WO2017018153A1 - Stabilizer compound, liquid crystal composition, and display element - Google Patents

Stabilizer compound, liquid crystal composition, and display element Download PDF

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Publication number
WO2017018153A1
WO2017018153A1 PCT/JP2016/070105 JP2016070105W WO2017018153A1 WO 2017018153 A1 WO2017018153 A1 WO 2017018153A1 JP 2016070105 W JP2016070105 W JP 2016070105W WO 2017018153 A1 WO2017018153 A1 WO 2017018153A1
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group
general formula
compound
hydrogen atom
carbon atoms
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PCT/JP2016/070105
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French (fr)
Japanese (ja)
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清香 野瀬
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Dic株式会社
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Priority to JP2017523015A priority Critical patent/JP6255633B2/en
Publication of WO2017018153A1 publication Critical patent/WO2017018153A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/10—Spiro-condensed systems
    • C07D491/113—Spiro-condensed systems with two or more oxygen atoms as ring hetero atoms in the oxygen-containing ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells

Definitions

  • the present invention relates to a stabilizer compound.
  • Liquid crystal display elements are used in various measuring instruments, automobile panels, word processors, electronic notebooks, printers, computers, televisions, watches, advertisement display boards, etc., including clocks and calculators.
  • Typical liquid crystal display methods include TN (twisted nematic) type, STN (super twisted nematic) type, VA (vertical alignment) type using TFT (thin film transistor), and IPS (in-plane Switching) type or FFS (fringe field switching) type.
  • the main characteristics required for the liquid crystal composition are (1) being stable against external stimuli such as moisture, air, heat, light, etc. There are four examples: (3) low viscosity, and (4) low driving voltage.
  • dielectric anisotropy ( ⁇ ) and refractive index anisotropy ( ⁇ n) In general, the liquid crystal composition is composed of several to several tens of kinds of compounds in order to obtain an optimal value.
  • a positive value composition and a negative value composition are used separately.
  • examples of a display method using a liquid crystal material in which ⁇ has a positive value include TN type, STN type, IPS type, and FFS type.
  • examples of the display method using a liquid crystal material in which ⁇ has a negative value include ECB type, VA type, and FFS type.
  • low voltage driving, high-speed response, and a wide operating temperature range are required in all driving systems. That is, the absolute value of ⁇ is large, the viscosity ( ⁇ ) is small, and a high nematic phase-isotropic liquid phase transition temperature (T ni ) is required.
  • ⁇ n ⁇ d which is the product of ⁇ n and the cell gap (d)
  • ⁇ n of the liquid crystal composition it is necessary to adjust ⁇ n of the liquid crystal composition to an appropriate range according to the cell gap.
  • a liquid crystal composition having a small ⁇ 1 is required.
  • the problem to be solved by the present invention is to prevent deterioration of the liquid crystal composition by adding it to the liquid crystal composition, high compatibility with the liquid crystal composition, without impairing the storage stability of the liquid crystal composition, and It is to provide a stabilizer compound that can be easily produced.
  • R a0 represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or an alkenyl group having 3 to 12 carbon atoms
  • R a1 , R a2 , R a3 and R a4 each independently represents an alkyl group having 1 to 8 carbon atoms, or R a1 and R a2 and / or R a3 and R a4 together form a ring structure.
  • R a5 and R a6 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, n represents 0 or 1, t represents 1 to 4; U represents a 2 ⁇ t-valent organic group forming a ring structure, and when a plurality of R a0 , R a1 , R a2 , R a3 , R a4 , R a5 , R a6 and n are present, they are the same. Or different. ) And a liquid crystal composition containing the compound and a display element are provided.
  • the stabilizer compound according to the present invention prevents the liquid crystal composition from being deteriorated by light, has high compatibility with the liquid crystal composition, and can be easily produced without impairing the storage stability of the liquid crystal composition.
  • a fast response liquid crystal display element can be provided.
  • R a0 is preferably a hydrogen atom or a hydroxyl group, and particularly preferably a hydrogen atom, in order to enhance the ability to prevent photodegradation.
  • an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 3 to 12 carbon atoms is preferable.
  • R a1 , R a2 , R a3 and R a4 are each independently preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group.
  • R a1 and R a2 and / or R a3 and R a4 are preferably combined to form a ring structure.
  • R a5 and R a6 are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and particularly preferably a hydrogen atom for ease of production.
  • n is preferably 1.
  • t is preferably 1 or 2 and particularly preferably 1 in order to increase the storage stability of the liquid crystal composition.
  • the number is preferably 3 or 4 because the number of hindered amine structures per unit weight increases.
  • U represents the general formula (Ia)
  • each broken line represents a bond to an oxygen atom
  • R a7 and R a8 each independently represents a hydrogen atom or a monovalent organic group, or R a7 and R a8 together form a ring structure.
  • m is 0 or 1.
  • R a7 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms Is particularly preferred
  • m is particularly preferably 1.
  • R a8 represents the general formula (Ic)
  • Sp a1 and Sp a2 each independently represent a single bond or an alkylene group having 1 to 12 carbon atoms. , more preferably a single bond or an alkylene group having 1 to 8 carbon atoms, one -CH 2 present in the alkyl group - or nonadjacent two or more -CH 2 - is -O- , —COO—, —OCO—, —CH ⁇ CH— or —C ⁇ C— are preferred, and a single bond is particularly preferred.
  • a a1 and A a2 each independently (a) 1,4-cyclohexylene group (this is present in the group one -CH 2 - or nonadjacent two or more -CH 2 - is -O- May be replaced by.) (B) a 1,4-phenylene group (one —CH ⁇ present in the group or two or more non-adjacent —CH ⁇ may be replaced by —N ⁇ ) and (c) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or 1,2 , 3,4-tetrahydronaphthalene-2,6-diyl group, one —CH ⁇ or two or more non-adjacent —CH ⁇ may be replaced by —N ⁇ .
  • a group selected from the group consisting of the above groups is preferable, and the groups (a), (b) and (c) are each independently a cyano group, fluorine More preferably, it is substituted with an atom, a chlorine atom, a methyl group or a methoxy group.
  • R a9 preferably represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and one — CH 2 — or two or more non-adjacent —CH 2 — are replaced by —O—, —S—, —COO—, —OCO—, —CO—, —CH ⁇ CH— or —C ⁇ C—. And is preferably replaced by —O— or —CH ⁇ CH—.
  • R a9 represents the general formula ( Id )
  • R d0 , R d1 , R d2 , R d3 , R d4 , R d5 and R d6 are R a0 , R a1 , R a2 , R a3 , R a4 , R a5 and R in the general formula (I)).
  • R a10 represents a hydrogen atom or a monovalent organic group
  • Sp a3 represents the same meaning as Sp a1 or Sp a2
  • s and v each independently represent 0 or 1.
  • a structure represented by R d0 is preferably a hydrogen atom or a hydroxyl group for enhancing the ability to prevent photodegradation, and particularly preferably a hydrogen atom for ease of production.
  • an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 3 to 12 carbon atoms is preferable.
  • R d1 , R d2 , R d3 and R d4 are each independently preferably an alkyl group having 1 to 4 carbon atoms, particularly preferably a methyl group. In order to facilitate removal of polar impurities mixed during production, it is preferable that R d1 and R d2 and / or R d3 and R d4 together form a ring structure.
  • R d5 and R d6 are preferably each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and particularly preferably a hydrogen atom from the standpoint of ease of production.
  • Sp a3 is preferably each independently a single bond or an alkylene group having 1 to 8 carbon atoms, and one —CH 2 — present in the alkyl group or two or more —CH 2 — not adjacent to each other. Is preferably replaced by —O—, —COO—, —OCO—, —CH ⁇ CH— or —C ⁇ C—, and particularly preferably a single bond.
  • R a10 is particularly preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • s and v are each preferably 1.
  • p and q are each preferably 0 or 1.
  • each broken line represents a bond to an oxygen atom, and l and o each independently represents 0 or 1.
  • each broken line represents a bond to an oxygen atom
  • le and oe each independently represent 0 or 1
  • R e1 and R e2 each independently represent a hydrogen atom or a monovalent organic group
  • V e represents a divalent organic group.
  • a structure represented by l, o, le and oe are each preferably 1 in order to improve the storage stability of the liquid crystal composition.
  • R e1 and R e2 are preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 3 is preferable, and a hydrogen atom, a methyl group, and an ethyl group are more preferable.
  • the general formula (Ie) is preferably a structure represented by the general formula (Ie1).
  • each broken line represents a bond to an oxygen atom
  • le and oe each independently represent 0 or 1
  • R e1 and R e2 each independently represent a hydrogen atom or a monovalent organic group
  • sp ae represents a single bond or an alkylene group having a carbon number of from 12
  • the alkylene group in present in one -CH 2 - or nonadjacent two or more -CH 2 - is -O-
  • Sp ae is more preferably a single bond or an alkylene group having 1 to 8 carbon atoms.
  • the general formula (Ie) is preferably a structure represented by the general formula (Ie2).
  • each broken line represents a bond to an oxygen atom
  • le and oe each independently represent 0 or 1
  • R e1 and R e2 each independently represent a hydrogen atom or a monovalent organic group
  • Sp ae1 and Sp ae2 each independently represent the same meaning as Sp a1 in the general formula (Ic)
  • a ad1 represents the same meaning as A a1 in the general formula (Ic)
  • pe is 1 or 2
  • U represents the general formula (If)
  • a broken line represents a bond to an oxygen atom
  • lf represents 0 or 1
  • R f7 represents a hydrogen atom or a monovalent organic group
  • Sp af1 and Sp af2 are each independently represented by the general formula (I -A ) represents the same meaning as Sp a1 in -c)
  • a afl represents the same meaning as A a1 in the general formula (Ic)
  • pf represents 0, 1 or 2
  • tf represents 3 or 4
  • V f represents a trivalent or tetravalent group, but the valence of V f is the same as the number represented by tf, and when there are a plurality of Sp af1 , Sp af2 and A af1 , they may be the same May be different.
  • a structure represented by R f7 is preferably an alkyl group having 1 to 10 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 5 carbon
  • V f preferably represents a hydrocarbon group having 1 to 15 carbon atoms, One or two or more non-adjacent —CH 2 — present in the carbon atom in the group are each independently —O—, —S—, —CO—, —COO—, —OCO—, — CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —CH ⁇ CH—COO—, —CH ⁇ CH—OCO—, —COO— It may be substituted with CH ⁇ CH—, —OCO—CH ⁇ CH—, —CH ⁇ CH—, —CF ⁇ CF—, —OCF 2 —, —CF 2 O—, or —C ⁇ C—.
  • V f is more preferably a group selected from the groups represented by formulas (V3-1) to (V3-12).
  • R v31 and R v32 represent a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 10 carbon atoms, and one or two or more —CH 2 — present in the alkyl group are each independently May be substituted with —O—, —S—, —CH ⁇ CH—, —C ⁇ C—, —CO—O—, —O—CO—, and the hydrogen atom in the cyclic structure is fluorine.
  • Atom chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group , A trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or an alkyl group having 1 to 12 carbon atoms may be substituted, and one or not present in the alkyl group Two or more —CH 2 — are each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—.
  • R V31 and R V32 preferably represent a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 8 carbon atoms, and are preferably linear.
  • the formulas (V3-4) to (V3-12) are preferably each independently unsubstituted, and the hydrogen atoms in the formulas (V3-4) to (V3-12) are cyano groups , Fluorine atom, chlorine atom, methyl group or methoxy group may be substituted.
  • Vf preferably represents a hydrocarbon group having 1 to 15 carbon atoms.
  • One or two or more non-adjacent —CH 2 — present in the carbon atom in the group are each independently —O—, —S—, —CO—, —COO—, —OCO—, — CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —CH ⁇ CH—COO—, —CH ⁇ CH—OCO—, —COO— It may be substituted with CH ⁇ CH—, —OCO—CH ⁇ CH—, —CH ⁇ CH—, —CF ⁇ CF—, —OCF 2 —, —CF 2 O—, or —C ⁇ C—.
  • V f is more preferably a group selected from the groups represented by formulas (V4-1) to (V4-21).
  • the hydrogen atom in the cyclic structure is fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino.
  • —CH 2 — Two or more —CH 2 — are each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—.
  • the compound represented by the general formula (I) is preferably a compound represented by the general formula (I-1).
  • R a01 represents a hydrogen atom or a hydroxyl group
  • R a71 represents a hydrogen atom or a monovalent organic group
  • Sp a11 and Sp a21 represent the same meaning as Sp a1 and Sp a2 in formula (Ic)
  • a a11 and A a21 represent the same meaning as A a1 and A a2 in formula (Ic)
  • R a91 represents the same meaning as R a9 in formula (Ic)
  • m1, p1 and q1 each independently represents 0 or 1.
  • R a01 is preferably a hydrogen atom.
  • R a71 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • Sp a11 and Sp a21 are preferably each independently a single bond or an alkylene group having 1 to 6 carbon atoms, and one —CH 2 — present in the alkyl group or two or more non-adjacent — CH 2 — is preferably replaced by —O—, —COO—, —OCO—, —CH ⁇ CH— or —C ⁇ C—, and particularly preferably a single bond.
  • a a11 and A a21 each independently (a) 1,4-cyclohexylene group (this is present in the group one -CH 2 - or nonadjacent two or more -CH 2 - is -O- May be replaced by.) (B) a 1,4-phenylene group (one —CH ⁇ present in the group or two or more non-adjacent —CH ⁇ may be replaced by —N ⁇ ) and (c) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or 1,2 , 3,4-tetrahydronaphthalene-2,6-diyl group, one —CH ⁇ or two or more non-adjacent —CH ⁇ may be replaced by —N ⁇ .
  • R a91 is a hydrogen atom or preferably from 1 carbon atoms is 6 alkyl group, one -CH 2 present in the alkyl group - or nonadjacent two or more -CH 2 - is -O It is also preferred that it is replaced by — or —CH ⁇ CH—.
  • R a91 represents the general formula (I-d1)
  • R d01 represents a hydrogen atom or a hydroxyl group
  • Sp a31 represents the same meaning as Sp a3 in formula ( Id )
  • R a101 represents a hydrogen atom or a monovalent organic group
  • s1 represents 0 Or a structure represented by 1
  • R a101 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R d01 is preferably a hydrogen atom.
  • Sp a31 is preferably an alkylene group of a single bond or a C 1 -C 6, one -CH 2 present in the alkyl group - or nonadjacent two or more -CH 2 - is -O It is preferably replaced by —, —COO—, —OCO—, —CH ⁇ CH— or —C ⁇ C—, and particularly preferably a single bond.
  • s1 is preferably 1.
  • m1 and p1 are preferably 1.
  • q1 is preferably 0.
  • R a02 and R a03 are the same meaning as R a01 in the general formula (I-1)
  • R a72 and R a102 has the same meaning as R a71 in the general formula (I-1)
  • R a92 represents the same meaning as R a91 in the general formula (I-1)
  • Sp a12 , Sp a13 and Sp a14 represent the same meaning as Sp a11 or Sp a21 in the general formula (I-1).
  • a a12 and A a13 represent the same meaning as A a11 or A a21 in formula (I-1).
  • the composition containing one or more compounds represented by general formula (I) preferably has a liquid crystal phase at room temperature.
  • the compound represented by the general formula (I) is preferably contained in the composition at a lower limit of 0.01% or more, preferably 0.02% or more, and 0.03% or more.
  • it contains 0.05% or more, preferably 0.07% or more, preferably 0.1% or more, preferably 0.15% or more, 0.2 % Or more, preferably 0.25% or more, preferably 0.3% or more, preferably 0.5% or more, and preferably 1% or more.
  • the upper limit is preferably 5% or less, preferably 3% or less, preferably 1% or less, preferably 0.5% or less, and 0.45% or less. It is preferable to contain 0.4% or less, preferably 0.35% or less, preferably 0.3% or less, preferably 0.25% or less. 2% or less, preferably 0.15% or less, preferably 0.1% or less, preferably 0.07% or less, preferably 0.05% or less It is preferable to contain 0.03% or less.
  • the content is preferably 0.01 to 5% by mass, preferably 0.01 to 0.3% by mass, more preferably 0.02 to 0.3% by mass, Particularly preferred is 0.05 to 0.25% by mass. More specifically, when emphasizing the suppression of precipitation at low temperatures, the content is preferably 0.01 to 0.1% by mass.
  • composition containing the compound represented by the general formula (I) may contain a compound having a liquid crystal phase in addition to the compound represented by the general formula (I), or a compound having no liquid crystal phase. It may contain.
  • a compound represented by general formula (I) can be obtained by reacting a compound represented by general formula (S-1) with a compound represented by general formula (S-2).
  • Examples of the reaction include a method in which the compound represented by the general formula (S-1) and the compound represented by the general formula (S-2) are heated in the presence of an acid catalyst to cause a dehydration reaction.
  • the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and potassium bisulfate, Lewis acids such as boron trifluoride, organic acids such as fumaric acid, phthalic acid, oxalyl acid, camphorsulfonic acid, and p-toluenesulfonic acid, And solid acids such as Amberlyst-15.
  • the acid catalyst can be added in an amount exceeding 1 equivalent, if necessary.
  • R s1 represents the same meaning as R a02 or R a03 in the general formula (I-1a), (I-1b), (I-1k) or (I-1l), and R s7 represents the general formula R a71 has the same meaning as in formula (I-1), A s1 has the same meaning as A a12 or A a13 in formula (I-1b) or (I-1l), and Y s1 has the same formula as in formula (I-1b).
  • R s1 represents the same meaning as R a02 or R a03 in the general formula (I-1c), (I-1j), (I-1m) or (I-1t), and R s7 represents the general formula R a71 has the same meaning as in formula (I-1), and A s1 represents A a12 or A a13 in formula (I-1c), (I-1j), (I-1m) or (I-1t).
  • Y s1 has the same meaning as R a92 in formula (I-1c) or (I-1j), or the same as Sp a13 in formula (I-1m) or (I-1t).
  • Sp s1 represents the same meaning as Sp a12 or Sp a14 in the general formula (I-1c), (I-1j), (I-1m) or (I-1t), and m s1 and p s1 represents 0 or 1 each independently is, t s1 is 1 or 2 Represent.
  • a compound represented by general formula (S-6) can be obtained by reacting a compound represented by general formula (S-3) with a compound represented by general formula (S-5).
  • a reaction example for example, a method in which the compound represented by the general formula (S-3) and the compound represented by the general formula (S-5) are dehydrated by heating in the presence of an acid catalyst in the same manner as in Production Method 1. Can be mentioned.
  • R s1 represents the same meaning as R a02 or R a03 in the general formula (I-1d), (I-1i), (I-1n) or (I-1s), and R s7 represents the general formula R a71 has the same meaning as in formula (I-1), and A s1 represents A a12 or A a13 in formula (I-1d), (I-1i), (I-1n) or (I-1s).
  • Y s1 has the same meaning as R a92 in the general formula (I-1d) or (I-1i), or the same as Sp a13 in the general formula (I-1n) or (I-1s).
  • Sp s1 represents the same meaning as Sp a12 or Sp a14 in the general formula (I-1d), (I-1i), (I-1n) or (I-1s), and m s1 and p s1 represents 0 or 1 each independently is, t s1 is 1 or 2 Represent.
  • the compound represented by the general formula (S-9) can be obtained by reacting the compound represented by the general formula (S-3) with the compound represented by the general formula (S-8).
  • a reaction example for example, in the same manner as in production method 1, there is a method in which a compound represented by general formula (S-3) and a compound represented by general formula (S-8) are heated in the presence of an acid catalyst to cause a dehydration reaction. Can be mentioned.
  • the general formula (I-1d), (I-1i), (I-1n) or A compound represented by (I-1s) can be obtained.
  • the reaction include a method in which a halogenating agent is allowed to act on the carboxyl group of the general formula (S-9) to form an acid halide and then reacted with the compound represented by the general formula (S-7). It is done.
  • the halogenating agent include thionyl chloride, oxalyl chloride, phosphoryl chloride, sulfuryl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus tribromide and the like.
  • Mitsunobu reaction in which the hydroxyl group of the general formula (S-7) is activated with an azocarboxylic acid ester and triphenylphosphine and reacted with the carboxyl group of the general formula (S-9) can be mentioned.
  • the azocarboxylic acid ester include diethyl azodicarboxylate and diisopropyl azodicarboxylate.
  • R s1 represents the same meaning as R a02 or R a03 in the general formula (I-1e) or (I-1o), and R s7 represents the same meaning as R a71 in the general formula (I-1).
  • a s1 represents the same meaning as A a12 or A a13 in the general formula (I-1e) or (I-1o)
  • Y s1 has the same meaning as R a92 in the general formula (I-1e)
  • it represents the same meaning as Sp a13 in the general formula (I-1o)
  • p s1 represents 0 or 1
  • t s1 represents 1 or 2.
  • a compound represented by the general formula (S-11) can be obtained by reacting the compound represented by the general formula (S-3) with a compound represented by the general formula (S-10).
  • reaction example for example, in the same manner as in Production Method 1, there is a method in which the compound represented by the general formula (S-3) and the compound represented by the general formula (S-10) are heated in the presence of an acid catalyst to cause a dehydration reaction. Can be mentioned.
  • a compound represented by general formula (I-1e) or (I-1o) is obtained by reacting a compound represented by general formula (S-11) with a compound represented by general formula (S-12). be able to.
  • reaction example for example, p-toluenesulfonyl chloride, methylsulfonyl chloride and the like are reacted with the hydroxyl group of the general formula (S-12) to form a leaving group, and then reacted with (S-11) in the presence of a base.
  • the Williamson reaction is mentioned.
  • the base include sodium hydride.
  • the Mitsunobu reaction which activates a hydroxyl group with azocarboxylic acid ester and triphenylphosphine and reacts with alcohol is mentioned.
  • the azocarboxylic acid ester include diethyl azodicarboxylate and diisopropyl azodicarboxylate.
  • R s1 represents the same meaning as R a02 or R a03 in the general formula (I-1f) or (I-1p), and R s7 has the same meaning as R a71 in the general formula (I-1).
  • a s1 represents the same meaning as A a12 or A a13 in the general formula (I-1f) or (I-1p)
  • Y s1 has the same meaning as R a92 in the general formula (I-1f)
  • it represents the same meaning as Sp a13 in the general formula (I-1p)
  • p s1 represents 0 or 1
  • t s1 represents 1 or 2.
  • Examples of the reaction include a method in which a halogenating agent is allowed to act on the carboxyl group of the general formula (S-13) to form an acid halide and then reacted with the compound represented by the general formula (S-11). It is done.
  • Examples of the halogenating agent include thionyl chloride, oxalyl chloride, phosphoryl chloride, sulfuryl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus tribromide and the like.
  • Mitsunobu reaction in which the hydroxyl group of the general formula (S-11) is activated with an azocarboxylic acid ester and triphenylphosphine and reacted with the carboxyl group of the general formula (S-13) can be mentioned.
  • the azocarboxylic acid ester include diethyl azodicarboxylate and diisopropyl azodicarboxylate.
  • R s1 represents the same meaning as R a02 or R a03 in formula (I-1g), (I-1q), (I-1h) or (I-1r), and R s2 represents an alkyl group
  • R s7 represents the same meaning as R a71 in the general formula (I-1)
  • a s1 represents the general formula (I-1g), (I-1q), (I-1h) or (I ⁇ 1r) has the same meaning as A a12 or A a13
  • Y s1 has the same meaning as R a92 in General Formula (I-1g) or (I-1h), or General Formula (I-1q) or (I -1r) represents the same meaning as Sp a13
  • X represents chlorine, bromine or iodine
  • p s1 represents 0 or 1
  • t s1 represents 1 or 2.
  • a compound represented by general formula (S-14) can be obtained by reacting a compound represented by general formula (S-3) with a compound represented by general formula (S-17).
  • a reaction example for example, a method of heating and dehydrating the compound represented by the general formula (S-3) and the compound represented by the general formula (S-13) in the presence of an acid catalyst in the same manner as in Production Method 1. Can be mentioned.
  • a compound represented by the general formula (S-15) can be obtained by reducing the compound represented by the general formula (S-14).
  • the reducing agent include diisobutylaluminum hydride.
  • the compound represented by the general formula (S-15) can be obtained by reducing the compound represented by the general formula (S-14) to an alcohol and then oxidizing the compound to obtain an aldehyde.
  • the reducing agent include lithium aluminum hydride, diisobutylaluminum hydride, sodium bis (2-methoxyethoxy) aluminum hydride, and the like.
  • the oxidizing agent include pyridinium chlorochromate and oxalyl chloride.
  • a compound represented by general formula (I-1g) or (I-1q) is obtained by reacting a compound represented by general formula (S-15) with a compound represented by general formula (S-16).
  • Examples of the reaction include a Wittig reaction in which a compound represented by the general formula (S-16) is reacted with a base to form phosphorus ylide and then reacted with a compound represented by the general formula (S-15). .
  • examples of the base include t-butoxypotassium.
  • a compound represented by the general formula (I-1h) or (I-1r) can be obtained by reducing the compound represented by the general formula (I-1g) or (I-1q).
  • Examples of the reaction include a method in which a compound represented by the general formula (I-1g) or (I-1q) and a catalyst coexist in a hydrogen atmosphere. In this case, examples of the catalyst include palladium carbon.
  • a compound represented by general formula (S-6) can be obtained by reacting a compound represented by general formula (S-3) with a compound represented by general formula (S-5).
  • reaction example for example, a method in which the compound represented by the general formula (S-3) and the compound represented by the general formula (S-5) are dehydrated by heating in the presence of an acid catalyst in the same manner as in Production Method 1.
  • a compound represented by general formula (I-1u) or (I-1v) is obtained by reacting a compound represented by general formula (S-6) with a compound represented by general formula (S-18).
  • Examples of the reaction include a method in which a halogenating agent is allowed to act on the carboxyl group of the general formula (S-18) to form an acid halide and then reacted with the compound represented by the general formula (S-6). It is done.
  • halogenating agent examples include thionyl chloride, oxalyl chloride, phosphoryl chloride, sulfuryl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus tribromide and the like.
  • Mitsunobu reaction in which the hydroxyl group of the general formula (S-6) is activated with an azocarboxylic acid ester and triphenylphosphine and reacted with the carboxyl group of the general formula (S-18) can be mentioned.
  • the azocarboxylic acid ester examples include diethyl azodicarboxylate and diisopropyl azodicarboxylate.
  • reaction conditions other than those described in the above steps include, for example, Experimental Chemistry Course (edited by the Chemical Society of Japan, published by Maruzen Co., Ltd.), Organic Synthesis (A John Wiley & Sons, Inc., Publication), and Bilstein Handbook of Organic Chemistry (Chemical Chemistry). -Described by Institut Futeriter der Organischen Chemie, Springer-Verlag Berlin and Heidelberg GmbH, Co. K, Fiesers' Reagents for Organic Science. racts Service, American Chemical Society), include those listed in databases such as Reaxys (Elsevier Ltd.).
  • a reaction solvent can be appropriately used in each step.
  • the solvent include ethanol, tetrahydrofuran, toluene, dichloromethane, water and the like.
  • a phase transfer catalyst can be added.
  • the phase transfer catalyst include benzyltrimethylammonium bromide and tetrabutylammonium bromide.
  • purification can be performed as necessary.
  • the purification method include chromatography, recrystallization, distillation, sublimation, reprecipitation, adsorption, and liquid separation treatment.
  • Specific examples of the purification agent include silica gel, NH 2 silica gel, alumina, activated carbon and the like.
  • tert-butoxypotassium 13.0 g was added and suspended in tetrahydrofuran (400 mL). Diethyl malonate (18.6 g) was added followed by 1,8-dibromooctane (15.8 g). Stir at room temperature for 3 days. The solution was concentrated under reduced pressure and acidified with 10% hydrochloric acid. Extracted twice with dichloromethane (150 mL). After concentration under reduced pressure, the residue was purified by column chromatography to obtain 15.0 g of 1,1,8,8-tetra (ethoxycarbonyl) octane as a colorless liquid.
  • a lithium aluminum hydride (10.6 g) was added to a reaction vessel equipped with a stirrer, a thermometer, and a cooling tube, and suspended in tetrahydrofuran (279 mL).
  • 1,1,8,8-Tetra (ethoxycarbonyl) octane (20.0 g) was added, and the mixture was stirred at 60 ° C. for 5 hours. Ice-cooled and water (57.0 g) was carefully added. Stir at 40 ° C. for 1 hour and filter to remove solids.
  • the tetrahydrofuran solution was concentrated to obtain 10.1 g of 1,1,8,8-tetra (hydroxymethyl) octane as a colorless solid.
  • Example 26 (Compound (I-1c-B6)) to Example 39 (Compound (I-1t-BB)) ) was manufactured.
  • Example 56 (Compound (I-1e-B6)) to Example 64 (Compound (I-1o-BEBEB)) were carried out using the same reaction as in Example 55 and, if necessary, a method based on a known method. ) was manufactured.
  • Example 66 Compound (I-1f-B6)
  • Example 74 Compound (I-1p-BEBEB)
  • Example 76 (Compound (I-1g-B6)) to Example 82 (Compound (I-1q-BEBEB)) ) was manufactured.
  • Example 84 (Compound (I-1h-B6)) to Example 90 (Compound (I-1r-BEBEB)) ) was manufactured.
  • Measured characteristics of the liquid crystal composition containing any of the compounds obtained in Examples 1 to 90 are as follows.
  • VHR A voltage holding ratio (%) at 333 K was evaluated in three stages under the conditions of a frequency of 60 Hz and an applied voltage of 1 V.
  • VHR Light resistance
  • the liquid crystal composition is irradiated with ultraviolet rays at 180 J / m 2 using an ultrahigh pressure mercury lamp through a glass having a thickness of 0.5 mm.
  • the voltage holding ratio of the liquid crystal after ultraviolet irradiation is measured by the same method as the above VHR measurement.
  • the irradiation intensity was 366 nm and 0.1 W / m 2 . Evaluation was performed in the following three stages.
  • Example 1 To this base liquid crystal (H), 500 ppm of the compound (I-1a-5) obtained in Example 1 was added.
  • the measured properties of the composition examples in the examples are as follows.
  • VHR A Light resistant VHR: A Compatibility: A Storage stability: A
  • VHR A Light resistant VHR: A Compatibility: A Storage stability: A
  • Example 182 (Compound (I-1u-B6)) to Example 187 (Compound (I-1u-T3)) ) was manufactured.
  • VHR A Light resistant VHR: C Storage stability: A From this result, it can be seen that the compound of the present invention has an effect of preventing deterioration of the liquid crystal composition due to light without impairing the storage stability of the liquid crystal composition.
  • Comparative Example 2 500 ppm of compound (R-1) was added to the base liquid crystal (H), and the measurement results were as follows.
  • VHR A Light resistant VHR: A Compatibility: B Storage stability: C (Comparative Examples 3 and 4)
  • Comparative Examples 3 and 4 the results of measurement in Comparative Examples 3 and 4 in the same manner as in Comparative Example 2 are shown below.
  • the compound of the present invention has high compatibility with the liquid crystal composition without impairing the storage stability of the liquid crystal composition, and has an effect of preventing deterioration of the liquid crystal composition due to light.

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Abstract

The present invention provides a compound represented by general formula (I) (wherein Ra0 represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 12 carbon atoms, or an alkenyl group having 3 to 12 carbon atoms; Ra1, Ra2, Ra3 and Ra4 independently represent an alkyl group having 1 to 8 carbon atoms, or Ra1 and Ra2 and/or Ra3 and Ra4 may together form a cyclic structure; Ra5 and Ra6 independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; n represents 0 or 1; t represents 1 to 4; and U represents an organic group which can form a cyclic structure and has a valency of 2 × t).

Description

安定剤化合物、液晶組成物および表示素子Stabilizer compound, liquid crystal composition, and display element
　本発明は安定剤化合物に関する。 The present invention relates to a stabilizer compound.
　液晶表示素子は、時計、電卓をはじめとして、各種測定機器、自動車用パネル、ワードプロセッサー、電子手帳、プリンター、コンピューター、テレビ、時計、広告表示板等に用いられるようになっている。液晶表示方式としては、その代表的なものにＴＮ（ツイステッド・ネマチック）型、ＳＴＮ（スーパー・ツイステッド・ネマチック）型、ＴＦＴ（薄膜トランジスタ）を用いたＶＡ（垂直配向）型やＩＰＳ（イン・プレーン・スイッチング）型またはＦＦＳ（フリンジ・フィールド・スイッチング）型等がある。液晶組成物に求められる主な特性としては、（１）水分、空気、熱、光などの外的刺激に対して安定であること、（２）室温を中心としてできるだけ広い温度範囲で液晶相を示していること、（３）低粘性であること、および（４）駆動電圧が低いことの４つが挙げられ、個々の表示素子にとって誘電率異方性（Δε）や屈折率異方性（Δｎ）等を最適な値とするために、液晶組成物は数種類から数十種類の化合物から構成されていることが一般的である。 Liquid crystal display elements are used in various measuring instruments, automobile panels, word processors, electronic notebooks, printers, computers, televisions, watches, advertisement display boards, etc., including clocks and calculators. Typical liquid crystal display methods include TN (twisted nematic) type, STN (super twisted nematic) type, VA (vertical alignment) type using TFT (thin film transistor), and IPS (in-plane Switching) type or FFS (fringe field switching) type. The main characteristics required for the liquid crystal composition are (1) being stable against external stimuli such as moisture, air, heat, light, etc. There are four examples: (3) low viscosity, and (4) low driving voltage. For each display element, dielectric anisotropy (Δε) and refractive index anisotropy (Δn) In general, the liquid crystal composition is composed of several to several tens of kinds of compounds in order to obtain an optimal value.
　上記の液晶組成物の特性のうち、Δεについては、正の値である組成物と負の値である組成物が各々使い分けられている。これらのうち、Δεが正の値を示す液晶材料を用いる表示方式としては、ＴＮ型、ＳＴＮ型、ＩＰＳ型、更にＦＦＳ型などが挙げられる。Δεが負の値を示す液晶材料を用いる表示方式としては、ＥＣＢ型、ＶＡ型、更にＦＦＳ型などが挙げられる。一方、全ての駆動方式において低電圧駆動、高速応答、広い動作温度範囲が求められている。すなわち、Δεの絶対値が大きく、粘度（η）が小さく、高いネマチック相－等方性液体相転移温度（Ｔｎｉ）が要求されている。また、Δｎとセルギャップ（ｄ）との積であるΔｎ×ｄの設定から、液晶組成物のΔｎをセルギャップに合わせて適当な範囲に調節する必要がある。加えて液晶表示素子をテレビ等へ応用する場合においては高速応答性が重視されるため、γ１の小さい液晶組成物が要求される。 Among the characteristics of the liquid crystal composition described above, for Δε, a positive value composition and a negative value composition are used separately. Among these, examples of a display method using a liquid crystal material in which Δε has a positive value include TN type, STN type, IPS type, and FFS type. Examples of the display method using a liquid crystal material in which Δε has a negative value include ECB type, VA type, and FFS type. On the other hand, low voltage driving, high-speed response, and a wide operating temperature range are required in all driving systems. That is, the absolute value of Δε is large, the viscosity (η) is small, and a high nematic phase-isotropic liquid phase transition temperature (T ni ) is required. Further, from the setting of Δn × d, which is the product of Δn and the cell gap (d), it is necessary to adjust Δn of the liquid crystal composition to an appropriate range according to the cell gap. In addition, when applying a liquid crystal display element to a television or the like, since high-speed response is important, a liquid crystal composition having a small γ 1 is required.
　これら液晶組成物の物性における要求に加え、（１）の外的刺激に対する安定性についても更なる改善が求められている（特許文献１参照）。 In addition to the demands on the physical properties of these liquid crystal compositions, further improvement is required for the stability to external stimuli in (1) (see Patent Document 1).
特開２００６－３７０５４号JP 2006-37054 A 特開２００８－１４４１３５号JP 2008-144135 A
本願発明が解決しようとする課題は、液晶組成物に添加することにより液晶組成物の劣化を防止し、液晶組成物との相溶性が高く、液晶組成物の保存安定性を損なうことなく、かつ簡便に製造可能な安定剤化合物を提供することである。 The problem to be solved by the present invention is to prevent deterioration of the liquid crystal composition by adding it to the liquid crystal composition, high compatibility with the liquid crystal composition, without impairing the storage stability of the liquid crystal composition, and It is to provide a stabilizer compound that can be easily produced.
　本願発明者は上記課題を解決するために鋭意検討した結果、本願発明の完成に至った。
すなわち、本発明は、一般式（Ｉ） The inventor of the present application has intensively studied to solve the above problems, and as a result, the present invention has been completed.
That is, the present invention relates to the general formula (I)
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
（式中、Ｒａ０は水素原子、水酸基、炭素数１～１２のアルキル基、又は炭素数３～１２のアルケニル基を表し、
Ｒａ１，Ｒａ２，Ｒａ３及びＲａ４はそれぞれ独立して炭素数１～８のアルキル基を表し、あるいはＲａ１とＲａ２，及び／又はＲａ３とＲａ４は一緒になって環構造を形成していてもよく、
Ｒａ５及びＲａ６はそれぞれ独立して水素原子又は炭素数１～６のアルキル基を表し、
ｎは０又は１を表し、
ｔは１から４を表し、
Ｕは環構造を形成する２×ｔ価の有機基を表し、Ｒａ０、Ｒａ１、Ｒａ２、Ｒａ３、Ｒａ４、Ｒａ５、Ｒａ６及びｎが複数存在する場合、それらは同一であっても異なっていてもよい。）
で表される化合物を提供し、併せて当該化合物を含有する液晶組成物及び表示素子を提供する。 (Wherein R a0 represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or an alkenyl group having 3 to 12 carbon atoms,
R a1 , R a2 , R a3 and R a4 each independently represents an alkyl group having 1 to 8 carbon atoms, or R a1 and R a2 and / or R a3 and R a4 together form a ring structure. May be formed,
R a5 and R a6 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
n represents 0 or 1,
t represents 1 to 4;
U represents a 2 × t-valent organic group forming a ring structure, and when a plurality of R a0 , R a1 , R a2 , R a3 , R a4 , R a5 , R a6 and n are present, they are the same. Or different. )
And a liquid crystal composition containing the compound and a display element are provided.
本発明に係る安定剤化合物は、液晶組成物の光による劣化を防止し、液晶組成物との相溶性が高く、液晶組成物の保存安定性を損なうことなく、かつ簡便に製造可能である。本発明に係る安定剤化合物を用いた液晶組成物を用いると高速応答液晶表示素子の提供が可能となる。 The stabilizer compound according to the present invention prevents the liquid crystal composition from being deteriorated by light, has high compatibility with the liquid crystal composition, and can be easily produced without impairing the storage stability of the liquid crystal composition. When the liquid crystal composition using the stabilizer compound according to the present invention is used, a fast response liquid crystal display element can be provided.
　一般式（Ｉ）において、Ｒａ０は光劣化防止能を高めるには水素原子又は水酸基であることが好ましく、水素原子であることが特に好ましい。また、液晶組成物との相溶性を高めるためには炭素数１～１２のアルキル基又は炭素数３～１２のアルケニル基であることが好ましい。
Ｒａ１，Ｒａ２，Ｒａ３及びＲａ４はそれぞれ独立して炭素数１～４のアルキル基であることが好ましく、メチル基であることが特に好ましい。また、製造時に混入する極性不純物の除去を容易にするためにはＲａ１とＲａ２，及び／又はＲａ３とＲａ４は一緒になって環構造を形成することが好ましい。
Ｒａ５及びＲａ６はそれぞれ独立して水素原子又は炭素数１～４のアルキル基であることが好ましく、製造の容易さから水素原子であることが特に好ましい。
ｎは１であることが好ましい。
ｔは液晶組成物の保存安定性を高めるためには１または２であることが好ましく、１であることが特に好ましい。また、光劣化防止能を高めるためには、単位重量あたりのヒンダードアミン構造の数が多くなることから３または４であることが好ましい。
Ｕは、一般式（Ｉ－ａ） In general formula (I), R a0 is preferably a hydrogen atom or a hydroxyl group, and particularly preferably a hydrogen atom, in order to enhance the ability to prevent photodegradation. In order to improve compatibility with the liquid crystal composition, an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 3 to 12 carbon atoms is preferable.
R a1 , R a2 , R a3 and R a4 are each independently preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group. In order to facilitate removal of polar impurities mixed during production, R a1 and R a2 and / or R a3 and R a4 are preferably combined to form a ring structure.
R a5 and R a6 are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and particularly preferably a hydrogen atom for ease of production.
n is preferably 1.
t is preferably 1 or 2 and particularly preferably 1 in order to increase the storage stability of the liquid crystal composition. In order to enhance the ability to prevent photodegradation, the number is preferably 3 or 4 because the number of hindered amine structures per unit weight increases.
U represents the general formula (Ia)
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
（式中、破線は各々酸素原子への結合を表し、Ｒａ７及びＲａ８はそれぞれ独立して水素原子または１価の有機基を表し、あるいはＲａ７及びＲａ８は一緒になって環構造を形成していてもよく、ｍは０または１を表す。）で表される構造であることが液晶組成物の保存安定性を高めるためには好ましい。ここで、一般的な液晶化合物と同様の直線状の構造をとりやすく、結果として液晶組成物への相溶性が高まることから、Ｒａ７は水素原子又は炭素数１～４のアルキル基であることが特に好ましく、ｍは１であることが特に好ましい。 (In the formula, each broken line represents a bond to an oxygen atom, R a7 and R a8 each independently represents a hydrogen atom or a monovalent organic group, or R a7 and R a8 together form a ring structure. In order to improve the storage stability of the liquid crystal composition, it is preferable that m is 0 or 1. Here, a general liquid crystal compounds easily take the same linear structure and, since the increased compatibility with the liquid crystal composition as a result, it R a7 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms Is particularly preferred, and m is particularly preferably 1.
　一般式（Ｉ）中のｔが１を表す場合、Ｒａ８は一般式（Ｉ－ｃ） When t in the general formula (I) represents 1, R a8 represents the general formula (Ic)
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
で表される構造であることが液晶組成物との相溶性を高めるためには特に好ましく、Ｓｐａ１及びＳｐａ２はそれぞれ独立に単結合又は炭素原子数１から１２のアルキレン基を表すことが好ましく、単結合又は炭素原子数１から８のアルキレン基であることがより好ましく、アルキル基中に存在する１個の－ＣＨ２－又は隣接していない２個以上の－ＣＨ２－は－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－ＣＨ＝ＣＨ－又は－Ｃ≡Ｃ－により置き換えられていることが好ましく、単結合であることが特に好ましい。Ａａ１及びＡａ２はそれぞれ独立に
（ａ）　１，４－シクロヘキシレン基（この基中に存在する１個の－ＣＨ２－又は隣接していない２個以上の－ＣＨ２－は－Ｏ－に置き換えられてもよい。）
（ｂ）　１，４－フェニレン基（この基中に存在する１個の－ＣＨ＝又は隣接していない２個以上の－ＣＨ＝は－Ｎ＝に置き換えられてもよい。）及び
（ｃ）　ナフタレン－２，６－ジイル基、１，２，３，４－テトラヒドロナフタレン－２，６－ジイル基又はデカヒドロナフタレン－２，６－ジイル基（ナフタレン－２，６－ジイル基又は１，２，３，４－テトラヒドロナフタレン－２，６－ジイル基中に存在する１個の－ＣＨ＝又は隣接していない２個以上の－ＣＨ＝は－Ｎ＝に置き換えられても良い。）
からなる群より選ばれる基であることが液晶組成物の保存安定性を高めるためには好ましく、上記の基（ａ）、基（ｂ）及び基（ｃ）はそれぞれ独立してシアノ基、フッ素原子、塩素原子、メチル基又はメトキシ基で置換されていることがより好ましい。Ｒａ９は水素原子または炭素原子数１から１２のアルキル基を表すことが好ましく、水素原子または炭素原子数１から６のアルキル基であることがより好ましく、アルキル基中に存在する１個の－ＣＨ２－又は隣接していない２個以上の－ＣＨ２－は－Ｏ－、－Ｓ－、－ＣＯＯ－、－ＯＣＯ－、－ＣＯ－、－ＣＨ＝ＣＨ－又は－Ｃ≡Ｃ－により置き換えられても良く、－Ｏ－または－ＣＨ＝ＣＨ－より置き換えられていることが好ましい。 In order to improve compatibility with the liquid crystal composition, it is particularly preferable that Sp a1 and Sp a2 each independently represent a single bond or an alkylene group having 1 to 12 carbon atoms. , more preferably a single bond or an alkylene group having 1 to 8 carbon atoms, one -CH 2 present in the alkyl group - or nonadjacent two or more -CH 2 - is -O- , —COO—, —OCO—, —CH═CH— or —C≡C— are preferred, and a single bond is particularly preferred. A a1 and A a2 each independently (a) 1,4-cyclohexylene group (this is present in the group one -CH 2 - or nonadjacent two or more -CH 2 - is -O- May be replaced by.)
(B) a 1,4-phenylene group (one —CH═ present in the group or two or more non-adjacent —CH═ may be replaced by —N═) and (c) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or 1,2 , 3,4-tetrahydronaphthalene-2,6-diyl group, one —CH═ or two or more non-adjacent —CH═ may be replaced by —N═.
In order to improve the storage stability of the liquid crystal composition, a group selected from the group consisting of the above groups is preferable, and the groups (a), (b) and (c) are each independently a cyano group, fluorine More preferably, it is substituted with an atom, a chlorine atom, a methyl group or a methoxy group. R a9 preferably represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and one — CH 2 — or two or more non-adjacent —CH 2 — are replaced by —O—, —S—, —COO—, —OCO—, —CO—, —CH═CH— or —C≡C—. And is preferably replaced by —O— or —CH═CH—.
　また、Ｒａ９は一般式（Ｉ－ｄ） R a9 represents the general formula ( Id )
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
（式中、Ｒｄ０、Ｒｄ１，Ｒｄ２，Ｒｄ３、Ｒｄ４、Ｒｄ５及びＲｄ６は一般式（Ｉ）におけるＲａ０、Ｒａ１，Ｒａ２，Ｒａ３、Ｒａ４、Ｒａ５及びＲａ６と同じ意味を表し、Ｒａ１０は水素原子または１価の有機基を表し、Ｓｐａ３はＳｐａ１又はＳｐａ２と同じ意味を表し、ｓ及びｖはそれぞれ独立に０又は１を表す。）
で表される構造であることが光劣化防止能を高めるためには好ましい。Ｒｄ０は光劣化防止能を高めるには水素原子又は水酸基であることが好ましく、製造の容易さから水素原子であることが特に好ましい。また、液晶組成物との相溶性を高めるためには炭素数１～１２のアルキル基又は炭素数３～１２のアルケニル基であることが好ましい。
Ｒｄ１，Ｒｄ２，Ｒｄ３及びＲｄ４はそれぞれ独立して炭素数１～４のアルキル基であることが好ましく、メチル基であることが特に好ましい。また、製造時に混入する極性不純物の除去を容易にするためにはＲｄ１とＲｄ２，及び／又はＲｄ３とＲｄ４は一緒になって環構造を形成することが好ましい。
Ｒｄ５及びＲｄ６はそれぞれ独立して水素原子又は炭素数１～４のアルキル基であることが好ましく、製造の容易さから水素原子であることが特に好ましい。 (In the formula, R d0 , R d1 , R d2 , R d3 , R d4 , R d5 and R d6 are R a0 , R a1 , R a2 , R a3 , R a4 , R a5 and R in the general formula (I)). The same meaning as a6 is represented, R a10 represents a hydrogen atom or a monovalent organic group, Sp a3 represents the same meaning as Sp a1 or Sp a2, and s and v each independently represent 0 or 1.)
In order to enhance the ability to prevent light degradation, a structure represented by R d0 is preferably a hydrogen atom or a hydroxyl group for enhancing the ability to prevent photodegradation, and particularly preferably a hydrogen atom for ease of production. In order to improve compatibility with the liquid crystal composition, an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 3 to 12 carbon atoms is preferable.
R d1 , R d2 , R d3 and R d4 are each independently preferably an alkyl group having 1 to 4 carbon atoms, particularly preferably a methyl group. In order to facilitate removal of polar impurities mixed during production, it is preferable that R d1 and R d2 and / or R d3 and R d4 together form a ring structure.
R d5 and R d6 are preferably each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and particularly preferably a hydrogen atom from the standpoint of ease of production.
　Ｓｐａ３はそれぞれ独立に単結合又は炭素原子数１から８のアルキレン基であることが好ましく、アルキル基中に存在する１個の－ＣＨ２－又は隣接していない２個以上の－ＣＨ２－は－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－ＣＨ＝ＣＨ－又は－Ｃ≡Ｃ－により置き換えられていることが好ましく、単結合であることが特に好ましい。 Sp a3 is preferably each independently a single bond or an alkylene group having 1 to 8 carbon atoms, and one —CH 2 — present in the alkyl group or two or more —CH 2 — not adjacent to each other. Is preferably replaced by —O—, —COO—, —OCO—, —CH═CH— or —C≡C—, and particularly preferably a single bond.
　Ｒａ１０は水素原子又は炭素数１～４のアルキル基であることが特に好ましい。
ｓ及びｖはそれぞれ１であることが好ましい。
ｐ及びｑはそれぞれ０または１であることが好ましい。 R a10 is particularly preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
s and v are each preferably 1.
p and q are each preferably 0 or 1.
　一般式（Ｉ）中のｔが２を表す場合、Ｕは、一般式（Ｉ－ｂ）または一般式（Ｉ－ｅ） When t in general formula (I) represents 2, U represents general formula (Ib) or general formula (Ie)
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
（式中、破線は各々酸素原子への結合を表し、ｌ及びｏはそれぞれ独立に０または１を表す。） (In the formula, each broken line represents a bond to an oxygen atom, and l and o each independently represents 0 or 1.)
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
（式中、破線は各々酸素原子への結合を表し、ｌｅ及びｏｅはそれぞれ独立して０又は１を表し、Ｒｅ１及びＲｅ２はそれぞれ独立して水素原子または１価の有機基を表し、Ｖｅは２価の有機基を表す。）
で表される構造であることが光劣化防止能を高めるためには好ましい。ｌ、ｏ，ｌｅ及びｏｅは各々１であることが液晶組成物の保存安定性を高めるためには好ましい。Ｒｅ１及びＲｅ２は水素原子又は炭素原子数１～１０のアルキル基であることが好ましく、水素原子又は炭素原子数１～５のアルキル基であることが好ましく、水素原子又は炭素原子数１～３のアルキル基であることが好ましく、水素原子、メチル基、エチル基であることがより好ましい。 (In the formula, each broken line represents a bond to an oxygen atom, le and oe each independently represent 0 or 1, R e1 and R e2 each independently represent a hydrogen atom or a monovalent organic group, V e represents a divalent organic group.)
In order to enhance the ability to prevent light degradation, a structure represented by l, o, le and oe are each preferably 1 in order to improve the storage stability of the liquid crystal composition. R e1 and R e2 are preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 3 is preferable, and a hydrogen atom, a methyl group, and an ethyl group are more preferable.
　一般式（Ｉ－ｅ）は、一般式（Ｉ－ｅ１）で表される構造であることが好ましい。 The general formula (Ie) is preferably a structure represented by the general formula (Ie1).
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
（式中、破線は各々酸素原子への結合を表し、ｌｅ及びｏｅはそれぞれ独立して０又は１を表し、Ｒｅ１及びＲｅ２はそれぞれ独立して水素原子または１価の有機基を表し、Ｓｐａｅは単結合又は炭素原子数１から１２のアルキレン基を表し、該アルキレン基中に存在する１個の－ＣＨ２－又は隣接していない２個以上の－ＣＨ２－は－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－ＣＨ＝ＣＨ－又は－Ｃ≡Ｃ－により置き換えられていてもよい。）
　Ｓｐａｅは単結合又は炭素原子数１から８のアルキレン基であることがより好ましい。 (In the formula, each broken line represents a bond to an oxygen atom, le and oe each independently represent 0 or 1, R e1 and R e2 each independently represent a hydrogen atom or a monovalent organic group, sp ae represents a single bond or an alkylene group having a carbon number of from 12, the alkylene group in present in one -CH 2 - or nonadjacent two or more -CH 2 - is -O-, (It may be replaced by —COO—, —OCO—, —CH═CH— or —C≡C—.)
Sp ae is more preferably a single bond or an alkylene group having 1 to 8 carbon atoms.
　また、一般式（Ｉ－ｅ）は、一般式（Ｉ－ｅ２）で表される構造であることが好ましい。 The general formula (Ie) is preferably a structure represented by the general formula (Ie2).
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
（式中、破線は各々酸素原子への結合を表し、ｌｅ及びｏｅはそれぞれ独立して０又は１を表し、Ｒｅ１及びＲｅ２はそれぞれ独立して水素原子または１価の有機基を表し、Ｓｐａｅ１及びＳｐａｅ２はそれぞれ独立して一般式（Ｉ－ｃ）におけるＳｐａ１と同じ意味を表し、Ａａｄ１は一般式（Ｉ－ｃ）におけるＡａ１と同じ意味を表し、ｐｅは１又は２を表し、Ｓｐａｅ１、Ｓｐａｅ２及びＡａｅ１が複数存在する場合、それらは同一であっても異なっていてもよい。）
　一般式（Ｉ）中のｔが３又は４を表す場合、Ｕは、一般式（Ｉ－ｆ） (In the formula, each broken line represents a bond to an oxygen atom, le and oe each independently represent 0 or 1, R e1 and R e2 each independently represent a hydrogen atom or a monovalent organic group, Sp ae1 and Sp ae2 each independently represent the same meaning as Sp a1 in the general formula (Ic), A ad1 represents the same meaning as A a1 in the general formula (Ic), and pe is 1 or 2 And when there are a plurality of Sp ae1 , Sp ae2 and A ae1 , they may be the same or different.)
When t in the general formula (I) represents 3 or 4, U represents the general formula (If)
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
（式中、破線は酸素原子への結合を表し、ｌｆは０又は１を表し、Ｒｆ７は水素原子または１価の有機基を表し、Ｓｐａｆ１及びＳｐａｆ２はそれぞれ独立して一般式（Ｉ－ｃ）におけるＳｐａ１と同じ意味を表し、Ａａｆ１は一般式（Ｉ－ｃ）におけるＡａ１と同じ意味を表し、ｐｆは０、１又は２を表し、ｔｆは３又は４を表し、Ｖｆは３価又は４価の基を表すが、Ｖｆの価数はｔｆが表す数と同じ数であり、Ｓｐａｆ１、Ｓｐａｆ２及びＡａｆ１が複数存在する場合、それらは同一であっても異なっていてもよい。）
で表される構造であることが光劣化防止能を高めるためには好ましい。Ｒｆ７は炭素原子数１～１０のアルキル基であることが好ましく、水素原子又は炭素原子数１～５のアルキル基であることが好ましく、水素原子又は炭素原子数１～３のアルキル基であることが好ましく、水素原子、メチル基、エチル基であることがより好ましい。 (In the formula, a broken line represents a bond to an oxygen atom, lf represents 0 or 1, R f7 represents a hydrogen atom or a monovalent organic group, and Sp af1 and Sp af2 are each independently represented by the general formula (I -A ) represents the same meaning as Sp a1 in -c), A afl represents the same meaning as A a1 in the general formula (Ic), pf represents 0, 1 or 2, tf represents 3 or 4, V f represents a trivalent or tetravalent group, but the valence of V f is the same as the number represented by tf, and when there are a plurality of Sp af1 , Sp af2 and A af1 , they may be the same May be different.)
In order to enhance the ability to prevent light degradation, a structure represented by R f7 is preferably an alkyl group having 1 to 10 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Of these, a hydrogen atom, a methyl group, and an ethyl group are more preferable.
　一般式（Ｉ－ｆ）中のｔｆが３を表す場合、すなわち、Ｖｆの価数が３の場合、Ｖｆは炭素原子数１から１５の炭化水素基を表すことが好ましく、当該炭化水素基中の炭素原子中に存在する１個又は隣接していない２個以上の－ＣＨ２－はそれぞれ独立して－Ｏ－、－Ｓ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＣＯ－Ｓ－、－Ｓ－ＣＯ－、－Ｏ－ＣＯ－Ｏ－、－ＣＯ－ＮＨ－、－ＮＨ－ＣＯ－、－ＣＨ＝ＣＨ－ＣＯＯ－、－ＣＨ＝ＣＨ－ＯＣＯ－、－ＣＯＯ－ＣＨ＝ＣＨ－、－ＯＣＯ－ＣＨ＝ＣＨ－、－ＣＨ＝ＣＨ－、－ＣＦ＝ＣＦ－、－ＯＣＦ２－、－ＣＦ２Ｏ－、又は－Ｃ≡Ｃ－で置換されてもよい。Ｖｆは、式（Ｖ３－１）～式（Ｖ３－１２）で表される基から選択される基であることがより好ましい。 When tf in the general formula (If) represents 3, that is, when the valence of V f is 3, V f preferably represents a hydrocarbon group having 1 to 15 carbon atoms, One or two or more non-adjacent —CH 2 — present in the carbon atom in the group are each independently —O—, —S—, —CO—, —COO—, —OCO—, — CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —CH═CH—COO—, —CH═CH—OCO—, —COO— It may be substituted with CH═CH—, —OCO—CH═CH—, —CH═CH—, —CF═CF—, —OCF 2 —, —CF 2 O—, or —C≡C—. V f is more preferably a group selected from the groups represented by formulas (V3-1) to (V3-12).
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
（式中の、Ｒｖ３１及びＲｖ３２は、水素原子、水酸基又は炭素原子数１～１０のアルキル基を表し、該アルキル基中に存在する１個又は２個以上の－ＣＨ２－はそれぞれ独立して－Ｏ－、－Ｓ－、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－、－ＣＯ－Ｏ－、－Ｏ－ＣＯ－に置換されてもよい。また、環状構造中の水素原子はフッ素原子、塩素原子、臭素原子、ヨウ素原子、ペンタフルオロスルフラニル基、ニトロ基、シアノ基、イソシアノ基、アミノ基、ヒドロキシル基、メルカプト基、メチルアミノ基、ジメチルアミノ基、ジエチルアミノ基、ジイソプロピルアミノ基、トリメチルシリル基、ジメチルシリル基、チオイソシアノ基又は炭素原子数１から１２のアルキル基で置換されていてもよく、該アルキル基中に存在する１個又は隣接していない２個以上の－ＣＨ２－はそれぞれ独立して－Ｏ－、－Ｓ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＣＯ－Ｓ－、－Ｓ－ＣＯ－、－Ｏ－ＣＯ－Ｏ－、－ＣＯ－ＮＨ－、－ＮＨ－ＣＯ－、－ＣＨ＝ＣＨ－ＣＯＯ－、－ＣＨ＝ＣＨ－ＯＣＯ－、－ＣＯＯ－ＣＨ＝ＣＨ－、－ＯＣＯ－ＣＨ＝ＣＨ－、－ＣＨ＝ＣＨ－、－ＣＦ＝ＣＦ－、－ＯＣＦ２－、－ＣＦ２Ｏ－、又は－Ｃ≡Ｃ－で置換されてもよい。）
　ＲＶ３１及びＲＶ３２は、水素原子、水酸基又は炭素原子数１～８のアルキル基を表すことが好ましく、直鎖状であることが好ましい。また、式（Ｖ３－４）～式（Ｖ３－１２）はそれぞれ独立して無置換であることが好ましく、又、式（Ｖ３－４）～式（Ｖ３－１２）中の水素原子はシアノ基、フッ素原子、塩素原子、メチル基又はメトキシ基で置換されていてもよい。 ( Wherein R v31 and R v32 represent a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 10 carbon atoms, and one or two or more —CH 2 — present in the alkyl group are each independently May be substituted with —O—, —S—, —CH═CH—, —C≡C—, —CO—O—, —O—CO—, and the hydrogen atom in the cyclic structure is fluorine. Atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group , A trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or an alkyl group having 1 to 12 carbon atoms may be substituted, and one or not present in the alkyl group Two or more —CH 2 — are each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—. O—, —CO—NH—, —NH—CO—, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —CH═ (CH—, —CF═CF—, —OCF 2 —, —CF 2 O—, or —C≡C— may be substituted.)
R V31 and R V32 preferably represent a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 8 carbon atoms, and are preferably linear. The formulas (V3-4) to (V3-12) are preferably each independently unsubstituted, and the hydrogen atoms in the formulas (V3-4) to (V3-12) are cyano groups , Fluorine atom, chlorine atom, methyl group or methoxy group may be substituted.
　原料の入手容易さ及び製造の容易さの観点から、式（Ｖ３－１）、式（Ｖ３－２）、及び無置換の式（Ｖ３－３）～（Ｖ３－１２）から選ばれる基を表すことが特に好ましい。 Represents a group selected from Formula (V3-1), Formula (V3-2), and unsubstituted Formulas (V3-3) to (V3-12) from the viewpoint of availability of raw materials and ease of production. It is particularly preferred.
　一般式（Ｉ－ｆ）中のｔｆが４を表す場合、すなわち、Ｖｆの価数が４の場合、Ｖｆは炭素原子数１から１５の炭化水素基を表すことが好ましく、当該炭化水素基中の炭素原子中に存在する１個又は隣接していない２個以上の－ＣＨ２－はそれぞれ独立して－Ｏ－、－Ｓ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＣＯ－Ｓ－、－Ｓ－ＣＯ－、－Ｏ－ＣＯ－Ｏ－、－ＣＯ－ＮＨ－、－ＮＨ－ＣＯ－、－ＣＨ＝ＣＨ－ＣＯＯ－、－ＣＨ＝ＣＨ－ＯＣＯ－、－ＣＯＯ－ＣＨ＝ＣＨ－、－ＯＣＯ－ＣＨ＝ＣＨ－、－ＣＨ＝ＣＨ－、－ＣＦ＝ＣＦ－、－ＯＣＦ２－、－ＣＦ２Ｏ－、又は－Ｃ≡Ｃ－で置換されてもよい。Ｖｆは、式（Ｖ４－１）～式（Ｖ４－２１）で表される基から選択される基であることがより好ましい。 When tf in the general formula (If) represents 4, that is, when the valence of Vf is 4, Vf preferably represents a hydrocarbon group having 1 to 15 carbon atoms. One or two or more non-adjacent —CH 2 — present in the carbon atom in the group are each independently —O—, —S—, —CO—, —COO—, —OCO—, — CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —CH═CH—COO—, —CH═CH—OCO—, —COO— It may be substituted with CH═CH—, —OCO—CH═CH—, —CH═CH—, —CF═CF—, —OCF 2 —, —CF 2 O—, or —C≡C—. V f is more preferably a group selected from the groups represented by formulas (V4-1) to (V4-21).
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　環状構造中の水素原子はフッ素原子、塩素原子、臭素原子、ヨウ素原子、ペンタフルオロスルフラニル基、ニトロ基、シアノ基、イソシアノ基、アミノ基、ヒドロキシル基、メルカプト基、メチルアミノ基、ジメチルアミノ基、ジエチルアミノ基、ジイソプロピルアミノ基、トリメチルシリル基、ジメチルシリル基、チオイソシアノ基又は炭素原子数１から１２のアルキル基で置換されていてもよく、該アルキル基中に存在する１個又は隣接していない２個以上の－ＣＨ２－はそれぞれ独立して－Ｏ－、－Ｓ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＣＯ－Ｓ－、－Ｓ－ＣＯ－、－Ｏ－ＣＯ－Ｏ－、－ＣＯ－ＮＨ－、－ＮＨ－ＣＯ－、－ＣＨ＝ＣＨ－ＣＯＯ－、－ＣＨ＝ＣＨ－ＯＣＯ－、－ＣＯＯ－ＣＨ＝ＣＨ－、－ＯＣＯ－ＣＨ＝ＣＨ－、－ＣＨ＝ＣＨ－、－ＣＦ＝ＣＦ－、－ＯＣＦ２－、－ＣＦ２Ｏ－、又は－Ｃ≡Ｃ－で置換されてもよい。また、式（Ｖ４－３）～式（Ｖ４－２１）はそれぞれ独立して無置換であることが好ましく、又、式（Ｖ４－３）～式（Ｖ４－２１）中の水素原子はシアノ基、フッ素原子、塩素原子、メチル基又はメトキシ基で置換されていてもよい。 The hydrogen atom in the cyclic structure is fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino. May be substituted by a group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group or an alkyl group having 1 to 12 carbon atoms, and one or not present in the alkyl group Two or more —CH 2 — are each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—. O—, —CO—NH—, —NH—CO—, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH , -CH = CH -, - CF = CF -, - OCF 2 -, - CF 2 O-, or may be substituted with -C≡C-. The formulas (V4-3) to (V4-21) are preferably each independently unsubstituted, and the hydrogen atom in the formulas (V4-3) to (V4-21) is a cyano group , Fluorine atom, chlorine atom, methyl group or methoxy group may be substituted.
　原料の入手容易さ及び製造の容易さの観点から、式（Ｖ４－１）、式（Ｖ４－２）、及び無置換の式（Ｖ－３）～（Ｖ－２１）から選ばれる基を表すことが特に好ましい。 Represents a group selected from Formula (V4-1), Formula (V4-2), and unsubstituted Formulas (V-3) to (V-21) from the viewpoint of availability of raw materials and ease of production. It is particularly preferred.
　本発明の一般式（Ｉ）に示す化合物の好ましい化合物の具体例を以下に示すが、本発明はこれらに限定されるものではない。 Specific examples of preferable compounds of the compound represented by the general formula (I) of the present invention are shown below, but the present invention is not limited thereto.
　一般式（Ｉ）で表される化合物は、一般式（Ｉ－１）で表される化合物が好ましい。 The compound represented by the general formula (I) is preferably a compound represented by the general formula (I-1).
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
（式中、Ｒａ０１は水素原子または水酸基を表し、
Ｒａ７１は水素原子または一価の有機基を表し、
Ｓｐａ１１及びＳｐａ２１は一般式（Ｉ－ｃ）におけるＳｐａ１及びＳｐａ２と同じ意味を表し、
Ａａ１１及びＡａ２１は一般式（Ｉ－ｃ）におけるＡａ１及びＡａ２と同じ意味を表し、
Ｒａ９１は一般式（Ｉ－ｃ）におけるＲａ９と同じ意味を表し、
ｍ１、ｐ１及びｑ１はそれぞれ独立に０又は１を表す。）
Ｒａ０１は水素原子であることが好ましい。
Ｒａ７１は水素原子又は炭素数１～４のアルキル基であることが好ましい。 (Wherein R a01 represents a hydrogen atom or a hydroxyl group,
R a71 represents a hydrogen atom or a monovalent organic group,
Sp a11 and Sp a21 represent the same meaning as Sp a1 and Sp a2 in formula (Ic),
A a11 and A a21 represent the same meaning as A a1 and A a2 in formula (Ic),
R a91 represents the same meaning as R a9 in formula (Ic),
m1, p1 and q1 each independently represents 0 or 1. )
R a01 is preferably a hydrogen atom.
R a71 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
　Ｓｐａ１１及びＳｐａ２１はそれぞれ独立に単結合又は炭素原子数１から６のアルキレン基であることが好ましく、アルキル基中に存在する１個の－ＣＨ２－又は隣接していない２個以上の－ＣＨ２－は－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－ＣＨ＝ＣＨ－又は－Ｃ≡Ｃ－により置き換えられていることが好ましく、単結合であることが特に好ましい。
Ａａ１１及びＡａ２１はそれぞれ独立に
（ａ）　１，４－シクロヘキシレン基（この基中に存在する１個の－ＣＨ２－又は隣接していない２個以上の－ＣＨ２－は－Ｏ－に置き換えられてもよい。）
（ｂ）　１，４－フェニレン基（この基中に存在する１個の－ＣＨ＝又は隣接していない２個以上の－ＣＨ＝は－Ｎ＝に置き換えられてもよい。）及び
（ｃ）　ナフタレン－２，６－ジイル基、１，２，３，４－テトラヒドロナフタレン－２，６－ジイル基又はデカヒドロナフタレン－２，６－ジイル基（ナフタレン－２，６－ジイル基又は１，２，３，４－テトラヒドロナフタレン－２，６－ジイル基中に存在する１個の－ＣＨ＝又は隣接していない２個以上の－ＣＨ＝は－Ｎ＝に置き換えられても良い。）
からなる群より選ばれる基であることが液晶組成物の保存安定性を高めるためには好ましく、上記の基（ａ）、基（ｂ）及び基（ｃ）はそれぞれ独立してシアノ基、フッ素原子、塩素原子、メチル基又はメトキシ基で置換されていることが液晶組成物との相溶性を高めるためには好ましい。Ｒａ９１は水素原子又は炭素原子数１から６のアルキル基であることが好ましく、アルキル基中に存在する１個の－ＣＨ２－又は隣接していない２個以上の－ＣＨ２－は－Ｏ－又は－ＣＨ＝ＣＨ－により置き換えられていることも好ましい。また、Ｒａ９１は一般式（Ｉ－ｄ１） Sp a11 and Sp a21 are preferably each independently a single bond or an alkylene group having 1 to 6 carbon atoms, and one —CH 2 — present in the alkyl group or two or more non-adjacent — CH 2 — is preferably replaced by —O—, —COO—, —OCO—, —CH═CH— or —C≡C—, and particularly preferably a single bond.
A a11 and A a21 each independently (a) 1,4-cyclohexylene group (this is present in the group one -CH 2 - or nonadjacent two or more -CH 2 - is -O- May be replaced by.)
(B) a 1,4-phenylene group (one —CH═ present in the group or two or more non-adjacent —CH═ may be replaced by —N═) and (c) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or 1,2 , 3,4-tetrahydronaphthalene-2,6-diyl group, one —CH═ or two or more non-adjacent —CH═ may be replaced by —N═.
In order to improve the storage stability of the liquid crystal composition, a group selected from the group consisting of the above groups is preferable, and the groups (a), (b) and (c) are each independently a cyano group, fluorine Substitution with an atom, a chlorine atom, a methyl group or a methoxy group is preferable in order to enhance the compatibility with the liquid crystal composition. R a91 is a hydrogen atom or preferably from 1 carbon atoms is 6 alkyl group, one -CH 2 present in the alkyl group - or nonadjacent two or more -CH 2 - is -O It is also preferred that it is replaced by — or —CH═CH—. R a91 represents the general formula (I-d1)
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
（式中、Ｒｄ０１は水素原子又は水酸基を表し、Ｓｐａ３１は一般式（Ｉ－ｄ）におけるＳｐａ３と同じ意味を表し、Ｒａ１０１は水素原子または一価の有機基を表し、ｓ１は０又は１を表す。）で表される構造であることが光劣化防止能を高めるためには特に好ましい。Ｒａ１０１は水素原子又は炭素数１～４のアルキル基であることが好ましい。Ｒｄ０１は水素原子であることが好ましい。Ｓｐａ３１は単結合又は炭素原子数１から６のアルキレン基であることが好ましく、アルキル基中に存在する１個の－ＣＨ２－又は隣接していない２個以上の－ＣＨ２－は－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－ＣＨ＝ＣＨ－又は－Ｃ≡Ｃ－により置き換えられていることが好ましく、単結合であることが特に好ましい。ｓ１は１であることが好ましい。
ｍ１及びｐ１は１であることが好ましい。ｑ１は０であることが好ましい。 (Wherein R d01 represents a hydrogen atom or a hydroxyl group, Sp a31 represents the same meaning as Sp a3 in formula ( Id ), R a101 represents a hydrogen atom or a monovalent organic group, and s1 represents 0 Or a structure represented by 1) is particularly preferable in order to enhance the ability to prevent light degradation. R a101 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R d01 is preferably a hydrogen atom. Sp a31 is preferably an alkylene group of a single bond or a C 1 -C 6, one -CH 2 present in the alkyl group - or nonadjacent two or more -CH 2 - is -O It is preferably replaced by —, —COO—, —OCO—, —CH═CH— or —C≡C—, and particularly preferably a single bond. s1 is preferably 1.
m1 and p1 are preferably 1. q1 is preferably 0.
　一般式（Ｉ－１）で表される化合物としては、以下の一般式（Ｉ－１ａ）～（Ｉ－１ｖ）が特に好ましい。 As the compound represented by the general formula (I-1), the following general formulas (I-1a) to (I-1v) are particularly preferable.
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
（式中、Ｒａ０２及びＲａ０３は、前記一般式（Ｉ－１）におけるＲａ０１と同じ意味を表し、Ｒａ７２およびＲａ１０２は、前記一般式（Ｉ－１）におけるＲａ７１と同じ意味を表し、Ｒａ９２は前記一般式（Ｉ－１）におけるＲａ９１と同じ意味を表し、Ｓｐａ１２，Ｓｐａ１３及びＳｐａ１４は前記一般式（Ｉ－１）におけるＳｐａ１１又はＳｐａ２１と同じ意味を表し、Ａａ１２及びＡａ１３は前記一般式（Ｉ－１）におけるＡａ１１又はＡａ２１と同じ意味を表す。）
　一般式（Ｉ）で表される化合物を１種又は２種以上含有する組成物は、室温において液晶相を有することが好ましい。一般式（Ｉ）で表される化合物は、組成物中に下限値として、０．０１％以上含有することが好ましく、０．０２％以上含有することが好ましく、０．０３％以上含有することが好ましく、０．０５％以上含有することが好ましく、０．０７％以上含有することが好ましく、０．１％以上含有することが好ましく、０．１５％以上含有することが好ましく、０．２％以上含有することが好ましく、０．２５％以上含有することが好ましく、０．３％以上含有することが好ましく、０．５％以上含有することが好ましく、１％以上含有することが好ましい。また、上限値として５％以下含有することが好ましく、３％以下含有することが好ましく、１％以下含有することが好ましく、０．５％以下含有することが好ましく、０．４５％以下含有することが好ましく、０．４％以下含有することが好ましく、０．３５％以下含有することが好ましく、０．３％以下含有することが好ましく、０．２５％以下含有することが好ましく、０．２％以下含有することが好ましく、０．１５％以下含有することが好ましく、０．１％以下含有することが好ましく、０．０７％以下含有することが好ましく、０．０５％以下含有することが好ましく、０．０３％以下含有することが好ましい。 (Wherein, R a02 and R a03 are the same meaning as R a01 in the general formula (I-1), R a72 and R a102 has the same meaning as R a71 in the general formula (I-1) R a92 represents the same meaning as R a91 in the general formula (I-1), and Sp a12 , Sp a13 and Sp a14 represent the same meaning as Sp a11 or Sp a21 in the general formula (I-1). A a12 and A a13 represent the same meaning as A a11 or A a21 in formula (I-1).)
The composition containing one or more compounds represented by general formula (I) preferably has a liquid crystal phase at room temperature. The compound represented by the general formula (I) is preferably contained in the composition at a lower limit of 0.01% or more, preferably 0.02% or more, and 0.03% or more. Preferably, it contains 0.05% or more, preferably 0.07% or more, preferably 0.1% or more, preferably 0.15% or more, 0.2 % Or more, preferably 0.25% or more, preferably 0.3% or more, preferably 0.5% or more, and preferably 1% or more. The upper limit is preferably 5% or less, preferably 3% or less, preferably 1% or less, preferably 0.5% or less, and 0.45% or less. It is preferable to contain 0.4% or less, preferably 0.35% or less, preferably 0.3% or less, preferably 0.25% or less. 2% or less, preferably 0.15% or less, preferably 0.1% or less, preferably 0.07% or less, preferably 0.05% or less It is preferable to contain 0.03% or less.
　より具体的には、０．０１から５質量％含有することが好ましく、０．０１から０．３質量％であることが好ましく、０．０２から０．３質量％であることが更に好ましく、０．０５から０．２５質量％であることが特に好ましい。更に詳述すると、低温における析出の抑制を重視する場合にはその含有量は０．０１から０．１質量％が好ましい。 More specifically, the content is preferably 0.01 to 5% by mass, preferably 0.01 to 0.3% by mass, more preferably 0.02 to 0.3% by mass, Particularly preferred is 0.05 to 0.25% by mass. More specifically, when emphasizing the suppression of precipitation at low temperatures, the content is preferably 0.01 to 0.1% by mass.
　一般式（Ｉ）で表される化合物を含有する組成物は、一般式（Ｉ）で表される化合物以外に、液晶相を有する化合物を含有してもよいし、液晶相を有さない化合物を含有してもよい。 The composition containing the compound represented by the general formula (I) may contain a compound having a liquid crystal phase in addition to the compound represented by the general formula (I), or a compound having no liquid crystal phase. It may contain.
　本発明において、一般式（Ｉ）で表される化合物は、以下のようにして製造することができる。勿論本発明の趣旨及び適用範囲は、これら製造例により制限されるものではない。 In the present invention, the compound represented by the general formula (I) can be produced as follows. Of course, the spirit and scope of the present invention are not limited by these production examples.
　（製法１）一般式（Ｉ）で表される化合物の製造方法 (Production method 1) Method for producing compound represented by general formula (I)
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
（式中、Ｒａ０、Ｒａ１，Ｒａ２，Ｒａ３、Ｒａ４、Ｒａ５、Ｒａ６、ｎ、ｔ及びＵは前記一般式（Ｉ）におけるＲａ０、Ｒａ１，Ｒａ２，Ｒａ３、Ｒａ４、Ｒａ５、Ｒａ６、ｎ、ｔ及びＵと同じ意味を表す。）
　一般式（Ｓ－１）で表される化合物を一般式（Ｓ－２）で表される化合物と反応させることにより一般式（Ｉ）で表される化合物を得ることができる。反応例として例えば、一般式（Ｓ－１）で表される化合物及び一般式（Ｓ－２）で表される化合物を酸触媒の存在下加熱し脱水反応させる方法が挙げられる。酸触媒としては例えば塩酸、硫酸、重硫酸カリウムなどの無機酸や、三フッ化ホウ素などのルイス酸、フマル酸、フタル酸、オギザリル酸、カンファースルホン酸、ｐ－トルエンスルホン酸などの有機酸、アンバーリスト－１５などの固体酸等が挙げられる。この際、一般式（Ｓ－１）で表される化合物が塩基性化合物である場合、必要に応じて酸触媒は1当量を超える量を加えることができる。 (Wherein R a0 , R a1 , R a2 , R a3 , R a4 , R a5 , R a6 , n, t and U are R a0 , R a1 , R a2 , R a3 , R a4 , R a5 , R a6 , n, t and U represent the same meaning.)
A compound represented by general formula (I) can be obtained by reacting a compound represented by general formula (S-1) with a compound represented by general formula (S-2). Examples of the reaction include a method in which the compound represented by the general formula (S-1) and the compound represented by the general formula (S-2) are heated in the presence of an acid catalyst to cause a dehydration reaction. Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and potassium bisulfate, Lewis acids such as boron trifluoride, organic acids such as fumaric acid, phthalic acid, oxalyl acid, camphorsulfonic acid, and p-toluenesulfonic acid, And solid acids such as Amberlyst-15. At this time, when the compound represented by the general formula (S-1) is a basic compound, the acid catalyst can be added in an amount exceeding 1 equivalent, if necessary.
　（製法２）一般式（Ｉ－１ａ）、（Ｉ－１ｂ）、（Ｉ－１ｋ）又は（Ｉ－１ｌ）で表される化合物の製造方法 (Production method 2) Method for producing a compound represented by the general formula (I-1a), (I-1b), (I-1k) or (I-1l)
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
（式中、Ｒｓ１は前記一般式（Ｉ－１ａ）、（Ｉ－１ｂ）、（Ｉ－１ｋ）又は（Ｉ－１ｌ）におけるＲａ０２又はＲａ０３と同じ意味を表し、Ｒｓ７は前記一般式（Ｉ－１）におけるＲａ７１と同じ意味を表し、Ａｓ１は前記一般式（Ｉ－１ｂ）又は（Ｉ－１ｌ）におけるＡａ１２又はＡａ１３と同じ意味を表し、Ｙｓ１は前記一般式（Ｉ－１ａ）及び／又は（Ｉ－１ｂ）におけるＲａ９２と同じ意味、若しくは前記一般式（Ｉ－１ｋ）及び／又は（Ｉ－１ｌ）におけるＳｐａ１３と同じ意味を表し、ｐｓ１は０又は１を表し、ｔｓ１は１又は２を表す。）
　一般式（Ｓ－３）で表される化合物を一般式（Ｓ－４）で表される化合物と反応させることにより一般式（Ｉ－１ａ）、（Ｉ－１ｂ）、（Ｉ－１ｋ）又は（Ｉ－１ｌ）で表される化合物を得ることができる。反応例として例えば、製法１と同様にして、一般式（Ｓ－３）で表される化合物及び一般式（Ｓ－４）で表される化合物を酸触媒の存在下加熱し脱水反応させる方法が挙げられる。 Wherein R s1 represents the same meaning as R a02 or R a03 in the general formula (I-1a), (I-1b), (I-1k) or (I-1l), and R s7 represents the general formula R a71 has the same meaning as in formula (I-1), A s1 has the same meaning as A a12 or A a13 in formula (I-1b) or (I-1l), and Y s1 has the same formula as in formula (I-1b). The same meaning as R a92 in (I-1a) and / or (I-1b), or the same meaning as S pa13 in the general formulas (I-1k) and / or (I-1l), and p s1 is 0 Or 1 and t s1 represents 1 or 2.)
By reacting the compound represented by the general formula (S-3) with the compound represented by the general formula (S-4), the general formula (I-1a), (I-1b), (I-1k) or A compound represented by (I-1l) can be obtained. As a reaction example, for example, in the same manner as in Production Method 1, there is a method in which a compound represented by the general formula (S-3) and a compound represented by the general formula (S-4) are heated in the presence of an acid catalyst to cause a dehydration reaction. Can be mentioned.
　（製法３）一般式（Ｉ－１ｃ）、（Ｉ－１ｊ）、（Ｉ－１ｍ）又は（Ｉ－１ｔ）で表される化合物の製造方法 (Production method 3) Method for producing a compound represented by the general formula (I-1c), (I-1j), (I-1m) or (I-1t)
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
（式中、Ｒｓ１は前記一般式（Ｉ－１ｃ）、（Ｉ－１ｊ）、（Ｉ－１ｍ）又は（Ｉ－１ｔ）におけるＲａ０２又はＲａ０３と同じ意味を表し、Ｒｓ７は前記一般式（Ｉ－１）におけるＲａ７１と同じ意味を表し、Ａｓ１は前記一般式（Ｉ－１ｃ）、（Ｉ－１ｊ）、（Ｉ－１ｍ）又は（Ｉ－１ｔ）におけるＡａ１２又はＡａ１３と同じ意味を表し、Ｙｓ１は前記一般式（Ｉ－１ｃ）又は（Ｉ－１ｊ）におけるＲａ９２と同じ意味、若しくは前記一般式（Ｉ－１ｍ）又は（Ｉ－１ｔ）におけるＳｐａ１３と同じ意味を表し、Ｓｐｓ１は前記一般式（Ｉ－１ｃ）、（Ｉ－１ｊ）、（Ｉ－１ｍ）又は（Ｉ－１ｔ）におけるＳｐａ１２又はＳｐａ１４と同じ意味を表し、ｍｓ１及びｐｓ１は各々独立して０又は１を表し、ｔｓ１は１又は２を表す。）
　一般式（Ｓ－３）で表される化合物を一般式（Ｓ－５）で表される化合物と反応させることにより一般式（Ｓ－６）で表される化合物を得ることができる。反応例として例えば、製法１と同様にして、一般式（Ｓ－３）で表される化合物及び一般式（Ｓ－５）で表される化合物を酸触媒の存在下加熱し脱水反応させる方法が挙げられる。
一般式（Ｓ－６）で表される化合物を一般式（Ｓ－７）で表される化合物と反応させることにより一般式（Ｉ－１ｃ）、（Ｉ－１ｊ）、（Ｉ－１ｍ）又は（Ｉ－１ｔ）で表される化合物を得ることができる。反応例として例えば、一般式（Ｓ－６）の水酸基に対して塩化ｐ－トルエンスルホニル、塩化メチルスルホニルなどを反応させて脱離基とした後、塩基の存在下で（Ｓ－７）と反応させるウィリアムソン反応が挙げられる。塩基としては例えば炭酸カリウム、炭酸セシウムなどが挙げられる。また、水酸基をアゾカルボン酸エステルとトリフェニルホスフィンで活性化し、アルコールと反応させる光延反応が挙げられる。アゾカルボン酸エステルとしては例えばアゾジカルボン酸ジエチル、アゾジカルボン酸ジイソプロピルなどが挙げられる。（製法４）一般式（Ｉ－１ｄ）、（Ｉ－１ｉ）、（Ｉ－１ｎ）又は（Ｉ－１ｓ）で表される化合物の製造方法 Wherein R s1 represents the same meaning as R a02 or R a03 in the general formula (I-1c), (I-1j), (I-1m) or (I-1t), and R s7 represents the general formula R a71 has the same meaning as in formula (I-1), and A s1 represents A a12 or A a13 in formula (I-1c), (I-1j), (I-1m) or (I-1t). Y s1 has the same meaning as R a92 in formula (I-1c) or (I-1j), or the same as Sp a13 in formula (I-1m) or (I-1t). Sp s1 represents the same meaning as Sp a12 or Sp a14 in the general formula (I-1c), (I-1j), (I-1m) or (I-1t), and m s1 and p s1 represents 0 or 1 each independently is, t s1 is 1 or 2 Represent.)
A compound represented by general formula (S-6) can be obtained by reacting a compound represented by general formula (S-3) with a compound represented by general formula (S-5). As a reaction example, for example, a method in which the compound represented by the general formula (S-3) and the compound represented by the general formula (S-5) are dehydrated by heating in the presence of an acid catalyst in the same manner as in Production Method 1. Can be mentioned.
By reacting a compound represented by the general formula (S-6) with a compound represented by the general formula (S-7), the general formula (I-1c), (I-1j), (I-1m) or A compound represented by (I-1t) can be obtained. As a reaction example, for example, p-toluenesulfonyl chloride, methylsulfonyl chloride and the like are reacted with a hydroxyl group of the general formula (S-6) to form a leaving group, and then reacted with (S-7) in the presence of a base. The Williamson reaction is mentioned. Examples of the base include potassium carbonate and cesium carbonate. Moreover, the Mitsunobu reaction which activates a hydroxyl group with azocarboxylic acid ester and triphenylphosphine and reacts with alcohol is mentioned. Examples of the azocarboxylic acid ester include diethyl azodicarboxylate and diisopropyl azodicarboxylate. (Production Method 4) Method for producing a compound represented by the general formula (I-1d), (I-1i), (I-1n) or (I-1s)
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
（式中、Ｒｓ１は前記一般式（Ｉ－１ｄ）、（Ｉ－１ｉ）、（Ｉ－１ｎ）又は（Ｉ－１ｓ）におけるＲａ０２又はＲａ０３と同じ意味を表し、Ｒｓ７は前記一般式（Ｉ－１）におけるＲａ７１と同じ意味を表し、Ａｓ１は前記一般式（Ｉ－１ｄ）、（Ｉ－１ｉ）、（Ｉ－１ｎ）又は（Ｉ－１ｓ）におけるＡａ１２又はＡａ１３と同じ意味を表し、Ｙｓ１は前記一般式（Ｉ－１ｄ）又は（Ｉ－１ｉ）におけるＲａ９２と同じ意味、若しくは前記一般式（Ｉ－１ｎ）又は（Ｉ－１ｓ）におけるＳｐａ１３と同じ意味を表し、Ｓｐｓ１は前記一般式（Ｉ－１ｄ）、（Ｉ－１ｉ）、（Ｉ－１ｎ）又は（Ｉ－１ｓ）におけるＳｐａ１２又はＳｐａ１４と同じ意味を表し、ｍｓ１及びｐｓ１は各々独立して０又は１を表し、ｔｓ１は１又は２を表す。）
　一般式（Ｓ－３）で表される化合物を一般式（Ｓ－８）で表される化合物と反応させることにより一般式（Ｓ－９）で表される化合物を得ることができる。反応例として例えば、製法１と同様にして、一般式（Ｓ－３）で表される化合物及び一般式（Ｓ－８）で表される化合物を酸触媒の存在下加熱し脱水反応させる方法が挙げられる。
一般式（Ｓ－９）で表される化合物を一般式（Ｓ－７）で表される化合物と反応させることにより一般式（Ｉ－１ｄ）、（Ｉ－１ｉ）、（Ｉ－１ｎ）又は（Ｉ－１ｓ）で表される化合物を得ることができる。反応例として例えば、一般式（Ｓ－９）のカルボキシル基に対してハロゲン化剤を作用させて酸ハロゲン化物とした後、一般式（Ｓ－７）で表される化合物と反応させる方法が挙げられる。ハロゲン化剤としては例えば、塩化チオニル、塩化オキサリル、塩化ホスホリル、塩化スルフリル、三塩化リン、五塩化リン、三臭化リンなどが挙げられる。また、一般式（Ｓ－７）の水酸基をアゾカルボン酸エステルとトリフェニルホスフィンで活性化し、一般式（Ｓ－９）のカルボキシル基と反応させる光延反応が挙げられる。アゾカルボン酸エステルとしては例えばアゾジカルボン酸ジエチル、アゾジカルボン酸ジイソプロピルなどが挙げられる。 Wherein R s1 represents the same meaning as R a02 or R a03 in the general formula (I-1d), (I-1i), (I-1n) or (I-1s), and R s7 represents the general formula R a71 has the same meaning as in formula (I-1), and A s1 represents A a12 or A a13 in formula (I-1d), (I-1i), (I-1n) or (I-1s). Y s1 has the same meaning as R a92 in the general formula (I-1d) or (I-1i), or the same as Sp a13 in the general formula (I-1n) or (I-1s). Sp s1 represents the same meaning as Sp a12 or Sp a14 in the general formula (I-1d), (I-1i), (I-1n) or (I-1s), and m s1 and p s1 represents 0 or 1 each independently is, t s1 is 1 or 2 Represent.)
The compound represented by the general formula (S-9) can be obtained by reacting the compound represented by the general formula (S-3) with the compound represented by the general formula (S-8). As a reaction example, for example, in the same manner as in production method 1, there is a method in which a compound represented by general formula (S-3) and a compound represented by general formula (S-8) are heated in the presence of an acid catalyst to cause a dehydration reaction. Can be mentioned.
By reacting a compound represented by the general formula (S-9) with a compound represented by the general formula (S-7), the general formula (I-1d), (I-1i), (I-1n) or A compound represented by (I-1s) can be obtained. Examples of the reaction include a method in which a halogenating agent is allowed to act on the carboxyl group of the general formula (S-9) to form an acid halide and then reacted with the compound represented by the general formula (S-7). It is done. Examples of the halogenating agent include thionyl chloride, oxalyl chloride, phosphoryl chloride, sulfuryl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus tribromide and the like. Further, Mitsunobu reaction in which the hydroxyl group of the general formula (S-7) is activated with an azocarboxylic acid ester and triphenylphosphine and reacted with the carboxyl group of the general formula (S-9) can be mentioned. Examples of the azocarboxylic acid ester include diethyl azodicarboxylate and diisopropyl azodicarboxylate.
　（製法５）一般式（Ｉ－１ｅ）又は（Ｉ－１ｏ）で表される化合物の製造方法 (Production method 5) Method for producing a compound represented by the general formula (I-1e) or (I-1o)
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
（式中、Ｒｓ１は前記一般式（Ｉ－１ｅ）又は（Ｉ－１ｏ）におけるＲａ０２又はＲａ０３と同じ意味を表し、Ｒｓ７は前記一般式（Ｉ－１）におけるＲａ７１と同じ意味を表し、Ａｓ１は前記一般式（Ｉ－１ｅ）又は（Ｉ－１ｏ）におけるＡａ１２又はＡａ１３と同じ意味を表し、Ｙｓ１は前記一般式（Ｉ－１ｅ）におけるＲａ９２と同じ意味、若しくは前記一般式（Ｉ－１ｏ）におけるＳｐａ１３と同じ意味を表し、ｐｓ１は０又は１を表し、ｔｓ１は１又は２を表す。）
　一般式（Ｓ－３）で表される化合物を一般式（Ｓ－１０）で表される化合物と反応させることにより一般式（Ｓ－１１）で表される化合物を得ることができる。反応例として例えば、製法１と同様にして、一般式（Ｓ－３）で表される化合物及び一般式（Ｓ－１０）で表される化合物を酸触媒の存在下加熱し脱水反応させる方法が挙げられる。
一般式（Ｓ－１１）で表される化合物を一般式（Ｓ－１２）で表される化合物と反応させることにより一般式（Ｉ－１ｅ）又は（Ｉ－１ｏ）で表される化合物を得ることができる。反応例として例えば、一般式（Ｓ－１２）の水酸基に対して塩化ｐ－トルエンスルホニル、塩化メチルスルホニルなどを反応させて脱離基とした後、塩基の存在下で（Ｓ－１１）と反応させるウィリアムソン反応が挙げられる。塩基としては例えば水素化ナトリウムなどが挙げられる。また、水酸基をアゾカルボン酸エステルとトリフェニルホスフィンで活性化し、アルコールと反応させる光延反応が挙げられる。アゾカルボン酸エステルとしては例えばアゾジカルボン酸ジエチル、アゾジカルボン酸ジイソプロピルなどが挙げられる。 Wherein R s1 represents the same meaning as R a02 or R a03 in the general formula (I-1e) or (I-1o), and R s7 represents the same meaning as R a71 in the general formula (I-1). A s1 represents the same meaning as A a12 or A a13 in the general formula (I-1e) or (I-1o), Y s1 has the same meaning as R a92 in the general formula (I-1e), Or, it represents the same meaning as Sp a13 in the general formula (I-1o), p s1 represents 0 or 1, and t s1 represents 1 or 2.)
A compound represented by the general formula (S-11) can be obtained by reacting the compound represented by the general formula (S-3) with a compound represented by the general formula (S-10). As a reaction example, for example, in the same manner as in Production Method 1, there is a method in which the compound represented by the general formula (S-3) and the compound represented by the general formula (S-10) are heated in the presence of an acid catalyst to cause a dehydration reaction. Can be mentioned.
A compound represented by general formula (I-1e) or (I-1o) is obtained by reacting a compound represented by general formula (S-11) with a compound represented by general formula (S-12). be able to. As a reaction example, for example, p-toluenesulfonyl chloride, methylsulfonyl chloride and the like are reacted with the hydroxyl group of the general formula (S-12) to form a leaving group, and then reacted with (S-11) in the presence of a base. The Williamson reaction is mentioned. Examples of the base include sodium hydride. Moreover, the Mitsunobu reaction which activates a hydroxyl group with azocarboxylic acid ester and triphenylphosphine and reacts with alcohol is mentioned. Examples of the azocarboxylic acid ester include diethyl azodicarboxylate and diisopropyl azodicarboxylate.
　（製法６）一般式（Ｉ－１ｆ）又は（Ｉ－１ｐ）で表される化合物の製造方法 (Production method 6) Production method of compound represented by general formula (I-1f) or (I-1p)
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
（式中、Ｒｓ１は前記一般式（Ｉ－１ｆ）又は（Ｉ－１ｐ）におけるＲａ０２又はＲａ０３と同じ意味を表し、Ｒｓ７は前記一般式（Ｉ－１）におけるＲａ７１と同じ意味を表し、Ａｓ１は前記一般式（Ｉ－１ｆ）又は（Ｉ－１ｐ）におけるＡａ１２又はＡａ１３と同じ意味を表し、Ｙｓ１は前記一般式（Ｉ－１ｆ）におけるＲａ９２と同じ意味、若しくは前記一般式（Ｉ－１ｐ）におけるＳｐａ１３と同じ意味を表し、ｐｓ１は０又は１を表し、ｔｓ１は１又は２を表す。）
一般式（Ｓ－１１）で表される化合物を一般式（Ｓ－１３）で表される化合物と反応させることにより一般式（Ｉ－１ｆ）又は（Ｉ－１ｐ）で表される化合物を得ることができる。反応例として例えば、一般式（Ｓ－１３）のカルボキシル基に対してハロゲン化剤を作用させて酸ハロゲン化物とした後、一般式（Ｓ－１１）で表される化合物と反応させる方法が挙げられる。ハロゲン化剤としては例えば、塩化チオニル、塩化オキサリル、塩化ホスホリル、塩化スルフリル、三塩化リン、五塩化リン、三臭化リンなどが挙げられる。また、一般式（Ｓ－１１）の水酸基をアゾカルボン酸エステルとトリフェニルホスフィンで活性化し、一般式（Ｓ－１３）のカルボキシル基と反応させる光延反応が挙げられる。アゾカルボン酸エステルとしては例えばアゾジカルボン酸ジエチル、アゾジカルボン酸ジイソプロピルなどが挙げられる。 Wherein R s1 represents the same meaning as R a02 or R a03 in the general formula (I-1f) or (I-1p), and R s7 has the same meaning as R a71 in the general formula (I-1). A s1 represents the same meaning as A a12 or A a13 in the general formula (I-1f) or (I-1p), Y s1 has the same meaning as R a92 in the general formula (I-1f), Or, it represents the same meaning as Sp a13 in the general formula (I-1p), p s1 represents 0 or 1, and t s1 represents 1 or 2.)
A compound represented by general formula (I-1f) or (I-1p) is obtained by reacting a compound represented by general formula (S-11) with a compound represented by general formula (S-13). be able to. Examples of the reaction include a method in which a halogenating agent is allowed to act on the carboxyl group of the general formula (S-13) to form an acid halide and then reacted with the compound represented by the general formula (S-11). It is done. Examples of the halogenating agent include thionyl chloride, oxalyl chloride, phosphoryl chloride, sulfuryl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus tribromide and the like. Further, Mitsunobu reaction in which the hydroxyl group of the general formula (S-11) is activated with an azocarboxylic acid ester and triphenylphosphine and reacted with the carboxyl group of the general formula (S-13) can be mentioned. Examples of the azocarboxylic acid ester include diethyl azodicarboxylate and diisopropyl azodicarboxylate.
　（製法７）一般式（Ｉ－１ｇ）、（Ｉ－１ｑ）、（Ｉ－１ｈ）又は（Ｉ－１ｒ）で表される化合物の製造方法 (Production method 7) Method for producing a compound represented by the general formula (I-1g), (I-1q), (I-1h) or (I-1r)
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
（式中、Ｒｓ１は前記一般式（Ｉ－１ｇ）、（Ｉ－１ｑ）、（Ｉ－１ｈ）又は（Ｉ－１ｒ）におけるＲａ０２又はＲａ０３と同じ意味を表し、Ｒｓ２はアルキル基を表し、Ｒｓ７は前記一般式（Ｉ－１）におけるＲａ７１と同じ意味を表し、Ａｓ１は前記一般式（Ｉ－１ｇ）、（Ｉ－１ｑ）、（Ｉ－１ｈ）又は（Ｉ－１ｒ）におけるＡａ１２又はＡａ１３と同じ意味を表し、Ｙｓ１は前記一般式（Ｉ－１ｇ）又は（Ｉ－１ｈ）におけるＲａ９２と同じ意味、若しくは前記一般式（Ｉ－１ｑ）又は（Ｉ－１ｒ）におけるＳｐａ１３と同じ意味を表し、Ｘは塩素、臭素又はヨウ素を表し、ｐｓ１は０又は１を表し、ｔｓ１は１又は２を表す。）
　一般式（Ｓ－３）で表される化合物を一般式（Ｓ－１７）で表される化合物と反応させることにより一般式（Ｓ－１４）で表される化合物を得ることができる。反応例として例えば、製法１と同様にして、一般式（Ｓ－３）で表される化合物及び一般式（Ｓ－１３）で表される化合物を酸触媒の存在下加熱し脱水反応させる方法が挙げられる。 (Wherein R s1 represents the same meaning as R a02 or R a03 in formula (I-1g), (I-1q), (I-1h) or (I-1r), and R s2 represents an alkyl group) R s7 represents the same meaning as R a71 in the general formula (I-1), and A s1 represents the general formula (I-1g), (I-1q), (I-1h) or (I− 1r) has the same meaning as A a12 or A a13, and Y s1 has the same meaning as R a92 in General Formula (I-1g) or (I-1h), or General Formula (I-1q) or (I -1r) represents the same meaning as Sp a13 , X represents chlorine, bromine or iodine, p s1 represents 0 or 1, and t s1 represents 1 or 2.
A compound represented by general formula (S-14) can be obtained by reacting a compound represented by general formula (S-3) with a compound represented by general formula (S-17). As a reaction example, for example, a method of heating and dehydrating the compound represented by the general formula (S-3) and the compound represented by the general formula (S-13) in the presence of an acid catalyst in the same manner as in Production Method 1. Can be mentioned.
　一般式（Ｓ－１４）で表される化合物を還元することにより、一般式（Ｓ－１５）で表される化合物を得ることができる。還元剤としては、例えば水素化ジイソブチルアルミニウムなどが挙げられる。あるいは、一般式（Ｓ－１４）で表される化合物を還元してアルコールとし、続いて酸化してアルデヒドとすることにより、一般式（Ｓ－１５）で表される化合物を得ることも出来る。この場合、還元剤としては、例えば水素化リチウムアルミニウム、水素化ジイソブチルアルミニウム、水素化ビス(2-メトキシエトキシ)アルミニウムナトリウムなどが挙げられる。また、酸化剤としてはクロロクロム酸ピリジニウム、塩化オキサリルなどが挙げられる。 A compound represented by the general formula (S-15) can be obtained by reducing the compound represented by the general formula (S-14). Examples of the reducing agent include diisobutylaluminum hydride. Alternatively, the compound represented by the general formula (S-15) can be obtained by reducing the compound represented by the general formula (S-14) to an alcohol and then oxidizing the compound to obtain an aldehyde. In this case, examples of the reducing agent include lithium aluminum hydride, diisobutylaluminum hydride, sodium bis (2-methoxyethoxy) aluminum hydride, and the like. Examples of the oxidizing agent include pyridinium chlorochromate and oxalyl chloride.
　一般式（Ｓ－１５）で表される化合物を一般式（Ｓ－１６）で表される化合物と反応させることにより一般式（Ｉ－１ｇ）又は（Ｉ－１ｑ）で表される化合物を得ることができる。反応例として例えば、一般式（Ｓ－１６）で表される化合物に対して塩基を反応させてリンイリドとした後、一般式（Ｓ－１５）で表される化合物と反応させるヴィティヒ反応が挙げられる。この際、塩基としては、例えばｔ－ブトキシカリウムなどが挙げられる。
一般式（Ｉ－１ｇ）又は（Ｉ－１ｑ）で表される化合物を還元することにより、一般式（Ｉ－１ｈ）又は（Ｉ－１ｒ）で表される化合物を得ることができる。反応例として例えば、一般式（Ｉ－１ｇ）又は（Ｉ－１ｑ）で表される化合物と触媒を水素雰囲気下で共存させる方法が挙げられる。この際、触媒としては例えばパラジウム炭素などが挙げられる。 A compound represented by general formula (I-1g) or (I-1q) is obtained by reacting a compound represented by general formula (S-15) with a compound represented by general formula (S-16). be able to. Examples of the reaction include a Wittig reaction in which a compound represented by the general formula (S-16) is reacted with a base to form phosphorus ylide and then reacted with a compound represented by the general formula (S-15). . In this case, examples of the base include t-butoxypotassium.
A compound represented by the general formula (I-1h) or (I-1r) can be obtained by reducing the compound represented by the general formula (I-1g) or (I-1q). Examples of the reaction include a method in which a compound represented by the general formula (I-1g) or (I-1q) and a catalyst coexist in a hydrogen atmosphere. In this case, examples of the catalyst include palladium carbon.
　（製法８）一般式（Ｉ－１ｕ）又は（Ｉ－１ｖ）で表される化合物の製造方法 (Production method 8) Method for producing compound represented by general formula (I-1u) or (I-1v)
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
（式中、Ｒｓ１は前記一般式（Ｉ－１ｕ）又は（Ｉ－１ｖ）におけるＲａ０２又はＲａ０３と同じ意味を表し、Ｒｓ７は前記一般式（Ｉ－１）におけるＲａ７１と同じ意味を表し、Ａｓ１は前記一般式（Ｉ－１ｕ）又は（Ｉ－１ｖ）におけるＡａ１２又はＡａ１３と同じ意味を表し、Ｙｓ１は前記一般式（Ｉ－１ｕ）におけるＲａ９２と同じ意味、若しくは前記一般式（Ｉ－１ｖ）におけるＳｐａ１３と同じ意味を表し、Ｓｐｓ１は前記一般式（Ｉ－１ｕ）又は（Ｉ－１ｖ）におけるＳｐａ１２又はＳｐａ１４と同じ意味を表し、ｍｓ１及びｐｓ１は各々独立して０又は１を表し、ｔｓ１は１又は２を表す。）
　一般式（Ｓ－３）で表される化合物を一般式（Ｓ－５）で表される化合物と反応させることにより一般式（Ｓ－６）で表される化合物を得ることができる。反応例として例えば、製法１と同様にして、一般式（Ｓ－３）で表される化合物及び一般式（Ｓ－５）で表される化合物を酸触媒の存在下加熱し脱水反応させる方法が挙げられる。
一般式（Ｓ－６）で表される化合物を一般式（Ｓ－１８）で表される化合物と反応させることにより一般式（Ｉ－１ｕ）又は（Ｉ－１ｖ）で表される化合物を得ることができる。反応例として例えば、一般式（Ｓ－１８）のカルボキシル基に対してハロゲン化剤を作用させて酸ハロゲン化物とした後、一般式（Ｓ－６）で表される化合物と反応させる方法が挙げられる。ハロゲン化剤としては例えば、塩化チオニル、塩化オキサリル、塩化ホスホリル、塩化スルフリル、三塩化リン、五塩化リン、三臭化リンなどが挙げられる。また、一般式（Ｓ－６）の水酸基をアゾカルボン酸エステルとトリフェニルホスフィンで活性化し、一般式（Ｓ－１８）のカルボキシル基と反応させる光延反応が挙げられる。アゾカルボン酸エステルとしては例えばアゾジカルボン酸ジエチル、アゾジカルボン酸ジイソプロピルなどが挙げられる。
前記各工程において記載した以外の反応条件として、例えば実験化学講座（日本化学会編、丸善株式会社発行）、Ｏｒｇａｎｉｃ　Ｓｙｎｔｈｅｓｅｓ（Ａ　Ｊｏｈｎ　Ｗｉｌｅｙ　＆　Ｓｏｎｓ，Ｉｎｃ．，Ｐｕｂｌｉｃａｔｉｏｎ）、Ｂｅｉｌｓｔｅｉｎ　Ｈａｎｄｂｏｏｋ　ｏｆ　Ｏｒｇａｎｉｃ Ｃｈｅｍｉｓｔｒｙ（Ｂｅｉｌｓｔｅｉｎ－Ｉｎｓｔｉｔｕｔ　ｆｕｅｒ　Ｌｉｔｅｒａｔｕｒ　ｄｅｒ　Ｏｒｇａｎｉｓｃｈｅｎ　Ｃｈｅｍｉｅ、Ｓｐｒｉｎｇｅｒ－Ｖｅｒｌａｇ　Ｂｅｒｌｉｎ　ａｎｄ　Ｈｅｉｄｅｌｂｅｒｇ　ＧｍｂＨ　＆　Ｃｏ．Ｋ）、Ｆｉｅｓｅｒｓ’　Ｒｅａｇｅｎｔｓ　ｆｏｒ　Ｏｒｇａｎｉｃ　Ｓｙｎｔｈｅｓｉｓ（Ｊｏｈｎ　Ｗｉｌｅｙ　＆　Ｓｏｎｓ，Ｉｎｃ．）等の文献に記載のもの又はＳｃｉＦｉｎｄｅｒ（Ｃｈｅｍｉｃａｌ　Ａｂｓｔｒａｃｔｓ　Ｓｅｒｖｉｃｅ，Ａｍｅｒｉｃａｎ　Ｃｈｅｍｉｃａｌ　Ｓｏｃｉｅｔｙ）、Ｒｅａｘｙｓ（Ｅｌｓｅｖｉｅｒ　Ｌｔｄ．）等のデータベースに収載のものが挙げられる。 (Wherein R s1 represents the same meaning as R a02 or R a03 in formula (I-1u) or (I-1v), and R s7 represents the same meaning as R a71 in formula (I-1)). A s1 represents the same meaning as A a12 or A a13 in the general formula (I-1u) or (I-1v), Y s1 has the same meaning as R a92 in the general formula (I-1u), Or Sp s1 has the same meaning as Sp a13 in the general formula (I-1v), and Sp s1 has the same meaning as Sp a12 or Sp a14 in the general formula (I-1u) or (I-1v), and m s1 and Each p s1 independently represents 0 or 1, and t s1 represents 1 or 2.)
A compound represented by general formula (S-6) can be obtained by reacting a compound represented by general formula (S-3) with a compound represented by general formula (S-5). As a reaction example, for example, a method in which the compound represented by the general formula (S-3) and the compound represented by the general formula (S-5) are dehydrated by heating in the presence of an acid catalyst in the same manner as in Production Method 1. Can be mentioned.
A compound represented by general formula (I-1u) or (I-1v) is obtained by reacting a compound represented by general formula (S-6) with a compound represented by general formula (S-18). be able to. Examples of the reaction include a method in which a halogenating agent is allowed to act on the carboxyl group of the general formula (S-18) to form an acid halide and then reacted with the compound represented by the general formula (S-6). It is done. Examples of the halogenating agent include thionyl chloride, oxalyl chloride, phosphoryl chloride, sulfuryl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus tribromide and the like. Further, Mitsunobu reaction in which the hydroxyl group of the general formula (S-6) is activated with an azocarboxylic acid ester and triphenylphosphine and reacted with the carboxyl group of the general formula (S-18) can be mentioned. Examples of the azocarboxylic acid ester include diethyl azodicarboxylate and diisopropyl azodicarboxylate.
Examples of reaction conditions other than those described in the above steps include, for example, Experimental Chemistry Course (edited by the Chemical Society of Japan, published by Maruzen Co., Ltd.), Organic Synthesis (A John Wiley & Sons, Inc., Publication), and Bilstein Handbook of Organic Chemistry (Chemical Chemistry). -Described by Institut Futeriter der Organischen Chemie, Springer-Verlag Berlin and Heidelberg GmbH, Co. K, Fiesers' Reagents for Organic Science. racts Service, American Chemical Society), include those listed in databases such as Reaxys (Elsevier Ltd.).
　また、各工程において適宜反応溶媒を用いることができる。溶媒の具体例としてはエタノール、テトラヒドロフラン、トルエン、ジクロロメタン、水等が挙げられる。有機溶媒及び水の二相系で反応を行う場合、相間移動触媒を添加することも可能である。相間移動触媒の具体例としてはベンジルトリメチルアンモニウムブロミド、テトラブチルアンモニウムブロミド等が挙げられる。 Moreover, a reaction solvent can be appropriately used in each step. Specific examples of the solvent include ethanol, tetrahydrofuran, toluene, dichloromethane, water and the like. When the reaction is carried out in an organic solvent and water two-phase system, a phase transfer catalyst can be added. Specific examples of the phase transfer catalyst include benzyltrimethylammonium bromide and tetrabutylammonium bromide.
　また、各工程において必要に応じて精製を行うことができる。精製方法としてはクロマトグラフィー、再結晶、蒸留、昇華、再沈殿、吸着、分液処理等が挙げられる。精製剤の具体例としてはシリカゲル、ＮＨ２シリカゲル、アルミナ、活性炭等が挙げられる。 In each step, purification can be performed as necessary. Examples of the purification method include chromatography, recrystallization, distillation, sublimation, reprecipitation, adsorption, and liquid separation treatment. Specific examples of the purification agent include silica gel, NH 2 silica gel, alumina, activated carbon and the like.
　以下、実施例を挙げて本発明を更に記述するが、本発明はこれらの実施例に限定されるものではない。以下の実施例及び比較例の組成物における「％」は『質量％』を意味する。化合物の純度はＧＣ又はＵＰＬＣによって分析した。化合物および反応溶媒の略称は以下の通りである：テトラヒドロフラン（ＴＨＦ）、２,２,６,６－テトラメチル－４－ピペリドン（ＴＭＰ）、Ｎ，Ｎ－ジメチルホルムアミド（ＤＭＦ）、水素化ジイソブチルアルミニウム（ＤＩＢＡＬ）
（実施例１）化合物（Ｉ－１ａ－５）の製造 EXAMPLES Hereinafter, although an Example is given and this invention is further described, this invention is not limited to these Examples. “%” In the compositions of the following examples and comparative examples means “% by mass”. The purity of the compound was analyzed by GC or UPLC. Abbreviations of compounds and reaction solvents are as follows: tetrahydrofuran (THF), 2,2,6,6-tetramethyl-4-piperidone (TMP), N, N-dimethylformamide (DMF), diisobutylaluminum hydride (DIBAL)
Example 1 Production of Compound (I-1a-5)
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
　窒素雰囲気下、撹拌装置、温度計、冷却管、ディーンスターク管を備えた反応容器に、ｐ－トルエンスルホン酸一水和物（６．７９ｇ）及びトルエン１００ｍｌを加え、３０分間加熱還流し、生じた水を除去した。この混合物を室温まで冷却した後、ＴＭＰ（５．１１ｇ）及び２－ペンチル－１、３－プロパンジオール（４．８２ｇ）を加え、３時間加熱還流し、生じた水を除去した。この反応混合物を室温まで冷却した後、１．０Ｍ水酸化ナトリウム水溶液１５０ｍｌを加えて攪拌し、有機層を分けとり、１．０Ｍ水酸化ナトリウム水溶液１５０ｍｌ、水１００ｍｌ、飽和食塩水１００ｍｌで洗浄した。得られた有機層を濃縮し、カラムクロマトグラフィー（ＮＨ２シリカゲル、トルエン）を通過させた。得られた溶液を濃縮し、化合物（Ｉ－１ａ－５）（７．８７ｇ）を得た。
ＧＣ－ＭＳ：ｍ／ｚ　２６８．２２　[Ｍ－１５＋]
相転移温度：Ｏｉｌ（凝固点は－２０℃以下）
1H-NMR (400MHz, CDCl3)δ: 0.71-0.74(t,3H), 1.09-1.34(m,8H), 1.21(d, 12H), 1.59(s,2H), 1.79(s, 2H), 1.83-1.96(m,1H), 3.56-3.61(t,2H), 3.80-3.85(dd,2H)
　実施例１と同様の反応、および必要に応じて公知の方法に準拠した方法を用いて、実施例２（化合物（Ｉ－１ａ－３））～実施例３（化合物（Ｉ－１ｋ－４））を製造した。 Under a nitrogen atmosphere, p-toluenesulfonic acid monohydrate (6.79 g) and 100 ml of toluene were added to a reaction vessel equipped with a stirrer, thermometer, condenser, and Dean-Stark tube, and heated to reflux for 30 minutes. Water was removed. After the mixture was cooled to room temperature, TMP (5.11 g) and 2-pentyl-1,3-propanediol (4.82 g) were added, and the mixture was heated to reflux for 3 hours to remove the generated water. After cooling the reaction mixture to room temperature, 150 ml of a 1.0 M aqueous sodium hydroxide solution was added and stirred, and the organic layer was separated and washed with 150 ml of a 1.0 M aqueous sodium hydroxide solution, 100 ml of water, and 100 ml of saturated brine. The resulting organic layer was concentrated and passed through column chromatography (NH 2 silica gel, toluene). The resulting solution was concentrated to obtain compound (I-1a-5) (7.87 g).
GC-MS: m / z 268.22 [M-15 + ]
Phase transition temperature: Oil (freezing point below -20 ° C)
1 H-NMR (400MHz, CDCl 3 ) δ: 0.71-0.74 (t, 3H), 1.09-1.34 (m, 8H), 1.21 (d, 12H), 1.59 (s, 2H), 1.79 (s, 2H) , 1.83-1.96 (m, 1H), 3.56-3.61 (t, 2H), 3.80-3.85 (dd, 2H)
Example 2 (Compound (I-1a-3)) to Example 3 (Compound (I-1k-4)) were carried out using the same reaction as in Example 1 and, if necessary, a method based on a known method. ) Was manufactured.
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
（実施例７）化合物（Ｉ－１ｋ－８）の製造 Example 7 Production of Compound (I-1k-8)
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
　撹拌装置、温度計を備えた反応容器に、tert－ブトキシカリウム（１３．０ｇ）を加え、テトラヒドロフラン（４００ｍＬ）に懸濁させた。マロン酸ジエチル（１８．６ｇ）を加え、続いて１，８－ジブロモオクタン（１５．８ｇ）を加えた。室温で３日間攪拌した。減圧濃縮をおこない、１０％塩酸を加えて酸性にした。ジクロロメタン（１５０ｍＬ）で２回抽出した。減圧濃縮後、カラムクロマトグラフィーにより精製し、１，１，８，８－テトラ（エトキシカルボニル）オクタンを１５．０ｇ、無色液体として得た。 To a reaction vessel equipped with a stirrer and a thermometer, tert-butoxypotassium (13.0 g) was added and suspended in tetrahydrofuran (400 mL). Diethyl malonate (18.6 g) was added followed by 1,8-dibromooctane (15.8 g). Stir at room temperature for 3 days. The solution was concentrated under reduced pressure and acidified with 10% hydrochloric acid. Extracted twice with dichloromethane (150 mL). After concentration under reduced pressure, the residue was purified by column chromatography to obtain 15.0 g of 1,1,8,8-tetra (ethoxycarbonyl) octane as a colorless liquid.
　撹拌装置、温度計、冷却管を備えた反応容器に、水素化リチウムアルミニウム（１０．６ｇ）を加え、テトラヒドロフラン（２７９ｍＬ）に懸濁させた。１，１，８，８－テトラ（エトキシカルボニル）オクタン（２０．０ｇ）を加え、６０℃で５時間攪拌した。氷冷し、水（５７．０ｇ）を注意深く加えた。４０℃で１時間攪拌し、濾過して固形分を除いた。テトラヒドロフラン溶液を濃縮し、１，１，８，８－テトラ（ヒドロキシメチル）オクタンを１０．１ｇ、無色個体として得た。 A lithium aluminum hydride (10.6 g) was added to a reaction vessel equipped with a stirrer, a thermometer, and a cooling tube, and suspended in tetrahydrofuran (279 mL). 1,1,8,8-Tetra (ethoxycarbonyl) octane (20.0 g) was added, and the mixture was stirred at 60 ° C. for 5 hours. Ice-cooled and water (57.0 g) was carefully added. Stir at 40 ° C. for 1 hour and filter to remove solids. The tetrahydrofuran solution was concentrated to obtain 10.1 g of 1,1,8,8-tetra (hydroxymethyl) octane as a colorless solid.
　撹拌装置、温度計、冷却管、ディーンスターク管を備えた反応容器に、１，１，８，８－テトラ（ヒドロキシメチル）オクタンを１０．０ｇと２，２，６，６－テトラメチルピペリジン－４－オン（１０．６ｇ）、４－トルエンスルホン酸一水和物（１５．２ｇ）を加え、トルエン（１００ｍＬ）に懸濁させた。窒素雰囲気下、３時間加熱還流させ、途中で生成する水をディーンスターク管で除いた。室温に冷却後、炭酸カリウム水溶液を加えてアルカリ性した。テトラヒドロフラン（１３８ｍＬ）で２回抽出した。減圧濃縮後、カラムクロマトグラフィーと再結晶にて精製し、化合物（Ｉ－１ｋ－８）（１１．６ｇ）を無色結晶として得た。
ＧＣ－ＭＳ（ＥＩ）：ｍ／ｚ　５３６　[Ｍ＋]、５２１　[Ｍ－１５＋]
相転移温度：Ｃｒｙ　１０１　Ｉｓｏ
　実施例７と同様の反応、および必要に応じて公知の方法に準拠した方法を用いて、実施例４（化合物（Ｉ－１ｋ－２））～実施例６（化合物（Ｉ－１ｋ－６））を製造した。 In a reaction vessel equipped with a stirrer, thermometer, condenser, and Dean-Stark tube, 10.0 g of 1,1,8,8-tetra (hydroxymethyl) octane and 2,2,6,6-tetramethylpiperidine- 4-one (10.6 g) and 4-toluenesulfonic acid monohydrate (15.2 g) were added and suspended in toluene (100 mL). In a nitrogen atmosphere, the mixture was heated to reflux for 3 hours, and water produced during the removal was removed with a Dean-Stark tube. After cooling to room temperature, an aqueous potassium carbonate solution was added to make it alkaline. Extracted twice with tetrahydrofuran (138 mL). After concentration under reduced pressure, purification by column chromatography and recrystallization gave compound (I-1k-8) (11.6 g) as colorless crystals.
GC-MS (EI): m / z 536 [M + ], 521 [M-15 + ]
Phase transition temperature: Cry 101 Iso
Using the same reaction as in Example 7, and if necessary, a method based on a known method, Example 4 (Compound (I-1k-2)) to Example 6 (Compound (I-1k-6)) ) Was manufactured.
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
（実施例８）化合物（Ｉ－１ｂ－Ｃ３）の製造 Example 8 Production of Compound (I-1b-C3)
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
　窒素雰囲気下、撹拌装置、温度計、冷却管、ディーンスターク管を備えた反応容器に、ｐ－トルエンスルホン酸一水和物（５．０２ｇ）及びトルエン１００ｍｌを加え、３０分間加熱還流し、生じた水を除去した。この混合物を室温まで冷却した後、ＴＭＰ（３．８２ｇ）及び２－（トランス－４－プロピルシクロヘキシル）－１、３－プロパンジオール（４．９２ｇ）を加え、４時間加熱還流し、生じた水を除去した。この反応混合物を室温まで冷却した後、１．０Ｍ水酸化ナトリウム水溶液１５０ｍｌを加えて攪拌し、有機層を分けとり、１．０Ｍ水酸化ナトリウム水溶液１５０ｍｌ、水１００ｍｌ、飽和食塩水１００ｍｌで洗浄した。得られた有機層を濃縮し、ヘキサン３ｍｌを加えて－２０℃で再結晶を行った。析出した固体をろ過し、トルエンに溶解させ、カラムクロマトグラフィー（ＮＨ２シリカゲル、トルエン）を通過させた。得られた溶液を濃縮し、ヘキサン３ｍｌを加えて－２０℃で再結晶を行った。析出した固体をろ過し、真空乾燥させ、化合物（Ｉ－１ｂ－３Ｃ）（１．９７ｇ）を得た。
ＧＣ－ＭＳ：ｍ／ｚ　３２２．２７　[Ｍ－１５＋]
相転移温度：Ｃｒｙ　７０　Ｉｓｏ
1H-NMR (400MHz, CDCl3)δ: 0.78-1.02(m,4H), 0.84-0.88(t,3H), 1.05-1.17(m,4H), 1.21(d,12H), 1.24-1.36(m,2H), 1.57(s,2H), 1.68-1.76(m,5H), 1.79(s,2H), 3.67-3.72(t,2H), 3.85-3.89(dd,2H)
　実施例８と同様の反応、および必要に応じて公知の方法に準拠した方法を用いて、実施例９（化合物（Ｉ－１ｂ－０Ｃ））～実施例２４（化合物（Ｉ－１ｌ－Ｂ２Ｂ））を製造した。 In a nitrogen atmosphere, p-toluenesulfonic acid monohydrate (5.02 g) and 100 ml of toluene are added to a reaction vessel equipped with a stirrer, thermometer, condenser, and Dean-Stark tube, and heated to reflux for 30 minutes. Water was removed. The mixture was cooled to room temperature, TMP (3.82 g) and 2- (trans-4-propylcyclohexyl) -1,3-propanediol (4.92 g) were added, and the mixture was heated to reflux for 4 hours. Was removed. After cooling the reaction mixture to room temperature, 150 ml of a 1.0 M aqueous sodium hydroxide solution was added and stirred, and the organic layer was separated and washed with 150 ml of a 1.0 M aqueous sodium hydroxide solution, 100 ml of water, and 100 ml of saturated brine. The obtained organic layer was concentrated, 3 ml of hexane was added, and recrystallization was performed at −20 ° C. The precipitated solid was filtered, dissolved in toluene, and passed through column chromatography (NH 2 silica gel, toluene). The obtained solution was concentrated, 3 ml of hexane was added, and recrystallization was performed at −20 ° C. The precipitated solid was filtered and dried under vacuum to obtain compound (I-1b-3C) (1.97 g).
GC-MS: m / z 322.27 [M-15 + ]
Phase transition temperature: Cry 70 Iso
1 H-NMR (400MHz, CDCl 3 ) δ: 0.78-1.02 (m, 4H), 0.84-0.88 (t, 3H), 1.05-1.17 (m, 4H), 1.21 (d, 12H), 1.24-1.36 ( m, 2H), 1.57 (s, 2H), 1.68-1.76 (m, 5H), 1.79 (s, 2H), 3.67-3.72 (t, 2H), 3.85-3.89 (dd, 2H)
Using the same reaction as in Example 8, and if necessary, a method based on a known method, Example 9 (Compound (I-1b-0C)) to Example 24 (Compound (I-1l-B2B)) ) Was manufactured.
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000036
（実施例２５）化合物（Ｉ－１ｃ－Ｂ３）の製造 Example 25 Production of Compound (I-1c-B3)
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000037
　（化合物（Ｅ－２）の製造）窒素雰囲気下、撹拌装置、温度計、冷却管、ディーンスターク管を備えた反応容器に、ｐ－トルエンスルホン酸一水和物（５．０２ｇ）及びトルエン１００ｍｌを加え、３０分間加熱還流し、生じた水を除去した。この混合物を室温まで冷却した後、ＴＭＰ（３．８２ｇ）、ＤＭＦ３０ｍｌ及び化合物（Ｅ－１）（２．６０ｇ）を加え、４時間加熱還流し、生じた水を除去した。この反応混合物を室温まで冷却した後、１．０Ｍ水酸化ナトリウム水溶液１５０ｍｌを加えて攪拌し、有機層を分けとり、水１００ｍｌ、飽和食塩水１００ｍｌで洗浄した。得られた有機層を濃縮し、化合物（Ｅ－２）（５．７１ｇ）を得た。 (Production of Compound (E-2)) Under a nitrogen atmosphere, in a reaction vessel equipped with a stirrer, a thermometer, a condenser tube, and a Dean-Stark tube, p-toluenesulfonic acid monohydrate (5.02 g) and 100 ml of toluene were added. And heated to reflux for 30 minutes to remove the resulting water. After the mixture was cooled to room temperature, TMP (3.82 g), 30 ml of DMF and compound (E-1) (2.60 g) were added, and the mixture was heated to reflux for 4 hours to remove the generated water. The reaction mixture was cooled to room temperature, 150 ml of 1.0 M aqueous sodium hydroxide solution was added and stirred, the organic layer was separated, and washed with 100 ml of water and 100 ml of saturated brine. The obtained organic layer was concentrated to obtain compound (E-2) (5.71 g).
　（化合物（Ｉ－１ｃ－Ｂ３）の製造）窒素雰囲気下、撹拌装置、温度計を備えた反応容器に、化合物（Ｅ－２）（５．７１ｇ）、化合物（Ｅ－４）（３．００ｇ）、トリフェニルホスフィン（６．１６ｇ）及びＴＨＦ４５ｍｌを加え、５℃以下に冷却し攪拌した後、アゾジカルボン酸ジイソプロピル（４．４５ｇ）を５℃以下を保ちながら滴下し、室温で１時間撹拌した。この反応混合物に対し、水０．１ｍｌを加えて攪拌した後、溶媒を留去し、メタノール４０ｍｌ及び水２０ｍｌを加えて室温で１時間攪拌した。この反応混合物をろ過して得られた固体をヘキサン／トルエン混合溶媒に溶解させ、カラムクロマトグラフィー（ＮＨ２シリカ１０ｇ）を通した。得られた溶液を濃縮し、ヘキサン５ｍｌを加えて－２０℃で再結晶を行った。析出した固体をろ過し、真空乾燥させ、化合物（Ｉ－１ｃ－Ｂ３）（６．６６ｇ）を得た。
ＧＣ－ＭＳ：ｍ／ｚ　３６２．２６　[Ｍ－１５＋]
　実施例２５と同様の反応、および必要に応じて公知の方法に準拠した方法を用いて、実施例２６（化合物（Ｉ－１ｃ－Ｂ６））～実施例３９（化合物（Ｉ－１ｔ－ＢＢ））を製造した。 (Production of Compound (I-1c-B3)) In a nitrogen atmosphere, a reaction vessel equipped with a stirrer and a thermometer was charged with compound (E-2) (5.71 g) and compound (E-4) (3.00 g). ), Triphenylphosphine (6.16 g) and 45 ml of THF were added, and the mixture was cooled to 5 ° C. or lower and stirred. Then, diisopropyl azodicarboxylate (4.45 g) was added dropwise while maintaining the temperature at 5 ° C. or lower and stirred at room temperature for 1 hour. . To this reaction mixture, 0.1 ml of water was added and stirred, then the solvent was distilled off, 40 ml of methanol and 20 ml of water were added, and the mixture was stirred at room temperature for 1 hour. The solid obtained by filtering the reaction mixture was dissolved in a hexane / toluene mixed solvent and passed through column chromatography (NH 2 silica 10 g). The obtained solution was concentrated, 5 ml of hexane was added, and recrystallization was performed at −20 ° C. The precipitated solid was filtered and dried under vacuum to obtain compound (I-1c-B3) (6.66 g).
GC-MS: m / z 362.26 [M-15 + ]
Using a reaction similar to that of Example 25 and, if necessary, a method based on a known method, Example 26 (Compound (I-1c-B6)) to Example 39 (Compound (I-1t-BB)) ) Was manufactured.
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000039
（実施例４０）化合物（Ｉ－１ｄ－Ｂ３）の製造 Example 40 Production of Compound (I-1d-B3)
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000040
　（化合物（Ｅ－６）の製造）窒素雰囲気下、撹拌装置、温度計、冷却管、ディーンスターク管を備えた反応容器に、ｐ－トルエンスルホン酸一水和物（５．０２ｇ）及びトルエン１００ｍｌを加え、３０分間加熱還流し、生じた水を除去した。この混合物を室温まで冷却した後、ＴＭＰ（３．８２ｇ）、ＤＭＦ３０ｍｌ及び化合物（Ｅ－５）（３．３３ｇ）を加え、４時間加熱還流し、生じた水を除去した。この反応混合物を室温まで冷却した後、１．０Ｍ水酸化ナトリウム水溶液および水を加えてｐＨ＝７～８程度に調整して攪拌し、有機層を分けとり、水１００ｍｌで２回及び飽和食塩水１００ｍｌで洗浄した。得られた有機層を濃縮し、化合物（Ｅ－６）（５．３５ｇ）を得た。
（化合物（Ｉ－１ｄ－Ｂ３）の製造）窒素雰囲気下、撹拌装置、温度計を備えた反応容器に、化合物（Ｅ－６）（５．３５ｇ）、化合物（Ｅ－７）（２．６６ｇ）、Ｎ，Ｎ－ジメチルアミノピリジン（ＤＭＡＰ）０．１２ｇ、ジクロロメタン２５ｍｌを加え、５～１０℃で１０分間攪拌した。攪拌下、Ｎ，Ｎ－ジイソプロピルカルボジイミド（ＤＩＣ）６．２ｇを５～１０℃を保ちながら滴下し、続いて２５度まで昇温し７時間攪拌した。この反応混合物に対して水２５ｍｌを加えた後、有機層を分離し、さらに水層をジクロロメタン２５ｍｌで抽出した。得られた有機層を混合して一つにした後、ＮＨ２シリカ１０ｇを充填したカラム上に加え、さらにヘキサン１００ｍｌを流して通過させた。得られた溶液の溶媒をおおむね留去した後、ヘキサン／トルエンを用いて－２０℃で再結晶を行った。析出した固体をろ過、乾燥することで化合物（Ｉ－１ｄ－Ｂ３）を４．９０ｇ得た。
ＧＣ－ＭＳ：ｍ／ｚ　３７６．２４　[Ｍ－１５＋]
　実施例４０と同様の反応、および必要に応じて公知の方法に準拠した方法を用いて、実施例４１（化合物（Ｉ－１ｄ－０Ｃ））～実施例５４（化合物（Ｉ－１ｓ－ＢＢ））を製造した。 (Production of Compound (E-6)) In a reaction vessel equipped with a stirrer, a thermometer, a condenser tube, and a Dean-Stark tube under a nitrogen atmosphere, p-toluenesulfonic acid monohydrate (5.02 g) and 100 ml of toluene were added. And heated to reflux for 30 minutes to remove the resulting water. After the mixture was cooled to room temperature, TMP (3.82 g), 30 ml of DMF and compound (E-5) (3.33 g) were added, and the mixture was heated to reflux for 4 hours to remove the generated water. After cooling the reaction mixture to room temperature, 1.0 M aqueous sodium hydroxide solution and water were added to adjust the pH to about 7-8 and stirred. The organic layer was separated, twice with 100 ml of water and saturated brine. Washed with 100 ml. The obtained organic layer was concentrated to obtain compound (E-6) (5.35 g).
(Production of Compound (I-1d-B3)) In a nitrogen atmosphere, a reaction vessel equipped with a stirrer and a thermometer was charged with compound (E-6) (5.35 g) and compound (E-7) (2.66 g). ), 0.12 g of N, N-dimethylaminopyridine (DMAP) and 25 ml of dichloromethane were added, and the mixture was stirred at 5 to 10 ° C. for 10 minutes. Under stirring, 6.2 g of N, N-diisopropylcarbodiimide (DIC) was added dropwise while maintaining the temperature at 5 to 10 ° C., and then the temperature was raised to 25 degrees and stirred for 7 hours. After adding 25 ml of water to the reaction mixture, the organic layer was separated, and the aqueous layer was further extracted with 25 ml of dichloromethane. After the obtained organic layers were mixed to make one, it was added onto a column packed with 10 g of NH 2 silica and further passed through 100 ml of hexane. After the solvent of the obtained solution was distilled off, recrystallization was performed at −20 ° C. using hexane / toluene. The precipitated solid was filtered and dried to obtain 4.90 g of compound (I-1d-B3).
GC-MS: m / z 376.24 [M-15 + ]
Using a reaction similar to that in Example 40 and, if necessary, a method based on a known method, Example 41 (Compound (I-1d-0C)) to Example 54 (Compound (I-1s-BB)) ) Was manufactured.
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000042
（実施例５５）化合物（Ｉ－１ｅ－Ｃ３）の製造 Example 55 Production of Compound (I-1e-C3)
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000043
　（化合物（Ｅ－９）の製造）窒素雰囲気下、撹拌装置、温度計、冷却管、ディーンスターク管を備えた反応容器に、ｐ－トルエンスルホン酸一水和物（５０．２ｇ）及びトルエン１０００ｍｌを加え、３０分間加熱還流し、生じた水を除去した。この混合物を室温まで冷却した後、ＴＭＰ（３８．２ｇ）、ＤＭＦ３００ｍｌ及び化合物（Ｅ－８）（２２．５ｇ）を加え、４時間加熱還流し、生じた水を除去した。この反応混合物を室温まで冷却した後、１．０Ｍ水酸化ナトリウム水溶液１５００ｍｌを加えて攪拌し、有機層を分けとり、水１０００ｍｌで２回及び飽和食塩水１０００ｍｌで洗浄した。得られた有機層を濃縮し、化合物（Ｅ－９）（２２．４ｇ）を得た。
（化合物（Ｉ－１ｅ－Ｃ３）の製造）窒素雰囲気下、撹拌装置、温度計を備えた反応容器に、化合物（Ｅ－９）（１１．２ｇ）、水素化ナトリウム１．２ｇおよびＤＭＦ１００ｍｌを加え、室温で２０分撹拌した後、化合物（Ｅ－１０）（１１．５ｇ）、を加えて９０℃で３時間撹拌した。反応混合物を室温に冷却後、トルエン１００ｍｌ、水１００ｍｌを加え有機層を分離し、さらに水層をトルエン１００ｍｌで抽出した。得られた有機層を合わせ、水１５０ｍｌ、飽和食塩水１５０ｍｌで洗浄し、得られた有機層に無水硫酸ナトリウムを加えて乾燥した。得られた溶液を濃縮し、カラムクロマトグラフィー（ＮＨ２シリカ２０ｇ）に対し、あらかじめヘキサン５０ｍｌに溶解しておいた粗体を通し、さらにヘキサン５０ｍｌで溶出させた。得られた溶液を濃縮し、ヘキサン１０ｍｌを加えて－２０℃で再結晶を行った。析出した固体をろ過し、真空乾燥させ、化合物（Ｉ－１ｅ－Ｃ３）（１２．５８ｇ）を得た。 (Production of compound (E-9)) In a reaction vessel equipped with a stirrer, a thermometer, a condenser tube, and a Dean-Stark tube under a nitrogen atmosphere, p-toluenesulfonic acid monohydrate (50.2 g) and 1000 ml of toluene were added. And heated to reflux for 30 minutes to remove the resulting water. The mixture was cooled to room temperature, TMP (38.2 g), DMF 300 ml and compound (E-8) (22.5 g) were added, and the mixture was heated to reflux for 4 hours to remove the generated water. The reaction mixture was cooled to room temperature, 1500 ml of a 1.0 M aqueous sodium hydroxide solution was added and stirred, the organic layer was separated, and washed twice with 1000 ml of water and 1000 ml of saturated brine. The obtained organic layer was concentrated to obtain compound (E-9) (22.4 g).
(Production of Compound (I-1e-C3)) In a nitrogen atmosphere, a compound (E-9) (11.2 g), sodium hydride 1.2 g and DMF 100 ml were added to a reaction vessel equipped with a stirrer and a thermometer. After stirring at room temperature for 20 minutes, compound (E-10) (11.5 g) was added and stirred at 90 ° C. for 3 hours. After cooling the reaction mixture to room temperature, 100 ml of toluene and 100 ml of water were added to separate the organic layer, and the aqueous layer was further extracted with 100 ml of toluene. The obtained organic layers were combined, washed with 150 ml of water and 150 ml of saturated saline, and dried by adding anhydrous sodium sulfate to the obtained organic layer. The resulting solution was concentrated, passed through a crude product previously dissolved in 50 ml of hexane through column chromatography (NH 2 silica 20 g), and further eluted with 50 ml of hexane. The obtained solution was concentrated, 10 ml of hexane was added, and recrystallization was performed at −20 ° C. The precipitated solid was filtered and dried under vacuum to obtain compound (I-1e-C3) (12.58 g).
　実施例５５と同様の反応、および必要に応じて公知の方法に準拠した方法を用いて、実施例５６（化合物（Ｉ－１ｅ－Ｂ６））～実施例６４（化合物（Ｉ－１ｏ－ＢＥＢＥＢ））を製造した。 Example 56 (Compound (I-1e-B6)) to Example 64 (Compound (I-1o-BEBEB)) were carried out using the same reaction as in Example 55 and, if necessary, a method based on a known method. ) Was manufactured.
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000044
（実施例６５）化合物（Ｉ－１ｆ－Ｃ３）の製造 Example 65 Production of Compound (I-1f-C3)
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000045
（化合物（Ｉ－１ｆ－Ｃ３）の製造）窒素雰囲気下、撹拌装置、温度計を備えた反応容器に、化合物（Ｅ－９）（１１．２ｇ）、化合物（Ｅ－１１）（８．３２ｇ）、Ｎ，Ｎ－ジメチルアミノピリジン（ＤＭＡＰ）０．３０ｇ、ジクロロメタン８０ｍｌを加え、５～１０℃で１０分間攪拌した。攪拌下、Ｎ，Ｎ－ジイソプロピルカルボジイミド（ＤＩＣ）８．０ｇを５～１０℃を保ちながら滴下し、続いて２５度まで昇温し７時間攪拌した。この反応混合物に対して水２ｍｌを加えて攪拌した後、析出した固体を除去し、得られた溶液を濃縮した。得られた固体をヘキサン２０ｍｌに溶かし、ＮＨ２シリカ２０ｇを充填したカラム上に加え、さらにヘキサン１００ｍｌを流して通過させた。得られた溶液の溶媒をおおむね留去した後、ヘキサン／トルエンを用いて－２０℃で再結晶を行った。析出した固体をろ過、乾燥することで化合物（Ｉ－１ｆ－Ｂ３）を１６．０ｇ得た。
ＧＣ－ＭＳ：ｍ／ｚ　３６６．２６　[Ｍ－１５＋]
　実施例６５と同様の反応、および必要に応じて公知の方法に準拠した方法を用いて、実施例６６（化合物（Ｉ－１ｆ－Ｂ６））～実施例７４（化合物（Ｉ－１ｐ－ＢＥＢＥＢ））を製造した。 (Production of Compound (I-1f-C3)) In a nitrogen atmosphere, a reaction vessel equipped with a stirrer and a thermometer was charged with compound (E-9) (11.2 g) and compound (E-11) (8.32 g). ), 0.30 g of N, N-dimethylaminopyridine (DMAP) and 80 ml of dichloromethane were added, and the mixture was stirred at 5-10 ° C. for 10 minutes. Under stirring, 8.0 g of N, N-diisopropylcarbodiimide (DIC) was added dropwise while maintaining the temperature at 5 to 10 ° C., followed by heating to 25 ° C. and stirring for 7 hours. After 2 ml of water was added to the reaction mixture and stirred, the precipitated solid was removed, and the resulting solution was concentrated. The obtained solid was dissolved in 20 ml of hexane, added onto a column packed with 20 g of NH 2 silica, and further passed through 100 ml of hexane. After the solvent of the obtained solution was distilled off, recrystallization was performed at −20 ° C. using hexane / toluene. The precipitated solid was filtered and dried to obtain 16.0 g of compound (I-1f-B3).
GC-MS: m / z 366.26 [M-15 + ]
Using a reaction similar to that of Example 65 and, if necessary, a method based on a known method, Example 66 (Compound (I-1f-B6)) to Example 74 (Compound (I-1p-BEBEB)) ) Was manufactured.
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000046
（実施例７５）化合物（Ｉ－１ｇ－Ｃ３）の製造 Example 75 Production of Compound (I-1g-C3)
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000047
　（化合物（Ｅ－１４）の製造）窒素雰囲気下、撹拌装置、温度計、冷却管、ディーンスターク管を備えた反応容器に、ｐ－トルエンスルホン酸一水和物（５．０２ｇ）及びトルエン１００ｍｌを加え、３０分間加熱還流し、生じた水を除去した。この混合物を室温まで冷却した後、ＴＭＰ（３．８２ｇ）及び化合物（Ｅ－１３）（３．２８ｇ）を加え、４時間加熱還流し、生じた水を除去した。この反応混合物を室温まで冷却した後、１．０Ｍ水酸化ナトリウム水溶液１５０ｍｌ攪拌し、有機層を分けとり、水１００ｍｌで２回及び飽和食塩水１００ｍｌで洗浄した。得られた有機層を濃縮し、化合物（Ｅ－１４）（６．３１ｇ）を得た。 (Production of Compound (E-14)) In a reaction vessel equipped with a stirrer, a thermometer, a condenser tube, and a Dean-Stark tube under a nitrogen atmosphere, p-toluenesulfonic acid monohydrate (5.02 g) and 100 ml of toluene were added. And heated to reflux for 30 minutes to remove the resulting water. The mixture was cooled to room temperature, TMP (3.82 g) and compound (E-13) (3.28 g) were added, and the mixture was heated to reflux for 4 hours to remove the generated water. The reaction mixture was cooled to room temperature, stirred with 150 ml of 1.0 M aqueous sodium hydroxide solution, and the organic layer was separated and washed twice with 100 ml of water and 100 ml of saturated brine. The obtained organic layer was concentrated to obtain compound (E-14) (6.31 g).
　（化合物（Ｅ－１５）の製造）窒素雰囲気下、撹拌装置、温度計、滴下漏斗を備えた反応容器に、化合物（Ｅ－１４）（６．３１ｇ）および乾燥トルエン５０ｍｌを加え、－７３℃に冷却した。この混合物中にＤＩＢＡＬ（１．５Ｍトルエン溶液）２７ｍｌを－６５℃以下を保ちながら滴下し、更にー７３℃で２時間攪拌した。この反応混合物に対し、－６５℃以下を保ちながら水／ＴＨＦ混合溶媒１０ｍｌを滴下した。この反応混合物を室温まで昇温させた後、１５％水酸化ナトリウム水溶液５ｍｌ、水１５ｍｌを加えて３時間攪拌した。得られた反応混合物をろ過して固体を除去し、得られた有機層から溶媒を留去し、化合物（Ｅ－１５）（５．３２ｇ）を得た。 (Production of Compound (E-15)) In a nitrogen atmosphere, a compound (E-14) (6.31 g) and 50 ml of dry toluene were added to a reaction vessel equipped with a stirrer, a thermometer, and a dropping funnel. Cooled to. To this mixture, 27 ml of DIBAL (1.5 M toluene solution) was added dropwise while maintaining at −65 ° C. or lower, and further stirred at −73 ° C. for 2 hours. To this reaction mixture, 10 ml of a water / THF mixed solvent was added dropwise while maintaining at −65 ° C. or lower. The temperature of the reaction mixture was raised to room temperature, 5 ml of 15% aqueous sodium hydroxide solution and 15 ml of water were added, and the mixture was stirred for 3 hours. The resulting reaction mixture was filtered to remove solids, and the solvent was distilled off from the obtained organic layer to obtain compound (E-15) (5.32 g).
　（化合物（Ｅ－１７）の製造）窒素雰囲気下、撹拌装置、温度計、滴下漏斗を備えた反応容器に、化合物（Ｅ－１６）（１２．２２ｇ）及びＴＨＦ２５ｍｌを加え、ここへｔ－ブトキシカリウム（２．８５ｇ）を１０℃以下で加えて攪拌した。この反応混合物中に、ＴＨＦ１５ｍｌに溶解させた化合物（Ｅ－１５）（５．３２ｇ）を１０℃以下を保ちながら滴下し、５℃で２時間攪拌した。この反応混合物へ水０．５ｍｌ、ヘキサン４０ｍｌを加えて室温で１時間攪拌した。得られた反応混合物をろ過して固体を除去し、得られた有機層に５％次亜塩素酸ナトリウム水溶液５ｍｌを加えて室温で１時間攪拌した。この反応混合物の有機層を分けとり、水／メタノール混合溶媒２０ｍｌ、飽和食塩水２０ｍｌで洗浄し、濃縮した。得られた混合物をカラム（ＮＨ２シリカ、ヘキサン）を通過させ、得られた溶液を濃縮し、化合物（Ｅ－１７）（７．２２ｇ）を得た。 (Production of Compound (E-17)) Under a nitrogen atmosphere, a compound (E-16) (12.22 g) and 25 ml of THF were added to a reaction vessel equipped with a stirrer, a thermometer, and a dropping funnel, and t-butoxy was added thereto. Potassium (2.85 g) was added at 10 ° C. or lower and stirred. To this reaction mixture, the compound (E-15) (5.32 g) dissolved in 15 ml of THF was added dropwise while maintaining the temperature at 10 ° C. or lower, and the mixture was stirred at 5 ° C. for 2 hours. To this reaction mixture, 0.5 ml of water and 40 ml of hexane were added and stirred at room temperature for 1 hour. The resulting reaction mixture was filtered to remove solids, 5 ml of 5% aqueous sodium hypochlorite solution was added to the resulting organic layer, and the mixture was stirred at room temperature for 1 hour. The organic layer of the reaction mixture was separated, washed with 20 ml of a water / methanol mixed solvent and 20 ml of saturated brine, and concentrated. The obtained mixture was passed through a column (NH 2 silica, hexane), and the obtained solution was concentrated to obtain compound (E-17) (7.22 g).
　（化合物（Ｉ－１ｇ－Ｃ３）の製造）窒素雰囲気下、撹拌装置、温度計を備えた反応容器に、化合物（Ｅ－１７）（３．６１ｇ）、ベンゼンスルフィン酸ナトリウム・２水和物（０．５ｇ）及びトルエン２０ｍｌを加えて攪拌した。この混合物中に１０％塩酸１．１ｇを加え、３時間加熱還流した。この反応混合物を室温まで冷却し、水５ｍｌを加えた。有機層を分けとり、10%炭酸水素ナトリウム水溶液５ｍｌ、10%食塩水５ｍｌで洗浄後、硫酸ナトリウムで乾燥し、有機層を濃縮した。得られた混合物をカラム（ＮＨ２シリカ、ヘキサン）を通過させた。得られた溶液を濃縮し、ヘキサン１０ｍｌを 加えて－２０℃で再結晶を行い、化合物（Ｉ－１ｇ－Ｃ３）（２．５０ｇ）を得た。
ＧＣ－ＭＳ：ｍ／ｚ　３４８．２８　[Ｍ－１５＋]
　実施例７５と同様の反応、および必要に応じて公知の方法に準拠した方法を用いて、実施例７６（化合物（Ｉ－１ｇ－Ｂ６））～実施例８２（化合物（Ｉ－１ｑ－ＢＥＢＥＢ））を製造した。 (Production of Compound (I-1g-C3)) In a nitrogen atmosphere, a reaction vessel equipped with a stirrer and a thermometer was charged with compound (E-17) (3.61 g), sodium benzenesulfinate dihydrate ( 0.5 g) and 20 ml of toluene were added and stirred. To this mixture, 1.1 g of 10% hydrochloric acid was added and heated to reflux for 3 hours. The reaction mixture was cooled to room temperature and 5 ml of water was added. The organic layer was separated, washed with 5 ml of 10% aqueous sodium hydrogen carbonate solution and 5 ml of 10% brine, dried over sodium sulfate, and the organic layer was concentrated. The resulting mixture was passed through a column (NH 2 silica, hexane). The obtained solution was concentrated, 10 ml of hexane was added, and recrystallization was performed at −20 ° C. to obtain compound (I-1g-C3) (2.50 g).
GC-MS: m / z 348.28 [M-15 + ]
Using the same reaction as in Example 75 and, if necessary, a method based on a known method, Example 76 (Compound (I-1g-B6)) to Example 82 (Compound (I-1q-BEBEB)) ) Was manufactured.
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-C000048
（実施例８３）化合物（Ｉ－１ｈ－Ｃ３）の製造 Example 83 Production of Compound (I-1h-C3)
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000049
　（化合物（Ｉ－１ｈ－Ｃ３）の製造）窒素雰囲気下、撹拌装置、温度計を備えた耐圧反応容器に、化合物（Ｅ－１７）（３．６１ｇ）、５％パラジウム炭素（５０％含水品）（０．１８ｇ）及びＴＨＦ１５ｍｌを加え、容器内に水素（０．５ＭＰａ）を加圧充填して室温で５時間攪拌した。この反応混合物をろ過し、さらに除去された固体をＴＨＦ１００ｍｌで洗浄した。得られた溶液を濃縮し、カラム（ＮＨ２シリカ、ヘキサン）を通過させた後に濃縮し、ヘキサン１０ｍｌを 加えて－２０℃で再結晶を行い、化合物（Ｉ－１ｈ－Ｃ３）（３．４４ｇ）を得た。
ＧＣ－ＭＳ：ｍ／ｚ　３５０．３０　[Ｍ－１５＋]
　実施例８３と同様の反応、および必要に応じて公知の方法に準拠した方法を用いて、実施例８４（化合物（Ｉ－１ｈ－Ｂ６））～実施例９０（化合物（Ｉ－１ｒ－ＢＥＢＥＢ））を製造した。 (Production of Compound (I-1h-C3)) Compound (E-17) (3.61 g), 5% palladium carbon (50% water-containing product) in a pressure-resistant reaction vessel equipped with a stirrer and a thermometer in a nitrogen atmosphere ) (0.18 g) and 15 ml of THF were added, hydrogen (0.5 MPa) was pressure-filled in the container, and the mixture was stirred at room temperature for 5 hours. The reaction mixture was filtered, and the removed solid was washed with 100 ml of THF. The obtained solution was concentrated, concentrated after passing through a column (NH 2 silica, hexane), recrystallized at −20 ° C. by adding 10 ml of hexane, and compound (I-1h-C3) (3.44 g) )
GC-MS: m / z 350.30 [M-15 + ]
Using a reaction similar to that in Example 83 and, if necessary, a method based on a known method, Example 84 (Compound (I-1h-B6)) to Example 90 (Compound (I-1r-BEBEB)) ) Was manufactured.
Figure JPOXMLDOC01-appb-C000050
Figure JPOXMLDOC01-appb-C000050
　上記、実施例１～９０で得られた化合物のいずれかを含有する液晶組成物について、測定した特性は以下の通りである。 Measured characteristics of the liquid crystal composition containing any of the compounds obtained in Examples 1 to 90 are as follows.
　ＶＨＲ：周波数６０Ｈｚ，印加電圧１Ｖの条件下で３３３Ｋにおける電圧保持率（％）を３段階評価した。 VHR: A voltage holding ratio (%) at 333 K was evaluated in three stages under the conditions of a frequency of 60 Hz and an applied voltage of 1 V.
　　Ａ：９８～１００％
　　Ｂ：９５～９８％
　　Ｃ：９５％以下
　耐光ＶＨＲ：液晶組成物に対して、厚さ０．５ｍｍのガラスを介して超高圧水銀ランプを用いて紫外線を１８０Ｊ／ｍ２照射する。紫外線照射後の液晶の電圧保持率を上述のＶＨＲ測定と同様の方法で測定する。但し、照射強度は３６６ｎｍで０．１Ｗ／ｍ２とした。評価は以下の３段階で行った。 A: 98-100%
B: 95-98%
C: 95% or less Light resistance VHR: The liquid crystal composition is irradiated with ultraviolet rays at 180 J / m 2 using an ultrahigh pressure mercury lamp through a glass having a thickness of 0.5 mm. The voltage holding ratio of the liquid crystal after ultraviolet irradiation is measured by the same method as the above VHR measurement. However, the irradiation intensity was 366 nm and 0.1 W / m 2 . Evaluation was performed in the following three stages.
　　Ａ：９０～１００％
　　Ｂ：７５～９０％
　　Ｃ：７５％以下
　相溶性：液晶組成物に、実施例１～９０で得られた化合物のいずれかを５００ｐｐｍ添加した際の溶解の様子を目視で３段階評価した。 A: 90-100%
B: 75-90%
C: 75% or less Compatibility: The state of dissolution when 500 ppm of any of the compounds obtained in Examples 1 to 90 was added to the liquid crystal composition was visually evaluated in three stages.
　　Ａ：すべて溶解する
　　Ｂ：わずかに溶解せず分離している
　　Ｃ：一部溶解せず分離している
　保存安定性：液晶組成物を－２０℃で１週間保存し、析出物の有無を目視で３段階評価した。 A: All dissolved B: Slightly dissolved and separated C: Partially dissolved and separated Storage stability: The liquid crystal composition was stored at −20 ° C. for 1 week and visually checked for the presence of precipitates It was evaluated in three stages.
　　Ａ：析出物なし
　　Ｂ：わずかに白濁が見られる
　　Ｃ：析出物が明らかに確認できる
（実施例９１）液晶組成物の調製－１
　以下の組成からなるホスト液晶組成物（Ｈ）を調製した。 A: No precipitate B: Slight cloudiness is observed C: Precipitate can be clearly confirmed (Example 91) Preparation of liquid crystal composition-1
A host liquid crystal composition (H) having the following composition was prepared.
Figure JPOXMLDOC01-appb-C000051
Figure JPOXMLDOC01-appb-C000051
　この母体液晶（Ｈ）に対し、実施例１で得られた化合物（Ｉ－１ａ－５）を５００ｐｐｍ添加した。
実施例中の組成例を、測定した特性は以下の通りである。 To this base liquid crystal (H), 500 ppm of the compound (I-1a-5) obtained in Example 1 was added.
The measured properties of the composition examples in the examples are as follows.
　ＶＨＲ：Ａ
　耐光ＶＨＲ：Ａ
　相溶性：Ａ
　保存安定性：Ａ　
以下、実施例９１と同様にして、実施例２～実施例９０で製造した化合物を用いて、実施例９２～実施例１８０の測定を行った結果を以下に示す。 VHR: A
Light resistant VHR: A
Compatibility: A
Storage stability: A
Hereinafter, in the same manner as in Example 91, the results of measurement in Examples 92 to 180 using the compounds produced in Examples 2 to 90 are shown below.
Figure JPOXMLDOC01-appb-T000052
Figure JPOXMLDOC01-appb-T000052
Figure JPOXMLDOC01-appb-T000053
Figure JPOXMLDOC01-appb-T000053
Figure JPOXMLDOC01-appb-T000054
Figure JPOXMLDOC01-appb-T000054
Figure JPOXMLDOC01-appb-T000055
Figure JPOXMLDOC01-appb-T000055
Figure JPOXMLDOC01-appb-T000056
Figure JPOXMLDOC01-appb-T000056
Figure JPOXMLDOC01-appb-T000057
Figure JPOXMLDOC01-appb-T000057
（実施例１８１）化合物（Ｉ－１ｕ－Ｂ３）の製造 Example 181 Production of Compound (I-1u-B3)
Figure JPOXMLDOC01-appb-C000058
Figure JPOXMLDOC01-appb-C000058
　（化合物（Ｉ－１ｕ－Ｂ３）の製造）窒素雰囲気下、撹拌装置、温度計を備えた反応容器に、化合物（Ｅ－２）（１１．４ｇ）、化合物（Ｅ－１８）（８．２ｇ）、Ｎ，Ｎ－ジメチルアミノピリジン（ＤＭＡＰ）０．３０ｇ、ジクロロメタン８０ｍｌを加え、５～１０℃で１０分間攪拌した。攪拌下、Ｎ，Ｎ－ジイソプロピルカルボジイミド（ＤＩＣ）７．９ｇを５～１０℃を保ちながら滴下し、続いて２５度まで昇温し７時間攪拌した。この反応混合物に対して水２ｍｌを加えて攪拌した後、析出した固体を除去し、得られた溶液を濃縮した。得られた固体をヘキサン２０ｍｌに溶かし、ＮＨ２シリカ２０ｇを充填したカラム上に加え、さらにヘキサン１００ｍｌを流して通過させた。得られた溶液の溶媒をおおむね留去した後、ヘキサン／トルエンを用いて－２０℃で再結晶を行った。析出した固体をろ過、乾燥することで化合物（Ｉ－１ｕ－Ｂ３）を１３．６ｇ得た。
ＧＣ－ＭＳ：ｍ／ｚ　３８９．２６　[Ｍ－１５＋]　
実施例１８１と同様の反応、および必要に応じて公知の方法に準拠した方法を用いて、実施例１８２（化合物（Ｉ－１ｕ－Ｂ６））～実施例１８７（化合物（Ｉ－１ｕ－Ｔ３））を製造した。 (Production of Compound (I-1u-B3)) Under a nitrogen atmosphere, in a reaction vessel equipped with a stirrer and a thermometer, compound (E-2) (11.4 g), compound (E-18) (8.2 g) ), 0.30 g of N, N-dimethylaminopyridine (DMAP) and 80 ml of dichloromethane were added, and the mixture was stirred at 5 to 10 ° C. for 10 minutes. Under stirring, 7.9 g of N, N-diisopropylcarbodiimide (DIC) was added dropwise while maintaining the temperature at 5 to 10 ° C., followed by heating to 25 ° C. and stirring for 7 hours. After 2 ml of water was added to the reaction mixture and stirred, the precipitated solid was removed, and the resulting solution was concentrated. The obtained solid was dissolved in 20 ml of hexane, added onto a column packed with 20 g of NH 2 silica, and further passed through 100 ml of hexane. After the solvent of the obtained solution was distilled off, recrystallization was performed at −20 ° C. using hexane / toluene. The precipitated solid was filtered and dried to obtain 13.6 g of Compound (I-1u-B3).
GC-MS: m / z 389.26 [M-15 + ]
Using a reaction similar to that in Example 181 and, if necessary, a method based on a known method, Example 182 (Compound (I-1u-B6)) to Example 187 (Compound (I-1u-T3)) ) Was manufactured.
Figure JPOXMLDOC01-appb-C000059
Figure JPOXMLDOC01-appb-C000059
（実施例１８８）化合物（Ｉ－１ｖ－８）の製造 Example 188 Production of compound (I-1v-8)
Figure JPOXMLDOC01-appb-C000060
Figure JPOXMLDOC01-appb-C000060
　（化合物（Ｉ－１ｖ－８）の製造）窒素雰囲気下、撹拌装置、滴下ろうと（モレキュラーシーブ４Ａペレット３．５ｇを中に詰めてある）、冷却管、オイルバス、温度計を備えた反応容器に、化合物（Ｅ－２）（２．２２ｇ）、化合物（Ｅ－１９）（１．０ｇ）、酸化ジブチルすず（０．１１ｇ）、キシレン１５ｍｌを加え、５時間加熱還流しながら攪拌した。この反応混合物を室温まで冷却し、ヘキサン１５ｍｌを加えた。この反応混合物を、ＮＨ２シリカ６ｇを充填したカラム上に加え、さらにヘキサン／トルエン（体積比１：１、１００ｍｌ）を流して通過させた。得られた溶液の溶媒を留去した後、ヘキサン／酢酸エチルを用いて－２０℃で再結晶を行った。析出した固体をろ過、乾燥することで化合物（Ｉ－１ｖ－８）を１．６８ｇ得た。
ＧＣ－ＭＳ：ｍ／ｚ　６３７．４７　[Ｍ－１５＋]
相転移：Ｃｒｙ　７６　Ｉｓｏ
（実施例１８９）化合物（Ｉ－１ｖ－Ｂ）の製造 (Production of Compound (I-1v-8)) A reaction vessel equipped with a stirrer, a dropping funnel (containing 3.5 g of molecular sieve 4A pellets), a cooling tube, an oil bath, and a thermometer in a nitrogen atmosphere. Compound (E-2) (2.22 g), compound (E-19) (1.0 g), dibutyltin oxide (0.11 g), and 15 ml of xylene were added to the mixture, and the mixture was stirred for 5 hours while heating under reflux. The reaction mixture was cooled to room temperature and 15 ml of hexane was added. The reaction mixture was added onto a column packed with 6 g of NH 2 silica, and further passed through hexane / toluene (volume ratio 1: 1, 100 ml). After the solvent of the obtained solution was distilled off, recrystallization was performed at −20 ° C. using hexane / ethyl acetate. The precipitated solid was filtered and dried to obtain 1.68 g of compound (I-1v-8).
GC-MS: m / z 637.47 [M-15 + ]
Phase transition: Cry 76 Iso
Example 189 Production of Compound (I-1v-B)
Figure JPOXMLDOC01-appb-C000061
Figure JPOXMLDOC01-appb-C000061
　（化合物（Ｉ－１ｖ－Ｂ）の製造）窒素雰囲気下、撹拌装置、滴下ろうと（モレキュラーシーブ４Ａペレット１０ｇを中に詰めてある）、冷却管、オイルバス、温度計を備えた反応容器に、化合物（Ｅ－２）（８．２９ｇ）、化合物（Ｅ－２０）（３．１５ｇ）、酸化ジブチルすず（０．４０ｇ）、キシレン３５ｍｌを加え、５時間加熱還流しながら攪拌した。この反応混合物を室温まで冷却し、ヘキサン４０ｍｌを加えた。この反応混合物を、ＮＨ２シリカ６ｇを充填したカラム上に加え、さらにヘキサン／トルエン（体積比１：１、２００ｍｌ）を流して通過させた。得られた溶液の溶媒を留去した後、ＴＨＦを用いて－２０℃で再結晶を行った。析出した固体をろ過、乾燥することで化合物（Ｉ－１ｖ－Ｂ）を６．３ｇ得た。
ＧＣ－ＭＳ：ｍ／ｚ　６０１．３７　[Ｍ－１５＋]
相転移：Ｃｒｙ　１７０．４　Ｉｓｏ
（実施例１９０）化合物（Ｉ－１ｖ－ＭＢ）の製造 (Production of compound (I-1v-B)) In a reaction vessel equipped with a stirrer, a dropping funnel (10 g of molecular sieve 4A pellets), a condenser, an oil bath, and a thermometer in a nitrogen atmosphere, Compound (E-2) (8.29 g), compound (E-20) (3.15 g), dibutyltin oxide (0.40 g) and xylene 35 ml were added, and the mixture was stirred for 5 hours while heating under reflux. The reaction mixture was cooled to room temperature and 40 ml of hexane was added. This reaction mixture was added onto a column packed with 6 g of NH 2 silica, and further passed through hexane / toluene (volume ratio 1: 1, 200 ml). After the solvent of the obtained solution was distilled off, recrystallization was performed at −20 ° C. using THF. The precipitated solid was filtered and dried to obtain 6.3 g of Compound (I-1v-B).
GC-MS: m / z 601.37 [M-15 + ]
Phase transition: Cry 170.4 Iso
Example 190 Production of Compound (I-1v-MB)
Figure JPOXMLDOC01-appb-C000062
Figure JPOXMLDOC01-appb-C000062
　（化合物（Ｅ－２２）の製造）窒素雰囲気下、撹拌装置、温度計、冷却管、ディーンスターク管を備えた反応容器に、ｐ－トルエンスルホン酸一水和物（６４．４ｇ）及びトルエン８００ｍｌを加え、２０分間加熱還流し、生じた水を除去した。この混合物を室温まで冷却した後、ＴＭＰ（５１．０ｇ）、ＤＭＦ３０ｍｌ及び化合物（Ｅ－２１）（３８．８ｇ）を加え、４時間加熱還流し、生じた水を除去した。この反応混合物を室温まで冷却した後、１．０Ｍ水酸化ナトリウム水溶液４００ｍｌを加えて攪拌し、有機層を分けとり、水１００ｍｌ、飽和食塩水１００ｍｌで洗浄した。得られた有機層を濃縮し、得られた固体を再結晶（トルエン）することで、化合物（Ｅ－２２）（６０．８ｇ）を得た。 (Production of Compound (E-22)) In a reaction vessel equipped with a stirrer, a thermometer, a condenser tube, and a Dean-Stark tube under a nitrogen atmosphere, p-toluenesulfonic acid monohydrate (64.4 g) and 800 ml of toluene were added. And heated to reflux for 20 minutes to remove the resulting water. The mixture was cooled to room temperature, TMP (51.0 g), DMF 30 ml and compound (E-21) (38.8 g) were added, and the mixture was heated to reflux for 4 hours to remove the generated water. After cooling the reaction mixture to room temperature, 400 ml of 1.0 M aqueous sodium hydroxide solution was added and stirred, and the organic layer was separated and washed with 100 ml of water and 100 ml of saturated brine. The obtained organic layer was concentrated, and the obtained solid was recrystallized (toluene) to obtain Compound (E-22) (60.8 g).
　（化合物（Ｉ－１ｖ－ＭＢ）の製造）窒素雰囲気下、撹拌装置、滴下ろうと（モレキュラーシーブ４Ａペレット４０ｇを中に詰めてある）、冷却管、オイルバス、温度計を備えた反応容器に、化合物（Ｅ－２２）（３４．３ｇ）、化合物（Ｅ－２０）（１２．２４ｇ）、酸化ジブチルすず（１．５３ｇ）、キシレン１８０ｍｌを加え、５時間加熱還流しながら攪拌した。この反応混合物を室温まで冷却し、トルエン１５０ｍｌを加えた。この反応混合物を、ＮＨ２シリカ８０ｇを充填したカラム上に加え、さらにトルエン１５０ｍｌを流して通過させた。得られた溶液の溶媒を留去した後、ヘキサンとＴＨＦの混合溶媒（１：１、８０ｍｌ）を用いて－２０℃で再結晶を行った。析出した固体をろ過、乾燥することで化合物（Ｉ－１ｖ－ＭＢ）を２９．５ｇ得た。
ＧＣ－ＭＳ：ｍ／ｚ　６２９．４０　[Ｍ－１５＋]
相転移：Ｃｒｙ　１４８　Ｉｓｏ
1H-NMR (400MHz, CDCl3)δ: 0.96(s,6H), 1.20(s,12H), 1.23(S, 12H), 1.63(s,4H), 1.82(s,4H), 3.75(s,8H), 4.47(s,4H), 8.11(s,4H)
　実施例１９０と同様の反応、および必要に応じて公知の方法に準拠した方法を用いて、実施例１９１（化合物（Ｉ－１ｖ－ＥｔＢ））～実施例１９７（化合物（Ｉ－１ｖ－ＥｔＢＦ））を製造した。 (Production of Compound (I-1v-MB)) Under a nitrogen atmosphere, in a reaction vessel equipped with a stirring device, a dropping funnel (40 g of molecular sieve 4A pellets packed therein), a condenser, an oil bath, and a thermometer. Compound (E-22) (34.3 g), compound (E-20) (12.24 g), dibutyltin oxide (1.53 g), and 180 ml of xylene were added and stirred for 5 hours while heating under reflux. The reaction mixture was cooled to room temperature and 150 ml of toluene was added. This reaction mixture was added onto a column packed with 80 g of NH 2 silica, and further 150 ml of toluene was passed therethrough. After the solvent of the obtained solution was distilled off, recrystallization was performed at −20 ° C. using a mixed solvent of hexane and THF (1: 1, 80 ml). The precipitated solid was filtered and dried to obtain 29.5 g of Compound (I-1v-MB).
GC-MS: m / z 629.40 [M-15 + ]
Phase transition: Cry 148 Iso
1 H-NMR (400MHz, CDCl 3 ) δ: 0.96 (s, 6H), 1.20 (s, 12H), 1.23 (S, 12H), 1.63 (s, 4H), 1.82 (s, 4H), 3.75 (s , 8H), 4.47 (s, 4H), 8.11 (s, 4H)
Using a reaction similar to that of Example 190 and, if necessary, a method based on a known method, Example 191 (Compound (I-1v-EtB)) to Example 197 (Compound (I-1v-EtBF)) ) Was manufactured.
Figure JPOXMLDOC01-appb-C000063
Figure JPOXMLDOC01-appb-C000063
　上記実施例１８１～１９７で製造した化合物を用いて、実施例９１と同様にして実施例１９８～２１４の液晶組成物を調製し、測定を行った結果を以下に示す。 The liquid crystal compositions of Examples 198 to 214 were prepared in the same manner as in Example 91 using the compounds produced in Examples 181 to 197, and the measurement results are shown below.
Figure JPOXMLDOC01-appb-T000064
Figure JPOXMLDOC01-appb-T000064
（比較例１）
　比較例として、母体液晶（Ｈ）に対し、特にさらなる化合物を添加することなく特性を測定した結果は以下の通りである。 (Comparative Example 1)
As a comparative example, the results of measuring the characteristics of the base liquid crystal (H) without particularly adding additional compounds are as follows.
　ＶＨＲ：Ａ
　耐光ＶＨＲ：Ｃ
　保存安定性：Ａ
この結果から、本願発明の化合物は、液晶組成物の保存安定性を損なうことなく、液晶組成物の光による劣化を防止する効果があることが分かる。
（比較例２）
　母体液晶（Ｈ）に対し、化合物（Ｒ－１）を５００ｐｐｍ添加し、測定を測定した結果は以下の通りである。 VHR: A
Light resistant VHR: C
Storage stability: A
From this result, it can be seen that the compound of the present invention has an effect of preventing deterioration of the liquid crystal composition due to light without impairing the storage stability of the liquid crystal composition.
(Comparative Example 2)
500 ppm of compound (R-1) was added to the base liquid crystal (H), and the measurement results were as follows.
Figure JPOXMLDOC01-appb-C000065
Figure JPOXMLDOC01-appb-C000065
　ＶＨＲ：Ａ
　耐光ＶＨＲ：Ａ
　相溶性：Ｂ
　保存安定性：Ｃ
（比較例３，４）
以下、比較例２と同様にして、比較例３，４の測定を行った結果を以下に示す。 VHR: A
Light resistant VHR: A
Compatibility: B
Storage stability: C
(Comparative Examples 3 and 4)
Hereinafter, the results of measurement in Comparative Examples 3 and 4 in the same manner as in Comparative Example 2 are shown below.
Figure JPOXMLDOC01-appb-C000066
Figure JPOXMLDOC01-appb-C000066
Figure JPOXMLDOC01-appb-T000067
Figure JPOXMLDOC01-appb-T000067
　この結果から、本願発明の化合物は、液晶組成物の保存安定性を損なうことなく、液晶組成物との相溶性が高く、液晶組成物の光による劣化を防止する効果があることが分かる。 From this result, it can be seen that the compound of the present invention has high compatibility with the liquid crystal composition without impairing the storage stability of the liquid crystal composition, and has an effect of preventing deterioration of the liquid crystal composition due to light.

Claims (7)

  1. 一般式（Ｉ）
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｒａ０は水素原子、水酸基、炭素数１～１２のアルキル基、又は炭素数３～１２のアルケニル基を表し、
    Ｒａ１，Ｒａ２，Ｒａ３及びＲａ４はそれぞれ独立して炭素数１～６のアルキル基を表し、あるいはＲａ１とＲａ２，及び／又はＲａ３とＲａ４は一緒になって環構造を形成していてもよく、
    Ｒａ５及びＲａ６はそれぞれ独立して水素原子又は炭素数１～６のアルキル基を表し、
    ｎは０又は１を表し、
    ｔは１から４を表し、
    Ｕは環構造を形成する２×ｔ価の有機基を表し、Ｒａ０、Ｒａ１、Ｒａ２、Ｒａ３、Ｒａ４、Ｒａ５、Ｒａ６及びｎが複数存在する場合、それらは同一であっても異なっていてもよい。）
    で表される化合物。     Formula (I)
    Figure JPOXMLDOC01-appb-C000001
     (Wherein R a0 represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or an alkenyl group having 3 to 12 carbon atoms,
    R a1 , R a2 , R a3 and R a4 each independently represents an alkyl group having 1 to 6 carbon atoms, or R a1 and R a2 and / or R a3 and R a4 together form a ring structure. May be formed,
    R a5 and R a6 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
    n represents 0 or 1,
    t represents 1 to 4;
    U represents a 2 × t-valent organic group forming a ring structure, and when a plurality of R a0 , R a1 , R a2 , R a3 , R a4 , R a5 , R a6 and n are present, they are the same. Or different. )
    A compound represented by
  2. 　一般式（Ｉ）において、Ｕが一般式（Ｉ－ａ）
    Figure JPOXMLDOC01-appb-C000002
     （式中、破線は各々酸素原子への結合を表し、Ｒａ７及びＲａ８はそれぞれ独立して水素原子または１価の有機基を表し、あるいはＲａ７及びＲａ８は一緒になって環構造を形成していてもよく、ｍは０または１を表す。）で表される、請求項１に記載の化合物。     In general formula (I), U represents general formula (Ia)
    Figure JPOXMLDOC01-appb-C000002
     (In the formula, each broken line represents a bond to an oxygen atom, R a7 and R a8 each independently represents a hydrogen atom or a monovalent organic group, or R a7 and R a8 together form a ring structure. The compound according to claim 1, which may be formed, and m represents 0 or 1.
  3. 　一般式（Ｉ）において、ｔが２を表し、Ｕが一般式（Ｉ－ｂ）
    Figure JPOXMLDOC01-appb-C000003
     （式中、破線は各々酸素原子への結合を表しｌ及びｏはそれぞれ独立に０または１を表す。）
    又は一般式（Ｉ－ｅ）
    Figure JPOXMLDOC01-appb-C000004
     （式中、破線は各々酸素原子への結合を表し、ｌｅ及びｏｅはそれぞれ独立して０又は１を表し、Ｒｅ１及びＲｅ２はそれぞれ独立して水素原子または１価の有機基を表し、Ｖｅは２価の有機基を表す。）
    で表される、請求項１又は２に記載の化合物。     In the general formula (I), t represents 2 and U represents the general formula (Ib)
    Figure JPOXMLDOC01-appb-C000003
     (In the formula, each broken line represents a bond to an oxygen atom, and l and o each independently represents 0 or 1.)
    Or general formula (Ie)
    Figure JPOXMLDOC01-appb-C000004
     (In the formula, each broken line represents a bond to an oxygen atom, le and oe each independently represent 0 or 1, R e1 and R e2 each independently represent a hydrogen atom or a monovalent organic group, V e represents a divalent organic group.)
    The compound of Claim 1 or 2 represented by these.
  4. 　　一般式（Ｉ－ａ）において、Ｒａ７及び／又はＲａ８が一般式（Ｉ－ｃ）
    Figure JPOXMLDOC01-appb-C000005
     （式中、Ｓｐａ１及びＳｐａ２はそれぞれ独立に単結合又は炭素原子数１から１２のアルキレン基を表すが、アルキル基中に存在する１個の－ＣＨ２－又は隣接していない２個以上の－ＣＨ２－は－Ｏ－、－Ｓ－、－ＣＯＯ－、－ＯＣＯ－、－ＣＯ－、－ＣＨ＝ＣＨ－又は－Ｃ≡Ｃ－により置き換えられても良く、
    Ａａ１及びＡａ２はそれぞれ独立に
    （ａ）　１，４－シクロヘキシレン基（この基中に存在する１個の－ＣＨ２－又は隣接していない２個以上の－ＣＨ２－は－Ｏ－に置き換えられてもよい。）
    （ｂ）　１，４－フェニレン基（この基中に存在する１個の－ＣＨ＝又は隣接していない２個以上の－ＣＨ＝は－Ｎ＝に置き換えられてもよい。）及び
    （ｃ）　ナフタレン－２，６－ジイル基、１，２，３，４－テトラヒドロナフタレン－２，６－ジイル基又はデカヒドロナフタレン－２，６－ジイル基（ナフタレン－２，６－ジイル基又は１，２，３，４－テトラヒドロナフタレン－２，６－ジイル基中に存在する１個の－ＣＨ＝又は隣接していない２個以上の－ＣＨ＝は－Ｎ＝に置き換えられても良い。）
    からなる群より選ばれる基を表し、上記の基（ａ）、基（ｂ）及び基（ｃ）はそれぞれ独立してシアノ基、フッ素原子、塩素原子、メチル基又はメトキシ基で置換されていても良く、分子内にＳｐａ１、Ｓｐａ２、Ａａ１及びＡａ２が複数存在する場合にはそれらは同一であっても異なっていても良く、
    Ｒａ９は水素原子または炭素原子数１から１２のアルキル基を表すが、アルキル基中に存在する１個の－ＣＨ２－又は隣接していない２個以上の－ＣＨ２－は－Ｏ－、－Ｓ－、－ＣＯＯ－、－ＯＣＯ－、－ＣＯ－、－ＣＨ＝ＣＨ－又は－Ｃ≡Ｃ－により置き換えられても良く、あるいはＲａ９は一般式（Ｉ－ｄ）
    Figure JPOXMLDOC01-appb-C000006
     （式中、Ｒｄ０、Ｒｄ１，Ｒｄ２，Ｒｄ３、Ｒｄ４、Ｒｄ５及びＲｄ６は一般式（Ｉ）におけるＲａ０、Ｒａ１，Ｒａ２，Ｒａ３、Ｒａ４、Ｒａ５及びＲａ６と同じ意味を表し、Ｒａ１０は水素原子または１価の有機基を表し、Ｓｐａ３はＳｐａ１又はＳｐａ２と同じ意味を表し、ｓ及びｖはそれぞれ独立に０又は１を表す。）で表されても良く、
    ｐ及びｑはそれぞれ独立に０、１又は２を表す。）
    である請求項１又は２に記載の化合物。     In the general formula (Ia), R a7 and / or R a8 represents the general formula (Ic)
    Figure JPOXMLDOC01-appb-C000005
     (Wherein Sp a1 and Sp a2 each independently represents a single bond or an alkylene group having 1 to 12 carbon atoms, but one —CH 2 — present in the alkyl group or two or more not adjacent to each other) —CH 2 — may be replaced by —O—, —S—, —COO—, —OCO—, —CO—, —CH═CH— or —C≡C—,
    A a1 and A a2 each independently (a) 1,4-cyclohexylene group (this is present in the group one -CH 2 - or nonadjacent two or more -CH 2 - is -O- May be replaced by.)
    (B) a 1,4-phenylene group (one —CH═ present in the group or two or more non-adjacent —CH═ may be replaced by —N═) and (c) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or 1,2 , 3,4-tetrahydronaphthalene-2,6-diyl group, one —CH═ or two or more non-adjacent —CH═ may be replaced by —N═.
    The group (a), the group (b) and the group (c) are each independently substituted with a cyano group, a fluorine atom, a chlorine atom, a methyl group or a methoxy group. When there are a plurality of Sp a1 , Sp a2 , A a1 and A a2 in the molecule, they may be the same or different,
    R a9 each represents a hydrogen atom or an alkyl group having a carbon atom number of 1 to 12, one -CH 2 present in the alkyl group - or nonadjacent two or more -CH 2 - is -O-, May be replaced by —S—, —COO—, —OCO—, —CO—, —CH═CH— or —C≡C—, or R a9 may have the general formula ( Id )
    Figure JPOXMLDOC01-appb-C000006
     (In the formula, R d0 , R d1 , R d2 , R d3 , R d4 , R d5 and R d6 are R a0 , R a1 , R a2 , R a3 , R a4 , R a5 and R in the general formula (I)). a6 represents the same meaning as, R a10 represents a hydrogen atom or a monovalent organic group, Sp a3 has the same meaning as Sp a1 or Sp a2, s and v each independently represent 0 or 1.) in May be represented,
    p and q each independently represents 0, 1 or 2. )
    The compound according to claim 1 or 2.
  5. 　請求項１から４のいずれか一項に記載の化合物を一種又は二種以上含有する組成物。 A composition containing one or more compounds according to any one of claims 1 to 4.
  6. 　室温において液晶相を有する請求項５記載の組成物。 The composition according to claim 5, which has a liquid crystal phase at room temperature.
  7. 　請求項５又は６記載の組成物を使用した表示素子。 A display element using the composition according to claim 5 or 6.
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