JPS60177089A - Photochromic compound - Google Patents

Abstract

NEW MATERIAL:The compound of formula I or II (R1 is 1-20C alkyl; R2 and R3 are H, 1-5C alkyl, 1-5C alkoxy, 2-10C alkoxyalkyl, halogen, nitro or cyano). EXAMPLE:1', 3', 3'-Trimethyl-6-nitrospiro[2H-1-benzothiopyran-2, 2'-benz[ g ]indoline] of formula III. USE:Medium for the recording and displaying with a semiconductor laser, various recording materials, optical filters, displaying materials, masking materials, etc. PREPARATION:The objective compound can be prepared e.g. by reacting the 1- alkyl-2,3,3-trimethylbenz[g]indolenium compound of formula IV with 5-nitrothiosalicylaldehyde (derivative) of formula V in ethanol under reflux.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel photochromic compound, and more particularly to spiropyran, which has high absorption characteristics in the long wavelength region of 700 μm or more, particularly around 7804, and has good coloring and storage stability. This invention relates to photochromic compounds.

Spiropyran-based photochromic photosensitive materials include (1),
High resolution with no graininess; (2) special development;
It is characterized by not requiring fixing treatment, (3) being able to be made into a thin film due to its high color density, and (4) being erasable and rewritable. Applications have been attempted. Particularly recently, spiropyran-based photochromic photosensitive materials are expected to be applied as laser recording media such as optical video disks, taking advantage of the above-mentioned characteristics.

However, in the conventional spiropyran-based photochromic light-sensitive materials, the absorption wavelength range in the coloring state is at most 40
Since the wavelength is in the range of 0 nm to 700 nm, when performing υ recording and reproduction using a laser, Ar+ laser or He-Ne laser is used.
It is necessary to use a gas laser such as a laser, which necessitates an increase in the size of the device, and the color development is also unstable.

Recently, small-sized, light-liquid semiconductor lasers have made remarkable progress, and for this reason, semiconductor lasers are about to replace gas lasers as recording and reproducing lasers.

However, semiconductor lasers for laser recording or reproduction that are put into practical use are particularly those having an oscillation wavelength of 780 to 850 am. Furthermore, the development of semiconductor lasers that oscillate at much shorter wavelengths is currently being actively conducted, and it is thought that there is a high possibility that semiconductor lasers that oscillate at around 700 nm will be put into practical use in the near future (for example, ,
Fujibe Saito, “Current status and future of semiconductor laser recording,” Journal of the Photographic Society of Japan, 44 (2) 128 (1981), Sanbe Shiraki et al., “Development and current status of visible light semiconductor lasers,” Optronics (A9) 41 (1982) reference).

Therefore, if a photochromic material has high absorption characteristics in the long wavelength region of 700 nm or more, especially around 780 nm, it is possible to use a small and lightweight semiconductor laser for recording and reproduction. In addition, photochromic materials whose coloring state is stable for a long period of time have been desired.

The following spiroteopine compounds are known as substances that have high absorption characteristics in a colored state for light in this wavelength range (H, 8, Becker and J.
.

Kolc, J., Phys.Ohem,, 72997
(1981)).

(Colorless state) (Colored state) However, in 6-methylpentane solution at 77', this compound has high absorption characteristics in the colored state for light in the wavelength range of 600 to 850rLWL. Among them, it does not develop color at room temperature, only develops color at low temperatures below 0°C, and immediately disappears when the temperature returns to room temperature, so it is not practical.

The present inventors synthesized various compounds in order to solve the above-mentioned problems, and the light absorption properties of these compounds in the colored state,
As a result of investigating the coloring and decoloring characteristics, it was found that in the coloring state, the long wavelength region of 700 nm or more, especially 780rLrrL
The present inventors have completed the invention of a photochromic compound that has high absorption characteristics in the vicinity, has good stability in the coloring state, and is capable of repeating coloring and decoloring.

That is, the novel photochromic compound of the present invention has the following general formula (wherein R1 represents an alkyl group having 1 to 20 carbon atoms, R2 and 3 represent hydrogen, an alkyl group having 1 to 5 carbon atoms, a carbon number 1 -5 alkoxy group, alkoxyalkyl group having 2 to 10 carbon atoms, ) 10 gen, nitro group or cyano group) or (in the formula, kLl and R2 have the same meanings as above).

Examples of the novel photochromic compounds of the present invention are shown in Examples and Tables 1 and 2 below.

The photochromic compound of the present invention is synthesized by the following reactions. In addition, in each compound in each reaction formula below, kL1 to 几5 have the same meanings as above.

(1), Synthesis of the general formula (1) (reaction formula (A)): (
I) (Compound of the present invention) (In formula (II), xet; 1.p-) represents a luenesulfonic acid ion, a 1so4 ion, or a 4 ion). X in the following formulas also has the same meaning as above.

It can be easily synthesized by refluxing 1-alkyl-2,5,5-trimethylbenz (i-noindolenicum compound I) and 5-nitrothiosalicylaldehyde or its derivative (IV) in ethanol.

The benz[1]indolenium compound (I) is prepared by combining 1-s7tylhydrazine and 6-methyl-2-butanone under acidic conditions according to Fischer's indole synthesis method, as shown in the following reaction formula. It can be synthesized by alkylating the N-position of an indolenine compound, which can be easily obtained by heating under reflux, with an alkylating agent such as RIX.

The synthesis of 1-su7tylhydrazine (6-methyl-2-butanone) and 5-nitrothiosalicylaldehyde or its derivative OV) can be carried out by the following two methods.

(1) Aldehyde compound with no-rogen at the ortho position.
Method of changing the halogen in the snout to 8H = (See Example 1 below) (11) Method of synthesizing dimethylthiocarbamate of salicylaldehyde and utilizing this 0→S transfer reaction: (See Example 2 below) Substitution For the synthesis of 5-nitrothiosalicylaldehyde having a group, method (11) is easier and provides a good yield of intermediate products, and is a convenient synthetic means.

(2) Synthesis of the general formula (It) (reaction formula (C)):
In place of the compound (II), 1-alkyl-2,5,
5-trimethylbenz(fJi/drenium compound (V
It can be synthesized according to the following reaction formula Ω in the same manner as in the reaction formula (a) except that l is used.

(II) C, compound of the present invention) The benz(f) indolenium compound (■ is prepared in the same manner as in the reaction formula (I3) except that 2-s7tylhydrazine is used instead of 1-naphthylhydrazine. , (2-naphthylhydrazine) The photochromic photosensitive material using the photochromic compound of the present invention has the advantage that it can be used as a medium for recording and reproducing semiconductor lasers, and can also be used for various recording materials, storage materials, copying materials, photoreceptors for printing, Cathode.

It can be used as a variety of recording materials such as recording materials for wire tubes, photosensitive materials for holography, and photosensitive materials for phototypesetting. It can also be used as a material for optical filters, display materials, masking materials, light intensity needles, decorations, etc., and has a wide range of uses.

The photochromic compound of the present invention includes alcohols such as methanol, ethanol, and inglobil alcohol;
Ketones such as acetone, methyl ethyl lactone, and cyclohexanone; ethers such as ethyl ether, dioxane, and dihydrofuran; esters such as ethyl acetate and n-butyl acetate; and benzene, toluene, xylene, n-hexane, and cyclohexane. , acetonitrile,
Dissolves in various solvents such as dimethylformamide, dimethylsulfoxide, chloroform, and mixed solvents thereof. In order to use this compound as a photochromic light-sensitive material, the compound is dissolved together with a polymer substance in the solvent, and the compound is formed into a film or coated on a support and dried, or the compound is cross-dissolved in the polymer substance without using a solvent. , it can be used by forming a film.

As the polymeric substance, the general formulas (1) and (II
) and have good film-forming ability. Examples include polymethyl methacrylate, polystyrene, polyvinyl acetate, polyvinyl butyral, W['ll cellulose, polychlorinated Examples include vinyl, polyvinylidene chloride, vinyl chloride-vinyl acetate copolymer, polypropylene, polyethylene, polyacrylonitrile, urethane resin, epoxy resin, polyester, phenol/'4Eft resin, and phenoxy resin. Among these, chlorine-based polymer substances are preferable because they have better stability after color development.

Further, as the support material, polyethylene terephthalate, cellulose acetate, polycarbonate,
There are regular paper, baryta paper, glass, metal, etc.

Next, the present invention will be described in further detail with reference to Examples.〇Example 1 1',3':3'-)dimethyl-6-nitrospiro(2
Synthesis of H-1-benzothiopyran-2,2'-benz[1noindoline]: First, the starting materials, an indolenium compound and 5-nitrothiosalicylaldehyde, were each synthesized as follows.

(1), 1,2,3,3-tetramethylbenz [Synthesis of phantom indolenium iodite: 1-naphthylhydrazine hydrochloride 18y- was dissolved in ethanol, and 6-methyl-2-butanone 9.6P and concentrated After adding 10 cc of sulfuric acid, the mixture was heated under reflux for 60 minutes. After removing the solvent, the mixture was made alkaline with an aqueous IJ solution and extracted with ether. Then, after purification by vacuum distillation (boiling point 116°C/0.1 mmHg), n
- recrystallized from hexane (melting point 76-77.5°C1
yield 71%). The thus obtained 2,3,3-trimethylbenz(5')indolenine 1.5F, methioiodide #1.
Seal 5P and 1 ce of methanol and heat at 110°C for 2
After reacting for an hour, the product was thoroughly washed with acetone/ether mixed solvent and recrystallized with ethanol.
．． 3-tetramethylbenz(P) indolenium iodite (melting point 260-262°C1 yield 95%) was obtained.

(Synthesis of 21,5-nitrothiosalicylaldehyde = 2
- Chloro 5-nitrobe/dualdehyde 5F- 10c
The mixture was added to ethanol in step c and heated to reflux.

Next, Na28 ・9H204,669- and 80.62
The mixture with F was heated to synthesize Na2S2. This synthesized Na2S2 was added to the boiled 2-chloro-5-nitrobenzaldehyde ethanol solution over 15 minutes. After adding, 95 containing 1.08t of NaOH
% ethanol solution was added over 60 minutes.

After the addition is complete, cool it and add it to ice water (ice 50F, water 400C).
c) and then filtered out insoluble matter.

When the filtrate was neutralized with HO/, a yellow precipitate was deposited.

This precipitate was collected by filtration. Since this yellow precipitate contains impurities, it was first dissolved in 20 cc of ethanol while heating, a 95% ethanol solution containing 1,085F NaOH was added, and insoluble materials were removed by filtration.

The filtrate was again neutralized with l-10/ and cooled to obtain yellow crystals of 5-nitrothiosalicylaldehyde. Yield is 3.1
5P C64%), and the melting point was 85-88°C.

The thus obtained 1,2,3.3-tetramethylbenz IJ) indolenium iodite 1.5y-15-nitrothiosalicylaldehyde 1.1? and piperidine 0.44F as a base were added to ethanol, heated under reflux for 60 minutes, and after removing the solvent, column chromatography was performed to obtain [ii
L, recrystallized from a chloroform/n-hexane mixed solvent to obtain 1',3',5'-)dimethyl-6-nitrospiro[2H-1-benzothiopyran-2,2'-benz[?
[India Tori] was obtained. Yield: 60%, melting point: 222~
The temperature was 225°C.

Example 2 5'-chloro0-8-methoxy-1z5?5'-)dimethyl-6-nitrospiro[2H-1-benzothiopyran-
2,2'-benz [? Synthesis of [indotri]: First, the raw materials 5-chloro-2,3,3-)limethylbenz[li/drenium iodide and 3-methoxy-5-
Each ditrothiosalicylaldehyde was synthesized as follows.

(1), 5-chloro-2,3,3-trimethylbenz (
Synthesis of 5'J indolenium iodite: 4-chloroo-
Meenaphthylamine 4,811- was dissolved in ethanol, 2.56 cc of concentrated hydrochloric acid was added, and while stirring under water cooling, sodium nitrite (NaNO2) 1.88) was dissolved in 10 cc of water.
The cclC dissolved solution was added at such a rate that the reaction temperature did not exceed 5°C. Then, stannous chloride (5nO1
Add a solution of 2) in concentrated hydrochloric acid all at once, and stir at room temperature for 6 minutes.
After reacting for 0 minutes and then at 80°C for 1 hour, the mixture was cooled and the precipitate was filtered.

After dissolving the precipitate in hot water, the solution was made alkaline with an aqueous sodium hydroxide solution, and the resulting colorless crystals of 4-chloro-1-su7tylhydrazine were filtered. was reacted with 6-methyl-2-butanone in the same manner as in Example 1, and after extraction with ether, unreacted naphthylamine was extracted, and 5-di-4-2,3,3-trimethylbenz (5' ) Indolenine was obtained (55% yield from naphthylamine). This indolenine was methylated with methyl iodide to obtain 5-chloro-2<5.5-t') mef rubens (5') indolenium iodite (yield 78%).

(2) Synthesis of 3-methoxy-5-nitrothiosalicylaldehyde: 6-methoxy-5-nitrosalicylaldehyde iog-
and 1,4-diazabicyclo(2,2,2) octane i
Dimethylthiocarbamoyl chloride 2.i and 4F are dissolved in DMF (dimethylformamide).
Add a solution of 4P dissolved in DMF' and heat at 50-60°
After reacting at C for 1.5 hours, 300 cc of water was added, and the resulting precipitate was filtered and recrystallized from methanol to obtain dimethylthiocarbamate t-i,i-y (yield 77%). This dimethylthiocarbamate was heated in an oil bath at 160°C, and once dissolved, it was cooled, methanol was added, and the precipitated crystals were filtered to obtain 10.3P (yield: 96%). This compound is
/I7300 cc, 4N, -NaO at room temperature
Add 30 cc of H aqueous solution, react for 1 hour while blowing N2 gas, make acidic by adding concentrated hydrochloric acid, reflux for 40 minutes, cool, add 100 cc of water, filter the precipitated crystals, and filter methoxy 5. -Nitrothiosalicylaldehyde 7.65FC yield 99%, melting point 169-170
°C) was obtained.

Once obtained, monochloro2.3.3-)limethylbenz(S')indolenium iodite and 3-methoxy-5-nitrothiosalicylaldehyde were reacted in the same manner as in Example 1 in the presence of piperidine. 5'-chloro-
8-methoxy-166'-trimethyl-6-nitrospiro (2H-1-benzothiopyran-2,2'-benz[1]indoline) was obtained (melting point 209-211°C
1 yield 29%).

Example 6 Synthesis of 1'-n-hexyl-6t6'-dimethyl-8-methoxy-6-nitrospiro(2H-1-pensothiobinine-2,2'-benz[reindoline]OH50H3: 2-nanothylhydrazine 6-hydrochloride in the same manner as in Example 1.
j5.2 by reaction with methyl-2-butanone,
3.3-TrimethylbenzCO indolenine was obtained (yield 84%, melting point 112-114°C (literature value 114-1
15°C)). This indolenine and n-hexyl iodide were reacted in a sealed tube at 90°C for 14 hours, and 2. ．．
5.3-trimethyl-1-n-hexylbenz(f) indolenium iodide salt was obtained (yield 91%). This indolenium salt and 6-medoxy 5 used in Example 2
-Nitrothiosalicylaldehyde in ethanol in the presence of piperidine was heated to reflux for 60 minutes, purified by column chromatography, and then recrystallized from a mixed solvent of ethanol/chlorotetraform to obtain the desired 1'-n-hexyl-316. '-Dimethyl-8-methoxy-6-nitrospiro(2H-1-benzothiopyran-2,2'-benz[f]indotorino was obtained (yield 40%, melting point 102-106°C).

Example 4 8-ethoxymethyl-1;3-3'-)rimethyl-6
-nitotetraspiro(2H-1-benzothiopyran-2,2
Synthesis of '-benz (fJ Indotri): 6-ethoxymethyl-5-ditrothiosalicylaldehyde, which is one of the raw materials, is a new substance and was synthesized according to the reaction route shown below.

(a) tt) J (c) (d) 6-chloromethyl-5-nitrosaliteraldehyde (a) 3. OF and 0.991 sodium ethylate were reacted in anhydrous ethal at room temperature overnight, resulting in etal/n
- Recrystallize from hexane mixed solvent to obtain 6-ethoxymethyl-5-nitrosalicylaldehyde (b) 2.04
P was obtained (melting point 66-69°C1 yield 65%).

Then, this aldehyde (b) 2.0y- and 1,4-diazabisiform o(2,2,2)octay (Air Pr
products and chemicals, Inc.
1.1 t of thiocarbamoyl chloride was dissolved in 10 cc of DMF (dimethylformamide).
Add a solution of 3 cc of DMF and add 60
After reacting at °C for 2 hours, water was added and the resulting precipitate was filtered. This precipitate was recrystallized from an aqueous ethanol solution to obtain carbame) (cl) (yield 72%). This carbame) (C) was heated at 140°C for 60 minutes to cause a rearrangement reaction, resulting in compound (d). ) was obtained (yield 100%)
Further, the reaction was carried out at room temperature for 1 hour while bubbling nitrogen gas in an aqueous sodium hydroxide solution, and then acidified with hydrochloric acid, and the resulting precipitate was filtered to obtain 1-ethoxymethyl-5-nitrothiosalicylaldehyde (e). obtained (yield 82%)
. This aldehyde (el and 2, 5 synthesized in Example 6)
．． 5-) Limethylbenz Cf) A benzindolenium compound synthesized by reacting indolenine with methyl iodide is reacted in the same manner as in Example 1 in the presence of piperidine as a base to obtain the desired 8-ethoxymethyl-1z61.
6'-Trimethyl-6-nitrospiro(2H-1-benzothiopyran-2,2'-benz (fJ Indotri)) was obtained (yield 62%, melting point 156-158°C).

6 parts by weight of the benzothiopyra/spiropyran compound thus obtained and vinyl chloride-vinylidene chloride copolymer (
'Itki Kagaku Kogyo Co., Ltd. Denkavinyl≠1000100O
Jube, tetrahydrofuran and cyclohexanone are 1:
A solution consisting of 100 parts by weight of a mixture of 1 (volume ratio) was applied onto a quartz glass plate using a spinner, and after vacuum drying at 80°C for 2 hours, a sample with a photosensitive layer having a thickness of 1 μm was prepared. A 500W ultra-high pressure mercury lamp (manufactured by Ushio Electric Co., Ltd.) was used for this sample, and a Toshiba filter (UV-360, IRA-258) was used.
When it is selectively irradiated with ultraviolet light around 6 Onm using a filter, the color changes to dark green in a saturated coloring state. When this dark green sample is heated to 80°C or exposed to visible light, its color disappears, and when it is exposed to ultraviolet light again, it develops a dark green color, and this process is repeated over many summers. I can do it.

Using the same synthesis method as in Examples 1 to 4, the benzothiopyran spiropyran compound of the present invention having various substituents was synthesized, and in the same manner as above, it was irradiated with ultraviolet light until it reached a saturated coloring state to develop color. , absorption spectra were measured. The following Tables 1 and 2 show the melting points, maximum absorption wavelengths (in order of λ), and values measured for a total of 16 types of benzothiopyran spiropyran compounds of the present invention, including the compounds of Examples 1 to 4.
The results of the absorbance at the absorption maximum wavelength and the absorbance at the wavelength 780tLyx are shown.

Note that compounds A1 and A5 in Table 1 correspond to Example 1 and Example 2, respectively, and compounds A9 and A10 in Table 2 correspond to Example 4 and Example 6, respectively.

'H of the metal fittings of the present invention illustrated in Tables 1 and 2
NMR spectra) y and their assignments are shown below for compounds A2 and A8. For measurement, JNM-F manufactured by JEOL Ltd.
Using X60Q NMR instrument, TM8 as internal reference
(tetramethylsilane) and 0DO15 (deuterated chloroform) was used as a solvent.

(a), Compound A2: δ (ppm) 3.41 3H-double N -0H3 3,943H-double 0-0H3 6,021H doublet Coupling constant = 10.8Hz Hydrogen at 6th position 6.90 1H2 Double line, bonding constant = 10.8Hz Hydrogen at 4th position 7.04-7,504H line, 425z7ζ8' position (7) hydrogen 7.54 1H doublet, bonding constant = 2.5
Hz Hydrogen at 7th position 7.79 1H doublet, coupling constant = 2.5Hz Hydrogen at 5th position 7.60-7.901 H multiplet, Hydrogen at 6' position 8.1
0-8.201 H multiplet, hydrogen (b) at position 9', compound A8 a (ppm) 2.86 3H-multiplet N -0Hs 3.98 3H-multiplet 0-0Hs 6.08 1H doublet line, coupling constant = 10.8Hz, 3
Hydrogen at position 6.96 1H doublet, bond constant = 10.8H
z, hydrogen at position 4 7.56 1H doublet, bond constant = 2
．． 4 Hz, hydrogen at the 7th position 7.82 1H doublet, bond constant = 2.4 Hz, hydrogen at the 5th position or higher, the spiropyran compound has an NO2 group at the 6th position in the benzothiopyran moiety, and an indoline skeleton By synthesizing the benzothiobilane-based spiropyran compound of the present invention in which the benzindoline skeleton is changed, the wavelength becomes longer by about 1100 rL at 2m11M than the conventional spiropyran compound,
A photochromic material compatible with semiconductor lasers having large absorption near 780 nm can be obtained. In addition, by changing the indoline skeleton to a benzindoline skeleton, λm
The aae is the same or longer wavelength by about 10 ycm, and the coloring stability is extremely good.

Agent Masaru Ueya, Yoshio Tsuneko (spontaneous)' Procedural Amendment May 20, 1985, Patent Application No. 31828 of 1988 6, Number of inventions increased by amendment 7, Subject of amendment (1) , "rrooμm" on the fourth line from the bottom of the first page of the specification is corrected to r700nmJ.

(2), r (1981) J in the first line of page 4 at r (19
68) Correct as J.

(3), next to "derivative (IV)" on page 7, line 3.

Insert "in the presence of an organic base catalyst."

(4), 3rd to 2nd lines above from the formula on the last line of page 21
"Nitro-thiosalicylaldehyde" is corrected to "Nitrothiosalicylaldehyde".

−1 or more

Claims (1)

[Claims] A photochromic compound represented by the general formula below (in the formula s
R1 represents an alkyl group having 1 to 20 carbon atoms; R2
and R3 is hydrogen, an alkyl group having 1 to 5 carbon atoms, and 1 carbon number.
-5 alkoxy group, alkoxyalkyl group having 2 to 10 carbon atoms, halogen, 2) t=I group or cyano group)