be substituted by a fluorine atom or 1
A 1,4-phenylene group which may be substituted by 1 to 2 fluorine atoms is preferred. In particular, when Ring E is a trans-1,4-cyclohexylene group or transdecahydronaphthalene-trans-2,6-diyl group, Ring D is trans-1,4-
It is preferably a cyclohexylene group, and when ring F is a trans-1,4-cyclohexylene group or transdecahydronaphthalene-trans-2,6-diyl group, ring D and ring E are trans-1 It is preferably a 4,4-cyclohexylene group. Further, in (B3), ring D is preferably a trans-1,4-cyclohexylene group.

L ^d , ^Le and L ^f are linking groups, each independently being a single bond, an ethylene group (-CH ₂ CH _2- ), a 1,2-propylene group
_{(-CH (CH 3) CH 2} - and _{-CH 2 CH (CH 3) -} ), 1,4- butylene group, -COO
-, -OCO-, -OCF _2- , -CF ₂ O-, -CH = CH-, -CH = CF-, -CF = CH-, -CF =
CF -, - C≡C -, - OCH 2 -, - CH 2 O-, or represent a -CH = NN = CH-,
A single bond, an ethylene group, —COO—, —OCF ₂ —, —CF ₂ O—, —CFCFCF— or —C≡C— is preferred, and a single bond, an ethylene group or —COO— is particularly preferred. In (B2), at least one of them preferably represents a single bond in (B3).

Ring Y is an aromatic ring represented by the following general formulas (Ld) to (L
f).

Embedded image In the formula, Y ^{k to} Y ^g each independently represent a hydrogen atom or a fluorine atom, but in (Le), Y ⁿ and ^Yo are preferably hydrogen atoms. Terminal group P ^b is a cyano group (-CN), cyanato group (-OCN) or -C≡
Represents CCN, preferably a cyano group.

In (B2), the compound of the general formula (I) of the present invention is excluded. The fourth component is a nonpolar liquid crystal having a dielectric anisotropy of about 0, and is composed of compounds represented by the following general formulas (C1) to (C3).

Embedded image

In the above formula, R ^d and ^Pe each independently represent an alkyl group having 1 to 12 carbon atoms, which may be linear or have a methyl or ethyl branch; 3-6
Any -CH _2- present in the group may have a ring structure of a membered ring, -O-, -CH = CH-, -CH = CF-, -CF = CH-, -CF = It may be replaced by CF- or -C≡C-, and any hydrogen atom present in the group may be replaced by a fluorine atom or a trifluoromethoxy group. A linear alkyl group, a linear 1-alkenyl group having 2 to 7 carbon atoms, a linear 3-alkenyl group having 4 to 7 carbon atoms, a linear alkoxyl group having 1 to 3 carbon atoms or a terminal Number of carbon atoms
A straight-chain alkyl group having 1 to 5 carbon atoms substituted by a 1-3 alkoxyl group is preferable, and at least one is a straight-chain alkyl group having 1 to 7 carbon atoms and a straight-chain alkyl group having 2 to 7 carbon atoms. 1-alkenyl group or linear 3-alkoxy having 4 to 7 carbon atoms
Particularly preferred is an alkenyl group.

Ring G, ring H, ring I and ring J are each independently
Trans-1,4-cyclohexylene group, transdecahydronaphthalene-trans-2,6-diyl group, 1,4-phenylene group optionally substituted by 1 to 2 fluorine atoms or methyl group, 1 Naphthalene-2,6-diyl group optionally substituted by two or more fluorine atoms, tetrahydronaphthalene-2,6 optionally substituted by 1 to 2 fluorine atoms
-Diyl group, 1,4-cyclohexenylene group optionally substituted by 1 to 2 fluorine atoms, 1,3-dioxane-trans-2,5-diyl group, pyrimidine-2,5-diyl group Or a pyridine-2,5-diyl group, but in each compound, transdecahydronaphthalene-trans-2,6-diyl group, naphthalene which may be substituted with one or more fluorine atoms
-2,6-diyl group, tetrahydronaphthalene-2,6-diyl group optionally substituted by 1 to 2 fluorine atoms, 1,4-cyclohexenylene group optionally substituted by fluorine atom, 1,3-dioxane-trans-2,5-diyl group, pyrimidine-2,5-diyl group or pyridine-2,5-diyl group is preferably one or less, the other ring is trans-1, It is preferably a 4-cyclohexylene group or a 1,4-phenylene group which may be substituted by one or two fluorine atoms or methyl groups.

L ^g , L ^h and L ⁱ are linking groups, each independently being a single bond, an ethylene group (—CH ₂ CH ₂ —), a 1,2-propylene group
_{(-CH (CH 3) CH 2} - and _{-CH 2 CH (CH 3) -} ), 1,4- butylene group, -COO
-, -OCO-, -OCF _2- , -CF ₂ O-, -CH = CH-, -CH = CF-, -CF = CH-, -CF =
CF -, - C≡C- or represents a -CH = NN = CH-, a single bond, ethylene group, 1,4-butylene group, -COO -, - OCO -, - OCF 2 -, - CF 2 O -, -CF = CF
-, -C≡C- or -CH = NN = CH- is preferable, and at least one of them is (C2) and at least 2 is (C3).
Preferably, each represents a single bond. In (C2), the compound of the general formula (I) of the present invention is excluded. More preferred form in (C1) is the following general formula (C1a) ~
(C1h).

[0066]

Embedded image In each of the above formulas, R ^f and R ^g are each independently 1 to carbon atoms.
7 straight-chain alkyl group, linear 1-alkenyl group having 2 to 7 carbon atoms, linear 3-alkenyl group having 4 to 7 carbon atoms, linear alkoxyl group having 1 to 3 carbon atoms Or 1 terminal carbon atom substituted by an alkoxyl group having 1 to 3 carbon atoms
Represents a linear alkyl group of 5 to 5, at least one of which is a linear alkyl group having 1 to 7 carbon atoms, a linear 1-alkenyl group having 2 to 7 carbon atoms or 4 to 7 carbon atoms. Represents a linear 3-alkenyl group. However, when the ring G1 ~ ring G3 is an aromatic ring, the corresponding R ^f except 1-alkenyl group and alkoxyl group,
When ring H1 to ring H3 are aromatic rings, the corresponding R ^g excludes a 1-alkenyl group and an alkoxyl group.

Ring G1 and ring H1 are each independently trans
-1,4-cyclohexylene group, transdecahydronaphthalene-trans-2,6-diyl group, 1,4-phenylene group optionally substituted by 1 to 2 fluorine atoms or methyl groups, 1 Naphthalene-2,6-diyl group optionally substituted by the above fluorine atom, tetrahydronaphthalene-2,6-diyl group optionally substituted by 1 to 2 fluorine atoms, 1 to 2 fluorine 1,4 optionally substituted by atoms
-Cyclohexenylene group, 1,3-dioxane-trans-2,5-
Diyl group, pyrimidine-2,5-diyl group or pyridine-2,5
-Diyl group, but in each compound, transdecahydronaphthalene-trans-2,6-diyl group, naphthalene-2,6-diyl group optionally substituted by one or more fluorine atoms, 1-2 Tetrahydronaphthalene-2,6-diyl group which may be substituted by fluorine atoms, 1,4-cyclohexenylene group which may be substituted by fluorine atom,
1,3-dioxane-trans-2,5-diyl group, pyrimidine-2,
It is preferred that the number of 5-diyl group or pyridine-2,5-diyl group is one or less, in which case the other ring is trans-1,4-
A cyclohexylene group or a 1,4-phenylene group which may be substituted by one or two fluorine atoms or a methyl group. Ring G2 and ring H2 are each independently trans-1,4-
Cyclohexylene group, transdecahydronaphthalene-trans-2,6-diyl group, 1,4-phenylene group which may be substituted by 1 to 2 fluorine atoms or methyl group, by 1 or more fluorine atoms Optionally substituted naphthalene-2,6-diyl group, which represents a tetrahydronaphthalene-2,6-diyl group optionally substituted by 1 to 2 fluorine atoms, and in each compound, transdecahydronaphthalene
-Trans-2,6-diyl group, naphthalene-2,6-diyl group optionally substituted by one or more fluorine atoms, tetrahydronaphthalene-2 optionally substituted by one or two fluorine atoms , 6-diyl group is preferably 1 or less, in which case the other ring may be substituted with a trans-1,4-cyclohexylene group or 1 to 2 fluorine atoms or methyl groups 1,4-phenylene group. Ring G3 and ring H3 are each independently a 1,4-phenylene group which may be substituted by 1 to 2 fluorine atoms or methyl groups, a naphthalene-2 which may be substituted by one or more fluorine atoms. , 6-diyl group, represents a tetrahydronaphthalene-2,6-diyl group which may be substituted by 1 to 2 fluorine atoms, but in each compound, naphthalene which may be substituted by 1 or more fluorine atoms -2,6-diyl group, 1-2
It is preferable that the number of tetrahydronaphthalene-2,6-diyl groups which may be substituted by two fluorine atoms is one or less. A more preferred form in (C2) is the following general formula (C2
a) to (C2m).

[0068]

Embedded image In the above formula, ring G1, ring G2, ring G3, ring H1, ring H2 and ring H3 represent the above-mentioned meanings, ring I1 is the same as ring G1, ring I2 is the same as ring G2, and ring I3 is the same as the ring G3. Represent meaning. In each of the above compounds,
Transdecahydronaphthalene-trans-2,6-diyl group, naphthalene-2,6-diyl group which may be substituted by one or more fluorine atoms, may be substituted by 1 to 2 fluorine atoms Tetrahydronaphthalene-2,6-diyl group, 1,4-cyclohexenylene group optionally substituted by fluorine atom, 1,3-dioxane-trans-2,5-diyl group, pyrimidine-2,5-diyl Group or pyridine-2,5-diyl group is preferably one or less, in which case the other ring is substituted by trans-1,4-cyclohexylene group or one or two fluorine atoms or methyl groups A 1,4-phenylene group which may be Next, more preferred embodiments of (C3) can be represented by the following general formulas (C3a) to (C3f).

[0069]

Embedded image

In the above formula, ring G1, ring G2, ring H1, ring H2, ring I1, and ring I
2 has the same meaning as described above, and ring J1 has the same meaning as ring G1 and ring J2 has the same meaning as ring G2. In each of the above compounds, transdecahydronaphthalene-trans-2,6-diyl group, 1
Naphthalene-2,6-diyl group optionally substituted by two or more fluorine atoms, tetrahydronaphthalene-2,6-diyl group optionally substituted by 1 to 2 fluorine atoms, substituted by fluorine atom 1,4-cyclohexenylene, 1,3-dioxane-trans-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl may have 1
It is preferable that the other ring is a trans-1,4-cyclohexylene group or 1,4-optionally substituted with one or two fluorine atoms or methyl groups.
It is a phenylene group. Compounds similar to general formula (I) related to the present invention are already
As reported in JP-A-6-80603 and JP-A-7-215927, the former is an object of the invention to improve the characteristics as a ferroelectric liquid crystal, and the latter is an object of the invention to increase Δε and reduce viscosity. However, there is no description of Δn in either of the inventions, and it is for the first time clarified that a skeleton having an exomethylene group is effective in reducing a small Δn in the present invention.

[0071]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Further, “%” in the compositions of the following Examples and Comparative Examples means “% by mass”.

Example 1 Synthesis of 4- (4-methylenecyclohexyl) 2,6-difluorobenzonitrile (Compound No. 1)

Embedded image (1) Synthesis of 4- (3,5-difluorophenyl) cyclohexane-1-one ethylene acetal 42 g of magnesium was suspended in 80 ml of THF, and 3,5-difluoro 1-
A solution of 297 g of bromobenzene in 900 ml of THF is added dropwise at a rate at which THF is gently refluxed, and the mixture is further stirred for 1 hour. 1,4-cyclohexanedione monoethylene acetal 200g THF600
The ml solution is added dropwise at room temperature and stirred for another hour. 1.5 l of saturated ammonium chloride was added, and the mixture was extracted with 1.5 l of toluene, and washed three times with saturated saline. After drying over anhydrous magnesium sulfate, the solvent is distilled off, 1.6 l of toluene and 49 g of p-toluenesulfonic acid monohydrate are added, and the mixture is refluxed under heating for 6 hours. The mixture is allowed to cool to room temperature, washed with saturated aqueous sodium hydrogen carbonate, water and saturated saline, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and 1.5 l of ethyl acetate and 30 g of 5% palladium carbon were added, and 0.5 MPa
Stir at a hydrogen pressure of 6 hours. The catalyst is removed by filtration, and the solvent is distilled off to obtain 317 g of 4- (3,5-difluorophenyl) cyclohexane-1-one ethylene acetal.

(2) Synthesis of 4- (3,5-difluoro-4-iodophenyl) cyclohexane-1-one Ethylene acetal 4- (3,5-difluorophenyl) cyclohexane-1-one
Dissolve 60 g of ethylene acetal in 300 ml of THF and adjust the internal temperature to -40.
N-Butyllithium n-hexane solution cooled to below ℃
160 ml of (1.60 mol / l) is added dropwise at a rate such that the internal temperature does not exceed -40 ° C, and the mixture is further stirred for 1 hour. A solution of 66 g of iodine in 270 ml of THF is added dropwise at a rate such that the internal temperature does not exceed -40 ° C., and the mixture is further stirred for 1 hour. The temperature is returned to room temperature, 300 ml of ethyl acetate is added, and the mixture is washed successively with a 10% aqueous sodium hydrogen sulfite solution, water and saturated saline, and dried over anhydrous magnesium sulfate. Evaporate the solvent,
4- (3,5-difluoro-4-iodophenyl) cyclohexane-
78 g of 1-one ethylene acetal are obtained.

(3) Synthesis of 4- (3,5-difluoro-4-cyanophenyl) cyclohexane-1-one ethylene acetal 4- (3,5-difluoro-4-iodophenyl) cyclohexane-
N-methylpyrrolidone 3 in 70 g of 1-one ethylene acetal
50 ml and 21.6 g of copper (I) cyanide are added, and the mixture is heated and stirred at 160 ° C. for 6 hours. The mixture was allowed to cool to room temperature, added with 500 ml of water, extracted with 500 ml of ethyl acetate, washed with water and saturated saline, and dried over anhydrous magnesium sulfate. The solvent was distilled off and recrystallized from methanol to give 4- (3,5-difluoro-4-cyanophenyl)
Cyclohexane-1-one 32.4 g of ethylene acetal is obtained.

(4) Synthesis of 4- (3,5-difluoro-4-iodophenyl) cyclohexanone 4- (3,5-difluoro-4-cyanophenyl) cyclohexane-
160 ml of formic acid and 160 ml of toluene are added to 32.4 g of 1-one ethylene acetal, and the mixture is heated and stirred at 60 ° C. for 3 hours. Cool to room temperature, add water and 160 ml, and separate the organic layer. The extract is washed successively with a saturated aqueous solution of sodium bicarbonate, water and a saturated saline solution and dried over anhydrous magnesium sulfate. The solvent was distilled off and 4- (3,5-difluoro-
27.4 g of 4-iodophenyl) cyclohexanone are obtained.

(5) 4- (4-methylenecyclohexyl) -2,6-
Synthesis of difluorobenzonitrile (compound No. 1) methyltriphenylphosphonium iodide 54 g in THF 240 m
l, cool the internal temperature to 10 ° C or lower, and add 15 g of potassium-t-butoxide. The internal temperature was cooled to 0 ° C or less, and 4- (3,5-
Difluoro-4-iodophenyl) cyclohexanone 27.4g
Is added dropwise at a rate such that the internal temperature does not exceed 0 ° C.
Stir for 1 hour. After returning to room temperature, 10 ml of water is added, the solvent is distilled off, 250 ml of hexane is added, and insolubles are filtered off. The solvent was distilled off, the residue was purified by silica gel column chromatography (solvent: toluene), and further recrystallized from methanol to give 4- (4-methylenecyclohexyl) -2,6-difluorobenzonitrile (Compound No. 1) in 8.3. g obtained. The melting point of this compound was 42 ° C.

Example 2 trans-4- (3,4,5-trifluorophenyl) -4′-methylenebicyclohexyl (compound N
Synthesis of o.2)

Embedded image

(1) Synthesis of trans-4 ′-(3,4,5-trifluorophenyl) -bicyclohexyl-4-one 13.6 g of magnesium was suspended in 26 ml of THF, and 3,4,5-trifluoro1- A solution of 107 g of bromobenzene in 430 ml of THF is added dropwise at a rate at which THF is gently refluxed, and the mixture is further stirred for 1 hour. Four,
4'-bicyclohexanedione monoethylene acetal 100
g of THF in 400 ml was added dropwise at room temperature, and the mixture was further stirred for 1 hour. One liter of saturated ammonium chloride is added, extracted with 1 liter of toluene, and washed three times with a saturated saline solution. After drying over anhydrous magnesium sulfate, the solvent is distilled off, and the residue is dissolved in 750 ml of pyridine. Under ice cooling, thionyl chloride (55.5) was added dropwise at a rate such that the internal temperature did not exceed 10 ° C, and the mixture was further stirred for 3 hours. The solution is poured onto crushed ice, and the precipitated crystals are filtered, washed, and dried under reduced pressure. 750 ml of ethyl acetate and 15 g of 5% palladium carbon
And stirred at a hydrogen pressure of 0.5 MPa for 6 hours. The catalyst was filtered off, the solvent was distilled off, 600 ml of DMF and potassium t-butoxide
Add 48 g and stir at room temperature for 3 hours. The solution was poured on crushed ice, and the precipitated crystals were filtered, washed, dried under reduced pressure, recrystallized from ethanol, and trans-4 ′-(3,4,5-trifluorophenyl) -bicyclohexyl-4. -89 g of ethylene acetal are obtained.

(2) Synthesis of trans-4 '-(3,4,5-trifluorophenyl) -bicyclohexyl-4-one trans-4'-(3,4,5-trifluorophenyl) -bicyclohexyl -4-one Ethylene acetal 88g to formic acid 350ml
And 350 ml of toluene, and the mixture is heated and stirred at 60 ° C. for 3 hours. Cool to room temperature, add 350 ml of water and separate the organic layer. The extract is washed successively with a saturated aqueous solution of sodium bicarbonate, water and a saturated saline solution, and dried over anhydrous magnesium sulfate. The solvent is distilled off and
-4 '-(3,4,5-trifluorophenyl) -bicyclohexyl-
Obtain 74 g of 4-one.

(3) Synthesis of trans-4- (3,4,5-trifluorophenyl) -4′-methylenebicyclohexyl (Compound No. 2) 47 g of methyltriphenylphosphonium iodide was added to 200 m of THF.
The suspension is cooled to an internal temperature of 10 ° C. or lower, and 13 g of potassium-t-butoxide is added. A solution of trans-4 ′-(3,4,5-trifluorophenyl) -bicyclohexyl-4-one (26 g) in THF (110 ml) is added dropwise at a rate such that the internal temperature does not exceed 10 ° C., and the mixture is further stirred for 1 hour. Return to room temperature, add 10 ml of water, evaporate the solvent,
Hexane (260 ml) is added, and the insolubles are filtered off. The solvent was distilled off, the residue was purified by silica gel column chromatography (solvent: hexane), and further recrystallized from ethanol to give trans-4- (3,4,5-trifluorophenyl) -4'-methylenebicyclohexyl (compound No. 2) was obtained in an amount of 9.0 g. The melting point of this compound was 24 ° C.

Example 3 Preparation of Liquid Crystal Composition (1) Host Liquid Crystal Composition (H)

Embedded image Was prepared, and the Δn of this composition was measured to be 0.090.

Next, 80% of the host liquid crystal (H) and the embodiment
Compound No. 1 of the present invention produced in No. 1

Embedded image A liquid crystal composition (H-1) consisting of 20% was prepared, and its Δn was measured. As a result, it was 0.083, and it was possible to significantly reduce Δn.

Comparative Example 1 Comparative compound A having a similar skeleton in Example 3 in place of No. 1 compound

Embedded image Was mixed with the composition (H) by 20% to prepare a composition (HA), and its Δn
Was 0.091, which was lower than that of compound No. 1. (

Example 4) Preparation of liquid crystal composition (2) Compound No. 2 of the present invention produced in Example 2

Embedded image A liquid crystal composition (H-2) consisting of 20% and 80% of the host liquid crystal (H)
Was measured and Δn was measured to be 0.079, indicating that Δn could be significantly reduced.

(Comparative Example 2) Comparative Example B having a similar skeleton in Example 4 in place of the compound of No. 2

Embedded image Was mixed with the composition (H) by 20% to prepare a composition (HB), and its Δn
Was 0.083, which was lower than that of compound No. 2.

Example 5 and Comparative Example 3 Preparation of Liquid Crystal Composition
(3) Liquid crystal composition containing No. 2 compound produced in Example 2
(M)

Embedded image And a liquid crystal composition (MR) containing no compound of No. 2

[0087]

Embedded image Was adjusted, and the physical properties thereof were measured. The results are shown in Table 1.

[0088]

[Table 1] As shown in Table 1, the liquid crystal composition of Example 5 has the general formula (I)
It can be seen that it has an extremely low Δn as compared with the liquid crystal composition of Comparative Example 3 not containing the compound of Using this liquid crystal composition, a TFT liquid crystal display element having excellent display quality could be produced.

Example 6 Preparation of Liquid Crystal Composition (4) Liquid Crystal Composition (J) Currently Practical

Embedded image

The Δn of this composition was 0.142. A liquid crystal composition (J-1) composed of 90% of this liquid crystal composition (J) and 10% of the compound of the present invention No. 1 obtained in Example 1 (J-1) was prepared, and the measured Δn was 0.086. Was. (

Example 7) Preparation of Liquid Crystal Composition (5) A liquid crystal composition comprising 90% of the liquid crystal composition (J) and 10% of the compound of the present invention No. 2 obtained in Example 2 (10%) Jn) was prepared and measured, and the Δn was 0.077. From the above, No. 1 and N
The addition of the compound of o.2 shows a clear improvement in Δn.

As described above, it can be seen that the compounds No. 1 and No. 2 according to the present invention have an effect superior to the conventional compounds in obtaining a liquid crystal composition having a small Δn.

[0093]

The compound having an exomethylene group provided by the present invention is extremely excellent in compatibility with a liquid crystal compound or a composition generally used at present, and has a small Δn. Further, as shown in Examples, it is industrially easy to produce, colorless and chemically stable.

Accordingly, a liquid crystal composition containing the same is extremely useful as a practical liquid crystal, particularly for a liquid crystal display requiring a small Δn.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) G02F 1/13 500 G02F 1/13 500 (72) Inventor Haruyoshi Takatsu 3-6 Nakahara, Higashiyamato City, Tokyo 27 F term (reference) 4H006 AA01 AA03 AB64 EA35 4H027 BA01 BB04 BC04 BD01 BD03 BD07 BD09 BD24 BE04 CB01 CB02 CC04 CD04 CL01 CL04 CM01 CM04 CN01 CN04 CQ01 CQ04 CR04 CT02 CT04 CU04 CW01 CW02 DE04 DK04 DK05

Claims (12)

[Claims] [Claim 1] General formula (I) (In the formula, R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms,
Represents an alkoxyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms or an alkenyloxy group having 3 to 10 carbon atoms, wherein A, B and C are Each independently represents a single bond, -CO-,-
COO -, - OCO -, - CH = N -, - N = CH -, - C≡C -, - CH 2 CH 2 -, -
CH ₂ CH ₂ CH _2- , -CH ₂ CH ₂ CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -CF ₂ O
-, -OCF _2- , -CH = NN = CH-, -CF = CF-, -CH = CH-, -CH ₂
CH ₂ CH = CH-, -CH = CHCH ₂ CH _2- , -CH ₂ CH = CHCH _2- ,
L, M and N are each independently a 1,4-phenylene group (in which 1, 2, or 3 hydrogen atoms may be replaced by a fluorine atom), a 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group,
1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group,
Decahydronaphthalene-2,6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2 , 6-diyl group
(One, two or three hydrogen atoms in this group may be replaced by fluorine atoms), 2,6-naphthylene group (in this group
1, 2 or 3 hydrogen atoms may be replaced by fluorine atoms), a phenanthrene-2,7-diyl group (1 in this group)
Or two hydrogen atoms may be replaced by fluorine atoms), a 9,10-dihydrophenanthrene-2,7-diyl group (in which one or two hydrogen atoms are replaced by fluorine atoms) 1,2,3,4,4a, 9,10a-octahydrophenanthrene 2,7-diyl group (in which 1, 2, or 3 hydrogen atoms have been replaced by fluorine atoms) Represents a fluorene 2,7-diyl group (1 or 2 hydrogen atoms in this group may be replaced by a fluorine atom), X is a hydrogen atom, an alkyl having 1 to 10 carbon atoms. Group, an alkoxyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms or an alkenyloxy group having 3 to 10 carbon atoms, a cyano group, a fluorine atom, Chlorine atom, trifluoromethoxy group, trifluoromethyl group, difluoromethoxy group, 2,2,2-trifluoro Represents a butoxy group, l and n each independently represents an integer of to 0 or 1, Here, R is an alkyl group, l and n
0, A is a single bond, N is a 1,4-phenylene group, when X represents a cyano group, the phenylene group of N has at least one fluorine atom, R is an alkyl group, l and n are 0 A is a single bond, N is a 1,4-phenylene group, when X represents an alkoxyl group, R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X is an alkoxyl group having 1 to 5 carbon atoms. Represent. ). 2. A compound according to claim 1, wherein R in formula (I) represents a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms.
The compound according to 1. 3. The compound according to claim 1, wherein 1 and n represent 0 in the general formula (I). 4. The compound according to claim 1, wherein A in formula (I) represents a single bond. 5. The compound according to claim 1, wherein 1 represents 1 and n represents 0 in the general formula (I). 6. The compound according to claim 1, wherein B in formula (I) represents a single bond. 7. The compound according to claim 1, wherein R in formula (I) represents a hydrogen atom. 8. A liquid crystal composition comprising the compound represented by the general formula (I) according to claim 1, 2, 3, 4, 5, 6, or 7. 9. A liquid crystal device comprising the liquid crystal composition according to claim 8 as a constituent. 10. Use of the liquid crystal composition according to claim 8,
An ultra-twisted nematic (STN) liquid crystal display device having a twist angle of 220 ° to 270 °. 11. An active matrix (AM) liquid crystal display device using the liquid crystal composition according to claim 8. 12. A reflective liquid crystal display device using the liquid crystal composition according to claim 9.