JPH09124645A - Chromene compound - Google Patents

Abstract

(57) [Abstract] [PROBLEMS] A photochromic compound having excellent durability, which is characterized by high color density and high fading speed. The present invention relates to a chromene compound having a 2-furyl group at the 3-position as a basic structure and having a structure in which a benzene ring is condensed at the f-position, and a photochromic material comprising the same.

Description

Detailed Description of the Invention

TECHNICAL FIELD The present invention relates to a novel chromene compound which changes to a colored form upon irradiation with light containing ultraviolet rays such as sunlight or light from a mercury lamp, and the change is reversible and exhibits excellent durability. Regarding

2. Description of the Related Art Photochromism is a phenomenon that has been attracting attention for several years, and when a compound is irradiated with light including ultraviolet rays such as sunlight or the light of a mercury lamp, the color of the compound rapidly changes and the irradiation of light is prevented. It is a reversible action that returns to the original color when stopped and placed in the dark. A compound having this property is called a photochromic compound, and various compounds have been conventionally synthesized, but no special commonality is recognized in its structure. USP3567605 describes a chromene compound represented by the following formula (A).

Embedded image Although this chromene compound exhibits photochromic properties near room temperature (20 to 30 ° C.), it has a low color density when irradiated with ultraviolet rays and is not practical. In addition, WO9
317071 discloses the following formula (B)

Embedded image And a chromene compound represented by
In the publication No. 00867, the following formula (C)

Embedded image Chromene compounds represented by are disclosed. These two compounds had a higher color density than the compounds described in US Pat. No. 3,567,605, but had a slow fading rate, and the durability of the photochromic properties was not sufficient, which was not practically satisfactory. Furthermore, EP6
In JP 29620, a chromene compound represented by the following formula (D) is described.

Embedded image Although this chromene compound has a high fading rate, it is not practical because the color density is insufficient.

SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide a chromene compound having improved photochromic properties, high color density and excellent durability as compared with the above compounds.

DISCLOSURE OF THE INVENTION The present invention has been proposed in order to achieve the above object, and is obtained by the present inventors that a novel chromene compound has a high color density and excellent durability of photochromic properties. It was completed based on the knowledge obtained. That is, the present invention provides the following general formula (1)

[Chemical 6] [Wherein R ¹ , R ² , R ³ and R ⁴ are the same or different hydrogen atoms, alkyl groups, alkoxy groups, aralkyl groups, acyl groups, cyano groups, substituted amino groups, aryl groups,
It is an acyloxy group, a nitro group, a hydroxyl group or a halogen atom, and a, b and c each represent the number of the substituents R ¹ , R ² and R ³ and are 1 or 2. ] It is a chromene compound shown by these. Another invention is the above general formula (1).
It is a photochromic material composed of a chromene compound represented by. In the general formula (1), the substituent at the 3-position of the chromene ring is a phenyl group and a 2-furyl group. By introducing a 2-furyl group, the chromene compound represented by the general formula (1) has high color density and excellent durability. On the other hand, introduction of a 3-furyl group had no effect on the improvement of color density and durability. As the alkyl group, the alkoxy group, the aralkyl group, the acyl group, the substituted amino group, the aryl group, the acyloxy group and the halogen atom of R ^{1 to} R ^{4 in} the general formula (1), known groups can be used without any limitation. You can The above alkyl group is not particularly limited,
Generally, it has 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms.
Is an alkyl group. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a t-butyl group. The above alkoxy group is not particularly limited, but is generally an alkoxy group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group and a t-butoxy group. The above aralkyl group is not particularly limited, but generally has 7 to 1 carbon atoms.
6, preferably 7 to 10 aralkyl groups. Specific examples of the aralkyl group include benzyl group, phenylethyl group, phenylpropyl group and phenylbutyl group. The acyl group is not particularly limited, but is generally an acyl group having 1 to 15 carbon atoms, preferably 1 to 7 carbon atoms. Specific examples of the acyl group include a formyl group, an acetyl group, a propionyl group, a butyryl group and a benzoyl group. The above-mentioned substituted amino group is not particularly limited, but generally includes an amino group having a substituent such as an alkyl group having 1 to 10 carbon atoms and a hetero atom-containing alkyl group, and the substituents of these amino groups are Together, they can form a ring. Specific examples of the substituted amino group include methylamino group, ethylamino group, propylamino group, isopropylamino group, dimethylamino group, diethylamino group, methylethylamino group, 2-hydroxyethylamino group, di (2- Hydroxyethyl) amino group,
Examples thereof include piperidinyl group, morpholinyl group, N-methylpiperazinyl group, thiomorpholinyl group, aziridinyl group and pyrrolidinyl group. The aryl group is not particularly limited, but is generally an aryl group having 6 to 20 carbon atoms, preferably 6 to 14 carbon atoms.
Specific examples of the aryl group include a phenyl group, a naphthyl group and a tolyl group. The acyloxy group is not particularly limited, but is generally an acyloxy group having 1 to 15 carbon atoms, preferably 2 to 7 carbon atoms. Specific examples of the acyloxy group include an acetoxy group, a propionyloxy group, a benzoyloxy group and a (meth) acryloyloxy group. The halogen atom is not particularly limited, but specific examples of the halogen atom preferably used in the present invention include a fluorine atom, a chlorine atom and a bromine atom. In the general formula (1), a is the number of R ¹ and b
Indicates the number of R ² , and c indicates the number of R ³ , which are 1 or 2, respectively. The substitution positions of the substituents R ¹ , R ² , R ³ and R ⁴ are not particularly limited, but R ¹ is at the 2 or 4 position of the phenyl group in the general formula (1) and R ² is an aromatic heterocyclic group. Of 5
Position, R ³ is preferably the 8 or 9 position of the 3H-benzo (f) chromene skeleton, and R ⁴ is preferably the 6 position. Specific examples of chromene compounds suitable for the present invention include the following compounds. 1) 3- (2-furyl) -3-phenyl-3H-benzo (f) chromene 2) 3- (2-furyl) -3- (2,4-dimethoxyphenyl) -3H-benzo (f) chromene 3 ) 8-Methoxy-3- (2-furyl) -3- (2-fluorophenyl) -3H-benzo (f) chromene 4) 6-piperidinyl-3- (2-furyl) -3- (4
-Methoxyphenyl) -3H-benzo (f) chromene 5) 9-methoxy-3- [2- (5-ethoxy) furyl] -3-phenyl-3H-benzo (f) chromene 6) 8-benzyl-3- [2- (4,5-Dichloro) furyl) -3-phenyl-3H-benzo (f) chromene 7) 8-benzoyl-3- (2-furyl) -3- (4-
Fluorophenyl) -3H-benzo (f) chromene 8) 8-hydroxy-3- (2-furyl) -3- [4-
(N-Methylpiperazinyl) phenyl] -3H-benzo (f) chromene 9) 9-isopropoxy-3- [2- (5-cyano) furyl] -3-tolyl-3H-benzo (f) chromene 10 ) 7-Phenyl-3- (2-furyl) -3- (4-
Nitrophenyl) -3H-benzo (f) chromene The compound represented by the general formula (1) of the present invention generally exists as a colorless or pale yellow solid or viscous liquid at room temperature and normal pressure, and It can be confirmed by means such as (a) to (d). (A) Proton nuclear magnetic resonance spectrum ( ¹ H-NMR)
The peak due to the aromatic proton and the proton of the alkene appears near δ 6.0 to 9.0 ppm, and the peak due to the protons of the alkyl group and the alkylene group appears around δ 0.8 to 5.0 ppm.
Further, the number of protons of each bonding group can be known by comparing the respective spectrum intensities relatively. (B) The composition of the corresponding product can be determined by elemental analysis. (C) by measuring the ¹³ C- nuclear magnetic resonance spectrum ⁽¹³ C-NMR), the peak based on the carbons of an aromatic hydrocarbon group near δ110~160ppm, δ80~140
Carbon-based peak of alkene near ppm, δ20-
A peak based on the carbons of the alkyl group and the alkylene group appears around 80. The method for producing the compound represented by the general formula (1) of the present invention is
It is not particularly limited and may be obtained by any synthetic method. A typical method that is generally preferably used will be described below.
The following general formula (2)

Embedded image And a compound represented by the general formula (3)

Embedded image The compound represented by is reacted in the presence of an acid catalyst. However,
R ^{1 to} R ⁴ in the general formulas (2) and (3) are represented by the general formula (1).
Is the same as each substituent in the above. The reaction between the compound represented by the general formula (2) and the compound represented by the general formula (3) is usually performed as follows. That is, these two
The reaction ratio of the compounds of the species is adopted from a wide range,
Generally, it is selected from the range of 1:10 to 10: 1 (molar ratio). Further, sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid or the like is used as the acid catalyst, and the amount of the reaction substrate represented by the general formulas (2) and (3) is 0.
It is used in the range of 1 to 10 parts by weight. The reaction temperature is usually 0 to 200 ° C., and an aprotic organic solvent such as N-methylpyrrolidone, dimethylformamide, tetrahydrofuran, benzene or toluene is used as the reaction solvent. The chromene compound represented by the above general formula (1) of the present invention is well soluble in general organic solvents such as toluene, chloroform and tetrahydrofuran. When the chromene compound represented by the general formula (1) is dissolved in such a solvent, the solution is generally almost colorless and transparent, and when it is exposed to sunlight or ultraviolet rays, it rapidly develops color, and when it is shielded from light, it returns to the original colorless state. It has a good reversible photochromic effect. The photochromic action of the compound represented by the general formula (1) exhibits similar characteristics even in the polymer solid matrix. The target polymer solid matrix may be one in which the chromene compound represented by the general formula (1) of the present invention is uniformly dispersed. Optically preferably, for example, polymethyl acrylate, polyacrylic acid Examples thereof include thermoplastic resins such as ethyl, polymethylmethacrylate, polyethylmethacrylate, polystyrene, polyacrylonitrile, polyvinyl alcohol, polyacrylamide, poly (2-hydroxyethylmethacrylate), polydimethylsiloxane, and polycarbonate. Furthermore, ethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, ethylene glycol bisglycidyl methacrylate, bisphenol A dimethacrylate, 2,2-bis (4-methacryloyloxyethoxyphenyl) propane, 2 , 2
-Poly (acrylic acid) and poly (meth) acrylate compounds such as bis (3,5-dibromo-4-methacryloyloxyethoxyphenyl) propane; diallyl phthalate,
Polyallyl compounds such as diallyl terephthalate, diallyl isophthalate, diallyl tartrate, diallyl epoxysuccinate, diallyl fumarate, diallyl chlorendate, diallyl hexaphthalate, diallyl carbonate, allyl diglycol carbonate, trimethylolpropane triallyl carbonate; 2-bis (methacryloylthio) ethane, bis (2-acryloylthioethyl) ether, 1,4-bis (methacryloylthiomethyl) benzene, and other polyvalent thioacrylic acid and polyvalent thiomethacrylic acid ester compounds; glycidyl acrylate, glycidyl Methacrylate, β-methylglycidyl methacrylate, bisphenol A-monoglycidyl ether-methacrylate, 4-glycidyloxymethacrylate, 3- (glycidyl 2-oxyethoxy) -2-hydroxypropyl methacrylate, 3- (glycidyloxy-1-isopropyloxy) -2-hydroxypropyl acrylate, 3-glycidyloxy-2-hydroxypropyloxy) -2-hydroxypropyl acrylate, etc. Acrylic acid ester compounds and methacrylic acid ester compounds; thermosetting resins obtained by polymerizing radically polymerizable polyfunctional monomers such as divinylbenzene. Further, each of these monomers and unsaturated carboxylic acids such as acrylic acid, methacrylic acid and maleic anhydride; acrylic acid such as methyl acrylate, methyl methacrylate, benzyl methacrylate, phenyl methacrylate and 2-hydroxyethyl methacrylate. And methacrylic acid ester compounds; fumaric acid ester compounds such as diethyl fumarate and diphenyl fumarate; thioacrylic acid and thiomethacrylic acid ester compounds such as methylthioacrylate, benzylthioacrylate, benzylthiomethacrylate; styrene, chlorostyrene, methylstyrene, Examples thereof include copolymers with radically polymerizable monofunctional monomers such as vinyl compounds such as vinylnaphthalene, α-methylstyrene dimer and bromostyrene. The method for dispersing the chromene compound represented by the general formula (1) of the present invention in the polymer solid matrix is not particularly limited, and a general method can be used. For example, a method in which the thermoplastic resin and the chromene compound are kneaded in a molten state and dispersed in the resin, or after the chromene compound is dissolved in the polymerizable monomer, a polymerization catalyst is added to polymerize by heat or light. And a method of dispersing the chromene compound in the resin by dyeing the surfaces of the thermoplastic resin and the thermosetting resin with a chromene compound. The chromene compound of the present invention can be widely used as a photochromic material. For example, various storage materials replacing silver salt photosensitive materials, copying materials, printing photoreceptors, cathode ray tube storage materials, laser photosensitive materials, holographic photosensitive materials. It can be used as various storage materials such as. In addition, the photochromic material using the chromene compound of the present invention can be used as a material for a photochromic lens material, an optical filter material, a display material, a photometer, a decoration and the like. For example, when used for a photochromic lens, it is not particularly limited as long as it is a method capable of obtaining uniform dimming performance, and if specifically exemplified, a polymer film obtained by uniformly dispersing the photochromic material of the present invention. A method of sandwiching in a lens, or a method of dispersing the chromene compound of the present invention in the polymerizable monomer and polymerizing by a predetermined method, or dissolving this compound in, for example, silicone oil. 1 at 150-200 ° C
There is a method of impregnating the lens surface for 0 to 60 minutes and then coating the surface with a curable substance to form a photochromic lens. Further, a method of applying the above polymer film to the lens surface and coating the surface with a curable substance to form a photochromic lens is also conceivable. In the chromene compound of the present invention, a particularly preferred chromene compound is represented by the following general formula (4) from the viewpoints of good durability, high absorbance, fast fading speed, ease of synthesis and the like.

Embedded image (However, R ⁵ , R ⁶ , R ⁷ , and R ⁸ are each the same or different hydrogen atom, an alkyl group, an alkoxy group, a substituted amino group in which the substituents form a ring, or a fluorine atom.)

INDUSTRIAL APPLICABILITY The chromene compound of the present invention exhibits excellent durability and high color density in a solution or a polymer solid matrix. For example, the photochromic lens using the chromene compound of the present invention shows little deterioration even after being mounted for a long period of time, exhibits an excellent light-shielding property, and has a small change in hue. Furthermore, since the chromene compound of the present invention has a high fading speed, a lens that does not block the field of view when returning from indoors to indoors is possible.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Example 1 The following compound

Embedded image 1.44 g (0.01 mol) and the following compound

Embedded image 1.98 g (0.01 mol) was dissolved in 50 ml of toluene, 0.05 g of p-toluenesulfonic acid was further added, and the mixture was refluxed for 2 hours. After the reaction, the solvent was removed, and the product was purified by chromatography on silica gel to obtain 1.30 g of a pale yellow powdery product. The elemental analysis values of this product are C85.02%, H4.93%, O
10.05%, which is the calculated value of C ₂₃ H ₁₆ O _2.
It was very well in agreement with 85.16%, H 4.97%, and O 9.86%. In addition, the proton nuclear magnetic resonance spectrum was measured, and it was found that a value of 16 based on aromatic protons and alkene protons was found around δ 6.0 to 9.0 ppm.
An H peak was shown. Further, when the ¹³ C-nuclear magnetic resonance spectrum was measured, a peak due to the carbon of the aromatic ring was shown at around δ110 to 160 ppm, and a peak due to the carbon of the alkene was shown at around δ80 to 140 ppm. From the above results, it was confirmed that the isolated product was a compound represented by the following structural formula (5).

Embedded image Example 2 The following compound

Embedded image 1.44 g (0.01 mol) and the following compound

Embedded image 2.58 g (0.01 mol) was dissolved in 50 ml of toluene, 0.05 g of sulfuric acid was further added, and the mixture was refluxed for 2 hours. After the reaction, the solvent was removed and the product was purified by chromatography on silica gel to obtain 1.34 g of a pale yellow powdery product. The elemental analysis value of this product is
C78.02%, H5.30%, a O16.68%, C78.11% calculated values of C ₂₅ H ₂₀ O _4, H
Very good agreement was obtained with 5.24% and O 16.65%. When the proton nuclear magnetic resonance spectrum was measured,
δ peak of 14 H based on aromatic protons and alkene protons around 6.0 to 9.0 ppm, δ
A peak of 6H based on a methoxy group proton was shown in the vicinity of 3.0 to 4.5 ppm. Further, when ¹³ C-nuclear magnetic resonance spectrum was measured, a peak due to carbon of the aromatic ring at δ 110 to 160 ppm, δ 80 to 140 pp.
A peak due to carbon of alkene near m, δ50-60
A peak based on carbon of the methoxy group was shown at around ppm. From the above results, it was confirmed that the isolated product was a compound represented by the following structural formula (6).

Embedded image Examples 3 to 20 The chromene compounds shown in Table 1 were synthesized in the same manner as in Example 1. The obtained product was subjected to structural analysis by the same means for confirming structure as in Example 1, and as a result, it was confirmed to be a compound represented by the structural formula shown in Table 1. In addition, Table 2 shows the elemental analysis values of these compounds, the calculated values obtained from the structural formula of each compound, and the characteristic spectra of ¹ H-NMR spectrum.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

[Table 8] Examples 21 to 40, Comparative Examples 1 to 4 0.1 part of the chromene compound obtained in Example 1 was added to 70 parts of tetraethylene glycol dimethacrylate, 15 parts of triethylene glycol dimethacrylate, 10 parts of glycidyl methacrylate, and 2-hydroethyl. Methacrylate 5
Part and mixed well. This mixture was poured into a mold composed of a glass plate and a gasket made of an ethylene-vinyl acetate copolymer, and cast polymerization was performed. Polymerization was carried out by using an air furnace, gradually increasing the temperature from 30 ° C to 90 ° C over 18 hours, and maintaining the temperature at 90 ° C for 2 hours. After completion of the polymerization, the polymer was removed from the glass mold of the mold. A xenon lamp L-2480 (300W) SHL-100 manufactured by Hamamatsu Photonics was added to the obtained polymer (thickness 2 mm) at 20 ° C. through an aeromas filter (manufactured by Corning).
Beam intensity on polymer surface at 1 ° C, 365 nm = 2.4 m
The photochromic property was measured by irradiating with W / cm ² and 245 nm = 24 μW / cm ² for 120 seconds to develop color.
The photochromic characteristics are also expressed as follows. The results are shown in Table 3. Maximum absorption wavelength (λmax): spectrophotometer manufactured by Otsuka Electronics Co., Ltd. (instantaneous multi-channel photo detector M
Λmax after color development of this polymer by CPD1000)
I asked. ε (120): Absorbance of this polymer at the maximum absorption wavelength after 120 seconds of irradiation under the above-mentioned conditions. ε (0): Absorbance of unirradiated polymer at the same wavelength as the maximum absorption wavelength when irradiated with light. [epsilon] (120)-[epsilon] (0): Color density Density rate [t1 _{/ 2} ]: After irradiation for 120 seconds, the absorbance of this polymer decreases to 1/2 of [[epsilon] (120)-[epsilon] (0)]. Time it takes. Durability [T _1/2 ]: Expressed by the time required for the absorbance at the maximum absorption wavelength to decrease to 1/2 of the initial absorbance by a Xenon Fade Meter FAC-25AX-HC manufactured by Suga Test Instruments Co., Ltd. Further, a photochromic polymer was obtained in the same manner as above except that the compounds obtained in Examples 2 to 20 were used as the chromene compound, and the properties thereof are shown in Table 3. Further, for comparison, the following formulas (A), (B), (D) and (E)

Embedded image

Embedded image

Embedded image

Embedded image The characteristics of the compound represented by are shown in Table 3.

[Table 9] The compound of the present invention has a color density about twice higher than that of the compounds of Comparative Examples 1, 3 and 4, and is also excellent in durability. Further, the durability is about twice as high as that of the compound of Comparative Example 2, and the fading speed is excellent.

[Brief description of the drawings]

1 is a proton nuclear magnetic resonance spectrum of the compound of Example 1. FIG.

Claims (2)

[Claims] [Claim 1] The following general formula (1) [Wherein R ¹ , R ² , R ³ and R ⁴ are the same or different hydrogen atoms, alkyl groups, alkoxy groups, aralkyl groups, acyl groups, cyano groups, substituted amino groups, aryl groups,
It is an acyloxy group, a nitro group, a hydroxyl group or a halogen atom, and a, b and c each represent the number of the substituents R ¹ , R ² and R ³ and are 1 or 2. ] The chromene compound shown by these. 2. A photochromic material comprising the chromene compound according to claim 1.