JPH032147B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to new dithizone compounds that exhibit particularly good photochromic performance. Conventional, general formula

The dithizone compound represented by the formula is generally well known. It is also a known fact that this known compound forms a dithizone metal complex when heated and reacted with a metal salt in the presence of a solvent, and exhibits photochromism in a benzene or chloroform solution or in its crystalline state, depending on the type of metal. It is. Nitrates, sulfides, chlorides, or acetates are generally used as such metal salts, and the types of metals include Pd, Ag,
Hg, Zn, Cd, Pb, Pt, and Bi are preferred, and dithizone metal complexes made from other metal salts are said not to exhibit photochromism. The mechanism by which the dithizone metal complex exhibits photochromism as described above is thought to be due to cis-trans isomerization and tautomerism upon irradiation with light. Therefore, in a solution, the dithizone metal complex is not constrained in its movement and has a high degree of freedom, so that changes in color development due to light and fading due to light blocking occur quickly and reversibly. However, dithizone metal complexes in solid matrices such as polymeric compounds
There is a problem in that this movement is restricted, the degree of freedom is lost, and the speed of color development and fading becomes extremely slow compared to that in a solution. The present inventor has conducted intensive research to improve the photochromic performance of this type of dithizone metal complex, especially in terms of color development and fading speed in polymeric solids, and as a result, the inventors have discovered that radical polymerization from dithizone compounds having vinyl or divinyl groups has been achieved. The copolymer of the dithizone metal complex and the radically polymerizable monomer constituting each polymer compound increases the degree of freedom of the dithizone metal complex in the polymer solid, and the speed of color development and fading approaches that in solution. Based on this finding, we have come to make this invention. That is, according to the present invention, the general formula (However, R is a hydrogen atom, a vinyl group, a halogen atom other than fluorine, or an alkoxy group) A dithizone compound having a novel vinyl group is provided. The dithizone compound having a vinyl group represented by the above general formula of the present invention generally exists as a dark purple solid at room temperature and normal pressure. Furthermore, the vinyl group-containing dithizone compound of the present invention generally has the following properties (a) to (c).
Each compound of the general formula can be confirmed by means such as. (b) By measuring the infrared absorption spectrum (IR), it was found that absorption due to stretching of -NH was detected at 3200 to 3400 cm ^-1 , and aromatic C=C was detected near 1600 cm ^-1 .
Absorption due to bond expansion and contraction, N- around 1360 cm ^-1
Absorption peculiar to the Phenyl bond and absorption peculiar to the N-C-S bond appear around 1120 to 1130 cm ^-1 . Also, there are two -CH=CH ₂ near 910cm ^-1 and 990cm ^-1 .
Two strong absorption lines characteristic of bonding appear. (b) Proton nuclear magnetic resonance spectrum (H-NM
By measuring R), it is possible to know the type and number of protons present in the molecule. That is, vinyl groups (CH ₂ =
CH−) peak, a peak based on the proton of the phenyl group around 6.1 to 8.1 ppm and a peak of −NHNH−
A peak based on the protons of the bond appears. Note that the number of protons in each bonding group can be determined by relatively comparing the respective peak intensities. (c) The weight percentages of carbon, hydrogen, and nitrogen can be determined by elemental analysis. Each compound of the general formula is confirmed by the means (a) to (c) above. The vinyl group-containing dithizone compound of the present invention includes benzene, toluene, chloroform, carbon tetrachloride,
Soluble in common organic solvents such as acetonitrile. The vinyl group-containing dithizone compound of the present invention dissolved in such a solvent is mixed with an alcoholic solution of the metal salt as described above and heated to react, and then the solvent is removed to obtain the general formula (However, R is a hydrogen atom or a nuclear substituent, and M is an n-valent metal.) A dithizone metal complex having a vinyl group is synthesized. Such a new compound of dithizone metal complex having a vinyl group is a metal (M)
As Pd, Ag, Hg, Zn, Cd, Pb, Pt, Bi, etc., metal complexes exhibit a photochromic function, and in particular, metal complexes of Hg, Pd, and Ag show clear color changes (coloring and fading).
and is relatively stable. They are usually colored crystalline solids at room temperature and pressure;
Some metal complexes exhibit photochromism even in their crystalline state, and they are also well soluble in organic solvents; for example, solutions dissolved in benzene, chloroform, etc. exhibit photochromism when irradiated with visible light. Furthermore, the novel vinyl group-containing dithizone metal complex represented by the above general formula 1) can be copolymerized with other copolymerizable unsaturated monomers, and as one such copolymer composition. The dithizone metal complex can be uniformly dispersed in the polymer matrix. Other copolymerizable unsaturated monomers are not particularly limited, but preferably ethyl acrylate, methyl acrylate, methyl methacrylate, vinyl acetate, etc. can be used to obtain a soft copolymer having a glass temperature around room temperature. . As the polymerization initiator, a non-oxidizing initiator such as azobisisobutyronitrile (AIBN) is preferably used. By dispersing the dithizone metal complex in the polymer matrix in this way, the degree of freedom for cis-trans isomerization and tautomerism of the dithizone metal complex is increased, making it easy to change the color development and fading of photochromism. The rate of change approaches the same rate as that in solution. Furthermore, a polymer obtained by independently polymerizing the dithizone metal complex having a vinyl group also exhibits photochromic performance, which is far superior to that obtained by simply dispersing the conventional dithizone metal complex by kneading it into a polymer. It has a high degree of freedom, and changes in photochromic color development and fading occur easily. The method for producing the vinyl group-containing dithizone compound of the present invention is not particularly limited and may be obtained by any method. Representative methods that are generally suitably adopted will be explained below. That is, such a dithizone compound having a vinyl group is produced using m-hydrazide styrene as an intermediate, and first of all, a general method for producing this m-hydrazide styrene is shown below. The method for producing m-hydrazide styrene is not particularly limited, and it may be obtained by any other known method. Further, if necessary, a nuclear substituted product of m-hydrazide styrene can also be produced and used. Next, the above m-hydrazide styrene and phenylhydrazines or m-hydrazide styrene were reacted with carbon disulfide in diethyl ether at room temperature, the resulting precipitate was dissolved in methanol, and a polymerization inhibitor was added. After adding a small amount of and heating at 100℃ or less for 2 to 3 hours, add a small amount of methanol and caustic alkali to the resulting reaction solution and dissolve.
The solution is refluxed for several minutes. Thereafter, the solution is rapidly cooled, a weakly acidic solution is added to form a precipitate, and the precipitate is recrystallized to obtain the desired dithizone compound having a vinyl group in a good yield. The polymerization inhibitor used in this manufacturing method is not particularly limited as long as it is a commonly used polymerization inhibitor, but generally P
-tert-butylcatechol and the like are preferably used. In addition, the above reaction conditions are not particularly limited, and may vary depending on the type of raw materials, the type of catalyst, and the presence or absence or type of solvent.
It is preferable to select and carry out suitable conditions in advance. In addition, the phenylhydrazines to be reacted with the above m-hydrazide styrene are phenylhydrazide

[Formula] as well as its nuclear substitution body

It is a general term including [Formula], and the nuclear substituent R in the formula is, for example, a vinyl group at the meta position, a halogen atom other than fluorine at the para position, an alkoxy group having 1 to 5 carbon atoms at the para position, an ortho It may also be a trichloromethyl group at the position. Therefore,
According to the invention, the general formula A dithizone compound having a vinyl group represented by (wherein R is a hydrogen atom, a vinyl group, a halogen atom other than fluorine, or an alkoxy group) is obtained. The above-mentioned phenylhydrazines are not limited to the manufacturing method, and those obtained by known manufacturing methods can be used without particular restriction. The thus obtained novel dithizone compound having a vinyl group of the present invention is dissolved in a solvent such as benzene or chloroform, and the solution is heated and mixed with a metal salt in an alcohol solution at 40 to 100°C for 10 to 60 minutes. According to the general formula (However, R is a hydrogen atom or a nuclear substituent as described above, and M is an n-valent metal.) A dithizone metal complex having a novel vinyl group is produced. As the above metal salts, nitrates, sulfides, acetates, etc. are generally used, and as the metal (M), for example,
Especially Pd, Ag, Hg, Zn, Cd, Pb, Pt, Bi etc.
Hg, Ag, Pd, and Zn are preferred. That is, by polymerizing this novel compound alone or with an unsaturated monomer, a polymeric material having photochromic performance can be obtained. Also, R in the above formula
By changing this, the color tone of the photochromic compound during color development and fading can be changed, that is, the absorption wavelength can be shifted. For example, when R is an electron-donating group such as an alkoxy group or a halogen, the absorption wavelength of the photochrome compound can be shifted to the longer wavelength side. As described above, the compound of the present invention is reacted with a predetermined metal salt to form a novel polymerizable dithizone metal complex, and when it is polymerized alone or with other copolymerizable unsaturated monomers, it can form a new polymerizable dithizone metal complex in a polymer solid matrix. The degree of freedom for cis-trans isomerization and tautomerism of the dithizone metal complex increases, and the excellent effect of increasing the speed of color development and fading is exhibited. Hereinafter, the present invention will be explained in more detail with reference to Examples and Application Examples, but the present invention is not limited to these Examples. Example 1 m-aminoacetophenone

[Formula] (26.2 g., 0.194 mol), sodium borohydride NaBH ₄ (7.3 g., 0.193 mol) in a mixture of tetrahydrofuran THF (150 ml)
was gradually added, and 50 c.c. of absolute ethanol was added to increase the solubility of NaBH ₄ . This is stirred at room temperature for about 12 hours. Concentrate the reaction solution to about 50ml, then
150 ml of 1N sodium hydroxide solution was added and stirred for 5 minutes for hydrolysis. 2 with ethyl ether
Extract ~3 times, add sulfur salt, dehydrate, remove ethyl ether, and m-aminophenylmethyl carbinol

25.3 g (yield 95.2) of white yellow powder crystals (melting point 66-67℃) of [formula]
%) obtained. Next, the m-aminophenyl carbinol was dissolved at 20-30 mmHg and 270°C-300°C using neutral powdered alumina in an amount four times that of the obtained m-aminophenyl carbinol (25.3 g (0.184 mol)).
It was dehydrated and distilled. The resulting liquid was purified again by vacuum distillation to give a colorless, aromatic liquid with a temperature of 12 mmHg and a bp of 65-67°C. m-aminostyrene

[Formula] 10.4g (yield 47.33%) was obtained. Add 105.7 ml of concentrated hydrochloric acid to 10.4 g (0.087 mol) of this m-aminostyrene at 3°C or below to make 47.7 ml.
of stannous chloride dihydrate SnCl ₂ dissolved in 34.1 ml of concentrated hydrochloric acid at 0-2°C.
10~ with 39.2 g (0.173 mol) of 2H ₂ O added drop by drop
Stir for 15 minutes, filter the resulting precipitate, and incubate at 170 °C at 35 °C.
ml of water and the whole was poured into a solution of 27.3 g of sodium hydroxide, NaOH, dissolved in 136.4 ml of water. The resulting reaction mixture was subjected to steam distillation, and the resulting fraction was extracted with benzene, dehydrated with sulfur salt, and then benzene was removed to obtain 5.3 g of a reddish-yellow liquid (yield 44.7%). . When I measured the infrared absorption spectrum, it was 3000 ~
Absorption based on stretching of −NH ₂ to 3500 cm ^-1 , 1600 cm ^-1
At 990 cm -1 and 900 cm -1 , absorptions based on the stretching of aromatic conjugated double bonds were shown, and absorptions based on the stretching of -CH=CH ₂ at 990 cm ^-1 and 900 cm ^-1 were shown. In addition, when we measured the proton nuclear magnetic resonance spectrum, it was found to be -3.0 to 4.3 ppm.
2H peak based on _NH2 , _CH2 = at 5.1-5.8 ppm
A 2H peak based on , and a 5H peak based on -CH=aromatic ring proton at 6.3 to 7.5 ppm were shown. Furthermore, its elemental analysis values are C71.52%, H7.54%,
N21.22%, calculated _{for C8H10N2 (} 134.18). It matched extremely well with C71.64%, H7.46%, and N20.90%. From the above results, it became clear that the isolated product was m-hydrazide styrene. The yield was 20.14% based on the m-aminoacetophenone used. m-hydrazide styrene obtained above (2.5
g, 0.019 mol) was dissolved in 8.6 ml of diethyl ether, 0.74 ml of carbon disulfide was added at room temperature, and the mixture was stirred. The resulting precipitate was filtered, washed with a small amount of diethyl ether, and then dissolved in about 50 c.c. of methanol. Approximately p-tert-butylcatechol was added as a polymerization inhibitor.
0.2g was added and refluxed for 2 to 3 hours. A solution of 0.8 g of potassium hydroxide dissolved in 8.8 ml of methanol was added to the resulting reaction solution, and the mixture was refluxed for about 5 minutes. Then, the solution was rapidly cooled and about 15 ml of 1N sulfuric acid was added.
The obtained precipitate was filtered, dissolved in a mixed solution of hexane/diethyl ether=3/1, separated from by-products through a column, and the solvent was removed. Furthermore, this separated product was mixed with benzene/
Purification by recrystallization from a hexane mixture yields a dark purple crystalline solid product (0.953 g).
I got it. When infrared absorption spectrum was measured
Absorption based on -NH- stretching near 3320cm ^-1 , 1600
Absorption based on the stretching of aromatic conjugated double bonds near cm ^-1 and 1580 cm ^-1 , N-C near 1120 cm ^-1
-S absorption, -CH= around 985cm ^-1 and 905cm ^-1
It showed absorption based on stretching of CH ₂ . In addition, when we measured the proton nuclear magnetic resonance spectrum, it was found that 5.0~
2H peak based on CH ₂ = at 6.2 ppm, 6.3 ~
-CH-, -NHNH-, and 12H peaks based on aromatic ring protons were shown at 8.1 ppm. Furthermore, its elemental analysis values are C66.42%, H5.41%, N18.33%, which are calculated values for C ₁₇ H ₁₆ N ₄ S ₁ (308.41).
It matched extremely well with C66.21%, H5.19%, and N18.18%. From the above results, the isolated product also has a divinyl group represented by the following structural formula. It was revealed that the compound was a dithizone compound.
The yield is based on the m-hydrazide styrene used.
It was 33.4%. Example 2 m-hydrazide styrene (1.28 g., 9.55 mmol), phenylhyrazine

[Formula] (1.03 g., 9.62 mmol) was dissolved in 8.82 ml of diethyl ether, and the mixture was subjected to the same reaction and post-treatment as in Example 1 to obtain a black-purple crystalline solid (0.932 g). Ta. When we measured the infrared absorption spectrum, we found absorption due to the stretching of -NH- around 3280 cm ^-1 , absorption due to stretching of aromatic conjugated double bonds around 1600 cm ^-1 , and absorption due to N-C- ^S around 1130 cm -1. Absorption based on, 990 cm ^-1 and 905 cm ^-1
Absorption due to stretching of -CH=CH ₂ was observed near the peak.
In addition, when proton nuclear magnetic resonance spectra were measured, there was a 2H peak based on CH ₂ = at 5.0 to 6.2 ppm,
11H peaks based on =CH, -NHNH-, and aromatic ring protons were shown at 6.3 to 8.1 ppm. Furthermore, its elemental analysis values are C63.21%, H5.01%, _N19.52 %, and the calculated values _{for C15H14N4S} (282.36) are C63.74%, H4.95%, It matched extremely well with N19.83%. From the above results, the isolated product is a vinyl compound represented by the following structural formula. It was revealed that it is a dithizone compound with a group. The yield was 34.2% based on the m-hydrazide styrene used. Example 3 m-hydrazide styrene (1.28 g., 9.55 mmol), p-bromophenylhydrazine

[Formula] (1.76 g., 9.42 mmol) was dissolved in 8.82 ml diethyl ether, and the mixture was subjected to the same reaction and post-treatment as in Example 1 to obtain a black-purple crystalline solid (1.192 g). . When I measured the infrared absorption spectrum, it was 3280
Absorption based on stretching of -NH- near cm ^-1 , 1600 cm
Absorption based on the stretching of aromatic conjugated double bonds near ^-1 , absorption based on N-C-S near 1120 cm ^-1 , and absorption based on the stretching of -CH=CH ₂ near 990 cm ^-1 and 905 cm ^-1 . Indicated. In addition, when we measured the proton nuclear magnetic resonance spectrum, it was found to be 5.0 to 6.2 ppm.
_CH2 = 2H peak, 6.2-8.1ppm = CH
-, -NHNH-, and 10H peaks based on aromatic ring protons were shown. Furthermore, its elemental analysis value is
C49.96%, H3.42%, N15.62%
This is the calculated value for C ₁₅ H ₁₃ N ₄ S ₁ Br ₁ (361.28)
It matched extremely well with C49.82%, H3.60%, and N15.50%. From the above results, the isolated product has a vinyl group represented by the following structural formula. It was revealed that it is a dithizone compound with the following properties. The yield was 34.6% based on the m-hydrazide styrene used. <Synthesis example of dithizone metal> Synthesis example 1 0.26 g (0.82 mmol) of mercuric acetate is dissolved in absolute ethanol until saturated. to this
Dithizone 0.51g dissolved in 100ml benzene
(1.99 mmol) while stirring. Reflux this mixture at 65-70°C for 1 hour. After cooling, the solvent was removed using an evaporator, and the residue was recrystallized from chloroform and purified to obtain 0.34 g of mercury dithizone. The yield was 48.1% based on the dithizone used. Synthesis Examples 2 to 3 The same procedure as Synthesis Example 1 was carried out except that dithizone of another polymerizable type was used instead of dithizone. The results are shown in Table 1. Synthesis Example 4 In Synthesis Example 1, 0.22 g (1.20 mmol) of zinc acetate was used instead of mercuric acetate, and dithizone was replaced with 0.6g (2 mmol) of the dithizone compound represented by
The same procedure as in Synthesis Example 1 was carried out except that . The results are shown in Table 1. Synthesis Example 5 Instead of the dithizone compound shown in Synthesis Example 4 The same procedure as in Synthesis Example 4 was carried out except that 0.65 g (1.99 mmol) of the dithizone compound represented by was used.
The results are shown in Table 1.

[Table] Application example 1 4 mg of dithizone mercury with a vinyl group represented by
(0.0052 mmol) in 1.00 g of ethyl acrylate
and N,N-dimethylformamide in 4 ml DMF.
Using _0.02g of AIBN as a polymerization initiator,
Ampoule polymerization was carried out at ℃×72hr. The resulting dark red photochromic polymer was washed with distilled water. The yield was 92.5%. Therefore, the amount of dithizone mercury with vinyl groups contained in the polymer chain is 4
mg/0.925=3.7 mg (0.0045 mmol). After that, I made a cast film using a glass slide (11.2 x 3.7 cm). Toshiba's sunlight lamp DR-400/T is attached to this photochromic film.
The film was irradiated for 90 seconds at a distance of 10 cm at 25°C±1°C to develop color, and its photochromic properties were measured. The photochromic characteristics were expressed as follows. Maximum absorption wavelength (λmax): λmax of this coloring film was determined using a spectrophotometer 220A manufactured by Hitachi, Ltd. ε (90 seconds): Absorbance at the maximum absorption wavelength after 90 seconds of light irradiation for this film under the above conditions, corrected for the film thickness. ε (0 seconds): Absorbance corrected for the thickness of the unirradiated film at the maximum absorption wavelength during light irradiation. Half-life t ^1/2 : Time required for the absorbance of the film to decrease to 1/2 of {ε(90 seconds)−ε(0 seconds)} after irradiation with light for 90 seconds. The photochromic characteristics were expressed by the above λmax, ε (90 seconds), and ε (0 seconds) t ^1/2 . The results are shown in Table 2. Application example 2 4.26 mg of dithizone mercury with a divinyl group represented by
(0.0054 mmol) was copolymerized with 1.0 g of ethyl acrylate in the same manner as in Application Example 1. The yield at that time was 93.5%, and the amount of dithizone mercury with a divinyl group contained in the polymer side chain was 4.26 mg/
0.935=3.98 mg (0.0046 mmol). A photochromic film was prepared using this polymer in the same manner as in Application Example 1. The photochromic properties shown in Application Example 1 were measured for this film. The results are shown in Table 2. Comparative Example 1 3.80 mg (0.0054 mmol) of dithizone mercury was dissolved in 1.0 g of polyethyl acrylate and chloroform, a cast film was prepared using a slide glass, and the photochromic properties shown in Application Example 1 were measured for this film. Table 2 shows the results.
Shown below.

[Table] Application example 3 3.8 mg of dithizone zinc with a vinyl group represented by
(0.0057 mmol) was copolymerized with 1.00 g of vinyl acetate in the same manner as in Application Example 1. The yield at that time is
It was 93.5%. Application example 1 for this film
The photochromic characteristics shown in were measured. The results are shown in Table 3. Comparative example 2 3.67 mg (0.0057 mmol) of dithizone zinc represented by was dissolved in 1.0 g of polyvinyl acetate and chloroform to prepare a cast film in the same manner as in Comparative Example 1, and the photochromic properties of this film were measured. The results are shown in Table 3. Comparative Example 3 3.18 mg (0.0053 mmol) of dithizone zinc was dissolved in 1.0 g of polyvinyl acetate and chloroform, and a cast film was prepared in the same manner as in Comparative Example 1.
The photochromic properties of this film were measured. The results are shown in Table 3.

【table】

Claims (1)

[Claims] 1. General formula [However, R is a hydrogen atom, a vinyl group, a halogen atom other than fluorine, or an alkoxy group] A polymerizable dithizone compound having a vinyl group represented by the following.