JPH09110837A - Pyrimidine compound, liquid crystal composition and liquid crystal element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new pyrimidine compound useful as a constituent component of a liquid crystal compound or a liquid crystal composition suitable for improving various characteristics such as high-speed responsiveness, orienting properties and a high contrast ratio when blending thereof in a ferroelectric liquid crystal composition. SOLUTION: This pyrimidine compound is represented by formula I [R1 and R2 are each an alkyl, an alkoxy, an alkenyl or an alkenyloxy; A1 and A2 are each 1,4-phenylene, pyridine-2,5-diyl or trans-1,4-cyclohexylene; X1 and X2 are each a single bond, COO, OCO, OCH2 , etc.; (a), (b), (p) and (q) are each 0 or 1] or formula II [R3 and R4 are each an alkyl or an alkenyl; (m) and (n) are each 0 or 1], e.g. a compound represented by formula III or IV. The compound represented by formula I, e.g. a compound represented by formula V (Z1 is R1 , R3 , etc.) is obtained from, e.g. a 2-bromonaphthalene derivative by passing through 6 steps. The compound represented by formula II is obtained by reacting, e.g. the final intermediate for producing the compound represented by formula I with a compound represented by the formula R4 -Hal (Hal is a halogen), R4 -OTs (Ts is tosyl) or R4 OH.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel pyrimidine compound. More specifically, it relates to a novel pyrimidine compound useful as a component of a liquid crystal composition used for a liquid crystal display device, a liquid crystal composition containing the compound, and a liquid crystal device using the liquid crystal composition.

[0002]

2. Description of the Related Art At present, a TN (twisted nematic) type display system is most widely used as a liquid crystal display device. This TN type display system is inferior to a light emitting type device (cathode tube, electroluminescence, plasma display, etc.) in response time.
Therefore, an STN (super twisted nematic) type display device having a twist angle of 180 to 270 ° has been developed, but the response time is still poor. In this way, various efforts have been made to improve, but the response time is short.
N-type liquid crystal display elements have not been realized yet. However, in a new display method using a ferroelectric liquid crystal, which has been actively researched in recent years, there is a possibility of significantly improving the response time [NA Clark et.al., Applied Phy
s. lett., 36, 899 (1980)].

This method utilizes a chiral smectic phase such as a chiral smectic C phase exhibiting ferroelectricity. The ferroelectric phase is chiral smectic C
Not only phase but also chiral smectic F, G, H, I
It is known that such phases are also ferroelectric liquid crystal phases exhibiting ferroelectricity. These smectic liquid crystal phases belong to a tilt type chiral smectic phase, but practically, chiral smectic C, which has a low viscosity among them, is used.
Phases are preferred. Various liquid crystal compounds exhibiting a chiral smectic C phase have been studied so far, and many compounds have already been searched for and manufactured. However, many characteristics (high-speed response, orientation, high contrast ratio, etc.) required when actually applied to ferroelectric liquid crystal display elements
To optimize the memory stability and the temperature dependence of these properties), a single compound cannot be used at present, but a ferroelectric liquid crystal obtained by mixing several liquid crystal compounds The composition is used.

Further, as the ferroelectric liquid crystal composition, not only a ferroelectric liquid crystal composition consisting only of a compound exhibiting a ferroelectric liquid crystal phase, but also a non-chiral smectic C in JP-A-60-36003 is disclosed. , F, G, H, I, etc. are used as a basic substance, and one or a plurality of compounds showing a ferroelectric liquid crystal phase are mixed with the basic substance to obtain the whole as a ferroelectric liquid crystal composition. It has been reported. Further, a compound and a composition showing a phase such as a smectic C phase are used as a basic substance, and one or a plurality of compounds which are optically active but do not show a ferroelectric liquid crystal phase are mixed to obtain a whole ferroelectric liquid crystal composition. There are also reports (Mol.Cryst.Liq.Cryst., 89,327 (1982)). To summarize these, one or more compounds that are optically active regardless of whether or not they exhibit a ferroelectric liquid crystal phase and a compound that exhibits a phase such as a non-chiral smectic C phase It is understood that the liquid crystal composition can be constituted.
As described above, it is possible to use various compounds as constituent components of the liquid crystal composition, but practically, a liquid crystal compound or a liquid crystal compound exhibiting a smectic C phase or a chiral smectic C phase in a wide temperature range including room temperature is used. A mixture is desirable. As the components of these smectic C liquid crystal compositions, phenylbenzoate-based liquid crystal compounds, biphenyl-based liquid crystal compounds, phenylpyrimidine-based liquid crystal compounds, and tolan-based liquid crystal compounds are known. However, it cannot be said that the liquid crystal compositions containing these compounds as constituents still have sufficient properties. Many of the chiral smectic C liquid crystal compositions studied up to now have a chevron structure (a layer structure bent in a V shape), and therefore, spontaneous polarization response to an applied electric field is efficiently performed. However, the response time may be increased or the contrast ratio may be decreased due to the zigzag alignment defect. Therefore, a liquid crystal material having a bookshelf layer structure or a non-chiral or chiral smectic C phase having a structure close to that of the bookshelf layer is desired. As a liquid crystal compound and a composition having a bookshelf layer structure, a compound having a naphthalene ring and a liquid crystal composition containing the same (Japanese Patent Application Laid-Open No. 6-122875) are known, and various compounds having a naphthalene ring are known. Synthetic and under investigation [US Pat. No. 4,585,575, JP-A-6
-2055, JP-A-6-25060, JP-A-6-40985, JP-A-6-228057 (German Patent Publication No. 4240041) and the like].

However, these compounds still have the following problems. Compatibility with various liquid crystal compounds when used as a liquid crystal composition, that is, when a liquid crystal composition is mixed with several kinds of compounds, specific components are precipitated as crystals from the liquid crystal phase due to poor compatibility. And to significantly reduce the liquid crystal temperature range of the liquid crystal compound by mixing. Optimization of tilt angle (tilt angle) θ of liquid crystal molecules in smectic C phase [Relational expression between incident light intensity I and transmitted light intensity I ₀ [I / I ₀ in a liquid crystal device utilizing birefringence of liquid crystal]
= Sin ² 4θ · sin ² (πdΔn / λ), where
d is the cell thickness, Δn is the refractive index anisotropy, and λ is the wavelength of incident light.], the contrast ratio becomes maximum at θ = 22.5 °]. Alignment characteristics on various alignment films (elimination of alignment defects such as zigzag alignment defects and alignment uniformity). Therefore, under the present circumstances, various materials showing a smectic C phase or a chiral smectic C phase were tested, and the response time, memory stability,
It is necessary to optimize the layer structure in the smectic C phase, the tilt angle, the alignment characteristics on the alignment film, and the compatibility between the liquid crystal compounds in the liquid crystal composition.

[0006]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention An object of the present invention is to achieve high-speed response, orientation, high contrast ratio, etc. when compounded in a ferroelectric liquid crystal composition for practical use of the ferroelectric liquid crystal element. The present invention provides a liquid crystal compound suitable for improving various properties of the above, or a compound useful as a constituent component of a liquid crystal composition, a liquid crystal composition containing the compound, and a liquid crystal device using the composition. .

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found a certain pyrimidine compound, and have reached the present invention. That is,
The present invention relates to a pyrimidine compound represented by the general formula (1) (chemical formula 5), and the present invention relates to a pyrimidine compound represented by the general formula (2) (chemical formula 6). Furthermore, the present invention provides a compound represented by the general formula (3)
Alternatively, the present invention relates to a pyrimidine compound represented by the general formula (4) (Chemical formula 8), and further comprises at least one pyrimidine compound represented by the general formula (1) or the general formula (2). And a liquid crystal element using the composition.

[0008]

Embedded image [Wherein, R ₁ and R ₂ are a linear or branched alkyl group or alkoxy group having 1 to 24 carbon atoms which may be substituted with a halogen atom, or a linear or branched chain having 2 to 24 carbon atoms. Represents an alkenyl group or an alkenyloxy group, and is not adjacent to each other in these groups-CH ₂ -groups (excluding Y ₁ , Y ₂ or -CH ₂ -groups bonded to an aromatic ring). Is an oxygen atom, a sulfur atom, −
It may be replaced by a CO- group, a -COO- group or a -OCO- group, and R ₁ and R ₂ may have an asymmetric carbon, which is optically active. Also, A ₁ and A ₂ represent a substituted or unsubstituted 1,4-phenylene group, pyridine-2,5-diyl group or trans-1,4-cyclohexylene group,
X ₁ and X ₂ are a single bond, a —COO— group, and —OCO—
A group, an —OCH ₂ — group or a —CH ₂ O— group, Y ₁
And Y ₂ is a —COO— group or a —OCO— group (provided that
When Y ₁ is an —OCO— group, R ₁ is not an alkoxy group or an alkenyloxy group, and Y ₂ is —COO—.
In the case of a group, R ₂ is not an alkoxy group or an alkenyloxy group), a, b, p and q each represent 0 or 1, and a + b + p + q is not 0]

[0009]

Embedded image [In the formula, R ₃ and R ₄ represent a linear or branched alkyl group or alkenyl group having 3 to 24 carbon atoms which may be substituted with a halogen atom, m and n represent 0 or 1, and R _At least one-present in the alkyl group or alkenyl group of at least one of ₃ and R ₄ ;
CH ₂ - group (provided that adjacent -CH ₂ - except for the group - group, and -CH ₂ that is bound to an oxygen atom or an aromatic ring)
Is replaced by an oxygen atom, and the branched alkyl group or alkenyl group may have an asymmetric carbon, and the asymmetric carbon may be optically active.]

[0010]

Embedded image [In the formula, B ₁ represents a hydrogen atom or a benzyl group, and R ₂
Has 1 to 24 carbon atoms which may be substituted with a halogen atom.
Straight or branched chain alkyl group or an alkoxy group having, or represents a straight-chain or branched alkenyl group or alkenyloxy group having 2 to 24 carbon atoms, -CH ₂ nonadjacent present in the group -Group (however,
Y ₁ , Y ₂ or a —CH ₂ — group bonded to the aromatic ring is excluded) is an oxygen atom, a sulfur atom, a —CO— group, a —COO—
Or a —OCO— group, R ₂ may have an asymmetric carbon, the asymmetric carbon may be optically active, and A ₂ may be substituted or Unsubstituted 1,4-phenylene group, pyridine-2,5-
Represents a diyl group or a trans-1,4-cyclohexylene group, and X ₂ represents a single bond, a —COO— group, a —OCO—
A group, a —OCH ₂ — group or a —CH ₂ O— group, and Y ₂
Is a —COO— group or a —OCO— group (provided that Y ₂ is —C.
When it is an OO- group, R ₂ is not an alkoxy group or an alkenyloxy group), b and q each represent 0 or 1, and b + q is not 0]

[0011]

Embedded image [In the formula, B ₁ represents a hydrogen atom or a benzyl group, and R ₄
Has 3 to 24 carbon atoms which may be substituted with a halogen atom.
Represents a straight chain or branched chain alkyl group or alkenyl group, n represents 0 or 1, and at least one -CH ₂ present in the alkyl group or alkenyl group of R ₄
- group (provided that adjacent -CH ₂ - groups, and -CH ₂ attached to an oxygen atom or an aromatic ring - excluding groups) is replaced by an oxygen atom, The alkyl group or alkenyl branched The group may have an asymmetric carbon, and the asymmetric carbon may be optically active.]

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The pyrimidine compound represented by the general formula (1) of the present invention has the following (1-A), (1-B), (1-C) or (1) when p and q are 0 or 1, respectively. −
D) has four types of structures (Chemical Formula 9). Furthermore, (1-
In A), (1-B), (1-C) and (1-D), the compounds in which a and b are 0 or 1 respectively,
(1-A1 to A3) and (1-B1 to
B4), (1-C1 to C4) or (1-D1 to D4)
The structure of (Chemical Formula 10) is adopted. Preferably, (1-A),
(1-B) or (1-C), and more preferably
(1-A1), (1-A2), (1-A3), (1-B
1), (1-B3), (1-C1) or (1-C3)
There are seven types of structures represented by.

[0013]

Embedded image

[0014]

Embedded image

In the pyrimidine compound represented by the general formula (1) of the present invention, R ₁ and R ₂ are linear or branched alkyl groups or alkoxy having 1 to 24 carbon atoms which may be substituted with a halogen atom. Or a linear or branched alkenyl group or alkenyloxy group having 2 to 24 carbon atoms, R ₁ and R ₂ may have an asymmetric carbon, and the asymmetric carbon is optically active. It may be. Further, non-adjacent —CH ₂ — groups present in these alkyl group, alkoxy group, alkenyl group and alkenyloxy group (provided that Y ₁ , Y ₂ or —CH ₂ — group bonded to an aromatic ring is present. May be replaced by an oxygen atom, a sulfur atom, a -CO- group, a -COO- group and a -OCO- group.

Examples of R ₁ and R ₂ include (1) a linear or branched alkyl or alkoxy group (hereinafter abbreviated as an alkyl group or an alkoxy group) (2) a hydrogen atom is replaced with a halogen atom. Linear or branched alkyl group or alkoxy group (hereinafter abbreviated as haloalkyl group or haloalkoxy group) (3) Linear or branched alkyl group or alkoxy group in which a —CH ₂ — group is replaced by an oxygen atom (Hereinafter, abbreviated as an alkoxyalkyl group and an alkoxyalkoxy group.) (4) A linear or branched alkenyl group or alkenyloxy group in which a —CH ₂ — group is replaced by an oxygen atom (hereinafter, alkenyloxyalkyl group, alkenyl group). abbreviated as oxy alkoxy group) (5) -CH ₂ - group is replaced by an oxygen atom, a hydrogen atom Straight or branched chain alkyl or alkoxy group has been replaced with a halogen atom (hereinafter, halo alkoxyalkyl group, abbreviated as halo alkoxyalkoxy group) (6) -CH ₂ - straight-chain groups is replaced by a sulfur atom Or a branched chain alkyl group or alkoxy group (hereinafter abbreviated as an alkylthioalkyl group or an alkylthioalkoxy group) (7) a straight chain or branched chain alkyl group or alkoxy in which a —CH ₂ — group is replaced by a —CO— group Group (hereinafter, abbreviated as alkylcarbonylalkyl group, alkylcarbonylalkoxy group) (8) A linear or branched alkyl group or alkoxy group in which a —CH ₂ — group is replaced by a —COO— group (hereinafter, alkylcarbonyl) Abbreviated as oxyalkyl group and alkylcarbonyloxyalkoxy group (9) A linear or branched alkyl group or alkoxy group in which a —CH ₂ — group is replaced by an —OCO— group (hereinafter abbreviated as an alkoxycarbonylalkyl group or an alkoxycarbonylalkoxy group) (10) Examples thereof include linear or branched alkenyl or alkenyloxy groups.

The carbon number of R ₁ and R ₂ is preferably
It is 4 to 22, and more preferably 5 to 20. R ₁ and R ₂ are preferably an alkyl group, an alkoxy group, an alkoxyalkyl group, an alkoxyalkoxy group, an alkylthioalkyl group, an alkylthioalkoxy group, an alkylcarbonylalkyl group, an alkylcarbonylalkoxy group, an alkylcarbonyloxyalkyl group, an alkyl group. A carbonyloxyalkoxy group, an alkoxycarbonylalkyl group, an alkoxycarbonylalkoxy group, an alkenyl group and an alkenyloxy group, more preferably an alkyl group, an alkoxy group, an alkoxyalkyl group, an alkoxyalkoxy group, an alkylcarbonyloxyalkyl group, an alkylcarbonyl. Oxyalkoxy group, alkoxycarbonylalkyl group, alkoxycarbonylalkoxy group, alkenyl group and alkenyloxy group is there.

Specific examples of the groups represented by R ₁ and R ₂ include, for example, methyl group, ethyl group, n-propyl group,
n-butyl group, n-pentyl group, n-hexyl group, n-
Heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n
-Hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, n-heneicosyl group, n-docosyl group, n-tricosyl group, n
-Tetracosyl group, 1-methylethyl group, 1,1-dimethylethyl group, 1-methylpropyl group, 1-methylbutyl group, 1-methylpentyl group, 1-methylhexyl group,
1-methylheptyl group, 1-methyloctyl group, 1-methylnonyl group, 1-methyldecyl group, 2-methylpropyl group, 2-methylbutyl group, 2-ethylbutyl group, 2-
Methylpentyl, 2-methylhexyl, 2-methylheptyl, 2-ethylhexyl, 2-methyloctyl, 2-methylnonyl, 2-methyldecyl, 2,
3-dimethylbutyl group, 2,3,3-trimethylbutyl group, 3-methylbutyl group, 3-methylpentyl group, 3-
Ethylpentyl, 4-methylpentyl, 4-ethylhexyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 2,4,4-trimethylpentyl, 2,3,3,4-tetra Methylpentyl group, 3-methylhexyl group, 2,5-dimethylhexyl group, 3-ethylhexyl group, 3,5,5, -trimethylhexyl group, 4-methylhexyl group, 6-methylheptyl group,
An alkyl group such as a 3,7-dimethyloctyl group or a 6-methyloctyl group and a corresponding alkoxy group (the corresponding alkoxy group means, for example, a methoxy group for a methyl group, the same applies hereinafter),

2-fluoroethyl group, 1,2-difluoroethyl group, 2-fluoro-n-propyl group, 3-fluoro-n-propyl group, 1,3-difluoro-n-propyl group, 2,3- Difluoro-n-propyl group, 2-fluoro-n-butyl group, 3-fluoro-n-butyl group,
4-fluoro-n-butyl group, 3-fluoro-2-methylpropyl group, 2,3-difluoro-n-butyl group,
2,4-difluoro-n-butyl group, 3,4-difluoro-n-butyl group, 2-fluoro-n-pentyl group, 3
-Fluoro-n-pentyl group, 5-fluoro-n-pentyl group, 2,4-difluoro-n-pentyl group, 2,5
-Difluoro-n-pentyl group, 2-fluoro-3-methylbutyl group, 2-fluoro-n-hexyl group, 3-fluoro-n-hexyl group, 4-fluoro-n-hexyl group, 5-fluoro-n- Hexyl group, 6-fluoro-n
-Hexyl group, 2-fluoro-n-heptyl group, 4-fluoro-n-heptyl group, 5-fluoro-n-heptyl group, 2-fluoro-n-octyl group, 3-fluoro-n
-Octyl group, 6-fluoro-n-octyl group, 4-fluoro-n-nonyl group, 7-fluoro-n-nonyl group,
3-fluoro-n-decyl group, 6-fluoro-n-decyl group, 4-fluoro-n-dodecyl group, 8-fluoro-
n-dodecyl group, 5-fluoro-n-tetradecyl group,
9-fluoro-n-tetradecyl group, 2-chloroethyl group, 3-chloro-n-propyl group, 2-chloro-n-butyl group, 4-chloro-n-butyl group, 2-chloro-n-
Pentyl group, 5-chloro-n-pentyl group, 5-chloro-n-hexyl group, 4-chloro-n-heptyl group, 6-
A chloro-n-octyl group, a 7-chloro-n-nonyl group,
3-chloro-n-decyl group, 8-chloro-n-dodecyl group, trifluoromethyl group, perfluoroethyl group, perfluoro-n-propyl group, perfluoro-n-butyl group, perfluoro-n-pentyl Group, perfluoro-
n-hexyl group, perfluoro-n-heptyl group, perfluoro-n-octyl group, perfluoro-n-nonyl group, perfluoro-n-decyl group, perfluoro-n-
Undecyl group, perfluoro-n-dodecyl group, perfluoro-n-tetradecyl group,

1-hydroperfluoroethyl group, 1-hydroperfluoro-n-propyl group, 1-hydroperfluoro-n-butyl group, 1-hydroperfluoro-n-
Pentyl group, 1-hydroperfluoro-n-hexyl group, 1-hydroperfluoro-n-heptyl group, 1-hydroperfluoro-n-octyl group, 1-hydroperfluoro-n-nonyl group, 1-hydro Perfluoro-n-
Decyl group, 1-hydroperfluoro-n-undecyl group, 1-hydroperfluoro-n-dodecyl group, 1-hydroperfluoro-n-tetradecyl group, 1,1-dihydroperfluoroethyl group, 1,1- Dihydroperfluoro-n-propyl group, 1,1-dihydroperfluoro-n-butyl group, 1,1-dihydroperfluoro-n-
Pentyl group, 1,1-dihydroperfluoro-n-hexyl group, 1,1-dihydroperfluoro-n-heptyl group, 1,1-dihydroperfluoro-n-octyl group,
1,1-dihydroperfluoro-n-nonyl group, 1,1
-Dihydroperfluoro-n-decyl group, 1,1-dihydroperfluoro-n-undecyl group, 1,1-dihydroperfluoro-n-dodecyl group, 1,1-dihydroperfluoro-n-tetradecyl group, 1 , 1-Dihydroperfluoro-n-pentadecyl group, 1,1-dihydroperfluoro-n-hexadecyl group, 1,1,2-trihydroperfluoroethyl group, 1,1,3-trihydroperfluoro-n -Propyl group, 1,1,3-trihydroperfluoro-n-butyl group, 1,1,4-trihydroperfluoro-n-butyl group, 1,1,4-trihydroperfluoro-n-pentyl Group, 1,1,5-trihydroperfluoro-n-pentyl group, 1,1,3-trihydroperfluoro-n-hexyl group, 1,1,6-trihydroperfluoro -n- hexyl group, 1,1,5-tri hydro perfluoro -n- heptyl, 1,1,7-
Trihydroperfluoro-n-heptyl group, 1,1,8
-Trihydroperfluoro-n-octyl group, 1,1,
9-trihydroperfluoro-n-nonyl group, 1,1,
11-trihydroperfluoro-n-undecyl group,

2- (perfluoroethyl) ethyl group, 2
-(Perfluoro-n-propyl) ethyl group, 2- (perfluoro-n-butyl) ethyl group, 2- (perfluoro-n-pentyl) ethyl group, 2- (perfluoro-n
-Hexyl) ethyl group, 2- (perfluoro-n-heptyl) ethyl group, 2- (perfluoro-n-octyl)
Ethyl group, 2- (perfluoro-n-decyl) ethyl group, 2- (perfluoro-n-nonyl) ethyl group, 2-
(Perfluoro-n-dodecyl) ethyl group, 2-trifluoromethylpropyl group, 3- (perfluoro-n-propyl) propyl group, 3- (perfluoro-n-butyl) propyl group, 3- (perfluoro -N-hexyl)
Propyl group, 3- (perfluoro-n-heptyl) propyl group, 3- (perfluoro-n-octyl) propyl group, 3- (perfluoro-n-decyl) propyl group, 3
-(Perfluoro-n-dodecyl) propyl group, 4-
(Perfluoroethyl) butyl group, 4- (perfluoro-n-propyl) butyl group, 4- (perfluoro-n-
Butyl) butyl group, 4- (perfluoro-n-pentyl) butyl group, 4- (perfluoro-n-hexyl) butyl group, 4- (perfluoro-n-heptyl) butyl group, 4- (perfluoro-) n-octyl) butyl group, 4
-(Perfluoro-n-decyl) butyl group, 5- (perfluoro-n-propyl) pentyl group, 5- (perfluoro-n-butyl) pentyl group, 5- (perfluoro-
n-pentyl) pentyl group, 5- (perfluoro-n-
Hexyl) pentyl group, 5- (perfluoro-n-heptyl) pentyl group, 5- (perfluoro-n-octyl) pentyl group, 6- (perfluoroethyl) hexyl group, 6- (perfluoro-n-propyl) ) Hexyl group,
6- (perfluoro-n-butyl) hexyl group, 6-
(Perfluoro-n-hexyl) hexyl group, 6- (perfluoro-n-heptyl) hexyl group, 6- (perfluoro-n-octyl) hexyl group, 7- (perfluoroethyl) heptyl group, 7- ( Perfluoro-n-propyl) heptyl group, 7- (perfluoro-n-butyl)
A haloalkyl group such as a heptyl group, a 7- (perfluoro-n-pentyl) heptyl group and a corresponding haloalkoxy group,

Methoxymethyl group, 2-methoxyethyl group, 3-methoxypropyl group, 4-methoxybutyl group,
5-methoxypentyl group, 6-methoxyhexyl group, 7
-Methoxyheptyl group, 8-methoxyoctyl group, 9-
Methoxynonyl group, 10-methoxydecyl group, ethoxymethyl group, 2-ethoxyethyl group, 3-ethoxypropyl group, 4-ethoxybutyl group, 5-ethoxypentyl group, 6-ethoxyhexyl group, 7-ethoxyheptyl group, 8-ethoxyoctyl group, 9-ethoxynonyl group,
10-ethoxydecyl group, n-propoxymethyl group, 2
-N-propoxyethyl group, 3-n-propoxypropyl group, 4-n-propoxybutyl group, 5-n-propoxypentyl group, 6-n-propoxyhexyl group, 7-n
-Propoxyheptyl group, 8-n-propoxyoctyl group, 9-n-propoxynonyl group, 10-n-propoxydecyl group, n-butoxymethyl group, 2-n-butoxyethyl group, 3-n-butoxypropyl group , 4-n-butoxybutyl group, 5-n-butoxypentyl group, 6-n-
Butoxyhexyl group, 7-n-butoxyheptyl group, 8
-N-butoxyoctyl group, 9-n-butoxynonyl group, 10-n-butoxydecyl group, n-pentyloxymethyl group, 2-n-pentyloxyethyl group, 3-n-
Pentyloxypropyl group, 4-n-pentyloxybutyl group, 5-n-pentyloxypentyl group, 6-n-
Pentyloxyhexyl group, 7-n-pentyloxyheptyl group, 8-n-pentyloxyoctyl group, 9-n
-Pentyloxynonyl group, 10-n-pentyloxydecyl group, n-hexyloxymethyl group, 2-n-hexyloxyethyl group, 3-n-hexyloxypropyl group, 4-n-hexyloxybutyl group, 5 -N-hexyloxypentyl group, 6-n-hexyloxyhexyl group, 7-n-hexyloxyheptyl group, 8-n-hexyloxyoctyl group, 9-n-hexyloxynonyl group, 10-n-hexyloxy Decyl group, n-heptyloxymethyl group, 2-n-heptyloxyethyl group, 3
-N-heptyloxypropyl group, 4-n-heptyloxybutyl group, 5-n-heptyloxypentyl group, 6
-N-heptyloxyhexyl group, 7-n-heptyloxyheptyl group, 8-n-heptyloxyoctyl group,
9-n-heptyloxynonyl group, 10-n-heptyloxydecyl group, octyloxymethyl group, 2-n-octyloxyethyl group, 3-n-octyloxypropyl group, 4-n-octyloxybutyl group, 5-n-octyloxypentyl group, 6-n-octyloxyhexyl group, 7-n-octyloxyheptyl group, 8-n-octyloxyoctyl group, 9-n-octyloxynonyl group, 10-n-octyl group Oxydecyl group, n-nonyloxymethyl group, 2-n-nonyloxyethyl group, 3-
n-nonyloxypropyl group, 4-n-nonyloxybutyl group, 5-n-nonyloxypentyl group, 6-n-nonyloxyhexyl group, 7-n-nonyloxyheptyl group, 8-n-nonyloxyoctyl Group, 9-n-nonyloxynonyl group, 10-n-nonyloxydecyl group, n
-Decyloxymethyl group, 2-n-decyloxyethyl group, 3-n-decyloxypropyl group, 4-n-decyloxybutyl group, 5-n-decyloxypentyl group, 6
-N-decyloxyhexyl group, 7-n-decyloxyheptyl group, 8-n-decyloxyoctyl group, 9-n
-Decyloxynonyl group, 10-n-decyloxydecyl group, 2-n-undecyloxyethyl group, 4-n-undecyloxybutyl group, 6-n-undecyloxyhexyl group, 8-n-un Decyloxyoctyl group, 10
-N-undecyloxydecyl group, 2-n-dodecyloxyethyl group, 4-n-dodecyloxybutyl group, 6-
n-dodecyloxyhexyl group, 8-n-dodecyloxyoctyl group, 10-n-dodecyloxydecyl group,

1-methyl-2-methoxyethyl group, 1-
Methyl-2-ethoxyethyl group, 1-methyl-2-n-
Propoxyethyl group, 1-methyl-2-n-butoxyethyl group, 1-methyl-2-n-pentyloxyethyl group, 1-methyl-2-n-hexyloxyethyl group, 1
-Methyl-2-n-heptyloxyethyl group, 1-methyl-2-n-octyloxyethyl group, 1-methyl-2
-N-nonyloxyethyl group, 1-methyl-2-n-decyloxyethyl group, 1-methyl-2-n-undecyloxyethyl group, 1-methyl-2-n-dodecyloxyethyl group, 2- Methoxypropyl group, 2-ethoxypropyl group, 2-n-propoxypropyl group, 2-n-butoxypropyl group, 2-n-pentyloxypropyl group,
2-n-hexyloxypropyl group, 2-n-heptyloxypropyl group, 2-n-octyloxypropyl group, 2-n-nonyloxypropyl group, 2-n-decyloxypropyl group, 2-n-un Decyloxypropyl group, 2-n-dodecyloxypropyl group, 1-methyl-
3-methoxypropyl group, 1-methyl-3-ethoxypropyl group, 1-methyl-3-n-propoxypropyl group, 1-methyl-3-n-butoxypropyl group, 1-methyl-3-n-pentyloxy Propyl group, 1-methyl-3-n-hexyloxypropyl group, 1-methyl-3
-N-heptyloxypropyl group, 1-methyl-3-n
-Octyloxypropyl group, 1-methyl-3-n-nonyloxypropyl group, 1-methyl-3-n-decyloxypropyl group, 1-methyl-3-n-undecyloxypropyl group, 1-methyl- 3-n-dodecyloxypropyl group, 3-methoxybutyl group, 3-ethoxybutyl group, 3-n-propoxybutyl group, 3-n-butoxybutyl group, 3-n-pentyloxybutyl group, 3-n- Hexyloxybutyl group, 3-n-heptyloxybutyl group, 3-n-octyloxybutyl group, 3-n-nonyloxybutyl group, 3-n-decyloxybutyl group, 3-
n-undecyloxybutyl group, 3-n-dodecyloxybutyl group, isopropoxymethyl group, 2-isopropoxyethyl group, 3-isopropoxypropyl group, 4-isopropoxybutyl group, 5-isopropoxypentyl group, 6-isopropoxyhexyl group, 7-isopropoxyheptyl group, 8-isopropoxyoctyl group, 9-isopropoxynonyl group, 10-isopropoxydecyl group,

Isobutoxymethyl group, 2-isobutoxyethyl group, 3-isobutoxypropyl group, 4-isobutoxybutyl group, 5-isobutoxypentyl group, 6-isobutoxyhexyl group, 7-isobutoxyheptyl group, 8
-Isobutoxyoctyl group, 9-isobutoxynonyl group, 10-isobutoxydecyl group, tert-butoxymethyl group, 2-tert-butoxyethyl group, 3-tert-butoxypropyl group, 4-tert-butoxybutyl group, 5-tert
-Butoxypentyl group, 6-tert-butoxyhexyl group, 7-tert-butoxyheptyl group, 8-tert-butoxyoctyl group, 9-tert-butoxynonyl group, 10-te
rt-butoxydecyl group, (2-ethylbutoxy) methyl group, 2- (2′-ethylbutoxy) ethyl group, 3-
(2'-Ethylbutoxy) propyl group, 4- (2'-ethylbutoxy) butyl group, 5- (2'-ethylbutoxy) pentyl group, 6- (2'-ethylbutoxy) hexyl group, 7- (2 '-Ethylbutoxy) heptyl group, 8-
(2'-Ethylbutoxy) octyl group, 9- (2'-ethylbutoxy) nonyl group, 10- (2'-ethylbutoxy) decyl group, (3-ethylpentyloxy) methyl group, 2- (3'- Ethylpentyloxy) ethyl group, 3
-(3'-ethylpentyloxy) propyl group, 4-
(3′-ethylpentyloxy) butyl group, 5- (3 ′
-Ethylpentyloxy) pentyl group, 6- (3'-ethylpentyloxy) hexyl group, 7- (3'-ethylpentyloxy) heptyl group, 8- (3'-ethylpentyloxy) octyl group, 9- ( 3'-ethylpentyloxy) nonyl group, 10- (3'-ethylpentyloxy) decyl group, 6- (1'-methyl-n-heptyloxy) hexyl group, 4- (1'-methyl-n-heptyl) (Oxy) butyl group,

2- (2'-methoxyethoxy) ethyl group, 2- (2'-ethoxyethoxy) ethyl group, 2-
(2'-n-propoxyethoxy) ethyl group, 2-
(2'-isopropoxyethoxy) ethyl group, 2-
(2'-n-butoxyethoxy) ethyl group, 2- (2 '
-Isobutoxyethoxy) ethyl group, 2- (2'-tert
-Butoxyethoxy) ethyl group, 2- (2'-n-pentyloxyethoxy) ethyl group, 2- [2 '-(2 "-
Ethylbutoxy) ethoxy] ethyl group, 2- (2′-n
-Hexyloxyethoxy) ethyl group, 2- [2'-
(3 "-ethylpentyloxy) ethoxy] ethyl group,
2- (2'-n-heptyloxyethoxy) ethyl group,
2- (2'-n-octyloxyethoxy) ethyl group,
2- (2'-n-nonyloxyethoxy) ethyl group, 2
-(2'-n-decyloxyethoxy) ethyl group, 2-
(2'-n-undecyloxyethoxy) ethyl group, 2
-(2'-n-dodecyloxyethoxy) ethyl group, 2
-[2 '-(2 "-methoxyethoxy) ethoxy] ethyl group, 2- [2'-(2" -ethoxyethoxy) ethoxy] ethyl group, 2- [2 '-(2 "-n-propoxyethoxy) Ethoxy] ethyl group, 2- [2 ′-(2 ″ -isopropoxyethoxy) ethoxy] ethyl group, 2-
[2 '-(2 "-n-butoxyethoxy) ethoxy] ethyl group, 2- [2'-(2" -isobutoxyethoxy)
Ethoxy] ethyl group, 2- [2 ′-(2 ″ -tert-butoxyethoxy) ethoxy] ethyl group, 2- {2′-
[2 "-(2"'-ethylbutoxy) ethoxy] ethoxy} ethyl group, 2- [2'-(2 "-n-pentyloxyethoxy) ethoxy] ethyl group, 2- [2 '-(2"
-N-hexyloxyethoxy) ethoxy] ethyl group,
2- {2 '-[2 "-(3"'-ethylpentyloxy) ethoxy] ethoxy} ethyl group, 2- [2'-
(2 "-n-heptyloxyethoxy) ethoxy] ethyl group, 2- [2 '-(2" -n-octyloxyethoxy) ethoxy] ethyl group, 2- [2'-(2 "-n-nonyloxy) Ethoxy) ethoxy] ethyl group, 2- [2 ′
-(2 "-n-decyloxyethoxy) ethoxy] ethyl group, 2- [2 '-(2" -n-undecyloxyethoxy) ethoxy] ethyl group, 2- [2'-(2 "-n-
Dodecyloxyethoxy) ethoxy] ethyl group,

2- {2 '-[2 "-(2'"-methoxyethoxy) ethoxy] ethoxy} ethyl group, 2- {2 '
-[2 "-(2"'-n-dodecyloxyethoxy) ethoxy] ethoxy} ethyl group, 2- {2'-{2 "-
[2 '"-(2-methoxyethoxy) ethoxy] ethoxy {ethoxy} ethyl group, 2- {2'-{2"-
[2 ′ ″-(2-n-dodecyloxyethoxy) ethoxy] ethoxy} ethoxy} ethyl group, 2- {2′-
{2 "-{2 '"-[2- (2-methoxyethoxy) ethoxy] ethoxy} ethoxy} ethoxy} ethyl group, 2
-(2'-methoxypropoxy) propyl group, 2-
(2'-ethoxypropoxy) propyl group, 2- (2 '
-N-propoxypropoxy) propyl group, 2- (2 '
-Isopropoxypropoxy) propyl group, 2- (2 '
-N-butoxypropoxy) propyl group, 2- (2'-
Isobutoxypropoxy) propyl group, 2- (2'-te
rt-butoxypropoxy) propyl group, 2- (2′-n
-Pentyloxypropoxy) propyl group, 2- (2 '
-N-hexyloxypropoxy) propyl group, 2-
(2'-n-heptyloxypropoxy) propyl group,
2- (2'-n-octyloxypropoxy) propyl group, 2- (2'-n-nonyloxypropoxy) propyl group, 2- (2'-n-decyloxypropoxy) propyl group, 2- (2 ' -N-undecyloxypropoxy) propyl group, 2- (2'-n-dodecyloxypropoxy) propyl group, 2- [2 '-(2 "-methoxypropoxy) propoxy] propyl group, 2- [2'-
(2 "-ethoxypropoxy) propoxy] propyl group, 2- [2 '-(2" -n-propoxypropoxy)
Propoxy] propyl group, 2- [2 '-(2 "-isopropoxypropoxy) propoxy] propyl group, 2-
[2 '-(2 "-n-butoxypropoxy) propoxy] propyl group, 2- [2'-(2" -isobutoxypropoxy) propoxy] propyl group, 2- [2'-
(2 "-tert-butoxypropoxy) propoxy] propyl group, 2- [2 '-(2" -n-pentyloxypropoxy) propoxy] propyl group, 2- [2'-(2 "
-N-hexyloxypropoxy) propoxy] propyl group, 2- [2 '-(2 "-n-heptyloxypropoxy) propoxy] propyl group, 2- [2'-(2"-
n-octyloxypropoxy) propoxy] propyl group, 2- [2 '-(2 "-n-nonyloxypropoxy) propoxy] propyl group, 2- [2'-(2" -n
-Decyloxypropoxy) propoxy] propyl group,
2- [2 '-(2 "-n-undecyloxypropoxy) propoxy] propyl group, 2- [2'-(2" -n
-Dodecyloxypropoxy) propoxy] propyl group, 2- (2'-pentyloxyethylthio) ethyl group,

2-ethoxyethoxymethyl group, 2-n-
Butoxyethoxymethyl group, 2-n-hexyloxyethoxymethyl group, 3-ethoxypropoxymethyl group, 3
-N-propoxypropoxymethyl group, 3-n-pentyloxypropoxymethyl group, 3-n-hexyloxypropoxymethyl group, 2-methoxy-1-methylethoxymethyl group, 2-ethoxy-1-methylethoxymethyl group, 2-n-butoxy-1-methylethoxymethyl group,
4-methoxybutoxymethyl group, 4-ethoxybutoxymethyl group, 4-n-butoxybutoxymethyl group, 2-
(3'-methoxypropoxy) ethyl group, 2- (3'-
Ethoxypropoxy) ethyl group, 2- (2'-methoxy-1'-methylethoxy) ethyl group, 2- (2'-ethoxy-1'-methylethoxy) ethyl group, 2- (2'-
n-butoxy-1′-methylethoxy) ethyl group, 2-
(4'-methoxybutoxy) ethyl group, 2- (4'-ethoxybutoxy) ethyl group, 2- [4 '-(2 "-ethylbutoxy) butoxy] ethyl group, 2- [4'-(3")
-Ethylpentyloxy) butoxy] ethyl group, 3-
(2'-methoxyethoxy) propyl group, 3- (2'-
Ethoxyethoxy) propyl group, 3- (2'-n-pentyloxyethoxy) propyl group, 3- (2'-n-hexyloxyethoxy) propyl group, 3- (3'-ethoxypropoxy) propyl group, 3- (3'-n-propoxypropoxy) propyl group, 3- (3'-n-butoxypropoxy) propyl group, 3- (4'-ethoxybutoxy) propyl group, 3- (5'-ethoxypentyloxy) propyl group , 4- (2'-methoxyethoxy) butyl group, 4- (2'-ethoxyethoxy) butyl group, 4-
(2'-isopropoxyethoxy) butyl group, 4-
(2'-isobutoxyethoxy) butyl group, 4- (2 '
-N-butoxyethoxy) butyl group, 4- (2'-n-
Hexyloxyethoxy) butyl group, 4- (3'-n-
Propoxypropoxy) butyl group, 4- (2'-n-propoxy-1'-methylethoxy) butyl group, 4-
[2 '-(2 "-methoxyethoxy) ethoxy] butyl group, 4- [2'-(2" -n-butoxyethoxy) ethoxy] butyl group, 4- [2 '-(2 "-n-hexyloxy) Ethoxy) ethoxy] butyl group, 5- (2′-n-
Hexyloxyethoxy) pentyl group, 2- [2'-
(2 "-n-butoxyethoxy) ethoxy] ethyl group,

A (2-ethylhexyloxy) methyl group,
(3,5,5-trimethylhexyloxy) methyl group,
(3,7-dimethyloctyloxy) methyl group, 2-
(2′-ethylhexyloxy) ethyl group, 2-
(3 ', 5', 5'-Trimethylhexyloxy) ethyl group, 2- (3 ', 7'-dimethyloctyloxy) ethyl group, 3- (2'-ethylhexyloxy) propyl group, 3- (3' , 5 ', 5'-trimethylhexyloxy) propyl group, 3- (3', 7'-dimethyloctyloxy) propyl group, 4- (2'-ethylhexyloxy) butyl group, 4- (3 ', 5' , 5'-Trimethylhexyloxy) butyl group, 4- (3 ', 7'-dimethyloctyloxy) butyl group, 5- (2'-ethylhexyloxy) pentyl group, 5- (3', 5 ', 5' -Trimethylhexyloxy) pentyl group, 5- (3 ', 7'
-Dimethyloctyloxy) pentyl group, 6- (2'-
Ethylhexyloxy) hexyl group, 6- (3 ′,
5 ′, 5′-trimethylhexyloxy) hexyl group,
Alkoxyalkyl groups such as 6- (3 ′, 7′-dimethyloctyloxy) hexyl group, and corresponding alkoxyalkoxy groups, 2-propenyloxymethyl groups, 2-
(2′-propenyloxy) ethyl group, 2- [2′-
(2 "-propenyloxy) ethoxy] ethyl group, 3-
(2′-propenyloxy) propyl group, 4- (2′-
Propenyloxy) butyl group, 5- (2′-propenyloxy) pentyl group, 6- (2′-propenyloxy)
Hexyl group, 7- (2′-propenyloxy) heptyl group, 8- (2′-propenyloxy) octyl group, 9-
(2'-propenyloxy) nonyl group, 10- (2'-
An alkenyloxyalkyl group such as a propenyloxy) decyl group, and a corresponding alkenyloxyalkoxy group,

2- (2'-trifluoromethylpropoxy) ethyl group, 4- (2'-trifluoromethylpropoxy) butyl group, 6- (2'-trifluoromethylpropoxy) hexyl group, 8- (2 ' -Trifluoromethylpropoxy) octyl group, 2- (2'-trifluoromethylbutoxy) ethyl group, 4- (2'-trifluoromethylbutoxy) butyl group, 6- (2'-trifluoromethylbutoxy) hexyl group , 8- (2'-trifluoromethylbutoxy) octyl group, 2- (2'-trifluoromethylheptyloxy) ethyl group, 4- (2'-trifluoromethylheptyloxy) butyl group, 6- (2 '
-Trifluoromethylheptyloxy) hexyl group, 8
-(2'-trifluoromethylheptyloxy) octyl group, 2- (2'-fluoroethoxy) ethyl group, 4-
(2'-fluoroethoxy) butyl group, 6- (2'-fluoroethoxy) hexyl group, 8- (2'-fluoroethoxy) octyl group, 2- (2'-fluoro-n-propoxy) ethyl group, 4 -(2'-fluoro-n-propoxy) butyl group, 6- (2'-fluoro-n-propoxy) hexyl group, 8- (2'-fluoro-n-propoxy) octyl group, 2- (3'- Fluoro-n-propoxy) ethyl group, 4- (3'-fluoro-n-propoxy) butyl group, 6- (3'-fluoro-n-propoxy) hexyl group, 8- (3'-fluoro-n-propoxy) ) Octyl group, 2- (3'-fluoro-2'-methylpropoxy) ethyl group, 4- (3'-fluoro-2'-
Methylpropoxy) butyl group, 6- (3'-fluoro-
2'-methylpropoxy) hexyl group, 8- (3'-fluoro-2'-methylpropoxy) octyl group, 2-
(2 ', 3'-difluoro-n-propoxy) ethyl group, 4- (2', 3'-difluoro-n-propoxy)
Butyl group, 6- (2 ', 3'-difluoro-n-propoxy) hexyl group, 8- (2', 3'-difluoro-n
-Propoxy) octyl group, 2- (2'-fluoro-n
-Butoxy) ethyl group, 4- (2'-fluoro-n-butoxy) butyl group, 6- (2'-fluoro-n-butoxy) hexyl group, 8- (2'-fluoro-n-butoxy) octyl group , 2- (3'-fluoro-n-butoxy) ethyl group, 4- (3'-fluoro-n-butoxy)
Butyl group, 6- (3'-fluoro-n-butoxy) hexyl group, 8- (3'-fluoro-n-butoxy) octyl group, 2- (4'-fluoro-n-butoxy) ethyl group, 4- (4′-fluoro-n-butoxy) butyl group,
6- (4'-fluoro-n-butoxy) hexyl group, 8
-(4'-fluoro-n-butoxy) octyl group, 2-
(2 ', 3'-difluoro-n-butoxy) ethyl group,
4- (2 ′, 3′-difluoro-n-butoxy) butyl group, 6- (2 ′, 3′-difluoro-n-butoxy) hexyl group, 8- (2 ′, 3′-difluoro-n-butoxy) ) Octyl group,

2- (2'-trichloromethylpropoxy) ethyl group, 4- (2'-trichloromethylpropoxy) butyl group, 6- (2'-trichloromethylpropoxy) hexyl group, 8- (2'-trichloromethyl) Propoxy) octyl group, 2- (2'-trichloromethylbutoxy) ethyl group, 4- (2'-trichloromethylbutoxy) butyl group, 6- (2'-trichloromethylbutoxy) hexyl group, 8- (2'- Trichloromethylbutoxy) octyl group, 2- (2'-trichloromethylheptyloxy) ethyl group, 4- (2'-trichloromethylheptyloxy) butyl group, 6- (2'-trichloromethylheptyloxy) hexyl group, 8 -(2'-trichloromethylheptyloxy) octyl group, 2- (2'-chloroethoxy) ethyl group, 4- (2'oke Roetokishi) butyl group, 6- (2'-chloroethoxy) hexyl, 8- (2'-chloroethoxy) octyl, 2-
(2'-chloro-n-propoxy) ethyl group, 4-
(2'-chloro-n-propoxy) butyl group, 6-
(2'-chloro-n-propoxy) hexyl group, 8-
(2'-chloro-n-propoxy) octyl group, 2-
(3'-chloro-n-propoxy) ethyl group, 4-
(3'-chloro-n-propoxy) butyl group, 6-
(3'-chloro-n-propoxy) hexyl group, 8-
(3'-chloro-n-propoxy) octyl group, 2-
(3'-chloro-2'-methylpropoxy) ethyl group,
4- (3'-chloro-2'-methylpropoxy) butyl group, 6- (3'-chloro-2'-methylpropoxy) hexyl group, 8- (3'-chloro-2'-methylpropoxy) octyl group , 2- (2 ', 3'-dichloro-n-propoxy) ethyl group, 4- (2', 3'-dichloro-n
-Propoxy) butyl group, 6- (2 ', 3'-dichloro-n-propoxy) hexyl group, 8- (2', 3'-dichloro-n-propoxy) octyl group, 2- (2'-chloro- n-butoxy) ethyl group, 4- (2'-chloro-
n-butoxy) butyl group, 6- (2'-chloro-n-butoxy) hexyl group, 8- (2'-chloro-n-butoxy) octyl group, 2- (3'-chloro-n-butoxy)
Ethyl group, 4- (3'-chloro-n-butoxy) butyl group, 6- (3'-chloro-n-butoxy) hexyl group,
8- (3'-chloro-n-butoxy) octyl group, 2-
(4'-chloro-n-butoxy) ethyl group, 4- (4 '
-Chloro-n-butoxy) butyl group, 6- (4'-chloro-n-butoxy) hexyl group, 8- (4'-chloro-
n-butoxy) octyl group, 2- (2 ′, 3′-dichloro-n-butoxy) ethyl group, 4- (2 ′, 3′-dichloro-n-butoxy) butyl group, 6- (2 ′, 3 '-Dichloro-n-butoxy) hexyl group, 8- (2', 3 '
-Dichloro-n-butoxy) octyl group and other haloalkoxyalkyl groups, and the corresponding haloalkoxyalkoxy groups,

Methylthiomethyl group, 2-methylthioethyl group, 3-methylthiopropyl group, 4-methylthiobutyl group, 5-methylthiopentyl group, 6-methylthiohexyl group, 7-methylthioheptyl group, 8-methylthiooctyl group, 9 -Methylthiononyl group, 10-methylthiodecyl group, ethylthiomethyl group, 2-ethylthioethyl group, 3-ethylthiopropyl group, 4-ethylthiobutyl group, 5-ethylthiopentyl group, 6-ethylthiohexyl group , 7-ethylthioheptyl group, 8-ethylthiooctyl group, 9-ethylthiononyl group, 10-ethylthiodecyl group, n-propylthiomethyl group, 2-n-propylthioethyl group, 3-n-propyl Thiopropyl group, 4-
n-propylthiobutyl group, 5-n-propylthiopentyl group, 6-n-propylthiohexyl group, 7-n-propylthioheptyl group, 8-n-propylthiooctyl group, 9-n-propylthiononyl group Group, 10-n-propylthiodecyl group, n-butylthiomethyl group, 2-n-butylthioethyl group, 3-n-butylthiopropyl group, 4
-N-butylthiobutyl group, 5-n-butylthiopentyl group, 6-n-butylthiohexyl group, 7-n-butylthioheptyl group, 8-n-butylthiooctyl group, 9-
n-butylthiononyl group, 10-n-butylthiodecyl group, n-pentylthiomethyl group, 2-n-pentylthioethyl group, 3-n-pentylthiopropyl group, 4-n-
Pentylthiobutyl group, 5-n-pentylthiopentyl group, 6-n-pentylthiohexyl group, 7-n-pentylthioheptyl group, 8-n-pentylthiooctyl group,
9-n-pentylthiononyl group, 10-n-pentylthiodecyl group, n-hexylthiomethyl group, 2-n-hexylthioethyl group, 3-n-hexylthiopropyl group,
4-n-hexylthiobutyl group, 5-n-hexylthiopentyl group, 6-n-hexylthiohexyl group, 7-n
-Hexylthioheptyl group, 8-n-hexylthiooctyl group, 9-n-hexylthiononyl group, 10-n-hexylthiodecyl group,

N-heptylthiomethyl group, 2-n-heptylthioethyl group, 3-n-heptylthiopropyl group,
4-n-heptylthiobutyl group, 5-n-heptylthiopentyl group, 6-n-heptylthiohexyl group, 7-n
-Heptylthioheptyl group, 8-n-heptylthiooctyl group, 9-n-heptylthiononyl group, 10-n-heptylthiodecyl group, octylthiomethyl group, 2-n-
Octylthioethyl group, 3-n-octylthiopropyl group, 4-n-octylthiobutyl group, 5-n-octylthiopentyl group, 6-n-octylthiohexyl group, 7
-N-octylthioheptyl group, 8-n-octylthiooctyl group, 9-n-octylthiononyl group, 10-n
-Octylthiodecyl group, n-nonylthiomethyl group, 2
-N-nonylthioethyl group, 3-n-nonylthiopropyl group, 4-n-nonylthiobutyl group, 5-n-nonylthiopentyl group, 6-n-nonylthiohexyl group, 7-n
-Nonylthioheptyl group, 8-n-nonylthiooctyl group, 9-n-nonylthiononyl group, 10-n-nonylthiodecyl group, n-decylthiomethyl group, 2-n-decylthioethyl group, 3-n-decyl group Thiopropyl group, 4-n
-Decylthiobutyl group, 5-n-decylthiopentyl group, 6-n-decylthiohexyl group, 7-n-decylthioheptyl group, 8-n-decylthiooctyl group, 9-n
-Decylthiononyl group, 10-n-decylthiodecyl group, 2- (2'-ethylhexylthio) ethyl group, 2-
(3 ', 5', 5'-Trimethylhexylthio) ethyl group, 2- (3 ', 7'-dimethyloctylthio) ethyl group, 4- (2'-ethylhexylthio) butyl group, 4-
(3 ′, 5 ′, 5′-trimethylhexylthio) butyl group, 4- (3 ′, 7′-dimethyloctylthio) butyl group, 6- (2′-ethylhexylthio) hexyl group, 6
An alkylthioalkyl group such as a-(3 ', 5', 5'-trimethylhexylthio) hexyl group and a 6- (3 ', 7'-dimethyloctylthio) hexyl group, and a corresponding alkylthioalkoxy group,

Ethylcarbonylmethyl group, 2-ethylcarbonylethyl group, 3-ethylcarbonylpropyl group,
4-ethylcarbonylbutyl, 5-ethylcarbonylpentyl, 6-ethylcarbonylhexyl, 7-ethylcarbonylheptyl, 8-ethylcarbonyloctyl, 9-ethylcarbonylnonyl, n-propylcarbonylmethyl, 2 -N-propylcarbonylethyl group, 3-n-propylcarbonylpropyl group, 4-n
-Propylcarbonylbutyl group, 5-n-propylcarbonylpentyl group, 6-n-propylcarbonylhexyl group, 7-n-propylcarbonylheptyl group, 8-n
-Propylcarbonyloctyl group, 9-n-propylcarbonylnonyl group, n-butylcarbonylmethyl group, 2
-N-butylcarbonylethyl group, 3-n-butylcarbonylpropyl group, 4-n-butylcarbonylbutyl group, 5-n-butylcarbonylpentyl group, 6-n-butylcarbonylhexyl group, 7-n-butylcarbonyl Heptyl group, 8-n-butylcarbonyloctyl group, 9
-N-butylcarbonylnonyl group, n-pentylcarbonylmethyl group, 2-n-pentylcarbonylethyl group,
A 3-n-pentylcarbonylpropyl group, a 4-n-pentylcarbonylpentyl group, a 5-n-pentylcarbonylpentyl group, a 6-n-pentylcarbonylhexyl group,
7-n-pentylcarbonylheptyl group, 8-n-pentylcarbonyloctyl group, 9-n-pentylcarbonylnonyl group, n-hexylcarbonylmethyl group, 2-n
-Hexylcarbonylethyl group, 3-n-hexylcarbonylpropyl group, 4-n-hexylcarbonylbutyl group, 5-n-hexylcarbonylpentyl group, 6-n-
Alkylcarbonylalkyl groups such as hexylcarbonylhexyl group, 7-n-hexylcarbonylheptyl group, 8-n-hexylcarbonyloctyl group, 9-n-hexylcarbonylnonyl group, and corresponding alkylcarbonylalkoxy groups,

Methylcarbonyloxymethyl group, 2-methylcarbonyloxyethyl group, 3-methylcarbonyloxypropyl group, 4-methylcarbonyloxybutyl group, 5-methylcarbonyloxypentyl group, 6-methylcarbonyloxyhexyl group, 7 -Methylcarbonyloxyheptyl group, 8-methylcarbonyloxyoctyl group, 9-methylcarbonyloxynonyl group, ethylcarbonyloxymethyl group, 2-ethylcarbonyloxyethyl group, 3-ethylcarbonyloxypropyl group, 4
-Ethylcarbonyloxybutyl group, 5-ethylcarbonyloxypentyl group, 6-ethylcarbonyloxyhexyl group, 7-ethylcarbonyloxyheptyl group, 8
-Ethylcarbonyloxyoctyl group, 9-ethylcarbonyloxynonyl group, n-propylcarbonyloxymethyl group, 2-n-propylcarbonyloxyethyl group, 3-n-propylcarbonyloxypropyl group, 4
-N-propylcarbonyloxybutyl group, 5-n-propylcarbonyloxypentyl group, 6-n-propylcarbonyloxyhexyl group, 7-n-propylcarbonyloxyheptyl group, 8-n-propylcarbonyloxyoctyl group, 9 -N-propylcarbonyloxynonyl group, n-butylcarbonyloxymethyl group, 2-n
-Butylcarbonyloxyethyl group, 3-n-butylcarbonyloxypropyl group, 4-n-butylcarbonyloxybutyl group, 5-n-butylcarbonyloxypentyl group, 6-n-butylcarbonyloxyhexyl group,
7-n-butylcarbonyloxyheptyl group, 8-n-
Butylcarbonyloxyoctyl group, 9-n-butylcarbonyloxynonyl group, n-pentylcarbonyloxymethyl group, 2-n-pentylcarbonyloxyethyl group, 3-n-pentylcarbonyloxypropyl group, 4
-N-pentylcarbonyloxybutyl group, 5-n-pentylcarbonyloxypentyl group, 6-n-pentylcarbonyloxyhexyl group, 7-n-pentylcarbonyloxyheptyl group, 8-n-pentylcarbonyloxyoctyl group, 9 -N-pentylcarbonyloxynonyl group, n-hexylcarbonyloxymethyl group, 2-
n-hexylcarbonyloxyethyl group, 3-n-hexylcarbonyloxypropyl group, 4-n-hexylcarbonyloxybutyl group, 5-n-hexylcarbonyloxypentyl group, 6-n-hexylcarbonyloxyhexyl group, 7- n-hexylcarbonyloxyheptyl group, 8-n-hexylcarbonyloxyoctyl group,
9-n-hexylcarbonyloxynonyl group, n-heptylcarbonyloxymethyl group, 2-n-heptylcarbonyloxyethyl group, 3-n-heptylcarbonyloxypropyl group, 4-n-heptylcarbonyloxybutyl group, 5- n-heptylcarbonyloxypentyl group, 6-n-heptylcarbonyloxyhexyl group, 7
-N-heptylcarbonyloxyheptyl group, 8-n-
Heptylcarbonyloxyoctyl group, 9-n-heptylcarbonyloxynonyl group, n-octylcarbonyloxymethyl group, 2-n-octylcarbonyloxyethyl group, 3-n-octylcarbonyloxypropyl group, 4-n-octylcarbonyl Oxybutyl group, 5-
n-octylcarbonyloxypentyl group, 6-n-octylcarbonyloxyhexyl group, 7-n-octylcarbonyloxyheptyl group, 8-n-octylcarbonyloxyoctyl group, 9-n-octylcarbonyloxynonyl group, n- Nonylcarbonyloxymethyl group,
2-n-nonylcarbonyloxyethyl group, 3-n-nonylcarbonyloxypropyl group, 4-n-nonylcarbonyloxybutyl group, 5-n-nonylcarbonyloxypentyl group, 6-n-nonylcarbonyloxyhexyl group, 7-n-nonylcarbonyloxyheptyl group, 8
An alkylcarbonyloxyalkyl group such as a -n-nonylcarbonyloxyoctyl group and a 9-n-nonylcarbonyloxynonyl group, and a corresponding alkylcarbonyloxyalkoxy group,

Methoxycarbonylmethyl group, 2-methoxycarbonylethyl group, 3-methoxycarbonylpropyl group, 4-methoxycarbonylbutyl group, 5-methoxycarbonylpentyl group, 6-methoxycarbonylhexyl group, 7-methoxycarbonylheptyl group, 8-methoxycarbonyloctyl group, 9-methoxycarbonylnonyl group, ethoxycarbonylmethyl group, 2-ethoxycarbonylethyl group, 3-ethoxycarbonylpropyl group,
4-ethoxycarbonylbutyl group, 5-ethoxycarbonylpentyl group, 6-ethoxycarbonylhexyl group,
A 7-ethoxycarbonylheptyl group, an 8-ethoxycarbonyloctyl group, a 9-ethoxycarbonylnonyl group,
n-propoxycarbonylmethyl group, 2-n-propoxycarbonylethyl group, 3-n-propoxycarbonylpropyl group, 4-n-propoxycarbonylbutyl group,
5-n-propoxycarbonylpentyl group, 6-n-propoxycarbonylhexyl group, 7-n-propoxycarbonylheptyl group, 8-n-propoxycarbonyloctyl group, 9-n-propoxycarbonylnonyl group, n
-Butoxycarbonylmethyl group, 2-n-butoxycarbonylethyl group, 3-n-butoxycarbonylpropyl group, 4-n-butoxycarbonylbutyl group, 5-n-butoxycarbonylpentyl group, 6-n-butoxycarbonylhexyl group , 7-n-butoxycarbonylheptyl group, 8-n-butoxycarbonyloctyl group, 9-n-
Butoxycarbonylnonyl group, n-pentyloxycarbonylmethyl group, 2-n-pentyloxycarbonylethyl group, 3-n-pentyloxycarbonylpropyl group, 4-n-pentyloxycarbonylbutyl group, 5-
n-pentyloxycarbonylpentyl group, 6-n-pentyloxycarbonylhexyl group, 7-n-pentyloxycarbonylheptyl group, 8-n-pentyloxycarbonyloctyl group, 9-n-pentyloxycarbonylnonyl group, n- Hexyloxycarbonylmethyl group, 2-n-hexyloxycarbonylethyl group, 3-
n-hexyloxycarbonylpropyl group, 4-n-hexyloxycarbonylbutyl group, 5-n-hexyloxycarbonylpentyl group, 6-n-hexyloxycarbonylhexyl group, 7-n-hexyloxycarbonylheptyl group, 8- n-hexyloxycarbonyloctyl group, 9-n-hexyloxycarbonylnonyl group,
n-heptyloxycarbonylmethyl group, 2-n-heptyloxycarbonylethyl group, 3-n-heptyloxycarbonylpropyl group, 4-n-heptyloxycarbonylbutyl group, 5-n-heptyloxycarbonylpentyl group, 6- n-heptyloxycarbonylhexyl group, 7-n-heptyloxycarbonylheptyl group, 8
-N-heptyloxycarbonyloctyl group, 9-n-
Heptyloxycarbonylnonyl group, n-octyloxycarbonylmethyl group, 2-n-octyloxycarbonylethyl group, 3-n-octyloxycarbonylpropyl group, 4-n-octyloxycarbonylbutyl group,
5-n-octyloxycarbonylpentyl group, 6-n
-Octyloxycarbonylhexyl group, 7-n-octyloxycarbonylheptyl group, 8-n-octyloxycarbonyloctyl group, 9-n-octyloxycarbonylnonyl group, n-nonyloxycarbonylmethyl group, 2-n-nonyl Oxycarbonylethyl group, 3-n
-Nonyloxycarbonylpropyl group, 4-n-nonyloxycarbonylbutyl group, 5-n-nonyloxycarbonylpentyl group, 6-n-nonyloxycarbonylhexyl group, 7-n-nonyloxycarbonylheptyl group, 8-n -Nonyloxycarbonyloctyl group, 9-
an alkoxycarbonylalkyl group such as an n-nonyloxycarbonylnonyl group, and a corresponding alkoxycarbonylalkoxy group,

2-propenyl group, 2-butenyl group, 3-
Butenyl group, 2-pentenyl group, 3-pentenyl group, 4
-Pentenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 2-heptenyl group, 3-heptenyl group, 4-heptenyl group, 5-heptenyl group, 6-heptenyl group, 2 -Octenyl group, 3
-Octenyl group, 4-octenyl group, 5-octenyl group, 6-octenyl group, 7-octenyl group, 2-nonenyl group, 3-nonenyl group, 4-nonenyl group, 5-nonenyl group, 6-nonenyl group, 7 -Nonenyl group, 8-nonenyl group, 2-decenyl group, 3-decenyl group, 4-decenyl group, 5-decenyl group, 6-decenyl group, 7-decenyl group, 8-decenyl group, 9-decenyl group, 2 -Butynyl group, 3-hexynyl group, 3-heptynyl group, 4-heptynyl group, 5-heptynyl group, 7-octynyl group, 3,7
Examples thereof include alkenyl groups such as -dimethyl-6-octenyl group, and corresponding alkenyloxy groups.

In the pyrimidine compound represented by the general formula (1) of the present invention, A ₁ and A ₂ are substituted or unsubstituted 1,4-phenylene group, pyridine-2,5-diyl group or trans-1, It represents a 4-cyclohexylene group, and examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, a cyano group, a nitro group, a methyl group, a trifluoromethyl group, and a hydroxyl group. A
₁ and A ₂ are preferably a fluorine atom, a cyano group, a methyl group, a trifluoromethyl group, or a 1,4-phenylene group substituted by a hydroxyl group, a pyridine-2,5-diyl group or trans-1,4- A cyclohexylene group, or an unsubstituted 1,4-phenylene group, a pyridine-2,5-diyl group or a trans-1,4-cyclohexylene group, more preferably a fluorine atom or a hydroxyl group. 1,4-phenylene group, or unsubstituted 1,4-phenylene group, pyridine-
It is a 2,5-diyl group or a trans-1,4-cyclohexylene group. X ₁ and X ₂ are single bonds, —COO—
Group, -OCO- group, -OCH ₂ - group and -CH ₂ O-
Represents a linking group selected from the group. Y ₁ and Y ₂ are -C
It represents an OO- group or an -OCO- group. In addition, Y ₁ is -O
If a CO- group, R ₁ is not an alkoxy group or an alkenyloxy group, and when Y ₂ is a -COO- group, R ₂ is not an alkoxy group or an alkenyloxy group. a, b, p and q each represent 0 or 1, and a + b + p + q is not 0, preferably a + b
+ P + q is 1, 2 or 3, and more preferably a +
b + p + q is 1 or 2.

Pyrimidine compound represented by the general formula (1)
, A, b, p, q, Y₁, Y_Two, A₁, A_Two,
X₁And X_TwoThe combination of 1) below is preferable.
~ 18). 1) a is 1, b, p and q are 0, Y₁Is -COO-group 2) a is 1, b, p and q are 0, Y₁Is -OCO-group 3) b is 1, a, p and q are 0, Y_TwoIs -OCO-group 4) p is 1, a, b and q are 0, A₁Is 1,4-pheny
Len group, X₁Is a single bond 5) p is 1, a, b and q are 0, A₁Is 1,4-pheny
Len group, X₁Is a —COO— group 6) p is 1, a, b and q are 0, A₁Is 1,4-pheny
Len group, X₁Is -CH_TwoO-group 7) p is 1, a, b and q are 0, A₁Is 1,4-pheny
Len group, X₁Is -OCH _Two-Group 8) p is 1, a, b and q are 0, A₁Is pyridine-2,
5-diyl group, X₁Is -COO-group 9) q is 1, a, b and p are 0, A_TwoIs 1,4-pheny
Len group, X_TwoIs -OCO-group 10) q is 1, a, b and p are 0, A_TwoIs pyridine-
2,5-diyl group, X_TwoIs an —OCO— group 11) q is 1, a, b and p are 0, A_TwoIs a transformer
1,4-cyclohexylene group, X_TwoIs an —OCO— group 12) q is 1, a, b and p are 0, A_TwoIs 1,4-fe
Nylene group, X_TwoIs -OCH_Two-Group 13) a and b are 1, p and q are 0, Y₁Is -COO
-Group, Y_TwoIs -OCO- group 14) a and b are 1, p and q are 0, Y₁Is -OCO
-Group, Y_TwoIs an —OCO— group 15) p and b are 1, a and q are 0, A₁Is 1,4-
Phenylene group, X₁Is a single bond, Y_TwoIs an —OCO— group 16) p and b are 1, a and q are 0, A₁Is 1,4-
Phenylene group, X₁Is a -COO- group, Y_TwoIs -OCO-
Group 17) p and b are 1, a and q are 0, A₁Is pyridine
-2,5-diyl group, X ₁Is a -COO- group, Y_TwoIs -O
CO- group 18) a and q are 1, p and b are 0, Y₁Is -COO
-Group, A_TwoIs a 1,4-phenylene group, X_TwoIs -OCO-
Group Component of pyrimidine compound represented by general formula (1) of the present invention
Examples of the body include the compounds shown below.
it can.

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Embedded image The compound of the present invention can be produced, for example, through the steps shown below. a) Process for producing pyrimidine compound represented by general formula (1-A2) (Chemical formula 59)

[0087]

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2 obtained by reacting copper (I) cyanide with a 2-bromonaphthalene derivative represented by the general formula (5)
By reacting the -cyanonaphthalene derivative with hydrogen chloride in absolute ethanol and then with ammonia, the amidine hydrochloride represented by the general formula (6) can be obtained. A compound represented by the general formula (8) is obtained by reacting this amidine hydrochloride with the acrolein represented by the general formula (7) in ethanol in the presence of a base (eg, sodium methoxide, sodium ethoxide). wherein, Z ₁ is R ₁ - group, R ₃ - group, R ₃ O-group, Bz
O-group (Bz represents a benzyl group), R ₁ -Ar- group (Ar represents a 1,4-phenylene group, a pyridine-2,5-diyl group or a trans-1,4-cyclohexylene group) or Represents an R ₁ OOC- group, Z ₂ represents an -OH group,
-COOH group, -COOR ₂ group, -OCOR ₂ group, -H
al group (Hal represents a halogen atom), -R ₂ group,-
It can be produced representing the R ₄ group or -OR ₄ group]. Alternatively, the diethylmalonic acid derivative is reacted with the amidine hydrochloride represented by the general formula (6) in the presence of a base, and then halogenated with a halogenating reagent such as phosphorus oxychloride, which is then reductively dehalogenated. By doing so, the compound represented by the general formula (8) can be produced. In the general formula (8), a compound (general formula (8-A)) in which Z ₂ is an OH group is converted into a base (for example, pyridine,
(Triethylamine, sodium hydroxide, potassium carbonate)
In the presence of carboxylic acid chloride, or in the presence of dicyclohexylcarbodiimide (hereinafter abbreviated as DCC) and a base catalyst (for example, 4-pyrrolidinopyridine, 4-dimethylaminopyridine) to react with carboxylic acid. By the method, a pyrimidine compound represented by the general formula (1-A2) can be produced. Also,
A method of chlorinating a compound of the general formula (8), wherein Z ₂ is a COOH group [general formula (8-B)] with a chlorinating agent such as thionyl chloride or oxalyl chloride and reacting with an alcohol in the presence of a base. Alternatively, the pyrimidine compound represented by the general formula (1-A2) can be synthesized by a method of reacting with DCC and an alcohol in the presence of a base catalyst. b) Process for producing acrolein derivative represented by general formula (7)

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The acrolein represented by the general formula (7) is
Some compounds are available as commercial products, or can be produced through the following steps. That is, by reacting a Grignard reagent prepared from an alkyl halide and metallic magnesium with triethyl orthoformate to produce diethyl acetal (7 ′), or by reacting bromoacetaldehyde diethyl acetal with an alkoxide, alkoxyacetaldehyde diethyl acetal ( 7 ″) is produced. Next, acrolein represented by the general formula (7) can be produced by a method of reacting these diethyl acetals with Vilsmeier reagent. C) General formula (1-A1) A process for producing a pyrimidine compound represented by

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In formula (8), the protecting group of the compound [general formula (8-C)] in which Z ₁ is a protecting group for an OH group such as a benzyloxy group (BzO-group) is removed, and then a base ( For example, a method of reacting with carboxylic acid chloride in the presence of pyridine, triethylamine, sodium hydroxide, potassium carbonate), or DCC and a base catalyst (for example,
The pyrimidine compound represented by the general formula (1-A1) can be produced by a method of reacting with a carboxylic acid in the presence of 4-pyrrolidinopyridine, 4-dimethylaminopyridine). d) Process for producing pyrimidine compound represented by general formula (1-A3) (Chemical Formula 62)

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In the general formula (8), Z ₁ is a protecting group for an OH group such as a benzyloxy group and Z ₂ is an OH group [general formula (8-C1)] to a base (eg, pyridine, By reacting carboxylic acid chloride in the presence of triethylamine, sodium hydroxide, potassium carbonate) or by reacting with carboxylic acid in the presence of DCC and a base catalyst (eg, 4-pyrrolidinopyridine, 4-dimethylaminopyridine). In the method or in the general formula (8), Z ₁ is a protecting group for an OH group such as a benzyloxy group and Z ₂ is a COOH group, and the compound is represented by general formula (8-C2)] with thionyl chloride, or A method of reacting oxalyl chloride to form a carboxylic acid chloride, and then reacting with an alcohol, or DCC in the state of a carboxylic acid and a base catalyst The method of reacting an alcohol to standing down to prepare the ester derivative. After that, the protecting group of Z ₁ is removed, and the reaction is further performed with a carboxylic acid chloride in the presence of a base (eg, pyridine, triethylamine, potassium carbonate), or DCC and a base catalyst (eg, 4-pyrrolidinopyridine, 4 -Dimethylaminopyridine), a pyrimidine compound represented by the general formula (1-A3) can be produced by a method of reacting with a carboxylic acid. e) Process for producing pyrimidine compound represented by general formula (1-B) (Chemical Formulas 63 and 64)

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The compound in which X ₁ is a single bond can be prepared by using α-aryl-β-dimethylaminoacrolein or α-aryl-β-ethoxyacrolein (7 ″ ′) and amidine hydrochloride (6) as a base (for example, sodium). methoxide, can be produced by the process of reacting in the presence of sodium ethoxide). X ₁ is -COO- compounds wherein the compound Z ₁ is OH in the general formula (8) [formula (8 -D)],
Aromatic carboxylic acid derivative, DCC and a method of reacting with a base catalyst (for example, 4-pyrrolidinopyridine, 4-dimethylaminopyridine), or to the general formula (8-D), an aromatic carboxylic acid halide is used as a base (for example, It can be produced by a method of acting in the presence of (triethylamine, sodium hydroxide). The compound in which X ₁ is —OCO— is a compound of the general formula (8), in which Z ₁ is an R ₁ OOC— group [general formula (8
-E)] is obtained by hydrolyzing carboxylic acid or its acid halide derivative [general formula (8-E ')]:
A compound in which Z ₈ is an OH group and a phenol derivative are
Method of reacting in the presence of CC and a base catalyst (for example, 4-piperidinopyridine, 4-dimethylaminopyridine), or a compound of the general formula (8-E ′), wherein Z ₈ is a halogen atom (Hal). With a phenol derivative in the presence of a base (eg, pyridine, triethylamine, sodium hydroxide, potassium carbonate). The compound in which X ₁ is —CH 2 O— has the general formula (8-
It can be produced by a method of reacting the compound represented by D) with a benzyl halide derivative. It can also be produced by a method of reacting a compound represented by the general formula (8-D) with a benzyl alcohol derivative in the presence of diethylazodicarboxylic acid (hereinafter abbreviated as DEAD) and triphenylphosphine. . The compound in which X ₁ is —OCH ₂ — is a compound in which Z ₁ is a methyl group in the general formula (8) [general formula (8-
F)]] to azobisisobutyronitrile (hereinafter referred to as AIBN
Abbreviated) or in the presence of benzoyl peroxide,
N-bromosuccinimide (hereinafter abbreviated as NBS)
A bromomethylpyrimidine derivative can be produced by reacting a brominating agent such as the above, and can be produced by reacting this with a phenol derivative. f) Process for producing pyrimidine compound represented by general formula (1-C) (Chemical formula 65, 66)

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The compound in which X ₂ is -OCO- is a compound in which Z ₂ is OH in the general formula (8) [general formula (8
-A)] and an aromatic carboxylic acid derivative are allowed to react. The compound in which X ₂ is —COO— is a compound of the general formula (8), in which Z ₂ is a COZ ₁₄ group {Z ₁₄ is OH or a halogen atom (Hal)} [general formula (8-
B ')] and a desired phenol. The compound in which X ₂ is —OCH ₂ — is a compound in which Z ₂ is an OH group in the general formula (8) [general formula (8-
It can be produced by reacting A)] with a benzyl halide derivative in the presence of a base such as potassium carbonate. It can also be produced by a method of reacting a compound represented by the general formula (8-A) with a benzyl alcohol derivative in the presence of DEAD and triphenylphosphine. The compound in which X ₂ is —CH ₂ O— is a compound of the general formula (8), in which Z ₂ is a methyl group [general formula (8-
G)] is treated with a brominating agent such as NBS in the presence of AIBN or benzoyl peroxide,
It can be produced by producing a bromomethylnaphthalene derivative and reacting this with a phenol derivative. The compound in which X ₂ is a single bond is a compound in which Z ₂ is halogen in the general formula (8) [general formula (8-H)] and a borate ester (this is a Grignard prepared from a halogenated benzene derivative). (It is obtained by reacting a reagent with trimethyl borate and then hydrolyzing it.)
Can be produced in the presence of a palladium catalyst.

Next, the pi represented by the general formula (2) of the present invention will be described.
The limidine compound will be described in detail. General formula of the present invention
In the pyrimidine compound represented by (2), R_ThreeAnd
And R_FourIs a linear or branched alkyl having 3 to 24 carbon atoms
Represents a group or an alkenyl group, R _ThreeAnd R_FourLess of
Present in one of the alkyl or alkenyl groups
At least one -CH_Two-Group (however, adjacent-
CH_Two-Bonded to groups and oxygen atoms or aromatic rings
-CH_Two(Except the group) is replaced by an oxygen atom.
R_ThreeAnd R_FourIs halogen such as fluorine, chlorine or bromine
Optionally substituted by atoms, also branched-chain alkyl
The group or alkenyl group may have an asymmetric carbon atom.
Alternatively, the asymmetric carbon may be optically active. Also, m
And n represent 0 or 1. Table of the general formula (2) of the present invention
In the pyrimidine compound, m and n are each 0 or
Or 1 represents the following (2-A), (2-B),
Four types of structures of (2-C) or (2-D)
Take.

[0102]

Embedded image Of these, preferably m + n is 1 or 2 (2
-B), (2-C) or (2-D) structure. Further, an alkyl group or an alkenyl group in which at least one of R ₃ and R ₄ in which a non-adjacent —CH ₂ — group is replaced with an oxygen atom is Q ₁ and Q _2, and an alkyl group or an alkenyl containing no oxygen atom is used. When the groups are R ₅ and R ₆ , the pyrimidine compound represented by the general formula (2) is represented by the following (2-A1 to 2-A3),
It has a structure of (2-B1 to 2-B3), (2-C1 to 2-C3) or (2-D1 to 2-D3) (formula 68).

[0103]

Embedded image The groups represented by Q ₁ and Q ₂ are preferably groups represented by the following general formula (9) (formula 69).

[0104]

Embedded image In the general formula (9), R ₇ represents a linear or branched alkyl group having 1 to 15 carbon atoms which may be substituted with a halogen atom, X ′ _{1 to} X ′ ₁₄ represent a hydrogen atom, a halogen atom, It is a group selected from a methyl group, an ethyl group and an n-propyl group, and i ₁ , i ₂ , i ₃ , i ₄ , i ₅ , i ₆ and i ₇ represent 0 or 1, i _{1 to} i ₇ Not all represent 0 at the same time. j ₁ , j ₂ , j ₃ , j ₄ ,
j ₅ , j ₆ and j ₇ represent an integer of 0 to 10, and the total number of carbon atoms in the general formula (9) is 2 to 23.

Specific examples of the groups represented by Q ₁ and Q ₂ include, for example, the alkoxyalkyl group, the alkenyloxyalkyl group and the haloalkoxyalkyl group in the specific examples of R ₁ and R ₂ in the general formula (1). Can be mentioned. Of these, an alkoxyalkyl group and an alkenyloxyalkyl group are preferable. Specific examples of the linear or branched alkyl group or alkenyl group represented by R ₅ and R ₆ include, for example, R in the general formula (1).
The alkyl group, haloalkyl group and alkenyl group in the specific examples of ₁ and R ₂ can be mentioned. Preferably,
An alkyl group and an alkenyl group are preferred, and an alkyl group is more preferred. In the groups represented by Q ₁ , Q ₂ , R ₅ and R ₆ , the group having a branched chain may have an asymmetric carbon. The asymmetric carbon may be optically active or non-optically active. It is preferably a group having no optically active asymmetric carbon. Specific examples of the pyrimidine compound represented by the general formula (2) include the compounds shown below (Formula 70 to Formula 89).

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Embedded image The compound represented by the general formula (2) of the present invention can be produced, for example, through the steps shown below. g) Process for producing pyrimidine compound represented by general formula (2) (Chemical Formula 90)

[0126]

Embedded image In the compound represented by the general formula (8), the compound in which Z ₂ is R ₄ represents the compound of the general formula (2-A) or (2-C). Moreover, the compound whose Z < ₂ > is -OR < ₄ > represents the compound of general formula (2-B) or (2-D). Further, in the general formula (8), a compound in which Z ₂ is an OH group [general formula (8-A)] is converted into R ₄ —Hal or R ₄ —
A compound represented by the general formula (2- A compound represented by B) or (2-D) can be produced.
Further, the compound represented by the general formula (8-A) and R ₄ —OH
The compound represented by the general formula (2-B) or (2
A compound represented by -D) can be produced.

Next, the compound represented by formula (3) or (4) of the present invention will be described. The compound represented by the general formula (3) or (4) of the present invention is a compound that can be used as a production intermediate of the compound represented by the general formula (1) or (2) of the present invention, respectively. . The pyrimidine compound of the present invention includes a compound that exhibits liquid crystallinity by itself and a compound that does not exhibit liquid crystallinity. Further, a compound exhibiting liquid crystallinity includes smectic C (hereinafter abbreviated as Sc phase) or chiral smectic C (hereinafter Sc
* Abbreviated as "phase") and liquid crystallinity but S
Some compounds do not exhibit the c phase or the Sc * phase. Each of these compounds can be effectively used as a component of a liquid crystal composition.

Next, the liquid crystal composition of the present invention will be described. The liquid crystal composition generally comprises two or more components,
The liquid crystal composition of the present invention contains at least one pyrimidine compound of the present invention as an essential component. Examples of the pyrimidine compound of the present invention used in the liquid crystal composition of the present invention include a pyrimidine compound that does not exhibit liquid crystallinity, a pyrimidine compound that exhibits a Sc phase, a pyrimidine compound that exhibits a Sc * phase, and a Sc phase and Sc that exhibit liquid crystallinity. * Pyrimidine compound showing no phase. As the liquid crystal composition of the present invention, preferably, chiral smectic C, F,
A liquid crystal composition exhibiting a phase such as G, H, or I may be mentioned, and a liquid crystal composition exhibiting a Sc * phase is more preferable. The liquid crystal composition exhibiting the Sc * phase of the present invention includes a pyrimidine compound of the present invention, a liquid crystal compound exhibiting the Sc * phase other than the pyrimidine compound of the present invention, a liquid crystal compound exhibiting the Sc phase other than the pyrimidine compound of the present invention, and an optical compound. A composition prepared by combining a plurality of compounds selected from active compounds and containing at least one pyrimidine compound of the present invention.

The liquid crystal compound showing the Sc * phase other than the pyrimidine compound of the present invention is not particularly limited, and examples thereof include an optically active phenylbenzoate liquid crystal compound and an optically active biphenylbenzoate liquid crystal compound.
Optically active naphthalene-based liquid crystal compound, optically active phenylnaphthalene-based liquid crystal compound, optically active tolan-based liquid crystal compound,
An optically active phenylpyrimidine-based liquid crystal compound can be exemplified. The liquid crystal compound exhibiting the Sc phase other than the pyrimidine compound of the present invention is not particularly limited, and examples thereof include a phenylbenzoate liquid crystal compound, a biphenylbenzoate liquid crystal compound, a naphthalene liquid crystal compound, a phenylnaphthalene liquid crystal compound, Examples include a tolan-based liquid crystal compound and a phenylpyrimidine-based liquid crystal compound. The optically active compound refers to a compound that does not exhibit liquid crystallinity by itself, but has the ability to develop a Sc * phase when mixed with a liquid crystal compound or a liquid crystal composition that exhibits an Sc phase. As, although not particularly limited, for example, an optically active phenylbenzoate non-liquid crystal compound, an optically active biphenylbenzoate non-liquid crystal compound, an optically active naphthalene non-liquid crystal compound, an optically active phenyl naphthalene non-liquid crystal compound,
Examples thereof include optically active phenylpyrimidine non-liquid crystal compounds and optically active tolan non-liquid crystal compounds. In addition to the above-mentioned essential components, the liquid crystal composition of the present invention includes, as an optional component, a smectic or nematic liquid crystal compound that does not exhibit a Sc phase, a compound that does not exhibit liquid crystallinity other than the pyrimidine compound of the present invention (for example, anthraquinone Type dyes, azo type dyes and other dichroic dyes, and conductivity-imparting agents, life improvers, etc.) may be contained. The content of the pyrimidine compound of the present invention in the liquid crystal composition of the present invention is not particularly limited, but is usually 5 to 99% by weight, preferably 10 to 90% by weight.

In the liquid crystal composition of the present invention, the liquid crystal composition exhibiting chiral smectic C, F, G, H and I phases is a liquid crystal composition exhibiting ferroelectricity. A liquid crystal composition exhibiting ferroelectricity causes a switching phenomenon when a voltage is applied, and a liquid crystal display element having a short response time can be manufactured by utilizing this phenomenon [see, for example, JP-A-56-107216 and JP-A-SHO-216216. 59-118744, Applied Physics Letters (Applied Physics)
Letter, 36, 899 (1980)]. A liquid crystal composition containing at least one pyrimidine compound of the present invention has a response time, memory stability, a layer structure in the Sc phase, a tilt angle, and an alignment film, which are higher than those of conventionally known liquid crystal compositions. It is excellent in terms of orientation characteristics and compatibility between liquid crystal compounds.

Next, the liquid crystal element of the present invention will be described. The liquid crystal element of the present invention comprises the liquid crystal composition of the present invention arranged between a pair of electrode substrates. FIG. 1 is a schematic cross-sectional view showing an example of a liquid crystal element having a chiral smectic phase for explaining the configuration of a liquid crystal element utilizing ferroelectricity. In the liquid crystal element, a liquid crystal layer 1 exhibiting a chiral smectic phase is disposed between a pair of substrates 2 provided with a transparent electrode 3 and an insulating alignment control layer 4, respectively, and the layer thickness is set by a spacer 5. And a connection is made between a pair of transparent electrodes 3 via a lead wire 6 so that a voltage can be applied from a power supply 7. Further, the pair of substrates 2 is sandwiched by a pair of polarizing plates 8 arranged in a crossed Nicols state, and a light source 9 is arranged outside one of them. Examples of the material of the substrate 2 include glass such as soda lime glass and borosilicate glass and polycarbonate, polyether sulfone,
Transparent polymers such as polyacrylates are exemplified. The transparent electrodes 3 provided on the two substrates 2 include, for example, I
n ₂ O ₃ , SnO ₂ or ITO (indium tin
A transparent electrode formed of a thin film of oxide (Indium Tin Oxide) may be used.

The insulating orientation control layer 4 is for rubbing a polymer thin film of polyimide or the like with gauze or acetate flocking cloth to orient the liquid crystal. Examples of the material of the insulating orientation control layer 4 include silicon nitride, silicon nitride containing hydrogen, silicon carbide, silicon carbide containing hydrogen, silicon oxide, boron nitride, boron nitride containing hydrogen. Insulating layer of inorganic materials such as cerium oxide, aluminum oxide, zirconium oxide, titanium oxide and fluorinated magnesium, polyvinyl alcohol, polyimide, polyamide imide, polyester imide, polyether imide, polyether ketone, polyether ether ketone , Polyether sulfone, polyparaxylene, polyester, polycarbonate, polyvinyl acetal, polyvinyl chloride, polyvinyl acetate, polyamide, polystyrene, cellulose resin,
An organic insulating layer such as a melamine resin, a urea resin, or an acrylic resin may be used. The insulating orientation control layer may have a two-layer structure in which an organic insulating layer is formed on an inorganic insulating layer. An insulating orientation control layer composed of only a layer may be used. When the insulating orientation control layer is an inorganic insulating layer, it can be formed by an evaporation method or the like. In the case of an organic insulating layer, its precursor solution is applied by a spinner coating method, a permeation coating method, a screen printing method, a spray coating method, a roll coating method, or the like under predetermined curing conditions (for example, under heating). ) And can be formed by curing. The thickness of the insulating orientation control layer 4 is usually 1 nm to 1 μm, preferably 1 to 300 nm, more preferably 1 to 10 nm.
0 nm.

The two substrates 2 are held by the spacer 5 at arbitrary intervals. For example, by sandwiching silica beads and alumina beads having a predetermined diameter as spacers between the substrates 2 and sealing the periphery of the two substrates 2 with a sealing material (for example, an epoxy-based adhesive), an arbitrary interval is provided. Can be kept. Further, a polymer film or glass fiber may be used as the spacer. A liquid crystal exhibiting a chiral smectic phase is sealed between the two substrates. The thickness of the liquid crystal layer 1 is generally set to 0.5 to 20 μm, preferably 1 to 5 μm. The transparent electrode 3 is connected to an external power supply 7 by a lead wire. Also,
Outside the substrate 2, a pair of polarizing plates 8 whose polarization axes are, for example, in a crossed Nicols state are arranged. The example shown in FIG. 1 is of a transmission type and includes a light source 9. Also,
The liquid crystal device using the liquid crystal composition of the present invention can be applied not only as a transmissive device shown in FIG. 1 but also as a reflective device.

The display system of the liquid crystal device using the liquid crystal composition of the present invention is not particularly limited,
For example, (a) helical distortion type, (b) SSFLC (Surface Stabilized Ferroelectric Liquid Crystal) type, (c) TSM (Transient Scattering Mode) type, (d) GH ( A guest-host type display scheme can be used.
Further, the pyrimidine compound of the present invention and a liquid crystal composition containing the compound may be used in a field other than a liquid crystal element for display (for example, an electronic material such as a nonlinear optical function element and a capacitor material, a limiter, a memory, an amplifier, and a modulator). It can be applied to electronic elements such as, for example, conversion elements for heat, light, pressure, mechanical deformation and the like and voltage conversion elements and sensors, and power generation elements such as thermoelectric power generation elements.

[0135]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples. The symbols I, N, N in the examples and tables
*, SA, Sc, Sc *, Sx and C have the following meanings. I: isotropic liquid N: nematic phase N *: cholesteric phase SA: smectic A phase Sc: smectic C phase Sc *: chiral smectic C phase Sx: unidentified smectic phase C: crystalline phase

Preparation Example 1: Preparation of 6-amidino-2-hydroxynaphthalene hydrochloride 202.8 g (1.2 mo) of 6-cyano-2-naphthol
l) was dissolved in 1500 ml of absolute ethanol and cooled to 5 ° C or lower on an ice bath. While stirring, 438 g of hydrogen chloride was blown in at 15 ° C or lower, and then the mixture was stirred for 2 hours on an ice bath. After stirring at room temperature for 4 hours, the mixture was left for 15 hours. After standing, ethanol was removed to obtain a yellow solid.
This solid was suspended in 500 ml of absolute ethanol, and this suspension was mixed with anhydrous ethanol 1 saturated with ammonia.
300 ml was added dropwise under ice cooling, and the mixture was stirred at the same temperature for 1 hour. After further stirring at room temperature for 2 hours, the mixture was left for 15 hours. Ethanol was removed and the resulting solid was washed with ether to obtain a brown solid of 6-amidino-2-hydroxynaphthalene hydrochloride (262.3 g). Production Example 2: Production of 6-amidino-2-benzyloxynaphthalene hydrochloride In Production Example 1, 6-cyano-2-benzyloxynaphthalene was used instead of 6-cyano-2-naphthol. According to the procedure described in Production Example 1,
6-amidino-2-benzyloxynaphthalene hydrochloride 3
71.3 g was obtained.

Production Example 3: Production of 6- (5'-substituted-2'-pyrimidyl) -2-hydroxynaphthalene Production of 2-alkoxyacetaldehyde diethyl acetal 12.7 g of sodium hydride (60% by weight) was suspended in toluene. It was made turbid, 0.3 mol of the alcohol shown in Table 1 (Table 1) was added thereto, the mixture was heated to 100 ° C., and stirred until hydrogen generation was completed, to prepare a sodium alkoxide. A solution prepared by dissolving 60.9 g (0.309 mol) of 2-bromoacetaldehyde diethyl acetal in 68 g of N, N-dimethylacetamide was added dropwise. After heating at 80 ° C. for 20 hours, the solvent was distilled off, the mixture was extracted with toluene, washed with water, and then distilled under reduced pressure to obtain 2-alkoxyacetaldehyde diethyl acetal. The yield and boiling point are shown in Table 1. Production of Alkanal Diethyl Acetal 0.275 mol of alkyl bromide shown in Table 2,
From 6.68 g of metallic magnesium, a Grignard reagent was prepared in 250 ml of tetrahydrofuran, and a solution of 44.45 g (0.3 mol) of triethyl orthoformate in 50 ml of tetrahydrofuran was added thereto to give 40
Heated to reflux for an hour. Then, tetrahydrofuran was distilled off, and ethyl acetate and an aqueous solution of ammonium chloride were added to the residue and mixed, the organic layer was separated, washed with water, and then distilled under reduced pressure to obtain alkanal diethyl acetal. The yield and boiling point are shown in Table 2 (Table 1). Production of 6- (5′-substituted-2′-pyrimidyl) -2-hydroxynaphthalene A mixed solution of 50.0 g of N, N-dimethylformamide and 100 ml of dichloroethane was ice-cooled, and 60.4 g of phosphorus oxychloride was added thereto. A solution of 40 ml of dichloroethane was added dropwise. In this solution, 0.2 mol of diethyl acetal and 40 m of dichloroethane shown in Table 1 and Table 2 were added.
The solution consisting of 1 was added dropwise, and after completion of the addition, reaction was carried out at 60 ° C. for 3 hours. After the reaction was completed, a saturated aqueous solution of potassium carbonate was added, and the mixture was extracted with toluene. Toluene was distilled off to obtain a crude α-substituted-β-dimethylaminoacrolein derivative. Next, the α-substituted-β-dimethylaminoacrolein derivative and 44.3 g (0.2 mol) of 6-amidino-2-hydroxynaphthalene hydrochloride obtained in Production Example 1 were suspended in 200 ml of absolute ethanol, and here, Methanol solution of sodium methoxide (28% by weight) 115.8
g was added dropwise. After heating under reflux for 10 hours, ethanol was distilled off, the mixture was extracted with ethyl acetate, neutralized with hydrochloric acid, and washed with water. Ethyl acetate was distilled off to obtain 6- (5'-substituted-2'-pyrimidyl) -2-hydroxynaphthalene shown in Table 3. The yield and melting point are shown in Table 3 (Table 2).

[0138]

[Table 1]

[0139]

[Table 2]

Production Example 4: Production of 6- [5 '-(4 "-n-octyloxyphenyl) -2'-pyrimidyl] -2-hydroxynaphthalene α- (4-n-octyloxyphenyl) -β- Preparation of ethoxyacrolein 34.28 g of methoxymethyltriphenylphosphonium chloride was suspended in 190 ml of anhydrous ether,
11.22 g of potassium-t-butoxide was added. To this was added 22.26 g of 4-n-octyloxybenzaldehyde dissolved in 110 ml of anhydrous ether, and the mixture was stirred at room temperature for 12 hours. The formed triphenylphosphine oxide was removed by filtration, and the filtrate was added with 300 ml of ice water.
Was injected. The ether layer was separated, washed with water, and dried over anhydrous sodium sulfate. The ether was distilled off and the crude (4 '
-N-octyloxyphenyl) -2-methoxyethylene was obtained. Further, it was purified by distillation under reduced pressure to obtain 25.4 g of (4'-n-octyloxyphenyl) -2-methoxyethylene. Next, 240 g of triethyl orthoformate
And a mixed solution of boron trifluoride ethyl ether complex salt 6.53 g were cooled to 0 ° C., and 25.39 g of (4′-n-octyloxyphenyl) -2-methoxyethylene was added. Then, after stirring at room temperature for 12 hours, toluene 20
0 ml and 10 wt% sodium hydrogen carbonate aqueous solution 1
After adding 50 ml and mixing, the toluene layer was separated.
After drying over anhydrous sodium sulfate, toluene was distilled off to give 4-
Obtained n-octyloxyphenyl malonotetraethyl acetal. Next, 21.2 g of this 4-n-octyloxyphenyl malonotetraethyl acetal was added to water 12
ml, p-toluenesulfonic acid 0.05 g, and 8
The reaction was performed at 0 ° C. for 3 hours. After cooling to room temperature, 0.52 g of sodium carbonate was added for neutralization, and the product was extracted with toluene. Washed with a 10 wt% sodium hydroxide aqueous solution,
After further washing with water, the toluene layer is separated, dried over anhydrous sodium sulfate, and the toluene is distilled off to obtain α- (4-n-octyloxyphenyl) -β-ethoxyacrolein 1
Obtained 6.62 g. Production of 6- [5 ′-(4 ″ -n-octyloxyphenyl) -2′-pyrimidyl] -2-hydroxynaphthalene α- (4-n-octyloxyphenyl) -β-ethoxyacrolein 14.57 g, 9.06 g of 6-amidino-2-hydroxynaphthalene hydrochloride obtained in Preparation Example 1 was suspended in 113 ml of absolute ethanol, and 40.40% of a methanol solution of sodium methoxide (28% by weight) was suspended therein.
51 g was added dropwise. After heating to 60 ° C. and stirring for 10 hours, ethanol was distilled off, the mixture was neutralized with hydrochloric acid, and extracted with ethyl acetate. Then, ethyl acetate was distilled off, and 6-
[5 '-(4 "-n-octyloxyphenyl) -2'
-Pyrimidyl] -2-hydroxynaphthalene 12.25
g was obtained (melting point: 148 ° C.).

Production Example 5: Production of 6- (5'-n-decyloxycarbonyl-2'-pyrimidyl) -2-hydroxynaphthalene 6- (5'-ethoxycarbonyl-2'-pyrimidyl) -2-benzyloxy Production of naphthalene A mixed solution of 30.7 g of N, N-dimethylformamide and 35 ml of dichloroethane was ice-cooled, and a solution consisting of 36.8 g of phosphorus oxychloride and 15 ml of dichloroethane was added dropwise thereto. A solution consisting of 19.0 g (0.1 mol) of ethyl 3,3'-diethoxypropionate and 15 ml of dichloroethane was added dropwise to this solution, and after completion of the addition, 70
The reaction was carried out at a temperature of 1 hour. After the reaction was completed, a saturated aqueous solution of potassium carbonate was added, and the mixture was extracted with toluene. Toluene was distilled off to obtain crude α-ethoxycarbonyl-β-dimethylaminoacrolein. Next, 6-amidino-2-benzyloxynaphthalene hydrochloride 31.2 obtained in Production Example 2
g (0.1 mol) and sodium ethoxide 20.5 g
Is suspended in 100 ml of absolute ethanol, and α-
A solution consisting of ethoxycarbonyl-β-dimethylaminoacrolein and 20 ml of absolute ethanol was added dropwise. 1
After heating under reflux for 0 hours, the mixture was cooled to room temperature, discharged into 500 ml of an aqueous solution containing 25 ml of concentrated hydrochloric acid, and the resulting solid was filtered,
6- (5'-ethoxycarbonyl-2'-pyrimidyl)
28.7 g of 2-benzyloxynaphthalene was obtained (melting point: 181 ° C.). Preparation of 6- (5'-hydroxycarbonyl-2'-pyrimidyl) -2-benzyloxynaphthalene 6- (5'-ethoxycarbonyl-2'-pyrimidyl)
28.7 g of 2-benzyloxynaphthalene and 3.2 g of sodium hydroxide were suspended in ethanol containing 75% by weight of water and reacted at 80 ° C. for 20 hours. Then acidified with hydrochloric acid, the resulting solid was filtered off, washed with toluene,
23.9 g of 6- (5′-hydroxycarbonyl-2′-pyrimidyl) -2-benzyloxynaphthalene was obtained (melting point: 250 ° C. or higher). 6- (5'-n-decyloxycarbonyl-2'-
Preparation of pyrimidyl) -2-benzyloxynaphthalene 6- (5'-hydroxycarbonyl-2'-pyrimidyl) -2-benzyloxynaphthalene 9.3 g, oxalyl chloride 3.0 g and toluene 50 ml suspension 60 The mixture was stirred at 0 ° C for 5 hours. Then, toluene and excess oxalyl chloride were distilled off, and n
-4.2 g of decyl alcohol and 50 ml of toluene were added, and 5.05 g of triethylamine was added dropwise under ice cooling. The mixture was reacted at room temperature for 10 hours, neutralized with an aqueous hydrochloric acid solution, washed with water, and then toluene was distilled off. The residue was purified by silica gel column chromatography (eluent: chloroform) to give 9.06 g of 6- (5'-n-decyloxycarbonyl-2'-pyrimidyl) -2-benzyloxynaphthalene (melting point: 144 ° C. ). 6- (5'-n-decyloxycarbonyl-2'-
Preparation of pyrimidyl) -2-hydroxynaphthalene 6- (5'-n-decyloxycarbonyl-2'-pyrimidyl) -2-benzyloxynaphthalene 9.06 g was dissolved in 100 ml of ethyl acetate, and 50% by weight of water-containing Pd was added thereto. / C 0.9g was added, and the mixture was stirred under a hydrogen atmosphere for 20 hours. Thereafter, Pd / C was removed by filtration, and ethyl acetate was distilled off from the filtrate to obtain 7.3 g of 6- (5'-n-decyloxycarbonyl-2'-pyrimidyl) -2-hydroxynaphthalene ( Melting point: 123 ° C).

Production Example 6: 6- (5'-benzyloxy-
Preparation of 2'-pyrimidyl) -2-n-octyloxynaphthalene 6- (5'-benzyloxy-2'-pyrimidyl) -2
-Hydroxynaphthalene 3.28 g (10 mmol)
And n-octyl bromide 2.32 g (12 mmo
1) and 0.96 g of potassium carbonate were suspended in 10 ml of N, N-dimethylformamide and reacted at 60 ° C. for 5 hours. After the reaction, water was added and the mixture was extracted with chloroform. Chloroform was distilled off, and the residue was purified by silica gel column chromatography (eluent: chloroform) to obtain 6.74 g of 6- (5′-benzyloxy-2′-pyrimidyl) -2-n-octyloxynaphthalene. It was The phase transition temperature (° C.) of this compound is shown below. Production Example 7: Production of 6- (5'-benzyloxy-2'-pyrimidyl) -2-n-decyloxynaphthalene In Production Example 6, n-decyl bromide was used instead of n-octyl bromide. Except 6- (5'-benzyloxy-
4.12 g of 2'-pyrimidyl) -2-n-decyloxynaphthalene was obtained. The phase transition temperature (° C.) of this compound is shown below. Production Example 8: Production of 6- (5'-hydroxy-2'-pyrimidyl) -2-n-octyloxynaphthalene 6- (5'-benzyloxy-2'-pyrimidyl) -2
-N-octyloxynaphthalene 3.56 g (8 mmo
l) was dissolved in 100 ml of ethyl acetate, 0.35 g of Pd / C containing 50% by weight of water was added thereto, and the mixture was stirred for 8 hours under a hydrogen atmosphere. Then, Pd / C was removed by filtration, and ethyl acetate was distilled off from the filtrate to obtain 2.79 g of 6- (5′-hydroxy-2′-pyrimidyl) -2-n-octyloxynaphthalene (melting point). 161 ° C).

Production Example 9: 6- (5'-hydroxy-2 '
Production of -pyrimidyl) -2-n-decyloxynaphthalene In Production Example 8, 6- (5'-benzyloxy-2 '
Instead of using -pyrimidyl) -2-n-octyloxynaphthalene, 6- (5'-benzyloxy-2 '
6- (5 'according to the procedure described in Preparation Example 8 except that -pyrimidyl) -2-n-decyloxynaphthalene was used.
2.98 g of -hydroxy-2'-pyrimidyl) -2-n-decyloxynaphthalene were obtained (melting point: 159 ° C).

Example 1: 6- (5'-benzyloxy-
Preparation of 2'-pyrimidyl) -2- (2 "-n-hexyloxyethoxy) naphthalene 6- (5'-benzyloxy-2'-pyrimidyl) -2
-Hydroxynaphthalene 3.28 g (10 mmol)
And ethylene glycol mono-n-hexyl ether tosylate (3.60 g, 12 mmol) and potassium carbonate (0.96 g) were added to N, N-dimethylformamide 10
It was suspended in ml and reacted at 60 ° C. for 5 hours. After the reaction, water was added and the mixture was extracted with chloroform. Chloroform was distilled off, and the residue was purified by silica gel column chromatography (eluent: chloroform) to give 6- (5 '
-Benzyloxy-2'-pyrimidyl) -2- (2 "-
4.14 g of n-hexyloxyethoxy) naphthalene was obtained (melting point: 112 ° C.).

Example 2: 6- (5'-benzyloxy-
Preparation of 2'-pyrimidyl) -2- (2 "-n-butoxyethoxy) naphthalene In Example 1, instead of using ethylene glycol mono-n-hexyl ether tosylate, ethylene glycol mono-n-butyl ether tosylate. 6-according to the procedure described in Example 1 except that
(5'-benzyloxy-2'-pyrimidyl) -2-
(2 "-n-butoxyethoxy) naphthalene 3.67 g
Was obtained (melting point: 119 ° C.).

Example 3: 6- (5'-benzyloxy-
Preparation of 2'-pyrimidyl) -2-n-octylcarbonyloxynaphthalene 6- (5'-benzyloxy-2'-pyrimidyl) -2
-Hydronaphthalene 3.28 g (10 mmol), pelargonic acid chloride 2.11 g (11 mmol), and chloroform 30 ml were added dropwise with triethylamine 1.11 g under ice-cooling, and then reacted at room temperature for 5 hours. After the reaction, an aqueous hydrochloric acid solution was added, neutralized, washed with water, chloroform was distilled off, and the residue was purified by silica gel column chromatography (eluent: chloroform) to give 6- (5′-benzyloxy-2′-). Pyrimidyl) -2-n-octylcarbonyloxynaphthalene (4.19 g) was obtained. The phase transition temperature (° C.) of this compound is shown below. Example 4: Preparation of 6- (5'-benzyloxy-2'-pyrimidyl) -2-n-octyloxycarbonyloxynaphthalene In Example 3, instead of using pelargonic acid chloride, n-octyl chloroformate was used. Was followed by the procedure described in Example 3 to obtain 4.45 g of 6- (5′-benzyloxy-2′-pyrimidyl) -2-n-octyloxycarbonyloxynaphthalene. The phase transition temperature (° C.) of this compound is shown below.

Example 5: 6- (5'-benzyloxy-
Preparation of 2'-pyrimidyl) -2- {4 "-[2- (2-n-hexyloxyethoxy) ethoxy] phenylcarbonyloxy} naphthalene 6- (5'-benzyloxy-2'-pyrimidyl) -2
-Hydroxynaphthalene 3.28 g (10 mmol),
4- [2 '-(2 "-n-hexyloxyethoxy) ethoxy] benzoic acid 3.10 g (10 mmol) and 4
-Pyrrolidinopyridine 0.20g and DCC2.06g were melt | dissolved in chloroform 30ml, and it was made to react at room temperature for 5 hours. After the reaction, insoluble matter was filtered off, chloroform was distilled off,
The residue was purified by silica gel gel column chromatography (eluent: chloroform), and 6- (5'-benzyloxy-2'-pyrimidyl) -2- {4 "-[2-
5.83 g of (2-n-hexyloxyethoxy) ethoxy] phenylcarbonyloxy} naphthalene was obtained. The phase transition temperature (° C.) of this compound is shown below. Example 6: Preparation of 6- (5'-benzyloxy-2'-pyrimidyl) -2- [4 "-(2-n-hexyloxyethoxy) phenylcarbonyloxy] naphthalene In Example 5, 4- [2 Instead of using '-(2 "-n-hexyloxyethoxy) ethoxy] benzoic acid, 4- (2'-n-hexyloxyethoxy) benzoic acid was used according to the procedure described in Example 5 −
(5'-benzyloxy-2'-pyrimidyl) -2-
4.91 g of [4 ″-(2-n-hexyloxyethoxy) phenylcarbonyloxy] naphthalene was obtained. The phase transition temperature (° C.) of this compound is shown below. Example 7: Preparation of 6- (5'-hydroxy-2'-pyrimidyl) -2- (2 "-n-hexyloxyethoxy) naphthalene 6- (5'-benzyloxy-2'-pyrimidyl) -2
3.76 g (8 mmol) of-(2 "-n-hexyloxyethoxy) naphthalene was dissolved in 100 ml of ethyl acetate, 0.37 g of Pd / C containing 50% by weight of water was added thereto, and the mixture was stirred for 8 hours under a hydrogen atmosphere. I went, then
Pd / C was removed by filtration, ethyl acetate was distilled off from the filtrate, and 6- (5′-hydroxy-2′-pyrimidyl)-
2.97 g of 2- (2 ″ -n-hexyloxyethoxy) naphthalene was obtained (melting point: 143 ° C.).

Example 8: 6- (5'-hydroxy-2 '
-Pyrimidyl) -2- (2 "-n-butoxyethoxy)
Production of naphthalene In Example 7, 6- (5'-benzyloxy-2 '
Instead of using -pyrimidyl) -2- (2 "-n-hexyloxyethoxy) naphthalene, 6- (5'-benzyloxy-2'-pyrimidyl) -2- (2" -n-
6- (5'-hydroxy-2 'according to the procedure described in Example 7 except that butoxyethoxy) naphthalene was used.
-Pyrimidyl) -2- (2 "-n-butoxyethoxy)
2.98 g of naphthalene was obtained (melting point: 146 ° C.).

Example 9: 6- (5'-hydroxy-2 '
Preparation of -pyrimidyl) -2-n-octylcarbonyloxynaphthalene In Example 7, 6- (5'-benzyloxy-2 '
-Pyrimidyl) -2- (2 "-n-hexyloxyethoxy) naphthalene was used instead of using 6- (5'-benzyloxy-2'-pyrimidyl) -2-n-octylcarbonyloxynaphthalene. Is 6- (5'-hydroxy-2'- according to the procedure described in Example 7.
3.10 g of pyrimidyl) -2-n-octylcarbonyloxynaphthalene was obtained (melting point: 138 ° C.).

Example 10: 6- (5'-hydroxy-
Production of 2'-pyrimidyl) -2-n-octyloxycarbonyloxynaphthalene In Example 7, 6- (5'-benzyloxy-2 '
-Pyrimidyl) -2- (2 "-hexyloxyethoxy) naphthalene was used instead of 6- (5'-benzyloxy-2'-pyrimidyl) -2-n-octyloxycarbonyloxynaphthalene. According to the procedure described in Example 7, 6- (5'-hydroxy-
2.10 g of 2'-pyrimidyl) -2-n-octyloxycarbonyloxynaphthalene was obtained (melting point: 143
° C).

Example 11: 6- (5'-hydroxy-
Preparation of 2′-pyrimidyl) -2- {4 ″-[2- (2-n-hexyloxyethoxy) ethoxy] phenylcarbonyloxy} naphthalene In Example 7, 6- (5′-benzyloxy-2 ′)
Instead of using -pyrimidyl) -2- (2 "-n-hexyloxyethoxy) naphthalene, 6- (5'-benzyloxy-2'-pyrimidyl) -2- {4"-[2
Except that-(2-n-hexyloxyethoxy) ethoxy] phenylcarbonyloxy} naphthalene was used.
Following the procedure described in Example 7, 6- (5'-hydroxy-2'-pyrimidyl) -2- {4 "-[2- (2-n-
Hexyloxyethoxy) ethoxy] phenylcarbonyloxy} naphthalene (4.13 g) was obtained (melting point: 133
° C).

Example 12: 6- (5'-hydroxy-
Production of 2′-pyrimidyl) -2- [4 ″-(2-n-hexyloxyethoxy) phenylcarbonyloxy] naphthalene In Example 7, 6- (5′-benzyloxy-2 ′)
Instead of using -pyrimidyl) -2- (2 "-n-hexyloxyethoxy) naphthalene, 6- (5'-benzyloxy-2'-pyrimidyl) -2- [4"-(2
6- (5'-hydroxy-2'-pyrimidyl) -2- [4 "-(2-n according to the procedure described in Example 7, except that -n-hexyloxyethoxy) phenylcarbonyloxy] naphthalene was used. -Hexyloxyethoxy) phenylcarbonyloxy] naphthalene 4.13 g
Was obtained (melting point: 143 ° C.).

Example 13: Preparation of Exemplified Compound 13 6- (5'-n-octyloxy-2'-pyrimidyl)
-2-Hydroxynaphthalene 8.78g (25mmo
l) and sodium acetate 63 mg, acetic anhydride 90 ml
And dissolved in 100 ° C. for 30 minutes. After the completion of the reaction, water was added, the mixture was extracted with toluene, the toluene layer was washed with water, and then the toluene was distilled off to obtain a white solid. The obtained solid was separated and purified by silica gel column chromatography (eluent: toluene), and recrystallized twice from isopropanol to obtain 8.00 g of Exemplified Compound 13 as colorless crystals. The phase transition temperatures of this compound are shown in Table 4 (Tables 3 to 13). In Table 4, "・"
Indicates that the liquid crystal phase exists, and “−” indicates that the liquid crystal phase does not exist. The numbers in parentheses in Table 4 represent the temperature during the temperature decreasing process. ¹ H-NMR (CDCl ₃ ; ppm) δ = 0.8 to 2.0 (m, 15 H), 2.3 (s, 3)
H), 4.1 (t, 2H), 7.3 (m, 1H), 7.
5 (d, 1H), 8.0 (t, 2H), 8.4 (m, 3
H), 8.9 (s, 1H)

Example 14: Preparation of Exemplified Compound 14 6- (5'-n-decyl-2'-pyrimidyl) -2-hydroxynaphthalene 361 mg (1.0 mmol), palmitic acid 256 mg (1.0 mmol), 4- 21 mg of pyrrolidinopyridine and 206 mg of DCC were dissolved in 10 ml of chloroform, and the mixture was stirred at room temperature for 15 hours. After that, the insoluble matter was filtered off, chloroform was distilled off, and the residue was subjected to silica gel chromatography (eluent: chloroform).
And was recrystallized twice from isopropanol to obtain 492 mg of Exemplified Compound 14 as colorless crystals. The phase transition temperature of this compound is shown in Table 4. ¹ H-NMR (CDCl ₃ ; ppm) δ = 0.8 to 1.8 (m, 48H), 2.6 (dt, 4)
H), 7.2 (d, 2H), 7.4 (d, 2H), 7.
8 (s, 1H), 7.2 (m, 2H), 7.9 (t, 2)
H), 8.5 (d, 1H), 8.6 (s, 2H), 8.
9 (s, 1H)

Examples 15 to 50 6- (5'-substituted-2'-pyrimidyl) -shown in Table 3
A pyrimidine compound was prepared according to the procedure described in Example 14 using 2-hydroxynaphthalene or 6- (5'-hydroxy-2'-pyrimidyl) -2-substituted-naphthalene and various carboxylic acids. The phase transition temperatures of these compounds are shown in Table 4. Further, the tilt angle (θ) was measured by adding 5.0% by weight of the formula (10) (Chemical Formula 91) to the compound of Example 31 as a chiral component. Tilt angle (θ)
Is a glass test cell having a thickness of about 2 μm and having an ITO electrode and an alignment film of rubbed polyvinyl alcohol (PVA), and is filled with a liquid crystal compound.
It was determined from the angle difference (2θ) between two switching states under a polarizing microscope when a 10 V rectangular wave (1 Hz) was applied. The results (Fig. 2) (in the figure, Tc is Sc * during the temperature decreasing process)
Represents the temperature at which the phase transitioned, and T represents the measured temperature). As is clear from (FIG. 2), the pyrimidine compound of the present invention has a relatively large tilt angle (around 20 °), and the temperature dependence of the tilt angle (change in tilt angle due to temperature change) is small. I understand. In addition, a good uniform alignment state was observed by observing the test cell with a polarizing microscope.

[0156]

Embedded image Comparative Example 1 For comparison, the compound of formula (11)
No. 40985 gazette) was manufactured and the tilt angle was measured. The measurement method was the same as the measurement of the tilt angle of the compound of Example 31. The results are shown in (Fig. 2). As is clear from FIG. 2, the compound of formula (11) has a relatively small tilt angle.

[0157]

Embedded image Example 51: Production of Exemplified Compound 183 6- (5'-n-decyloxycarbonyl-2'-pyrimidyl) -2-hydroxynaphthalene 406 mg (1.
0 mmol), 158 mg of n-decyl alcohol (1.
0 mmol) and 262 mg of triphenylphosphine
Was dissolved in 16 ml of tetrahydrofuran, 0.19 ml of diethylazodicarboxylic acid was added to this solution under ice cooling, and then the mixture was reacted at room temperature for 12 hours. After the reaction, tetrahydrofuran was distilled off, the residue was purified by silica gel column chromatography (eluent: chloroform), and recrystallized twice from methanol-ethyl acetate to obtain 415 mg of Exemplified compound 183 as colorless crystals. The phase transition temperature of this compound is shown in Table 4.

Example 52: Preparation of Exemplified Compound 202 6- (5'-n-dodecyl-2'-pyrimidyl) -2-
389 mg (1.0 mmol) of hydroxynaphthalene and 212 mg (1.1 mm) of n-octyl chloroformate
solution) and chloroform (10 ml) were added dropwise with triethylamine (111 mg) under ice-cooling and then reacted at room temperature for 5 hours. After the reaction, add aqueous hydrochloric acid,
Neutralize, wash with water, distill off chloroform, and residue is subjected to silica gel column chromatography (eluent: chloroform).
And was recrystallized twice from methanol to obtain 440 mg of Exemplified Compound 202 as colorless crystals. The phase transition temperature of this compound is shown in Table 4. Further, the tilt angle of the compound was measured by the same operation as that of the compound of Example 31. The results are shown in FIG. As is clear from FIG. 2, the pyrimidine compound of the present invention has a larger tilt angle than the conventionally known compounds. Also,
A very good uniform alignment state was observed by the polarization microscope observation of the test cell.

Examples 53 to 60 6- (5'-substituted-2'-pyrimidyl) -shown in Table 3
The pyrimidine compound was prepared according to the procedure described in Example 52 using 2-hydroxynaphthalene or 6- (5'-hydroxy-2'-pyrimidyl) -2-substituted-naphthalene. The phase transition temperatures of these compounds are shown in Table 4.

Example 61: Preparation of Exemplified Compound 279 6- (5'-n-octyloxy-2'-pyrimidyl)
-2-Hydroxynaphthalene 350 mg (1.0 mmo
1) and 138 mg of potassium carbonate were suspended in 2 ml of N, N-dimethylformamide, and 4- (3 ′,
5 ', 5'-trimethylhexyloxy) benzyl bromide (313 mg) was added to N, N-dimethylformamide (3 m).
A solution dissolved in 1 was added. After stirring for 4 hours, chloroform and hydrochloric acid were added and the chloroform layer was separated. Further, the chloroform layer was washed with water, chloroform was distilled off, the residue was separated and purified by silica gel column chromatography (eluent: toluene), and recrystallized twice from isopropanol to obtain 466 mg of Exemplified compound 279 as colorless crystals. It was The phase transition temperature of this compound is shown in Table 4.
It was shown to. ¹ H-NMR (CDCl ₃ ; ppm) δ = 0.9 to 1.8 (m, 32 H), 3.9 (t, 2)
H), 4.1 (t, 2H), 5.1 (s, 2H), 6.
9 (d, 2H), 7.2 (m, 3H), 7.4 (d, 2)
H), 7.8 (dd, 2H), 8.4 (d, 1H),
8.5 (s, 1H), 8.8 (s, 1H) Examples 62 to 69 6- (5′-substituted-2′-pyrimidyl)-shown in Table 3
A pyrimidine compound was prepared according to the procedure described in Example 61 using 2-hydroxynaphthalene or 6- (5'-hydroxy-2'-pyrimidyl) -2-substituted-naphthalene and 4-substituted-benzyl bromide. The phase transition temperatures of these compounds are shown in Table 4.

Example 70: Preparation of Exemplified Compound 375 6- (5'-n-decyl-2'-pyrimidyl) -2-hydroxynaphthalene 361 mg (1.0 mmol), 4
-N-undecyloxybenzoic acid 306 mg (1.0 m
mol), 21 mg of 4-pyrrolidinopyridine and DC
C206 mg was dissolved in chloroform 10 ml and stirred at room temperature for 15 hours. After that, the insoluble matter was filtered off, chloroform was distilled off, and the residue was purified by silica gel chromatography (eluent: chloroform) and recrystallized twice from isopropanol to obtain 492 mg of Exemplified compound 375 as colorless crystals. The phase transition temperature of this compound is shown in Table 4. ¹ H-NMR (CDCl ₃ ; ppm) δ = 0.9 to 1.8 (m, 44 H), 2.7 (t, 2)
H), 4.1 (t, 2H), 7.0 (d, 2H), 7.
4 (d, 2H), 7.8 (s, 1H), 8.0 (d, 1)
H), 8.1 (d, 1H), 8.2 (d, 2H), 8.
6 (d, 1H), 8.7 (s, 2H), 9.0 (s, 1
H)

Examples 71 to 89 6- (5'-substituted-2'-pyrimidyl) -shown in Table 3
Examples using 2-hydroxynaphthalene or 6- (5'-hydroxy-2'-pyrimidyl) -2-substituted-naphthalene and 4-substituted-benzoic acid, 4-substituted-cyclohexanecarboxylic acid or 6-substituted nicotinic acid A pyrimidine compound was produced according to the procedure described in 70. The phase transition temperatures of these compounds are shown in Table 4. In addition, Example 79
With respect to the compound (1), the tilt angle was measured by the same operation as the measurement of the tilt angle of the compound of Example 31. The results are shown below. Tilt angle (°) 37.5 [Tc-10 ° C] 41.3 [Tc-20 ° C] Here, Tc represents the temperature at the time of transition to the Sc phase in the temperature lowering process. It can be seen that the pyrimidine compound of the present invention has a large tilt angle.

Example 90 Preparation of Exemplified Compound 498 6- [5 ′-(4 ″ -n) was added to 5 ml of tetrahydrofuran.
-Octyloxyphenyl) -2'-pyrimidyl] -2
-Hydroxynaphthalene 426 mg (1.0 mmol)
And 3,5,5-trimethylhexanol 144 mg,
262 mg of triphenylphosphine was added and cooled with ice water. Here, diethyl azodicarboxylic acid 0.19m
1 was added and stirred at room temperature for 15 hours. Then, tetrahydrofuran was distilled off, the residue was purified by silica gel column chromatography (eluent: toluene), and recrystallized twice from isopropanol-ethyl acetate to obtain 425 mg of Exemplified compound 498 as colorless crystals. The phase transition temperature of this compound is shown in Table 4. ¹ H-NMR (CDCl ₃ ; ppm) δ = 0.8 to 1.9 (m, 32 H), 4.0 (t, 2)
H), 4.1 (t, 2H), 7.0 (d, 2H), 7.
2 (m, 2H), 7.6 (d, 2H), 7.8 (dd,
2H), 8.5 (d, 1H), 8.9 (s, 1H),
9.0 (s, 1H) Examples 91-92 Instead of using 3,5,5-trimethylhexanol in Example 90, R-2-octanol and S-
A pyrimidine compound was produced according to the procedure described in Example 90 except that (+)-4-methyl-1-hexanol was used. The phase transition temperatures of these compounds are shown in Table 4.

Example 93: Preparation of Exemplified Compound 494 Instead of using 6- (5'-n-octyloxy-2'-pyrimidyl) -2-hydroxynaphthalene in Example 13, 6- [5'- Exemplified compound 494 was prepared according to the procedure described in Example 13 except that (4 ″ -n-octyloxyphenyl) -2′-pyrimidyl] -2-hydroxynaphthalene was used. It was shown to.

Example 94: Preparation of Exemplified Compound 672 6- (5'-n-octyloxy-2'-pyrimidyl)
350 mg of 2-hydroxynaphthalene, 161 mg of ethylene glycol mono-n-hexyl ether and 262 mg of triphenylphosphine are dissolved in 16 ml of tetrahydrofuran, and 0.19 ml of diethylazodicarboxylic acid is added to this solution under ice cooling, and then at room temperature. In 1
The reaction was performed for 2 hours. Next, tetrahydropyran was distilled off, the residue was separated and purified by silica gel column chromatography (eluent: toluene), and recrystallized twice from methanol to obtain 366 mg of Exemplified compound 672 as colorless crystals. The phase transition temperature of this compound is shown in Table 4. ¹ H-NMR (CDCl ₃ ; ppm) δ = 0.7 to 1.8 (m, 26H), 3.48 (t, 2)
H), 3.5 to 4.4 (m, 6H), 7.0 to 7.3.
(M, 2H), 7.7 to 8.0 (m, 2H), 8.4
(Bs, 1H), 8.48 (s, 2H), 8.8 (b
s, 1H) Examples 95-100 6- (5'-substituted-2'-pyrimidyl)-shown in Table 3
A pyrimidine compound was prepared according to the procedure described in Example 94 using 2-hydroxynaphthalene or 6- (5'-hydroxy-2'-pyrimidyl) -2-substituted-naphthalene and alkoxy alcohols. The phase transition temperatures of these compounds are shown in Table 4.

Example 101: Production of Exemplified Compound 673 6- (5'-n-tetradecyloxy-2'-pyrimidyl) -2-hydroxynaphthalene 433 mg, diethylene glycol monohexyl ether tosylate 413
mg and potassium carbonate 140 mg to 5 ml of N, N-
Dissolve in dimethylformamide and heat to 60 ° C for 12
Stirred for hours. Then, 20 ml of chloroform and 1/2 N hydrochloric acid were added to the reaction solution to neutralize it, and after liquid separation, the chloroform phase was washed twice with water, then chloroform was distilled off, and the residue was subjected to silica gel column chromatography. (Eluent: chloroform / hexane / ethyl acetate = 1
0: 3: 1 vol / vol / vol) and further recrystallized twice from methanol to obtain 398 mg of Exemplified Compound 673 as colorless crystals. The phase transition temperature of this compound is shown in Table 4.
It was shown to. ¹ H-NMR (CDCl ₃ ; ppm) δ = 0.7 to 1.6 (m, 38 H), 3.48 (t, 2)
H), 3.5 to 4.48 (m, 10H), 7.1 to 7.
3 (m, 2H), 7.7 to 8.0 (m, 2H), 8.4
~ 8.6 (m, 1H), 8.64 (s, 2H), 8.8
(Bs, 1H)

Examples 102 to 122 6- (5'-substituted-2'-pyrimidyl) -shown in Table 3
Example 10 using 2-hydroxynaphthalene or 6- (5'-hydroxy-2'-pyrimidyl) -2-substituted-naphthalene and the alkoxy alcohol tosylate.
A pyrimidine compound was produced according to the procedure described in 1. The phase transition temperatures of these compounds are shown in Table 4. Further, regarding the compound of Example 109, the tilt angle was measured by the same operation as the measurement of the tilt angle of the compound of Example 31. The results are shown in FIG. As is clear from FIG. 2, the pyrimidine compound of the present invention has a relatively large tilt angle (around 20 °), and the tilt angle also has a small temperature dependency. A good uniform alignment state was observed by the polarization microscope observation of the test cell. Example 123: Preparation of liquid crystal composition The following compound group (Chemical Formula 93) was mixed and used at the ratios shown below and heated and melted at 100 ° C to prepare a liquid crystal composition (ferroelectric liquid crystal composition). did.

[0168]

Embedded image The phase transition temperature (° C.) of this liquid crystal composition is shown below.

[0169]

[Table 3]

[0170]

[Table 4]

[0171]

[Table 5]

[0172]

[Table 6]

[0173]

[Table 7]

[0174]

[Table 8]

[0175]

[Table 9]

[0176]

[Table 10]

[0177]

[Table 11]

[0178]

[Table 12]

[0179]

[Table 13]

Example 124: Preparation of liquid crystal element Two 1.1 mm thick glass plates were prepared, ITO and a film were formed on each glass plate, and surface treatment was further performed. A liquid crystal aligning agent [CRD8616 manufactured by Sumitomo Bakelite Co., Ltd.] was spin-coated on the glass plate with the ITO film, and after film formation, prebaking was performed at 70 ° C.
Calcination was carried out at ℃ for 1 hour. The alignment film was rubbed and then washed with isopropyl alcohol, and silica beads having an average particle size of 2 μm were scattered on one glass plate. Thereafter, a glass plate was laminated using a sealing agent so that the respective rubbing treatment axes were antiparallel to each other, thereby producing a cell shown in FIG. Example 12 in this cell
The liquid crystal composition prepared in 3 was injected to prepare a liquid crystal element. When this liquid crystal element was sandwiched between two polarizing plates arranged in a crossed Nicols state and a voltage of ± 10 V was applied, a clear switching phenomenon was observed. In addition, a good uniform alignment state was observed by observation with a polarizing microscope. Also, the optical response time under crossed Nicols (change in transmitted light amount 10
90%) and tilt angle were measured. The results are shown in Table 5 (Table 1
4). Comparative Example 2 For comparison, the compound of the formula (12) (Chemical formula 94) (JP-A-6-
228057), and a liquid crystal composition comprising the following compound group (Chemical Formula 95) was prepared.

[0181]

Embedded image

[0182]

Embedded image This liquid crystal composition changes from an isotropic phase to an N phase at 69 ° C.
Part of the crystals crystallized at 8 ° C, and crystal phase and Sa
The phases were mixed and could not be used as a liquid crystal element. Example 125: Preparation of liquid crystal composition The following compound group (Chemical Formula 96) was mixed and used in the ratio shown below, and a liquid crystal composition (ferroelectric liquid crystal composition) was obtained by the same operation as in Example 123. Prepared.

[0183]

Embedded image The phase transition temperature (° C.) of this liquid crystal composition is shown below.

Example 126: Preparation of Liquid Crystal Element The same as Example 124 except that the liquid crystal composition prepared in Example 125 was used instead of the liquid crystal composition prepared in Example 123 in Example 124. A liquid crystal element was produced by the operation. A good uniform alignment state was observed under a polarizing microscope. Table 5 shows the measurement results of the optical response time and the tilt angle. Example 127: Preparation of liquid crystal composition The following compounds (Chemical Formula 97) were mixed and used in the ratios shown below, and a liquid crystal composition (ferroelectric liquid crystal composition) was prepared in the same manner as in Example 123. Prepared.

[0185]

Embedded image The phase transition temperature (° C.) of this liquid crystal composition is shown below. Example 128: Preparation of liquid crystal element Liquid crystal was prepared in the same manner as in Example 124 except that the liquid crystal composition prepared in Example 127 was used instead of the liquid crystal composition prepared in Example 123. A device was produced. A good uniform alignment state was observed under a polarizing microscope. Table 5 shows the measurement results of the optical response time and the tilt angle.

Comparative Example 3 For comparison, a liquid crystal composition of the following (Chemical Formula 98) containing the compound produced in Comparative Example 1 was prepared. The phase transition temperature (° C.) of this liquid crystal composition is shown below. In addition, a liquid crystal element was prepared in the same manner as in Example 124, and the optical response time and tilt angle were measured. Table 5 shows the measurement results.

[0187]

Embedded image

[0188]

[Table 14] As is clear from Table 5, the liquid crystal composition of the present invention has a comparative example 3
It can be seen that the tilt angle is larger and the response time is shorter than that of the liquid crystal composition.

[0189]

INDUSTRIAL APPLICABILITY According to the present invention, a pyrimidine compound useful as a constituent component of a liquid crystal composition, in particular, excellent alignment characteristics, good compatibility with other liquid crystal compounds, a large tilt angle, and an effect of improving response time can be obtained. It has become possible to provide certain pyrimidine compounds.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view of an example of a liquid crystal element using a liquid crystal exhibiting a chiral smectic phase.

FIG. 2 is a graph showing the tilt angles of the compounds of Examples and Comparative Examples and the temperature dependence thereof.

[Explanation of symbols]

1: Liquid crystal layer having chiral smectic phase 2: Glass substrate 3: Transparent electrode 4: Insulating alignment control layer 5: Spacer 6: Lead wire 7: Power supply 8: Polarizing plate 9: Light source I _O : Incident light I: Transmitted light

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Tsutomu Ishida 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Hiroe Kayashima 1190, Kasama-cho, Sakae-ku, Yokohama, Kanagawa Mitsui Toatsu Chemical Incorporated (72) Inventor Masakatsu Nakatsuka 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd.

Claims (14)

[Claims] 1. A pyrimidine compound represented by the general formula (1). Embedded image [Wherein, R ₁ and R ₂ are a linear or branched alkyl group or alkoxy group having 1 to 24 carbon atoms which may be substituted with a halogen atom, or a linear or branched chain having 2 to 24 carbon atoms. Represents an alkenyl group or an alkenyloxy group, and is not adjacent to each other in these groups-CH ₂ -groups (excluding Y ₁ , Y ₂ or -CH ₂ -groups bonded to an aromatic ring). Is an oxygen atom, a sulfur atom, −
It may be replaced by a CO- group, a -COO- group or a -OCO- group, and R ₁ and R ₂ may have an asymmetric carbon, which is optically active. Also, A ₁ and A ₂ represent a substituted or unsubstituted 1,4-phenylene group, pyridine-2,5-diyl group or trans-1,4-cyclohexylene group,
X ₁ and X ₂ are a single bond, a —COO— group, and —OCO—
A group, an —OCH ₂ — group or a —CH ₂ O— group, Y ₁
And Y ₂ is a —COO— group or a —OCO— group (provided that
When Y ₁ is an —OCO— group, R ₁ is not an alkoxy group or an alkenyloxy group, and Y ₂ is —COO—.
In the case of a group, R ₂ is not an alkoxy group or an alkenyloxy group), a, b, p and q each represent 0 or 1, and a + b + p + q is not 0] 2. The pyrimidine compound according to claim 1, which has liquid crystallinity. 3. In the general formula (1), R ₁ and R ₂
Is an alkyl group having no halogen atom, an alkoxy group,
An alkenyl group or an alkenyloxy group.
The pyrimidine compound described. 4. In the general formula (1), R ₁ and R ₂
4. The pyrimidine compound according to claim 1 or 3, wherein at least one of them is an alkyl group, an alkoxy group, an alkenyl group or an alkenyloxy group having an optically active asymmetric carbon. 5. In the general formula (1), R ₁ and R ₂
However, both are alkyl groups having no optically active asymmetric carbon,
The pyrimidine compound according to claim 1 or 3, which is an alkoxy group, an alkenyl group or an alkenyloxy group. 6. In the general formula (1), A ₁ and A ₂
Is a substituted or unsubstituted 1,4-phenylene group, The pyrimidine compound according to claim 1. 7. In the general formula (1), a + b + p + q
Is 1 or 2, The pyrimidine compound according to claim 1. 8. A pyrimidine compound represented by the general formula (2) (formula 2). Embedded image [In the formula, R ₃ and R ₄ represent a linear or branched alkyl group or alkenyl group having 3 to 24 carbon atoms which may be substituted with a halogen atom, m and n represent 0 or 1, and R _At least one-present in the alkyl group or alkenyl group of at least one of ₃ and R ₄ ;
CH ₂ - group (provided that adjacent -CH ₂ - except for the group - group, and -CH ₂ that is bound to an oxygen atom or an aromatic ring)
Is replaced by an oxygen atom, and the branched alkyl group or alkenyl group may have an asymmetric carbon, and the asymmetric carbon may be optically active.] 9. The pyrimidine compound according to claim 8, wherein m + n is 1 or 2 in the general formula (2). 10. The pyrimidine compound according to claim 8, wherein in the general formula (2), R ₄ is an alkyl group or an alkenyl group containing at least one oxygen atom. 11. In the general formula (2), R ₃ and R
The pyrimidine compound according to claim 8, wherein both ₄ are an alkyl group or an alkenyl group having no optically active asymmetric carbon. 12. The general formula (3) (formula 3) or (4)
A pyrimidine compound represented by Chemical formula 4. Embedded image [In the formula, B ₁ represents a hydrogen atom or a benzyl group, and R ₂
Has 1 to 24 carbon atoms which may be substituted with a halogen atom.
Straight or branched chain alkyl group or an alkoxy group having, or represents a straight-chain or branched alkenyl group or alkenyloxy group having 2 to 24 carbon atoms, -CH ₂ nonadjacent present in the group -Group (however,
Y ₁ , Y ₂ or a —CH ₂ — group bonded to the aromatic ring is excluded) is an oxygen atom, a sulfur atom, a —CO— group, a —COO—
Or a —OCO— group, R ₂ may have an asymmetric carbon, the asymmetric carbon may be optically active, and A ₂ may be substituted or Unsubstituted 1,4-phenylene group, pyridine-2,5-
Represents a diyl group or a trans-1,4-cyclohexylene group, and X ₂ represents a single bond, a —COO— group, a —OCO—
A group, a —OCH ₂ — group or a —CH ₂ O— group, and Y ₂
Is a —COO— group or a —OCO— group (provided that Y ₂ is —C.
In the case of an OO- group, R ₂ is not an alkoxy group or an alkenyloxy group), b and q each represent 0 or 1, and b + q is not 0] [In the formula, B ₁ represents a hydrogen atom or a benzyl group, and R ₄
Has 3 to 24 carbon atoms which may be substituted with a halogen atom.
Represents a straight chain or branched chain alkyl group or alkenyl group, n represents 0 or 1, and at least one -CH ₂ present in the alkyl group or alkenyl group of R ₄
- group (provided that adjacent -CH ₂ - groups, and -CH ₂ attached to an oxygen atom or an aromatic ring - excluding groups) is replaced by an oxygen atom, The alkyl group or alkenyl branched The group may have an asymmetric carbon, and the asymmetric carbon may be optically active.] 13. A liquid crystal composition comprising at least one pyrimidine compound according to claim 1 or 8. 14. A liquid crystal device using the liquid crystal composition according to claim 13.