• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Formula (I) The tetrahydronaphthalene derivative represented by this, and a liquid crystal composition containing it. The compound of general formula (I) is excellent in liquid crystallinity and compatibility with liquid crystal compounds or compositions which are currently general purpose. In addition, it is possible to greatly reduce the threshold voltage with almost no deterioration in response. It is also easy to manufacture industrially, and is colorless and chemically stable. Therefore, the liquid crystal composition containing this is very useful as a practical liquid crystal, especially for liquid crystal display which has a wide temperature range and requires low voltage drive and high speed response.
    公开号:KR20020023965A
    申请号:KR1020017016642
    申请日:1999-09-10
    公开日:2002-03-29
    发明作者:구스모토데쓰오；사이토요시타카；네기시마코토；나가시마유타카；다케하라사다오；다카쓰하루요시；그라헤게르발트；프링스라이너브루너；피트하르트코르넬리아
    申请人:오쿠무라 고조；다이니혼 잉키 가가쿠 고교 가부시키가이샤；
    IPC主号:
    专利说明:

    Compound having tetrahydronaphthalene skeleton and liquid crystal composition containing same {COMPOUND HAVING TETRAHYDRONAPHTHALENE SKELETON AND LIQUID CRYSTAL COMPOSITION CONTAINING THE SAME}
    [2] Liquid crystal display devices are used in watches, electronic calculators, various measuring instruments, automobile panels, word processors, electronic notebooks, printers, computers, televisions, and the like. Examples of liquid crystal displays include TN (twisted nematic) type, STN (super twisted nematic) type, DS (dynamic light scattering) type, GH (guest host) type, or FLC (ferroelectric liquid crystal) capable of fast response. AFLC (antiferroelectric liquid crystal) etc. are mentioned. In addition, as a driving method, multiplex driving is common in conventional static driving, and a simple matrix system and an active matrix system have been put to practical use in recent years.
    [3] As a liquid crystal material used for these, very many kinds of liquid crystalline compounds have been synthesized so far, and these are used depending on the display method, the driving method or the use thereof. However, the demand for improving the performance of the liquid crystal display device (improving the display quality, increasing the size of the display screen, etc.) has only become stronger year by year, and development of new liquid crystal compounds has been continued to satisfy it.
    [4] The liquid crystal compound is usually composed of a central skeleton portion called a core and end portions on both sides. Usually, as a ring structure which comprises the core part of a liquid crystal compound, a 1, 4- phenylene group (it may be substituted by 1-2 halogen atoms, a cyano group, a methyl group, etc.) and a trans-1, 4- cyclohexylene group Occupies most of it. However, the liquid crystalline compound constituted only by the 1,4-phenylene group and the trans-1,4-cyclohexylene group also has limitations in its kind and properties, and it is a fact that the above-mentioned requirements cannot be met alone.
    [5] As ring structures other than a 1, 4- phenylene group and a trans-1, 4- cyclohexylene group, a pyridine-2, 5- diyl group, a pyrimidine-2, 5- diyl group, a 1, 3- dioxane Heterocyclic systems such as trans-2,5-diyl groups, trans-decane-2,6-diyl groups, naphthalene-2,6-diyl groups, tetrahydronaphthalene-2,6-diyl groups, and dicyclo [2.2 .2] Condensed ring systems such as octane-1,4-diyl groups and spiro [3.3] heptane-2,6-diyl groups have also been studied, but are currently in practical use due to manufacturing problems (technology, cost, etc.) and stability problems. It is only a few things.
    [6] In these condensed ring systems, although the tetrahydronaphthalene-2,6-diyl group has been reported for a long time, the synthesis examples are very few, and characteristics other than liquid crystalline (phase transition temperature), especially as a nematic liquid crystal The characteristics are little known. (Recently, optically active alcohol esters of tetrahydronaphthalene-2-carboxylic acid have been reported to exhibit interesting properties as skeletons for smectic liquid crystals, especially ferroelectric liquid crystals and antiferroelectric liquid crystals. It has recently been reported to have a tetrahydronaphthalene structure.)
    [7] Usually, in a liquid crystal compound, at least one of a terminal part is a chain | strand-type (side chain) group, and in the case of what is called p-type liquid crystal whose dielectric anisotropy is positive, the other is a polar group in many cases.
    [8] In the TN or STN display system, a compound (p-type) having a high dielectric anisotropy and positive dielectric constant is required to reduce the driving voltage thereof. For this purpose, a compound having a cyano group at the terminal of the molecule and at least one fluorine atom in the same direction of the molecule is usually used. Tetrahydronaphthalene derivatives reported at present are mostly so-called n-type liquid crystals having a dielectric constant anisotropy of 0 to negative, and rarely are p-type liquid crystals in which a polar group is introduced into a tetrahydronaphthalene skeleton, or a phenyltetrahydronaphthalene skeleton or tetrahydronaphthalene-2-. Only compounds having a phenyl phenyl skeleton are reported, and electro-optical properties and applications are not described [Helv. Chim. Acta, 65, 1318-1330 (1982)]
    [9] As the p-type compound to be used in the active matrix driving method described above, a compound having only a fluorine atom, a fluoroalkoxy group, and a fluoroalkyl group is used as the polar group, but there is no such report as a tetrahydronaphthalene compound. Moreover, although the liquid crystalline compound which is a tetrahydro naphthalene derivative generally has the poor compatibility with other liquid crystalline compounds, for the improvement, the introduction of a lateral substituent to a tetrahydro naphthalene skeleton (especially a fluorine atom) is effective. I think. In the use of the active matrix system, even when a polar group is introduced directly into the tetrahydronaphthalene ring, substitution by a fluorine atom is considered effective. Such fluorotetraline derivatives have not been synthesized in practice, and it is not possible to estimate what characteristics such compounds have.
    [10] In liquid crystal compounds, it is known that excellent effects such as improvement in liquid crystallinity, reduction in viscosity, and improvement in steepness in display characteristics can be obtained by changing an alkyl group commonly used as the side chain portion and introducing an alkenyl group. However, these alkenyl groups are usually introduced in the form of directly bonding to the cyclohexane ring, and no compounds introduced into the aromatic ring, particularly the tetrahydronaphthalene ring, have been reported.
    [11] Similarly, tetrahydronaphthalene derivatives having an alkoxylalkyl group, a fluoroalkyl group, a fluoroalkenyl group, a fluoroalkenyloxy group and the like as side chains have not been reported.
    [12] As the linking group of the ring structure in the core in the liquid crystal compound, in addition to the single bond or the ester group (-C00-, -0C0-), 1,2-ethylene group (-CH 2 CH 2- ) and ethynylene group (-C≡C Although many divalent organic groups, such as-) and a difluoroethynylene group (-CF = CF-), are known, they are not known in tetrahydronaphthalene derivatives.
    [1] The present invention relates to a novel liquid crystalline compound which is a tetrahydronaphthalene derivative useful as an electro-optical liquid crystal display material, a liquid crystal composition containing the same, and a liquid crystal display device using the same.
    [13] The problem to be solved by the present invention is to provide a novel compound having a tetrahydronaphthalene skeleton, and to provide a practical liquid crystal composition using the same.
    [14] MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the present inventors can easily manufacture the compound which has a tetrahydro naphthalene frame | skeleton, and many of these show liquid crystallinity in a wide temperature range, and it is independent of liquid crystal presence, Regardless, adding it to the composition does not slow down the response (in many cases, speed up the response), without significantly narrowing the target liquid crystal temperature range (in many cases, widening the temperature range), and without mixing the layers. It has been found that the present invention can be accomplished, and the present invention has been completed.
    [15] Invention 1: general formula (I)
    [16]
    [17] (Wherein R may be substituted by 1 to 7 fluorine atoms or an alkoxyl group having 1 to 7 carbon atoms, and a saturated or unsaturated alkyl group having 1 to 20 carbon atoms which may include a branched chain) Or an alkoxyl group, and the linking groups La, Lb, Lc and Ld are each independently a single bond, -CH 2 CH 2- , -CH = CH-, -CH (CH 3 ) CH 2- , -CH 2 CH ( CH 3 )-, -CH (CH 3 ) CH (CH 3 )-, -CF 2 CF 2- , -CF = CF-, -CH 2 O-, -OCH 2- , -OCH (CH 3 )-, -CH (CH 3 ) O-, -C≡C-, -CF 2 O-, -OCF 2- , -COO-, -OCO-, -COS- or -SCO-, Z is a fluorine atom, chlorine Represents an atom, a cyano group, a cyanate group, a trifluoromethoxy group or a difluoromethoxy group, and ring A, ring B and ring D each independently represent a trans-1,4-cyclohexylene group and a trans-decahydro 1,4-phenyl which may be substituted by naphthalene-2,6-diyl group, trans-1,3-dioxane-2,4-diyl group or one or two fluorine atoms Group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, pyridazine-3,6-diyl group and one or two fluorine atoms Which may represent a naphthalene-2,6-diyl group, and each ring E may be independently substituted with 1,4-phenylene group and 1 or 2 fluorine atoms, which may be substituted with 1 or 2 fluorine atoms. Naphthalene-2,6-diyl group, and ring C represents general formula (IIa) or (IIb)
    [18]
    [19] (Wherein X 1 , X 2 , X 3 , X 4 , X 5 and X 6 represent a hydrogen atom or a fluorine atom), and n a , n b , n c and n d are each independently 0 or 1 Indicates
    [20] Provided that when n c = 1 and n d = 0, ring D is a 1,4-phenylene group which may be substituted with one or two fluorine atoms and / or a naphthalene that may be substituted with one or two fluorine atoms- 2,6-diyl group,
    [21] In addition, Z is a cyano group, R is an unsubstituted and saturated alkyl or alkoxyl group, n a = n c = n d = 0, n b = 1, n b = n c = n d = 0, and n a = 1, when ring A and ring B are 1,4-phenylene groups, La and Lb are single bonds, and ring C is formula (IIa), at least one of X 1 , X 2 and X 3 represents a fluorine atom ,
    [22] In addition, Z is a cyano group, R is an unsubstituted and saturated alkyl or alkoxyl group, n a = n b = n c = 0, n d = 1, n a = n b = n d = 0, and n c = 1, when ring C and ring D are 1,4-phenylene groups, Lc and Ld are single bonds or -COO-, and ring C is formula (IIa), at least one of X 1 , X 2 and X 3 is Represents a fluorine atom,
    [23] In addition, Z is a cyano group, R is an unsubstituted and saturated alkyl or alkoxyl group, n a = n b = n c = 0, n d = 1, n a = n b = n d = 0, and n c = 1, when ring C and ring D are 1,4-phenylene groups, Lc and Ld are single bonds or -COO-, and ring C is formula (IIb), at least one of X 4 , X 5 and X 6 is Represents a fluorine atom,
    [24] In addition, Z is a fluorine atom, R is an unsubstituted and saturated alkyl or alkoxyl group, n a = n b = n c = 0, n d = 1, n a = n b = n d = 0, and n c = 1, when ring C and ring D are 1,4-phenylene groups, Lc and Ld are -COO-, and ring C is formula (IIb), at least one of X 4 , X 5 and X 6 represents a fluorine atom; Indicate,
    [25] And when ring C is of formula (IIb) at least one of n c and n d is 1)
    [26] Tetrahydronaphthalene derivative represented by.
    [27] Invention 2: In the general formula (I), the tetrahydronaphthalene derivative according to invention 1 when ring C is formula (IIa).
    [28] Invention 3: In the general formula (I), the tetrahydronaphthalene derivative according to invention 1 when ring C is formula (IIb).
    [29] Invention 4: In the general formula (I), the tetrahydronaphthalene derivative as described in inventions 1-3 when n a or n b is 0.
    [30] Invention 5: In the general formula (I), the tetrahydronaphthalene derivative according to inventions 1 to 4 when n c or n d is 0.
    [31] Invention 6: In the general formula (I), the tetrahydronaphthalene derivative according to inventions 1 to 5 when n a = n b = 0.
    [32] Invention 7: In the general formula (I), tetrahydronaphthalene derivatives according to Inventions 1, 2, 4, 5 when n c = n d = 0.
    [33] Invention 8: In the general formula (I), tetrahydronaphthalene derivatives according to inventions 1 to 7 in which at least one of n a , n b , n c and n d is 1.
    [34] Invention 9: In the general formula (I), the linking groups La, Lb, Lc, and Ld are each independently selected from a single bond, -CH 2 CH 2-, and -C≡C-. Hydronaphthalene derivatives.
    [35] Invention 10: In the general formula (I), the tetrahydronaphthalene derivatives according to inventions 1 to 9 when the linking groups La, Lb, Lc, and Ld are each independently selected from a single bond or -CH 2 CH 2- .
    [36] Invention 11: In the general formula (I), the tetrahydronaphthalene derivatives according to the inventions 1 to 10 when the linking groups La, Lb, Lc, and Ld are single bonds.
    [37] Invention 12: In formula (I), ring A, ring B, and ring D are each independently a trans-1,4-cyclohexylene group, a trans-decahydronaphthalene-2,6-diyl group, a trans-1, 3-dioxane-2,4-diyl group or 1,4-phenylene group which may be substituted by one or two fluorine atoms, and naphthalene-2,6-diyl group which may be substituted by one or two fluorine atoms Tetrahydronaphthalene derivatives according to inventions 1 to 11 when selected from.
    [38] Invention 13: The tetrahydronaphthalene derivative as described in inventions 1-12 when Z is fluorine in general formula (I).
    [39] Invention 14: In the general formula (I), tetrahydronaphthalene derivatives according to inventions 1 to 12 when Z is a cyano group.
    [40] Invention 15: The tetrahydronaphthalene derivative according to inventions 1 to 12 when Z is a trifluoromethoxy group in general formula (I).
    [41] Invention 16: In general formula (I), saturated or unsaturated C1-C1 which R may be substituted by 1-7 fluorine atoms or the alkoxyl group of 1-7 carbon atoms, and may contain a branched chain The tetrahydronaphthalene derivative as described in inventions 1-15 when it is an alkyl group of 20.
    [42] Invention 17: The tetrahydronaphthalene derivative as described in inventions 1-16 when R is a saturated or unsaturated C1-C20 linear alkyl group.
    [43] Invention 18: The tetrahydronaphthalene derivative according to inventions 1 to 17 in which X 3 , X 4 and X 5 in formulas (IIa) and (IIb) are hydrogen atoms.
    [44] Invention 19: The tetrahydronaphthalene derivative as described in inventions 1-18 in which X <2> of Formula (IIa) is a hydrogen atom and X <1> is a fluorine atom in general formula (I).
    [45] Invention 20: The tetrahydronaphthalene derivative as described in inventions 1-18 in which X <1> of Formula (IIa) is a hydrogen atom and X <2> is a fluorine atom in general formula (I).
    [46] Invention 21: The tetrahydronaphthalene derivative according to Inventions 1 to 20, which shows liquid crystallinity.
    [47] Invention 22: Tetrahydronaphthalene derivative showing a nematic phase.
    [48] Invention 23: The tetrahydronaphthalene derivative according to inventions 1 to 22, which exhibits a nematic phase when added to the nematic liquid crystal composition.
    [49] Invention 24: The liquid crystal composition containing at least one compound of the general formula (I) according to the inventions 1 to 23.
    [50] Invention 25: The liquid crystal composition according to Inventive 24 used for driving an active matrix.
    [51] Invention 26: A liquid crystal element comprising the liquid crystal composition of Invention 25 as a component.
    [52] Invention 27: An active matrix drive liquid crystal display device using the liquid crystal composition according to Invention 26.
    [53] As described above, in the compound of the general formula (I), its R, linking group La, Lb, Lc, and Ld, polar group Z, ring A, ring B, ring C, ring D, and ring E, n a , Examples of n b , n c and n d include the following.
    [54] n a , n b , n c and n d are 0 or 1 and may be any combination except when ring C is of formula (IIb), but n a + n b + n c + n d = 3 or 4 When melting point and viscosity become high and n a = n b = n c = n d = 0, since liquid crystallinity falls, n a + n b + n c + n d = 1 or 2 is preferable.
    [55] As R, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, peptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, peptadecyl group, hexa Decyl group, heptadecyl group, octadecyl group, nonadecyl group, linear saturated alkyl group of eicosyl group, 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1,2-dimethylpropyl group, 1- Methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1-methylpentyl group, 2-methylphene group Tyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4- Methylhexyl group, 5-methylhexyl group, 1,2-dimethylhexyl group, 1,3-dimethylhexyl group, 1-methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 5-methylheptyl group, 6-methylheptyl group, 1,2-dimethylheptyl group, 1,3-dimethylheptyl group, 1-methyloctyl group, 2-methyloctane Methyl, 3-methyloctyl, 4-methyloctyl, 5-methyloctyl, 6-methyloctyl, 7-methyloctyl, 1,2-dimenyloctyl, 1,3-dimenyloctyl, 1- Methylnonyl, 2-methylnonyl, 3-methylnonyl, 4-methylnonyl, 5-methylnonyl, 6-methylnonyl, 7-methylnonyl, 8-methylnonyl, 1,2- Dimethylnonyl group, 1,3-dimethylnonyl group, 1-methyldecyl group, 2-methyldecyl group, 3-methyldecyl group, 1,2-dimethyldecyl group, 1,3-dimethyldecyl group, 1-methylound Real group, 2-methyl undecyl group, 3-methyl undecyl group, 1,2-dimethyl undecyl group, 1,3-dimethyl undecyl group, 1-methyl dodecyl group, 2-methyl dodecyl group, 3-methyl dodecyl group, 1, 2-dimethyldodecyl group, 1,3-dimethyldodecyl group, 1-methyltridecyl group, 2-methyltridecyl group, 3-methyltridecyl group, 1,2-dimethyltridecyl group, 1,3-dimethyltri Branched saturated alkyl groups such as decyl groups, vinyl groups, trans-1-propenyl groups, 2-propenyl groups, trans-1-butenyl groups, trans-2-butenyl groups, 3-butenyl groups, and trans -1-pentenyl group, trans-2-pentenyl group, trans-3-pentenyl group, 4-pentenyl group, trans-1-hexenyl group, trans-2-hexenyl group, trans-3-hexenyl group, trans -4-hexenyl group, 5-hexenyl group, trans-1-heptenyl group, trans-2-heptenyl group, trans-3-heptenyl group, trans-4-heptenyl group, trans-5-heptenyl group, 6- Heptenyl group, trans-1-octenyl group, trans-2-octenyl group, trans-3-octenyl group, trans-4-octenyl group, trans-5-octenyl group, trans-6-octenyl group, 7-octenyl group, Trans-1-nonenyl group, 8-nonenyl group, trans-1-decenyl group, 9-decenyl group, trans-1-undecenyl group, 10-undecenyl group, trans-1-dodecenyl group, 11- Dodecenyl, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pente Nilyl group, 1-hexynyl group, 2-hexynyl group, 3-hexynyl group, 4-hexynyl group, 5-hexynyl group, 1-heptinyl group, 2-heptinyl group, 3-heptinyl group, 4- Heptynyl, 5-heptinyl, 6-heptinyl, 1-octynyl, 2-octynyl, 3-octynyl, 4-octinyl, 5-octynyl, 6-octinyl, 7-octinyl, 1- Noninyl, 8-noninyl, 1-decynyl, 9-decynyl, 1-undecynyl, 10-undecynyl, 1-dodecynyl, 11-dodecynyl, 1-tridecynyl, 12- Unsaturated alkyl groups such as tridecynyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoromethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 1, 1,2,2,2-pentafluoroethyl group, 3-fluoropropyl group, 2-fluoropropyl group, 1-fluoropropyl group, 3,3-difluoropropyl group, 3,3,3- Trifluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 1,1,2,2,3,3,3- Heptafluoropropyl group, 4-fluorobutyl group, 3-fluorobutyl group, 2-fluorobutyl group, 1-fluorobutyl group, 4,4-difluorobutyl group, 4,4,4- Trifluorobutyl group, 3,3,4,4-tetrafluorobutyl group, 3,3,4,4,4-pentafluorobutyl group, 2,2,3,3,4,4,4- Heptafluorobutyl group, 5-fluoropentyl group, 4-fluoropentyl group, 3-fluoropentyl group, 2-fluoropentyl group, 1-fluoropentyl group, 5,5-difluoropentyl group , 5,5,5-trifluoropentyl group, 4,4,5,5-tetrafluoropentyl group, 4,4,5,5,5-pentafluoropentyl group, 3,3,4,4 , 5,5,5-heptafluoropentyl group, 6-fluorohexyl group, 5-fluorohexyl group, 4-fluorohexyl group, 3-fluorohexyl group, 2-fluorohexyl group, 1- Fluorohexyl group, 6,6-difluorohexyl group, 6,6,6-trifluorohexyl group, 5,5,6,6,6-pentafluorohexyl group, 4,4,5,5 , 6,6,6-heptafluorohexyl group, 7-fluoroheptyl group, 6-fluoroheptyl group, 5-fluoroheptyl group, 4-fluoroheptyl group, 3-fluoroheptyl group, 2- Fluoroheptyl group, 1-fluoroheptyl group, 7,7-difluoroheptyl group, 7,7,7-trifluoroheptyl group, 6,6,7,7-tetrafluoroheptyl group, 6,6,7,7,7-pentafluoroheptyl group, 5,5,6,6,7,7,7-heptafluoroheptyl group, 8-fluorooctyl group, 7-fluorooctyl group, 6-fluorooctyl group, 5-fluorooctyl group, 4-fluorooctyl group, 3-fluorooctyl group, 2-fluorooctyl group, 1 -Fluorooctyl group, 8,8-difluorooctyl group, 8,8,8-trifluorooctyl group, 7,7,8,8-tetrafluorooctyl group, 7,7,8,8, Fluorine-substituted alkyl groups such as 8-pentafluorooctyl group, 6,6,7,7,8,8,8-heptafluorooctyl group, 2,2-difluoroethenyl group, (E) -1, 2-difluoroethenyl group, (Z) -1,2-difluoroethenyl group, 3,3-difluoro-2-propenyl group, (E) -2,3-difluoro-2 -Propenyl group, (Z) -2,3-difluoro-2-propenyl group, 4,4-difluoro-3-butenyl group, (E) -3,4-difluoro-3-butenyl group , (Z) -3,4-difluoro-3-butenyl group, 5,5-difluoro-4-pentenyl group, (E) -4,5-difluoro-4-pentenyl group, (Z ) -4,5-difluoro-4-pentenyl , 6,6-difluoro-5-hexenyl group, (E) -5,6-difluoro-5-hexenyl group, (Z) -5,6-difluoro-5-hexenyl group , (E) -1,2-difluoro-1-propenyl group, (E) -1,2-difluoro-1-butenyl group, (E) -1,2-difluoro-1-pente Neyl group, (E) -1,2-difluoro-1-hexenyl group, (Z) -1-fluoro-1-propenyl group, (Z) -1-fluoro-1-butenyl group, (Z ) -1-fluoro-1-pentenyl group, (Z) -1-fluoro-1-hexenyl group, (Z) -2-fluoro-1-propenyl group, (Z) -2-fluoro- 1-butenyl group, (Z) -2-fluoro-1-pentenyl group, (Z) -2-fluoro-1-hexenyl group, (E) -2,3-difluoro-2-butenyl group , (E) -2,3-difluoro-2-pentenyl group, (E) -2,3-difluoro-2-hexenyl group, (Z) -2-fluoro-2-butenyl group, (Z) -2-fluoro-2-pentenyl group, (Z) -2-fluoro-2-hexenyl group, (Z) -3-fluoro-2-butenyl group, (Z) -3-fluoro Fluorine-substituted unsaturated alkyl groups such as rho-2-pentenyl group and (Z) -3-fluoro-2-hexenyl group, methoxymethyl group, ethoxymethyl group, propoxymethyl , Butoxymethyl group, pentyloxymethyl group, hexyloxymethyl group, heptyloxymethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 1-propoxyethyl group, 1-butoxyethyl group, 1-pentyloxyethyl group, 1-hexyl Oxyethyl group, 1-heptyloxyethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-propoxyethyl group, 2-butoxyethyl group, 2-pentyloxyethyl group, 2-hexyloxyethyl group, 2-heptyloxyethyl group , 1-methoxypropyl group, 1-ethoxypropyl group, 1-propoxypropyl group, 1-butoxypropyl group, 1-pentyloxypropyl group, 1-hexyloxypropyl group, 1-heptyloxypropyl group, 2-methoxypropyl group, 2-ethoxypropyl group, 2-propoxypropyl group, 2-butoxypropyl group, 2-pentyloxypropyl group, 2-hexyloxypropyl group, 2-heptyloxypropyl group, 3 -Methoxypropyl group, 3-ethoxypropyl group, 3-propoxypropyl group, 3-butoxypropyl group, 3-pentyloxypropyl group, 3-hexyloxypropyl group, 3-heptyloxypropyl group, 4- Methoxy part Group, 4-ethoxybutyl group, 4-propoxybutyl group, 4-butoxybutyl group, 4-pentyloxybutyl group, 4-hexyloxybutyl group, 4-heptyloxybutyl group, 5-methoxypentyl group , 5-ethoxypentyl group, 5-propoxypentyl group, 5-butoxypentyl group, 5-pentyloxypentyl group, 5-hexyloxypentyl group, 5-heptyloxypentyl group, 6-methoxyhexyl group, Alkoxy group substituted alkyl groups, such as 6-ethoxyhexyl group, 6-propoxyhexyl group, 6-butoxyhexyl group, 6-pentyloxyhexyl group, 6-hexyloxyhexyl group, and 6-heptyloxyhexyl group, and those Although an alkoxyl group is mentioned, Alkyl group is preferable. Among them, linear saturated alkyl groups and unsaturated alkyl groups are preferable, and methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, vinyl, trans-1-propenyl, 2-propenyl, Trans-1-butenyl group, trans-2-butenyl group, 3-butenyl group, trans-1-pentenyl group, trans-2-pentenyl group, trans-3-pentenyl group, 4-pentenyl group, trans-1-hex Senyl group, trans-2-hexenyl group, trans-3-hexenyl group, trans-4-hexenyl group, 5-hexenyl group, trans-1-heptenyl group, trans-2-heptenyl group, trans-3 -Heptenyl group, trans-4-heptenyl group, trans-5-heptenyl group, 6-heptenyl group, etc. are especially preferable.
    [56] The linkers La, Lb, Lc, and Ld are single bonds, -CH 2 CH 2- , -CH = CH-, -CH (CH 3 ) CH 2- , -CH 2 CH (CH 3 )-, -CH (CH 3 ) CH (CH 3 )-, -CF 2 CF 2- , -CF = CF-, -CH 2 O-, -OCH 2- , -OCH (CH 3 )-, -CH (CH 3 ) O-, -C≡C-, -CF 2 O-, -OCF 2- , -COO-, -OCO-, -COS- or -SCO-, among them, a single bond, -CH 2 CH 2 -,- C≡C- is preferable and a single bond is especially preferable.
    [57] Z may be a fluorine atom, a chlorine atom, a cyano group, a cyanate group, a trifluoromethoxy group or a difluoromethoxy group, but a fluorine atom, a cyano group, a trifluoromethoxy group is preferable, and fluorine and trifluoro Lomethoxy groups are particularly preferred.
    [58] Examples of the ring A, the ring B, and the ring D include the structure shown in Formula Group 1.
    [59]
    [60] Especially, the structure described in Formula group 2 is preferable.
    [61]
    [62] Especially, the structure described in Formula 3 is especially preferable.
    [63]
    [64] Examples of the ring D in the case of the ring E and n d = 0 include the structure shown in the formula group 4.
    [65]
    [66] Especially, the structure described in Formula group 5 is preferable.
    [67]
    [68] Especially, the structure described in Formula group 6 is preferable.
    [69]
    [70] The structure shown in Formula group 7 is mentioned as Formula (IIa) or Formula (IIb) of ring C.
    [71]
    [72] Especially, the structure described in Formula group 8 is preferable.
    [73]
    [74] As described above, the compound of the general formula (I) has R, a linking group La, Lb, Lc, and Ld, a polar group Z, a ring A, a ring B, a ring C, a ring D and a ring E, n a , n Although a large number of compounds may be included depending on the selection of b , n c and n d, the selection of each structural moiety can make the compound suitable for a wider field of use. As a result, the general formula (I) The compound of is very useful as it has desirable characteristics for electro-optical devices such as wide nematic temperature range, light and heat stability, high voltage retention, in particular STN-LCD and AM-LCD. In more detail, the following compounds are mentioned as a especially preferable compound among the compounds of general formula (I).
    [75] In addition, the following symbol is used for a compound base material, and R <1> is a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a vinyl group, a trans-1-propenyl group, and 2-propenyl group , Trans-1-butenyl group, trans-2-butenyl group, 3-butenyl group, trans-1-pentenyl group, trans-2-pentenyl group, trans-3-pentenyl group, 4-pentenyl group, trans-1- Hexenyl, trans-2-hexenyl, trans-3-hexenyl, trans-4-hexenyl, 5-hexenyl, trans-1-heptenyl, trans-2-heptenyl, trans- Any one of a 3-heptenyl group, a trans-4-heptenyl group, a trans-5-heptenyl group, and a 6-heptenyl group is shown.
    [76]
    [77] If ring C is of formula (IIa),
    [78]
    [79]
    [80]
    [81]
    [82]
    [83]
    [84]
    [85]
    [86]
    [87]
    [88]
    [89]
    [90]
    [91]
    [92]
    [93]
    [94]
    [95]
    [96]
    [97]
    [98]
    [99]
    [100]
    [101]
    [102]
    [103]
    [104]
    [105]
    [106]
    [107]
    [108]
    [109]
    [110]
    [111]
    [112]
    [113]
    [114]
    [115]
    [116]
    [117]
    [118]
    [119]
    [120]
    [121]
    [122]
    [123]
    [124]
    [125]
    [126]
    [127]
    [128]
    [129]
    [130]
    [131]
    [132]
    [133]
    [134]
    [135]
    [136]
    [137]
    [138]
    [139]
    [140]
    [141]
    [142]
    [143]
    [144]
    [145]
    [146]
    [147]
    [148]
    [149]
    [150]
    [151]
    [152]
    [153] Compounds of general formula (I) have R, linkers La, Lb, Lc and Ld, polar groups Z, ring A, ring B, ring C, ring D and ring E, n a , n b , n c and n d Depending on the choice of, it can be produced by various synthetic methods, but a representative example thereof is given below.
    [154] When ring C is of formula (IIa)
    [155] n b = 1, n c = n d = 0, linker La single bond, -CH 2 CH 2- , -CH (CH 3 ) CH 2- , -CH 2 CH (CH 3 )-, -CH (CH 3 ) CH (CH 3 )-or -CF 2 CF 2- , when the linking group Lb is a single bond, it can be synthesized according to the following formula.
    [156]
    [157] Wherein R, polar group Z, ring A, ring B, n a , X 1 , X 2 and X 3 have the same meanings as in general formula (I), and La 1 is a single bond, -CH 2 CH 2- , -CH = CH-, -C≡C-, -CH (CH 3 ) CH 2- , -CH 2 CH (CH 3 )-, -CH (CH 3 ) CH (CH 3 )-or -CF 2 CF 2- , La 2 is a single bond, -CH 2 CH 2- , -CH (CH 3 ) CH 2- , -CH 2 CH (CH 3 )-, -CH (CH 3 ) CH (CH 3 )- Or -CF 2 CF 2- , and Mtl 1 represents metal ions such as Li, BrMg, IMg, etc.)
    [158] That is, after converting the phenylacetic acid represented by the general formula (IIIa-1) to an acid chloride using thionyl chloride or the like, and then reacting with ethylene in the presence of aluminum chloride, the tetraron derivative represented by the general formula (IVa-1) is obtained. You can get it. The alcohol represented by the general formula (VIa-1) is reacted with a lithium or magnesium reactant represented by the general formula (Va-1) in the presence or absence of a metal salt such as cerium chloride or manganese chloride or Lewis acid. The obtained dihydronaphthalene compound represented by general formula (VIIa-1) is obtained by heating in presence of acid catalyst, such as p-toluenesulfonic acid, and this is Pd-C, Rh-C, Pt-C, Pd (OH) 2 By hydrogenation in presence of metal catalysts, such as these, the target compound represented by general formula (Ia) can be obtained.
    [159] The lithium or magnesium reactant represented by the general formula (VIa-1) used here is well used in the production of liquid crystal, and can be easily prepared from the corresponding halide or the like.
    [160] Here, as shown in the following formula, when acetylide represented by general formula (Va-2) is used instead of the lithium or magnesium reactant represented by general formula (Va-1), it is represented by general formula (Ib) Losing compounds can be prepared.
    [161]
    [162] Wherein R, polar group Z, ring A, ring B, n a , X 1 , X 2 and X 3 have the same meanings as in general formula (I), and La 1 is a single bond, -CH 2 CH 2- , -CH = CH-, -C≡C-, -CH (CH 3 ) CH 2- , -CH 2 CH (CH 3 )-, -CH (CH 3 ) CH (CH 3 )-or -CF 2 CF 2- , La 2 is a single bond, -CH 2 CH 2- , -CH (CH 3 ) CH 2- , -CH 2 CH (CH 3 )-, -CH (CH 3 ) CH (CH 3 )- Or -CF 2 CF 2- , and Mtl 1 represents metal ions such as Li, BrMg, IMg, etc.)
    [163] In addition, as shown in the following formula, (VIIb-2) obtained by reacting a tetralone derivative represented by the general formula (IVa-1) with the ylide represented by the general formula (Vb-1) is reduced. The compound represented by general formula (Ib) can be manufactured.
    [164]
    [165] Wherein R, polar group Z, ring A, ring B, n a , X 1 , X 2 and X 3 have the same meanings as in general formula (I), and La 1 is a single bond, -CH 2 CH 2- , -CH = CH-, -C≡C-, -CH (CH 3 ) CH 2- , -CH 2 CH (CH 3 )-, -CH (CH 3 ) CH (CH 3 )-or -CF 2 CF 2- , La 2 is a single bond, -CH 2 CH 2- , -CH (CH 3 ) CH 2- , -CH 2 CH (CH 3 )-, -CH (CH 3 ) CH (CH 3 )- Or -CF 2 CF 2-
    [166] Moreover, also in the method shown by following formula, the compound represented by general formula (I-b) and (I-c) can be manufactured.
    [167]
    [168] Wherein R, polar group Z, ring A, ring B, n a , X 1 , X 2 and X 3 have the same meanings as in general formula (I), and La 1 is a single bond, -CH 2 CH 2- , -CH = CH-, -C≡C-, -CH (CH 3 ) CH 2- , -CH 2 CH (CH 3 )-, -CH (CH 3 ) CH (CH 3 )-or -CF 2 CF 2- , La 2 is a single bond, -CH 2 CH 2- , -CH (CH 3 ) CH 2- , -CH 2 CH (CH 3 )-, -CH (CH 3 ) CH (CH 3 )- Or -CF 2 CF 2-
    [169] When n b = 1, n c = n d = 0, ring C is a formula (IIa), X 1 , X 2 and X 3 are a hydrogen atom, Z is a cyano group or a trifluoromethoxy group, Can be synthesized.
    [170]
    [171] (Wherein R, La, Lb, ring A, ring B, and n a represent the same meanings as in general formula (I), and Z 1 represents a cyano group or a trifluoromethoxy group.)
    [172] That is, the cyclohexanone derivative represented by the general formula (IXa-1) is dehydrated and condensed with pyrrolidine, reacted with methyl vinyl ketone, and then treated with an acid to give the general formulas (IXb-1) and (IXb-2). A mixture of octahydronaphthalenone derivatives represented by) can be obtained. The compound represented by the general formula (IXc-1) can be obtained by hydrogenating this with a mixture of copper bromide (II) and lithium bromide. When this hydroxyl group is converted into a triflate and reacted with copper cyanide, the compound whose Z <1> is cyano group in general formula (Id) can be obtained. When the phenol derivative represented by the general formula (IXc-1) is reacted with carbon tetrachloride and then potassium fluoride is reacted, a compound in which Z 1 is a trifluoromethoxy group in general formula (Id) can be obtained.
    [173] In addition, after preparing the general formula (Xa-1) from the general formula (IIIa-2) in the same manner as the production of the general formula (Ia), Lithio using a base such as butyllithium or lithium diisopropylamide After the reaction, the carboxylic acid derivative represented by the general formula (Xb-1) can be obtained by reacting with carbon dioxide. After converting this carboxylic acid to an acid chloride, ammonia gas is made to act, an amide is made, and a dehydration condensation agent is made to act, and a compound represented by general formula (I-e) can be obtained.
    [174]
    [175] Wherein R, ring A, ring B and n a have the same meanings as in general formula (I), and La 2 is a single bond, -CH 2 CH 2- , -CH (CH 3 ) CH 2 -,- CH 2 CH (CH 3 ) —, —CH (CH 3 ) CH (CH 3 ) — or —CF 2 CF 2 —
    [176] In addition, the compound represented by the general formula (IXc-2) can be obtained by lithiating the compound represented by the general formula (Xa-1), followed by reacting with trimethyl borate and then reacting with hydrogen peroxide solution. This compound can be derived from the compound represented by the general formula (I-f) in the same manner as in the case of the compound represented by the general formula (IXc-1).
    [177]
    [178] Wherein R, ring A, ring B and n a have the same meanings as in general formula (I), and La 2 is a single bond, -CH 2 CH 2- , -CH (CH 3 ) CH 2 -,- CH 2 CH (CH 3 ) —, —CH (CH 3 ) CH (CH 3 ) — or —CF 2 CF 2 —, and Z 1 represents a cyano group or a trifluoromethoxy group)
    [179] When n d = 1, n c = 0, ring C is formula (IIa) and linking group Lb is a single bond, it can be synthesized according to the following formula.
    [180]
    [181] (Wherein R, ring A, ring B, ring E, n a , n b , X 1 , X 2 and X 3 represent the same meaning as in general formula (I), and Z 1 represents a fluorine atom or trifluorome Oxy, Tf represents a trifluoromethanesulfonyl group, Mtl 2 represents Li, ClMg, BrMg, IMg or (HO) 2 B.)
    [182] That is, the general formula (IXc-3) which can be produced by the same method as the compound represented by the general formula (IXc-1) or (IXc-2) in the presence of a base such as pyridine, diethylamine, triethylamine, By reacting with trifluoromethanesulfonic anhydride or trifluoromethanesulfonyl chloride and the like in a solvent such as dichloromethane or chloroform, triflate represented by the general formula (IXd-1) is obtained. General formula (Ig) is made by reacting this with the compound represented by general formula (XIa-1) in presence of transition metal catalysts, such as tetrakistriphenylphosphine palladium (O) or tetrakistriphenylphosphine nickel (O). The compound represented by) can be synthesize | combined.
    [183] Moreover, the acetylene compound represented by general formula (XIb-1) can be used for the compound represented by general formula (IXd-1), such as copper iodide, dichlorobistriphenylphosphine palladium, tetrakistriphenylphosphine palladium (O), etc. By reacting in presence of a transition metal catalyst, the compound represented by general formula (Ih) can be manufactured.
    [184]
    [185] Wherein R, polar group Z, ring A, ring B, ring E, n a , n b , X 1 , X 2 and X 3 have the same meanings as in general formula (I), and Tf is trifluoromethane Sulfonyl group.)
    [186] Moreover, the aryl lithium or magnesium represented by general formula (XIa-2) to general formula (IXb-3) which can be manufactured by the same method as the compound represented by general formula (IXb-1) or (IXb-2). After reacting the reactant, dehydration is performed to obtain a compound represented by the general formula (XIIa-1), followed by oxidizing agents such as 2,3-dichloro-5,6-dicyano-1,4-benzoquinone or bromine. By oxidation, the compound represented by general formula (Ii) can also be obtained.
    [187]
    [188] Wherein R, ring A, ring B, ring E, n a , and n b have the same meanings as in general formula (I), Z 1 represents a fluorine atom or trifluoromethoxy, and Mtl 1 is Li , ClMg, BrMg, or IMg.)
    [189] When ring C is of formula (IIb)
    [190] When n a = n b = n c = 0, n d = 1, and the linking group Ld is a single bond, it can synthesize | combine according to the following formula.
    [191]
    [192] (Wherein R, X 4 , X 5 and X 6 represent the same meaning as in general formula (I), and Z 2 represents a fluorine atom, a chlorine atom, a trifluoromethyl group, a trifluoromethoxy group or a difluoromethok Represents the period, and Mtl 1 represents metal ions such as Li, ClMg, BrMg, IMg, etc.)
    [193] That is, the aryl lithium or magnesium reactant represented by the general formula (XIa-3) is reacted with the ketone represented by the general formula (IVb-1) in the presence or absence of co-existence of metal salts such as cerium chloride or manganese chloride or Lewis acid. To obtain an alcohol represented by the general formula (XIIIa-1), and then heating in the presence of an acid catalyst such as p-toluenesulfonic acid to obtain a dihydronaphthalene compound represented by the general formula (XIVa-1), which is obtained by Pd-C, By hydrogenation in the presence of metal catalysts such as Rh-C, Pt-C, and Pd (OH) 2 , the compound represented by the general formula (Ij) can be obtained.
    [194] The compound represented by the general formula (IVb-1) can be prepared by several methods. As a representative method thereof, a phenylacetic acid derivative represented by the general formula (IIIb-1) is converted into an acid chloride as shown by the following formula. There is then a method of reacting with ethylene in the presence of aluminum chloride.
    [195]
    [196] (Wherein R, X 4 , X 5 and X 6 represent the same meaning as in general formula (I).)
    [197] In addition, when X 4 , X 5 and X 6 are all hydrogen, as shown in the following formula, the compound represented by the general formula (IVb-2) is a palladium, naphthol derivative represented by the general formula (XVa-1), It can synthesize | combine by hydrogenation in presence of transition metal catalysts, such as rhodium, platinum, ruthenium, and also oxidizing as needed.
    [198]
    [199] (Wherein R represents the same meaning as in general formula (I).)
    [200] In addition, as shown in the following formula, 1,4-cyclohexadione monoacetal is reacted with an amine such as pyrrolidine, and methyl vinyl ketone is further reacted with octahydronaphthaleneddione monoacetal to R 1 −. The organometallic reactant represented by Mtl 1 is made to work, and octahydronaphthalenone acetal is obtained by dehydration reaction. Metal catalysts such as palladium, rhodium, ruthenium and platinum are used as dehydrogenation catalysts, or an oxidizing agent such as 2,3-dichloro-5,6-dicyano-1,4-benzoquinone is reacted, or sulfur, After making it aromatic using bromine, iodine, etc., the compound represented by general formula (IVb-3) can be synthesize | combined by converting acetal to a ketone.
    [201]
    [202] (In formula, R <1> may be substituted by the 1-7 fluorine atom or the alkoxyl group of 1-7 carbon atoms, and represents the saturated C1-C20 alkyl group which may contain a branched chain.)
    [203] When n a = n b = n c = 0, n d = 1 and the linking group Ld is -CH 2 CH 2- , it can be synthesized according to the following formula.
    [204]
    [205] (Wherein R, X 4 , X 5, X 6 and ring E have the same meaning as in general formula (I), and Z 2 is a fluorine atom, a chlorine atom, a trifluoromethyl group, a trifluoromethoxy group or di Fluoromethoxy group, Mtl 1 represents metal ions such as Li, ClMg, BrMg, IMg.)
    [206] That is, the aryl lithium or magnesium reactant represented by the general formula (XIa-4) is reacted with the ketone represented by the general formula (IVb-1) in the presence or absence of a metal salt such as cerium chloride or manganese chloride or Lewis acid. To obtain an alcohol represented by the general formula (XIIIa-2), and then heating in the presence of an acid catalyst such as p-toluenesulfonic acid to obtain a dihydronaphthalene compound represented by the general formula (XIVa-2), which is obtained by Pd-C, By hydrogenation in presence of metal catalysts, such as Rh-C and Pd (OH) 2 , the compound represented by the target general formula (Ik) can be obtained.
    [207] In addition, when (XIa-5) and (XIa-6) is used instead of the above (XIa-3) and (XIa-4), compounds represented by the general formulas (I-1) and (I-m) can be prepared.
    [208]
    [209] (Wherein R, X 4 , X 5, X 6 , ring D and ring E have the same meanings as in general formula (I), and Z 2 is a fluorine atom, a chlorine atom, a trifluoromethyl group, trifluoromethok A period or a difluoromethoxy group, Ld 1 represents a single bond or -CH 2 CH 2- .)
    [210] In addition, as shown in the following formula, a hydrogenated olefin compound (XVIa-1) obtained by reacting a compound represented by the general formula (IVb-1) with an yilide compound represented by the general formula (Vc-1) or the like is generally used. The compound represented by a formula (In) can be manufactured.
    [211]
    [212] (Wherein R, X 4 , X 5, X 6 , rings E and Z have the same meaning as in formula (I).)
    [213] In addition, as shown in the following formula, the tetrahydronaphthalene represented by (IVb-1) is reacted with an yilide compound prepared from methoxymethylphosphonium salt, and treated with an acid to be represented by the general formula (VIIIb-1). To get aldehydes. The compound represented by general formula (I-n) can be manufactured by hydrogenating the olefin (I-o) obtained by making this compound react with the lide compound represented by (Vc-2).
    [214]
    [215] (Wherein R, X 4 , X 5 , X 6 , rings E and Z have the same meaning as in formula (I).)
    [216] In the above method, when (IVb-2) is used instead of (IVb-1), a compound represented by the general formula (XVIIa) can be prepared.
    [217]
    [218] (Wherein X 4 , X 5, X 6 , ring D, ring E and Z have the same meaning as in general formula (I), and Lc 1 and Ld 1 represent a single bond or —CH 2 CH 2 —). )
    [219] Many of the compounds of general formula (I) can be manufactured by substituting the bromine of this compound (XVIIa-1).
    [220] For example, an acetylene compound represented by (XVIIIa-1) is reacted with (XVIIa-1) in the presence of a palladium catalyst such as PdCl 2 (PPh 3 ) 2 or Pd (PPh 3 ) 4 and an amine such as triethyleneamine. If it is, the compound represented by general formula (Ip) can be obtained. In addition, hydrogenation may be carried out in the presence of a metal catalyst to convert an acetylenediyl group (-C≡C-) into an ethylene group (-CH 2 CH 2- ).
    [221]
    [222] (Wherein X 4 , X 5 , X 6 , ring D, ring E and Z have the same meaning as in general formula (I), and R 1 is 1-7 fluorine atoms or alkoxy having 1-7 carbon atoms) A saturated or unsaturated alkyl group having 1 to 18 carbon atoms which may be substituted by a practical group and may include a branched chain, and Lc 1 and Ld 1 represent a single bond or -CH 2 CH 2- .
    [223] Moreover, the compound represented by general formula (Iq) can be obtained by replacing (XVIIIa-1) with (XVIIIa-2). In addition, this may be hydrogenated in the presence of a metal catalyst to convert an acetylenediyl group (-C≡C-) into an ethylene group (-CH 2 CH 2- ).
    [224]
    [225] Wherein R, X 4 , X 5 , X 6 , ring A, ring D, ring E and Z have the same meaning as in general formula (I), and Lc 1 and Ld 1 are a single bond or -CH 2 CH 2- .)
    [226] Moreover, the compound represented by general formula (I-r) can be manufactured by making the organometallic reagent represented by (XIb-1) react with (XVIIa-1) in presence of a nickel or a palladium catalyst.
    [227]
    [228] (Wherein R, X 4 , X 5 , X 6 , ring D, ring E and Z have the same meaning as in formula (I), and ring A 1 may be substituted with one or two fluorine atoms) Represents a 1,4-phenylene group and a naphthalene-2,6-diyl group which may be substituted with one or two fluorine atoms, Lc 1 and Ld 1 represent a single bond or -CH 2 CH 2- , and Mtl 2 Represents Li, ClMg, BrMg, IMg or (HO) 2 B.)
    [229] Representative examples of the compound represented by General Formula (I) thus produced are given below.
    [230]
    [231] The present invention also provides a liquid crystal composition containing at least one kind of the compound represented by the general formula (I) as a constituent thereof.
    [232] In the liquid crystal composition containing at least one kind of the compound represented by the general formula (I) as its component, any compound other than the compound represented by the general formula (I) may be included as long as the composition exhibits liquid crystallinity. Although at least 1 type of compound represented by general formula (I) is contained as this 1st component, It is preferable to contain at least 1 sort (s) among the following 2nd-4th components especially as another component.
    [233] That is, the second component is a so-called fluorine-based (halogen-based) p-type liquid crystal compound, and is composed of a compound represented by the following general formulas (A1) to (A3).
    [234]
    [235] In the above formula, Alk a represents an alkyl group having 1 to 12 carbon atoms, which may be linear, may have a methyl or ethyl branch, may have a 3-6 membered cyclic structure, and any group present in the group Of -CH 2 -may be exchanged by -O-, -CH = CH-, -CH = CF-, -CF = CH-, -CF = CF- or -C≡C-, and are present in the group Any hydrogen atom to be substituted may be substituted with a fluorine atom or a trifluoromethoxy group, but a straight alkyl group having 2 to 7 carbon atoms, a straight 1-alkenyl group having 2 to 7 carbon atoms, or carbon atoms Preferred is a linear 3-alkenyl group having 4 to 7 carbon atoms and an alkyl group having 1 to 5 carbon atoms substituted by an alkoxyl group having 1 to 3 carbon atoms at the terminal. Moreover, when a subsidiary carbon generate | occur | produces by branching, it may be optically active as a compound, and may be a racemate.
    [236] Ring Fa, Ring Fb and Ring Fc are each independently a trans-1,4-cyclohexylene group, a transdecahydronaphthalene-trans-2,6-diyl group, 1 which may be substituted by one or more fluorine atoms , 4-phenylene group, naphthalene-2,6-diyl group which may be substituted by one or more fluorine atoms, tetrahydronaphthalene-2,6-diyl group which may be substituted by one or more fluorine atoms, 1,4-cyclohexenylene group, 1,3-dioxane-trans-2,5-diyl group, pyrimidine-2,5-diyl group or pyridine-2,5- which may be substituted by a fluorine atom The diyl group includes a trans-1,4-cyclohexylene group, a transdecahydronaphthalene-trans-2,6-diyl group, a naphthalene-2,6-diyl group which may be substituted with a fluorine atom, or 1 to Preference is given to 1,4-phenylene groups which may be substituted by two fluorine atoms. Particularly when ring Fb is a trans-1,4-cyclohexylene group or a transdecahydronaphthalene-trans-2,6-diyl group, it is preferable that the ring Fa is a trans-1,4-cyclohexylene group, and the ring When Fc is a trans-1,4-cyclohexylene group or a transdecahydronaphthalene-trans-2,6-diyl group, it is preferable that ring Fb and ring Fa are a trans-1,4-cyclohexylene group. Moreover, in (A3), it is preferable that ring Fa is a trans-1, 4- cyclohexylene group.
    [237] L a , L b and L c are linking groups, each independently, a single bond, an ethylene group (-CH 2 CH 2- ), a 1,2-propylene group [-CH (CH 3 ) CH 2-, and -CH 2 CH (CH 3 )-], 1,4-butylene group, -COO-, -OCO-, -OCF 2- , -CF 2 O-, -CH = CH-, -CH = CF-, -CF = CH -, -CF = CF-, -C≡C- or -CH = NN = CH-, which represents a single bond, ethylene group, 1,4-butylene group, -COO-, -OCF 2- , -CF 2 O -, -CF = CF- or -C≡C- is preferable, and a single bond or an ethylene group is especially preferable. In addition, in (A2), it is preferable that at least one of them represents a single bond in (A3).
    [238] The ring Fz is an aromatic ring and can be represented by the following general formulas (Ga) to (Gc).
    [239]
    [240] In the formula, each of J a to J j independently represents a hydrogen atom or a fluorine atom, and at least one of J a and J b in (Ga) is preferably a fluorine atom, and in J d to J f in (Gb) It is preferable that at least 1 is a fluorine atom, and it is more preferable that especially J d is a fluorine atom.
    [241] Terminal group Pa is a fluorine atom, a chlorine atom, a trifluoromethoxy group, a difluoromethoxy group, a trifluoromethyl group or a difluoromethyl group or an alkoxyl group having 2 or 3 carbon atoms substituted by two or more fluorine atoms , Alkyl group, alkenyl group or alkenyloxy group, a fluorine atom, a trifluoromethoxy group or a difluoromethoxy group is preferable, and a fluorine atom is particularly preferable.
    [242] In addition, in (A1)-(A3), the compound of General formula (I) of this invention is excluded.
    [243] The third component is a so-called cyano p-type liquid crystal compound, and is composed of a compound represented by the following general formulas (B1) to (B3).
    [244]
    [245] In the above formula, Alk b represents an alkyl group having 1 to 12 carbon atoms, these may be linear, may have a methyl or ethyl branch, may have a 3-6 membered cyclic structure, and any group present in the group Of -CH 2 -may be exchanged by -O-, -CH = CH-, -CH = CF-, -CF = CH-, -CF = CF- or -C≡C-, and are present in the group Any hydrogen atom to be substituted may be substituted with a fluorine atom or a trifluoromethoxy group, but a straight alkyl group having 2 to 7 carbon atoms, a straight 1-alkenyl group having 2 to 7 carbon atoms, or carbon atoms Preferred is a linear 3-alkenyl group having 4 to 7 carbon atoms and an alkyl group having 1 to 5 carbon atoms substituted by an alkoxyl group having 1 to 3 carbon atoms at the terminal. Moreover, when a subsidiary carbon produces | generates by branching, it may be optically active as a compound, and may be a racemate.
    [246] Ring Fd, Ring Fe and Ring Ff are each independently a trans-1,4-cyclohexylene group, a transdecahydronaphthalene-trans-2,6-diyl group, 1 which may be substituted by one or more fluorine atoms , 4-phenylene group, naphthalene-2,6-diyl group which may be substituted by one or more fluorine atoms, tetrahydronaphthalene-2,6-diyl group which may be substituted by one or more fluorine atoms, 1,4-cyclohexenylene group, 1,3-dioxane-trans-2,5-diyl group, pyrimidine-2,5-diyl group or pyridine-2,5- which may be substituted by a fluorine atom The diyl group includes a trans-1,4-cyclohexylene group, a transdecahydronaphthalene-trans-2,6-diyl group, a naphthalene-2,6-diyl group which may be substituted with a fluorine atom, or 1 to Preference is given to 1,4-phenylene groups which may be substituted by two fluorine atoms. Particularly when the ring Fe is a trans-1,4-cyclohexylene group or a transdecahydronaphthalene-trans-2,6-diyl group, the ring Fd is preferably a trans-1,4-cyclohexylene group, and the ring In the case where Ff is a trans-1,4-cyclohexylene group or a transdecahydronaphthalene-trans-2,6-diyl group, the ring Fd and the ring Fe are preferably a trans-1,4-cyclohexylene group. In addition, in (B3), the ring Fd is preferably a trans-1,4-cyclohexylene group.
    [247] L d , L e and L f are linking groups, each independently, a single bond, an ethylene group (-CH 2 CH 2- ), a 1,2-propylene group [-CH (CH 3 ) CH 2 -and -CH 2 CH (CH 3 )-], 1,4-butylene group, -COO-, -OCO-, -OCF 2- , -CF 2 O-, -CH = CH-, -CH = CF-, -CF = CH -, -CF = CF-, -C≡C-, -OCH 2- , -CH 2 O- or -CH = NN = CH-, which represents a single bond, an ethylene group, a 1,4-butylene group, -COO -, -OCF 2- , -CF 2 O-, -CF = CF- or -C≡C- are preferable, and a single bond, ethylene group, or -COO- is especially preferable. In addition, in (B2), it is preferable that at least one of them represents a single bond in (B3).
    [248] Ring Fy is an aromatic ring and can be represented by the following general formulas (Gd) to (Gf).
    [249]
    [250] In the above formula, J k to J q each independently represent a hydrogen atom or a fluorine atom, and in (Ge), J n and J o are preferably hydrogen atoms.
    [251] The terminal group P a represents a cyano group (-CN), a cyanate group (-0CN) or -C≡CCN, with a cyano group being preferred.
    [252] In addition, in (B1)-(B3), the compound of General formula (I) of this invention is excluded.
    [253] A 4th component is what is called n-type liquid crystal whose dielectric anisotropy is about 0 or less, and consists of a compound represented by the following general formula (C1)-(C3).
    [254]
    [255] In the above formula, Alk c and Alk d each independently represent an alkyl group having 1 to 12 carbon atoms, which may be linear, may have a methyl or ethyl branch, or may have a 3 to 6 membered cyclic structure. , Any -CH 2 -present in the group may be exchanged by -O-, -CH = CH-, -CH = CF-, -CF = CH-, -CF = CF- or -C≡C-. Any hydrogen atom present in the group may be substituted by a fluorine atom or a trifluoromethoxy group, but a linear alkyl group having 1 to 7 carbon atoms, or a straight 1-member having 2 to 7 carbon atoms 1 to 5 carbon atoms substituted by an alkenyl group, a straight 3-alkenyl group having 4 to 7 carbon atoms, a straight alkoxyl group having 1 to 3 carbon atoms, or an alkoxyl group having 1 to 3 carbon atoms at the end A phosphorus linear alkyl group is preferable, and at least one is a linear alkyl group having 1 to 7 carbon atoms and 2 to 7 carbon atoms. Straight-chain 1-alkenyl group or a 4 to 7 carbon atoms, a straight-chain 3-alkenyl group and it is particularly preferably Al.
    [256] Ring Fg, Ring Fh, and Ring Fi may each be independently substituted by a trans-1,4-cyclohexylene group, a transdecahydronaphthalene-trans-2,6-diyl group, 1 to 2 fluorine atoms or a methyl group. 1,4-phenylene group which may be substituted, naphthalene-2,6-diyl group which may be substituted by one or more fluorine atoms, tetrahydronaphthalene-2,6 which may be substituted by 1 to 2 fluorine atoms -Diyl group, 1,4-cyclohexenylene group which may be substituted by 1 to 2 fluorine atoms, 1,3-dioxane-trans-2,5-diyl group, pyrimidine-2,5-di Diary or pyridine-2,5-diyl group, in each compound a transdecahydronaphthalene-trans-2,6-diyl group, naphthalene-2,6-di, which may be substituted by one or more fluorine atoms Diary, a tetrahydronaphthalene-2,6-diyl group which may be substituted by 1 to 2 fluorine atoms, 1,4-cyclohexenylene group, 1,3-dioxane-trans-2,5-diyl group, pyrimidine-2,5-diyl group or pyridine-2,5- which may be substituted by a small atom The diyl group is preferably one or less, and the other ring is preferably a 1,4-phenylene group which may be substituted by a trans-1,4-cyclohexylene group or 1 to 2 fluorine atoms or a methyl group. .
    [257] L g , L h and L i are each independently a single bond, an ethylene group (-CH 2 CH 2- ), a 1,2-propylene group [-CH (CH 3 ) CH 2 -and -CH 2 CH (CH 3 )-], 1,4-butylene group, -COO-, -OCO-, -OCF 2- , -CF 2 O-, -CH = CH-, -CH = CF-, -CF = CH -, -CF = CF-, -C≡C-, or -CH = NN = CH-, which represents a single bond, an ethylene group, a 1,4-butylene group, -COO-, -OCO-, -OCF 2- , -CF 2 O-, -CF = CF-, -C≡C- or -CH = N = N = CH- is preferred, at least one of them in (C2) and at least two of them in (C3) It is preferable to represent a single bond.
    [258] More preferable aspect in (C1) can be represented by the following general formula (C1a)-(C1h).
    [259]
    [260] In each of the above formulas, Alk e and Alk f each independently represent a straight alkyl group having 1 to 7 carbon atoms, a straight 1-alkenyl group having 2 to 7 carbon atoms, and a straight 3 having 4 to 7 carbon atoms. An alkenyl group, a straight alkoxyl group having 1 to 3 carbon atoms, or a straight alkyl group having 1 to 5 carbon atoms substituted by an alkoxyl group having 1 to 3 carbon atoms, at least one of which has carbon atoms A straight alkyl group having 1 to 7, a straight 1-alkenyl group having 2 to 7 carbon atoms, or a straight 3-alkenyl group having 4 to 7 carbon atoms is shown. However, when ring Fg1-ring Fg3 is an aromatic ring, the corresponding Alk e is a 1-alkenyl group and an alkoxyl group, except when ring Fh1-ring Fh3 is an aromatic ring, the corresponding Alk f is a 1-alkenyl group and an alkoxyl group Exclude.
    [261] Ring Fg1 and Ring Fh1 are each independently substituted by a trans-1,4-cyclohexylene group, a transdecahydronaphthalene-trans-2,6-diyl group, 1 to 2 fluorine atoms or a methyl group. 1,4-phenylene group, naphthalene-2,6-diyl group which may be substituted by one or more fluorine atoms, tetrahydronaphthalene-2,6-di which may be substituted by 1 to 2 fluorine atoms Diary, 1,4-cyclohexenylene group, 1,3-dioxane-trans-2,5-diyl group, pyrimidine-2,5-diyl group which may be substituted by 1 to 2 fluorine atoms, or A pyridine-2,5-diyl group is shown, in each compound, a transdecahydronaphthalene-trans-2,6-diyl group and a naphthalene-2,6-diyl group which may be substituted by one or more fluorine atoms. A tetrahydronaphthalene-2,6-diyl group which may be substituted by 1 to 2 fluorine atoms, 1,4-cyclohexenylene group, 1,3-dioxane-trans-2,5-diyl group, pyrimidine-2,5-diyl group or pyridine-2,5- which may be substituted by a small atom It is preferable that it is one or less diyl groups, and the other ring in that case is the 1, 4- phenylene group which may be substituted by the trans-1, 4- cyclohexylene group or 1-2 fluorine atoms, or a methyl group. to be. Ring Fg2 and ring Fh2 are each independently substituted by a trans-1,4-cyclohexylene group, a transdecahydronaphthalene-trans-2,6-diyl group, 1 to 2 fluorine atoms or a methyl group. 1,4-phenylene group, naphthalene-2,6-diyl group which may be substituted by one or more fluorine atoms, tetrahydronaphthalene-2,6-di which may be substituted by 1 to 2 fluorine atoms A diary shows, in each compound, a transdecahydronaphthalene-trans-2,6-diyl group, a naphthalene-2,6-diyl group which may be substituted by one or more fluorine atoms, and one or two fluorine atoms. It is preferable that the tetrahydronaphthalene-2,6-diyl group which may be substituted by is less than one, and in that case, the other ring may be a trans-1,4-cyclohexylene group or 1 to 2 fluorine atoms. Or may be substituted by a methyl group It is a 1,4-phenylene group. The ring Fg3 and the ring Fh3 are each independently a 1,4-phenylene group which may be substituted by 1 to 2 fluorine atoms or a methyl group, and naphthalene-2,6- which may be substituted by one or more fluorine atoms. It represents a diyl group and tetrahydronaphthalene-2,6-diyl group which may be substituted by 1 to 2 fluorine atoms, In each compound, naphthalene-2 which may be substituted by one or more fluorine atoms, It is preferable that the tetrahydronaphthalene-2, 6- diyl group which may be substituted by the 6-diyl group and 1-2 fluorine atoms is one or less.
    [262] More preferable aspect in (C2) can be represented by the following general formula (C2a)-(C2m).
    [263]
    [264] In the above formula, ring Fg1, ring Fg2, ring Fg3, ring Fh1, ring Fh2 and ring Fh3 represent the above meanings, ring Fil means ring Fg1, ring Fi2 means ring Fg2, and ring Fi3 means ring Fg3, respectively. Indicates. In each of the above compounds, a transdecahydronaphthalene-trans-2,6-diyl group, a naphthalene-2,6-diyl group which may be substituted by one or more fluorine atoms, and one or two fluorine atoms Tetrahydronaphthalene-2,6-diyl group which may be substituted, 1,4-cyclohexenylene group which may be substituted by fluorine atom, 1,3-dioxane-trans-2,5-diyl group, The pyrimidine-2,5-diyl group or pyridine-2,5-diyl group is preferably one or less, in which case the other ring is a trans-1,4-cyclohexylene group or 1-2 fluorine. It is a 1, 4- phenylene group which may be substituted by the atom or the methyl group.
    [265] Next, the more preferable aspect in (C3) can be represented by the following general formula (C3a)-(C3f).
    [266]
    [267] In the above formula, the ring Fg1, the ring Fg2, the ring Fh1, the ring Fh2, the ring Fi1 and the ring Fi2 represent the above meanings, the ring Fjl represents the ring Fg1, and the ring Fj2 represents the same meaning as the ring Fg2, respectively. In each of the above compounds, a transdecahydronaphthalene-trans-2,6-diyl group, a naphthalene-2,6-diyl group which may be substituted by one or more fluorine atoms, and one or two fluorine atoms A tetrahydronaphthalene-2,6-diyl group which may be substituted, a 1,4-cyclohexenylene group which may be substituted by a fluorine atom, a 1,3-dioxane-trans-2,5-diyl group, The pyrimidine-2,5-diyl group or pyridine-2,5-diyl group is preferably one or less, in which case the other ring is a trans-1,4-cyclohexylene group or 1-2 fluorine. It is a 1, 4- phenylene group which may be substituted by the atom or the methyl group.
    [268] As shown in Examples described later, a liquid crystal composition having an upper limit temperature of 117 ° C in nematic phase was actually prepared using the compound, and 20% by weight of the compound represented by formula (I) was added thereto. It was found that the compound represented by formula (I) has excellent solubility in the host liquid crystal composition and can express a liquid crystal phase in a very wide temperature range.
    [269] Moreover, as a result of measuring the voltage retention of this composition, it showed the value sufficiently high similarly to a host liquid crystal composition at the time of preparation, after heating and after ultraviolet irradiation.
    [270] As described above, the compound of the present invention has excellent liquid crystallinity and excellent compatibility with liquid crystal compounds and liquid crystal compositions which are widely used at present. Moreover, it turns out that it has the effect superior to the conventional compound in preparing the liquid crystal composition which has a wide temperature range which shows a liquid crystal phase, is low in threshold voltage, and enables high-speed response.
    [271] Therefore, the compound of general formula (I) can be suitably used as a field effect type display cell such as TN type or STN type in a mixture with other nematic liquid crystal compounds, and particularly as a liquid crystal material having a wide temperature range and capable of low voltage driving. have. Moreover, the thing which does not contain a cyano group and ester bond among the compounds of (I) is easy to acquire a big specific resistance and high voltage retention, and can also be used as a component of the liquid crystal material for active matrix drive. Moreover, not only nematic liquid crystal but use as a low viscosity which is indispensable for realization of the high speed response of ferroelectric liquid crystal and antiferroelectric liquid crystal can also be expected.
    [272] Example
    [273] Specific examples will be given below to explain in detail the advantages of the tetrahydronaphthalene derivative of the present invention, a method for producing the same, and a liquid crystal composition obtained by using the tetrahydronaphthalene derivative of the present invention as a constituent component. The scope of application is not limited by these examples.
    [274] Example 1 Synthesis of 2- (4-propylphenyl) -6-fluoro-1,2,3,4-tetrahydronaphthalene (I-1-1)
    [275]
    [276] (1-1) Synthesis of 6-fluoro-3,4-dihydro-2 (1H) -naphthalenone
    [277] A catalytic amount of pyridine was added to 30 g of 4-fluorophenylacetic acid and 60 ml of 1,2-dichloroethane of 48.9 g of thionyl chloride, and the mixture was refluxed for 5 hours in a nitrogen atmosphere. After 1,2-dichloroethane was distilled off, it was dripped at the suspension solution of 200 ml of dichloromethane of 48.6g of aluminum chlorides under ice cooling. After stirring for 30 minutes, ethylene gas was blown in, and after stirring for another 5 hours, diluted hydrochloric acid was added, the organic layer was separated, and the aqueous layer was extracted with toluene. The organic layers were combined, washed with water, saturated sodium bicarbonate water, water, saturated brine in that order, dried over anhydrous sodium sulfate, dried with distillation of the solvent, and purified by distillation (75 ° C, 2 Torr) to give 6-fluoro- 19.4 g of 3,4-dihydro-2 (1H) -naphthalenone was obtained.
    [278] IR 1723, 1617 m 1596 cm -1
    [279] 1 H NMR (CDCl 3 ) δ 7.1-6.9 (m, 3H), 3.6 (s, 2H), 3.0-2.5 (m, 4H)
    [280] 13 C NMR (CDCl 3 ) δ 210, 160, 139, 130, 129, 115, 114, 44, 38, 28
    [281] MS m / z 164, 149, 135, 122, 115, 109, 101, 96, 83, 75, 63, 57
    [282] (1-2) Synthesis of 2- (4-propylphenyl) -6-fluoro-1,2,3,4-tetrahydronaphthalene (I-1-1)
    [283] 3.5 g of magnesium was suspended in 4 ml of tetrahydrofuran (THF), and 100 ml of THF 100 ml solution of 25.7 g of 4-propylbromobenzene was added dropwise over about 30 minutes at a rate at which THF was gently refluxed. After stirring again for 1 hour, a 80 ml solution of 9.4 g of 6-fluoro-3,4-dihydro-2 (1H) -naphthalenone obtained in (1-1) was added dropwise over 30 minutes. After stirring again for 1 hour, 50 ml of 10% hydrochloric acid was added. 100 ml of hexane was added, the organic layer was separated, and the aqueous layer was extracted with 100 ml of hexane to combine the organic layers. It was washed with water, saturated sodium bicarbonate water and brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, 100 ml of toluene and 2.0 g of p-toluenesulfonic acid monohydrate were added, and the mixture was heated and stirred at 110 ° C while separating and removing the distilled water. After the outflow of water disappeared, it returned to room temperature, 50 ml of water was added, and the organic layer was separated. The organic layer was washed with saturated sodium bicarbonate water, water and brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, the total amount was dissolved in 200 ml of ethyl acetate, 2.0 g of 5% palladium / carbon (function) was added, and the mixture was stirred in an autoclave under hydrogen pressure of 4 kg / cm &lt; 2 &gt; Removed by light filtration, the solvent was distilled off and purified by silica gel column chromatography (hexane), and then recrystallized twice from ethanol to give 2- (4-propylphenyl) -6-fluoro-1,2,3, 17.2 g of white crystals of 4-tetrahydronaphthalene were obtained.
    [284] Example 2 Synthesis of 2- (4-propylphenyl) -5,6,7-trifluoro-1,2,3,4-tetrahydronaphthalene (I-1-2)
    [285] 2- (4-propylphenyl) -5,6,7-trifluoro-1 using 3,4,5-trifluorophenylacetic acid instead of 4-fluorophenylacetic acid under the same conditions as in Example 1 , 2,3,4-tetrahydronaphthalene was obtained.
    [286] Example 3 Synthesis of 2- (4-propylphenyl) -5,7-difluoro-6-cyano-1,2,3,4-tetrahydronaphthalene
    [287]
    [288] 2- (4-propylphenyl) -5,7-difluoro-1,2,3, using 3,5-difluorophenylacetic acid instead of 4-fluorophenylacetic acid under the same conditions as in Example 1 4-tetrahydronaphthalene was obtained. 10 g of this 2- (4-propylphenyl) -5,7-difluoro-1,2,3,4-tetrahydronaphthalene was thiolated with butyllithium, and carbon dioxide was blown into benzoic acid, followed by chloride Synthesized by acidification with thionyl and blowing ammonia gas. This was dissolved in 40 ml of DMF, and 2.5 ml of phosphorus oxychloride was added and reacted at 25 ° C for 2 hours. The reaction solution was poured into iced water, diluted hydrochloric acid was added, and extracted with toluene from the aqueous layer. The organic layers were combined, washed with water, saturated aqueous sodium hydrocarbon solution and saturated brine, and dried over anhydrous sodium sulfate. Purification by silica gel column chromatography (hexane / dichloromethane = 6/4), and recrystallization from ethanol to give 2- (4-propylphenyl) -5,7-difluoro-6-cyano-1,2,3 6.3 g of, 4-tetrahydronaphthalene were obtained.
    [289] Example 4 Synthesis of 2- [2- (trans-4-propylcyclohexyl) ethyl] -6-fluoro-1,2,3,4-tetrahydronaphthalene (I-1-3)
    [290]
    [291] (4-1) Synthesis of 6-fluoro-1,2,3,4-tetrahydronaphthalene-2-carboaldehyde
    [292] 6-Fluoro-3,4-dihydro-2 obtained in (1-1) to a Wittich reactant prepared with 156.6 g of methoxymethyltriphenylphosphonium chloride and 51.3 g of t-butoxy potassium in THF under ice cooling A solution of 250 ml of THF of 50 g of (1H) -naphthalenone was added dropwise at 0 ° C. After reacting for 1 hour, the mixture was returned to room temperature, water was added, and the organic layer was concentrated. Hexane was added to dissolve and the insoluble triphenylphosphine oxide was separated by filtration and washed with a mixed solvent of methanol / water = 1/1. The crude product obtained by concentrating the hexane layer was dissolved in 250 ml of THF, and 250 ml of diluted hydrochloric acid was added to reflux for 3 hours. Toluene was added, washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off to give 46.7 g of 6-fluoro-1,2,3,4-tetrahydronaphthalene-2-carboaldehyde.
    [293] (4-2) Synthesis of 2- [2- (trans-4-propylcyclohexyl) ethyl] -6-fluoro-1,2,3,4-tetrahydronaphthalene (I-1-3)
    [294] 6-fluoro obtained in (4-1) to a Wittich reagent prepared with 188.7 g of 2- (trans-4-propylcyclohexyl) methyltriphenylphosphonium and 44.1 g of t-butoxypotassium in THF under ice cooling The total amount of -1,2,3,4-tetrahydronaphthalene-2-carboaldehyde was dissolved in 250 ml of THF and added dropwise at 0 占 폚. After reacting for 1 hour, the mixture was returned to room temperature, water was added, and the organic layer was concentrated. Hexane was added to dissolve and the insoluble triphenylphosphine oxide was filtered off and washed with a mixed solvent of methanol / water = 1/1. The crude product obtained by concentrating the hexane layer was dissolved in 200 ml of ethyl acetate, 10 g of 5% palladium / carbon (function) was added thereto, and stirred in an autoclave under hydrogen pressure of 4 kg / cm &lt; 2 &gt; Was removed by celite filtration, the solvent was distilled off, and the residue was purified by silica gel column chromatography (hexane), and then recrystallized twice from ethanol to give 2- [2- (trans-4-propylcyclohexyl) ethyl] -6. 50.7 g of white crystals of -fluoro-1,2,3,4-tetrahydronaphthalene (I-1-3) were obtained.
    [295] Example 5 2- [2- (trans-4-propylcyclohexyl) ethyl] -5,6,7-trifluoro-1,2,3,4-tetrahydronaphthalene (I-1-4) Synthesis of
    [296] 5,6,7-trifluoro-3,4-di synthesized in Example 2 instead of 6-fluoro-3,4-dihydro-2 (1H) -naphthalenone under the same conditions as in Example 4. 2- [2- (trans-4-propylcyclohexyl) ethyl] -5,6,7-trifluoro-1,2,3,4-tetrahydro using hydro-2 (1H) -naphthalenone Naphthalene was obtained.
    [297] Example 6 Synthesis of 2-propyl-6- (3,4-difluorophenyl) -1,2,3,4-tetrahydronaphthalene (I-2-1)
    [298]
    [299] (6-1) Synthesis of 6-propyl-4,4a, 5,6,7,8-hexahydro-3H-naphthalen-2-one
    [300] 212 g of 4-propylcyclohexanone and 200 ml of pyrrolidine were dissolved in 600 ml of toluene, and heated with stirring for 3 hours to remove azeotropic water. Excess pyrrolidin was azeotropically removed with toluene to afford 1- (4-propylcyclohexa-1-en-1-yl) -pyrrolidine. In this state, it cooled to room temperature, 800 ml of toluene was added again, and 120 ml of methyl vinyl ketones were dripped over 1 hour at 25 degrees C or less, cooling by water bath. After completion of dropping, the mixture was heated immediately and heated to reflux for 20 hours. After cooling to room temperature, a buffer solution of pH 5 prepared with 63 g of sodium acetate, 120 ml of acetic acid and 140 ml of water was added, and the mixture was further heated to reflux for 4 hours. After cooling to room temperature, the organic layer was separated and washed with water and brine. The mixture was dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain 320 g of a crude product of 6-propyl-4,4a, 5,6,7,8-hexahydro-3H-naphthalen-2-one.
    [301] (6-2) Synthesis of 2-propyl-6- (3,4-difluorophenyl) -1,2,3,4,8,8a-hexahydronaphthalene
    [302] 27.1 g of magnesium was suspended in 70 ml of tetrahydrofuran (THF), and 195.7 g of 3,4-difluorobromobenzene dissolved in 800 ml of THF was added dropwise under heating to reflux. After stirring for another 1 hour, 150 g of 6-propyl-4,4a, 5,6,7,8-hexahydro-3H-naphthalen-2-one obtained in (6-1) was dissolved in THF 600ml under water cooling. It dripped, stirring. After stirring again for 2 hours, ice was cooled and 1000 ml of 10% hydrochloric acid was added dropwise. The mixture was extracted with toluene, washed with water and brine, and dried over anhydrous magnesium sulfate. Subsequently, the crude product obtained by distilling a solvent off was dissolved in 1200 ml of toluene, 14.9 g of paratoluenesulfonic acid was added, and it heated with stirring for 3 hours, and azeotropic water was removed. After cooling to room temperature, the toluene layer was washed with water and saturated brine in that order, dried over anhydrous magnesium sulfate, and then the solvent was distilled off to obtain 2-propyl-6- (3,4-difluorophenyl) -1,2. 250 g of crude product of, 3,4,8,8a-hexahydronaphthalene was obtained.
    [303] (6-3) Synthesis of 2-propyl-6- (3,4-difluorophenyl) -1,2,3,4-tetrahydronaphthalene
    [304] The whole crude product of 2-propyl-6- (3,4-difluorophenyl) -1,2,3,4,8,8a-hexahydronaphthalene obtained in the above (6-2) was dissolved in 1200 ml of methylene chloride. Then, 44.2 ml of bromine was added dropwise while stirring under ice cooling, followed by further stirring for 3 hours. Subsequently, an aqueous sodium hydrogen sulfite solution was added and vigorously stirred for 30 minutes, and then the methylene chloride layer was washed with saturated brine, dried over anhydrous magnesium sulfate and concentrated to give 2-propyl-6- (3,4-difluorophenyl). A crude product of -1,2,3,4-tetrahydronaphthalene was obtained. Subsequently, the crude product was purified by silica gel column chromatography (hexane), dissolved in 800 ml of ethyl acetate, and stirred with 20 g of 5% palladium carbon for 6 hours under a hydrogen atmosphere of 4 kg / cm 2 in an autoclave. After filtration and distilling off the solvent, 20 g of the obtained crude product was purified by silica gel column chromatography (hexane), and then recrystallized three times from ethanol to give 2-propyl-6- (3,4-difluorophenyl). 6.5g of white crystals of -1,2,3,4-tetrahydronaphthalene were obtained.
    [305] Example 7 Synthesis of 2-propyl-6- (3,4,5-trifluorophenyl) -1,2,3,4-tetrahydronaphthalene (I-2-2)
    [306]
    [307] (7-1) Synthesis of 2-propyl-1,2,3,4-tetrahydro-6-naphthol
    [308] 5 g of 6-propyl-4,4a, 5,6,7,8-hexahydro-3H-naphthalen-2-one obtained in (6-1) was dissolved in 10 ml of acetonitrile, 11.6 g of copper bromide (II), and A solution of 50 ml of acetonitrile of lithium bromide 2,3 g was added dropwise at room temperature. After further stirring for 2 hours, the solvent was distilled off, dissolved in ethyl acetate again to remove insoluble matters by filtration, and then washed with water and brine. After drying over anhydrous sodium sulfate, the solvent was distilled off to obtain a crude product of 2-propyl-1,2,3,4-tetrahydro-6-naphthol.
    [309] (7-2) Synthesis of trifluoromethanesulfonic acid 2-propyl-1,2,3,4-tetrahydronaphthalen-6-yl
    [310] The crude product of 2-propyl-1,2,3,4-tetrahydro-6-naphthol obtained in (7-1) was dissolved in 20 ml of dichloromethane, and 4.7 ml of trifluoromethanesulfonic anhydride was added to suspend it. Cooled to C. 4.6 ml of pyridine was added dropwise with vigorous stirring, followed by further stirring for 1 hour. 20 ml of water was added to stop the reaction, and the organic layer was separated. The aqueous layer was extracted with 20 ml of dichloromethane, the organic layers were combined, washed with dilute hydrochloric acid, saturated sodium bicarbonate water, water, then saturated brine, and dried over anhydrous sodium sulfate. After distilling off the solvent, the residue was purified by silica gel column chromatography (hexane) to obtain 3.8 g of trifluoromethanesulfonic acid 2-propyl-1,2,3,4-tetrahydronaphthalen-6-yl.
    [311] (7-3) Synthesis of 2-propyl-6- (3,4,5-trifluorophenyl) -1,2,3,4-tetrahydronaphthalene
    [312] 3.8 g of trifluoromethanesulfonic acid 2-propyl-1,2,3,4-tetrahydronaphthalen-6-yl obtained, and 3,4,5-trifluorophenylboric acid (this is 3,4,5-trifluoro 3.0 g, tetrakis (triphenylphosphine) palladium (O), and potassium phosphate, 3.6 g, obtained by reacting a Grignard reactant prepared with lobromobenzene and magnesium with trimethyl boric acid, followed by hydrolysis with dilute hydrochloric acid. g was stirred in 80 ml of dimethylformamide (DMF) at 80 ° C. for 10 hours. Thereafter, the mixture was cooled to room temperature, 20 ml of water was added, extracted with toluene, the organic layer was washed with water and saturated brine in that order, and dried over anhydrous sodium sulfate. The crude product obtained by distilling off the solvent was purified by silica gel column chromatography (hexane), and recrystallized three times from ethanol to give 2-propyl-6- (3,4,5-trifluorophenyl) -1,2, 0.5 g of 3,4-tetrahydronaphthalene was obtained.
    [313] Example 8 2- (trans-4-propylcyclohexyl) -6- (3,4,5-trifluorophenyl) -1,2,3,4-tetrahydronaphthalene (I-2-3) Synthesis of
    [314]
    [315] (8-1) Synthesis of 2- (4-propylcyclohexyl) -6- (3,4,5-trifluorophenyl) -1,2,3,4,8,8a-hexahydronaphthalene
    [316] 6- (4-propylcyclohexyl) -4 in the same manner as in Example 6 (6-1), except that 4- (4-propylcyclohexyl) -cyclohexanone was used instead of 4-propylcyclohexanone. , 4a, 5,6,7,8-hexahydro-3H-naphthalen-2-one was obtained. Subsequently, 2- (4-propylcyclohexyl) -6- (in the same manner as in (6-2) except that 3,4,5-trifluorobromogen was used instead of 3,4-difluorobromobenzene. 3,4,5-trifluorophenyl) -1,2,3,4,8,8a-hexahydronaphthalene was obtained.
    [317] (8-2) Synthesis of 2- (4-propylcyclohexyl) -6- (3,4,5-trifluorophenyl) -1,2,3,4-tetrahydronaphthalene
    [318] 2- (4-propylcyclohexyl) -6- (3,4,5-trifluorophenyl) -1,2,3,4,8,8a-hexa in 80 ml of toluene obtained in the above (8-1) 20 g of hydronaphthalene and 14 g of DDQ were stirred at room temperature for 3 hours. Water and toluene were added and filtered, the toluene layer was separated, washed with water and saturated brine in that order, and dried over anhydrous magnesium sulfate. After distilling off the solvent, silica gel column chromatography (hexane) was performed to obtain 21.1 g of a crude product. Subsequently, this was dissolved in 80 ml of total ethyl acetate and stirred for 6 hours with 4 g of 5% palladium carbon under a hydrogen atmosphere of 4 kg / cm 2 in an autoclave. After filtration and distilling off the solvent, the obtained crude product was purified by silica gel column chromatography (hexane), and then recrystallized three times from ethanol / toluene to give 2- (4-propylcyclohexyl) -6- (3,4,5 6.2 g of -trifluorophenyl) -1,2,3,4-tetrahydronaphthalene was obtained.
    [319] Example 9 Synthesis of 2-propyl-6- (4-cyano-3,5-difluorophenyl) -1,2,3,4-tetrahydronaphthalene (I-2-4)
    [320]
    [321] (9-1) Synthesis of 2-propyl-6- (3,5-difluorophenyl) -1,2,3,4-tetrahydronaphthalene
    [322] 6-propyl-4,4a, 5,6,7 in the same manner as in (6-2), except that 3,4-difluorobromobenzene was replaced with 3,5-difluorobromobenzene in Example 6 212.5 g of 2-propyl-6- (3,5-difluorophenyl) -1,2,3,4,8,8a-hexahydronaphthalene were extracted from 200 g of 8-hexahydro-3H-naphthalen-2-one. Got it. Subsequently, in the same manner as in (8-2), distillation under reduced pressure was further performed to obtain 112 g of 2-propyl-6- (3,5-difluorophenyl) -1,2,3,4-tetrahydronaphthalene.
    [323] (9-2) Synthesis of 2-propyl-6- (3,5-difluoro-4-carbamoylphenyl) -1,2,3,4-tetrahydronaphthalene
    [324] 27.1 g of 2-propyl-6- (3,5-difluorophenyl) -1,2,3,4-tetrahydronaphthalene obtained in (9-1) was dissolved in 120 ml of THF and n- at -50 ° C. 68.9 ml of a 1.51 M hexane solution of butyllithium was added dropwise. Then, after blowing carbon dioxide gas, water was added, extraction was performed with ethyl acetate, the organic layer was washed with water and saturated brine in that order, and dried over anhydrous magnesium sulfate. After distilling off the solvent, the crude product was dissolved in 80 ml of 1,2-dichloroethane and 8.2 ml of thionyl chloride was added. After dropping a catalytic amount of pyridine thereto, the mixture was stirred at 50 ° C for 2 hours, and excess thionyl chloride and 1,2-dichloroethane were distilled off. The residue was dissolved in 100 ml of methylene chloride and blown with ammonia gas while stirring at room temperature. After the exotherm, water was added and extracted with ethyl acetate. The organic layer was washed with water, saturated brine, and dried over anhydrous magnesium sulfate. . The solvent was distilled off to obtain 2-propyl-6- (3,5-difluoro-4-carbamoylphenyl) -1,2,3,4-tetrahydronaphthalene crude product.
    [325] (9-3) Synthesis of 2-propyl-6- (4-cyano-3,5-difluorophenyl) -1,2,3,4-tetrahydronaphthalene
    [326] The total amount of the 2-propyl-6- (3,5-difluoro-4-carbamoylphenyl) -1,2,3,4-tetrahydronaphthalene crude product obtained in the above (9-2) was added to 120 ml of DMF. It dissolved, and 13 ml of phosphorus oxychloride was added, and it reacted at 25 degreeC for 2 hours. The reaction solution was poured into ice water, diluted hydrochloric acid was added, and the mixture was extracted with toluene from the aqueous layer. The organic layers were combined, washed with water, saturated aqueous sodium hydrogen carbonate solution and saturated brine, and then dried over anhydrous sodium sulfate. Silica gel column chromatography (toluene), followed by alumina column chromatography (toluene), followed by acetone solution and purification by activated charcoal treatment, recrystallized seven times from ethanol to give 2-propyl-6- (4-cyano-3, 4.0 g of 5-difluorophenyl) -1,2,3,4-tetrahydronaphthalene were obtained.
    [327] Example 10 2-propyl-5-fluoro-6- (3,4,5-trifluorophenyl) -1,2,3,4-tetrahydronaphthalene and 2-propyl-7-fluoro- Synthesis of 6- (3,4,5-trifluorophenyl) -1,2,3,4-tetrahydronaphthalene (I-2-5)
    [328]
    [329] (10-1) 2-propyl-5-fluoro-1,2,3,4-tetrahydro-6-naphthol and 2-propyl-7-fluoro-1,2,3,4-tetrahydro-6 Synthesis of Naphthol
    [330] 200 g of 2-propyl-1,2,3,4-tetrahydro-6-naphthol obtained in (7-1) was dissolved in 1000 ml of dichloromethane, 5 g of sodium trifluoromethanesulfonic acid was added and stirred vigorously. 243 g of bistetrafluoroboric acid N, N'-difluoro-2,2'- dipyridinium were added gradually, and it stirred at room temperature again for 5 hours. Water, followed by 10% aqueous sodium hydroxide solution was added, the excess fluorination agent was decomposed, returned to acidic with diluted hydrochloric acid, and the organic layer was separated. The aqueous layer was extracted with dichloromethane, the organic layers were combined, washed with water and brine, and dried over anhydrous sodium sulfate. The crude product obtained by distilling off the solvent was separated and purified by silica gel column chromatography (toluene) to give 57.0 g of 2-propyl-5-fluoro-1,2,3,4-tetrahydro-6-naphthol and 2-propyl-. 85.5 g of 7-fluoro-1,2,3,4-tetrahydro-6-naphthol were obtained, respectively.
    [331] (10-2) 2-propyl-5-fluoro-6- (3,4,5-trifluorophenyl) -1,2,3,4-tetrahydronaphthalene and 2-propyl-7-fluoro- Synthesis of 6- (3,4,5-trifluorophenyl) -1,2,3,4-tetrahydronaphthalene
    [332] 2-propyl-5-fluoro-1,2,3,4 obtained in (10-1) instead of 2-propyl-1,2,3,4-tetrahydro-6-naphthol in (7-2) The same method as (7-2) and (7-3), except that -tetrahydro-6-naphthol and 2-propyl-7-fluoro-1,2,3,4-tetrahydro-6-naphthol were used, respectively. 2-propyl-5-fluoro-6- (3,4,5-trifluorophenyl) -1,2,3,4-tetrahydronaphthalene 35 g and 2-propyl-7-fluoro-6- ( 53 g of 3,4,5-trifluorophenyl) -1,2,3,4-tetrahydronaphthalene were obtained, respectively.
    [333] Example 11 Synthesis of 2-propyl-6- (3,4,5-trifluorophenyl) ethynyl-1,2,3,4-tetrahydronaphthalene
    [334]
    [335] 50 g of trifluoromethanesulfonic acid 2-propyl-1,2,3,4-tetrahydronaphthalen-6-yl obtained from (7-2) and 2- (3,4,5-trifluorophenyl) -acetylene 33.9 g, tetrakis (triphenylphosphine) palladium (O) 3.6g, and 51.4g of potassium phosphate were stirred in 80 ml of DMF for 10 hours. Thereafter, the mixture was cooled to room temperature, water was added, extraction was performed with toluene, and the organic layer was washed with water and saturated brine in that order, and dried over anhydrous sodium sulfate. The crude product obtained by distilling off the solvent was purified by silica gel column chromatography (hexane), and recrystallized three times from ethanol to give 2-propyl-6- (3,4,5-trifluorophenyl) ethynyl-1, 32.6 g of 2,3,4-tetrahydronaphthalene were obtained.
    [336] Example 12 Synthesis of 6-propyl-2- (3,4,5-trifluorophenyl) -1,2,3,4-tetrahydronaphthalene (I-3-2)
    [337]
    [338] A Grignard reactant was prepared by dropwise adding 100 ml of tetrahydrofuran of 30 g of 3,4,5-trifluorobromobenzene to 4.0 g of magnesium. 150 ml of toluene was added to this, and about 100 ml of solvents were distilled off under room temperature and reduced pressure. This was heated to 60 degreeC and the 50 ml solution of 25 g of 6-propyl-1,2,3,4- tetrahydronaphthalen-2-one 25g was dripped over 20 minutes. After stirring again for 30 minutes, it returned to room temperature and the reaction liquid was poured into 10% hydrochloric acid. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate and concentrated. The residue was purified by silica gel column chromatography (hexane / ethyl acetate = 6/1) to give 2-hydroxy-6-propyl-2- (3,4,5-trifluorophenyl) -1,2,3,4 29 g of tetrahydronaphthalene was obtained. 100 ml of toluene and 3 g of p-toluenesulfonic acid were added to this, and it heated and stirred for 1 hour. The reaction solution was cooled, concentrated and the residue was purified by silica gel column chromatography (hexane) to give 26 g of 6-propyl-2- (3,4,5-trifluorophenyl) -3,4-dihydronaphthalene. To this was added 50 ml of ethanol, 50 ml of ethyl acetate and 3 g of 5% palladium-carbon, followed by stirring at room temperature under hydrogen atmosphere for 2 hours. The reaction solution was filtered through celite and the filtrate was concentrated. The residue was purified by silica gel column chromatography (hexane) to give 26 g of 6-propyl-2- (3,4,5-trifluorophenyl) -1,2,3,4-tetrahydronaphthalene. This compound had a purity of 99% by gas chromatography and a molecular weight of 304 by mass spectrometry.
    [339] Example 13 Synthesis of 2- (3,4-difluorophenyl) -6-propyl-1,2,3,4-tetrahydronaphthalene (I-3-1)
    [340] 2- (3,4-difluorophenyl) -6-propyl-1 using 3,4-difluorobromobenzene instead of 3,4,5-trifluorobromobenzene under the same conditions as in Example 12 , 2,3,4-tetrahydronaphthalene was synthesized. Purity 99%, molecular weight 286.
    [341] Example 14 Synthesis of 6-propyl-2- (4-trifluoromethoxyphenyl) -1,2,3,4-tetrahydronaphthalene (I-3-3)
    [342] 6-propyl-2- (4-trifluoromethoxyphenyl) -1, using 4-trifluoromethoxybromobenzene instead of 3,4,5-trifluorobromobenzene under the same conditions as in Example 12, 2,3,4-tetrahydronaphthalene was synthesized. Purity 99%, molecular weight 334.
    [343] Example 15 Synthesis of 2- (3,4-difluorophenyl) -6- (trans-4-propylcyclohexyl) -1,2,3,4-tetrahydronaphthalene (I-3-4)
    [344]
    [345] A Grignard reactant was prepared by dropwise adding 100 ml of tetrahydrofuran of 25 g of 3,4-difluorobromobenzene to 3.5 g of magnesium. This was filtered through a glass filter, and 150 ml of toluene was added to the filtrate, and about 100 ml of the solvent was distilled off under room temperature and reduced pressure. This was heated to 60 degreeC, and the 50 ml solution of 27 g of 6-bromo-1,2,3,4- tetrahydronaphthalen-2-one 27g was dripped over 20 minutes. After stirring again for 30 minutes, it returned to room temperature and the reaction liquid was poured into 10% hydrochloric acid. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate and concentrated. The residue was purified by silica gel column chromatography (hexane / ethyl acetate = 6/1) to give 6-bromo-2- (3,4-difluorophenyl) -2-hydroxy-1,2,3,4- 29 g of tetrahydronaphthalene was obtained. 100 ml of toluene and 3 g of p-toluenesulfonic acid were added to this, and it heated and stirred for 1 hour. The reaction solution was cooled, concentrated and the residue was purified by silica gel column chromatography (hexane) to give 26 g of 6-bromo-2- (3,4-difluorophenyl) -3,4-dihydronaphthalene. To this was added 50 ml of ethanol, 50 ml of ethyl acetate, and 3 g of 5% rhodium-carbon, followed by stirring at room temperature under hydrogen atmosphere for 2 hours. The reaction solution was filtered through celite and the filtrate was concentrated. The residue was purified by silica gel column chromatography (hexane) to give 26 g of 6-bromo-2- (3,4-difluorophenyl) -1,2,3,4-tetrahydronaphthalene. This compound had a purity of 99% by gas chromatography and a molecular weight of 304 by mass spectrometry.
    [346] A Grignard reactant was prepared by dropwise addition of 70 ml of tetrahydrofuran of 26 g of 6-bromo-2- (3,4-difluorophenyl) -1,2,3,4-tetrahydronaphthalene to 2.3 g of magnesium. . A 30 ml solution of tetrahydrofuran of 13.5 g of 4-propylcyclohexanone was added dropwise thereto. After 30 minutes of stirring, the reaction solution was poured into 10% hydrochloric acid. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate and concentrated. The residue was purified by silica gel column chromatography (hexane / ethyl acetate = 6/1) to give 2- (3,4-difluorophenyl) -2-hydroxy-6- (trans-4-propylcyclohexyl) -1. 23g of 2,3,4-tetrahydronaphthalene was obtained. 80 ml of toluene and 2 g of p-toluenesulfonic acid were added to this, and it heated and stirred for 1 hour. The reaction solution was cooled, concentrated and the residue was purified by silica gel column chromatography (hexane) to give 2- (3,4-difluorophenyl) -6- (trans-4-propylcyclohexyl) -3,4-di 26 g of hydronaphthalene was obtained. To this was added 30 ml of ethanol, 50 ml of ethyl acetate, and 2 g of 5% palladium-carbon, followed by stirring at room temperature under hydrogen atmosphere for 2 hours. The reaction solution was filtered through celite and the filtrate was concentrated. 50 ml of dimethylformamide and 5.5 g of t-butoxy potassium were added to the residue, and the mixture was stirred at 70 ° C for 2 hours. 10% hydrochloric acid was added to the reaction solution, the mixture was extracted with toluene, the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated. The residue was purified by silica gel column chromatography (hexane) and recrystallized from ethanol to give 2- (3,4-difluorophenyl) -6- (trans-4-propylcyclohexyl) -1,2,3,4- 20 g of tetrahydronaphthalene was obtained. This compound had a purity of 99.8% by gas chromatography and a molecular weight of 368 by mass spectrometry.
    [347] Example 16 Synthesis of 2- (3,4-difluorophenyl) -6- (4-propylphenyl) -1,2,3,4-tetrahydronaphthalene (I-3-5)
    [348]
    [349] 4.5 g of 4-propylphenyl boric acid obtained by reacting a Grignard reactant prepared with 4-propylbromobenzene and magnesium with trimethyl boric acid, followed by hydrolysis with dilute hydrochloric acid, synthesized in Example 15, 6-bromo-2 30 ml of dimethylformamide in 5.0 g of (3,4-difluorophenyl) -1,2,3,4-tetrahydronaphthalene, 0.3 g of tetrakis (triphenylphosphine) palladium (O) and 3.0 g of potassium phosphate It stirred at 80 degreeC in the middle. After cooling the reaction solution to room temperature, water was added and the mixture was extracted with toluene. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate and concentrated. The residue was purified by silica gel column chromatography (hexane) and recrystallized with ethanol to give 2- (3,4-difluorophenyl) -6- (4-propylphenyl) -1,2,3,4-tetrahydronaphthalene 4g was obtained. This compound had a purity of 99.7% by gas chromatography and a molecular weight of 362 by mass spectrometry.
    [350] Example 17 Preparation of Liquid Crystal Composition 1
    [351] Universal host liquid crystal (H) with wide temperature range, low viscosity and also for active matrix drive
    [352]
    [353] In which the cyclohexane ring represents a transmer. This (H) shows a nematic phase at 116.7 ° C or lower, and its melting point is 11 ° C. The measured value at 20 degrees C of the physical-property value of this composition and the threshold voltage (Vth) of the TN cell (cell thickness 4.5micrometer) made using this was as follows.
    [354] Nematic phase upper limit temperature (T N-1 ) 116.7 ℃
    [355] Dielectric constant anisotropy (Δε) 4.80
    [356] Threshold voltage (Vth) 1.88 V
    [357] Response time (τ) 21.5 m seconds
    [358] Next, a liquid crystal composition (M-1) composed of 80% of the host liquid crystal (H) and 20% of the compound of the present invention (I-1-2) obtained in Example 2 was prepared. T N-1 ) was 72.3 ° C. After leaving this (M-1) at 150 degreeC for 20 hours, its T N-1 was measured and there was no change before heating. Moreover, although ultraviolet-ray was irradiated for 20 hours, there was no change in TN -1 . Next, when the voltage retention of this composition was measured, in the case of preparation, after heating and ultraviolet irradiation, it showed the value high enough similarly to a host liquid crystal (H).
    [359] Next, (M-1) was filled into a TN cell having a cell thickness of 4.6 µm to form a liquid crystal device, and its electrooptic characteristics were measured, and the results were as follows.
    [360] Dielectric constant anisotropy (Δε) 5.20
    [361] Threshold Voltage (Vth) 1.51 V
    [362] Response time (τ) 29.3 m seconds
    [363] Therefore, by adding 20% of (I-1-2), the threshold voltage Vth could be reduced by 0.37V while suppressing the drop of the nematic phase upper limit temperature T N-1 at 44 ° C. Also, the response time could be suppressed by an increase of 8 m seconds. Moreover, even if it was left for one week at 0 degreeC, a crystal did not precipitate. The melting point (T CN ), which was quenched and crystallized, was found to be 13 ° C., almost unchanged from the host liquid crystal (H), and (I-2) was well dissolved in the host liquid crystal.
    [364] Next, the voltage retention of the device at room temperature and 80 ° C. was measured, but it was found that both were very good and could be sufficiently used for driving an active matrix.
    [365] (Example 18) Preparation 2 of the liquid crystal composition
    [366] In Example 17, the compound of the present invention (I-2-3) obtained in Example 8 in place of (I-1-2) was added to the host liquid crystal (H) by 20% by the same amount to form the liquid crystal composition (M-2 ) Was prepared. The nematic phase upper limit temperature (T N-1 ) of this composition was 118.1 degreeC. After leaving this (M-2) at 150 degreeC for 20 hours, its T N-1 was measured but there was no change before heating. Moreover, although ultraviolet-ray was irradiated for 20 hours, there was no change in TN -1 . Next, when the voltage retention of this composition was measured, the host liquid crystal H showed the same sufficiently high value at the time of preparation, after heating, and after ultraviolet irradiation.
    [367] Next, (M-2) was filled into a TN cell having a cell thickness of 6.0 µm to form a liquid crystal element, and its electrooptic characteristics were measured, and the results were as follows.
    [368] Dielectric constant anisotropy (Δε) 5.50
    [369] Threshold voltage (Vth) 1.92 V
    [370] Response time (τ) 34.2 m seconds
    [371] Therefore, by adding 20% of (I-2-3), the threshold voltage Vth could be reduced by 0.22V while widening the temperature range of the nematic phase thereof. Also, the response time could be suppressed by an increase of 9 m seconds.
    [372] Example 19 Preparation 3 of Liquid Crystal Composition
    [373] In Example 17, when the liquid crystal composition (M-3) which consists of 20% of (I-3-2) which is a compound of this invention obtained in Example 12 instead of (I-1-2) was prepared, an upper liquid crystal phase upper limit The temperature (T N-1 ) was 74 ° C. After leaving this (M-3) at 150 degreeC for 20 hours, its T N-1 was measured but there was no change before heating. Moreover, although ultraviolet-ray was irradiated for 20 hours, there was no change in TN -1 . Next, when the voltage retention of this composition was measured, the host liquid crystal H showed the same sufficiently high value at the time of preparation, after heating, and after ultraviolet irradiation.
    [374] Next, (M-3) was filled into a TN cell having a cell thickness of 4.5 mu m to make a liquid crystal element, and its electro-optical characteristics were measured, and the results were as follows.
    [375] Dielectric constant anisotropy (Δε) 5.50
    [376] Threshold voltage (Vth) 1.55 V
    [377] Response time (τ) 30.5 m seconds
    [378] Therefore, by adding 20% of (I-3-2), the threshold voltage Vth could be reduced by 0.33V while suppressing the drop of its nematic upper limit temperature T N-1 at 46 ° C. Also, the response time could be suppressed by an increase of 9 m seconds. Moreover, even if it was left for one week at 0 degreeC, a crystal did not precipitate. In addition, the melting point (T CN ) which was quenched and crystallized was found to be almost unchanged from the host liquid crystal (H) at 12 ° C., and (I-2) was well dissolved in the host liquid crystal.
    [379] Next, the voltage retention of the device at room temperature and at 80 ° C. was measured, but it was found that both were very good and could be sufficiently used for driving the active matrix.
    [380] (Comparative Example 1)
    [381] In Example 17, an equivalent amount of trans-4-propyl- (3,4,5-trifluorophenyl) cyclohexane was added to the host liquid crystal (H) in place of (I-1-2) to give a liquid crystal composition ( M-4) was prepared. The nematic upper limit temperature (T N-1 ) of this composition is 70 degreeC, and it turns out that liquid crystallinity is low.
    [382] The other physical properties of this composition and the electro-optical properties of the device made by the same method are as follows.
    [383] Nematic phase upper limit temperature (T N-1 ) 70.0 ℃
    [384] Dielectric constant anisotropy (Δε) 5.60
    [385] Threshold voltage (Vth) 1.58 V
    [386] Response time (τ) 30.0 m seconds
    [387] Index of Anisotropy (Δn): 0.080
    [388] The tetrahydronaphthalene derivatives provided by the present invention are excellent in liquid crystallinity and compatibility with current general-purpose liquid crystal compounds or compositions. In addition, it is possible to greatly reduce the threshold voltage with almost no deterioration in response. It is also easy to manufacture industrially, and is colorless and chemically stable. Therefore, the liquid crystal composition containing this is very practical as a practical liquid crystal, especially for the liquid crystal display which has a wide temperature range and requires low voltage drive and high speed response.
    权利要求:
    Claims (27)
    [1" claim-type="Currently amended] Tetrahydronaphthalene derivative represented by general formula (I):

    (Wherein R may be substituted with 1 to 7 fluorine atoms or an alkoxyl group having 1 to 7 carbon atoms, and a saturated or unsaturated carbon having 1 to 20 carbon atoms that may contain a branched chain) An alkyl group or an alkoxyl group, and the linking groups La, Lb, Lc and Ld each independently represent a single bond, -CH 2 CH 2- , -CH = CH-, -CH (CH 3 ) CH 2- , -CH 2 CH (CH 3 )-, -CH (CH 3 ) CH (CH 3 )-, -CF 2 CF 2- , -CF = CF-, -CH 2 O-, -OCH 2- , -OCH (CH 3 )- , -CH (CH 3 ) O-, -C≡C-, -CF 2 O-, -OCF 2- , -COO-, -OCO-, -COS- or -SCO-, Z represents a fluorine atom, Chlorine atom, cyano group, cyanate group, trifluoromethoxy group or difluoromethoxy group, and ring A, ring B and ring D each independently represent a trans-1,4-cyclohexylene group and a trans-deca 1,4- which may be substituted by hydronaphthalene-2,6-diyl group, trans-1,3-dioxane-2,4-diyl group or one or two fluorine atoms Is substituted with a phenylene group, a pyridine-2,5-diyl group, a pyrimidine-2,5-diyl group, a pyrazine-2,5-diyl group, a pyridazine-3,6-diyl group and one or two fluorine atoms May represent a naphthalene-2,6-diyl group, and each ring E may be independently substituted with 1,4-phenylene group and 1 or 2 fluorine atoms, which may be substituted with 1 or 2 fluorine atoms. Which may represent a naphthalene-2,6-diyl group, and ring C represents general formula (IIa) or (IIb).

    Wherein X 1 , X 2 , X 3 , X 4 , X 5 and X 6 represent a hydrogen atom or a fluorine atom, and n a , n b , n c and n d are each independently 0 or 1,
    Provided that when n c = 1 and n d = 0, ring D is a 1,4-phenylene group which may be substituted with one or two fluorine atoms and / or a naphthalene that may be substituted with one or two fluorine atoms- 2,6-diyl group,
    In addition, Z is a cyano group, R is an unsubstituted and saturated alkyl or alkoxyl group, n a = n c = n d = 0, n b = 1, n b = n c = n d = 0, and n a = 1, when ring A and ring B are 1,4-phenylene groups, La and Lb are single bonds, and ring C is formula (IIa), at least one of X 1 , X 2 and X 3 represents a fluorine atom ,
    In addition, Z is a cyano group, R is an unsubstituted and saturated alkyl or alkoxyl group, n a = n b = n c = 0, n d = 1, n a = n b = n d = 0, and n c = 1, when ring C and ring D are 1,4-phenylene groups, Lc and Ld are single bonds or -COO-, and ring C is formula (IIa), at least one of X 1 , X 2 and X 3 is Represents a fluorine atom,
    In addition, Z is a cyano group, R is an unsubstituted and saturated alkyl or alkoxyl group, n a = n b = n c = 0, n d = 1, n a = n b = n d = 0, and n c = 1, when ring C and ring D are 1,4-phenylene groups, Lc and Ld are single bonds or -COO-, and ring C is formula (IIb), at least one of X 4 , X 5 and X 6 is Represents a fluorine atom,
    In addition, Z is a fluorine atom, R is an unsubstituted and saturated alkyl or alkoxyl group, n a = n b = n c = 0, n d = 1, n a = n b = n d = 0, and n c = 1, when ring C and ring D are 1,4-phenylene groups, Lc and Ld are -COO-, and ring C is formula (IIb), at least one of X 4 , X 5 and X 6 represents a fluorine atom; Indicate,
    In addition, when ring C is of formula (IIb), at least one of n c and n d is 1).
    [2" claim-type="Currently amended] The method of claim 1,
    In the general formula (I), tetrahydronaphthalene derivative wherein ring C is formula (IIa).
    [3" claim-type="Currently amended] The method of claim 1,
    In the general formula (I), tetrahydronaphthalene derivative wherein ring C is formula (IIb).
    [4" claim-type="Currently amended] The method according to any one of claims 1 to 3,
    In the general formula (I), tetrahydronaphthalene derivative wherein n a or n b is 0.
    [5" claim-type="Currently amended] The method according to any one of claims 1 to 4,
    In the general formula (I), tetrahydronaphthalene derivative wherein n c or n d is 0.
    [6" claim-type="Currently amended] The method according to any one of claims 1 to 5,
    In the general formula (I), tetrahydronaphthalene derivative when n a = n b = 0.
    [7" claim-type="Currently amended] The method according to any one of claims 1, 2, 4 and 5,
    In the general formula (I), n c = n d = 0, tetrahydronaphthalene derivative.
    [8" claim-type="Currently amended] The method according to any one of claims 1 to 7,
    In the general formula (I), at least one of n a , n b , n c and n d is 1, tetrahydronaphthalene derivative.
    [9" claim-type="Currently amended] The method according to any one of claims 1 to 8,
    In the general formula (I), the linking groups La, Lb, Lc, and Ld are each independently selected from a single bond, -CH 2 CH 2-, and -C≡C-.
    [10" claim-type="Currently amended] The method according to any one of claims 1 to 9,
    In the general formula (I), the linking groups La, Lb, Lc, and Ld are each independently selected from a single bond or -CH 2 CH 2- .
    [11" claim-type="Currently amended] The method according to any one of claims 1 to 10,
    In the general formula (I), the linking groups La, Lb, Lc, and Ld are single bonds, tetrahydronaphthalene derivatives.
    [12" claim-type="Currently amended] The method according to any one of claims 1 to 11,
    In formula (I), ring A, ring B and ring D are each independently a trans-1,4-cyclohexylene group, a trans-decahydronaphthalene-2,6-diyl group, a trans-1,3- From a dioxane-2,4-diyl group, or a 1,4-phenylene group which may be substituted with one or two fluorine atoms, and a naphthalene-2,6-diyl group which may be substituted with one or two fluorine atoms Tetrahydronaphthalene derivatives selected.
    [13" claim-type="Currently amended] The method according to any one of claims 1 to 12,
    In the general formula (I), Z is fluorine tetrahydronaphthalene derivative.
    [14" claim-type="Currently amended] The method according to any one of claims 1 to 12,
    In the general formula (I), Z is a cyano group, tetrahydronaphthalene derivative.
    [15" claim-type="Currently amended] The method according to any one of claims 1 to 12,
    In the general formula (I), Z is a tetrahydronaphthalene derivative wherein trifluoromethoxy group.
    [16" claim-type="Currently amended] The method according to any one of claims 1 to 15,
    In the above general formula (I), R may be substituted by 1 to 7 fluorine atoms or an alkoxyl group having 1 to 7 carbon atoms, and may be a saturated or unsaturated carbon atom having 1 to 20 carbon atoms. Tetrahydronaphthalene derivative which is an alkyl group.
    [17" claim-type="Currently amended] The method according to any one of claims 1 to 16,
    In the general formula (I), tetrahydronaphthalene derivative wherein R is a saturated or unsubstituted linear alkyl group having 1 to 20 carbon atoms.
    [18" claim-type="Currently amended] The method according to any one of claims 1 to 17,
    In the general formula (I), tetrahydronaphthalene derivatives wherein X 3 , X 4 and X 5 of formulas (IIa) and (IIb) are hydrogen atoms.
    [19" claim-type="Currently amended] The method according to any one of claims 1 to 18,
    In said general formula (I), the tetrahydronaphthalene derivative whose X <2> of formula (IIa) is a hydrogen atom and X <1> is a fluorine atom.
    [20" claim-type="Currently amended] The method according to any one of claims 1 to 18,
    In said general formula (I), the tetrahydronaphthalene derivative whose X <1> of a formula (IIa) is a hydrogen atom and X <2> is a fluorine atom.
    [21" claim-type="Currently amended] The method according to any one of claims 1 to 20,
    Tetrahydronaphthalene derivative which shows liquid crystallinity.
    [22" claim-type="Currently amended] The method according to any one of claims 1 to 21,
    Tetrahydronaphthalene derivative which shows a nematic phase.
    [23" claim-type="Currently amended] The method according to any one of claims 1 to 22,
    Tetrahydronaphthalene derivative which shows a nematic phase when added to a nematic liquid crystal composition.
    [24" claim-type="Currently amended] The liquid crystal composition containing at least one type of the compound of the general formula (I) according to any one of claims 1 to 23.
    [25" claim-type="Currently amended] The method of claim 24,
    A liquid crystal composition used for driving an active matrix.
    [26" claim-type="Currently amended] A liquid crystal element comprising the liquid crystal composition according to claim 25 as a component.
    [27" claim-type="Currently amended] An active matrix drive liquid crystal display element using the liquid crystal composition according to claim 26.
    类似技术:
    公开号 | 公开日 | 专利标题
    KR101186241B1|2012-09-27|Process for the preparation of ring compounds
    TWI670264B|2019-09-01|4,6-difluorodibenzothiophene derivatives
    EP0110299B1|1988-06-29|Smectic liquid crystal compounds and liquid crystal compositions
    US5013478A|1991-05-07|Liquid crystals
    EP0167912B1|1990-01-03|Liquid crystal mixtures containing compounds with a 4-alkenyl or 2z-alkenyl lateral chain
    US4565425A|1986-01-21|Liquid crystals
    JP3790556B2|2006-06-28|Liquid crystalline copolymer
    KR100845994B1|2008-07-11|Liquid-crystalline compounds
    EP0786509B1|2001-09-12|Liquid crystal composition and liquid crystal display
    US7067179B1|2006-06-27|Fused ring compound
    JP2582031B2|1997-02-19|Hydroterphenyl compound and liquid crystal composition
    KR100254096B1|2000-07-01|Vinyl compounds and liquid-crystal medium
    DE3246440C2|1995-04-20|Acetylene
    TWI391475B|2013-04-01|Pyran-dioxane derivatives, and the use thereof in liquid-crystalline media
    TWI338034B|2011-03-01|Benzochromene derivatives
    KR100765554B1|2007-10-09|Liquid crystalline compounds
    DE10115955B4|2017-10-19|Fluorinated fluorene derivatives
    JP2927542B2|1999-07-28|Halogenated benzene derivatives and liquid crystal phase
    JP2951400B2|1999-09-20|Fluorobenzene derivative and liquid crystal phase
    JP4090073B2|2008-05-28|Benzene derivatives and liquid crystal media
    US4344856A|1982-08-17|Crystalline-liquid substituted 1,3-dioxanes and mixtures containing them
    EP0182054B1|1990-03-07|Heterocyclic compounds
    JP2787360B2|1998-08-13|Difluoromethyl compound
    JP4578761B2|2010-11-10|Fluorinated | phenanthrene derivatives and their use in liquid crystal media
    KR101048559B1|2011-07-11|Cyclopenta naphthalene derivatives
    同族专利:
    公开号 | 公开日
    EP1191008A1|2002-03-27|
    WO2001000548A1|2001-01-04|
    CN1356969A|2002-07-03|
    CN1223561C|2005-10-19|
    EP1191008B1|2005-02-09|
    DE69923713D1|2005-03-17|
    US6746728B1|2004-06-08|
    DE69923713T2|2005-12-29|
    HK1044529A1|2005-06-03|
    KR100591349B1|2006-06-19|
    TWI245794B|2005-12-21|
    EP1191008A4|2002-10-16|
    AU5649099A|2001-01-31|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1999-06-30|Priority to JP11184786A
    1999-06-30|Priority to JPJP-P-1999-00184786
    1999-07-06|Priority to JPJP-P-1999-00191670
    1999-07-06|Priority to JP19167099A
    1999-09-10|Application filed by 오쿠무라 고조, 다이니혼 잉키 가가쿠 고교 가부시키가이샤
    2002-03-29|Publication of KR20020023965A
    2006-06-19|Application granted
    2006-06-19|Publication of KR100591349B1
    优先权:
    申请号 | 申请日 | 专利标题
    JP11184786A|JP2001010991A|1999-06-30|1999-06-30|Tetrahydronaphthalene derivative|
    JPJP-P-1999-00184786|1999-06-30|
    JPJP-P-1999-00191670|1999-07-06|
    JP19167099A|JP4595142B2|1999-07-06|1999-07-06|Tetrahydronaphthalene derivative and liquid crystal composition containing the same|
    [返回顶部]