JPH04128255A - Intermediate for synthesizing photochromic compound - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I [R1, R3 and R5 are H, alkvl, aryl, allyl, OH, alkoxy, NH2, pyrrolyl, furyl, thienyl, CN, NO2, etc.; R2 and R4 are group shown by formula II (R7 is alkoxy, NH2, mono- or dialkylamino, etc.; and (m) are 1-5); R6 is H, alkyl, aryl, pyrrolyl, thiazolyl, aralkyl, etc.]. EXAMPLE:3,5-Bis(p-diethylaminostyryl)-2,6-dimethylbenzaldehyde. USE:An intermediate for photochromic compound. A fulgide showing high absorption in a long wavelength range can be synthesized. PREPARATION:A compound shown by formula III (X is halogen) is chloromethylated, the prepared compound shown by formula IV is subjected to Wittig reaction to give a compound shown by formula V (R8 and R9 are group shown by formula VI) and then reacted with a compound shown by formula VII to give a compound shown by formula I.

Description

[Detailed Description of the Invention] [Industrial Application Field] This invention relates to a novel organic compound, and in particular, to a novel organic compound used as an intermediate for the synthesis of photochromic compounds used in optical recording, optical storage, copying media, etc. This relates to compounds that can be used.

[Prior art and its problems] Fulgide, diallylethene, and the like have been widely known as photochromic compounds.

These photochromic compounds have the property of changing their structure when irradiated with light of a certain wavelength, and returning to their original structure when they are further irradiated with light of a specific wavelength. Therefore, by utilizing these properties, it becomes possible to perform optical reading and optical writing, and it can be used as various optical recording, optical storage, copying media, etc.

Various aromatic carbonyl compounds are used as intermediates in the synthesis of such photochromic compounds. For example, to synthesize the f-fulgide compound, the following compounds are used:

In addition, compounds such as diallylethene synthesis compound (f) are preferably used.

By the way, when using a photochromic compound as an optical recording medium, the following properties are required.

■Good repeat durability. (Repeatability of recording and erasing) - Good thermal stability in the dark. (Storability of color development/decoloration state) ■Sensitivity to long wavelength region. (Compatibility with semiconductor lasers) However, although all of the conventional fulgide compounds exhibit excellent performance with respect to the conditions (1) and (2) above, none that fully satisfies the condition (2) has been known.

This invention was made to solve the above problems, and aims to provide a compound capable of providing a photochromic compound that exhibits absorption in a long wavelength region and is compatible with semiconductor lasers. .

[Means for Solving the Problems] In the present invention, by providing an intermediate having a strong electron-donating group such as an amino group or a conjugated double bond, it is possible to synthesize fulgide that exhibits high absorption in the long wavelength region. made possible.

That is, the intermediate for photochromic compound synthesis of this invention (hereinafter simply referred to as intermediate) has the following general formula (1).
It is expressed as

Be4 (wherein R1, R8, and R5 are each a hydrogen atom, an alkyl group, an aryl group, an allyl group, a hydroquinol group, an alkoxyl group, an aryloxy group, an aralkyl group, an amino group, a pyrrolyl group, a furyl group, a thienyl group, thiazolyl group,
It represents an oxacylyl group, a cyano group, a nitro group, an ester group, or a trifluoromethyl group, and R2 and R4 each represent an electron-donating group (R is an alkoxyl group, an amino group,
Represents a monoalkylamino group, noalkylamino group, monoarylamino group, and arylamino group, and g and m
Each represents an integer from 1 to 5. ), and R6 represents a hydrogen atom, an alkyl group, an aryl group, a pyrrolyl group, a furyl group, a thienyl group, a thiazolyl group, an oxacylyl group, or an aralkyl group. ) The intermediate of this invention can be synthesized, for example, according to the following synthetic scheme.

(In the above formula, X represents a halogen atom, R1, R3, R6
, R6 and R7 all represent the same as in general formula (1). ) To synthesize photochromic compounds from the intermediates thus obtained, A, Kaneko et al., B.
ullChem,Soc,Jpn,,61.3569
(198g) and H.5uzuki et al.

Bull, Chem, Soc, Jpn, 62.39
68 (1989) etc. can be suitably used. In these methods, as shown in the scheme below, the intermediate of the present invention is subjected to stop condensation and then hydrolyzed.

(Fulgide) (In the above formula, R I""' Re are all the same as the substituents in general formula (1).) The fulgide compound synthesized in this way exhibits photochromic properties, and for example, as shown below. As shown, when irradiated with ultraviolet rays or wavelength ultraviolet rays, the colorless open ring form changes to a colored closed ring form, and when this closed ring form is further irradiated with visible light, it returns to the colorless open ring form.

(However, R and -R11 in the formula are both -maximum (1)
is the same as the substituent. ) All of these fulgide compounds have a benzene ring and have a strong electron-donating functional group or conjugated double bond introduced into a specific site, so the absorption region of the colored body is at a long wavelength. Shift into the area. In addition, the absorption strength of the colored body is further improved.

Moreover, the intermediate of this invention is M, 1rie, et al.
By using the method described in J. OrgChem, 53, 803 (1988) or Kamogawa, Dyes and Yakuhin, 34.100 (1989), not only fulgide compounds but also photochromic compounds such as diallylethene or spiropyran can be prepared. It can be used as a synthetic intermediate.

Because of these properties, compounds synthesized using the intermediate of this invention can be used for optical reading and writing using semiconductor lasers, and can be used for optical recording, optical storage materials, and copying. It can be suitably used as materials, photoreceptors for printing, optical filters, display materials, etc.

[Example] (Example 1) Synthesis of 3.5-his(p-diethylaminomethyl 1-nor)-2゜6-dimethylbenzaldehyde A mixture of 78 g of 2-bromo-m-xylene and 75 g of chloromethyl methyl ether↓ , water-cooled power (concentrated sulfuric acid 7
Added 5g. After stirring at room temperature for 6 hours, the reaction solution was poured into ice water and extracted with hexane. After washing and drying, the solvent was distilled off, and the resulting crude product was recrystallized from hexane to give 43 g of 2-bromo-4,6-cyclomethyl-xylene. (Melting point 113-117°C) Next, 65 g of ethyl nitrous acid was added to 43 g of this 2-bromo-4,6-cyclomethyl-m-xylene and heated to produce 62 g of diethyl nitrite derivative, which is the Witteitz reagent. I got it. This reaction can also be used directly without distillation.

(Wittig reaction) 5.4 g of sodium hydride and 160 m of dimethoxyethane
(29 g of diethyl arsenite derivative and p
-A mixed solution of 25 g of diethylaminobenzaldehyde was added dropwise at room temperature. When the reaction solution was heated to 60°C, gas was suddenly generated. After the gas generation was completed, the mixture was heated under reflux for 30 minutes to complete the reaction. After cooling, the reaction solution was poured into ice water, and the resulting solid was filtered and recrystallized from benzene-ethanol to give 23 g of 2-bromo-4,6-bis(p
-diethylaminostyryl)-machi-xylene was obtained. (
(Melting point: 154-156°C) (Formylation) 10 g of the above styryl derivative was mixed with 1 part of dry tetrahydrofuran.
It was dissolved in 50ml and cooled to -70°C.

A 1.6M n-butyllithium hexane solution 16- was added, and the mixture was stirred for 10 minutes while being cooled. Then, 5 ml of dimethylformamide was added, and after the dropwise addition was completed, the mixture was stirred at room temperature for 2 hours to react. After the reaction was completed, the reaction solution was poured into ice water and extracted with benzene. After washing and drying the organic layer, the solvent was distilled off and recrystallized from benzene-methanol to obtain 8.4 g of the title aldehyde. (Melting point 168-169℃)
Table 1 shows the identification results of the title aldehyde by NMR.

(Example 2) Synthesis of 3.5-bis[]-(4-p-dimethylaminophenyl-1,3-butadienyl)]-2,6-onemethylbenzaldehyde Instead of p-diethylaminohenzaldehyde, p-no The synthesis was carried out in the same manner as in Example 1 above except that methylaminononamaldehyde was used, and the title aldehyde 1 was synthesized.
．． Obtained 0g. (Melting point: 182-184°C) Table 2 shows the identification results of the title aldehyde by NMR.

(Example 3) Synthesis of fulgide compound 3,5-his(p-diethylaminostyryl)-2,6-nomethylbennolidene (isopropylidene) succinic anhydride Chem, Lett.
The stop condensation was carried out according to the method of Nikurita et al., described in 1988.1049.

While cooling a mixture of 5 mg of hyperinone, 0.7 mQ of noisoprobylamine, and 50 mC of tetrahydrofuran to -70°C, a solution of n-butyllithium in hexane (1.6 M
)2m(!). Then, 0.5g of isopropylidenenoethyl succinate and 3,5-bis(p-
10 g of (diethylaminostyryl)2.6-methylbenzaldehyde were added successively. After continuing to stir at room temperature for 2 hours, the mixture was poured into ice water, acidified with hydrochloric acid, and extracted with diethyl ether. After washing and drying the organic layer, the solvent was distilled off to obtain a pale yellow oily half ester. Then, 30III2 of a 10% potassium hydroxide ethanol solution was added, and the mixture was heated under reflux for 3 hours. The obtained doublet was heated in acetic anhydride to perform a dehydration reaction, and recrystallized from chloroform-hexane to obtain 70 mg of the title fulgide.

Dissolve the fulgide compound in toluene and add 5.0 x 10-5
A solution of moρ/Q was prepared.

Add a 250W ultra-high pressure mercury lamp (manufactured by Ushio Inc.) to this solution.
A glass filter (UV-3 manufactured by Toshiba Glass Co., Ltd.) was used as the light source.
5 and L; V-D36C), wavelength 365 r+
When irradiated with ultraviolet light of m, the solution was colored and changed to a closed ring. Next, when visible light with a wavelength of 500 nm or more was irradiated using a 300W xenon lamp (manufactured by Usoo Denki) as a light source, it quickly returned to an open ring form. This change could be repeated. Therefore, ultraviolet rays of 365 nm were irradiated for 2 seconds, 5 seconds, and 10 seconds, respectively, and the changes in the absorption spectrum of the solution at that time were investigated and are shown in FIG. In the figure, the solid line represents the spectrum of the fulgide compound before UV irradiation, and the broken line represents the spectrum after UV irradiation. Furthermore, the numbers attached to each spectrum represent the ultraviolet irradiation time (seconds).

By using the intermediate of this invention, it becomes easy to introduce a functional group or a conjugated double bond having strong electron donating properties. Therefore, as shown in FIG. 1, it is possible to make the absorption region of the colored body have a longer wavelength, and it is possible to obtain suitability as a recording medium using a semiconductor laser.

[Effects of the Invention] As explained above, the intermediate of the present invention is an aromatic aldehyde or an aromatic ketone into which a functional group or conjugated double bond with strong electron donating properties is introduced. The synthesized aromatic fulgide compound has a strong electron-donating functional group or a conjugated double bond introduced at a specific site. Such aromatic fulgide compounds have a closed ring substance with a longer wavelength absorption region without deteriorating the thermal and pre-emptive stability and repeated durability of conventional photochromic compounds, making it possible to use semiconductor lasers. This makes it possible to obtain compatibility as a recording medium.

Further, the intermediate of the present invention can be used not only as a fulgide compound but also as an intermediate for the synthesis of diallylethene or spiropyran. Furthermore, it can be used as an intermediate raw material for dyes such as cyanine and merocyanine, and by using the intermediate of this invention, it is possible to synthesize various new dyes having a desired absorption wavelength range.

[Brief explanation of drawings]

FIG. 1 is a graph showing the absorption spectrum of a photochromic compound synthesized using the intermediate of the present invention.

Claims (1)

[Claims] An intermediate for the synthesis of photochromic compounds represented by the following general formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ▼・・・・・・( I
) {In the formula, R_1, R_3, R_5 are each a hydrogen atom,
Alkyl group, aryl group, allyl group, hydroxyl group,
Represents an alkoxyl group, aryloxy group, aralkyl group, amino group, pyrrolyl group, furyl group, thienyl group, thiazolyl group, oxazolyl group, cyano group, nitro group, ester group or trifluoromethyl group, R_2 and R
_4 is an electron-donating group, and there are ▲mathematical formulas, chemical formulas, tables, etc.▼ (R_7 is an alkoxyl group, an amino group, a monoalkylamino group, a dialkylamino group, a monoarylamino group,
Represents a diarylamino group, l and m are both 1-
Represents an integer of 5. ), and R_6 represents a hydrogen atom, an alkyl group, an aryl group, a pyrrolyl group, a furyl group, a thienyl group, a thiazolyl group, an oxazolyl group, or an aralkyl group. }