JPS63253087A - Photochromic compound - Google Patents

Abstract

NEW MATERIAL:The compound of formula I [R1 is H or methyl; R2 is 1-30C alkylene or group of formula II (m and n are 0-15); R3-R6 and R10-R13 are lower alkyl, lower alkoxy, 2-21C alkoxyalkyl, etc.; R7 and R8 are H, lower alkyl, lower alkoxy, 2-21C alkoxyalkyl, aryl, etc.; R9 is lower alkyl, lower alkoxy, 2-21C alkoxyalkyl or H]. EXAMPLE:1'-( 3''-Methacryloyloxypropyl )-3', 3'-dimethylspiro [7-methoxy-2H-1,4- benzoxazine-2,2'-indoline]. USE:An image-displaying material and an optical recording material. It has high molar extinction coefficient. PREPARATION:An indole derivative of formula IV is made to react with a halogenated alcohol of formula X-R2-OH (X is halogen) and the resultant salt of formula V is made to react with a compound of formula VI and then with a compound of formula VII.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel 7 otochromic compound.

[Conventional technology]

Among photochromic substances, substances with spirocarbon exhibit a wide variety of color tone changes, and many have large molar extinction coefficients.As representative substances, they are expressed by general formulas (I), (n), and (II). Substances having the basic skeleton shown can be listed.

(I) (I[) Ward R (II) (R is any tit substituent) Such photochromic materials are often used in the form of being dispersed or dissolved in a binder such as a polymer compound. Image display materials, optical recording materials, etc. are known as such materials.

In addition, for the purpose of improving the thermal stability of photochromic compounds in the coloring state, attempts have been made to copolymerize heptamers having a spiropyran skeleton as shown in general formulas (■) and (V) with other component monomers. (J, Smets:,
T, Polym, Sc1,. 1'olym, Ohem,
md, 1U, 25CW> (V) (R is an arbitrary substituent) [Problem to be solved by the invention] However, the substance represented by the above general formula (I) has a major problem in durability. , this cause is 3'.

This is because the C, C double bond at the protein'-position is easily attacked by singlet oxygen and decomposed. Against this.

The substances represented by the general formulas (1) and (II) are 3', J
Since the l'-position is a double bond of O and H, it is not easily attacked by oxygen and has excellent durability. However, when such photochromic substances are used after being dispersed, dissolved, or impregnated in a polymer, there is a problem that the photochromic substance flows out due to long-term use, resulting in a change in concentration during color development. On the other hand, the general formula (ff), (
By copolymerizing the heptamer represented by V) with other monomers, it is possible to prevent the photochromic substance from flowing out, and at the same time it is possible to improve the thermal stability.

However, as mentioned above, in the case of spiropyran compounds having O2C double bonds at the 3/ and 4/- positions, the durability is poor, so the photochromic monomers represented by the general formulas (ff) and (V) are not durable. I can't go home.

The present invention is intended to solve these problems, and its objectives are to exhibit a wide variety of color changes, have a large molar absorption coefficient, be excellent in durability, and be resistant to other components. An object of the present invention is to provide a photochromic compound capable of copolymerizing.

[Means for solving problems]

That is, the present invention relates to a photochromic compound represented by the following general formula.

薯C=0 C=OH2 [In the formula, R1 is a hydrogen atom or a methyl group, R2 has a carbon number of 1
~50IvI alkylene group or general formula -(OH2>+
O tears) (Here, m and n are each Om
n represents an integer from 15 to 15) or derivatives having these substituents as the basic skeleton, R3, R4, R5
, R@, ELIO, R11, RIB and RIB have a lower alkyl group, a lower alkoxy group, an alkoxyalkyl group having 2 to 21 carbon atoms, a carboxyalkyl group having 1 to 20 carbon atoms, or a substituent thereof as a basic skeleton. Derivatives or hydrogen atoms, halogen atoms.

Nitro group, cyano group, ami7 group, hydroxyl group, -803M
CM is an alkali metal), R7 and R8 are hydrogen atoms.

Lower alkyl group, lower alkoxy group, alkoxyalkyl group having 2 to 21 carbon atoms, aryl group, benzyl group, or derivatives or R of these if substituents as the basic skeleton
7 and R8 form an unsaturated or saturated hydrocarbon ring, all is a lower alkyl group, a lower alkoxy group, an alkoxyalkyl group having 2 to 21 carbon atoms, or these 9
7 Otochronic compound of the present invention is a derivative having one substituent as its basic skeleton or representing a hydrogen atom.

Since the 4'-position is an O, H double bond, it is less likely to be attacked by -heavy ring oxygen, improving durability. Furthermore, because it has a polymerizable acrylic or methacrylic group in the molecule,
Other ingredients! By performing copolymerization with -, it is possible to prevent the outflow of the photochromic substance, and at the same time it is also possible to improve thermal stability. Furthermore, since the substituents are various, including electron-withdrawing groups and electron-donating groups, it has rich bathochromic and hypsochromic effects and changes in color tone. In this way, the present invention has solved the above-mentioned problems.

As the other component copolymerizable with the photochromic compound in the present invention, any commonly used polymerizable monomers can be used.For example, acrylic acid, methacrylic acid, acrylic ester, methacrylic acid, acid ester, styrene, vinyl acetate,
Examples include acrylonitrile, diethylene glycol bisallyl carbonate, and the like. In addition, these other ingredients! It is also possible to use two or more of - at the same time.

In addition, adding an antioxidant, a heavy ring oxygen quencher, and an ultraviolet absorber to the mixture of the 7 otochromic compounds and the other ingredients mentioned above in the present invention is effective in prolonging the life of hemorrhoids and changing the color tone of photochromic performance. It is true.

Furthermore, as a polymerization initiator when copolymerizing the above-mentioned hetamine, ketone peroxide, peroxyketal, N
In addition to organic peroxides such as idrobar oxide, dialkyl peroxide, diacyl peroxide, peroxydicarbonate, and peroxy ester, polymerization initiators such as azobisisobutyronitrile are suitable.

Incidentally, it is desirable that the polymerization of the seven otochromic compounds of the present invention in the copolymer be appropriately changed depending on the intended use thereof.

Here, the photochromic compound in the present invention was synthesized as follows.

First, an indole derivative represented by the general formula (■) is synthesized by the indole synthesis method of 718 h·r, and then this is reacted with a halogenated alcohol represented by the general formula (■) in a solvent under closed conditions. General formula % Formula % As above, X represents a halogen atom) Next, the salt of general formula C■) and the compound represented by general formula (IX) are reacted in a solvent in the presence of a catalyst, and A compound represented by formula (X) is obtained.

OR (■) (DC)H (X) (RIO, R11, R12, and R13 are the same as above) The compound of the general formula (X) thus obtained is dissolved in a solvent, and the compound of the general formula (X[ ) is added dropwise and reacted to obtain 7 otochromic compounds of the present invention.

■ 0Hol (X) (X[) ■ C=O a=Ca (R1 is the same as above) Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these. Examples] (Example 1) 1'-(5'-methacryloyloxypropyl)-3'
, 5'-dimethylspiro[7-medoxy 2H-1,4
-Benzoxazine-2,2'-indoline] Synthesis! "OH2 1a C℃ 0=OH! OH3 Phenyhydrazine L40t, 5-methyl-2-butanone &201 and concentrated sulfur @5.57cm were heated under reflux for 2 hours in ethanol, then the solvent was distilled off and the residue was dissolved in water. It was made alkaline with an aqueous sodium oxide solution, then extracted with ether, the solvent was distilled off, and then distilled under reduced pressure (101saiHf, 47°C).
and 2,5,3-trimethylindolenine &98r(
A yield of 8Z81) was obtained.

Subsequently, the above 2#ses)limethylindolenine and s-bromo-1-propatur t1oP were reacted in chloroform at 60° C. under sealed conditions for 24 hours. After distilling off the solvent, benzene was added and the precipitate was filtered to obtain 1-(3'-hydroxypropyl)-2,3,5
-) Limethylindolenine bromine salt 1α11f (yield 7
7.5%).

Next, 2-nitrone-5-methoxyphenol s obtained by nitrosating m-methoxyphenol, 19? 1 cL of the indolenine bromine salt 111 and 485 f of triethylamine were dissolved in ethanol and heated under reflux for 5 hours under a nitrogen stream. After completion of the reaction, the solvent was distilled off, and the organic layer was diluted by extraction with methylene chloride/water. As a result of layer separation,
1'-C5'-hydroxypropyl) sr, 51
-Dimethylspiro[7-Medoxy 2g-1,4-benzoxazine-2,2'-Indoapple Snake 421 (yield 4I]) was obtained.

Finally, the oxazine compound and triethylamine 2-
53y was dissolved in dioxane, 1.61 f of methacrylic acid chloride was gradually added dropwise at room temperature with stirring, and the α reaction was carried out for about 5 hours. After the completion of the reaction, the precipitated triethylamine hydrochloride was filtered and a! The solvent was distilled off. ? The resulting crystals were recrystallized several times using 4-person alcohol to obtain 1'-(3'-methacryloyloxypropyl A/).
-5',5'-dimethylspiro[7-medoxy2H-1,4-benzoxazine-2,2'-indoline] 453t (yield 7 [L1%)] was obtained. This crystal is
The thus obtained oxazine compound 0.5f and methyl methacrylate monomer 49.5? Furthermore, as a polymerization initiator, diisopropyl baroxydicarbonate) 1.
After mixing Of, in a flat mold glass (center thickness 31
m) and polymerization was carried out from 30°C to 90°C at a heating rate of 10°C/hour.

The obtained synthetic resin plate was colorless and transparent indoors, but was colored black-purple by irradiation with ultraviolet light.

The performance of this photochromic synthetic resin plate was evaluated as follows, and the results are shown in Table 1.

(1) Transmittance Transmittance was determined by irradiating light using a 500W ultra-high pressure mercury lamp (manufactured by Ushio Electric Co., Ltd.) at 25°C.
Table 1 shows the average transmittance of the s-700rc shoulder.

(2) Thermal stability Light irradiation was performed in the same manner as in the measurement of transmittance in (1), and the temperature was left in an environment of 50°C. Table 1 shows the time required for transmittance (transmittance)/2) after irradiation.

(3) Durability After being left in a xenon long life fade meter (IFAI+-25, AI manufactured by Suga Test Instruments Co., Ltd.) for 50 hours, <
The transmittance performance of (1) was evaluated and shown in Table 1. (4) Chemical resistance After being immersed in ethanol for a day and night, the transmittance performance of (1) was evaluated and shown in Table 1.

(Example 2) 1'-(3'-acryloyloxypropylAf)5/,
Synthesis of 3/-dimethylspiro[6-bromo-2H-1,4-benzoxazine-2,2'-indoline] *Hz 1i+Hl = 0 Obtained by nitroning P-bromophenol 2-
Nitron-4-bromophenol 7.111 and the same 1-(S'-hydroxypropyl)-2tsps-tylindolenine bromine salt 1 (L43F and triethylamine 7,07f were dissolved in ethanol) In the same manner as in Example 1, reaction and purification were carried out.
'-(5'-Hydroxypropyl)-3〆,3'-dimethylspiro[6-bromo2H-j,4-benzoxazine-2,2'-indoline]472F (yield 52.
0%) was obtained.

Next, the oxazine compound and triethylamine Otsu 76
1 and 1.65 f of acrylic acid chloride were reacted and purified in the same manner as in Example 1 to obtain 1'-(5'-acryloyloxypropy/S')-5'*5'-dimethylspiro[6-bromo 2H-1,4-benzoxazine-2,
2'-indoline]&64S' (yield 742%) was obtained. This crystal is a yellowish white crystal with a melting point of 168-1
The temperature was 69°C.

The thus obtained oxazine compound (L5F and 4952 methyl acrylate monomers were mixed with 1.02 mm of diisopropyl peroxydicarbonate as an initiator, and polymerization was carried out in the same manner as in Example 1. The obtained synthetic resin The board was colorless and transparent indoors, but was colored reddish-purple by irradiation with ultraviolet light.

The performance of this photochromic synthetic resin plate was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

(Example 3) 1'-(P-methacryloyloxymethylphenyl)-
5', 5', 5-) Synthesis of dimethyl spiro [6-nitro-2H-1,4-benzoxazine-2,2'-indoly/] Hydrochloride 7.93t)-
5-methyl-2-butanone 120r and concentrated sulfuric acid 5-57
After heating and refluxing the kernels in ethanol for 2 hours, the solvent was distilled off and the residue was made alkaline with an aqueous sodium hydroxide solution. After that, extraction with ether, distillation of the solvent, and vacuum distillation c
o, ooa area HP.

51℃) 2. S,5.5-tetramethylindolenine 7,01t (yield 81.0%) was obtained.

Next, the 2,5,5,5-tetramethylindolenine and P-brombenzylalkonyl 671 were reacted and purified in the same manner as in Example 1 to obtain 1-(P-hydroxymethylphenylated). -2,5,5β5-tetramethylindolenine bromine salt 12.191 (yield 82.6%) was obtained.

Next Gc, P-2! 2-nitrone-4-nitrophenol 569f obtained by nitroning trophenol and the above 1-(P-hydroxymethyl 7enyl) 2t3
Bromine salt of t5s5-tetramethylindolenine 12.1
5M' and triethylamine &871 were reacted and purified in ethanol in the same manner as in Example 1, and 1'-(F-hydroxymethylphenyl)-5',S',5'-)dimethylspiro[6-nitro-2H -1,4-benzoxazine-2,2'-i:/do'J y ) 9.54
f (yield 6S, 4%) was obtained.

Furthermore, the oxazine compound and triethylamine
51 and clotide methacrylate 2.302 in Example 1
React and purify in the same manner as 1'-(P-methacrytetrayloxymethylphenyl)-5', 5', 5
'-) Dimethylspiro [6-nitro211! -1,4
-benzoxazine-2,2'-indoline) &! 57
1F (yield 5&3%) was obtained, the crystals were yellow crystals and had a melting point of 184-185°C.

The thus obtained oxazine compounds o, sr and methyl methacrylate tomo/! -49,5F was further mixed with diisopropyl peroxydicarbonate (t02) as a polymerization initiator, and polymerization was carried out in the same manner as in Example 1 above. The obtained synthetic resin plate was colorless and transparent indoors, but was colored bluish-purple by irradiation with ultraviolet light.

The performance of this 7-value synthetic resin board was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

(Comparative Example 1) 1'-C5"-hydroxypropyl) 5/, 51-dimethylspiro [7-medoxy 2H-1,4-benzoxazine-2,2'-indoline) a, sr in Example 1 This was then mixed with methyl methacrylate tomo/!-4952, 1.02 g of diisopropyl peroxydicarbonate was added as a polymerization initiator, and polymerization was carried out in the same manner as in Example 1. The resulting synthetic resin board was colorless and transparent indoors, but was colored black-purple by irradiation with ultraviolet light.
Great deal! The performance of the synthetic resin board was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

(Comparative Example 2) Diethylene glycol bisallyl carbonate monomer 502 and polymerization initiator diisobrozel peroxydicarbonate) 1.0? was added and polymerization was carried out in the same manner as in Example 1 to obtain 7-rat plates of diethylene glycol bisallyl carbonate resin. This flat plate was used as 1'-C5'-hydroxypropyl in Example 1).
++ 5/, 5/dimethyl spiro [7-methoxy 2H-1,4-benzoxazine-2,2'-indoline)any and 100 y of dielene glycol were immersed for 15 minutes at 110°C, and then immersed in ethanol. A photochromic synthetic resin plate was obtained by washing away the adhered dielene glycol.

The obtained synthetic resin plate was colorless and transparent indoors, but was colored black-purple by irradiation with ultraviolet light.

The performance of this photochromic synthetic resin plate was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

〔Effect of the invention〕

As described above, the present invention has an oxazine skeleton and therefore has excellent durability. Furthermore, since it has a polymerizable double bond in the molecule, it can be copolymerized with other component monomers.
It is possible to improve thermal stability and prevent outflow of photochromic substances, and to obtain stable vI4 optical performance over a long period of time. Therefore, the present invention has a wide range of applications including recording materials, sunglasses, and ornaments, and is expected to be further developed in the future.

that's all

Claims (1)

[Claims] A photochromic compound characterized by being represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 is a hydrogen atom or a methyl group, R_2 is an alkylene group having 1 to 30 carbon atoms or a general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (Here, m and n each represent an integer of 0 to 15) or derivative points R_3, R_4, R_ with these substituents as the basic skeleton
5, R_6, R_1_0, R_1_1, R_1_2 and R_1_3 are lower alkyl groups, lower alkoxy groups, alkoxyalkyl groups having 2 to 21 carbon atoms, and 1 to 20 carbon atoms.
carboxyalkyl groups or derivatives having these substituents as the basic skeleton, or hydrogen atoms, halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, -SO_3M (M is an alkali metal), R_7 and R_8 are hydrogen atoms, lower Alkyl group, lower alkoxy group, alkoxyalkyl group having 2 to 21 carbon atoms, aryl group, benzyl group, or derivatives having these substituents as the basic skeleton, or R_7 and R
A substituent forming an unsaturated or saturated hydrocarbon ring at _8,
R_9 is lower alkyl group, lower alkoxy group, carbon number 2
~21 alkoxyalkyl groups or derivatives having these substituents as the basic skeleton, or a hydrogen atom. ]