JP6809410B2 - Stabilizer compounds, liquid crystal compositions and display devices - Google Patents

Description

The present invention relates to stabilizer compounds.

Liquid crystal display elements have come to be used in various measuring instruments such as clocks and calculators, automobile panels, word processors, electronic organizers, printers, computers, televisions, clocks, advertisement display boards and the like. Typical liquid crystal display methods are TN (twisted nematic) type, STN (super twisted nematic) type, VA (vertical orientation) type using TFT (thin film transistor), and IPS (in-plane). There are switching) type and FFS (fringe field switching) type. The main characteristics required of the liquid crystal composition are (1) stability to external stimuli such as moisture, air, heat, and light, and (2) the liquid crystal phase in the widest possible temperature range centered on room temperature. There are four things that are shown, (3) low viscosity, and (4) low drive voltage. For each display element, dielectric anisotropy (Δε) and refractive index anisotropy (Δn) can be mentioned. ) Etc. are generally set in the liquid crystal composition to be composed of several to several tens of kinds of compounds.

Among the characteristics of the above liquid crystal composition, for Δε, a composition having a positive value and a composition having a negative value are used properly. Among these, as a display method using a liquid crystal material in which Δε shows a positive value, TN type, STN type, IPS type, FFS type and the like can be mentioned. Examples of the display method using a liquid crystal material in which Δε shows a negative value include ECB type, VA type, and FFS type. On the other hand, all drive methods are required to have low voltage drive, high-speed response, and a wide operating temperature range. That is, a large absolute value of Δε, a small viscosity (η), and a high nematic phase-isotropic liquid phase transition temperature (T _ni ) are 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 a liquid crystal display element is applied to a television or the like, high-speed response is important, so a liquid crystal composition having a small γ ₁ is required.

In addition to the requirements for the physical characteristics of these liquid crystal compositions, further improvement in stability to external stimuli (1) is required (see Patent Document 1).

JP 2006-37054 Japanese Patent Application Laid-Open No. 2008-144135

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, to have 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 which can be easily produced.

As a result of diligent studies to solve the above problems, the inventor of the present application has completed the invention of the present application.
That is, the present invention has the general formula (I).

(In the formula, ^Ra0 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 represent 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 and represents
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. May be different. )
The compound represented by the above is provided, and a liquid crystal composition and a display element containing the compound are also provided.

The stabilizer compound according to the present invention prevents deterioration of the liquid crystal composition due to light, has high compatibility with the liquid crystal composition, and can be easily produced without impairing the storage stability of the liquid crystal composition. By using a liquid crystal composition using the stabilizer compound according to the present invention, it is possible to provide a high-speed response liquid crystal display element.

In the general formula (I), ^Ra0 is preferably a hydrogen atom or a hydroxyl group in order to enhance the photodegradation prevention ability, and particularly preferably a hydrogen atom. Further, in order to enhance the 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. Further, in order to facilitate the removal of polar impurities mixed in during production, it is preferable that Ra ¹ and Ra ² and / or Ra ³ and Ra ⁴ are 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 from the viewpoint of ease of production.
n is preferably 1.
t is preferably 1 or 2 in order to enhance the storage stability of the liquid crystal composition, and particularly preferably 1. Further, in order to enhance the photodegradation prevention ability, the number of hindered amine structures per unit weight increases, so that the number is preferably 3 or 4.
U is the general formula (Ia)

(In the equation, the broken ^lines represent bonds to oxygen atoms, respectively, R ^a7 and R ^a8 each independently represent a hydrogen atom or monovalent organic group, or R ^a7 and R ^a8 together form a ring structure. It may be formed, and m is preferably a structure represented by 0 or 1) in order to enhance the storage stability of the liquid crystal composition. Here, ^Ra7 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms because it is easy to have a linear structure similar to that of a general liquid crystal compound, and as a result, the compatibility with the liquid crystal composition is enhanced. Is particularly preferable, and m is particularly preferably 1.

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

The structure represented by is particularly preferable in order to enhance compatibility with the liquid crystal composition, and Spa ¹ and Spa ² 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-, and it is particularly preferable that it is a single bond. A ^a1 and A ^a2 are independently (a) 1,4-cyclohexylene groups (one -CH ₂ − present in this group or two or more non-adjacent −CH ₂ − are −O− May be replaced with.)
(B) 1,4-phenylene group (one -CH = existing in this group or two or more -CH = not adjacent to each other may be replaced with -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 with -N =).
A group selected from the group consisting of is preferable in order to enhance the storage stability of the liquid crystal composition, and the above groups (a), (b) and group (c) are independently cyano groups and fluorine, respectively. It is more preferably 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 an alkyl group having a hydrogen atom or 1 to 6 carbon atoms, and one − in the alkyl group. CH ₂ − or two or more non-adjacent −CH ₂ − are replaced by −O−, −S−, −COO−, −OCO−, −CO−, −CH = CH− or −C≡C−. It may be, and is preferably replaced by −O− or −CH = CH−.

Further, R ^a9 is a 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). It has the same meaning as ^a6 , R ^a10 represents a hydrogen atom or a monovalent organic group, Sp ^a3 has the same meaning as Sp ^a1 or Sp ^a2, and s and v independently represent 0 or 1).
The structure represented by is preferable in order to enhance the photodegradation prevention ability. R ^d0 is preferably a hydrogen atom or a hydroxyl group in order to enhance the photodegradation prevention ability, and is particularly preferably a hydrogen atom from the viewpoint of ease of production. Further, in order to enhance the 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.
It is preferable that R ^d1 , R ^d2 , R ^d3 and R ^d4 are independently alkyl groups having 1 to 4 carbon atoms, and particularly preferably methyl groups. Further, in order to facilitate the removal of polar impurities mixed in during production, it is preferable that R ^d1 and R ^d2 , and / or R ^d3 and R ^d4 are combined to form a ring structure.
It is preferable that R ^d5 and R ^d6 are independently hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, and it is particularly preferable that they are hydrogen atoms from the viewpoint of ease of production.

Sp ^a3 is preferably a single bond or an alkylene group having 1 to 8 carbon atoms, respectively, and is preferably 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 is particularly preferably a single bond.

It is particularly preferable that R ^a10 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
It is preferable that s and v are 1 respectively.
It is preferable that p and q are 0 or 1, respectively.

When t in the general formula (I) represents 2, U is the general formula (Ib) or the general formula (I-e).

(In the equation, the broken line represents the bond to the oxygen atom, and l and o independently represent 0 or 1, respectively.)

(In the formula, the broken lines each represent a bond to an oxygen atom, le and oe independently represent 0 or 1, respectively, and R ^e1 and R ^e2 independently represent a hydrogen atom or a monovalent organic group. V ^e represents a divalent organic group.)
The structure represented by is preferable in order to enhance the photodegradation prevention ability. It is preferable that each of l, o, le and oe is 1 in order to enhance the storage stability of the liquid crystal composition. R ^e1 and R ^e2 are preferably hydrogen atoms or alkyl groups having 1 to 10 carbon atoms, preferably hydrogen atoms or alkyl groups having 1 to 5 carbon atoms, and hydrogen atoms or 1 to 5 carbon atoms. It is preferably an alkyl group of 3, and more preferably a hydrogen atom, a methyl group, or an ethyl group.

The general formula (I-e) preferably has a structure represented by the general formula (I-e1).

(Wherein, a broken line each represent a bond to an oxygen atom, le and oe is 0 or 1 each independently, R ^e1 and R ^e2 each independently represents 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.

Further, the general formula (I-e) preferably has a structure represented by the general formula (I-e2).

(Wherein, a broken line each represent a bond to an oxygen atom, le and oe is 0 or 1 each independently, R ^e1 and R ^e2 each independently represents a hydrogen atom or a monovalent organic group, Sp ^ae1 and Sp ^ae2 independently represent the same meaning as Sp ^a1 in the general formula (Ic), A ^ad1 has the same meaning as A ^a1 in the general formula (Ic), and pe is 1 or 2 When there are a plurality of Sp ^ae1 , Sp ^{ae 2} and A ^{ae 1} , they may be the same or different.)
When t in the general formula (I) represents 3 or 4, U is the general formula (If).

(In the formula, the broken line represents the bond to the oxygen atom, lf represents 0 or 1, R ^f7 represents the hydrogen atom or the monovalent organic group, and Sp ^af1 and Sp ^{af 2} are independent general formulas (I). ^-C ) represents the same meaning as Sp ^a1 , A ^af1 represents the same meaning as A ^a1 in the general formula (I-c), pf represents 0, 1 or 2, tf represents 3 or 4, and V ^f each represents a trivalent or tetravalent radical, the valence of the ^{V f} is the same number as the number represented by ^tf, if Sp ^{af1, Sp af2} and ^{a af1} there are a plurality, even they are the same It may be different.)
The structure represented by is preferable in order to enhance the photodegradation prevention ability. 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. It is preferably a hydrogen atom, a methyl group, or an ethyl group.

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, and the hydrocarbon. two or more -CH ₂ that is not one or adjacent present in carbon atoms in the group - is 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 replaced by CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF-, -OCF _2- , -CF ₂ O-, or -C≡C-. It is more preferable that V ^f is a group selected from the groups represented by the formulas (V3-1) to (V3-12).

(In the ^{formula, R v31} and ^{R v32} represents a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 10 carbon atoms, one existing in the alkyl group or two or more -CH ₂ - are each independently Then, it may be substituted with −O−, −S−, −CH = CH−, −C≡C−, −CO−O−, −O−CO−, and the hydrogen atom in the cyclic structure is fluorine. Atomic, 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, and one or two or more -CH _2- that are not adjacent to each other in the alkyl group. Are 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. Further, it is preferable that the formulas (V3-4) to (V3-12) are independently unsubstituted, and the hydrogen atom in the formulas (V3-4) to (V3-12) is a cyano group. , Fluorine atom, chlorine atom, methyl group or methoxy group may be substituted.

Represents a group selected from formulas (V3-1), formulas (V3-2), and unsubstituted formulas (V3-3) to (V3-12) from the viewpoint of availability of raw materials and ease of production. Is particularly preferred.

When tf in the general formula (If) represents 4, that is, when the valence of V ^f is 4, V ^f preferably represents a hydrocarbon group having 1 to 15 carbon atoms, and the hydrocarbon. two or more -CH ₂ that is not one or adjacent present in carbon atoms in the group - is 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 replaced by CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF-, -OCF _2- , -CF ₂ O-, or -C≡C-. It is more preferable that V ^f is a group selected from the groups represented by the formulas (V4-1) to (V4-21).

The hydrogen atoms in the cyclic structure are fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group and dimethylamino. It may be substituted with 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 adjacent to the alkyl group. Two or more -CH _2-s are 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 = It may be substituted with CH-, -CF = CF-, -OCF _2- , -CF ₂ O-, or -C≡C-. Further, it is preferable that the formulas (V4-3) to (V4-21) are 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 the formulas (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. 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 the compound represented by the general formula (I-1).

(In the formula, R ^a01 represents a hydrogen atom or a hydroxyl group, and represents
^Ra71 represents a hydrogen atom or a monovalent organic group.
Sp ^a11 and Sp ^a21 have the same meanings as Sp ^a1 and Sp ^a2 in the general formula (Ic).
A ^a11 and A ^a21 have the same meanings as A ^a1 and A ^a2 in the general formula (Ic).
R ^a91 has the same meaning as R ^a9 in the general formula (Ic).
m1, p1 and q1 independently represent 0 or 1, respectively. )
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 single bonds or alkylene groups having 1 to 6 carbon atoms, respectively, and are present in the alkyl group with one -CH _2- or two or more non-adjacent-. CH ₂ − is preferably replaced by −O−, −COO−, −OCO−, −CH = CH− or −C≡C−, and is particularly preferably a single bond.
A ^a11 and A ^a21 are independently (a) 1,4-cyclohexylene groups (one -CH ₂ − present in this group or two or more non-adjacent −CH ₂ − are −O− May be replaced with.)
(B) 1,4-phenylene group (one -CH = existing in this group or two or more -CH = not adjacent to each other may be replaced with -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 with -N =).
A group selected from the group consisting of is preferable in order to enhance the storage stability of the liquid crystal composition, and the above groups (a), (b) and group (c) are independently cyano groups and fluorine, respectively. Substitution with an atom, a chlorine atom, a methyl group or a methoxy group is preferable in order to enhance 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 preferable that it is replaced by − or −CH = CH−. Further, R ^a91 is a general formula ( ^Id1 ).

(In the formula, R ^d01 represents a hydrogen atom or a hydroxyl group, Sp ^a31 has the same meaning as Sp ^a3 in the general formula ( ^Id ), R ^a101 represents a hydrogen atom or a monovalent organic group, and s1 is 0. Alternatively, a structure represented by 1) is particularly preferable in order to enhance the ability to prevent light deterioration. Ra ¹⁰¹ 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.
It is preferable that m1 and p1 are 1. It is preferable that q1 is 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 has the same meaning as R ^a91 in the general formula (I-1), and Sp ^a12 , Sp ^a13 and ^{Spa a14} have the same meaning as Sp ^a11 or Sp ^a21 in the general formula (I-1). , A ^a12 and A ^a13 have the same meaning as A ^a11 or A ^a21 in the general formula (I-1).)
The composition containing one or more compounds represented by the 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 as a lower limit value of 0.01% or more, preferably 0.02% or more, and 0.03% or more. Is preferable, 0.05% or more is preferably contained, 0.07% or more is preferably contained, 0.1% or more is preferably contained, 0.15% or more is preferably contained, and 0.2. % Or more is preferable, 0.25% or more is preferably contained, 0.3% or more is preferably contained, 0.5% or more is preferably contained, and 1% or more is preferably contained. Further, as an upper limit value, it is preferably contained in an amount of 5% or less, preferably 3% or less, preferably 1% or less, preferably 0.5% or less, and 0.45% or less. It is preferable, 0.4% or less is preferably contained, 0.35% or less is preferably contained, 0.3% or less is preferably contained, 0.25% or less is preferably contained, and 0. It is preferably contained in an amount of 2% or less, preferably 0.15% or less, preferably 0.1% or less, preferably 0.07% or less, and preferably 0.05% or less. Is preferable, and the content is preferably 0.03% or less.

More specifically, it is preferably contained in an amount of 0.01 to 5% by mass, preferably 0.01 to 0.3% by mass, and even more preferably 0.02 to 0.3% by mass. It is particularly preferably 0.05 to 0.25% by mass. More specifically, when the suppression of precipitation at low temperature is emphasized, the content thereof 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. May be contained.

In the present invention, the compound represented by the general formula (I) can be produced as follows. Of course, the gist and scope of the present invention are not limited by these production examples.

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

(In the formula, 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 , in the general formula (I). It has the same meaning as R ^a4 , R ^a5 , R ^a6 , n, t and U.)
By reacting the compound represented by the general formula (S-1) with the compound represented by the general formula (S-2), the compound represented by the general formula (I) can be obtained. Examples of the reaction include a method in which a compound represented by the general formula (S-1) and a 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 bicarbonate, Lewis acids such as boron trifluoride, fumaric acid, phthalic acid, oxalylic acid, camphorsulfonic acid and organic acids such as p-toluenesulfonic acid. Examples thereof include solid acids such as Amberlist-15. At this time, when the compound represented by the general formula (S-1) is a basic compound, an amount exceeding 1 equivalent can be added to the acid catalyst, if necessary.

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

(In the formula, R ^s1 has 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 is the general formula. represents the same meaning as ^{R a71} in formula ^{(I-1), a s1} has the same meaning as ^{a a12} or ^{a a13} in the general formula (I-1b) or ^{(I-1l), Y s1} is the formula (I-1a) and / or (I-1b) the same meaning as ^{R a92} in, or the same meaning as ^{S PA13} in formula (I-1k) and / or ^{(I-1l), 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 formulas (I-1a), (I-1b), (I-1k) or The compound represented by (I-1l) can be obtained. As a reaction example, for example, in the same manner as in Production Method 1, a method of heating a compound represented by the general formula (S-3) and a compound represented by the general formula (S-4) in the presence of an acid catalyst to cause a dehydration reaction is performed. Can be mentioned.

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

(In the formula, R ^s1 has 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 is the general formula. represents the same meaning as ^{R a71} in formula ^{(I-1), a s1} is the formula (I-1c), (I -1j), (I-1m) or (I-1t) in ^{a a12} or ^{a a13} Y ^s1 has the same meaning as Ra ⁹² in the general formula (I-1c) or (I-1j), or the same as Sp ^a13 in the general formula (I-1m) or (I-1t). Sp ^s1 represents the same meaning as Sp ^a12 or Sp ^a14 in the general formulas (I-1c), (I-1j), (I-1m) or (I-1t), and ^{sp s1} and p ^s1 Represents 0 or 1 independently, 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-5), the compound represented by the general formula (S-6) can be obtained. As a reaction example, for example, in the same manner as in Production Method 1, a method of heating a compound represented by the general formula (S-3) and a compound represented by the general formula (S-5) in the presence of an acid catalyst to cause a dehydration reaction is performed. Can be mentioned.
By reacting the compound represented by the general formula (S-6) with the compound represented by the general formula (S-7), the general formula (I-1c), (I-1j), (I-1m) or The compound represented by (I-1t) can be obtained. As an example of the reaction, for example, the hydroxyl group of the general formula (S-6) is reacted with p-toluenesulfonyl chloride, methylsulfonyl chloride, etc. to form a leaving group, and then reacted with (S-7) in the presence of a base. There is a Williamson reaction that causes it. Examples of the base include potassium carbonate and cesium carbonate. Another example is the Mitsunobu reaction in which a hydroxyl group is activated with an azocarboxylic acid ester and triphenylphosphine and reacted with an alcohol. Examples of the azocarboxylic acid ester include diethyl azodicarboxylate and diisopropyl azodicarboxylate. (Production Method 4) A method for producing a compound represented by the general formula (I-1d), (I-1i), (I-1n) or (I-1s).

(In the formula, R ^s1 has 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 is the general formula. represents the same meaning as ^{R a71} in formula ^{(I-1), a s1} is the formula (I-1d), (I -1i), (I-1n) or (I-1s) in ^{a a12} or ^{a a13} Y ^s1 has the same meaning as Ra ⁹² 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 formulas (I-1d), (I-1i), (I-1n) or (I-1s), and ^{sp s1} and p ^s1 Represents 0 or 1 independently, 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-8), the compound represented by the general formula (S-9) can be obtained. As a reaction example, for example, in the same manner as in Production Method 1, a method of heating a compound represented by the general formula (S-3) and a compound represented by the general formula (S-8) in the presence of an acid catalyst to cause a dehydration reaction is performed. Can be mentioned.
By reacting the compound represented by the general formula (S-9) with the compound represented by the general formula (S-7), the general formulas (I-1d), (I-1i), (I-1n) or The compound represented by (I-1s) can be obtained. As an example of the reaction, for example, 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 a compound represented by the general formula (S-7) can be mentioned. Be 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, a Mitsunobu reaction in which the hydroxyl group of the general formula (S-7) is activated by 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) A method for producing a compound represented by the general formula (I-1e) or (I-1o).

(In the formula, R ^s1 has the same meaning as R ^a02 or R ^a03 in the general formula (I-1e) or (I-1o), and R ^s7 has the same meaning as R ^a71 in the general formula (I-1). the ^{stands, a s1} has the same meaning as ^{a a12} or ^{a a13} in the general formula (I-1e) or ^{(I-1o), Y s1} is the same meaning as ^{R a92} in the general formula (I-1e), Alternatively, it has 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).
By reacting the compound represented by the general formula (S-3) with the compound represented by the general formula (S-10), the compound represented by the general formula (S-11) can be obtained. As a reaction example, for example, in the same manner as in Production Method 1, a method of heating a compound represented by the general formula (S-3) and a compound represented by the general formula (S-10) in the presence of an acid catalyst to cause a dehydration reaction is performed. Can be mentioned.
By reacting the compound represented by the general formula (S-11) with the compound represented by the general formula (S-12), the compound represented by the general formula (I-1e) or (I-1o) is obtained. be able to. As an example of the reaction, for example, the hydroxyl group of the general formula (S-12) is reacted with p-toluenesulfonyl chloride, methylsulfonyl chloride or the like to form a leaving group, and then reacted with (S-11) in the presence of a base. There is a Williamson reaction that causes it. Examples of the base include sodium hydride and the like. Another example is the Mitsunobu reaction in which a hydroxyl group is activated with an azocarboxylic acid ester and triphenylphosphine and reacted with an alcohol. Examples of the azocarboxylic acid ester include diethyl azodicarboxylate and diisopropyl azodicarboxylate.

(Production Method 6) A method for producing a compound represented by the general formula (I-1f) or (I-1p).

(In the formula, R ^s1 has 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). the ^{stands, a s1} has the same meaning as ^{a a12} or ^{a a13} in the general formula (I-1f) or ^{(I-1p), Y s1} is the same meaning as ^{R a92} in the general formula (I-1f), Alternatively, it has 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).
By reacting the compound represented by the general formula (S-11) with the compound represented by the general formula (S-13), the compound represented by the general formula (I-1f) or (I-1p) is obtained. be able to. As an example of the reaction, for example, 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 a compound represented by the general formula (S-11) can be mentioned. Be 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, a Mitsunobu reaction in which the hydroxyl group of the general formula (S-11) is activated by 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) A method for producing a compound represented by the general formula (I-1g), (I-1q), (I-1h) or (I-1r).

(In the formula, R ^s1 has the same meaning as R ^a02 or R ^a03 in the general formula (I-1g), (I-1q), (I-1h) or (I-1r), and R ^s2 is an alkyl group. the ^{stands, R s7} represents the same meaning as ^{R a71} in the general formula ^{(I-1), a s1} is the formula (I-1g), (I -1q), (I-1h) or (I- It has the same meaning as A ^a12 or A ^a13 in 1r), and Y ^s1 has the same meaning as Ra ⁹² in the general formula (I-1g) or (I-1h), or the general formula (I-1q) or (I-1h). represents the same meaning as ^{Sp a13} in -1R), X is chlorine, bromine or ^{iodine, p s1} is 0 or ^{1, t s1} is 1 or 2.)
By reacting the compound represented by the general formula (S-3) with the compound represented by the general formula (S-17), the compound represented by the general formula (S-14) can be obtained. As an example of the reaction, for example, in the same manner as in Production Method 1, a method of heating 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 to cause a dehydration reaction is performed. Can be mentioned.

By reducing the compound represented by the general formula (S-14), the compound represented by the general formula (S-15) can be obtained. Examples of the reducing agent include diisobutylaluminum hydride and the like. 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 it to an aldehyde. In this case, examples of the reducing agent include lithium aluminum hydride, diisobutylaluminum hydride, and sodium bis (2-methoxyethoxy) aluminum hydride. In addition, examples of the oxidizing agent include pyridinium chlorochromate and oxalyl chloride.

By reacting the compound represented by the general formula (S-15) with the compound represented by the general formula (S-16), the compound represented by the general formula (I-1g) or (I-1q) is obtained. be able to. Examples of the reaction include a Witich reaction in which a base is reacted with a compound represented by the general formula (S-16) to form phosphorus irid, and then the compound is reacted with a compound represented by the general formula (S-15). .. At this time, examples of the base include t-butoxypotassium and the like.
By reducing the compound represented by the general formula (I-1g) or (I-1q), the compound represented by the general formula (I-1h) or (I-1r) can be obtained. 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. At this time, examples of the catalyst include palladium carbon and the like.

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

(In the formula, R ^s1 has the same meaning as R ^a02 or R ^a03 in the general formula (I-1u) or (I-1v), and R ^s7 has the same meaning as R ^a71 in the general formula (I-1). the ^{stands, a s1} has the same meaning as ^{a a12} or ^{a a13} in the general formula (I-1u) or ^{(I-1v), Y s1} is the same meaning as ^{R a92} in the general formula (I-1u), Alternatively, it 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 has the same meaning as m ^s1 and sp ^a14. p ^s1 independently represents 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-5), the compound represented by the general formula (S-6) can be obtained. As a reaction example, for example, in the same manner as in Production Method 1, a method of heating a compound represented by the general formula (S-3) and a compound represented by the general formula (S-5) in the presence of an acid catalyst to cause a dehydration reaction is performed. Can be mentioned.
By reacting the compound represented by the general formula (S-6) with the compound represented by the general formula (S-18), the compound represented by the general formula (I-1u) or (I-1v) is obtained. be able to. An example of the reaction is 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 the reaction is carried out with a compound represented by the general formula (S-6). Be 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, a Mitsunobu reaction in which the hydroxyl group of the general formula (S-6) is activated by 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.
Reaction conditions other than those described in each of the above steps include, for example, Experimental Chemistry Course (edited by Japan Chemistry Society, published by Maruzen Co., Ltd.), Organic Syntheses (A John Wiley & Sons, Inc., Publication), Beilstein Handbook of Organic Chemistry (Beilstein Handbook of Organic Chemistry). -Institut fuer Literatur der Organischen Chemie, Springer-Verlag Berlin and Heidelberg GmbH & Co.K), Fiesers' Reagents for Organic Synthesis (John Wiley & Sons, Inc.) as described in the literature, such as or SciFinder (Chemical Abstracts Service, American Chemical Society), Reaxys (Elsevier Ltd.) and other databases.

In addition, 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 a two-phase system of an organic solvent and water, it is also possible to add a phase transfer catalyst. Specific examples of the phase transfer catalyst include benzyltrimethylammonium bromide and tetrabutylammonium bromide.

In addition, purification can be performed as needed in each step. Examples of the purification method include chromatography, recrystallization, distillation, sublimation, reprecipitation, adsorption, and liquid separation treatment. Specific examples of the purifying agent include silica gel, NH ₂ silica gel, alumina, activated carbon and the like.

Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited to these examples. “%” In the compositions of the following Examples and Comparative Examples means “% by mass”. The purity of the compounds was analyzed by GC or UPLC. Abbreviations for compounds and reaction solvents are as follows: tetrahydrofuran (THF), 2,2,6,6-tetramethyl-4-piperidin (TMP), N, N-dimethylformamide (DMF), diisobutylaluminum hydride. (DIBAL)
(Example 1) Production of compound (I-1a-5)

In 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, a thermometer, a condenser tube, and a Dean-Stark tube, and the mixture was heated under reflux for 30 minutes. The water was removed. After cooling the mixture to room temperature, TMP (5.11 g) and 2-pentyl-1,3-propanediol (4.82 g) were added, and the mixture was heated under reflux for 3 hours to remove the resulting water. After cooling the reaction mixture to room temperature, 150 ml of 1.0 M aqueous sodium hydroxide solution was added and stirred, and the organic layer was separated and washed with 150 ml of 1.0 M aqueous sodium hydroxide solution, 100 ml of water and 100 ml of saturated brine. The obtained organic layer was concentrated and passed through column chromatography (NH ₂ silica gel, toluene). The resulting solution was concentrated to give compound (I-1a-5) (7.87 g).
GC-MS: m / z 268.22 [M-15 ⁺ ]
Phase transition temperature: Oil (freezing point is -20 ° C or less)
^{1 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)
Examples 2 (Compound (I-1a-3)) to Example 3 (Compound (I-1k-4)) 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). The mixture was stirred at room temperature for 3 days. It was concentrated under reduced pressure and acidified by adding 10% hydrochloric acid. Extracted twice with dichloromethane (150 mL). After concentration under reduced pressure, the mixture was purified by column chromatography to obtain 15.0 g of 1,1,8,8-tetra (ethoxycarbonyl) octane as a colorless liquid.

Lithium aluminum hydride (10.6 g) was added to a reaction vessel equipped with a stirrer, a thermometer and a condenser, and the mixture was 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. It was ice-cooled and water (57.0 g) was carefully added. The mixture was stirred at 40 ° C. for 1 hour and filtered to remove solids. The tetrahydrofuran solution was concentrated to give 10.1 g of 1,1,8,8-tetra (hydroxymethyl) octane as a colorless solid.

10.0 g of 1,1,8,8-tetra (hydroxymethyl) octane and 2,2,6,6-tetramethylpiperidine-in a reaction vessel equipped with a stirrer, a thermometer, a cooling tube, and a Dean-Stark tube. 4-On (10.6 g) and 4-toluenesulfonic acid monohydrate (15.2 g) were added and suspended in toluene (100 mL). It was heated to reflux for 3 hours under a nitrogen atmosphere, and the water generated on the way 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 in tetrahydrofuran (138 mL). After concentration under reduced pressure, the mixture was purified by column chromatography and recrystallization to obtain 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
Examples 4 (Compound (I-1k-2)) to Example 6 (Compound (I-1k-6)) using the same reaction as in Example 7 and, if necessary, a method based on a known method. ) Was manufactured.

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

Under a nitrogen atmosphere, p-toluenesulfonic acid monohydrate (5.02 g) and 100 ml of toluene were added to a reaction vessel equipped with a stirrer, a thermometer, a condenser tube, and a Dean-Stark tube, and the mixture was heated under reflux for 30 minutes. The water was removed. After cooling this mixture 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 under reflux for 4 hours to produce water. Was removed. After cooling the reaction mixture to room temperature, 150 ml of 1.0 M aqueous sodium hydroxide solution was added and stirred, and the organic layer was separated and washed with 150 ml of 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 vacuum dried to give compound (I-1b-3C) (1.97 g).
GC-MS: m / z 322.27 [M-15 ⁺ ]
Phase transition temperature: Cry 70 Iso
^{1 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)
Examples 9 (Compound (I-1b-0C)) to Example 24 (Compound (I-1l-B2B)) using the same reaction as in Example 8 and, if necessary, a method based on a known method. ) Was manufactured.

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

(Production of compound (E-2)) p-toluenesulfonic acid monohydrate (5.02 g) and 100 ml of toluene are placed in a reaction vessel equipped with a stirrer, a thermometer, a condenser tube, and a Dean-Stark tube under a nitrogen atmosphere. Was added, and the mixture was heated under reflux for 30 minutes to remove the generated water. After cooling the mixture 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 under reflux for 4 hours to remove the resulting water. After cooling the reaction mixture to room temperature, 150 ml of a 1.0 M aqueous sodium hydroxide solution was added and stirred, the organic layer was separated, and the mixture was 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)) Compound (E-2) (5.71 g) and compound (E-4) (3.00 g) were placed in a reaction vessel equipped with a stirrer and a thermometer under a nitrogen atmosphere. ), Triphenylphosphine (6.16 g) and 45 ml of THF were added, cooled to 5 ° C. or lower and stirred, and then diisopropyl azodicarboxylate (4.45 g) was added dropwise while maintaining 5 ° C. or lower, and the mixture was 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 subjected to column chromatography (10 g of NH ₂ silica). The obtained solution was concentrated, 5 ml of hexane was added, and recrystallization was performed at −20 ° C. The precipitated solid was filtered and vacuum dried to obtain compound (I-1c-B3) (6.66 g).
GC-MS: m / z 362.26 [M-15 ⁺ ]
Examples 26 (Compound (I-1c-B6)) to Example 39 (Compound (I-1t-BB)) using the same reaction as in Example 25 and, if necessary, a method according to a known method. ) Was manufactured.

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

(Production of compound (E-6)) p-toluenesulfonic acid monohydrate (5.02 g) and 100 ml of toluene are placed in a reaction vessel equipped with a stirrer, a thermometer, a condenser tube, and a Dean-Stark tube under a nitrogen atmosphere. Was added, and the mixture was heated under reflux for 30 minutes to remove the generated water. After cooling the mixture 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 under reflux for 4 hours to remove the resulting water. After cooling this reaction mixture to room temperature, add 1.0 M aqueous sodium hydroxide solution and water to adjust the pH to about 7 to 8 and stir, separate the organic layer, and use 100 ml of water twice 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)) Compound (E-6) (5.35 g) and compound (E-7) (2.66 g) were placed in a reaction vessel equipped with a stirrer and a thermometer under a nitrogen atmosphere. ), 0.12 g of N, N-dimethylaminopyridine (DMAP) and 25 ml of nitrogen 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 5 to 10 ° C., and then the temperature was raised to 25 ° C. and the mixture was stirred for 7 hours. After adding 25 ml of water to this reaction mixture, the organic layer was separated and the aqueous layer was further extracted with 25 ml of dichloromethane. After mixing the obtained organic layers into one, the mixture was added onto a column packed with 10 g of NH ₂ silica, and 100 ml of hexane was further passed through the column. After the solvent of the obtained solution was generally distilled off, recrystallization was carried out 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 ⁺ ]
Examples 41 (Compound (I-1d-0C)) to Example 54 (Compound (I-1s-BB)) using the same reaction as in Example 40 and, if necessary, a method according to a known method. ) Was manufactured.

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

(Production of compound (E-9)) p-toluenesulfonic acid monohydrate (50.2 g) and 1000 ml of toluene are placed in a reaction vessel equipped with a stirrer, a thermometer, a condenser tube, and a Dean-Stark tube under a nitrogen atmosphere. Was added, and the mixture was heated under reflux for 30 minutes to remove the generated water. After cooling the mixture to room temperature, TMP (38.2 g), 300 ml of DMF and compound (E-8) (22.5 g) were added, and the mixture was heated under reflux for 4 hours to remove the resulting water. After cooling the reaction mixture to room temperature, 1500 ml of a 1.0 M aqueous sodium hydroxide solution was added and stirred, the organic layer was separated, and the mixture was washed twice with 1000 ml of water and with 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)) Under a nitrogen atmosphere, add compound (E-9) (11.2 g), sodium hydride 1.2 g and DMF 100 ml 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 the mixture was 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 brine, and anhydrous sodium sulfate was added to the obtained organic layer and dried. The obtained solution was concentrated, passed through a crude product previously dissolved in 50 ml of hexane by column chromatography (20 g of NH ₂ silica), 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 vacuum dried to obtain compound (I-1e-C3) (12.58 g).

Examples 56 (Compound (I-1e-B6)) to Example 64 (Compound (I-1o-BEBEB)) using the same reaction as in Example 55 and, if necessary, a method according to a known method. ) Was manufactured.

(Example 65) Production of compound (I-1f-C3)

(Production of compound (I-1f-C3)) Compound (E-9) (11.2 g) and compound (E-11) (8.32 g) were placed in a reaction vessel equipped with a stirrer and a thermometer under a nitrogen atmosphere. ), 0.30 g of N, N-dimethylaminopyridine (DMAP) and 80 ml of nitrogen were added, and the mixture was stirred at 5 to 10 ° C. for 10 minutes. Under stirring, 8.0 g of N, N-diisopropylcarbodiimide (DIC) was added dropwise while maintaining 5 to 10 ° C., and then the temperature was raised to 25 ° C. and the mixture was stirred for 7 hours. After adding 2 ml of water to the reaction mixture and stirring the mixture, the precipitated solid was removed and the obtained 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 100 ml of hexane was further passed through the column. After the solvent of the obtained solution was generally distilled off, recrystallization was carried out 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 ⁺ ]
Examples 66 (Compound (I-1f-B6)) to Example 74 (Compound (I-1p-BEBEB)) using the same reaction as in Example 65 and, if necessary, a method according to a known method. ) Was manufactured.

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

(Production of compound (E-14)) p-toluenesulfonic acid monohydrate (5.02 g) and 100 ml of toluene are placed in a reaction vessel equipped with a stirrer, a thermometer, a condenser tube, and a Dean-Stark tube under a nitrogen atmosphere. Was added, and the mixture was heated under reflux for 30 minutes to remove the generated water. After cooling the mixture to room temperature, TMP (3.82 g) and compound (E-13) (3.28 g) were added, and the mixture was heated under reflux for 4 hours to remove the resulting water. After cooling the reaction mixture to room temperature, 150 ml of a 1.0 M aqueous sodium hydroxide solution was stirred, the organic layer was separated, and the mixture was washed twice with 100 ml of water and with 100 ml of saturated brine. The obtained organic layer was concentrated to obtain compound (E-14) (6.31 g).

(Production of Compound (E-15)) Under a nitrogen atmosphere, compound (E-14) (6.31 g) and 50 ml of dried toluene were added to a reaction vessel equipped with a stirrer, a thermometer, and a dropping funnel, and the temperature was −73 ° C. Cooled to. 27 ml of DIBAL (1.5 M toluene solution) was added dropwise to this mixture while maintaining −65 ° C. or lower, and the mixture was 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 −65 ° C. or lower. After raising the temperature of this reaction mixture to room temperature, 5 ml of a 15% aqueous sodium hydroxide solution and 15 ml of water were added, and the mixture was stirred for 3 hours. The obtained reaction mixture was filtered to remove the solid, 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, add compound (E-16) (12.22 g) and 25 ml of THF to a reaction vessel equipped with a stirrer, a thermometer, and a dropping funnel, and add t-butoxy to this. Potassium (2.85 g) was added at 10 ° C. or lower and stirred. Compound (E-15) (5.32 g) dissolved in 15 ml of THF was added dropwise to this reaction mixture while maintaining a temperature of 10 ° C. or lower, and the mixture was stirred at 5 ° C. for 2 hours. 0.5 ml of water and 40 ml of hexane were added to the reaction mixture, and the mixture was stirred at room temperature for 1 hour. The obtained reaction mixture was filtered to remove solids, 5 ml of a 5% aqueous sodium hypochlorite solution was added to the obtained organic layer, and the mixture was stirred at room temperature for 1 hour. The organic layer of this reaction mixture was separated, washed with 20 ml of a mixed water / methanol solvent and 20 ml of saturated brine, and concentrated. The resulting mixture was passed through a column (NH ₂ silica, hexane) and the resulting solution was concentrated to give compound (E-17) (7.22 g).

(Production of compound (I-1g-C3)) Compound (E-17) (3.61g) and sodium benzenesulfinate dihydrate (3.61g) in a reaction vessel equipped with a stirrer and a thermometer under a nitrogen atmosphere. 0.5 g) and 20 ml of toluene were added and stirred. 1.1 g of 10% hydrochloric acid was added to this mixture, and the mixture was heated under 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 a 10% aqueous sodium hydrogen carbonate solution and 5 ml of a 10% saline solution, 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-1 g-C3) (2.50 g).
GC-MS: m / z 348.28 [M-15 ⁺ ]
Examples 76 (Compound (I-1g-B6)) to Example 82 (Compound (I-1q-BEBEB)) using the same reaction as in Example 75 and, if necessary, a method according to a known method. ) 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% hydrous product) in a pressure resistant reaction vessel equipped with a stirrer and a thermometer under 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, passed through a column (NH ₂ silica, hexane), then concentrated, 10 ml of hexane was added, and recrystallization was performed at −20 ° C., compound (I-1h-C3) (3.44 g). ) Was obtained.
GC-MS: m / z 350.30 [M-15 ⁺ ]
Examples 84 (Compound (I-1h-B6)) to Example 90 (Compound (I-1r-BEBEB)) using the same reaction as in Example 83 and, if necessary, a method according to a known method. ) Was manufactured.

The measured characteristics of the liquid crystal composition containing any of the compounds obtained in Examples 1 to 90 are as follows.

VHR: The voltage holding ratio (%) at 333K was evaluated on a three-point scale 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-resistant VHR: The liquid crystal composition is irradiated with ultraviolet rays at 180 J / m ² using an ultra-high pressure mercury lamp through a glass having a thickness of 0.5 mm. The voltage retention of the liquid crystal after irradiation with ultraviolet rays is measured by the same method as the above-mentioned VHR measurement. However, the irradiation intensity was 0.1 W / m ^{2 at} 366 nm. The 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 the presence or absence of precipitates was visually observed. Was evaluated on a three-point scale.

A: No precipitate B: Slightly cloudy 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 parent liquid crystal (H), 500 ppm of the compound (I-1a-5) obtained in Example 1 was added.
The measured characteristics of the composition examples in the examples are as follows.

VHR: A
Lightproof VHR: A
Compatibility: A
Storage stability: A
Hereinafter, the results of measurement of Examples 92 to 180 using the compounds produced in Examples 2 to 90 in the same manner as in Example 91 are shown below.

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

(Production of compound (I-1u-B3)) Compound (E-2) (11.4 g) and compound (E-18) (8.2 g) were placed in a reaction vessel equipped with a stirrer and a thermometer under a nitrogen atmosphere. ), 0.30 g of N, N-dimethylaminopyridine (DMAP) and 80 ml of nitrogen 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 5 to 10 ° C., and then the temperature was raised to 25 ° C. and the mixture was stirred for 7 hours. After adding 2 ml of water to the reaction mixture and stirring the mixture, the precipitated solid was removed and the obtained 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 100 ml of hexane was further passed through the column. After the solvent of the obtained solution was generally distilled off, recrystallization was carried out 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 ⁺ ]
Examples 182 (Compound (I-1u-B6)) to Example 187 (Compound (I-1u-T3)) using the same reaction as in Example 181 and, if necessary, a method according to a known method. ) 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 (3.5 g of molecular sieve 4A pellets packed therein), a cooling tube, an oil bath, and a thermometer under a nitrogen atmosphere. Compound (E-2) (2.22 g), compound (E-19) (1.0 g), dibutyl tin oxide (0.11 g), and 15 ml of xylene were added thereto, and the mixture was stirred with heating under reflux for 5 hours. The reaction mixture was cooled to room temperature and 15 ml of hexane was added. This reaction mixture was added onto a column packed with 6 g of NH ₂ silica, and hexane / toluene (volume ratio 1: 1, 100 ml) was further passed through the column. After distilling off the solvent of the obtained solution, recrystallization was carried out 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 are packed therein), a cooling tube, an oil bath, and a thermometer under a nitrogen atmosphere. Compound (E-2) (8.29 g), compound (E-20) (3.15 g), dibutyl tin oxide (0.40 g), and 35 ml of xylene were added, and the mixture was stirred with heating under reflux for 5 hours. 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 hexane / toluene (volume ratio 1: 1, 200 ml) was further passed through the column. After distilling off the solvent of the obtained solution, recrystallization was carried out 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)) p-toluenesulfonic acid monohydrate (64.4 g) and 800 ml of toluene are placed in a reaction vessel equipped with a stirrer, a thermometer, a condenser tube, and a Dean-Stark tube under a nitrogen atmosphere. Was added, and the mixture was heated under reflux for 20 minutes to remove the generated water. After cooling the mixture to room temperature, TMP (51.0 g), 30 ml of DMF and compound (E-21) (38.8 g) were added, and the mixture was heated under reflux for 4 hours to remove the resulting water. After cooling the reaction mixture to room temperature, 400 ml of a 1.0 M aqueous sodium hydroxide solution was added and stirred, the organic layer was separated, and the mixture was 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)) In a reaction vessel equipped with a stirrer, a dropping funnel (40 g of molecular sieve 4A pellets packed therein), a cooling tube, an oil bath, and a thermometer under a nitrogen atmosphere. Compound (E-22) (34.3 g), compound (E-20) (12.24 g), dibutyl tin oxide (1.53 g), and 180 ml of xylene were added, and the mixture was stirred with heating under reflux for 5 hours. 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 150 ml of toluene was further passed through. After distilling off the solvent of the obtained solution, recrystallization was carried out 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 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)
Examples 191 (Compound (I-1v-EtB)) to Example 197 (Compound (I-1v-EtBF)) using the same reaction as in Example 190 and, if necessary, a method according to a known method. ) Was manufactured.

Using the compounds produced in Examples 181 to 197, the liquid crystal compositions of Examples 198 to 214 were prepared in the same manner as in Example 91, and the results of measurement are shown below.

(Comparative Example 1)
As a comparative example, the results of measuring the characteristics of the parent liquid crystal (H) without adding any further compound are as follows.

VHR: A
Lightproof 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)
The results of the measurement obtained by adding 500 ppm of the compound (R-1) to the mother liquid crystal (H) are as follows.

VHR: A
Lightproof VHR: A
Compatibility: B
Storage stability: C
(Comparative Examples 3 and 4)
Hereinafter, the results of the measurements of 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 by light.

Claims (6)

General formula (I-1)

(In the formula, R ^a01 represents a hydrogen atom or a hydroxyl group, and represents
R ^a71 represents an alkyl group having 1 to 4 carbon atoms.
Sp ^a11 and ^{Sp a21} Although each independently represent a single bond or an alkylene group having a carbon number of 1 to 12, one -CH ₂ present in the alkylene group - or nonadjacent two or more -CH ₂ − May be replaced by −O−, −S−, −COO−, −OCO−, −CO−, −CH = CH− or −C≡C−.
A ^a11 and A ^a21 are independent of each other
(A) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - may be replaced by -O-.)
(B) A 1,4-phenylene group or a 1,3-phenylene group (one -CH = existing in this group or two or more -CH = not adjacent to each other may be replaced with -N =. Good.) 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 One -CH = existing in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or two or more non-adjacent -CH = may be replaced with -N =. )
Represents a group selected from the group consisting of, and the above groups (a), group (b) and group (c) are independently substituted with a cyano group, a fluorine atom, a chlorine atom, a methyl group or a methoxy group, respectively. If there are a plurality of Sp ^a1 , Sp ^a2 , A ^a1 and A a ² in the molecule, they may be the same or different.
m1 represents 1
p1 and q1 independently represent 0, 1 or 2, respectively, where p1 + q1 represents 1 or more.
R ^a91 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-, It may be replaced by −S−, −COO−, −OCO−, −CO−, −CH = CH− or −C≡C−, or R ^a9 is the general formula (Id1).

(In the formula, R ^d01 represents a hydrogen atom or a hydroxyl group, Sp ^a31 has the same meaning as Sp ^a11 or Sp ^a21 in the general formula (I-1) , and R ^a101 represents an alkyl group having 1 to 4 carbon atoms. s1 represents 1.)
However, at least one -COO-, -OCO- or -CO- is contained in Sp ^a11 , Sp ^a21 and Spa ³¹ present here . )
A liquid crystal composition containing one or more compounds represented by . In the general formula (I-1), R ^a9 The liquid crystal composition according to claim 1, wherein is represented by the general formula (Id1). In the general formula (I-1), A ^a11 And A ^a21 1 or 2 according to claim 1 or 2, wherein each represents a 1,4-phenylene group or a 1,3-phenylene group which may be independently substituted with a cyano group, a fluorine atom, a chlorine atom, a methyl group or a methoxy group. Liquid crystal composition. The compound represented by the general formula (I-1) is the following general formula (I-1u) or (I-1v).

(In the formula, R ^a02 And R ^a03 Is R in the general formula (I-1). ^a01 Represents the same meaning as R ^a72 And R ^a102 Is R in the general formula (I-1). ^a71 Represents the same meaning as R ^a92 Is R in the general formula (I-1) ^a91 Represents the same meaning as Sp ^a12 , Sp ^a13 And Sp ^a14 Is Sp in the general formula (I-1). ^a11 Or Sp ^a21 Represents the same meaning as A ^a12 Is A in the general formula (I-1). ^a11 Or A ^a21 Represents the same meaning as. )
The liquid crystal composition according to any one of claims 1 to 3, which is represented by. A display device using the liquid crystal composition according to any one of claims 1 to 4. The following compounds.