JPH02131444A - Liquid crystal compound - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I (R is 1-20C alkyl which may be replaced with halogen or alkoxy; X is single bond, O, OCO, etc.; A and B are cyclic group; Y is single bond, COO, OCO, CidenticalC, CH=N, S-CH2, etc.; Z is single bond, O, COO or S; m is 1-18; W is single bond, CO or COO; R' is 1-18C alkyl which may be replaced with halogen or alkoxy). EXAMPLE:4'-(4-Ethyloxy-5,5,5-trifluoropentyloxy)phenyl-4-(n-decyloxy)h enzoate. USE:A liquid crystal compound having large spontaneous polarization. PREPARATION:For example, a compound shown by formula II (p is 0-4) is reacted with a compound shown by formula III to give a compound shown by formula I wherein X is single bond or O, A is group shown by formula IV, Y is single bond, B is group shown by formula V and Z is 0.

Description

[Detailed description of the invention] [Industrial application fields] The present invention relates to liquid crystal compounds.

[Prior Art] Conventionally, various ferroelectric liquid crystals, such as 4-octyloxy-4'-biphenylcarboxylic acid-2, have been used as liquid crystal compounds.
-octyl ester and p-decyloxybenzoic acid p'-(2-methylbutoxycarbonyl)phenyl ester [EP 01102
99].

[Purpose of the Invention] The present inventors have discovered that the properties in the liquid crystal state can be controlled by changing the structure of the alkyl chain adjacent to the asymmetric carbon atom, and that the asymmetric carbon atom has a large polarization. The present invention was achieved as a result of intensive studies aimed at obtaining a liquid crystal compound capable of having large spontaneous polarization by directly bonding a fluoromethyl group and further having an oxygen atom adjacent to an asymmetric carbon atom.

Means for Achieving the Objects of the Invention In other words, the present invention is based on the general formula
is a single bond, 10-, 10001 or -OC00-, and A and B are KΣ, it, dai, dai, id, heat, it, shi}, ÷, -G{a, {} O-・Bet} {to, {>-K},
{ba}, {}O-, iX}, i) {}- {H}・{ba}・{>-G-・{ba}・{X}・i
X}・{)=C00-0-, -o-oco-o-,,OCI'
, -G@-, {X consideration, ÷8}, W, {R} and -0+ (the cyclic group is 1-
Y may be substituted with up to 4 fluorine atoms, or one or two substituents selected from the group consisting of chlorine atoms, bromine atoms, cyano groups, nitro groups, and trifluoromethyl groups; is a single bond, -COO-, -OCO-
, -C Town-, -CI+2-0-, -0-CI+2-,
-COS-, -SCO-, -CH=N-, -N=CH-
, -N=N-, -CH2-S- or -S-CH2-te, Z is a single bond, -0-, -COO- or -S, m is an integer from 1 to 18, W is a single bond, one CO-
or 1C00-, R' is an alkyl group having 1 to 18 carbon atoms which may be substituted with a halogen atom or an alkoxy group, and the wooden stamp indicates optical activity. ]
It is a liquid crystal compound represented by

The liquid crystal compounds of the present invention include those whose liquid crystal state can be observed by themselves, and substances which are useful as constituents of liquid crystal compositions even if the liquid crystal state cannot be observed by themselves.

In the general formula (1), the alkyl group having 1 to 2 carbon atoms which may be substituted with a halogen atom or an alkoxy group for R is a straight chain alkyl group (methyl group, ethyl group, proyl group, butyl group, bentyl group). , hexyl group, hebutyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, octadecyl group, etc.), branched alkyl group (isobrobyl group, l-methylpropylene group, etc.) Biru group, 1-methylbutyl group, 1-methylhexyl group, 1-methylheptyl group, 2-methylbutyl group, 2-methylbentyl group, 2-methylhexyl group, 2-methylhebutyl group, 2-methyloctyl group, 3-methylpentyl group, 4-
methylbentyl group, 4-methylhexyl group, 5-methylhebutyl group, 6-methyloctyl group, 7-methylnonyl group, 8-methyldecyl group, 9-methyldecyl group),
An alkyl group having a substituent [for example, an alkyl group substituted with CI (chlorine atom) (2-chloroprobyl group, 2
-chlorobutyl group, 2-crocobentyl group, 2-chlorohexyl group, 2-chlorohebutyl group, 2-chlorooctyl group, 1-chloro-2-methylpropyl group, 1-chloro-2-methylbutyl group, l-chloro-3- methylbutyl group, etc.), F-substituted alkyl group (2-fluoroprovir group, 2-fluorobutyl group, 2-fluorobentyl group, 2-fluorohexyl group, 2-fluorohbutyl group, 2-fluoro Octyl group, 1-fluoro-2-methylbrobyl group, 1-fluoro-2-methylbutyl group,
(1-fluoro-3-methylbutyl group, etc.), alkyl groups substituted with alkyloxy groups (2-methoxybutyl group, 2-ethoxybutyl group, 2-propyloxybutyl group, 3-methoxybutyl group), group, 3-ethoxybutyl group, 3-propyloxybutyl group, 4-methoxybentyl group, 4-ethoxypentyl group, 4-propyloxypentyl group, 3-methoxybutyl group, 3-ethoxybutyl group group, 3-propyloxybutyl group, 3-hexyloxybutyl group, 4-methyloxybutyl group, 4-propyloxybutyl group, 4-hexyloxybutyl group, etc.), optically active Alkyl groups (optically active 2-methylbutyl group, optically active 2-methylpentyl group, optically active 2-methylhexyl group, optically active 2-methylhebutyl group, optically active 2-methyloctyl group, optically active 3-methylpentyl group) , optically active 4-methylhexyl group, optically active 5-methylhebutyl group, optically active 6-methyloctyl group, optically active l-methylbrobyl group, optically active 1-methylbutyl group, optically active 1-methylheptyl group, optically active l
-methyloctyl group, etc.) and an optically active alkyl group having a substituent [for example, an optically active alkyl group substituted with CI (chlorine atom) (optically active 2-chloroprobyl group, optically active 2-chlorobutyl group, optically active Active 2-chloropentyl group, optically active 2-chlorohexyl group, optically active 2-chloroheptyl group, optically active 2-chlorooctyl group, optically active 1-chloro-2-methylprobyl group, optically active 1-chloro- 2-methylbutyl group, optically active l-chloro-3-methylbutyl group), optically active alkyl group substituted with F (fluorine atom) (optically active 2-fluorobrobyl group, optically active 2-fluorobutyl group, Optically active 2-fluoropentyl group, optically active 2-fluorohexyl group, optically active 2-fluoroheptyl group, optically active 2-fluoroheptyl group
-fluorooctyl group, optically active l-fluoro-2-methylpropyl group, optically active 1-fluoro-2-methylbutyl group, optically active 1-fluoro-3-methylbutyl group, etc.) and optically active groups substituted with alkyloxy groups. alkyl groups (optically active 2-methoxybutyl group, optically active 2-ethoxybutyl group, optically active 2-propyloxybutyl group, optically active 2-butyloxybrobyl group, optically active 2-hexyl Oxyprobyl group, optically active 3-methoxybutyl group, optically active 3-ethoxybutyl group, optically active 3-propyloxybutyl group, optically active 4-methoxypentyl group, optically active 4-ethoxypentyl group, optically active 4 -pro and hydroxypentyl group, optically active 4-butyloxypentyl group, optically active 4-hexyloxybentyl group, optically active 4-(2-methylbutyloxy)butyl group, optically active 2-ethyloxy-3, 3,3- }rifluoropropyl group, optically active 3-ethyloxy-4,
4.4- 1-Refluorobutyl group, optically active 4-ethyloxy-5,5.5- }Refluoropentyl group, optically active 5-ethyloxy-6,6.6-trifluorohexyl group, optically active 6- Ethyloxy7.7.7-}
Rifluorobheptyl group, optically active l-methyl-2-methyloxyethyl group, optically active l-methyl-2-ethyloxyethyl group, optically active 1-methyl-2-propyloxyethyl group, optically active 1-methyl- 2-butyloxyethyl group, optically active 1-methyl-2-hexyloxyethyl group, optically active l-methyl-3-methyloxybrobyl group, optically active 1-methyl-3-ethyloxybutyl group, optically active l-methyl-3-butyloxybutyl group,
Optically active 1-methyl-4-methyloxybutyl group, optically active l-methyl-4-ethyloxybutyl group, optically active l-methyl-4-butyloxybutyl group, optically active l-
Methyl-5-methyloxypentyl group, optically active 1-methyl-5-ethyloxypentyl group, optically active l-methyl-5-butyloxypentyl group, optically active l-methyl-7-methyloxyheptyl group, optically active l -Methyl-
7-ethyloxyhebutyl group, optically active l-methyl-7
-butyloxyheptyl group, optically active 1-}lifluoromethyl-2-ethyloxyethyl group, optically active 1-1.
Rifluoromethyl-3-ethyloxybutyl group, optically active 1-trifluoromethyl-4-ethyloxybutyl group, optically active l-trifluoromethyl-5-ethyloxybentyl group, optically active 1-trifluoromethyl-7 −
Examples include ethyloxyheptyl group, etc.).

Among these, preferably an alkyl group having 1 to 15 carbon atoms.

X is preferably a single bond or 101.

A and B are preferably a center, a bare, a core, which may be substituted with 1 to 2 fluorine atoms, a)-,-CK)=
, {pa}, bet} {to, bet} {to, iba}, -0{}, {
H}, {}{2, iX}, -o-coo-o- and +
oco-o-.

Y is preferably a single bond, -COO-, -OCO-, -0
-Cll2-, -CH2-0- and 10miC1.

Z is preferably 101 and -C00-.

Examples of the alkyl group having 1 to 18 carbon atoms which may be substituted with a halogen atom or an alkoxy group for R' include straight chain alkyl groups (methyl group, ethyl group, proyl group, butyl group,
Bentyl group, hexyl group, hebutyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, octadecyl group, etc.), branched alkyl group (isopropyl group, l -Methylbrobyl group, 1-methylbutyl group, 1-methylhexyl group, 1-methylhebutyl group, 2-methylbutyl group, 2-methylpentyl group, 2-methylhexyl group, 2-methylheptyl group, 2-methyloctyl group, 3-methylpentyl group, 4-methylbentyl group, 4
-methylhexyl group, 5-methylhebutyl group, 6-methyloctyl group, 7-methylnonyl group, 8-methyldecyl group, 9-methyldecyl group, etc.), alkyl groups having substituents [e.g., substituted with Cl (chlorine atom)] alkyl groups (2-chloroprobyl group, 2-chlorobutyl group, 2-chlorobutyl group,
-chlorobentyl group, 2-chlorohexyl group, 2-chlorohebutyl group, 2-chlorooctyl group, 1-chloro-2
-methylbrobyl group, 1-chloro-2-methylbutyl group, 1-chloro-3-methylbutyl group, etc.), F-substituted alkyl group (2-fluoropropyl group, 2-fluorobutyl group, 2-fluoropentyl group, 2-fluorohexyl group, 2-fluorohbutyl group, 2-fluorooctyl group, 1-fluoro-2-methylbrobyl group, 1-
fluoro-2-methylbutyl group, 1-fluoro-3-methylbutyl group, etc.), argyl groups substituted with alkyloxy groups (2-methoxypyl group, 2-ethoxypyl group, 2-propyloxypyl group), group, 3-methoxybutyl group, 3-ethoxybutyl group, 3-propyloxybutyl group, 4-methoxypentyl group, 4-ethoxypentyl group, 4-propyloxypentyl group, 3-methoxybutyl group, 3-methoxybutyl group Ethoxypyl group, 3-propyloxypyl group, 3-hexyloxypyl group, 4-
Methyloxybutyl group, 4-propyloxybutyl group,
4-hexyloxybutyl group, etc.), optically active alkyl groups (optically active 2-methylbutyl group, optically active 2-methylbutyl group, etc.), optically active alkyl groups (optically active 2-methylbutyl group, optically active
- methylbentyl group, optically active 2-methylhexyl group,
Optically active 2-methylheptyl group, optically active 2-methyloctyl group, optically active; 3-methylbentyl group, optically active 4-methylhexyl group, optically active 5-methylhebutyl group, optically active 6-methyloctyl group , optically active l-methylbrobyl group, optically active l-methylbutyl group, optically active l
- methylhebutyl group, optically active 1-methyloctyl group) and an optically active alkyl group having a substituent (for example, an optically active alkyl group substituted with CI (chlorine atom) (optically active 2-chloroprobyl group) , optically active 2-chlorobutyl group, optically active 2-chloropentyl group, optically active 2-chlorohexyl group, optically active 2-chlorohebutyl group, optically active 2-chlorooctyl group, optically active l-chloro-2- Methylbrobyl group, optically active 1-chloro2-
methylbutyl group, optically active 1-chloro-3-methylbutyl group), optically active alkyl group substituted with F (fluorine atom) (optically active 2-fluoropropyl group, optically active 2-fluorobutyl group, optically active 2-fluoropentyl group, optically active 2-fluorohexyl group, optically active 2-
Fluoroheptyl group, optically active 2-fluorooctyl group, optically active l-fluoro-2-methylbrobyl group, optically active 1-fluoro-2-methylbutyl group, optically active 1-
(fluoro-3-methylbutyl group, etc.) and an optically active alkyl group substituted with an alkyloxy group (optically active 2
-Me1-xybrovir group, optically active 2-ethoxybutyrovir group, optically active 2-propyloxibrovir group, optically active 2-butyloxybuylyl group, optically active 2-hexyloxybuylyl group, optically active 3 1-methyl-xybutyl group,
optically active 3-ethoxybutyl group, optically active 3-probyloxybutyl group, optically active 4-methoxybentyl group, optically active 4-ethoxypentyl group, optically active 4-probyloxybutyl group Cypentyl group, optically active 4-butyloxypentyl group, optically active hexyloxypentyl group, optically active (2-methylbutyloxy)butyl group, optically active 2-ethyloxy-3,3.3- }refluoro propyl group, optically active 3-ethyloxy-4,4.
5-}Refluoropentyl group, optically active 5-ethyloxy-6.6.6-}Refluorohexyl group, optically active 6-ethyloxy? ,7.7- }Refluorobutyl group, optically active l-methyloxyethyl group, optically active 1
monoethyloxyethyl group, optically active 1-propyloxyethyl group, optically active l-butyloxyethyl group, optically active l-hexyloxyethyl group, optically active l-methyloxy-2,2.2-}rifluoroethyl group, optically active 1-ethyloxy-2.2.2-trifluoroethyl group, optically active l-propyloxy-2.2.2-trifluoroethyl group, optically active 1-butyloxy-2,2,2
- }Lifluoroethyl group, optically active l-hexyloxy-2.2.2-}lifluoroethyl group, optically active l-
Methyl-2-methyloxyethyl group, optically active 1-methyl-2-ethyloxyethyl group, optically active l-methyl-
2-propyloxyethyl group, optically active 1-methyl-2
-butyloxyethyl group, optically active 1-methyl-2-hexyloxyethyl group, optically active 1-methyl-3-methyloxybrobyl group, optically active l-methyl-3-ethyloxybutyl group, optically active l -Methyl-3-butyloxybutyl group, optically active l-methyl-4-methyloxybutyl group, optically active l-methyl-4-ethyloxybutyl group, optically active l-methyl-4-butyloxybutyl group, optical Active 1-methyl-5-methyloxypentyl group, optically active 1-methyl-5-ethyloxypentyl group,
Optically active 1-methyl-5-butyloxypentyl group, optically active l-methyl-7-methyloxyhebutyl group, optically active 1-methyl-7-ethyloxyhebutyl group, optically active l-methyl-7-butyloxyhebutyl group hebutyl group, optically active 1-}refluoromethyl-2-ethyloxyethyl group,
Optically active 1-}rifluoromethyl-3-ethyloxybutyl group, optically active 1-trifluoromethyl-4-ethyloxybutyl group, optically active 1-trifluoromethyl-
5-ethyloxypentyl group, optically active 1-}refluoromethyl-7-ethyloxyhebutyl group, etc.).

Among these, preferably an alkyl group having 1 to 9 carbon atoms.

Specific examples of the liquid crystal compound represented by general formula (1) include:
Examples include compounds having groups and numbers as shown in Table 1.

Although the compound represented by the general formula (1) may be used alone, it is preferably used as a mixture of two or more of the compounds represented by the general formula (1) and/or other components.

The compound of general formula (1) can be synthesized, for example, through the following steps. [In the following formula, R, m and R' are general formula (1)
This is the same as in the case of . Ts- represents p-}luenesulfonyl group. Generally, other leaving groups such as Br (bromine atom) can be used in place of the Ts-0 group. p and q are integers from 0 to 4, and p+q≦4. CoCu2(CN)2 HCI, EtOH N}13, EtOH (1) X is a single bond or 101, A is it, Y is a single bond, ↓ Ts-0-(C}12)m-C CF3) H-0-W
-R', KO}l Sion Reagent (2) X is a single bond or 10-, A is {t, Y is a single bond, HO-(CH2)m-Cl:(CF3)H-0'W-
R', Simultaneous acid, DCC NaOH, EG'rs-0-(Cll2)m-C1:(CF3)fl-
0-W- R', KOHB is {}, Z is a single bond or 101, B is {}, Z is -COO-, or Z is 10-, El, -0 -CI-C(COOEt)2, EtONa
POCl3 ↓ Shi! Pd/C,}12,Cl3COOK ↓ NaO}1aq. SOCl2 1-10-(C112)m-C:l:(CF3)}l-
If 0-W-R'8 is 1, and Z is 101, then ↓ POCI3,DMF If B is K and Z is -C00-, ↓ Cu2(CN)2 ↓ KO}Iaq. SOCl2 NO-(C)f2)m-Cshi(CF3)}l-0-W-
When R' is -0-, ↓ NaO}1 ↓ 82NCONll2 , HCI ↓ POCl3 ↓ NaH , t10-(Cll2)m-C:l:(CF
3) T0-W-R' or ↓ Ts-0-(C}12)m-Cne(CF3)H -0-
W-R', KOH↓ Ts-0-(CII2)m-C:t(CF'3)H-0
-W-R',KOt{POCI3,DMF NaOH ↓ 02NCONH2 11C1 ↓ POCI3 ↓ Natl, R-OH or Mi↓ R-0-Ts, KOII If Z is -0-, ↓ Ts-0-(C112)+u -C pull: (CF3) Old 0-
WR', KO}lPOCI3, [lMF NaOtl ↓ KOHaq. SOC 12 }10-(CH2)m-C:I:(CF3)tl-0-
~ If R'Z is -C00-, POCl3, DMF NaOH If -C00-, ↓ Cu2(CN)2 POCl3, DMF Na011 ↓ H2NCONll2, HCI ↓ POCI3 ↓ t4aH, R-OH ↓ Cu (CN) 2 ↓ KOtlaq. SOCl2 HO-(Cll2)n+-C:i:(CF3)H-0-
When W-R'Z is 101, ↓ Ts-0-(CH2)m-Cl:(CF3)II-0-
WR', κ011↓ Q, Et-0-Et (12) X is a single bond or -0-, A#1-G-, Y
is a single bond, Br2,THF 11,0 ↓ Nall, IO-(Cll2)m-C:t(CF3
)If-0-W-R 'If B is id and Z is 10-, B is iF1 If Z is -C00-, ↓ BuL i ,Q ↓ Cu2(CN)2 ,NMP ↓ POCl3 ↓ KOtlaq ．． ↓ R-078, Naf( SOCl2 110-(CI2)m-C.1:(CF3)If-0-
WR' and ↓ R-Mg-tlal. (15) When X is a single bond or 10-, A is {t, ■ is a single bond, and Z is -COO-, ↓ Se02 ↓ Nll2CH2CONH2・IIcI ↓ R-0-1{, Nal{ (F)p R-BIH 鋺N ↓ KOllaq. SOCI2 tlO-(CH2)m-C:I:(CF3)tl-0-
If WR'Z is -COO-, ↓ KO}laq. SOC 12 110-(CH2)+++-C4:(CF3)If-0
-W-R'KOIIaq. HC1 ↓ -C02 SOC 12 NO-(CIl2)m-C:I:(CI'3)If-0
-W-R' or, ↓ POC 13 , Seamethyl7nirisi ↓ Cu2(CN)2 If B is CF3) If
-0-W-R'B? If Z is 1600-, ↓ κOHaq. If Z is 10-, ↓ Ts-0-(CH2)u+-C:l:(CF3)If-
0-W-R', KOIIB is 10-, when Z is 10-, succinic anhydride, AICI3 N2H4 competition 820 Dehydrogenation: When X is a single bond, Br2, AcO}IX is -0
- When Se02 Na}l, IO-(CI2)III-C2l:(C
F3) H-0-W-R 'Pd/C, ■2 Δ mouth 1 low ↓ 1'sO-(CH2)urc:I:(CF3)tl-0
-W-R', NaOH↓ Pd/C, H2 case・↓ }10- (Cll2)+n-C:i:(CF3)H-
0-W-R' Note that in the synthetic routes (22) to (24) above, A and B are respectively Kγ, {warm, {x}, be}{Σ, -o-coo-o-, -0-OCO -0-, zu summer, G {thought, {} {needle, 噸} {to, be} {i, -C
A cyclic group selected from the group consisting of IO@- and -0-0- (the cyclic group consists of 1 to 4 fluorine atoms, or chlorine atoms, bromine atoms, cyano groups, nitro groups, and trifluoromethyl groups) When C (optionally substituted with one or two substituents selected from the group) is present, the corresponding compound of general formula (1) can be obtained by carrying out the same reaction.

Δ Mouth 1 TsO-(Cll2)n+-C:l:(CF3)H-0
-W-R', KOII, }10-(CI-12)+++-C*(CF3)I1-
A compound of 0-W-R' can be obtained.

In the case of 1, in the synthetic routes (25) to (2G) above, A is .
A cyclic group selected from the group consisting of 1 to 4 fluorine atoms, or a chlorine atom, a bromine atom, a cyano group, a nitro group, and a trifluoromethyl group. (optionally substituted with one or two substituents selected from the group consisting of
A cyclic group selected from the group consisting of -, -0-COO{)- and -o-oco-o- (the cyclic group has 1 to 4 fluorine atoms, or a chlorine atom, a bromine atom, a cyano group, a (which may be substituted with one or two substituents selected from the group consisting of tro group and trifluoromethyl group) can also be converted to the corresponding general formula (1) by performing the same reaction. 27) In the synthetic routes of (28), A and .B are each a cyclic group selected from the group consisting of ÷ and -0-0- (the cyclic group has 1 to 4 fluorine atoms or chlorine atoms, 1 selected from the group consisting of bromine atom, cyano group, nitro group and trifluoromethyl group
or may be substituted with two substituents), the corresponding general formula (1
) can be obtained.

If ↓ NaollaQ @ ↓ SOCl2 ↓ HO-(C}f2)m-C*(CF3)}f-
0-W-R' In the above synthetic route, A is a pair, base}
{A cyclic group selected from the group consisting of Σ and Be (optionally substituted with 1 or 2 substituents), and B is a cyclic group selected from the group consisting of (Optionally substituted with one or two substituents selected from the group consisting of atom, bromine atom, cyano group, 21-mouth group, and trifluoromethyl group)
Even in the case where it is, the corresponding compound of general formula (1) can be obtained by performing the same reaction.

(30) X is a single bond or 10-, A is a group, Y is -C
00-, R-X{}COCI (31) Xh”i single bond mata is 101, A is it, Y
Car-COO-, R-Xbe:80C l R-X{80CI Δ mouth) ↓ ↓ ↓ C I-CO+OC}12-<F Pd/C, H2 HO- (Ctl2)m-C:t(CF3) H-0-W
- R', NaHΔ mouth 1 ↓ CI-CO{}0-(CH2)m-C*(CF3)H-
0-W-R' (35) X is a single bond or 10-, A is {t, Y is -OCO-, (33) X is a single bond or -
0-, A card, Y/71-COO-, R-X+OH ↓ HO-Q-o-(CH2)o+-(J(CF3)H-0
'W-R' or ↓ Na011,EG ↓ Ts-0-(Ctl2)+++-C:f:(CF3)to0-W-R', KOII↓ Ts-0-(CI2)m-C:l :(CF3)H-0-
W- R', KOt {single bond, B is {}, Z is 10-, ↓ Pd/C, H2 ↓ Ts-0-(CI2) to-C*(CF3)tl-0-
WR', KOII↓ C3-cis' reagent↓ HO-(C}12)il-C:I:(CF3)}I-0
--Gi Rj, ci methyl 1 minohi 0 reseen. DCC ↓ Pd/C, ■2 ↓ Ts-0-(CH2)m-(J(CF3)}l-0-W
- R' , KOHPOCl3, DMF Mg(CI04)2 ↓ [0-(CH2)m-Ct(CF3)f{-0-W-R
'(43) X is a single bond, A is a be}, and Y is a single bond,
B is Δ Mouth 1 ↓ 48χlBraq. ↓ TS-0-(C112)m-C:t(CF3)
H-0-W-R', KOII↓ Ts-0-(CH2)m-C*(CF3)tl-0-W
-R' (44) When X is -0-, A is Bay}, Y is a single bond, B is Iγ, and Z is -C00-, R-0{ΣOKΣCO-CI In the above synthetic route, A, A cyclic group in which B is each selected from the group consisting of -0- and -0-0- (the cyclic group is a fluorine atom with 1 to 4 atoms, or a chlorine atom, a bromine atom, a cyano group, a nitro group, and a trifluoro group). (optionally substituted with one or two substituents selected from the group consisting of methyl groups), the corresponding compound of general formula (1) can be obtained by performing the same reaction.

If ↓ )+0- (Cll2)+++-Cl: (CF
3) tl-0-W- R 'Δ Mouth 1 ↓ Ts-0-(CH2)m-C*(CF3)H-0-W-
R', KO}l↓ CISO3H In the above synthetic route, A and B are each a cyclic group selected from the group consisting of -0= and beta (the cyclic group has 1 to 4 fluorine atoms, or may be substituted with one or two substituents selected from the group consisting of a chlorine atom, a bromine atom, a cyano group, a ditro group, and a trifluoromethyl group). The corresponding compound of general formula (1) can be obtained.

↓ Zn, H2SO4 In the above synthetic route, A is -0-, -@-, -
G-01 {i also W, bet} {to, bet} {F, bet} {to, {
) -COO-Q-, +oco-o-, [[γ, Bet, Bet} (To, Be + {To, →} {and, K} ÷ selected from the group consisting of To and {He} Cyclic group (the cyclic group is not substituted with 1 to 4 fluorine atoms, or 1 or 2 substituents selected from the group consisting of chlorine atom, bromine atom, cyano group, nitro group, and trifluoromethyl group) ), and B is Kγ, Be}{and, +000+ and +
A cyclic group selected from the group consisting of OCO+ (the cyclic group is 1
~ up to 4 fluorine atoms, or chlorine atoms, bromine atoms,
cyano group, ditro group, and trifluoromethyl group), the corresponding general formula (1 ) can be obtained.

In addition, in the above synthetic route, A is -0-, powder, -o-
A cyclic group selected from the group consisting of coo-o- and +oco-o- (the cyclic group being 1 to 4 fluorine atoms, or a chlorine atom, a bromine atom, a cyano group, a nitro group, and a trifluoromethyl group) 1 or 2 selected from the group
), and B is -O
−． ÷, beX, iXji・iXa, -0+gu÷
-Q-COO{}-, -0-OCO-0- -0
A cyclic group selected from the group consisting of (optionally substituted with one or two substituents from the group consisting of methyl groups), the corresponding compound of general formula (1) can be obtained by carrying out the same reaction.

Δ Mouth 1 ↓ Ts-0-(Cll2)m-C*(CF3)}I-0-
WR', κOHIn the above synthetic route, A is ÷, ÷x}, -o-coo-o-, -o-oco+
,,0)',be}(and,-K}e-,!-G-,beD4
A cyclic group selected from the group consisting of fu, berry, and -0-0- (the cyclic group has 1 to 4 fluorine atoms, or a chlorine atom, a bromine atom, a cyano group, a nitro group, and a trifluoride group). 1 or 2 selected from the group consisting of fluoromethyl groups
), and B is
-, -0-0- and -0-coo+ (the cyclic group has 1 to 4 fluorine atoms,
or may be substituted with one or two substituents selected from the group consisting of a chlorine atom, a bromine atom, a cyano group, a nitro group, and a trifluoromethyl group). The corresponding compound of general formula (1) can be obtained.

↓ NaOHaQ. If ↓ SOC+2 ↓ HO-(C}12)m-C. t(CF3)}I-
In the case of 0-W-R', A,
B is a cyclic group selected from the group consisting of ÷ and KFO→) (the cyclic group consists of 1 to 4 fluorine atoms, or a chlorine atom, a bromine atom, a cyano group, a nitro group, and a trifluoromethyl group) (optionally substituted with one or two substituents selected from the group), the corresponding compound of general formula (1) can be obtained by performing the same reaction.

Note that the above (1), (3), (5), (7) to (8), (
11), (20), (22), (24)-(25), (
32), (37) to (39), (4l), (43), (
45), (47) and (49), in particular W
In the case of one CO- or -000-, the reaction of the tosylate with the phenolic hydroxyl group is carried out, for example, in a non-aqueous alcoholic solvent system; KOH or NaOtl
or Ts-0-(Ctl2)m-C1:(CF3)H-0-
Ts-0-(C112) to-C1:(CF3)H-0 instead of WR'
- Using TIP, perform the same reaction as each synthetic route, and R
-X-A-Y-8-0-(C}12) to-Cl: (C
F3) tl-0-THP [In the above formula, R, X, ASY and B are the same as in general formula (1). For example, R-X-A-Y-8-0-(CH2)m-C4:(CF
3) H-0-'I''IP↓ l{Acid catalyst such as CI or ion exchange resin R-X-A-Y-i3-0- (C
H2) m-C*(CF3)}to0■↓ C1-1 Lee R' R-X-A-Y-8-0-(CII2)m-(J(CF
3)}I-0-W-R' [In the above formula, R' is the general formula (
This is the same as in case 1). By performing the following reactions, the corresponding general formula (1
) can be obtained.

Liquid crystals are generally used as liquid crystal compositions consisting of two or more components, and the liquid crystal compound of the present invention can also be used as a component of liquid crystal silk compositions. Smectic liquid crystals, such as smectic liquid products without optically active sites [2-p-alkyloxyphenyl-5-alkylpyrimidine, 2-p-alkanoyloxyphenyl-
5-alkylpyrimidine, 2-p-alkyloxy-5-alkylpyrimidine, 2-p-alkyloxy-5-alkyloxyphenylpyrimidine, 2-(4'-argyloxy-3-fluorophenyl)- 5-alkylpyrimidine, 2-p-alkyloxyphenyl-5-(t-4-alkylcyclohexyl)pyrimidine, 2-p-alkyloxyphenyl-5
-alkylpyridine, 2-(4'-alkylpyridine 3
'-fluorophenyl)-5-alkylpyridine, 2-
(4ξalkylbiphenyl)-5-alkylpyrimidine, 2- (4'-alkylphenyl)-5- (4″-
(alkylphenyl)pyrimidine, p-alkyloxyphenyl-5-alkylpicolinate, 2-p-alkyloxyphenyl-5-alkyloxypyrazine, 2-p
-alkylphenyl-5-alkylpyrimidine, 2-p
-Alkyloxyphenyl-5-alkyloxybilimicin, 4-alkyloxy-4'-monobiphenylcarboxylic acid-p'-(alkyloxycarbonyl)phenyl ester, 4-alkyloxy-4'-biphenylcarboxylic acid monoalkyl esters, etc. and/or ferroelectric liquid crystals [optically active 4-methyl ester, optically active 4-n-alkyloxy-45-biphenylcarboxylic acid-2-methylbutyl ester, optically active p-alkyloxybenzylidene p? -Amino-2-chloropropylcinnamate, optically active 1]-alkyloxybenzylidene-p'-
amino-2-methylbutylcinnamate, etc.] and/
or ordinary chiral smectic liquid crystal [optically active 4-
(p-alkyloxybiphenyl-p'-oxycarbonyl)-4'-(2-methylbutyloxycarbonyl)-cyclohexane, optically active p-n-alkyloxybenzylidene-p'-(2-methylbutyloxycarbonyl) ) May contain aniline and other substances. It may also contain chiral compounds and/or dichroic dyes that do not exhibit liquid crystallinity, such as anthraquinone dyes and azo dyes.

Liquid crystal compounds and liquid crystal compounds exhibiting ferroelectricity cause optical switching phenomenon when voltage is applied, and it is possible to use this phenomenon to create display elements with fast response [for example, in JP-A-56
-107216 Publication, JP 59-118744 Publication, N.A. Clark
, S.T. Lager
wa11); Applied Physics Letter (Ap
plied I'hysics Letter)
36, 899 (1980), etc.

The above liquid crystal composition is vacuum-sealed in a liquid crystal cell with a cell spacing of 0.5 to 10 μm, preferably 0.5 to 3 μm, and polarizers are installed on both sides to obtain a light beam. It can be used as a switching element (display element).

The above-mentioned liquid crystal cell can be produced by bonding together two glass substrates, each having a transparent electrode and an orientated surface, with a spacer interposed therebetween.

Examples of the spacer include alumina beads, glass fiber, and polyimide film. As the orientation treatment method, ordinary orientation treatment such as polyimide film, rubbing treatment, SiO oblique evaporation, etc. can be applied.

[Examples] Hereinafter, the present invention will be further explained with reference to Examples, but the present invention is not limited thereto.

In addition, in the following explanation, the phase transition temperature is accompanied by some fluctuations depending on the measurement method and purity.

Example 1 Optically active 4'-(4-ethyloxy-5,
5.5-trifluoropentyloxy)phenyl-4-
Production of (n-decyloxy)penzoate (Table-1,
No. 288 Compound) (1) Production of optically active ρ-toluenesulfonic acid-4-ethyloxy-5,5,5-trifluoropentyloxy ester optically active 4-ethyloxy-5,5.5-}lifluoropentyl alcohol 2 .38g of p chloride under water-cooled conditions.
-} A solution of 2.67 g of luenesulfonyl in 6 ml of pyridine was added dropwise, and the mixture was stirred for 3 hours under water-cooling conditions. 1. Luen,
After making it acidic by adding 6N monohydrochloric acid, separating the liquid and washing with water, toluene was distilled off to obtain optically active ρ-toluenesulfonic acid-4.
-Ethyloxy-5,5.5- } 4.05 g of refluorescent pentyloxy ester was obtained.

(2) Optically active 1-penzyloxy-4-(4-ethyloxy-5,5,5-}lifluoropentyloxy)
Production of benzene Dissolve 0.98 g of hydroquinone monobenzyl ether and 0.32 g of potassium hydroxide in 6 ml of ethanol, and prepare optically active ρ-toluenesulfonic acid-4-ethyloxy-5.5.5-}rifluoropentyl at room temperature. A solution of 1.58 g of oxyester in 4 ml of ethanol was added dropwise, and the mixture was reacted under reflux for 5 hours. After distilling off the ethanol, the hexane-soluble portion was purified using a silica gel column to obtain 1.32 g of optically active l-penzyloxy-4-(4-ethyloxy-5,5,5-trifluoropentyloxy)benzene.

(3) Optically active 4-(4-ethyloxy-5.5.5-
}Production of optically active 1-pentyloxy-4-(4-ethyloxy-5) phenol
．． 5.5-}Refluoropentyloxy)benzene1.
After dissolving 32g in 60ml of ethanol, under hydrogen atmosphere,
0.3 g of 5% Pd/C (palladium/carbon) was debenzylated. After filtering off Pd/C, ethanol was distilled off and optically active 4-(4-ethyloxy-5,5
．． 5- }Refluoropentyloxy)phenol 0.
86g was obtained.

(4) Optically active 4'-(4-ethyloxy-5,5.5
- }Refluorbentyloxy) phenyl-4-(n
Preparation of 4-n-decyloxybenzoic acid 0.80 g in 14 ml of dry toluene was added 0.45 ml of anhydrous trifluoroacetic acid, and after stirring at room temperature for 3 hours, the optically active 4-(4- A solution of 0.86 g of ethyloxy(5,5.5-)phenol in 12 ml of dry toluene was added dropwise at room temperature and stirred for 1 day. Ether, Nozomi KOH
After making the mixture alkaline by adding an aqueous solution, the mixture was separated and washed with water, and then the Koichitel was distilled off. After purification using a silica gel column, the optically active 4'-(4-ethyloxy-5,5,5-trifluoropentyloxy)phenyl-4-(n-decyloxy)penzoate, which is a compound of the present invention, is reconsolidated from hexane. 0.76g was obtained.

The structure of the compound is H-NMR, 19F-NMR, IR
and confirmed by mass spectrometry. The H-NMRS F-NMR and IR spectra of this 19 compound are shown in FIGS. 1, 2, and 3, respectively.

Example 2 Optically active 4'-(4-ethyloxy-5,
5.5-trifluoropentyloxy)phenyl-4-
Production of (n-undecyloxy)penzoate (Table 1)
, No. Compound 289) Trifluoroacetic anhydride was added to a solution of 11.01 g of 4-n-undecyloxybenzoic acid in 15 ml of dry toluene. 54
After stirring at room temperature for 3 hours, optical activity 4 (4
-ethyloxy-5,5.5-}refluoropentyloxy)phenol i. o63 dry toluene l Out
Solution I was added dropwise at room temperature and stirred for 1 day. Example 1
The optically active 4'-(4-ethyloxy5,5.5-
}Refluoropentyloxy)phenyl-4-(n-
1.16 g of undecyloxy)penzoate were obtained.

I R (cm”): 2930, 1730, 16
05,1510,1255t1200,1170,11
25,1075H-NMR (300Mllz
,'cDCI3)δ(pI)01);8
10 (d, 2H) 7 10 (d, 2H) 09 (m, 4H) 40 (m, 4H) 3 9 (nl, IH) 3 65 (rn, 2H) 2 1~1.7 (m, OH) 1 5 ~ 1.2 (m, 19H) 090 (t
,3H) 19F-NMR (300Ml12,C[)CI3
): -1.14 ppm (d) Example 3 Optically active 5-n-octyloxy-2-(4
- Production of (4-ethyloxy-5.5,5-trifluoropentyloxy)-3-fluorophenyl copyrimidine (Table 1, compound No. 131) In 12.5 ml of ethanol, 0.24 g of KOH and 5 -n-octyloxy-2-(4-hydroxy-3
-fluorophenyl)pyrimidine 1. After adding 16 g and uniformly dissolving, 1.18 g of optically active p-}luenesulfonic acid-4-ethyloxy-5,5.5-}refluoropentyl ester was added and reacted under reflux for 11 hours. After distilling off ethanol under reduced pressure, toluene was added, washed with water, and diluted with diluted KO [1
After washing with an aqueous solution and water, toluene was distilled off. The hexane-soluble portion was purified using a silica gel column, and then recrystallized twice from ethanol to obtain the optically active 5-
n monooctyloxy-2- C4-(4-ethyloxy-5,5,5-trifluoropentyloxy)-3
-fluorophenyl]pyrimidine 1.04 g was obtained.

The H-NMR, 19F-NMR and IR spectrum of this compound are shown in FIGS. 4, 5 and 6, respectively.

Example 4 Optically active 5-n-nonyloxy-2-[4-
Production of (4-ethyloxy-5,5,5i-refluoropentyloxy)-3-fluorophenyl copyrimidine (Table 1, compound No. 132) In 12.5 ml of ethanol, 0.24 g of KOII and 5- nnonyloxy-2-(4-hydroxy-3
-Fluorophenyl)pyrimidine (1.21 g) was added, and after uniformly dissolving, optically active p-}luenesulfonic acid-4-ethyloxy 55. 5-} 1.18 g of refluorescent pentyl ester was added and reacted under reflux for 11 hours. Example 3
The optically active compound of the present invention, 5-nnonyloxy-2-[4-(4-ethyloxy-5j555-trifluorobentyloxy)-
1.15 g of 3-fluorophenylcopyrimidine was obtained.

I R (Cm-'); 2930,1620,1
545, 1525, 1450, 1280, 1170, 1
130,1060,790H NMR (300MH
2, CDCI3) δ (ppm); 8 40 (s,
2H) 8 10 (rn, 2B) Too (t., IH) 4 05 (rn, 4H) 42-4.05 (m, 41-I) 3 95-3.
60 (m, 3H)2 15~1.70 (m,
6H) 1 55-1.20 (m, 15H) 0.
9 (t,3H) 19F NMR (300MHz, CDCI3);
-1. 14 ppm (d) The properties (phase transition temperature) of the compounds shown in Examples 1 to 4 are shown in Table-2.

Table-2 In Table 2, each symbol has the following meaning.

K: Crystal phase sc": Chiral smectic C phase SA: Smectic A phase Ch: Cholesteric phase ■ Biisotropic liquid phase: Phase exists - Phase does not exist [Effects of the invention - The present invention is a novel liquid crystal These liquid crystal compounds have the following notable characteristics:

(1) Provide liquid crystal compounds with various structures. As a result, not only the liquid crystal compound of the present invention alone but also the type of liquid crystal phase, phase transition temperature, optical anisotropy, dielectric anisotropy, helical - It is possible to control physical properties or performance such as pitch, spontaneous polarization value, viscosity, compatibility with other liquid crystal compounds, and orientation.

(2) A liquid crystal compound with a structure in which one CF3 group with large polarization is directly connected to an asymmetric carbon atom, and an oxygen atom is present adjacent to the asymmetric carbon atom, and it can have a large spontaneous polarization value. It is.

(3) In addition to the use as a ferroelectric liquid smectic liquid crystal and the use as a compounding component in a ferroelectric liquid smectic liquid composition or a nonchiral smectic liquid crystal composition, the liquid crystal compound of the present invention can be blended into a nematic liquid crystal. This has the effect of controlling the occurrence of reverse domains in a TN type liquid crystal cell.

(4) It is easy to control the hydrophobicity required for LB membrane creation,
A monomolecular stacked film can be obtained.

(5) Good stability against light, heat, and moisture.

[Brief explanation of the drawing]

Figures 1, 2 and 3 show H-NMR, 19F-NMR and IR of the compound obtained in Example 1, respectively.
The spectra are shown, and FIGS. 4, 5 and 6 are H-NMR and 19F of the compound obtained in Example 3, respectively.
- Shows NMR and IR spectra.

Claims (1)

[Claims] General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (1) [In the formula, R is an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom or an alkoxy group, X
is a single bond, -O-, -OCO- or -OCOO-, and A and B are ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas, tables, etc. There are ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲
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A cyclic group selected from the group consisting of , ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ Contains mathematical formulas, chemical formulas, tables, etc. , 1 or 2 selected from the group consisting of cyano group, nitro group and trifluoromethyl group
), and Y is a single bond, -COO-, -OCO-, -C≡C-, -CH2-
O-, -O-CH2-, -COS-, -SCO-, -C
H=N-, -N=CH-, -N=N-, -CH2-S-
or -S-CH2-, Z is a single bond, -O-, -
COO- or -S-, m is an integer from 1 to 18, W is a single bond, -CO- or -COO-, and R'
is an alkyl group having 1 to 18 carbon atoms which may be substituted with a halogen atom or an alkoxy group, and the * symbol indicates optical activity. ] A liquid crystal compound represented by.