JP4702740B2 - Photochromic material and optical recording medium using thiophene derivative - Google Patents

Description

  The present invention relates to a novel thiophene derivative, a photochromic material using the thiophene derivative, and an optical recording medium.

A photochromic material is a material containing a molecule or molecular assembly that reversibly generates two isomers having different states upon irradiation with light.
In recent years, this photochromic material has been widely used in various applications such as optical recording media, optical filters such as sunglasses, masking materials, and display materials.
Metacyclophane derivatives have been reported as photochromic compounds, and are known to cause a reversible photochemical reaction represented by the following formula [I] in the absence of oxygen (see, for example, Non-Patent Document 1). ).

As for this metacyclophane derivative, many compounds have been synthesized for the purpose of obtaining a photochromic compound excellent in coloring, fading speed, wavelength characteristics, weather resistance and the like (for example, see Patent Documents 1 to 9).
Furthermore, research on photochromism using metacyclophane derivatives (for example, see Non-Patent Documents 2 to 6) and enantioselective photochromism using optically active metacyclophane (for example, see Patent Document 10) are also conducted. ing.
However, these all use metacyclophane compounds, and there is no synthesis example of a thiophene derivative related to the present invention and no application example to an optical recording medium.
In addition, enantioselective photochromism using an optically active thiophene derivative (for example, see Patent Document 11) has been reported, but this compound has a problem in the thermal stability of the ring-closed product.

U.S. Pat. No. 3,390,192 US Pat. No. 3,557,218 US Pat. No. 3,697,585 US Pat. No. 3,697,592 US Pat. No. 3,697,604 U.S. Pat. No. 3,716,595 US Pat. No. 3,719,709 US Pat. No. 3,723,547 U.S. Pat. No. 3,728,394 JP 2003-206271 A Japanese Patent Application Laid-Open No. 2004-262969 H. Cerfontain et al., Liebigs Ann./Recl., 1997, 5, 873-878 M. Takeshita, T. Yamato; Tetrahedron Lett., 2001, 42, 4345 R.H.Mitchell, T.R.Ward, Y.Wang; Heterocycles, 2001,54,249 Y.-H.Lai, P.Chen; J.Org.Chem., 1997,62,606 Y.-H.Lai, P.Chen; J.Org.Chem., 1996,61,935 S. Murakami, T. Tsutsui, S. Saito, A. Miyazawa, T. Yamato, M. Tashiro; Chem. Lett., 1988, 5

  The present invention has been made in view of such circumstances, and is a thiophene derivative that is excellent in thermal stability and causes a photocyclization reaction at a high quantum yield, a photochromic material using the thiophene derivative, and an optical recording medium The purpose is to provide.

  As a result of intensive studies to achieve the above object, the present inventors have determined that a thiophene derivative having both excellent thermal stability and high quantum yield of photocyclization reaction is obtained in both the ring-opened and closed ring isomers. The headline and the present invention were completed.

｛式中、Ａは、

を表し、Ｅは、−（ＣＨ₂）_n−（ｎは、０または１を表す。）、−Ｏ−、−Ｓ−、−Ｓ（Ｏ）−、−Ｓ（Ｏ）₂−、または−ＮＲ⁵−〔Ｒ⁵は、水素原子、炭素数３〜６のシクロアルキル基、炭素数１〜１０のアルキル基〈該アルキル基は、ハロゲン原子、ヒドロキシル基、炭素数１〜３のアルコキシ基、フェニル基（該フェニル基は、ハロゲン原子、炭素数１〜３のアルコキシ基、または炭素数１〜１０のアルキル基で任意に置換されていてもよい。）で任意に置換されていてもよい。〉、またはフェニル基（該フェニル基は、ハロゲン原子、炭素数１〜３のアルコキシ基、または炭素数１〜１０のアルキル基で任意に置換されていてもよい。）を表す。〕を表し、Ｒ¹およびＲ²は、それぞれ独立して、水素原子、ハロゲン原子、ニトロ基、シアノ基、炭素数１〜１０のアルキル基、炭素数３〜６のシクロアルキル基、またはフッ素原子もしくは塩素原子で任意に置換されてもよい炭素数１〜１０のハロゲン化アルキル基を表すか、Ｒ¹とＲ²とが一緒になってヘキサフルオロプロピレン基、−ＣＯ−ＮＨ−ＣＮＨ−、−ＣＯ−ＮＲ⁵−ＣＯ−（Ｒ⁵は、前記に同じ。）、またはカルボン酸無水物を表し、Ｒ³およびＲ⁴は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１〜３のアルコキシ基、炭素数３〜６のシクロアルキル基、炭素数３〜６のシクロアルコキシ基、炭素数１〜１０のアルキル基、フッ素原子もしくは塩素原子で任意に置換されてもよい炭素数１〜１０のハロゲン化アルキル基、またはジフェニルアミノ基を表す。｝
２． 前記Ｒ³およびＲ⁴が、それぞれ独立して水素原子、メトキシ基、メチル基、エチル基、イソプロピル基、ターシャリーブチル基、またはトリフルオロメチル基である１のチオフェン誘導体、
３． 前記Ａが、

であり、前記Ｅが、−Ｏ−、−Ｓ−、または−ＮＲ⁵−〔Ｒ⁵は、水素原子、メチル基、エチル基〈該メチル基およびエチル基は、フッ素原子、塩素原子、臭素原子、ヒドロキシル基、メトキシ基、フェニル基（該フェニル基はメトキシ基またはメチル基で置換されていてもよい。）で任意に置換されていてもよい。〉、またはフェニル基（該フェニル基はメトキシ基またはメチル基で置換されていてもよい。）を表す。〕であり、前記Ｒ¹およびＲ²が、それぞれ独立して、水素原子、フッ素原子、塩素原子、臭素原子、ニトロ基、シアノ基、メチル基、エチル基、イソプロピル基、ターシャリーブチル基、トリフルオロメチル基であるか、Ｒ¹とＲ²とが一緒になってヘキサフルオロプロピレン基、−ＣＯ−ＮＨ−ＣＮＨ−、−ＣＯ−ＮＲ⁵−ＣＯ−〔Ｒ⁵は、水素原子、メチル基、エチル基〈該メチル基およびエチル基は、フッ素原子、塩素原子、臭素原子、ヒドロキシル基、メトキシ基、フェニル基（該フェニル基は、メトキシ基またはメチル基で置換されていてもよい。）で任意に置換されていてもよい。〉、またはフェニル基（該フェニル基は、メトキシ基またはメチル基で置換されていてもよい。）を表す。〕、またはカルボン酸無水物である１または２のチオフェン誘導体、
４． 前記Ｅが、−Ｓ−であり、前記Ｒ¹およびＲ²が、これらが一緒になってヘキサフルオロプロピレン基であり、前記Ｒ³およびＲ⁴が、メチル基である１〜３のいずれかのチオフェン誘導体、
５． １〜４のいずれかのチオフェン誘導体から成るフォトクロミック材料、
６． １〜４のいずれかのチオフェン誘導体を含有する記録層を備える光記録媒体
を提供する。 That is, the present invention
1. A thiophene derivative represented by the formula [1] or the formula [2],

{Where A is

And E represents — (CH ₂ ) _n — (n represents 0 or 1), —O—, —S—, —S (O) —, —S (O) ₂ —, or — NR ⁵ — [R ⁵ is a hydrogen atom, a cycloalkyl group having 3 to 6 carbon atoms, 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, It may be optionally substituted with 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). > Or 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). R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or a fluorine atom. Alternatively, it represents a halogenated alkyl group having 1 to 10 carbon atoms which may be optionally substituted with a chlorine atom, or R ¹ and R ² together form a hexafluoropropylene group, —CO—NH—CNH—, — CO—NR ⁵ —CO— (R ⁵ is the same as above), or carboxylic anhydride, R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, or a carbon number of 1 to 3 C1-C10 which may be optionally substituted with an alkoxy group, a C3-C6 cycloalkyl group, a C3-C6 cycloalkoxy group, a C1-C10 alkyl group, a fluorine atom or a chlorine atom Al halides of It represents a group or a diphenylamino group. }
2. 1 thiophene derivative, wherein R ³ and R ⁴ are each independently a hydrogen atom, methoxy group, methyl group, ethyl group, isopropyl group, tertiary butyl group, or trifluoromethyl group,
3. A is

Wherein E is —O—, —S—, or —NR ⁵ — [R ⁵ is a hydrogen atom, 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, and a phenyl group (the phenyl group may be optionally substituted with a methoxy group or a methyl group). > Or a phenyl group (the phenyl group may be substituted with a methoxy group or a methyl group). And each of R ¹ and R ² independently represents 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 tertiary butyl group, a tributyl group, A fluoromethyl group, or R ¹ and R ² are combined to form a hexafluoropropylene group, —CO—NH—CNH—, —CO—NR ⁵ —CO— [wherein R ⁵ is a hydrogen atom, a methyl group, Ethyl group <The methyl group and the ethyl group may be any fluorine atom, chlorine atom, bromine atom, hydroxyl group, methoxy group, or phenyl group (the phenyl group may be substituted with a methoxy group or a methyl group). May be substituted. > Or a phenyl group (the phenyl group may be substituted with a methoxy group or a methyl group). Or 1 or 2 thiophene derivatives which are carboxylic anhydrides,
4). Any one of 1 to 3 wherein E is -S-, R ¹ and R ² together are a hexafluoropropylene group, and R ³ and R ⁴ are a methyl group Thiophene derivatives,
5. A photochromic material comprising any one of the thiophene derivatives 1 to 4,
6). An optical recording medium comprising a recording layer containing any one of 1-4 thiophene derivatives is provided.

  As will be described later, the thiophene derivative of the present invention exhibits photochromism with a high quantum yield. This thiophene derivative is useful as an optical recording medium because both the open and closed isomers are excellent in thermal stability and the quantum yield of the photocyclization reaction is high.

Hereinafter, the present invention will be described in more detail.
First, each substituent in the above formulas [1] and [2] will be specifically described.
In the above formulas [1] and [2], A is

Are preferably the groups shown below.

E represents — (CH ₂ ) _n — (n represents 0 or 1), —O—, —S—, —S (O) —, —S (O) ₂ —, or —NR ⁵ —. [R ⁵ is a hydrogen atom, a cycloalkyl group having 3 to 6 carbon atoms, an alkyl group having 1 to 10 carbon atoms (this alkyl group is a halogen atom, a hydroxyl group, an alkoxy group having 1 to 3 carbon atoms, a phenyl group ( This 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. > Or a phenyl group (this 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). ] Is represented.

Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Specific 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.
Specific examples of the alkoxy group having 1 to 3 carbon atoms include methoxy group, ethoxy group, propyloxy group, isopropyloxy group and the like.

Specific examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, normal butyl group, isobutyl group, secondary butyl group, tertiary butyl group, cyclobutyl group, normal Examples include a pentyl group, an amyl group, an isoamyl group, a tertiary amyl group, a neopentyl group, a cyclopentyl group, a normal hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group.
Specific examples of the alkyl group having 1 to 10 carbon atoms which may be optionally substituted with a halogen atom or the like include the trifluoromethyl group and hydroxyethyl group in addition to the groups exemplified as the alkyl group having 1 to 10 carbon atoms. Methoxymethyl group, benzyl group, methoxybenzyl group, methylbenzyl group, chlorobenzyl group and the like.
Examples of the phenyl group optionally substituted with a halogen atom and the like include a phenyl group, a tolyl group, a chlorophenyl group, a dichlorophenyl group, and a bromophenyl group.

Among them, as E, —O—, —S—, or —NR ⁵ — [R ⁵ is a hydrogen atom, a methyl group, an ethyl group (these methyl group and ethyl group are a fluorine atom, a chlorine atom, a bromine atom, , A hydroxyl group, a methoxy group, a phenyl group (this phenyl group may be optionally substituted with a methoxy group or a methyl group), or a phenyl group (this phenyl group is And may be substituted with a methoxy group or a methyl group. ) Is preferred, and -S- is more preferred.

R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or a fluorine atom or a chlorine atom. Represents a halogenated alkyl group having 1 to 10 carbon atoms which may be substituted, or R ¹ and R ² together form a hexafluoropropylene group, —CO—NH—CNH—, —CO—NR ⁵ —. CO- (R ⁵ is a hydrogen atom, a cycloalkyl group having 3 to 6 carbon atoms, an alkyl group having 1 to 10 carbon atoms (this alkyl group is a halogen atom, a hydroxyl group, an alkoxy group having 1 to 3 carbon atoms, phenyl (This 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). ,Also Represents a phenyl group (this 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), or carboxylic anhydride Represents a thing.

Here, specific examples of the halogenated alkyl group having 1 to 10 carbon atoms which may be optionally substituted with a fluorine atom or a chlorine atom include a trifluoromethyl group, a 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.
In addition, the C1-C10 optionally substituted with a halogen atom, a C3-C6 cycloalkyl group, a C1-C3 alkoxy group, a C1-C10 alkyl group, a halogen atom, etc. Specific examples of the phenyl group optionally substituted with an alkyl group, a halogen atom or the like include the same groups as those described above.

Among them, R ¹ and R ² are each independently hydrogen atom, fluorine atom, chlorine atom, bromine atom, nitro group, cyano group, methyl group, ethyl group, isopropyl group, tertiary butyl group, trifluoromethyl. Or R ¹ and R ² together form a hexafluoropropylene group, —CO—NH—CNH—, —CO—NR ⁵ —CO— (R ⁵ is a hydrogen atom, a methyl group, an ethyl group, , A trifluoromethyl group, a methoxymethyl group, a benzyl group, a methoxybenzyl group, a methylbenzyl group, a phenyl group, a methylphenyl group, or a methoxyphenyl group), or a carboxylic anhydride. A hydrogen atom or a cyano group, or R ¹ and R ² together form a hexafluoropropylene group, —CO—NR ⁵ —CO— (R ⁵ Represents a hydrogen atom or a methylbenzyl group.), Or a carboxylic anhydride.

R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, an alkoxy group having 1 to 3 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a cycloalkoxy group having 3 to 6 carbon atoms, or 1 carbon atom. Represents an alkyl group having 1 to 10 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 a diphenylamino group.
Here, specific examples of the C3-C6 cycloalkoxy group include a cyclopropyloxy group.
The halogen atom, an alkoxy group having 1 to 3 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a fluorine atom or a chlorine atom which may be optionally substituted. Specific examples of the 10 halogenated alkyl groups are the same as those described above.
Among these, as R ³ and R ⁴ , a hydrogen atom, a methyl group, a methoxy group, an isopropyl group, a tertiary butyl group, and a trifluoromethyl group are preferable, and a methyl group is more preferable.

Next, regarding the method for producing each compound represented by Formula [1] and Formula [2], when E is —O—, —S—, or —NR ⁵ — (R ⁵ is the same as above). Is described as an example.
The compounds represented by the above formulas [1] and [2] can be synthesized by the following method.

（式中、Ａ、Ｒ¹、Ｒ²、Ｒ³およびＲ⁴は、上記と同じ。Ｅは、−Ｏ−、−Ｓ−、または−ＮＲ⁵−（Ｒ⁵は上記と同じ。）を表し、Ｘはハロゲン原子を表す。）

(Wherein A, R ¹ , R ² , R ³ and R ⁴ are the same as above. E represents —O—, —S—, or —NR ⁵ — (R ⁵ is the same as above)). , X represents a halogen atom.)

That is, the bis (chloromethyl) dithienylethene derivative [A] is reacted with thiourea and then hydrolyzed with sodium hydroxide to obtain the bis (mercaptomethyl) dithienylethene derivative [B] (step (a)).
The desired thiophene derivative [1] is obtained by a coupling reaction between the obtained [B] and the dihalogen compound [C] (step (b)).
Furthermore, the thiophene derivative [1] can be cyclized by a photochemical reaction to lead to a closed ring thiophene derivative [2] (step (c)).

Hereinafter, each step will be described in detail.
[1] Step (a) In this step, the bis (chloromethyl) dithienylethene derivative [A] is reacted with thiourea in dimethyl sulfoxide (DMSO) and then hydrolyzed with sodium hydroxide to give bis (mercaptomethyl). In this step, a dithienylethene derivative [B] is synthesized.
As the reaction solvent, an aprotic polar solvent such as dimethyl sulfoxide (DMSO) is usually used. The reaction atmosphere is preferably an inert gas atmosphere such as nitrogen or argon.
The reaction temperature is not particularly limited, but is preferably about 20 to 50 ° C. for operation.
The reaction time depends on the reaction rate, but is usually about 10 to 20 hours.

[2] Step (b) This step consists in the presence of potassium hydroxide, sodium borohydride, dichloro compound [C] and bis (mercaptomethyl) dithienylethene derivative [B] coupled under dilution conditions, Is a step of synthesizing the thiophene derivative [1].
As the reaction solvent, alcohols such as methanol and ethanol, and aprotic polar solvents such as dimethylformamide (DMF) are usually used.
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 is preferably 0 to 100 ° C. in terms of operation. The reaction time depends on the reaction rate, but is usually from several hours to several days.

[3] Step (c) This step is a step of converting the thiophene derivative [1] obtained in the step (b) into a closed ring thiophene derivative [2] by intramolecular cyclization reaction by light irradiation.
The reaction solvent is not particularly limited as long as the starting material dissolves and does not inhibit light irradiation. However, methanol, ethanol, acetonitrile, acetone, diethyl ether, ethyl acetate, pyridine, hexane, cyclohexane, pentane, Heptane, benzene, toluene, xylene, tetrahydrofuran (THF), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), carbon tetrachloride, chloroform, dichloromethane and the like are preferable.
The reaction temperature is not particularly limited, but is preferably about 0 to 100 ° C. for operation.
The reaction time depends on the reaction rate, but is usually about 10 picoseconds to 1 minute.

The reaction solvent used in each step is not limited to the above-described various solvents as long as it is stable under the reaction conditions and is inert and does not interfere with the reaction. For example, water, Alcohols (methanol, ethanol, propanol, butanol, octanol, etc.), cellosolves (methoxyethanol, ethoxyethanol, etc.), aprotic polar organic solvents (dimethylformamide, dimethyl sulfoxide, dimethylacetamide, tetramethylurea, sulfolane) N, N-dimethylimidazolidinone, etc.), ethers (diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, etc.), aliphatic hydrocarbons (pentane, n-hexane, cyclohexane, octane, decalin, petroleum ether, etc.) Aromatic hydrocarbons (benzene, chlorobenzene, nitrobenzene, toluene, xylene, tetralin, etc.), halogenated hydrocarbons (chloroform, dichloromethane, dichloroethane, carbon tetrachloride, etc.), ketones (acetone, methyl ethyl ketone, methyl butyl ketone, etc.) , Lower aliphatic acid esters (methyl acetate, ethyl acetate, methyl propionate, etc.), alkoxyalkanes (dimethoxyethane, diethoxyethane, etc.), various solvents such as acetonitrile, etc. Can be used. These can be used alone or in combination of two or more.
In addition, these solvents can also be used as a non-aqueous solvent using an appropriate dehydrating agent or drying agent as necessary.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to the following Example. In addition, the analyzers employed in the examples are as follows.
NMR measuring device; JEOL AL300
Mass measuring device: JEOL JMS-GCMATE II
IR measuring device: Perkin Elmer FT-IR 200
Elemental analyzer; Yanaco CHN coder MT-5
Absorption spectrum measuring apparatus; Hitachi, Ltd. U-3310

[Example 1] 3,3,4,4,5,5-hexafluoro-9,24,26,27-tetramethyl-8,12,21,25-tetrathiapentacyclo- [21.2.1 .1 <7,10> 0 <2,6> 0 <14,19>] Heptacosa-1 (26), 2 (6), 7 (27), 9, 14 (19), 15, 17, 23 (24) -Octane synthesis

[1] Step (a) Synthesis of 1,2-bis (4-mercaptomethyl-3,5-dimethylthien-2-yl) -3,3,4,4,5,5-hexafluorocyclopentene [B]

  1.97 g (5.00 mmol) of 1,2-bis (4-chloromethyl-3,5-dimethylthien-2-yl) -3,3,4,4,5,5-hexafluoropentene and 760 mg of thiourea ( 10.0 mmol) was dissolved in 10 ml of dimethyl sulfoxide and stirred at room temperature for 14 hours under a nitrogen stream. The reaction mixture was poured into 25 ml of 5% aqueous sodium hydroxide solution, stirred for 1 hour, acidified with 10% hydrochloric acid, the deposited precipitate was extracted with chloroform, washed with brine, and dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was recrystallized from hexane to obtain 1.15 g of orange prism crystal compound [B] in a yield of 46%.

mp: 129.0-131.0 ℃
¹ HNMR (300 MHz, CDCl ₃ ): δ = 0.90 (t, J = 7 Hz, 2H), 1.70 (s, 6H), 2.45 (s, 6H), 3.50 (d, J = 7 Hz, 4H) ppm.
EI (m / z): 487 (M ⁺ ).

[2] Step (b) 3,3,4,4,5,5-hexafluoro-9,24,26,27-tetramethyl-8,12,21,25-tetrathiapentacyclo- [21.2 1.1 <7,10> 0 <2,6> 0 <14,19>] Heptacosa-1 (26), 2 (6), 7 (27), 9, 14 (19), 15, 17 , 23 (24) -Octane

  While dissolving 55.0 mg (1.00 mmol) of potassium hydroxide and 4.75 mg (0.13 mmol) of sodium borohydride in 75 ml of ethanol and refluxing, 1,2-bis (chloromethyl) benzene 43 0.5 mg (0.25 mmol) and a solution of 122 mg (0.25 mmol) of the compound (B) obtained in step (a) in 2.5 ml of ethanol / benzene (1: 1) were added dropwise over 24 hours. The solvent was distilled off, the residue was poured into ice water, extracted with dichloromethane, washed with brine, and dried over magnesium sulfate. The solvent was distilled off under reduced pressure, the residue was subjected to silica gel column chromatography, fractionated with hexane: chloroform = 2: 1, and recrystallized from hexane to give 32 mg of the title compound as pale yellow prisms, yield 22 %.

mp: 225.0-227.0 ° C.
¹ HNMR (300MHz, CD ₃ CN, 25 ° C, TMS): δ = 1.80 (s, 6H), 2.45 (s, 6H), 3.40 (d, J = 15 Hz, 2H), 3.50 (d, J = 10 Hz, 2H), 3.65 (d, J = 10 Hz, 2H), 4.10 (d, J = 15 Hz, 2H), 7.20-7.30 (m, 4H) ppm.
¹³ CNMR (75 MHz, CDCl ₃ ): δ = 14.5, 27, 28, 32, 37, 43, 118, 127, 128, 132, 135, 137, 138, 142 ppm.
EI (m / z): 589 (M ⁺ ).
IR (KBr): 1490, 1440, 1332, 1266, 1111, 1045, 982, 871, 864 cm ⁻¹ .
Elemental analysis: C ₂₇ H ₂₄ S ₄ F ₆ (590.73): calcd. C, 54.90, H, 4.10; found: C, 54.97, H, 4.13.

[Example 2] 10,10,11,11,12,12-hexafluoro-6,16,26,27-tetramethyl-3,7,15,19-tetrathiapentacyclo- [19.3.1 .1 <5,8> 1 <14,17> 0 <9,13>] Heptacosa-1 (25), 5 (6), 8 (26), 9 (13), 14 (27), 16, Synthesis of 21, (22), 23-octane

In the same manner as in Step (b) of Example 1, from the compound [B] obtained in Step (a) of Example 1 and 1,3-bis (chloromethyl) benzene, the title compound of pale yellow prism crystals Was obtained in a yield of 20%.
mp: 146.0-149.0 ° C.
_{^{1 HNMR: (300MHz, CDCl 3}} , 25 ℃, TMS): δ = 1.80 (s, 6H), 2.45 (s, 6H), 3.57 (s, 4H), 3.59 (s, 4H), 6.90-7.20 (m , 4H) ppm.
¹³ CNMR (75 MHz, CDCl ₃ ): δ = 14.4, 28, 29, 31, 37, 43, 119, 127, 128, 132, 135, 138, 140, 142 ppm.
EI (m / z): 589 (M ⁺ ).
IR (KBr): 1373, 1336, 1270, 1185, 1111, 1052, 982, 882, 709 cm ⁻¹ .
Elemental analysis: C ₂₇ H ₂₄ S ₄ F ₆ (590.73): C, 54.90, H, 4.10; found: C, 55.12, H, 4.22.

[Example 3] 10,10,11,11,12,12-hexafluoro-6,16,26,27-tetramethyl-3,7,15,19-tetrathiapentacyclo- [19.2.2 .1 <5,8> 1 <14,17> 0 <9,13>] Heptacosa-1 (23), 5 (6), 8 (26), 9 (13), 14 (27), 16, Synthesis of 21, (22), 24-octane

In the same manner as in Step (b) of Example 1, the title compound of yellow prism crystals was obtained from Compound [B] obtained in Step (a) of Example 1 and 1,4-bis (chloromethyl) benzene. 35 mg, 24% yield.
mp: 128.0-130.0 ° C.
_{^{1 HNMR: (300MHz, CDCl 3}} , 25 ℃, TMS): δ = 1.80 (s, 6H), 2.45 (s, 6H), 3.65 (s, 4H), 3.75 (s, 4H), 6.90 (s, 4H ) ppm.
¹³ CNMR: (75 MHz, CDCl ₃ ): δ = 14.5, 27, 29, 33, 37, 44, 118, 128, 129, 132, 135, 137, 139, 141 ppm.
EI (m / z): 589 (M ⁺ ).
IR (KBr): 1594, 1472, 1270, 1188, 1041, 971, 875, 849, 768 cm ⁻¹ .
Elemental analysis: C ₂₇ H ₂₄ S ₄ F ₆ (590.73): C, 54.90, H, 4.10; found: C, 55.09, H, 4.19.

[Example 4] Measurement of absorption spectrum The absorption spectrum was measured using an absorption spectrum measuring apparatus (U-3310, Hitachi, Ltd.). Table 1 shows the quantum yields of the photocyclization reaction and the photoopening reaction. The quantum yield of the photocyclization reaction and the ring-opening reaction was determined by comparison with the coloring and decoloring speed of a hexane solution of bis (2-methyl-1-benzothien-3-yl) hexafluorocyclopentene (K. Uchida, E. Tsuchida, Y. Aoi, S. Nakamura, M. Irie, Chem. Lett. 1999, 63-64.).
When the toluene solution of the compound obtained in Example 1 was sealed and stored in an oven at 100 ° C. for 5 hours, no change was observed between the first and last absorption spectra. This result shows that each photoisomer of the compound obtained in Example 1 is thermally stable, and isomerization occurs only by light irradiation at room temperature.

It is an absorption spectrum change by irradiation time when the hexane solution of the compound obtained in Example 1 is irradiated with ultraviolet light. The irradiation time is 0 second, 10 seconds, 20 seconds, 30 seconds, 40 seconds, 50 seconds, and 60 seconds. The absorbance showed changes with time in the direction of “↓” and “↑” in the figure. It is an absorption spectrum change by irradiation time when the hexane solution of the compound obtained in Example 2 is irradiated with ultraviolet light. The irradiation time is 0 second, 10 seconds, 20 seconds, 30 seconds, 40 seconds, 50 seconds, and 60 seconds. The absorbance showed changes with time in the direction of “↓” and “↑” in the figure. It is an absorption spectrum change by irradiation time when the hexane solution of the compound obtained in Example 3 is irradiated with ultraviolet light. The irradiation time is 0 second, 10 seconds, 20 seconds, 30 seconds, 40 seconds, 50 seconds, and 60 seconds. The absorbance showed changes with time in the direction of “↓” and “↑” in the figure.

Claims (6)

A thiophene derivative represented by the formula [1] or [2].

{Where A is

Represents
E represents — (CH ₂ ) _n — (n represents 0 or 1), —O—, —S—, —S (O) —, —S (O) ₂ —, or —NR ⁵ —. [R ⁵ is a hydrogen atom, a cycloalkyl group having 3 to 6 carbon atoms, 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 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. > Or 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). ],
R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or a fluorine atom or a chlorine atom. Represents an optionally substituted halogenated alkyl group having 1 to 10 carbon atoms, or R ¹ and R ² together represent a hexafluoropropylene group, —CO—NH—CNH—, —CO—NR ^5. -CO- (R ⁵ is as defined above), or carboxylic anhydride,
R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, an alkoxy group having 1 to 3 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a cycloalkoxy group having 3 to 6 carbon atoms, or 1 carbon atom. Represents an alkyl group having 1 to 10 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 a diphenylamino group. } The thiophene derivative according to claim 1, wherein R ³ and R ⁴ are each independently a hydrogen atom, a methoxy group, a methyl group, an ethyl group, an isopropyl group, a tertiary butyl group, or a trifluoromethyl group. A is

And
E is —O—, —S—, or —NR ⁵ — [R ⁵ is a hydrogen atom, 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, and a phenyl group (which may be substituted with a methoxy group or a methyl group). > Or a phenyl group (the phenyl group may be substituted with a methoxy group or a methyl group). ], And
R ¹ and R ² 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 tertiary butyl group, or a trifluoromethyl group. Or R ¹ and R ² together form a hexafluoropropylene group, —CO—NH—CNH—, —CO—NR ⁵ —CO— [wherein R ⁵ is a hydrogen atom, a methyl group, an ethyl group The methyl group and the ethyl group are optionally substituted with a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group, a methoxy group, or a phenyl group (the phenyl group may be substituted with a methoxy group or a methyl group). May be. > Or a phenyl group (the phenyl group may be substituted with a methoxy group or a methyl group). Or the thiophene derivative according to claim 1, which is a carboxylic acid anhydride. The E is -S-, the R ¹ and R ² together are a hexafluoropropylene group, and the R ³ and R ⁴ are methyl groups. The thiophene derivative according to claim 1.   A photochromic material comprising the thiophene derivative according to any one of claims 1 to 4. An optical recording medium comprising a recording layer containing the thiophene derivative according to any one of claims 1 to 4.

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