JPH06263704A - Optically rotatory compound - Google Patents

Abstract

PURPOSE:To obtain an optically rotatory compound which has larger optical rotation in the visible region, while substantially no absorption in the visible region. CONSTITUTION:A compound with optically active property caused by mutual action of asymmetric excitors, where the maximum absorption wavelength in a single ethanol solution of the chromophore expressing mutual excitor action in the molecule falls within a range of 300 to 400nm, preferably 350 to 390nm and the molecular absorption coefficient is >=35000l/mol<-1>/cm<-1>, preferably >=40000l/mol<-1>/cm<-1>. Further, a compound having more than 95% transmittance in the 1cm path length of 4X10<-4>mole/l ethanol solution at <=450nm, preferably <=440nm. Especially, the compound having the group of formula I (R<1>, R<2> are each H, alkyl, aryl, or both together form a ring; X, Y are each electrophilic group) is preferred, for example, compounds of formulae II and III [R<3>-R<6> are respectively identical with R<1>, R<2>; X'-X''', Y'-Y''' are respectively identical with V, Y; Z<1>, Z<4> are atomic groups necessary for ring formation; Z<2>, Z<3> are O, NR<9> (R<9>, H, alkyl); R<7>, R<8> are R<9>, aryl].

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel compound having a large optical activity.

[0002]

Optical rotation, which is the ability to rotate the plane of polarization of light, is a well-known phenomenon discovered in the early 19th century. It is known that some organic compounds have an asymmetric carbon atom and some have an optical chirality among those having a molecular asymmetry. In recent years, with the progress of laser technology and the development of liquid crystal display devices, linearly polarized light has been actively used, and controlling the rotation of the polarization plane has become an important technology. From this point of view, interest in compounds having large optical activity has begun.

In the field of organic chemistry, compounds having optical activity are called optically active compounds, and include many compounds related to the living body such as amino acids and sugars. However,
The optical rotatory power of these compounds is not necessarily large, and is insufficient for use in high-performance devices and the like. On the other hand, a method using asymmetric exciton interaction is known as a method for obtaining large optical activity. For example, see Nobuyuki Harada and Kaji Nakanishi, "Circular dichroism spectrum-application to organic stereochemistry", Tokyo Kagaku Dojin (1982). According to this method
By placing multiple chromophores in an asymmetric position relative to each other,
An increase in optical activity will be obtained.

However, although the conventionally known compound having asymmetric exciton interaction has a large optical rotatory power in the ultraviolet region, its optical rotatory power in the visible region is very small due to its dispersion property. On the other hand, a highly functional element is often required to have a large optical rotatory power in the visible region, and further, it may be required that there is no substantial absorption in the visible region.

[0005]

Therefore, it is an object of the present invention to provide a compound having a large optical activity in the visible region and having no substantial absorption in the visible region.

[0006]

Means for Solving the Problems As a result of intensive studies by the present inventor, in a compound having optical activity due to asymmetric exciton interaction, a color development that exhibits an exciton interaction contained as a part of the compound The absorption maximum wavelength in the ethanol solution when the group is alone is 300 nm or more and 400 nm or less,
And the molecular extinction coefficient is 35,000 liters · mol ⁻¹ · cm
^The present invention has been achieved by a compound characterized by being ⁻¹ or more.

The absorption maximum wavelength is 350 nm or more and 390
nm or less, and the molecular extinction coefficient is 40,
It is preferably 000 liter · mol ⁻¹ · cm ⁻¹ or more. Further, a 4 × 10 ⁻⁴ mol / liter ethanol solution of the compound has a transmittance of 95% at an optical path length of 1 cm at a wavelength of 4
It is preferably 50 nm or less. More preferably 4
It is 40 m or less. It is particularly preferable to use the compound represented by the general formula (I) as the chromophore. General formula (I)

[0008]

[Chemical 6]

More specifically, compounds represented by the following general formula (II), general formula (III), and further general formula (IV) and general formula (V) are mentioned. General formula (II)

[0010]

[Chemical 7]

General formula (III)

[0012]

[Chemical 8]

General formula (IV)

[0014]

[Chemical 9]

General formula (V)

[0016]

[Chemical 10]

The general formula (I), general formula (II), and general formula
Regarding formula (III), general formula (IV) and general formula (V),
Will be explained in detail. R¹And R²Is a hydrogen atom, Archi
Group and aryl group, examples of alkyl groups
Examples thereof include those having 24 or less carbon atoms, preferably carbon.
Those having a number of 15 or less, more preferably 8 or less carbon atoms
Chain or branched, such as methyl, ethyl,
n-propyl, i-propyl, n-butyl, n-hex
And n-octyl. These have been replaced
The substituent may be, for example, a hydroxy group or an alcohol.
Xy groups (eg methoxy, ethoxy, benzyloxy, 2
-Phenylethoxy, 2-methoxyethoxy), amino
Groups such as amino, methylamino, dimethylamino,
Loridino, piperidino, morpholino), acylamino group
(Eg acetylamino, pivaloylamino, benzyl
Oxycarbonylamino, benzoylamino, methan
Rufonylamino, benzenesulfonylamino), carbo
Xy, alkoxycarbonyl groups (eg methoxycarl
Bonyl, i-propylcarbonyl, 2-methoxyethoxy
Sicarbonyl, 2-ethylhexyloxycarbonyl,
Cyclohexyloxycarbonyl), carbamoyl group (eg
For example, carbamoyl, methylcarbamoyl, phenylcarboyl.
Luvamoyl, benzylcarbamoyl), sulfamoyl
A group (for example, sulfamoyl, methylsulfamoyl,
Phenylsulfamoyl, benzylsulfamoyl),
Sulfo group, aryl group (eg, phenyl, tolyl, 1
-Naphthyl), halogen atoms (e.g. fluorine, chlorine,
Bromine, iodine). Also R¹And R²By the ring
(For example, pyrrolidino ring, morpholino ring, piperidino ring)
May be formed. R¹And R²Same as but different
You may R ³And R^Four, R^FiveAnd R⁶, R
¹¹And R¹²Is R¹And R²Is synonymous with.

The aryl group has, for example, 6 carbon atoms.
To 30, preferably 6 to 16, and more preferably 6 to 11 (eg, phenyl, 1-naphthyl, 2-naphthyl and their substitution products),
Examples of the substituent include the alkyl groups (the above-mentioned substituted and unsubstituted alkyl groups) in addition to those described for the alkyl group.

The electron-withdrawing group represented by X and Y means a substituent having a positive substituent constant σ _p . The above-mentioned substituent constants can be found in the special issue “Chemistry” edited by the Structure-Activity Relations Forum
No. 2, “Structure-Activity Relationships of Drugs-Drug Design and Guidelines for Studying Mechanism of Action”, pp. 95-111, published by Nankodo Co., Corwin Hansch, Albert Leo, Sub. "Stituant Constants for Correlation Analysis in Chemistry and Biology" (Substituen
t Constants for Correlation Analysis in Chemistry
and Biology pp. 69-161 The values shown in John Wiley and Sons.

Examples thereof include cyano group, carbamoyl group, phenylsulfonyl group, acetyl group, alkoxycarbonyl group and carboxyl group. X and Y may be the same or different. X ′ and Y ′, X ″ and Y ″, X ′ ″ and Y ′ ″ are synonymous with X and Y.

Z ¹ and Z ⁴ represent an atomic group necessary for forming a ring, for example, cyclohexane, cyclopentane, 5α-cholestane-2α, 3β-diyl, α-D-.
Examples include glucose.

Z ² and Z ³ are an oxygen atom and N--R ⁹
Represents R ⁹ represents a hydrogen atom or an alkyl group,
Specific examples thereof include the same ones as R ¹ and R ² , but the alkyl group is preferably an alkyl group having a carbon number of 3 or less (for example, methyl or ethyl), and particularly preferably a hydrogen atom. Z ² and Z ³ may be the same or different.

R ⁷ and R ⁸ represent a hydrogen atom, an alkyl group and an aryl group, and specific examples are R ¹ and R ^2.
Examples of the alkyl group include, but an alkyl group is preferably an alkyl group having 3 or less carbon atoms (eg, methyl, ethyl), an aryl group is preferably phenyl, and a hydrogen atom is particularly preferable. R ⁷ and R ⁸ may be the same or different.

Specific examples of the compound of the present invention are shown below, but the scope of the present invention is not limited to these.

[0025]

[Chemical 11]

[0026]

[Chemical 12]

[0027]

[Chemical 13]

[0028]

[Chemical 14]

[0029]

[Chemical 15]

[0030]

[Chemical 16]

[0031]

[Chemical 17]

These compounds can basically be synthesized according to the following reaction formula.

[0033]

[Chemical 18]

[0034]

[Chemical 19]

This will be described in detail.

(I) Synthesis of Compound (B) It is preferable to react the compound represented by the general formula (A) with 1 molar equivalent or more of acetic anhydride. If the acetic anhydride is less than 1 molar equivalent, the yield will be significantly reduced.
The reaction does not necessarily require a solvent. However, depending on the combination of reaction compounds used and the reaction conditions, a small amount of solvent can be used if necessary. Examples of such a solvent include alcohols such as methanol, ethanol and isopropanol, hydrocarbons such as n-hexane, tetrahydrofuran, ethers such as 1,2-dimethoxyethane, N, N-dimethylformamide and N.
An amide such as methylpyrrolidone, a sulfur-containing compound such as dimethyl sulfoxide and sulfolane, a nitrile such as acetonitrile, an ester such as ethyl acetate and the like are used. Of these, amides, sulfur-containing compounds and nitriles are preferable. Further, one or more kinds can be used in consideration of reaction conditions, boiling point, solubility, reactivity, odor, price and the like. The reaction temperature is preferably 0 to 100 ° C, more preferably 10 to 50 ° C, and the temperature is 0 ° C.
If it is less than 100 ° C, the reaction proceeds slowly and it is difficult to completely eliminate the raw materials. If it exceeds 100 ° C, a byproduct is produced, resulting in a low yield. The reaction is preferably carried out with appropriate stirring.

(Ii) Synthesis of Compound (C) It is preferable to use thionyl chloride in an amount of 1 to 5 molar equivalents to the compound represented by the general formula (B), preferably 2 to 4 molar equivalents. More preferable. If thionyl chloride is less than 1 molar equivalent, the yield is not significantly reduced.
If the molar equivalent is exceeded, the production of by-products will increase. N, N
-Adding a catalytic amount of dimethylformamide produces the desired product in good yield. Examples of the solvent used in the reaction include aromatic hydrocarbons (eg benzene, toluene, xylene, ethylbenzene etc.), ethers (eg anilyl, tetrahydrofuran etc.), aliphatic hydrocarbons (eg hexane, ligroin, decalin etc.), halogenated hydrocarbons. (Eg, chloroform, dichloroethane, carbon tetrachloride, etc.), pyridine, nitrobenzene, acetonitrile, halogenated benzene (eg, chlorobenzene), etc., one kind in consideration of reaction conditions, boiling point, solubility, reactivity, odor, price, etc. Alternatively, more can be used. The reaction temperature is preferably 50 to 100 ° C., more preferably 80 to 100 ° C. If the temperature is less than 50 ° C., the reaction proceeds slowly and it is difficult to completely eliminate the raw materials. Low yield due to the production of organisms. The reaction is preferably carried out with appropriate stirring.

(Iii) Synthesis of Compound D As the base used in the reaction, pyridine, triethylamine, an organic base such as 1,8-diazabicyclo [5,4,0] -7-undecene (DBU), potassium carbonate, carbonate It may be an inorganic base such as sodium hydrogen, potassium t-butoxide, sodium hydride or sodium hydroxide. Examples of the solvent used in the reaction include alcohols such as methanol, ethanol and isopropanol, hydrocarbons such as n-hexane, tetrahydrofuran, ethers such as 1,2-dimethoxyethane, N,
An amide such as N-dimethylformamide, N-methylpyrrolidone, a sulfur-containing compound such as dimethyl sulfoxide and sulfolane, a nitrile such as acetonitrile, an ester such as ethyl acetate and the like are used. Of these, amides, sulfur-containing compounds and nitriles are preferable. Further, one or more kinds can be used in consideration of reaction conditions, boiling point, solubility, reactivity, odor, price and the like. The reaction temperature is preferably 0 to 100 ° C., more preferably 1
When the temperature is 0 to 50 ° C. and the temperature is lower than 0 ° C., the progress of the reaction is slow and it is difficult to completely eliminate the raw materials.
If the temperature exceeds ℃, the yield will be low due to the formation of by-products. The reaction is preferably carried out with appropriate stirring.

(Iv) Synthesis of compound (E) 1 to 2 amines are added to the compound represented by the general formula (D).
It is preferable to carry out the reaction using 0 molar equivalents.
It is more preferable to use 12 molar equivalents. If the amine is less than 1 molar equivalent, the yield will be significantly reduced, and if it exceeds 20 molar equivalent, the production of by-products will increase. Examples of the solvent used in the reaction include alcohols such as methanol, ethanol and isopropanol, hydrocarbons such as n-hexane, tetrahydrofuran, ethers such as 1,2-dimethoxyethane, N, N-dimethylformamide and N-.
Amides such as methylpyrrolidone, sulfur-containing compounds such as dimethyl sulfoxide and sulfolane, nitriles such as acetonitrile, esters such as ethyl acetate, etc. are used. Of these, amides, sulfur-containing compounds and nitriles are preferable. Further, one or more kinds can be used in consideration of reaction conditions, boiling point, solubility, reactivity, odor, price and the like. The reaction temperature is preferably 50 to 100 ° C., more preferably 80 to 100 ° C. If the temperature is less than 50 ° C., the reaction progresses slowly and it is difficult to completely eliminate the raw materials. Yields a low yield. The reaction is preferably carried out with appropriate stirring.

(V) Synthesis of Compound (F) As the base used in the reaction, pyridine, triethylamine, an organic base such as 1,8-diazabicyclo [5,4,0] -7-undecene (DBU), potassium carbonate , Sodium hydrogen carbonate, potassium t-butoxide, sodium hydride, sodium hydroxide. Examples of the solvent used in the reaction include alcohols such as methanol, ethanol and isopropanol, hydrocarbons such as n-hexane, tetrahydrofuran, ethers such as 1,2-dimethoxyethane, N,
An amide such as N-dimethylformamide, N-methylpyrrolidone, a sulfur-containing compound such as dimethyl sulfoxide and sulfolane, a nitrile such as acetonitrile, an ester such as ethyl acetate and the like are used. Of these, amides, sulfur-containing compounds and nitriles are preferable. Further, one or more kinds can be used in consideration of reaction conditions, boiling point, solubility, reactivity, odor, price and the like. The reaction temperature is preferably 0 to 100 ° C., more preferably 1
When the temperature is 0 to 50 ° C. and the temperature is lower than 0 ° C., the progress of the reaction is slow and it is difficult to completely eliminate the raw materials.
If the temperature exceeds ℃, the yield will be low due to the formation of by-products. The reaction is preferably carried out with appropriate stirring.

(Vi) Synthesis of compound of general formula (II) 1 to 2 amines are added to the compound of general formula (F).
It is preferable to carry out the reaction using 0 molar equivalent, and
It is more preferable to use ˜12 molar equivalents. If the amount of ami is less than 1 molar equivalent, the yield is significantly reduced, and if it exceeds 20 molar equivalent, the production of by-products is increased. Examples of the solvent used in the reaction include alcohols such as methanol, ethanol and isopropanol, hydrocarbons such as n-hexane, tetrahydrofuran, ethers such as 1,2-dimethoxyethane, N, N-dimethylformamide and N-.
Amides such as methylpyrrolidone, sulfur-containing compounds such as dimethyl sulfoxide and sulfolane, nitriles such as acetonitrile, esters such as ethyl acetate, etc. are used. Of these, amides, sulfur-containing compounds and nitriles are preferable. Further, one or more kinds can be used in consideration of reaction conditions, boiling point, solubility, reactivity, odor, price and the like. The reaction temperature is preferably 50 to 100 ° C.
And more preferably 80 to 100 ° C., 50 ° C.
If it is less than 100 ° C, the progress of the reaction is slow and it is difficult to completely eliminate the raw material. If it exceeds 100 ° C, a byproduct is produced, resulting in a low yield. The reaction is preferably carried out with appropriate stirring.

(Vii) Synthesis of Compound (G) Examples of the solvent used in the reaction include alcohols such as methanol, ethanol and isopropanol, hydrocarbons such as n-hexane, tetrahydrofuran and 1,2-
Ethers such as dimethoxyethane, amides such as N, N-dimethylformamide, N-methylpyrrolidone,
Sulfur-containing compounds such as dimethyl sulfoxide and sulfolane, nitriles such as acetonitrile, esters such as ethyl acetate, etc. are used. Of these, amides, sulfur-containing compounds and nitriles are preferable. Also, in consideration of reaction conditions, boiling point, solubility, reactivity, odor, price, etc., one or
More can be used. The reaction temperature is preferably 0 to 100 ° C., more preferably 10 to 50 ° C. If the temperature is lower than 0 ° C., the reaction progresses slowly and it is difficult to completely eliminate the raw materials, and the temperature exceeds 100 ° C. And the yield is low due to the production of by-products. The reaction is preferably carried out with appropriate stirring.

(Viii) Synthesis of Compound of General Formula (III) Examples of the solvent used in the reaction include alcohols such as methanol, ethanol and isopropanol, hydrocarbons such as n-hexane, tetrahydrofuran, 1,2-
Ethers such as dimethoxyethane, amides such as N, N-dimethylformamide, N-methylpyrrolidone,
Sulfur-containing compounds such as dimethyl sulfoxide and sulfolane, nitriles such as acetonitrile, esters such as ethyl acetate, etc. are used. Of these, amides, sulfur-containing compounds and nitriles are preferable. Also, in consideration of reaction conditions, boiling point, solubility, reactivity, odor, price, etc., one or
More can be used. The reaction temperature is preferably 0 to 100 ° C., more preferably 10 to 50 ° C. If the temperature is lower than 0 ° C., the reaction progresses slowly and it is difficult to completely eliminate the raw materials, and the temperature exceeds 100 ° C. And the yield is low due to the production of by-products. The reaction is preferably carried out with appropriate stirring.

Specific examples are shown below.

Synthesis Example 1: Synthesis of Compound 1 Synthesis was carried out by the following route.

[0046]

[Chemical 20]

(I) Synthesis of compound (b) Compound (a) 66.6 g (0.3 mol), cyanoacetic acid 2
300 ml of acetic anhydride was added to 5.5 g (0.3 mol), and the mixture was stirred at room temperature for 2 hours. The precipitated crystals were collected by filtration and washed with isopropanol to obtain the desired product. Yield 75.2 g (98% yield)

(Ii) Synthesis of compound (c) 42.2 g (0.16 mol) of compound (b) above, 59.4 g (0.30 mol) of thionyl chloride and 3 drops of N, N-dimethylformamide were added. 500 ml of benzene was added and the mixture was heated under reflux for 1 hour. After cooling, the precipitated crystals were collected by filtration and washed with benzene to obtain the desired product. Yield 23.2 g (yield 51.5%)

(Iii) Synthesis of Compound (d) A solution of 23.0 g (0.084 mol) of the above compound (c) in 30 ml of tetrahydrofuran was stirred at room temperature while (1R, 2R)-(-)- A solution of 4.8 g (0.042 mol) of 1,2-diaminocyclohexane and 10.2 g (0.101 mol) of triethylamine in 50 ml of tetrahydrofuran was added dropwise. After completion of dropping, the mixture was stirred at room temperature for 1 hour, and then the precipitated hydrochloride was collected by filtration. The filtrate was concentrated and then recrystallized from ethyl acetate to obtain the desired product. Yield 18.0 g (73% yield)

(Iv) Synthesis of Compound 1 80 ml of acetonitrile was added to 14.8 g (0.025 mol) of the compound (d) and 36.6 g (0.50 mol) of diethylamine, and the mixture was heated under reflux for 30 minutes. After allowing to cool, the solvent was distilled off under reduced pressure, and recrystallization was carried out with ethyl acetate to obtain the desired product. Yield 4.5 g (Yield 38%) Melting point 185 ° C. UV spectrum (in methylene chloride) λmax = 364 nm λcut off = 433 nm Specific optical rotation (in methylene chloride) [α] ₃₉₇ = + 25000 ° Elemental analysis value CHN calculated value 66.92 8.21 18.01 Found 66.66 8.09 17.88

Synthesis Example 2: Synthesis of Compound 20 Synthesis was carried out by the following route.

[0052]

[Chemical 21]

(1R, 2R)-(-)-1,2-diaminocyclohexane 1.7 g (0.015 mol) Compound (e) 7.1 g (0.03 mol) in acetonitrile 40
ml was added, and the mixture was stirred at room temperature for 2 hours. The precipitated crystals were collected by filtration and recrystallized from acetonitrile to obtain the desired product. Yield 2.8 g (59% yield) Melting point 155 ° C. UV spectrum (in tetrahydrofuran) λmax = 384 nm λcut off = 458 nm Specific optical rotation (in methylene chloride) [α] ₃₉₂ = + 65000 ° Elemental analysis value C H N calculated value 67 .91 5.70 26.40 Found 68.19 5.67 26.50

Reference Example The optical rotation ([α] ₄₄₀ ) and transmittance (T ₄₄₀ %) at ₄₄₀ nm in the wavelength range used as blue light of visible light were measured.
The results are shown in Table 1. From these results, it is clear that the compound of the present invention is a useful optical rotatory compound which exhibits a large optical rotatory power in that region in spite of its high blue light transmittance.

[0055]

[Table 1]

[0056]

EFFECTS OF THE INVENTION It is possible to provide a useful compound having a high blue light transmittance and a large optical rotatory power in a blue light region.

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[Procedure amendment]

[Submission date] April 23, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Correction content]

The absorption maximum wavelength is 350 nm or more and 390
nm or less, and the molecular extinction coefficient is 40,
It is preferably 000 liter · mol ⁻¹ · cm ⁻¹ or more. Further, a 4 × 10 ⁻⁴ mol / liter ethanol solution of the compound has a transmittance of 95% at an optical path length of 1 cm at a wavelength of 4
It is preferably 60 nm or less. More preferably 4
It is 50 m or less. It is particularly preferable to use the compound represented by the general formula (I) as the chromophore. General formula (I)

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0019

[Correction method] Change

[Correction content]

The electron-withdrawing group represented by X and Y means a substituent having a positive substituent constant σ _p . The above-mentioned substituent constants can be found in the special issue “Chemistry” edited by the Structure-Activity Relations Forum
No. 2, “Structure-Activity Relationships of Drugs—Drug Design and Guidelines for Studying Mechanism of Action”, pp. 95-111, published by Nankodo, Corwin Hansch, Albert Leo, “Sub” "Stituant Constants for Correlation Analysis in Chemistry and Biology" (Substituen
t Constants for Correlation Analysis in Chemistry
and Biology pp. 69-161 The values shown in John Wiley and Sons.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0021

[Correction method] Change

[Correction content]

Z ¹ and Z ⁴ represent an atomic group necessary for forming a ring, and examples of the ring formed by them include cyclohexane, cyclopentane, 5α-cholestane-2α, 3β-diyl and α-D-. Examples include glucose.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0036

[Correction method] Change

[Correction content]

(I) Synthesis of Compound (B) It is preferable to react the compound represented by the general formula (A) with 1 equivalent or more of acetic anhydride. If the amount of acetic anhydride is less than 1 equivalent, the yield is significantly reduced. The reaction does not necessarily require a solvent. However, depending on the combination of reaction compounds used and the reaction conditions, a small amount of solvent can be used if necessary. Examples of such a solvent include alcohols such as methanol, ethanol and isopropanol, hydrocarbons such as n-hexane,
Tetrahydrofuran, ether such as 1,2-dimethoxyethane, N, N-dimethylformamide, amide such as N-methylpyrrolidone, dimethyl sulfoxide,
Sulfur-containing compounds such as sulfolane, nitriles such as acetonitrile, esters such as ethyl acetate, etc. are used. Of these, amides, sulfur-containing compounds and nitriles are preferable. Further, one or more kinds can be used in consideration of reaction conditions, boiling point, solubility, reactivity, odor, price and the like. The reaction temperature is preferably 0 to 100 ° C.,
More preferably, it is 10 to 50 ° C., and if the temperature is lower than 0 ° C., the progress of the reaction is slow and it is difficult to completely eliminate the raw materials, and if it exceeds 100 ° C., a by-product is generated, resulting in a low yield. . The reaction is preferably carried out with appropriate stirring.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Name of item to be corrected] 0037

[Correction method] Change

[Correction content]

(Ii) Synthesis of Compound (C) It is preferable to react the compound represented by the general formula (B) with 1 to 5 equivalents of thionyl chloride,
It is more preferable to use 2 to 4 equivalents. 1 thionyl chloride
If it is less than the equivalent, the yield is not significantly reduced, and if it exceeds 5 equivalents, the production of by-products is increased. Addition of a catalytic amount of N, N-dimethylformamide produces the desired product in good yield. Examples of the solvent used in the reaction include aromatic hydrocarbons (eg benzene, toluene, xylene, ethylbenzene etc.), ethers (eg anisole, tetrahydrofuran etc.), aliphatic hydrocarbons (eg hexane, ligroin, decalin etc.), halogenated hydrocarbons. (Eg, chloroform, dichloroethane, carbon tetrachloride, etc.), pyridine, nitrobenzene, acetonitrile, halogenated benzene (eg, chlorobenzene), reaction conditions,
One or more kinds can be used in consideration of boiling point, solubility, reactivity, odor, price and the like. The reaction temperature is preferably 50 to 100 ° C., more preferably 80.
~ 100 ° C, the reaction progresses slowly below 50 ° C,
It is difficult to completely eliminate the raw materials, and if the temperature exceeds 100 ° C., the yield is low due to the formation of by-products. The reaction is preferably carried out with appropriate stirring.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0039

[Correction method] Change

[Correction content]

(Iv) Synthesis of compound (E) 1 to 2 amines are added to the compound represented by the general formula (D).
It is preferable to carry out the reaction with 0 equivalents, preferably 8-12.
It is more preferable to use an equivalent amount. When the amount of amine is less than 1 equivalent, the yield is remarkably reduced, and when it exceeds 20 equivalents, the production of by-products is increased. Examples of the solvent used in the reaction include alcohols such as methanol, ethanol and isopropanol, hydrocarbons such as n-hexane, tetrahydrofuran, ethers such as 1,2-dimethoxyethane,
Amides such as N, N-dimethylformamide and N-methylpyrrolidone, sulfur-containing compounds such as dimethylsulfoxide and sulfolane, nitriles such as acetonitrile, esters such as ethyl acetate and the like are used. Of these, amides, sulfur-containing compounds and nitriles are preferable. Further, one or more kinds can be used in consideration of reaction conditions, boiling point, solubility, reactivity, odor, price and the like.
The reaction temperature is preferably 50 to 100 ° C., more preferably 80 to 100 ° C. If the reaction temperature is lower than 50 ° C., the reaction progresses slowly and it is difficult to completely eliminate the raw materials.
When the temperature exceeds 00 ° C, the yield is low due to the production of by-products. The reaction is preferably carried out with appropriate stirring.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0041

[Correction method] Change

[Correction content]

(Vi) Synthesis of compound of general formula (II) 1 to 2 amines are added to the compound of general formula (F).
It is preferable to carry out the reaction using 0 equivalent, and 8 to 1
It is more preferable to use 2 equivalents. When the amount of amine is less than 1 equivalent, the yield is remarkably reduced, and when it exceeds 20 equivalents, the production of by-products is increased. Examples of the solvent used in the reaction include alcohols such as methanol, ethanol and isopropanol, hydrocarbons such as n-hexane, tetrahydrofuran, ethers such as 1,2-dimethoxyethane, N, N-dimethylformamide and N-methyl. Amides such as pyrrolidone, dimethyl sulfoxide, sulfur-containing compounds such as sulfolane, nitriles such as acetonitrile, esters such as ethyl acetate and the like are used.
Of these, amides, sulfur-containing compounds and nitriles are preferable. Further, one or more kinds can be used in consideration of reaction conditions, boiling point, solubility, reactivity, odor, price and the like. The reaction temperature is preferably 50 to 100 ° C., more preferably 80 to 100 ° C. If the temperature is less than 50 ° C., the reaction proceeds slowly and it is difficult to completely eliminate the raw materials. Low yield due to the production of organisms. The reaction is preferably carried out with appropriate stirring.

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Claims (7)

[Claims] 1. In a compound having optical activity due to asymmetric exciton interaction, an absorption maximum wavelength in an ethanol solution of a chromophore, which is included as a part of the compound and expresses exciton interaction, is 300 nm. Above 400 nm and molecular extinction coefficient of 35,000 liters mol
A compound characterized by being ^-1 · cm ^-1 or more. 2. The compound of claim 1, further comprising 4 of
The wavelength at which the transmittance of an x10 ^-4 mol / liter ethanol solution at an optical path length of 1 cm is 95% is 460 nm or less. 3. The absorption maximum wavelength in an ethanol solution of the chromophore alone according to claim 1, which is 350 nm or more 39.
It is 0 nm or less and the molecular extinction coefficient is 40,000 liter · mol ⁻¹ · cm ⁻¹ or more. 4. The compound of claim 3, further comprising
The wavelength at which the transmittance of a 10 ⁻⁴ mol / liter ethanol solution at an optical path length of 1 cm is 95% is 450 nm or less. 5. A plurality of compounds represented by the following general formula (I):
Characterized by the chromophores being in asymmetric positions relative to each other
Exciton interaction type asymmetric compound. General formula (I)Where R¹And R²Is a hydrogen atom and an alkyl group,
Represents a reel group, R ¹And R²Forming a ring by
Well, R¹And R²May be the same. X and
Y represents an electron-withdrawing group, and X and Y may be the same.
Yes. 6. A compound represented by the following general formulas (II) and (III):
Compound. General formula (II)General formula (III):Where R³And R^Four, R^FiveAnd R⁶Is R¹And R
²Is synonymous with X^'And Y^', X^''And Y^'', X
^'''And Y^'''Is synonymous with X and Y. Z¹,
Z^FourRepresents an atomic group necessary for forming a ring. Z²And
And Z³Is an oxygen atom and NR⁹Represents R⁹Is hydrogen
Represents an atom and an alkyl group. Z²And Z ³Are the same
You may. R⁷And R⁸Is a hydrogen atom or alkyl group
And an aryl group. R⁷And R⁸Are the same
Good. 7. The following general formula (IV) and general formula (V):
A compound represented by. General formula (IV): General formula (V) In the formula, R ¹¹ and R ¹² have the same meaning as R ¹ and R ² ,
R ¹³ has the same meaning as R ⁷ and R ⁸ .