JPH0466577A - Pyrimidine derivative and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I (R is 3-20C alkyl, 3-20C alkoxy, 3-20C alkoxyalkyl or 3-20C alkoxyalkyloxy; p is 1-16). EXAMPLE:5-Decyloxy-2-[4-(3-butenyl)phenyl]pyrimidine. USE:A component for ferroelectric liquid crystal material, providing a liquid crystal compound having a smectic C phase. PREPARATION:A halogenated phenylpyrimidine derivative shown by formula II (X1 is Cl, Br or I) is reacted with a Grignard reagent shown by formula III (X2 is Cl, Br or I) in the presence of a nickel catalyst in a solvent such as ethyl ether at -100 to 80 deg.C to give a compound shown by formula I. The amount of the Grigonard reagent used is >=1 equivalent based on the compound shown by formula I and that of the catalyst is 0.01-50 mol %.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a smectic liquid crystal compound used as a ferroelectric liquid crystal material.

<Prior Art> Currently, image display devices using liquid crystals are widely used in practical use, and a TN (twisted nematic) type display system is mainly adopted.

Although this method has advantages such as low power consumption and less eye fatigue because it is light-receiving and does not emit light itself, it has the disadvantage that the response speed of image display is slow.

However, in recent years, image display devices have tended to require particularly high-speed response, and for this reason, the response characteristics of liquid crystal compounds have been actively improved. Compared to display methods such as light emitting diodes, electroluminescence, or plasma displays, there is still a large difference in response time.

For this reason, efforts are being made to find new display methods that take advantage of the light-receptive, low-power consumption advantages of liquid crystal displays, as well as high-speed response.
Physical Letter (Appl.

Phys, Lette, ) 36.899 (19
80), a display device utilizing the optical switching phenomenon of ferroelectric liquid crystal has been proposed. This strong mN liquid crystal was discovered by R. B. and Mayer et al.
,)36. L69 (1975)), and chiral smectic C (hereinafter, Sc'''
It is said to belong to the phase (abbreviated as ).

It is known that the Sc'' phase is not the only phase that exhibits ferroelectricity, but chiral smectic F, G, H, ■, and other phases exhibit ferroelectricity.

Ferroelectric liquid crystal materials used in ferroelectric liquid crystal devices that are actually used are required to have many properties, but at present it is not possible to meet them with a single compound.
It is necessary to use a ferroelectric liquid crystal composition obtained by mixing several liquid crystal compounds or non-liquid crystal compounds.

In addition to the ferroelectric liquid crystal compositions consisting only of ferroelectric liquid crystal compounds, JP-A-61495187 discloses non-chiral smectic C, F, and G.

A compound and a composition exhibiting phases such as H and I (hereinafter abbreviated as phases such as Sc) are used as basic substances, and one or more compounds exhibiting a ferroelectric liquid crystal phase are mixed therewith to strengthen the whole. It has been reported that it can be obtained as a dielectric liquid crystal composition. Furthermore, even if one or more compounds that are optically active but do not exhibit a ferroelectric liquid crystal phase are mixed with a compound or composition exhibiting a phase such as Sc as a basic substance, the composition as a whole will not be a ferroelectric liquid crystal composition. There is also a report that [Molecular Crystal and Liquid Crystal (Mo1
．． Cryst, Lig, Cryst,) 893
27 (1982)).

Taken together, it can be seen that a ferroelectric liquid crystal composition can be constructed by mixing one or more optically active compounds with a basic substance, regardless of whether or not it exhibits a ferroelectric liquid crystal phase.

Various compounds exhibiting a phase such as Sc can be used as these basic substances, and liquid crystal compounds or mixtures exhibiting a smectic C phase are particularly desirable.

Components of these liquid crystal compounds or mixtures exhibiting smectic C include liquid crystal compounds such as phenylbenzoate, biphenyl, and 5-alkyl-2(4-alkoxyphenyl)pyrimidines.

For example, JP-A-61-291679 and JP-A-63-301872 disclose that a mixture of a phenylpyrimidine compound having an Sc phase and an optically active compound can be used as a ferroelectric liquid crystal material. .

<Problems to be Solved by the Invention> An object of the present invention is to provide a novel smectic C liquid crystal compound useful as a component of a ferroelectric liquid crystal material capable of realizing high-speed response.

<Means for Solving the Problems> As a result of intensive studies to solve the above problems, the present inventors have discovered a smectic C liquid crystal compound having excellent properties, resulting in the present invention.

That is, the present invention provides the general formula (1) (wherein R is an alkyl group having 3 to 20 carbon atoms;
20 alkoxy group, an alkoxyalkyl group having 3 to 20 carbon atoms, or an alkoxyalkyloxy group having 3 to 20 carbon atoms, and P represents an integer of 1 to 6. ) The present invention provides a pyrimidine derivative represented by the following, a method for producing the same, and a liquid crystal composition containing at least one of the above derivatives as an active ingredient.

The present invention will be explained in detail below.

- The pyrimidine derivative represented by Shipin (1) can be obtained, for example, as follows.

That is, a halogenated phenylpyrimidine derivative represented by -Funenin (I[) (wherein R represents the same meaning as above and X represents a chlorine, bromine or iodine atom), and -
In the presence of a catalyst, a Grignard reagent represented by Funato (I[[) % formula % () (in the formula, p represents the same meaning as above, and X2 represents a chlorine, bromine or iodine atom), By reacting, the desired pyrimidine derivative (1) can be obtained.

The Grignard reagent (I[[) is 1 equivalent or more times the raw material halogenated phenylpyrimidine derivative (I[),
Preferably, 1.1 to 3 equivalents are used.

The catalyst used in the above reaction is a nickel catalyst, and more specifically, nickel chloride, nickel bromide, nickel iodide, bis(acetylacetonato)nickel, dichlorobis(triphenylphosphine)nickel, dichloro( 1,2-bis(diphenylphosphino)ethane]nickel, dichloro(1,3-bis(diphenylphosphino)propane)nickel or dichloro[1,
Examples include 4-bis(diphenylphosphino)butane]nickel, and among these, nickel catalysts having a diphenylphosphino group or a triphenylphosphine group are preferably used. The nickel catalyst is usually used in an amount of 0.01 to 50 mol%, preferably 0.1 to 10 mol%, based on the raw material halogenated phenylpyrimidine derivative (II).

A solvent is usually used in the above reaction, and examples of the reaction solvent include ethers such as ethyl ether or tetrahydrofuran, or aromatic hydrocarbons such as benzene, toluene, or xylene, alone or in mixtures. The usage amount is not particularly limited.

The above reaction usually includes -100 to 80''C2, preferably
The reaction is carried out at -80 to 50°C, and the reaction time is not particularly limited.

The pyrimidine derivative (1) can be removed from the reaction mixture by conventional post-treatments such as extraction, separation or concentration, and if necessary, methods such as recrystallization or silica gel column chromatography. It can also be purified by

The raw material halogenated phenylpyrimidine derivative (It
) and Grignard reagent (I[l) can be obtained according to known methods.

Examples of the pyrimidine derivative represented by N) of the present invention include the following compounds.

5-Substituted-2-(4-(2-propenyl)phenyl]pyrimidine 5-substituted-2-(4-(3-butenyl)phenyl)pyrimidine 5-substituted-2-[4-(4-pentenyl)phenyl] pyrimidine 5-f-substituted-2-C4-(5-hexenyl)phenyl]pyrimidine 5-substituted-2-(4-(6-hebutenyl)phenyl)pyrimidine 5-substituted-2-(4-<7-octenyl ) phenyl]pyrimidine 5-W-substituted-2-(4-(8- 10-undecenyl)phenyl]pyrimidine 5-substituted-2-(4-(11-dodecenyl)phuninyl)
Pyrimidine 5-substituted-2-C4-(12-)lysocenyl)phenyl]pyrimidine 5-substituted-2-(4-(14-pentadecenyl)phenyl)pyrimidine 5-substituted-2-[4-(16-hebutadecenyl) phenyl]pyrimidine.

More specifically, substitution refers to propyl, butyl,
Alkyl groups represented by pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexedecyl; propoxy, butoxy,
Pentoxy, hexyloxy, hebutyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, alkoxyl groups represented by dodecyloxy, tetradecyloxy, hexadecyloxy; methoxyethyl, methoxypropyl, methoxybutylmethoxypentyl, methoxyhexyl, methoxyheptyl, Methoxyoctyl, methoxynonyl.

Methoxydecyl, methoxidedodecyl, ethoxymethyl
Ethoxyethyl, ethoxypropyl, ethoxybutyl
Ethoxypentyl, Ethoxyhexyl, Ethoxyhbutyl Ethoxyhexyl, Ethoxyhbethyl Ethoxyoctyl, Ethquinnonyl, Ethoxydecyl, Ethquinundecyl, Propoxymethyl, Propoquinethyl, Propoquinepropyl Propoxybutyl Propoxypentylpropoxyhexyl Propoxyhbutyl Propoxyoctyl , propoxynonyl, propoxydecyl-5-propoxyundecyl, butoxymethylbutoxyethyl,
Butoxypropyl Butoxybutyl, Butoxypentyl, Butoxyhexyl, Phthoxyheptyl, Butoxyoctyl, Butoxynonyl, Butoxydecyl Pentyloxymethylpentyloxyethyl Pentyloxypropyl Bentyloxybutyl Pentyloxypentyl.

Pentyloxyhexyl, pentyloxyoctyl, pentyloxydecyl Hegyloxymethyl, hexyloxyethyl, hexyloxypropyl, hexyloxybutyl, hexyloxypentyl, hexyloxyhexyl, hexyloxyoctyl Hexyloxynonyl Hexyloxydecyl, heptyl Oxymethyl, heptyloxyethyl, heptyloxypropyl, heptyloxyethyl hestyloxypentyl octyloxymethyl octyloxyethyl octyloxypropyl decyloxymethyl Desoloxyethyl, decyloxypropyl, octyloxybutyl, decyloxybutyl. Alkoxyalkyl group: methoxyethoxy9 methoxypropoxy, methoxybutoxy, methoxypentyloxy, methoxyhexyloxy,
Methoxyhebutyloxy methoxyoctyloxymethoxynonyloxy, methoxydecyloxymethoxydodecyloxy, ethoxyethoxy, ethoxypropoxy,
Ethoxybutoxy 2 ethoxypentyloxy, ethoxyhexyloxy, ethoxyhebutyloxy, ethoxyoctyloxyethoxynonyloxy, ethoxydecyloxy.

Ethoxyusidecyloxy, propoxyethoxybroboxybropoxy, propoxybutoxy, propoxypentyloxy, propoxyhexyloxy propoxyhebutyloxy, propoxyoctyloxy, propoxynonyloxy, propoxyocluoxy propoxyundesoloxybutoxyethoxy5 butoxypropoxy, butoxy Butoxy butoxypentyloxy, butoxohexyloxy, butoxyhebutyloxo butoxyoctyloxy, butoxynonyloxy phthoxydecyloxy, benzyloxyethoxybentyloxypentyloxy, pentyloxybutoxo, pentyloxypentyloxo, pentyloxo Hexyloxy, pentyloxyoctyloxy, pentyloxydecyloxy hexoloxine ethoxy, hexyloxopropoquine hexyloxybutquin hexyloxynoventyloxo, hexyloxyhekynluoquine hexyloxyoctyloxy hexyloxynonyloxy 2hexyloxo Decyloxy Hebutyloxyethoxy, Heptyloxopropoxy Hexyloxybutoxy Hebutyloxypentyloxy, Octyloxyethoxo,
octyloxypropoxy, octyloxobutoxy,
Decyloxyethoxy, Decyloxybutoxy Alcoquinoalkyloxy group represented by decyloxybutoxy.

The pyrimidine derivative (1) of the present invention is a compound that has a double bond at the end of its alkyl chain and has a smectic C liquid crystal phase.

Unlike conventional liquid crystal phases such as nematic phases, the smectic C liquid crystal phase can exhibit ferroelectricity by mixing an appropriate amount of an optically active substance. As described above, liquid crystal having a smectic C phase is the most important substance from the viewpoint of a component of a ferroelectric liquid crystal material.

The pyrimidine derivative having smectic C liquid crystal properties of the present invention can constitute a ferroelectric liquid crystal material by mixing it alone or in the form of a smectic C mixture with at least one optically active compound.

<Effects of the Invention> The present invention provides a novel smectic C liquid crystal compound, and by using the smectic liquid crystal compound in combination with an optically active compound, an excellent ferroelectric liquid crystal material can be provided.

<Example> Hereinafter, the present invention will be explained in more detail with reference to Examples. Example 1 5-decyloxy 2- to diethyl ether 100111
After adding 3.91 g of (4-bromophenyl)pyrimidine and 0.08 g of dichloro(1,3-bis(diphenylphosphino)propane)nickel and cooling to 10°C,
A diethyl ether solution (0.3M solution, 50d) of -butenylmagnesium bromide was added dropwise, and the mixture was stirred at room temperature for 6 hours and at reflux temperature for 1 hour.

After the reaction was completed, the mixture was poured into 200 d of water, and after extraction and separation, the organic layer was concentrated under reduced pressure to obtain a light brown residue.

This was subjected to silica gel column chromatography (eluent;
toluene/hexane) to give 5-decyloxy-2
-(4-(3-butenyl)phenyl]pyrimidine 3.1
g (yield 85%) was obtained.

NMR data (CDCl2 60MH2) 8 (ppm
) :0.7~3.0 (23H, m)4.1 (
2H,t, -CH2O-)4.7 ~5.3 (2
H, m, =CH,)5.5~6.2 (I H,
m, -CH=) Example 2 3.35 g of 5-hexyloxyethoxy-2-(4-chlorophenyl)pyrimidine on diethyl ether 100 paper
and 0.07 g of dichloro[1,4-bis(diphenylphosphino)butane]nickel were added, and after cooling to 10°C, diethyl ether d) of 8-nonenylmagnesium bromide was added dropwise, and the mixture was heated as it was at room temperature. The mixture was stirred at reflux temperature for 1 hour.

After the reaction was completed, the mixture was poured into 200 d of water, and after extraction and separation, the organic layer was concentrated under reduced pressure to obtain a white residue.

This was purified by silica gel column chromatography (78 eluent; toluene/hexane) to obtain 2.4 g (yield 56%) of 5-hexyloxyethoxy-2-[4-(8-nonenyl)phenyl]pyrimidine. .

Examples 3 to 7 Example 1 except that 5-decyloxy-2(4-bromophenyl)pyrimidine was replaced with the compound shown in Table 1, and 3-butenylmagnesium bromide was replaced with the Grignard reagent shown in Table 1. The reaction and post-treatment were carried out according to Example 1, and the results shown in Table 1 were obtained.

Examples 8 and 9 Liquid crystal compositions shown in Table 2 were prepared using liquid crystal compounds. The preparation was carried out by mixing a predetermined weight of a predetermined compound in a sample bottle while heating and melting it.

[Liquid crystal element manufacturing method 1: A polyimide polymer pole is provided on a glass substrate on which an indium oxide transparent electrode is provided, and rubbed with gauze in a certain direction so that the rubbing directions of the two substrates are parallel. A liquid crystal cell was assembled using glass Phino (5 μm in diameter) as a spacer, and the liquid crystal composition was vacuum-sealed into the cell to obtain a liquid crystal element.

This liquid crystal element was combined with a polarizer, an electric field of 20 V was applied on the temperature variable bullet, and a phase change was observed without reversing the polarity.

The results are shown in Table-2.

Claims (3)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R is an alkyl group with 3 to 20 carbon atoms, 3 to 20 carbon atoms
20 alkoxy group, an alkoxyalkyl group having 3 to 20 carbon atoms, or an alkoxyalkyloxy group having 3 to 20 carbon atoms, and p is an integer of 1 to 16. ) pyrimidine derivatives. (2) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R represents the same meaning as above, X_1 is chlorine,
Indicates a bromine or iodine atom. ) to the halogenated phenylpyrimidine derivative represented by the general formula X_2Mg(CH_2)_pCH=CH_2 (in the formula, p
represents the same meaning as above, and X_2 represents a chlorine, bromine or iodine atom. 2. The method for producing a pyrimidine derivative according to claim 1, wherein the Grignard reagent represented by the following formula is reacted in the presence of a catalyst. (3) A liquid crystal composition containing one or more of the pyrimidine derivatives according to claim 1 as an active ingredient.