JPS61165388A - Production of spirooxazine derivative - Google Patents

Abstract

PURPOSE:To produce the titled novel compound useful as a photochromic material, in high yield, by reacting a specific trimethylindolenine derivative, a sulfonate derivative, a nitrosonaphthol derivative and a basic substance. CONSTITUTION:The compound of formula IV {e.g. 1-(2-phenylethyl)-3,3- dimethylspiro[indoline-2,3'-(3H)-naph-tho[2, 1-b](1,4)oxazine]} is produced by reacting (A) the compound of formula I (R1 is H, halogen, nitro, cyano, 1-5C alkyl or alkoxy) (e.g. 2,3,3-trimethylindolenine) with (B) the compound of formula II [R2 is 1-2C(substituted)alkyl; R is 1-8C alkyl, halogenated alkyl, (halogenated) phenyl, nitro-substituted alkyl or nitro-substituted phenyl] (e.g. beta-phenylethyltosylate), (C) the compound of formula III (R3 and R4 are H, halo gen, SO3H, COOH, 1-5C alkyl, etc.) (e.g. alpha-nitroso-beta-naphthol) and (D) a basic substance.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for producing a photochromic compound useful as a photochromic material for printing, a photochromic material for optical equipment, a photochromic material for recording materials, or a photochromic material for clothing and decorative items. Regarding.

(Prior art) Spiropyran derivatives are typical photochromic compounds, and many derivatives are known (G,
H, Brown, @Photochromis
m”, Willeyrnterscience
, New York (1971)).

On the other hand, Japanese Patent Publication No. 49-48651 describes a method for producing spirooxazine derivatives.

(Problem that the invention attempts to solve) On the other hand, spiropyran derivatives are easy to synthesize.

The drawback is that it causes severe fatigue when coloring and fading due to light. That is, a substance dissolved in or added to a solvent or matrix polymer has a fatal practical drawback in that it no longer exhibits photochromic properties when exposed to ultraviolet light using a fade meter or the like for a long time.

On the other hand, spirooxazine derivatives are generally known to have better fatigue resistance than spiropyran derivatives. However, since the conventional production methods for these compounds use indolenium halide, which is difficult to isolate, as a starting material, the types of spirooxazine derivatives that can be synthesized are limited to a very small number. This poses two serious problems in obtaining spirooxazine compounds with various different photochromic properties.

(Means for Solving the Problems) The present invention aims to improve the above-mentioned problems and consists of the following configuration.

A method for producing a spirooxazine derivative represented by the general formula CD below.

A trimethylindolenine derivative represented by

General formula CB) R, -0+ So, RCB) and a sulfonate derivative represented by

General formula [C] N.

1. A method for producing a spirooxazine derivative, which comprises reacting a motroso-su7toyl derivative represented by the formula and a basic substance.

(Here, R6 is hydrogen, halogen, nitro group, cyano group,
Represents an alkyl group or alkoxy group having 1 to 5 carbon atoms, R2 represents an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, and R represents an alkyl group having 1 to 8 carbon atoms, a halogenated alkyl group, or a halogenated phenyl group. represents a nitro-substituted alkyl group, a nitro-substituted phenyl group or an alkyl-substituted phenyl group.

R8 and R4 are hydrogen, halogen, and sulfonic acid group.

Sodium sulfonate group, carboxyl group, 'C1-5
The alkyl group and alkoxy group represent an alkyloxycarbonyl group. )" The trimethylindolenine derivative represented by the general formula (A) used in the present invention is synthesized by, for example, a cyclization reaction of a substituted phenylhydrazone of methyl impropyl ketone (He1v, Chim, Acta).

25, 2471 (1940)).

R8 is hydrogen, nitrogen, nitro group, carbon number 1
-5 alkyl groups or alkoxy groups.

The sulfonate derivative represented by the general formula CB used in the present invention can be synthesized by a known method.
5ynthesis, Co11active'
Vol. I, 145.

R2 in the sulfonate derivative has 1 to 1 carbon atoms.
20 unsubstituted or substituted alkyl groups, represented by the general formula [
It is introduced into the N-position of the indoline ring of the spirooxazine derivative represented by D]. Further, as the substituent in Rf, various functional groups can be mentioned, and two examples include carboxyl group, hydroxy group, (substituted) phenyl group, cyano group, halogen, nitro group, and carbon number 1 to 5.
Examples of the alkoxy group include an alkyloxycarbonyl group. In particular, inopropyl group and diphenylmethyl group can maximize the characteristics of using sulfonate derivatives in the present invention.

Examples include those with large steric hindrance such as a benzyl group and various substituent derivatives.

R in the sulfonate derivative has 1 to 8 carbon atoms.
alkyl group, no-logenated alkyl group.

Halogenated phenyl group, nitro-substituted alkyl group.

Mention may be made of nitro-substituted phenyl groups or alkyl-substituted phenyl groups. Especially from the point of view of reactivity.

Halogenated alkyl group, para-substituted phenyl group, carbon number 1
-4 alkyl groups are preferably used.

Among them, trifluoromethyl group, 2,2.2-)lifluoroethyl group +
Examples include pl'f ruphenyl group + p-bromphenyl group, P-nitrophenyl group and butyl group.

Specific examples of these sulfonate derivatives include methyl tosylate (abbreviation for tosylate p-toluenesulfonate), methyl prosylate (abbreviation for prosylate p-frombenzenesulfonate), methyl trifluoromethanesulfonate, hexyl tosylate,
Examples include octyl tosylate and β-phenylethyl tosylate.

The nitrosonaphthol derivative represented by the general formula (C) used in the present invention is synthesized by nitronation of 2, for example, substituted naphthols. Examples of R3 and R4 include a water L halogen, a sulfonic acid group, a sodium sulfonate group, a carboxyl group, an alkyl group of Flfi1 to 5, an alkoxy group, or an alkyloxycarbonyl group.

The basic substance used in the present invention may be any organic or inorganic basic substance, but amines such as pyridine, piperidine, and triethylamine are preferably used.

In reacting the trimethylindolenine derivative represented by general formula (A), the sulfonate derivative represented by general formula CB), the nitrosonaphthol derivative represented by general formula (C) and a basic substance in the present invention,
Although any method can be used for the order of addition, the most common method is to mix the trimethylindolenine derivative represented by the general formula (A) and the sulfonate derivative represented by the general formula CB), and then add a base. A method of adding and mixing a chemical substance and a nitrosonaphthol derivative represented by the general formula [C] can be mentioned.

Other methods include adding and mixing a trimethylindolenine derivative, a sulfonate derivative, a nitrosonaphthol derivative, and a basic substance at the same time, or mixing a trimethylindolenine derivative and a nitrosonaphthol derivative, and then adding and mixing a basic substance and a sulfonate derivative. Examples include a method to do so.

As the reaction solvent of the present invention, various solvents can be used, and solvent-free reaction is also possible. From the viewpoint of removal after the reaction and control of the reaction system temperature, an organic solvent having a boiling point of 60 to 160°C is preferably used.

Specific examples include hydrocarbons such as benzene and hexane★
Chlorides such as chloroform and methylene chloride.

Sulfides such as carbon disulfide and dimethyl sulfoxide.

Examples include polar abrotic solvents such as aceto/, methyl ethyl keto/, ethyl acetate, and acetonitrile, ethers such as tetrahydrofuran and dioxane, and polar grootic solvents such as methanol, ethanol, methyl cellosolve, and ethylene glycol.

There is no problem with the above solvent containing a small amount of water, but
From the viewpoint of improving yield, it is preferable to use it after dehydration.

In the above reaction, it is possible to isolate the indolenium salt which is the reaction product of the trimethylindolenine derivative represented by the general formula (A) and the sulfonate derivative represented by the general formula CB), but it is possible to From the viewpoint of loss during purification, it is preferable to complete the reaction continuously.

The conditions for the above reaction are 9, for example, reaction temperature and 1 reaction time.

The reaction atmosphere, the mixing molar ratio of the two reactants, etc. should be determined experimentally for each of the two reactants.

Generally, from the point of view of reaction yield, one reaction time is 0,
The temperature can be changed at each reaction step, but the reflux temperature of the solvent used is usually preferably used.

Next, the reaction atmosphere is preferably replaced with an inert gas in order to prevent a decrease in yield due to oxidative decomposition or the like. It is particularly preferable to perform such inert gas substitution before mixing in order to improve the yield.

Any inert gas may be used as long as it does not reduce the yield, but nitrogen and helium are usually used.

Argon or the like is preferably used.

In the present invention, the molar ratio of the reactants added is 0 to 1 mole of trimethylindolenine,
It is preferable to use 5 to 50 moles, and especially KO18 to 5
Moles are preferred. Nitrosonaphthol derivatives are from 0.1 to
The strength used is preferably 10 mol, especially 0.5 to 1.5
Moles are preferred. The basic substance is preferably used in an amount of 0.5 mol or more, particularly preferably 0.5 to 50 mol.

Note that if the temperature or time under the above reaction conditions is lower than or shorter than the lower limit, each reaction will not proceed sufficiently, and the yield of the final product, the spirooxazine derivative, will tend to decrease. Also, if it is higher or longer than the upper limit.

This is not preferable because the reaction product and/or the reactant disappears due to thermal decomposition or the like, resulting in a decrease in the yield of the final product. On the other hand, if the molar ratio of the two reactants is out of the above range, it is not preferable because it will not only lower the yield of the final product but also make it difficult to isolate the final product.

The final product spirooxazine derivative represented by general formula [D] can be separated and purified by recrystallization using various solvents, column separation using various supports and organic solvents, activated carbon treatment, etc. However, it is also possible to combine these methods in a complex manner.

The solvent used in the recrystallization method may be any solvent as long as the spirooxazine derivative can be dissolved therein, and a single solvent or a mixed solvent may be used. Specific examples include benzene, toluene,
Hydrocarbons such as hexane, chloroform, methylene chloride, and carbon disulfide.

Sulfides such as dimethyl sulfoxide, polar abrotic solvents such as acetone, methyl ethyl ketone, ethyl acetate, and acetonitrile, ethers such as tetrahydrofuran, dioxane, and diethyl ether, methanol, ethanol, and methyl cellosolve.

Polar protic solvents such as ethylene glycol are used alone or in mixed baths/agents.

Specific examples of supports used in column separation methods include:
Examples include silica gel, alumina, cellulose, calcium hydroxide, and quicklime.

Any developing solvent may be used as long as the spirooxazine derivative is soluble and the support carrier is insoluble.

Specifically, benzene, toluene, hexv'', ', etc.

Hydrocarbons, chlorides such as chloroform and methylene chloride, polar abrotic solvents such as acetone, methyl ethyl ketone and ethyl acetate, ethers such as tetrahydrofuran and dioxane, polar protic solvents such as methanol and ethanol, etc. can be used as single or mixed solvents. It will be done.

The combination of various supporting carriers and various developing solvents should be determined experimentally depending on the solubility of the substance to be separated, the flow rate, etc.

The solvent used in the activated carbon treatment method may be any solvent as long as the spirooxazine derivative can be dissolved therein, and a single solvent or a mixed solvent may be used. As a specific example.

Hydrocarbons such as benzene, toluene and hexane, chlorides such as chloroform and methylene chloride, sulfides such as carbon disulfide and dimethyl sulfoxide, and acetone.

Polar abrotic solvents such as methyl ethyl ketone, ethyl acetate, and acetonitrile, ethers such as tetrahydrofuran and dioxane, and methanol.

Polar glotic solvents such as ethanol, methyl cellosolve, and ethylene glycol are used alone or as a mixed solvent.

The spirooxadi/derivative thus obtained is dissolved in a solution of the polymer in an appropriate solvent, and then coated on an object to be coated such as a plate or fiber, or made into a film. is possible.

A specific example of the polymer is polyvinyl acetate.

Polyvinyl chloride, polyvinyl butyral, polymer,
Til methacrylate, cellulose acetate, polyvinylpyrrolidone, foristyrol, hydroxyethylcellulose, hydroxypropylcellulose.

Epoxy resin, phenolic resin, polysiloxane resin,
Examples include various thermoplastic or thermosetting resins such as urethane resins.

Specific examples of the solvent include unsaturated hydrocarbons such as benzene and toluene, polar abrotic solvents such as acetone, methyl ethyl ketone, acetonitrile, and dimethylformamide, polar protic solvents such as ethanol and n-butanol, and methylene chloride.

Examples include chlorides such as chloroform, sulfides such as dimethyl sulfoxide, and the like.

It is also possible to use it by adding it to a polymerizable monomer such as methyl methacrylate, styrene, epoxy compound, or melamine compound and polymerizing it with a suitable polymerization initiator so that it is present in a cured resin. As a specific example of the polymerization initiator, an azo compound such as azobisisobutyronitrile is preferably used.

Also, for transparent substrates such as polycarbonate, polymethyl methacrylate, and diethylene glycol bisallyl carbonate polymer (CR-!i9).

It is also possible to add using a staining method. The dyeing method is a method in which the spirooxazine derivative is diffused into the transparent substrate by immersing the transparent substrate in a solution prepared by dissolving or dispersing the spirooxazine derivative in an appropriate solvent and heating and stirring. be.

Furthermore, it is also possible to attach it to the polymer surface by a vacuum evaporation method or the like.

Thus, the compounds of the present invention can be added to various matrix polymers in various ways.

The spirooxazine derivatives obtained by the present invention are photochromic materials for printing, photochromic materials for optical instruments such as plastic or glass lenses, filters and light meters, photochromic materials for chameleon fibers, photochromic materials for color-changing dolls, and photochromic materials for recording materials. It can be used for etc.

That is, the spirooxazine derivative obtained by the present invention is generally colorless regardless of the type of solvent or matrix polymer, but when irradiated with ultraviolet rays, it immediately changes into a compound having an absorption wavelength in the visible light region. When UV irradiation is stopped, it quickly returns to its original colorless state.

The spirooxazine derivative obtained by the present invention has a high rate of two-color development and a high rate of decolorization.

It is a photochromic compound that has the characteristics of high color density and very good fatigue resistance.

In addition, the spirooxazine derivative obtained by the present invention changes from colorless to a compound having an absorption wavelength in the visible light region when heated in a solvent or matrix polymer, and quickly returns to its original colorless state when cooled. It is a compound that also has chromic properties.

Therefore, the spirooxazine derivative obtained by the present invention can also be used as a thermochromic material for temperature sensors, a thermochromic material for recording materials, etc.

According to the production method of the present invention, it becomes possible to synthesize spirooxazine derivatives that are difficult or impossible to synthesize using conventional methods. A particularly preferably applied example is the general formula [D
Examples include derivatives in which R7 is a sterically bulky functional group such as an unsubstituted or substituted benzyl group or an α-phenylethyl group.

The reaction mechanism of the present invention is that the sulfonate derivative represented by the general formula [B) undergoes an electrophilic reaction with the trimethylindolenine derivative represented by the general formula (A), whereby the indolenium represented by the general formula (E) When the indolenium salt derivative is reduced by a basic substance, a 2-methyleneindoline derivative represented by the general formula CF) R7 is produced (an electrophilic substitution reaction), which produces a salt derivative (an electrophilic substitution reaction), The 2-methyleneindoline derivative and the nitrosonaphthol derivative represented by the general formula (C) undergo a reflux and dehydration reaction to produce a spirooxazine derivative represented by the general formula [D] (nucleophilic, dehydration reaction). Possible reaction mechanism.

(Example) Example 1 ■ 1-(2-phenylethyl)-5,5-dimethylspiro[indoline-2,5'-(3H)-naphtho(2
, 1-b) Synthesis of (1,4)oxazine] (In the general formula [D], R, = R, = R, = H, R, = c
a. After blowing in for 15 minutes, the mixture was mixed and refluxed in a nitrogen stream for 2 hours. After that, the temperature of 1 reaction solution was lowered to 50 °C, 10.0 g of triethylamine was added, and 50 °C was added.
Stir for a minute. after that.

Process 8.7 g of α-nitroso-β-naphthol and reflux for 2 hours. After the reaction, it is concentrated and separated by column using alumina as a support carrier and toluene as a developing solvent. After distilling off the toluene, the obtained solid was recrystallized from methanol and further recrystallized from hexane to give white 1-(2-72-2-ethyl)-
3,3-dimethylsuhi 0 mouths [indoline-2,5'-(
5H)-capto[2,1-bl(1,4)oxazine]
1.0 g of crystals were obtained.

■ Analysis result (melting point) 107°C (Elemental analysis value) Actual value (Chin Calculated directly (Chin C85)
,0R3,3 H6,26,2 N 6.7 6.7 ■ Application example A polyvinyl butyral/n-butanol solution in which this compound was dissolved at a concentration of 0.5 wt% was applied onto a glass plate and dried. When exposed to ultraviolet light, it turned blue, and when the light was removed, it quickly returned to its original colorless state. When the light resistance was examined by irradiating it with light for 20 hours using a fade meter, it showed exactly the same photochromic properties as before being placed in the fade meter, and was found to have excellent fatigue resistance.

Example 2 ■ Synthesis of 1-hexyl-3,3-dimethylspiro[indoline-2,5'-[5H)-naphtho(2,1-b)(1°4)oxazine] (in general formula [D]) l R+=Rz=Ra=HI
R2=(CHy)sCJ) 25.0 g of hexyl tosylate was dissolved in 40 mz absolute ethanol, and 2,3.3-trimethylindolenine 8
．． 0 g was dissolved in 40 rnt of absolute ethanol, mixed after blowing nitrogen gas into each solution for 15 minutes, and refluxed in a nitrogen stream for 2 hours. Thereafter, the temperature of the two reaction solutions was lowered to 50° C., and 8.7 g of α-nitrone-β-naphthol was added, followed by 10.0 g of triethylamine, and the mixture was refluxed for 2 hours. After the reaction, it is concentrated and separated by column using silica gel as a support carrier and toluene as a developing solvent. After distilling off the toluene, the obtained solid was recrystallized from toluene and further recrystallized from ethanol to give white 1-hexyl-5,5-dimethylspiro[indoline-2,3(3H)-naphtho(2,1 -b)
1.2 g of crystals of (1,4)oxazine] were obtained.

■ Analysis result (melting point) 95℃ (Elemental analysis value) Actual value (chi) Calculation 1st shift (chi) c
81.4 81.4H7,5Z5 N 7. OZ□ ■ Application example This compound was dissolved in methyl methacrylate.

Cast polymerization using azoisobutyronitrile as a polymerization initiator turned blue when irradiated with ultraviolet light, and quickly returned to its original colorless color when left in a dark place without light.

Example 6 ■ 1.3.5- IJ Methyl Spiro [Indoline-
2゜5'-(5H]-naphtho(2,1-b) (1,
4) Synthesis of [oxazine] (general formula CD'), R, =R, =R, =H,
R,=CH,) methyl-trifluoromethanesulfonate (15.0 g) was dissolved in 40 mt of absolute ethanol,
8.0g of 2,3.3-trimethylindolenine in 40m
of anhydrous ethanol, mixed after blowing in nitrogen gas for 15 minutes, and refluxed in a nitrogen stream for 2 hours. Thereafter, the temperature of the two reaction solutions was lowered to 50°C, 10.0 g of triethylamine was added, and the mixture was stirred for 50 minutes.

After sowing, 8.7 g of α-nitroso-β-naphthol was added, and the mixture was refluxed for 2 hours. After the reaction, it is concentrated and separated by column using alumina as a support carrier and toluene as a developing solvent. After distilling off the toluene, the obtained solid was recrystallized from hexane and further recrystallized from ethanol.

white 1.3.3- ) lynchylspiro [indoline-
2,5'-(5H]-naphtho(2,1-b)(1,4)
6.9 crystals of [Oxazine] were obtained.

■ Analysis result (melting point) 154-135"C (elemental analysis value) Actual value (chi) Calculated value (chi) c
80. ! l 80.5
H5,96,1 N 8.4 8.
5 (Effects of the Invention) As is clear from the above explanation, one effect of the present invention is as follows.

1) It became possible to produce a new spirooxazine derivative that could not be obtained by conventional methods.

■ It has become possible to produce various spirooxazine derivatives.

■ The yield of spirooxazine derivatives was improved.

Claims (1)

[Claims] (1) In the method for producing spirooxazine derivatives represented by the general formula [D] below, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [D] General formula [A] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [A ] A trimethylindolenine derivative represented by the general formula [B] R_2-O-SO_2R [B] A sulfonate derivative represented by the general formula [C] ▲ Numerical formulas, chemical formulas, tables, etc. ▼ [C] A method for producing a spirooxazine derivative, which comprises reacting a nitroso-naphthol derivative and a basic substance. (Here, R_1 represents hydrogen, a halogen, a nitro group, a cyano group, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group, R_1 represents an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, and R represents a carbon number 1 to 8 alkyl group, halogenated alkyl group, halogenated phenyl group, nitro-substituted alkyl group, nitro-substituted phenyl group or alkyl-substituted phenyl group, R_3 and R_4 are hydrogen, halogen, sulfonic acid group, sulfonic acid sodium group , represents a carboxyl group, an alkyl group having 1 to 5 carbon atoms, an alkoxy group, or an alkyloxycarbonyl group.)