KR101295435B1 - New phenanthropyran derivative and photochromic dye comprising the same - Google Patents

Abstract

The present invention relates to a novel phenanthropyran derivative and a photochromic dye comprising the same. The photochromic dye including the phenanthropyran derivative may exhibit purple or blue color, and is excellent in durability at high temperatures and has excellent discoloration characteristics. Therefore, it can be variously applied to industrial products.

Penantropha derivatives, photochromic, dyes

Description

Novel phenanthropyran derivatives and photochromic dyes comprising the same {NEW PHENANTHROPYRAN DERIVATIVE AND PHOTOCHROMIC DYE COMPRISING THE SAME}

The present invention relates to a novel phenanthroparan derivative and a photochromic dye comprising the same.

Photochromic refers to a characteristic of changing color under the influence of polychromatic light or monochromatic light, and means a property of changing color before and after light irradiation.

Photochromic compounds exhibiting such photochromic properties have an intramolecular conjugated structure to absorb a specific range of light, thereby changing the structure of the photochromic compound so that the color is expressed or lost as the conjugated structure is changed. Therefore, the photochromic compound exhibits repeatability of recording and erasing, and is effective for transferring information. Can be.

In addition, the photochromic compound may be used as a photochromic dye, and may be applied in a form dispersed in a dispersion medium on a support or mixed into the support to make an application. Such applications include a material that absorbs ultraviolet rays and exhibits discoloration characteristics, and thus can be used for various applications such as eyeglass lenses, building windows, and automotive windows.

Various types of compounds have been developed that can be used as the photochromic dye. In particular, photochromic dyes having a central structure of spirooxazine and naphthopa have been known.

Specifically, US Pat. Nos. 5,869,658 and 6,022,495 disclose 3-naphthoparan derived from 2-naphthol and derivatives thereof by annealing thereof, which are included in photochromic dyes. The long wavelength absorption maximum of these excitation forms is mainly in the spectral range of 420 nm-500 nm, and shows yellow, orange, and red orange color. However, photoreversible discolored glass, which requires dark colors, requires high performance purple or blue photochromic dyes. Currently available purple or blue photochromic dyes can usually be obtained from spiroxazine dyes, fulgide dyes or 2H-naphtho [1,2-b] pyrans. However, spirooxazine dyes are disadvantageous in high temperature performance, fullgied dyes are less durable, and 2H-naphthos are less satisfactory for use in photochromic products because of their slower color brightening.

To overcome this problem, there are examples of using phenanthroparan as disclosed in US 2006-0219990, but not many.

Accordingly, there is a continuing need for the development of new photochromic materials that can exhibit purple or blue color, have excellent durability even at high temperatures, and have excellent photochromic properties.

The inventors have discovered a phenanthroparan derivative having a novel structure. In addition, it has been found that the photochromic dye including the novel phenanthroparan derivative may exhibit purple or blue color, has excellent durability at high temperatures, and has excellent discoloration characteristics.

Accordingly, an object of the present invention is to provide a novel phenanthroparan derivative and a photochromic dye containing the same.

The present invention provides novel phenanthroparan derivatives.

The present invention also provides a method for preparing the novel phenanthroparan derivative.

The present invention also provides a photochromic dye, a photochromic coating composition, and a photochromic product including the novel phenanthroparan derivative.

The novel phenanthroparan derivative according to the present invention may exhibit purple or blue color by a light source, has excellent durability even at high temperatures, and has excellent discoloration characteristics. Such phenanthroparan derivatives can be applied to various industrial products that require photochromism.

The novel phenanthropyran derivatives according to the present invention are characterized in that the phenyl group in which the hetero ring is substituted and the phenyl group in which the methoxy is substituted are simultaneously substituted in the phenanthropyran group.

Specifically, the novel phenanthroparan derivative may be represented by the following formula (1).

In Formula 1,

n is 1 to 5, A is a phenanthropharan group,

Ar is an aliphatic or aromatic hetero ring comprising at least one selected from N, O and S.

The phenanthroparan derivative is preferably selected from the following Chemical Formulas 2 to 5.

The phenanthropyran derivative according to the present invention may be prepared by a method of preparing a phenanthrene substituted with a hydroxy group and a substituted propargyl alcohol compound.

Specifically, the phenanthroparan derivative may be prepared as in the following scheme.

[Reaction Scheme 1]

In Scheme 1, R and R 'are each independently a phenyl group substituted with an aliphatic or aromatic hetero ring including one or more selected from N, O and S or a phenyl group substituted with at least one methoxy.

One embodiment of the novel method for preparing a phenantropha derivative is as follows. First, propargyl alcohol, hydroxyl phenanthrene, p-toluenesulfonic acid (PPTS) and trimethyl orthoformate were refluxed in dichloromethane for 4 to 24 hours. ), Filter through an alumina pad at high temperature and wash with dichloromethane. The solvent is removed under vacuum, and the remaining residue is purified by chromatography and recrystallization, whereby a phenanthroparan derivative can be prepared.

The novel phenanthropyran derivatives may exhibit violet or blue color in the wavelength range of 550 nm to 650 nm by a light source, have excellent durability at high temperatures, and have excellent discoloration characteristics. Such phenanthroparan derivatives can be applied to various industrial products that require photochromism.

The present invention provides a photochromic dye comprising a phenanthroparan derivative prepared according to the above method and a photochromic coating composition comprising the photochromic dye, a polymer resin, a solvent and the like. The photochromic dye may be used as a coating film coated on the surface of various industrial products as the photochromic dye has a color changing color when activated by a light source such as solar radiation, mercury, xenon or UV radiation.

In this case, the coating film may be prepared by preparing a composition including a photochromic dye, a polymer resin, and a solvent including the phenanthroparan derivative of the present invention, and then coating the surface of an industrial product to be coated, followed by drying and curing. .

The polymer resin used in the coating film may use a conventional coating polymer without particular limitation, and preferably any one selected from the group consisting of polyolefin, polyester, polycarbonate, polyacrylate, polyurethane, and epoxy resin. The above polymer resin can be used.

The solvent suitable for the production of the coating film can also be selected within the usual range, there is no particular limitation, benzene, toluene, methyl ethyl ketone, acetone, ethanol, methanol, propanol, isopropanol, tetrahydrofuran, dioxane, ethyl Preference is given to using one or more selected from the group consisting of acetate, ethylene glycol, xylene, cyclohexane and N-methyl pyrrolidinone.

The coating method of the coating film may be a conventional wet coating method such as spray coating, spin coating, dip coating, and doctor blading coating, and is not particularly limited.

Industrial products to which such coatings can be applied are photochromic products in which photochromic materials are typically used (e.g. photochromic films, photochromic glasses, optical lenses and flat lenses, face shields, goggles, camera lenses, Windows, automotive transparencies), inks (eg liquid or paste containing photochromic dyes used for writing and printing), decorations (eg plastic films and sheets, textiles), coating compositions (eg paints), protective documents (E.g., passport, driver's license and check mark of bank notes) and the like.

The present invention will be described in more detail with reference to the following examples and comparative examples. However, the present invention is not limited to these examples.

Preparation Example 1 Preparation of a Phenanthryl Group Substituted with a Hydroxy Group

i) Naphthylacetones were prepared from naphthylacetic acids and methyllithium. A 0.9 M solution of methyllithium dissolved in anhydrous ether was slowly added to the naphthylacetic acid solution in anhydrous ether with stirring for 2 hours. The reaction was stirred for 12 hours at room temperature. After addition of water and extraction with ether, the organic solution was washed with water and dried to remove solvent. The residue was distilled off to give naphthyl acetone (a) in 75-80% yield. The breaking point of 1-naphthyl acetone (1-Naphthylacetone) is 150-158 ° C./8 Torr ³ (75%), and the breaking point of 2-naphthyl acetone (2-Naphthylacetone) is 130-135 ° C./10 Torr ⁴ (80%).

ii) 1) Sodium metal (0.01 mol) was added to a solution of naphthyl acetone (0.01 mol) and diethyl oxalate (0.01 mol) in 5 mL of anhydrous ethanol. The reaction mixture was stirred for 18 hours at room temperature. After confirming that the reaction was completed by TLC, the solvent was removed, and the remaining residue was chromatographed on silica with a solution of petroleum ether and ethyl acetate 6: 1.

2) NaOH and ethyl 5- (1-naphthyl) -2,4-dioxopentoate (or ethyl 5- (2-naphthyl) -2,4-dioxopentoate) prepared in 1) It was refluxed for 4 hours in methanol solvent. Then, after cooling the reaction mixture, conc. Acidified with HCl and the precipitate was filtered off. After drying the precipitate, compound (b) was obtained and used in the next step without further purification.

iii) 5- (1-naphthyl) -2,4-dioxopentanoic acid (5- (1-naphthyl) -2,4-dioxopentanoic acid) prepared in ii) 2) (or 5- (1- Naphthyl) -2,4-dioxopentanoic acid (5- (2-naphthyl) -2,4-dioxopentanoic acid) was refluxed in H ₃ PO ₄ for 10 hours at 100 ° C. After cooling, water was added, The precipitate was filtered to give 2-phenanthrol or 3-phenanthrol as compound (c).

Preparation Example 2 Preparation of Propargyl Alcohol Derivative

i) 0.1 mol of finely powdered aluminum chloride in 0.1 mol of N-phenyl substituted amine (a), 0.1 mol of substituted benzoyl chloride (b) and 250 ml of dichloromethane. A small amount was added while stirring at 20 ° C. After 2 hours at the same temperature, the reaction mixture was poured into ice (500 g) and conc. In HCl (100 ml). The organic layer was separated and the water layer was extracted with dichloromethane (3 × 150 ml). Combined organic phases were washed with 5% aqueous Na ₂ CO ₃ solution (150 ml), water (3 × 50 ml) and dried over MgSO ₄ anhydride. After removing the solvent, recrystallized with ethanol to give the crude benzophenone (c).

ii) To lithium acetylide (7.5 mmol) dissolved in 100 mL of anhydrous THF, a ketone (1.5 mmol) solution dissolved in 100 mL of anhydrous THF cooled to 0 ° C was slowly added. The mixture was stirred at room temperature for 1 hour and at 40 ° C for 1 hour, cooled to room temperature and hydrated with water (100 mL). Filter the organic layer with celite, wash with H ₂ O, MgSO ₄ Dried and evaporated. Residue-propazol alcohol (d) was obtained.

<Example 1> Preparation of the phenanthroparan derivative represented by the formula (2)

Synthesis of 2-phenanthrol by the preparation method of Preparation Example 1, using N-phenyl cycloheptane (a) as N-phenyl substituted amine in Preparation Example 2, 2 as substituted benzoyl chloride Propargyl alcohol was prepared using 2,4-dimethoxybenzoyl chloride (b).

Dissolve propargyl alcohol (0.55 mmol), 2-phenantrol (0.55 mmol), PPTS (0.05 mmol) and trimethyl orthoformate (0.55 mmol) in dichloromethane (3 mL). It was refluxed for 24 hours, filtered through a pad of alumina at high temperature and washed with dichloromethane. The solvent was removed in vacuo, and the residue was purified by chromatograph (silica gel, EtOAc: hexane = 1: 3) and recrystallized (EtOAc / hexane) to obtain a phenanthropyran derivative represented by the formula (2). Table 1 shows the NMR and MS values of the derivatives prepared.

<Example 2> Preparation of the phenanthroparan derivative represented by the formula (3)

Except for using N-phenyl pyridine (a) instead of N-phenyl cycloheptane in Preparation Example 2 was prepared in the same manner as in Example 1. Table 1 shows the NMR and MS values of the derivatives prepared.

Example 3 Preparation of a Penanthropyran Derivative Represented by Chemical Formula 4

Same as Example 1 except for using 3-phenantrol instead of 2-phenantrol in Preparation Example 1 and 4-phenylmorpholine (a) instead of N-phenyl cycloheptane in Preparation Example 2 It was prepared by the method. Table 1 shows the NMR and MS values of the derivatives prepared.

<Example 4> Preparation of the phenanthroparan derivative represented by the formula (5)

Same as Example 1 except for using 3-phenantrol instead of 2-phenantrol in Preparation Example 1 and N-phenyl pyridine (a) instead of N-phenyl cycloheptane in Preparation Example 2 It was prepared by the method. Table 1 shows the NMR and MS values of the derivatives prepared.

Each of the compounds of Formulas 2 to 5 prepared in 0.012wt% toluene solution was placed in a 1 cm cuvette and irradiated with UV light (1.35 mW / cm ² ) at a wavelength of 365 nm for 4 minutes, and then immediately visible light using a UV-Vis detector. Absorbance at was measured. Table 2 shows the measured values.

Photochromic dye λ _max in toluene Example 1 603 nm Example 2 580 nm Example 3 538 nm Example 4 560 nm

Claims (7)

Penantropharan derivatives represented by the formula:

or

In the above formulas, n is 1 to 5, Ar is an aliphatic heterocyclic ring having 4 to 7 carbon atoms containing at least one selected from N and O. The phenanthropyran derivative of claim 1, wherein the phenanthroparan derivative is selected from the following Chemical Formulas 2 to 5:

The phenanthropyran derivative of claim 1, wherein the phenanthropyran derivative is discolored by a light source in a wavelength range of 550 nm to 650 nm. delete Photochromic dye comprising the phenanthroparan derivative of claim 1. A photochromic coating composition comprising a photochromic dye, a polymer resin, and a solvent of claim 5. A photochromic article comprising the photochromic dye of claim 5.