JP3182840B2 - Method for producing photochromic maleimide derivative - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates relates to a method for producing a maleimide induction of novel asymmetric structure, details cyclized by light irradiation in 1-position and 2-position, the optical properties to form a cyclohexadiene ring method for producing a maleimide induction body having a heterocyclic ring of change allowed to asymmetric relates.

[0002]

2. Description of the Related Art In recent years, researches for using photochromic compounds as optical recording media have been actively conducted.
In order to use a photochromic compound as an optical recording medium, the following conditions are required.

[0003] The recording is thermally stable. Records are chemically stable. Excellent in repeated durability. It has sensitivity at a wavelength of 650 nm or more. It has a non-destructive read function. Have high sensitivity. Previously, the present inventors have proposed the following bisbenzothiophene-based compound [A] as a photochromic compound which overcomes the above-mentioned problems that the recording is thermally stable and the repetition durability is excellent.

[0004]

Embedded image

Further, as a photochromic compound having sensitivity at a wavelength of 650 nm or more, the following asymmetric maleic anhydride [B] has been proposed.

[0006]

Embedded image

[0007]

Among the above photochromic compounds, the bisbenzothiophene compound [A] has a drawback that it has no sensitivity at a wavelength of 650 nm or more. On the other hand, the asymmetric maleic anhydride of [B] has the conditions described above, but does not have the requirement that the recording is chemically stable because it has an acid anhydride group. There was also a problem in the synthesis yield.

An object of the present invention is to solve the above-mentioned conventional problems and to provide a method for producing a photochromic compound having all the required properties required for an optical recording medium.

[0009]

The method for producing the photochromic maleimide derivative of the present invention is represented by the following general formula [II].
Acid chloride derivative represented by the following general formula [III]
Reaction with oxamoyl derivative in the presence of amine
The photochromic represented by the following general formula [I]
It is characterized by producing a maleimide derivative .

[0010]

Embedded image

(In the above general formula [I], A and B are different substituents, A is a substituent represented by the following general formula [i] or [ii], and B is the following general formula [I] iii]
Or a substituent represented by [iv], and X represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, or an optionally substituted aryl group. )

[0012]

Embedded image

(The above general formulas [i], [ii], [iii] and [iv]
In the above, R ¹ and R ⁵ represent an alkyl group, an alkoxy group, a halogen atom or a trifluoromethyl group, and R ² and R 5
³ , R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group,
Alkoxy group, halogen atom, trifluoromethyl group,
Represents a cyano group or an optionally substituted aryl group, wherein R ² and R ³ , and R ⁶ and R ⁷ are linked to each other to be optionally substituted carbon ring or optionally substituted heterocyclic ring; May be formed. Y and Z are -O-, -S-
Or —NR ⁴ — (R ⁴ represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted cycloalkyl group). )

[0014]

Embedded image

(In the above general formulas [II] and [III], A,
B and X are the same as defined in the general formula [I] . Hereinafter, the present invention will be described in detail. The general formula
In the photochromic maleimide derivative represented by [i], the heterocyclic group represented by A is represented by the following formulas (1) to (1).
And (6).

[0016]

Embedded image

Here, R ¹ methyl, ethyl, n-propyl, iso-propyl, n-butyl, ter
C1-C6 alkyl group such as t-butyl group; C1-C6 alkoxy group such as methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group; fluorine atom, chlorine atom, a bromine atom, a halogen atom such as an iodine atom; represents or a trifluoromethyl group, R ²
And R ³ are each independently a hydrogen atom; a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a tert-butyl group or the like; an alkyl group having 1 to 6 carbon atoms; Ethoxy group, n-propoxy group, i
1 to 6 carbon atoms such as a so-propoxy group and an n-butoxy group
A halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; a trifluoromethyl group; a cyano group; or a lower alkyl group, a lower alkoxy group, a lower alkylamino group, a lower dialkylamino group, an amino group, C 6 to C 12 such as a phenyl group, a tolyl group, and a naphthyl group which may be substituted with a halogen atom, a cyano group, etc.
Or represents a aryl group, an alkylene ring having 3 to 5 carbon atoms linked with R ² and R ³ together, a benzene ring, a carbon ring or a pyridine ring such as a naphthalene ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, pyran It forms a heterocyclic ring such as a ring, a furan ring and a thiophene ring. R ⁴ is a hydrogen atom; each of which may have a substituent such as a halogen atom, a lower alkoxy group, a hydroxyl group, a cyano group, an amino group, a nitro group, an ethyl group, an n-propyl group, an iso- C1-C28 alkyl groups such as propyl group, n-butyl group, tert-butyl group, n-octyl group, 2-ethylhexyl group, n-decyl group, n-octadecyl group; phenyl group, tolyl group, naphthyl An aryl group having 6 to 12 carbon atoms, such as a group; or a cycloalkyl group having 3 to 8 carbon atoms, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group.

Examples of the heterocyclic group represented by B include those represented by the following formulas (7) to (12).

[0019]

Embedded image

Here, R ⁵ has the same meaning as the definition of the substituent of R ¹ , and R ⁶ and R ⁷ have the same meanings as the definition of the substituent of R ² and R ³ , respectively. The definition of the substituent of R ⁴ is as described above.

In the heterocyclic residue represented by A or B, when R ² and R ³ and R ⁶ and R ⁷ are respectively connected to form a carbocyclic or heterocyclic ring, Forms a benzofuran ring, a benzothiophene ring, an indole ring, a benzoxazole ring, a benzothiazole ring, an indazole ring, etc., may have one or more substituents on the ring. Such substituents include a fluorine atom,
A halogen atom such as a chlorine atom or a bromine atom; a hydroxyl group; an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an iso-propyl group or an n-butyl group; a methoxy group, an ethoxy group, n-propoxy group, is
an alkoxy group having 1 to 6 carbon atoms such as an o-propoxy group and an n-butoxy group; a cyano group; a nitro group; a carbon atom having 2 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group and an iso-propoxycarbonyl group; ~
A haloalkyl group having 1 to 6 carbon atoms such as a trifluoromethyl group; an aryl group having 6 to 12 carbon atoms such as a phenyl group, a tolyl group, and a naphthyl group; a cyclopropyl group, a cyclobutyl group, a cyclopentyl group; A cycloalkyl group having 3 to 8 carbon atoms such as a cyclohexyl group;
An aryloxycarbonyl group having 7 to 13 carbon atoms such as a phenoxycarbonyl group and a naphthyloxycarbonyl group; a methylaminocarbonyl group, an ethylaminocarbonyl group,
A monoalkylaminocarbonyl group having 2 to 7 carbon atoms such as a propylaminocarbonyl group; an N, N-dimethylaminocarbonyl group, an N, N-diethylaminocarbonyl group;
3 carbon atoms such as N, N-methylethylaminocarbonyl group
Dialkylaminocarbonyl group having 2 to 8 carbon atoms such as acetyloxy group, propionyloxy group, butyryloxy group, isobutyryloxy group; benzoyloxy group, toluoyloxy group;
An arylcarbonyloxy group having 7 to 13 carbon atoms such as a naphthoyloxy group; an aryloxy group having 6 to 12 carbon atoms such as a phenoxy group and a naphthyloxy group; a methoxycarbonyloxy group, an ethoxycarbonyloxy group and an n-propoxycarbonyloxy Group, an alkoxycarbonyloxy group having 2 to 8 carbon atoms such as an iso-propoxycarbonyloxy group; and an aryloxycarbonyloxy group having 7 to 13 carbon atoms such as a phenoxycarbonyloxy group and a naphthyloxycarbonyloxy group. , A cyano group or a methoxy group are preferred.

In the present invention, a compound wherein A or B forms a ring structure selected from the group consisting of an indole ring, a thiophene ring, a benzothiophene ring, a benzothiophene-1,1-dioxide ring, a thiazole ring and an oxazole ring, preferable.

In the above general formula [I], X is a hydrogen atom; it may have a substituent such as a halogen atom, a lower alkoxy group, a hydroxyl group, a cyano group, an amino group, a nitro group, a phenyl group and the like. Methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, ter
1 to 1 carbon atoms such as t-butyl group, n-octyl group, 2-ethylhexyl group, n-decyl group and n-octadecyl group
An alkyl group of 28; a halogen atom, a lower alkoxy group,
A hydroxyl group, a cyano group, an amino group, a nitro group, an aryl group having 6 to 12 carbon atoms such as a phenyl group, a tolyl group or a naphthyl group which may have a substituent such as a phenyl group; or a halogen atom, a lower alkoxy group Group, hydroxyl group,
C 3 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group which may have a substituent such as a cyano group, an amino group, a nitro group and a phenyl group;
-8 represents a cycloalkyl group.

Next, a method for producing the maleimide derivative of the present invention will be described.

The maleimide derivative represented by the general formula [I] can be obtained, for example, by converting an acid chloride derivative represented by the following general formula [II] and an oxamoyl derivative represented by the following general formula [III] in the presence of an amine. It can be obtained by reacting. In general formulas [II] and [III], A, B, X
Is the same as defined above.

[0026]

Embedded image

Specifically, in a halogenated solvent such as methylene chloride, chloroform, carbon tetrachloride, tetrachloroethane or the like, the compound of the general formula [II] and the compound of the general formula [III] are reacted at -10 to + 40 ° C. , Triethylamine, trimethylamine, triethanolamine and the like. More preferably, a halogenated solvent such as methylene chloride, chloroform, carbon tetrachloride, tetrachloroethane or the like containing the general formula [II] is added at 0 to 30 ° C.
The reaction is carried out by adding dropwise to a mixed solvent of the above-mentioned halogenated solvent containing the general formula [III] and an amine.

After the completion of the reaction, water was added, and the product was extracted with an organic solvent.
By purifying by recrystallization or the like, the maleimide derivative of the present invention can be obtained.

[0029]

Maleimide derivative produced in DETAILED DESCRIPTION OF THE INVENTION The present invention, when the light irradiation as shown in the following formula, heterocycle W _A and heterocycle W _B
Cyclizes to form a cyclohexadiene ring and has the formula [I-
1] to [I-2], causing a color change. This colored state can be reversibly restored by a photoreaction.

[0030]

Embedded image

Specifically, for example, when an indolyl phenyl maleimide derivative represented by the following formula [IV-1] is irradiated with, for example, an argon ion laser beam of 488 nm, the following structural change occurs. Formula [IV−
2], and changes from yellow to green. In addition, since this green colored state has an absorption wavelength extending to the semiconductor laser region, it can be reversibly returned to the original state by irradiation with a semiconductor laser beam of 780 nm, for example, as in the following formula.

[0032]

Embedded image

In particular, the maleimide derivative according to the present invention
It is obtained by converting the acid anhydride group of the asymmetric maleimide anhydride [B] into a maleimide group. Its thermal and chemical stability is remarkably improved, and the recording based on both isomers in the reversible reaction is good. Is held.

[0034]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples, but the present invention is not limited to the following Examples unless it exceeds the gist thereof. Example 1 Synthesis was performed according to the following reaction formula.

[0035]

Embedded image

76.5 mg in a 50 ml three-necked flask
(0.38 mmol) of 2-cyano-3,5-dimethyl-4-thienylacetic acid and 5 ml of thionyl chloride were added, and the mixture was stirred at room temperature. After 1 hour, thionyl chloride was distilled off. A solution obtained by adding 5 ml of dichloromethane thereto was added to 66 mg (0.15 mmol) of 1,2 prepared in advance.
-Dimethyl-3- (N-cyanomethyloxamoyl) indole, dropwise added to a mixed solution of 4 ml of triethylamine and 7 ml of dichloromethane at room temperature. After stirring for 3 hours, water was added, and the mixture was extracted three times with chloroform. The organic layer was washed with diluted hydrochloric acid, then with water, and then dried over anhydrous magnesium sulfate. The solvent was distilled off, and the obtained solid was separated with a silica gel column to give an orange solid 2- (1,1).
2-dimethyl-3-indolyl) -3- (2-cyano-
(3,5-Dimethyl-4-thenyl) -N-cyanomethylmaleimide was obtained.

Yield: 53 mg Yield: 50% ¹ H NMR (CDCl ₃ ) δ = 2.06 (s, 3 H, Ar—CH ₃ ) 2.09 (s, 3 H, Ar—CH ₃ ) 2.16 ( _{s, 3H, Ar-CH 3} ) 3.65 (s, 3H, N-CH 3) 4.49 (s, 2H, N-C H 2 -CN) 6.8-7.2 (m, 4H, Aromatic protons) The absorption spectrum of the obtained compound and the absorption spectrum after light irradiation at 480 nm are shown in FIG.

Example 2 Synthesis was performed according to the following reaction formula.

[0039]

Embedded image

In a 50 ml three-necked flask, 30 mg (0.
15 mmol) of 2-cyano-3,5-dimethyl-4-
Chenyl acetic acid and 3 ml of thionyl chloride were added and stirred at room temperature. After 1 hour, thionyl chloride was distilled off. A solution prepared by adding 3 ml of dichloromethane thereto was added to 52 mg (0.1 mmol) of N-octadecyl-2-methyl-3- (N-cyanomethyloxamoyl) prepared in advance.
It was added dropwise to a mixed solution of indole, 2 ml of triethylamine and 5 ml of dichloromethane at room temperature. After stirring for 17 hours, water was added, and the mixture was extracted three times with chloroform. The organic layer was washed with diluted hydrochloric acid, then with water, and then dried over anhydrous magnesium sulfate. The obtained solid was separated by a silica gel column and 2- (N-octadecyl-2-methyl-5-
Methoxy-3-indolyl) -3- (2-cyano-3,
5-Dimethyl-4-phenyl) -N-cyanomethylmaleimide was obtained.

Yield: 32 mg Yield: 47% ¹ H NMR (CDCl ₃ ) δ = 0.72 to 1.48 (m, 35 H, N—CH ₃ − (C
_{H 2) 16 CH 3) 2.06} (s, 3H, Ar-CH 3) 2.12 (s, 3H, Ar-CH 3) 2.20 (s, 3H, Ar-CH 3) 3.62 ( _{s, 3H, Ar-OCH 3} ) 4.00 (t, 2H, N-C H 2 - (CH 2) 16 CH
_{3) 4.53 (s, 2H,} H-C H 2 -CN) 6.26-7.08 (m, 3H, aromatic protons) in the corresponding formula with the compound obtained by the Experimental Example 1 Example 1 The maleic anhydride derivative shown was examined for its solvolysis resistance in ethanol, and the results are shown in FIG. FIG. 2 shows that the maleic anhydride derivative was easily solvolyzed,
It was confirmed that the maleimide derivative did not change at all and exhibited high chemical stability.

[0042]

Embedded image

[0043]

As described above in detail, according to the manufacturing method of the photochromic maleimide induction of the present invention is excellent in repetition durability, has good sensitivity than 650 nm, moreover, both thermally and chemically An extremely stable photochromic compound is provided. The photochromic maleimide derivative according to the present invention is extremely useful industrially as a high-performance optical recording medium.

[Brief description of the drawings]

FIG. 1 is an absorption spectrum diagram of a compound obtained in Example 1.

FIG. 2 is a graph showing the results of Experimental Example 1.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ identification symbol FI C07D 417/14 C07D 417/14 // C09K 9/02 C09K 9/02 B (58) Investigated fields (Int.Cl. ⁷ , DB name) C07D 409/14 C07D 207/452 C07D 403/14 C07D 405/14 C07D 413/14 C07D 417/14 C09K 9/02 CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] An acid chloride derivative represented by the following general formula [II]:
Conductor and oxamoyl derivative represented by the following general formula [III]
By reacting the door in the presence of an amine, a photochromic maleimide derivative represented by the following general formula [I]
Photochromic maleimide induction characterized by manufacturing
Manufacturing method of conductor. Embedded image (In the above general formula [I], A and B are different substituents, A is a substituent represented by the following general formula [i] or [ii], and B is the following general formula [iii] or a substituent represented by [iV], and X represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, or an optionally substituted aryl group.) Embedded image (In the above general formulas [i], [ii], [iii] and [iv], R
¹ and R ⁵ represent an alkyl group, an alkoxy group, a halogen atom or a trifluoromethyl group, and R ² , R ³ , R ⁶ , R
⁷ are each independently hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a trifluoromethyl group, although a cyano group or an optionally substituted aryl group, R ² and R
³ and R ⁶ and R ⁷ may be linked to each other to form an optionally substituted carbocycle or an optionally substituted heterocycle. Y and Z represent -O-, -S- or -NR ⁴
— (R ⁴ represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted cycloalkyl group). ) (In the above general formulas [II] and [III], A, B and X each have the same definition as in general formula [I] .)