JP2003206271A - Optically active metacyclophane derivative and photochromic material using the same and optical recording medium - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optically active metacyclophane derivative suitable for optical recording medium capable of carrying out a non-destructive reading utilizing change of degree of polarization. <P>SOLUTION: The invention includes the optically active metacyclophane derivative expressed by formula [1] or [2] and the photochromic material comprising the optically active metacyclophane derivative and the optical recording medium utilizing a recording layer comprising the optically active metacyclophane derivative and irradiating the recording layer with polarized light and reading information by utilizing the change of the degree of polarization. (In the formula, preferable examples of R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>and R<SP>4</SP>are each H, cyano group, R<SP>1</SP>and R<SP>2</SP>, or R<SP>3</SP>and R<SP>4</SP>jointly express a hexafluoropropylene group, etc., R<SP>5</SP>, R<SP>6</SP>or R<SP>7</SP>are each independently H, tertiary butyl group, R<SP>8</SP>, R<SP>9</SP>are each methyl group, a broken line means a single or a double bond). <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel optically active metacyclophane derivative, a photochromic material, and an optical recording medium which causes a change in optical rotation by light irradiation, and more particularly to a material for performing nondestructive read of recording by optical read. .

[0002]

[Prior art]

Photochromic materials are materials containing molecules or molecular aggregates that reversibly generate two isomers in different states upon irradiation with light, such as optical recording media, optical filters such as sunglasses, masking materials, and displays. Widely used for various purposes such as materials.

A metacyclophane derivative has been reported as a photochromic compound and has been reported to undergo a reversible photochemical reaction represented by the formula [III] in the absence of oxygen (H. Cerfontain et al., Liebigs. Ann./Recl., 1
997, 5, 873 to 878).

[0004]

[Chemical 3]

Many metacyclophane derivatives have been synthesized for the purpose of obtaining a photochromic compound excellent in coloring, fading speed, wavelength characteristics, weather resistance, etc. (US Patents, 3,390, 192, 3,557,218, 3,697,585, 3,697,592, 3,697,60
4, 3,716,595, 3,719,709, 3,723,547, 3,728,394), there is no synthesis example of the optically active metacyclophane derivative according to the present invention, and no application example to an optical recording medium characterized by a change in optical rotation.

In addition, studies on photochromism using a racemic metacyclophane derivative have been reported (M. Takeshita, T. Yamato; Tetrahe
dron Lett. 2001, 42, 4 345, Y.-H. Lai, P. Chen; J, Org. Chem. 1997, 62, 6
06, S. Murakami, T. Ts utsui, S. Saito, A. Miyazawa, T. Yamato, M. Tashir
Chem. Lett. 1988, 5), but these all use a racemic compound, and show an example of the synthesis of an optically active metacyclophane derivative according to the present invention and an optical recording medium characterized by a change in optical rotation. There is no application example of.

Studies on the synthesis of optically active 10b, 10c-dihydropyrene derivatives have been reported (V. Boekelheide, E. Sturm; J. Am. Chem. S.
oc. 1969, 91, 902) has not been investigated for metacyclophane derivatives involved in this study and applied to optical recording media characterized by a change in optical rotation.

[0008]

[Problems to be Solved by the Invention]

Research on photon-mode recording using an organic photochromic material for the recording layer is underway, but the drawback is that the photoreaction of the photochromic material progresses during reading of the recording, and the molecular structure changes to the unrecorded state when read many times. there were. As one of the methods for solving this drawback, a reproducing method utilizing the optical activity of a photochromic material is disclosed in JP-A-63-259850 and JP-A-3-18.
It is disclosed in Japanese Patent Application Laid-Open No. 4041 and Japanese Patent Application Laid-Open No. 4-141492, and an optically active photochromic material can be used as a photon mode recording medium. Studies have been reported in which a photochromic material was introduced into the side chain of an optically active polymer to change the optical rotation (L. Angiolini, D. Caretti, C. Carlini; J. Polym. Sci., Part A,
Polym. Chem. 1994, 32, 1159, A. Altomare, F. Ciardelli, N. Tirelli, R. So
laro; Macromolecules 1997, 30, 1298) has a small amount of change in optical rotation. Further, an example in which an asymmetric molecule is introduced into a diarylethene molecule (Japanese Patent Laid-Open No. 9-7776).
7) or an example of introducing an asymmetric molecule into a fulgide molecule (Y. Yokoyama, Y. Kurosa).
Ki, T. Sagisaka, H. Az ami; Mol. Cryst. Liq. Cryst., 2000, 344, 223), but the amount of change in optical rotation is not sufficient, and in these cases, the photochromic molecule The asymmetric molecule introduced into the compound induces asymmetric induction during the ring-closing reaction due to light irradiation, causing a change in optical rotation, which is problematic in that it is easily affected by the surrounding environment and in the stability of repeated optical activity. .

[0009]

[Means for Solving the Problems]

As a result of intensive studies, the present inventors have succeeded in synthesizing an optically active metacyclophane derivative, and the photochromism between this derivative and the optically active dihydropyrene (or tetrahydropyrene) derivative is 100% enantioselective and sufficient. The present invention has been completed based on the finding that it progresses with a change in optical rotation and that both optically active ring-closed and ring-opened isomers are thermally stable compounds and sufficiently maintain optical activity.

[0010] That is, the present invention has the formula [1]

[0011]

[Chemical 4]

[0012] Or formula [2]

[0013]

[Chemical 5]

(In the formula [1] or the formula [2], R ¹ , R ² , R ³ and R ⁴ are
Independently hydrogen atom, halogen atom, nitro group, cyano group, carbon number 1 to 1
An alkyl group consisting of 0, a cycloalkyl group having 3 to 6 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms which may be optionally substituted with a fluorine atom or a chlorine atom, or R ¹ and R ² , Or R ³ and R ⁴ together form a hexafluoropropylene group,
-CO-NH-CNH-, -CO- NR 10 -CO- (R 10 is a hydrogen atom, 3 carbon atoms
~ 6 cycloalkyl group or an alkyl group having 1 to 10 carbon atoms (the alkyl group is a halogen atom, a hydroxyl group, an alkoxy group having 1 to 3 carbon atoms, a phenyl group (the phenyl group is a halogen atom, a carbon number of 1 Optionally substituted with an alkoxy group composed of 3 to 3 or an alkyl group composed of 1 to 10 carbons). ) Or carboxylic acid anhydride, provided that R ¹ , R ² , R ³ and R ⁴ do not mean the same group, and R ⁵ , R ⁶ and R ⁷ are independently hydrogen atoms. , An alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and 1 to 1 carbon atoms which may be optionally substituted with a fluorine atom or a chlorine atom.
0 represents a halogenated alkyl group or a diphenylamino group, and R ⁸ and R ⁹ are each independently a hydrogen atom, a halogen atom, an alkoxy group having 1 to 3 carbon atoms,
An alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a cycloalkoxy group having 3 to 6 carbon atoms, and 1 to 10 carbon atoms which may be optionally substituted with a fluorine atom or a chlorine atom. It represents a halogenated alkyl group, and the broken line part represents a single bond or a double bond. ) Relates to an optically active metacyclophane derivative.

[0015]

DETAILED DESCRIPTION OF THE INVENTION

Hereinafter, the present invention will be described in detail. First, each substituent will be specifically described.

In formula [1] or formula [2], R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, or a carbon number of 1 to 1.
An alkyl group consisting of 0, a cycloalkyl group having 3 to 6 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms which may be optionally substituted with a fluorine atom or a chlorine atom, or R ¹ and R ² , Or R ³ and R ⁴ together form a hexafluoropropylene group,
-CO-NH-CNH-, -CO- NR 10 -CO- (R 10 is a hydrogen atom, 3 carbon atoms
~ 6 cycloalkyl group or an alkyl group having 1 to 10 carbon atoms (the alkyl group is a halogen atom, a hydroxyl group, an alkoxy group having 1 to 3 carbon atoms, a phenyl group (the phenyl group is a halogen atom, a carbon number of 1 Optionally substituted with an alkoxy group composed of 3 to 3 or an alkyl group composed of 1 to 10 carbons). ) Or carboxylic acid anhydride, specifically, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and an alkyl group having 1 to 10 carbon atoms includes a methyl group. , Ethyl group, propyl group, isopropyl group, normal butyl group, isobutyl group, secondary butyl group, tertiary butyl group, normal pentyl group, amyl group, isoamyl group, tertiary amyl group, neopentyl group, normal hexyl group, heptyl group , An octyl group, a nonyl group, and a decyl group, and examples of the cycloalkyl group having 3 to 6 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group, which are optionally substituted with a fluorine atom or a chlorine atom. As the halogenated alkyl group having 1 to 10 carbon atoms which may be Trifluoromethyl group,
2,2,2-trifluoroethyl group, 1,1,2,2,2-pentafluoroethyl group and 2,2,3,3,3-pentafluoropropyl group, R ¹ and R ² , Alternatively, R ³ and R ⁴ together form a hexafluoropropylene group, —CO—NR ¹⁰ —
An alkyl group having 1 to ¹⁰ carbon atoms of R ¹⁰ in CO- (the alkyl group is a halogen atom, a hydroxyl group, an alkoxy group having 1 to 3 carbon atoms, a phenyl group
(The phenyl group may be optionally substituted with a halogen atom, an alkoxy group having 1 to 3 carbon atoms, or an alkyl group having 1 to 10 carbon atoms.). ), A methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a normal butyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, a cyclobutyl group, a normal pentyl group, an amyl group,
Isoamyl group, tertiary amyl group, neopentyl group, cyclopentyl group, normalhexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group, trifluoromethyl group, hydroxyethyl group, methoxymethyl group, benzyl group, methoxy group Examples thereof include a benzyl group, a methylbenzyl group and a chlorobenzyl group.

R ¹ , R ² , R ³ , and R ⁴ are preferably each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, a methyl group, an ethyl group, an isopropyl group, It represents a tertiary butyl group, a trifluoromethyl group, or R ¹ and R ² , or R ³ and R ⁴ together form a hexafluoropropylene group, —CO—NH—C NH—, —CO—NR ¹⁰ —CO— (R ¹⁰ represents a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group, a methoxymethyl group, a benzyl group, a methoxybenzyl group, a methylbenzyl group) or a carboxylic acid anhydride (provided that R 10 ¹ , R ² , R ³ and R ⁴ do not mean the same group), and more preferably each independently a hydrogen atom, a cyano group, or R ¹ and R ² , or R ³ and R 4. ^Four
Together with hexafluoropropylene group, -CO-NH-CNH-, -CO
—NR ¹⁰ —CO— (R ¹⁰ represents a hydrogen atom or a methylbenzyl group), or a carboxylic acid anhydride. However, R ¹ , R ² , R ³ , and R ⁴ do not mean the same group.

In formula [1] or formula [2], R ⁵ , R ⁶ , and R ⁷ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms. , 1 to 1 carbon atoms which may be optionally substituted with a fluorine atom or a chlorine atom
It represents a halogenated alkyl group consisting of 10 or a diphenylamino group, and specific examples of the alkyl group consisting of 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a normal butyl group and an isobutyl group. , Secondary butyl group, tertiary butyl group, normal pentyl group, amyl group, isoamyl group, tertiary amyl group, neopentyl group, cyclopentyl group, normal hexyl group, heptyl group, octyl group, nonyl group and decyl group, Examples of the cycloalkyl group having 3 to 6 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group, and a halogen having 1 to 10 carbon atoms which may be optionally substituted with a fluorine atom or a chlorine atom. Examples of the alkyl group are trifluoromethyl group, 2, , 2 - trifluoroethyl group, a 1,1,2,2,2-pentafluoroethyl group, 2, 2,3,3,3 and pentafluorophenyl propyl group.

R ⁵ and R ⁶ are preferably hydrogen atoms. Also,
R ⁷ is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, or a trifluoromethyl group. More preferably, R ⁵ and R ⁶ are hydrogen atoms and R ⁷ is a tertiary butyl group.

In formula [1] or formula [2], R ⁸ and R ⁹ are each independently a hydrogen atom, a halogen atom, an alkoxy group having 1 to 3 carbon atoms, or 1 to 1 carbon atom.
An alkyl group consisting of 0, a cycloalkyl group having 3 to 6 carbon atoms, a cycloalkoxy group having 3 to 6 carbon atoms, and 1 to 1 carbon atoms which may be optionally substituted with a fluorine atom or a chlorine atom.
It represents a halogenated alkyl group consisting of 10. Specifically, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and the number of carbon atoms is 1 to 3.
The alkoxy group consisting of, methoxy group, ethoxy group, propyloxy group,
An isopropyloxy group can be mentioned, and examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a normal butyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, a normal pentyl group. , Amyl group, isoamyl group, tertiary amyl group, neopentyl group, normalhexyl group, heptyl group, octyl group, nonyl group and decyl group, and the cycloalkyl group having 3 to 6 carbon atoms includes cyclopropyl group, Examples thereof include a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the cycloalkoxy group having 3 to 6 carbon atoms include a cyclopropyloxy group, and 1 to 10 carbon atoms which may be optionally substituted with a fluorine atom or a chlorine atom. The halogenated alkyl group consisting of Cyl group, 2,2,2-trifluoroethyl group, 1,1,2,
2,2-pentafluoroethyl group, 2,2,3,3,3-pentafluoropropyl group and the like can be mentioned. A methyl group, a methoxy group or a trifluoromethyl group is preferable, and a methyl group is more preferable.

Next, a method for producing the compounds represented by the formulas [1] and [2] will be described. The compounds [1] and [2] of the present patented compound can be synthesized by the following method.

[0022]

[Chemical 6]

(In the formula, R ^{1 to} R ⁹ are the same as above) That is, the reaction of the 3,3′-diCH ₂ X-substituted diaryl derivative [A] (X represents a suitable leaving group) with hydrocyanic acid ion. Is converted into a 3,3′-diCH ₂ CN-substituted diaryl derivative [B] (step a) by an oxidative intramolecular coupling reaction between α-positions of nitrile groups, and the desired [2,2] metacyclo The fan derivative [1] can be synthesized (step b). Further, it can be led to a ring-closed dihydropyrene (or tetrahydropyrene) derivative [2] by a photochemical reaction (step c). The obtained racemate is resolved using an optically active column to obtain an optically active metacyclophane derivative and an optically active dihydropyrene (or tetrahydropyrene) derivative represented by the formulas [1] and [2]. Hereinafter, each step will be described in more detail.

(Step a) This step is a substitution reaction for introducing a nitrile at the benzyl position. Examples of the group X (leaving group) to be substituted include a halogen atom such as a chlorine atom, a bromine atom and an iodine atom, and a sulfonyl group such as tosylate and mesylate. The reaction may be either homogeneous or heterogeneous. As the homogeneous reaction solvent, polar solvents represented by methanol, ethanol, acetonitrile, acetone, THF, DMF, DMSO and the like are preferable. The heterogeneous reaction solvent is preferably a two-layer system of water and a non-polar solvent such as benzene, toluene, xylene, carbon tetrachloride, chloroform, methylene chloride or dichloroethane. The nitrating agent is preferably lithium cyanide, sodium cyanide, potassium cyanate, ammonium cyanate, or the like. In the heterogeneous system, it is more preferable to allow an interlayer transfer catalyst such as tetrabutylammonium chloride, benzyltrimethylammonium chloride or trioctylmethylammonium chloride to be present. The reaction temperature is not particularly limited as long as it is in the range of the freezing point to the boiling point of the solvent, but 0 ° C to 80 ° C is preferable in terms of operation. The reaction time depends on the reaction conditions, but is preferably several hours to several tens of days.

The diallylethane and diallylethene derivatives that are the starting materials for this step are described in M. Tashiro, T. Yamato; Synthesis, 214 (197).
8) and M. Tashiro, T. Yamato; J. Org. Chem., 1981, 46, 1543 and the like.

(Step b) In this step, the tetrahydro [2,2] metacyclophane derivative of the present invention represented by the formula [1] or dihydro [2,2] is formed by an oxidative intramolecular coupling reaction at the α-position of nitrile. 2] A step of obtaining a metacyclophane derivative. The oxidizing agent used may be air, and it is not necessary to add a specific oxidizing agent. In this oxidative coupling reaction, a base catalyst is required because it is necessary to generate an anion at the α-position of nitrile. Examples of the base catalyst include inorganic salts such as lithium hydroxide, sodium hydroxide and potassium hydroxide, and organic bases such as DBU, DABCO and triethylamine.

The reaction may be a homogeneous system or a heterogeneous system. In the case of a homogeneous system, the reaction solvent is preferably an aprotic polar solvent such as THF, DMF or DMSO, and in the case of a heterogeneous system, the reaction solvent is benzene. , Non-polar solvents such as toluene, xylene, carbon tetrachloride, chloroform, methylene chloride and tetrachloroethane, and water are preferred. In a heterogeneous system, a phase transfer catalyst such as tetrabutylammonium chloride, benzyltrimethylammonium chloride or trioctylmethylammonium chloride is more preferably present. The reaction temperature is not particularly limited as long as it is in the range from the freezing point to the boiling point of the solvent, but 0 ° C to 80 ° C is preferable in terms of operation. The reaction time depends on the reaction conditions, but is preferably several hours to several tens of days.

(Step c) In this step, the [2,2] metacyclophane derivative obtained in the step (b) is subjected to an intramolecular cyclization reaction by light irradiation to obtain the compound of the present invention represented by the formula [2]. Certain ring-closed dihydropyrene (or tetrahydropyrene) derivatives are obtained. The reaction solvent is not particularly limited as long as it is a transparent solvent in which the starting material is dissolved and does not inhibit light irradiation, but methanol, ethanol, acetonitrile, acetone, diethyl ether, ethyl acetate, pyridine, benzene, toluene, xylene, THF. , DM
F, DMSO, carbon tetrachloride, chloroform and methylene chloride are preferred.

A racemic compound represented by the formula [1], in which R ⁸ and R ⁹ are methoxy groups, is a racemic compound described in T. Yamato, K. Fujita, K. Okuyama, H. Tsuzuki;
It can be synthesized by the method described in New J. Chem., 2000, 24, 221 etc.

A racemic compound represented by the formula [1], in which R ¹ and R ⁷ are chlorine atoms, includes T. Yamato, T. Ando, K. Tokuhisa, S. Ide, M. Tashir.
o; can be synthesized by the method described in J. Chem. Research (S), 1991, 152 and the like.

In the derivative represented by the formula [2], R ¹ is a nitro group, R ¹ and R ² are nitro groups, R ¹ and R ³ are nitro groups, or R ¹ , R ² and R
^The racemic compound in which ³ is a nitro group is T. Yamato, K. Fujita, H. Kamimura; Tet
It can be synthesized by the method described in rahedron 1995, 51, 985 1, etc.

A racemic compound represented by the formula [2], in which R ¹ is a bromine atom, or R ¹ is a methyl group, an ethyl group, or a propyl group is described by A. Miyazawa,
T. Yamato, M. Tashiro; J. Org. Chem., 1991, 56, 1334 and the like.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

[0034]

【Example】

Example 1 Synthesis of 1,2-bis (5-tert-butyl-3-cyanomethyl-2-methylphenyl) ethane

[0035]

[Chemical 7]

1,2-bis (5-tert-butyl-3-chloromethyl-2-methylphenyl) ethane (for the synthetic method of this compound, see M. Tashi
ro, T. Yamato, Journal of Organic Chemistry (J. Org. Chem.), 1
981, 46, 1543-1552) 2.03 g (5.0 mmol) of benzene 30 m
10 g of water, 2.0 g of sodium cyanide (41 mmo)
l), 100 mg of tetrabutylammonium bromide were added, and the mixture was placed on an oil bath at 60 ° C. for 1
Stir vigorously for 2 hours. The reaction solution was extracted with benzene, the organic layer was washed with saline, and then anhydrous magnesium sulfate was added and dried. The solvent was evaporated under reduced pressure, and the residue was recrystallized from a hexane-acetone mixed solvent to give 1.7 g of the title compound.
(4.3 mmol) with a yield of 85%.

Light yellow prismatic crystal (hexane-acetone) mp 152.0 -155.0 ° C. ¹ H NMR (CDCl ₃ , 25 ° C., 270 MHz) δ 1.29 (18H, s),
2.17 (6H, s), 2.90 (4H, s), 3.66 (4H, s), 7.07 (2H, s), 7.19 (2H, s)

6,13-Ditert-butyl-15,16-dimethyl-tricyclo [9. 3.1.1 ^4,8 ] Hexadeca-1 (15), 2,4 (1
6), 5,7,11,1 Synthesis of 3-heptane-2,3-dicarbonitrile

[0039]

[Chemical 8]

1.0 g (2.5 mmol) of 1,2-bis (5-tert-butyl-3-cyanomethyl-2-methylphenyl) ethane was added to benzene 2
It was dissolved in a mixed solvent of 0 ml and 5 ml of carbon tetrachloride and vigorously stirred, 10 g of 50% aqueous sodium hydroxide solution, 100 mg of tetrabutylammonium bromide, and 5 parts of benzene.
ml and 5 ml of carbon tetrachloride were added dropwise at 50 ° C. over 12 hours. After further stirring vigorously at this temperature for 12 hours, the reaction solution was extracted with benzene. The organic layer was washed with brine, dried over anhydrous magnesium sulfate and dried. The solvent was evaporated under reduced pressure, the residue was subjected to silica gel column chromatography, and the hexane + dichloromethane (1: 1) fraction was recrystallized from a hexane-acetone mixed solvent to give 320 mg (0 0.81 mmol) and the yield was 32%.

Pale yellow prism crystal (hexane-acetone) mp 222.0 -224.0 ° C. ¹ H NMR (CDCl ₃ , 25 ° C., 270 MHz) δ 0.72 (6H, s), 1.
30 (18H, s), 2.50 (2H, d, J = 8 Hz), 2.98 (2H, d, J = 8 Hz), 7.19 (4H, s)

6,16-Ditertiarybutyl-18,19-dimethyl-11-oxatetracyclo [12.3.1.1 ^4,8 . 0 ^9,13] nonadec -
Synthesis of 1 (18), 4 (19), 5,7,9 (13), 14 (15), 16-heptaene-10,12-dione

[0043]

[Chemical 9]

6,13-Ditert-butyl-15,16-dimethyl-tricyclo [9. 3.1.1 ^4,8 ] Hexadeca-1 (15), 2,4 (1
6), 5,7,11,1 3-heptane-2,3-dicarbonitrile 400 mg
(1.0 mmol) is dissolved in 5 ml of ethylene glycol monomethyl ether,
To this, 2.0 ml of 50% potassium hydroxide aqueous solution was added, and the mixture was heated under reflux for 18 hours. The reaction mixture was poured into water and acidified with concentrated hydrochloric acid. The mixture was extracted with chloroform, the extract was washed with saline, and magnesium sulfate was added to dry the extract. The solvent was distilled off under reduced pressure, and the residue was recrystallized from hexane to give 350 mg of the title compound.
(0.84 mmol), and the yield was 84%.

Brown prism crystal (hexane) mp 214-216 ° C MS (EI) m / z 416 [M ⁺ ] ¹ H NMR (CDCl ₃ , 25 ° C, 270 MHz) δ 0.66 (6H, s), 1.31
(18H, s), 2.58 (2H, d, J = 8Hz), 3.00 (2H, d, J = 8Hz), 7.16 (2H, d, J = 2Hz), 7.18
(2H, d, J = 2Hz)

Example 2 11-Aza-6,16-ditertiarybutyl-12-
Imino-18,19-dimethyltetracyclo [12.3.1.1 ^4,8 . 0 ^9,13 ]
Nonadeka-1 (18), 4 (19), 5, 7, 9 (13), 14 (15), 16
-Synthesis of heptaen-10-one

[0047]

[Chemical 10]

6,13-Ditert-butyl-15,16-dimethyl-tricyclo [9. 3.1.1 ^4,8 ] Hexadeca-1 (15), 2,4 (1
6), 5,7,11,1 3-heptane-2,3-dicarbonitrile 100 mg
(0.25 mmol) was dissolved in 5 ml of toluene and cooled to −70 ° C., 0.70 ml of DIBAL-H (1.0 M toluene solution) was added thereto, and the mixture was stirred at this temperature for 30 minutes.
Stir for minutes. After warming to room temperature, the reaction mixture was poured into water and acidified with hydrochloric acid. The mixture was extracted with chloroform, the extract was washed with saline, and magnesium sulfate was added to dry the extract. The solvent was evaporated under reduced pressure, the residue was subjected to silica gel column chromatography, and the fraction of hexane / acetone (3: 1) was recrystallized from a hexane / acetone mixed solvent to give 70 mg (0.17 mmol of the title compound). ), And the yield was 68%.

Yellow prism crystal (hexane) mp 250-251 ° C MS (EI) m / z 415 [M ⁺ ] ¹ H NMR (CDCl ₃ , 25 ° C, 270 MHz) δ 0.61 (3H, s), 0.62
(3H, s), 1.30 (9H, s), 1.32 (9H, s), 2.57 (2H, d, J = 7Hz), 2.99 (2H, d, J = 7Hz),
6.91 (1H, s), 7.11 (2H, d, J = 2Hz), 7.19 (2H, d, J = 2Hz), 8.85 (1H, br.s)

Example 3 11-Aza-6,16-ditertiarybutyl-18,
19-Dimethyl-11-((4-methylphenyl) methyl) tetracyclo [1
2.3.1.1 ^4,8 . 0 ^{9,1 3]} nonadeca-1 (18), 4 (19), 5,7,9
Synthesis of (13), 14 (15), 16-heptaene-10,12-dione

[0051]

[Chemical 11]

6,16-Ditertiarybutyl-18,19-dimethyl-11-oxatetracyclo [12.3.1.1 ^4,8 . 0 ^9,13] nonadec -
1 (18), 4 (19), 5,7,9 (13), 14 (15), 16-heptaene-10,12-dione 50 mg (0.12 mmol) to 4-methylbenzylamine 50 mg (0.4 mm ol) and heated at 120 ° C. for 2 hours. The reaction mixture was cooled to room temperature and then subjected to silica gel column chromatography, and the hexane / acetone (3: 1) fraction was recrystallized from hexane to give 30 mg (0.058 mmol) of the title compound in a yield. Obtained in 48%.

Yellow prism (hexane) mp 69-71 ° C. MS (EI) m / z 519 [M ⁺ ] ¹ H NMR (CDCl ₃ , 25 ° C., 300 MHz) δ 0.62 (6H, s), 1.29
(18H, s), 2.36 (3H, s), 2.55 (d, 2H, J = 9Hz), 2.96 (d, 2H, J = 9Hz), 4.80 (2H,
d), 7.10-7.12 (5H, m), 7.20 (2H, 8Hz), 7.46 (2H, 8Hz)

[Optical Resolution of Enantiomer] Each of the compounds obtained in Examples 1, 2, and 3 was applied to a high-performance liquid chromatograph CCPM manufactured by Tosoh Corporation and an optically active column AD-H manufactured by Daicel Corporation.
, And the enantiomers were optically resolved by using a mixed solvent of normal hexane and isopropyl alcohol as a mobile phase. Examples 1, 2 and 3
The high performance liquid chromatograph charts of the compounds obtained in 2 and 3 are shown.

[Confirmation of Photochromism Phenomenon by Change in Absorption Spectrum of Enantiomer] Changes in absorption spectrum of optically resolved metacyclophan-1-enes by irradiation with ultraviolet light are shown in FIGS. The compounds obtained in Examples 1, 2, and 3 were dissolved in a mixed solvent of normal hexane and dichloromethane,
Irradiated with ultraviolet rays. The pale yellow solution became purple, and a new absorption band appeared in the visible region as shown by the arrow in the figure. Also, by irradiating visible light of 500 nm or more,
It was confirmed that this absorption band disappeared immediately and the photochromism phenomenon was returned to the original spectrum.

[Circular dichroism spectrum change of enantiomer] Circular dichroism spectrum changes of the compounds obtained in Examples 2 and 3 which are optically resolved are shown in FIGS. 7 and 8, respectively. FIG. 7 shows a case where each enantiomer (solid line) synthesized in Example 2 and optically divided is irradiated with 366 nm light (dotted line).
Is the change in the circular dichroism spectrum of. These compounds show completely symmetrical circular dichroism, indicating that they are optically active substances and antipodes having opposite optical rotations. Further, the circular dichroism spectrum obtained by irradiating light with 366 nm is also completely symmetrical, and it is understood that the ring-closed body generated by light irradiation is also an enantiomer. On the other hand, 50
When it was returned to the ring-opened body by irradiation with visible light of 0 nm or more, the exact same circular dichroism spectrum was obtained. This suggests that this compound can carry out a photochromic reaction between two states of an opened ring and a closed ring without any racemization. FIG. 8 shows the time change of the circular dichroism spectrum when one enantiomer of the compound obtained in Example 3 was irradiated with 313 nm ultraviolet light. As the irradiation time becomes longer, the amount of the ring-closed body (colored body) increases (FIG. 6), and the circular dichroism spectrum largely changes in the direction of the arrow in the figure. On the other hand, 5
Upon irradiation with visible light of 00 nm or more, the original circular dichroism spectrum was rapidly exhibited. This shows that even in the compound of Example 3, racemization did not proceed at all in the photochromic reaction.

Further, the enantiomer of the compound of Example 3 did not deteriorate in optical activity even after heating at 200 ° C. for 1 hour, and racemization did not proceed.

As described above, the optically active metacyclophane derivative is useful as a recording medium that uses optical activity for reading because it performs a photochromic reaction without racemization, and optical rotation of a recording layer using the same is achieved. Recording and reading are possible by measuring the degree.

[0059]

【The invention's effect】

The present invention has provided an optically active metacyclophane derivative useful as an optical recording medium. This derivative exhibits enantioselective photochromism with a large change in optical rotation, and information can be reproduced by utilizing the optical rotation of light in the wavelength region where the photochromic material has almost no absorption. You can

[Brief description of drawings]

1 is a high performance liquid chromatography chart equipped with a chiral column of the compound obtained in Example 1. FIG. (Numbers are retention time (minutes)
Indicates. )

FIG. 2 is a high performance liquid chromatography chart equipped with a chiral column of the compound obtained in Example 2. (Numbers are retention time (minutes)
Indicates. )

FIG. 3 is a high performance liquid chromatography chart equipped with a chiral column of the compound obtained in Example 3. (Numbers are retention time (minutes)
Indicates. )

FIG. 4 is a change in absorption spectrum with irradiation time when a hexane solution of the compound obtained in Example 1 was irradiated with ultraviolet light.

FIG. 5 is a change in absorption spectrum according to irradiation time when a hexane solution of the compound obtained in Example 2 is irradiated with ultraviolet light.

FIG. 6 is a change in absorption spectrum depending on irradiation time when a hexane solution of the compound obtained in Example 3 is irradiated with ultraviolet light.

FIG. 7 is a circular dichroism spectrum of a hexane solution of each of the divided antipodes of the compound obtained in Example 2 and a circular dichroism spectrum when each is irradiated with ultraviolet light. .

FIG. 8 shows the circular dichroism spectrum of the hexane solution of one of the divided antipodes of the compound obtained in Example 3 and the irradiation time of the circular dichroism spectrum when irradiated with ultraviolet light. It's a change.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G11B 7/24 516 G11B 7/24 516 // C07B 57/00 350 C07B 57/00 350 C07M 7:00 C07M 7:00

Claims (6)

[Claims] 1. A formula [1]: Or formula [2] (In the formula [1] or the formula [2], R ¹ , R ² , R ³ and R ⁴ are
Independently hydrogen atom, halogen atom, nitro group, cyano group, carbon number 1 to 1
An alkyl group consisting of 0, a cycloalkyl group having 3 to 6 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms which may be optionally substituted with a fluorine atom or a chlorine atom, or R ¹ and R ² , Or R ³ and R ⁴ together form a hexafluoropropylene group,
-CO-NH-CNH-, -CO- NR 10 -CO- (R 10 is a hydrogen atom, 3 carbon atoms
~ 6 cycloalkyl group or an alkyl group having 1 to 10 carbon atoms (the alkyl group is a halogen atom, a hydroxyl group, an alkoxy group having 1 to 3 carbon atoms, a phenyl group (the phenyl group is a halogen atom, a carbon number of 1 Optionally substituted with an alkoxy group composed of 3 to 3 or an alkyl group composed of 1 to 10 carbons). ) Or carboxylic acid anhydride, provided that R ¹ , R ² , R ³ and R ⁴ do not mean the same group, and R ⁵ , R ⁶ and R ⁷ are independently hydrogen atoms. , An alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and 1 to 1 carbon atoms which may be optionally substituted with a fluorine atom or a chlorine atom.
0 represents a halogenated alkyl group or a diphenylamino group, and R ⁸ and R ⁹ are each independently a hydrogen atom, a halogen atom, an alkoxy group having 1 to 3 carbon atoms,
An alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a cycloalkoxy group having 3 to 6 carbon atoms, and 1 to 10 carbon atoms which may be optionally substituted with a fluorine atom or a chlorine atom. It represents a halogenated alkyl group, and the broken line part represents a single bond or a double bond. ) An optically active metacyclophane derivative represented by: 2. In the formula [1] or the formula [2],
The optically active metacyclophane derivative according to claim 1, wherein R ⁵ and R ⁶ are hydrogen atoms, and R ⁸ and R ⁹ are methoxy groups, methyl groups, or trifluoromethyl groups. 3. In formula [1] or formula [2],
R ¹ , R ² , R ³ , and R ⁴ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a cyano group, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, or a tributyl group. Represents a fluoromethyl group, or R ¹ and R ² or R ³ and R ⁴ together form a hexafluoropropylene group, —CO—NH—CNH—, —CO—NR
^10- CO- (R ¹⁰ is a hydrogen atom, or a methyl group, an ethyl group (the methyl group and the ethyl group are a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group, a methoxy group, a phenyl group (the phenyl group is a methoxy group or Optionally substituted with a methyl group))) or a carboxylic acid anhydride (provided that R is R).
^{All of 1} , R ² , R ³ and R ⁴ do not mean the same group. ), R ⁵ and R ⁶ are hydrogen atoms, R ⁷ is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, or a trifluoromethyl group, and R ⁸ and R ⁹ are methoxy groups, The optically active metacyclophane derivative according to claim 1, which is a methyl group or a trifluoromethyl group. 4. In formula [1] or formula [2],
R¹, R², R³, R^FourBut, Each independently represent a hydrogen atom, a cyano group, or R¹When
R², Or R³And R^FourTogether Becomes a hexafluoropropylene group, -CO-NH-
CNH-, -CO-NR ^Ten -CO- (R^TenIs a hydrogen atom or 4-methylbenzyl
Represents a group. ), Or Cal Boric acid anhydride (provided that R¹, R², R³, R^FourAll of
Never mean the same group Yes. ), R^Five, R⁶Is a hydrogen atom, and R⁷Is tertiary
-Butyl group, R⁸, R⁹The optically active metasic according to claim 1, wherein is a methyl group.
Rophane derivative. 5. A photochromic material comprising the optically active metacyclophane derivative according to any one of claims 1 to 4. 6. Use of a recording layer containing the optically active metacyclophane derivative according to any one of claims 1 to 4 to irradiate polarized light to read information using a change in optical rotation of the recording layer. An optical recording medium characterized by performing.