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

Abstract

The present invention provides a compound represented by general formula (I) (wherein R^a0 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; R^a1, R^a2, R^a3 and R^a4 independently represent an alkyl group having 1 to 8 carbon atoms, or R^a1 and R^a2 and/or R^a3 and R^a4 may together form a cyclic structure; R^a5 and R^a6 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

Stabilizer compound, liquid crystal composition, and display element

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. 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.

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.

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).

JP 2006-37054 A JP 2008-144135 A

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.

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)

(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.

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.

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)

(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.

When t in the general formula (I) represents 1, R ^a8 represents the general formula (Ic)

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—.

R ^a9 represents the general formula ( ^Id )

(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.

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.

When t in general formula (I) represents 2, U represents general formula (Ib) or general formula (Ie)

(In the formula, each broken line represents a bond to an oxygen atom, and l and o each independently represents 0 or 1.)

(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.

The general formula (Ie) is preferably a structure represented by the general formula (Ie1).

(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.

The general formula (Ie) is preferably a structure represented by the general formula (Ie2).

(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)

(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.

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).

( ^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.

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.

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).

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.

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.

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.

The compound represented by the general formula (I) is preferably a compound represented by the general formula (I-1).

(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.

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)

(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.

As the compound represented by the general formula (I-1), the following general formulas (I-1a) to (I-1v) are particularly preferable.

^{(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.

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.

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.

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.

(Production method 1) Method for producing compound represented by general formula (I)

(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.

(Production method 2) Method for producing a compound represented by the general formula (I-1a), (I-1b), (I-1k) or (I-1l)

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.

(Production method 3) Method for producing a compound represented by the general formula (I-1c), (I-1j), (I-1m) or (I-1t)

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)

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.

(Production method 5) Method for producing a compound represented by the general formula (I-1e) or (I-1o)

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.

(Production method 6) Production method of compound represented by general formula (I-1f) or (I-1p)

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.

(Production method 7) Method for producing a compound represented by the general formula (I-1g), (I-1q), (I-1h) or (I-1r)

(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.

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.

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.

(Production method 8) Method for producing compound represented by general formula (I-1u) or (I-1v)

(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.).

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.

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.

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)

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.

Example 7 Production of Compound (I-1k-8)

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.

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.

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.

Example 8 Production of Compound (I-1b-C3)

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.

Example 25 Production of Compound (I-1c-B3)

(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).

(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.

Example 40 Production of Compound (I-1d-B3)

(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.

Example 55 Production of Compound (I-1e-C3)

(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).

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 65 Production of Compound (I-1f-C3)

(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.

Example 75 Production of Compound (I-1g-C3)

(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).

(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).

(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).

(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.

Example 83 Production of Compound (I-1h-C3)

(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.

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.

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% 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: 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: 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.

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
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.

Example 181 Production of Compound (I-1u-B3)

(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.

Example 188 Production of compound (I-1v-8)

(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)

(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)

(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).

(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.

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.

(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
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)
Hereinafter, the results of measurement in Comparative Examples 3 and 4 in the same manner as in Comparative Example 2 are shown below.

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. Formula (I)
   

   

   (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. In general formula (I), U represents general formula (Ia)
   

   

   (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. In the general formula (I), t represents 2 and U represents the general formula (Ib)
   

   

   (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)
   

   

   (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. In the general formula (Ia), R ^a7 and / or R ^a8 represents the general formula (Ic)
   

   

   (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 )
   

   

   (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. A composition containing one or more compounds according to any one of claims 1 to 4.
6. The composition according to claim 5, which has a liquid crystal phase at room temperature.
7. A display element using the composition according to claim 5 or 6.