CN1357594A

CN1357594A - Heterocycle substituted fulgides photochromic material and its synthesis process

Info

Publication number: CN1357594A
Application number: CN 00128274
Authority: CN
Inventors: 樊美公; 王聪敏; 赵利华; 明阳福
Original assignee: Institute of Photographic Chemistry of CAS
Current assignee: Institute of Photographic Chemistry of CAS
Priority date: 2000-12-13
Filing date: 2000-12-13
Publication date: 2002-07-10
Anticipated expiration: 2020-12-13
Also published as: CN1152110C

Abstract

The present invention belongs to the field of photochromism, light data storing and light signal converting material technology. The heterocycle substituted fulgenic anhydride photochromism material is synthesized through the processes of mixing diacid and dicyclohexyl carbodiimide in the molar ratio of 0.5-1 in anhydrous tetrahydrofuran solvent through lightproof stirring for 5-24 hr; filtering to eliminate white precipitate 1,3-dicyclohexyl urea; decompressing to eliminate solvent; and silica column separation with chloroform and petroleum in the ratio of 1:1 for 4:1 as eluent. The present invention has high yield.

Description

Heterocycle substituted fulgide photochromic material and its synthesis process

The invention belongs to the technical field of photochromic and optical information storage and optical signal conversion materials, and particularly relates to a heterocyclic substituted fulgide photochromic material and a synthesis method thereof.

The organic photochromic material has wide application prospect, and has the advantages of large storage density, high speed, easy processing, low cost and the like compared with inorganic materials.

The photochromic principle can be described generally as follows:

a certain photochromic substance A, light (hv) of a certain wavelength₁) Under irradiation, the molecular structure of the compound B can be changed to form a compound B, so that color change occursAnd (4) transforming. B may be at another wavelength of light (hv)₂) Or heat (△), the reversible process is called the photochromic phenomenon.

The fulgide compounds are the most important of a plurality of organic photochromic compounds, have a wide spectral response range, design different molecular structures, and the maximum light response wavelength of the fulgide compounds can be changed between 300 and 800 nm; secondly, the fatigue resistance is good.

The earliest study on heterocycle-substituted fulgides at home and abroad is furan-substituted fulgides, and thiophene, indole and pyrrole-substituted fulgides. Although fulgide has a wide application prospect, it has a fatal disadvantage of low yield in its synthesis, for example, the general yield is about 5% as reported in chinese patent publication No. CN1097453A, application nos. 97118941.2 and 97118942.0.

The invention aims to overcome the defect of low yield of synthesized fulgide and provides a heterocyclic substituted fulgide photochromic material and a synthesis method thereof.

The structural general formula of the synthesized heterocycle substituted fulgide is as follows:wherein X is S or NR¹When Y is equal to CR²(ii) a When X is 0, Y is N; r¹Is C₁-C₂₀Alkyl of R²、R³Methyl, ethyl, aryl or substituted aryl, and the like. R²、R³Or may be linked to form a benzene ring. S is sulfur, N is nitrogen, NR¹Is an azaalkyl group or an azaaryl group. Me is methyl.

Namely:

when X is nitrogen alkyl or nitrogen aryl, the target compound is pyrrole substituted fulgide;

when X is an azaalkyl or an azaaryl group, R²、R³When the compounds are linked to form a benzene ring, the target compound is indole substituted fulgide;

when X is oxygen and Y is nitrogen, the target compound is oxazole substituted fulgide;

when X is sulfur, the target compound is a thiophene-substituted fulgide.

The photochromic reaction of such compounds can be represented by the following general formula:wherein UV is ultraviolet light (250-400nm), and Vis-IR is visible to infrared light (600-850 nm).

The photochromic compound A is changed into a compound B under the irradiation of ultraviolet light, and the compound B can absorb red light or near infrared light. When B is irradiated with red or near infrared light, it may return to a. This cycle may be repeated multiple times.

The synthetic route of the invention is as follows:wherein X is S or NR¹When Y is equal to CR²(ii) a When X is 0, Y is N; r¹Is C₁-C₂₀Alkyl of R²、R³Methyl, ethyl, aryl or substituted aryl, and the like. R²、R³Or may be linked to form a benzene ring. S is sulfur, N is nitrogen, NR¹Is an azaalkyl group or an azaaryl group. Me is methyl.

Mixing the dried diacid and Dicyclohexylcarbodiimide (DCC) according to the molar ratio of 1: 1-1: 2, taking anhydrous tetrahydrofuran as a solvent, stirring for 5-24 hours at normal temperature in a dark place, filtering to remove white precipitate 1, 3-dicyclohexylurea, removing the solvent under reduced pressure, separating by using a silica gel column, taking chloroform and petroleum ether as eluent at the ratio of 1: 1-4: 1, and processing to obtain the fulgide.

The yields of fulgide synthesized by the process of the present invention are compared to the yields of fulgide synthesized by literature methods in Table 1.

The synthetic route and method of the raw material diacid required by the invention are as follows: (see patent publication No.: CN1097453A, patent application Nos. 97118941.2 and 97118942.0 for details).

The acetyl substituted heterocyclic compound with equal mole number and diethyl isopropylidene succinate are subjected to Stobbe condensation reaction in anhydrous toluene under the action of strong alkali sodium hydride, and the generated half ester is subjected to saponification reaction under the action of ethanol/potassium hydroxide to generate diacid.

The heterocyclic substituted fulgide compound synthesized by the invention can be used for the following aspects:

1. organic photochromic optical disk

Static test results of photochromic disks prepared by the compounds through a whirl coating method show that the photosensitive wavelength of a color former of the compounds can be well matched with the emission wavelength of a semiconductor laser so as to realize information storage.

2. Photochromic film

The compound is dissolved in high polymer, coated on glass, paper base or metal surface, and forms stable color-changing film after natural volatilization of the solvent. The ultraviolet light is used for irradiating to change from colorless to colored, and the visible light can be used for irradiating to return to the initial colorless state, and the phenomenon can be repeated for many times and is used for preparing anti-counterfeiting materials such as anti-counterfeiting trademarks and the like.

The invention has the following characteristics:

1. the yield of the heterocyclic substituted fulgide compound is greatly improved, and the general yield is improved by 5-10 times, and the data provided in the table 1 provide a wider prospect for the application of the fulgide.

2. The two states of the synthesized heterocyclic substituted fulgide compound are thermodynamically stable and can be stored for a long time at room temperature.

3. The synthesized heterocyclic substituted fulgide compound has good fatigue resistance.

4. The A, B absorption wavelengths of the synthesized heterocyclic ring substituted fulgide compound in two existing states are matched with a semiconductor laser, and the compound can be used for developing organic photochromic optical discs. TABLE 1

The technical solution of the present invention is further described with reference to the following examples.

Example 1

Synthesis of 1-P-methoxyphenyl-2-methyl-5-phenyl-3-pyrrole-ethylidene (isopropylidene) succinic anhydride (referred to as P1)

5.0g (0.01149mol) of 1-p-methoxyphenyl-2-methyl-5-phenyl-3-pyrrole-ethylidene (isopropylidene) succinic acid and 2.37g (0.01149mol) of Dicyclohexylcarbodiimide (DCC) were mixed, and about 50ml of anhydrous tetrahydrofuran was added thereto, and the mixture was stirred at room temperature in the dark for 10 hours. The white precipitate 1, 3-dicyclohexylurea was filtered off, the solvent was removed by rotary evaporation, the mixture was separated on a silica gel column, eluted with 1: 1 chloroform petroleum ether and recrystallized from chloroform petroleum ether to give 2.2g of pale yellow-green crystals in 45% yield.

Example 2

Preparation of 1, 2-dimethyl-3-indoleethylidene (isopropylidene) succinic anhydride (named P2)

2.2g (0.00673mol) of 1, 2-dimethyl-3-indoleethylidene (isopropylidene) succinic acid and 2.1g (0.01mol) of Dicyclohexylcarbodiimide (DCC) were mixed, and about 30ml of anhydrous tetrahydrofuran was added thereto, followed by stirring at room temperature in the dark for 6 hours. The white precipitate 1, 3-dicyclohexylurea was filtered off, the solvent was removed by rotary evaporation, the mixture was separated on a silica gel column, eluted with chloroform and petroleum ether at a ratio of 3: 2, and recrystallized from chloroform and petroleum ether to give 0.9g of pale yellow crystals in 43% yield. Example 3

Synthesis of 1-benzyl-2-methyl-3-indoleethylidene (isopropylidene) succinic anhydride (named P3)

4.8g (0.012mol) of 1-benzyl-2-methyl-3-indoleethylidene (isopropylidene) succinic acid and 2.5g (0.012mol) of Dicyclohexylcarbodiimide (DCC) were mixed, and about 50ml of anhydrous tetrahydrofuran was added thereto, followed by stirring in the dark at room temperature for 13 hours. The white precipitate 1, 3-dicyclohexylurea was filtered off, the solvent was removed by rotary evaporation, the mixture was separated on a silica gel column, eluted with 2: 1 chloroform petroleum ether and recrystallized from chloroform petroleum ether to give 1.4g of a pale yellow-green solid in 30% yield.

Example 4

Preparation of 1-allyl-2-methyl-3-indoleethylidene (isopropylidene) succinic anhydride (designated P4)

3.5g (0.01mol) of 1-allyl-2-methyl-3-indoleethylidene (isopropylidene) succinic acid and 2.47g (0.012mol) of Dicyclohexylcarbodiimide (DCC) were mixed, and about 40ml of anhydrous tetrahydrofuran was added thereto, followed by stirring at room temperature in the dark for 5 hours. The white precipitate 1, 3-dicyclohexylurea was filtered off, the solvent was removed by rotary evaporation, the mixture was separated on a silica gel column, rinsed 4: 1 with chloroform and petroleum ether and recrystallized from chloroform and petroleum ether to give 1.4g of colorless crystals in 42% yield.

Example 5

Synthesis of 4- (5-methyl-2-phenyloxazole) ethylidene (isopropylidene) succinic anhydride (named P5)

3.4g (0.01mol) of 4- (5-methyl-2-phenyloxazole) ethylidene (isopropylidene) succinic acid and 4.2g (0.02mol) of Dicyclohexylcarbodiimide (DCC) were mixed, and about 40ml of anhydrous tetrahydrofuran was added thereto, followed by stirring at room temperature in the dark for 23 hours. The white precipitate 1, 3-dicyclohexylurea was filtered off, the solvent was removed by rotary evaporation, the mixture was separated on a silica gel column, rinsed 3: 1 with chloroform and petroleum ether and recrystallized from chloroform and petroleum ether to give 1.1g of colorless crystals in 37% yield.

Claims

1. A method for preparing heterocycle substituted fulgide photochromic material ischaracterized in that the synthesis method comprises the following steps:

mixing the dried diacid and dicyclohexylcarbodiimide in a molar ratio of 1: 1-1: 2, taking anhydrous tetrahydrofuran as a solvent, stirring for 5-24 hours at normal temperature in a dark place, filtering to remove white precipitate 1, 3-dicyclohexylurea, removing the solvent under reduced pressure, separating by using a silica gel column, taking chloroform and petroleum ether as an eluent in a ratio of 1: 1-4: 1, and treating to obtain the fulgide.

2. The heterocyclic substituted fulgide photochromic material prepared according to claim 1, wherein the material has the general formula:

wherein X is S or NR¹When Y is equal to CR₂(ii) a When X is 0, Y is N; r¹Is C₁-C₂₀Alkyl of R²、R³Is methyl, ethyl, aryl or substituted aryl; me is methyl.