JPS6176445A - Vinylsalicylaldehyde derivative and its preparation - Google Patents

Abstract

NEW MATERIAL:5-Nitro-3-vinylsalicylaldehyde of formula I or 3-nitro-5- vinylsalicylaldehyde of formula II. USE:A synthetic intermediate of vinylspiropyran of formula III (R<1> is H, halogen, etc.) or formula IV giving a photochromic material useful in the fields of makeup cosmetics, fibers, toys, image-forming material, recording material, photosensitive material, optical filter, displaying material, masking material, etc. PREPARATION:The compound of formula I can be prepared by reacting the salicylaldehyde derivative of formula V with triphenylphosphine, and reacting the resultant phosphonium salt of formula VI with formaldehyde in a mixture of water and an aprotic polar solvent in the presence of an alkali (e.g. NaOH). In the similar manner, the compound of formula VII can be converted to the compound of formula II.

Description

[Detailed description of the invention]

The present invention relates to a vinyl salicylaldehyde derivative and a method for producing the same. The vinyl salicylaldehyde derivative according to the present invention can be used in the fields of cosmetics, textiles, decorative materials such as toys, image forming materials, recording materials, photosensitive materials, optical filters, display materials, masking materials, etc. It is a compound useful as an intermediate for the production of photochromic materials that can be used as photochromic materials.
-1 Problems to be solved by the conventional technology and the invention Many organic substances exhibiting photochromism have been found, and among them, although they are colorless in their normal state, they develop a color when irradiated with ultraviolet rays, and their spectra change. It is well known that spiropyran compounds are the most studied because they are large and have excellent photochromic properties that allow them to thermally return to their original colorless state when irradiated with visible light or left in a dark place. Conventionally known spiropyran monomers containing vinyl groups include JJ, 'l'olymer, 5cie.
nce C. Competition 231 pages (1968), Journal of the Chemical Society of Japan ■So, 13
23 pages, J, Polymer+ 5science,
Po1m, Chem, Ed, 12+ 2511 pages (
1974) and Japanese Patent Publication No. 54-30711, all of these are compounds in which a spiropyran compound and another vinyl compound are bonded via an ester bond or an acid amide bond. However, it has the disadvantage that the monomer decomposes, and even after copolymerization, it undergoes hydrolysis and the spiropyran compound is eluted from the polymer. Therefore, the object of the present invention is to provide a spiropyran compound which is essentially different from such conventional spiropyran compounds and in which a vinyl group is directly substituted on the spiropyran skeleton. An object of the present invention is to provide an intermediate useful for producing run monomers and a method for producing the same. That is, a vinyl spiropyran derivative in which a vinyl group is directly substituted on the spiropyran skeleton has never been synthesized before, and it is a stable and useful new compound that is not hydrolyzable and has become synthesized for the first time through the present invention. Means for Solving the Problems According to the present invention, the following general formula

[I] or

Vinyl salicylaldehyde derivatives represented by [■] are presented (shared hereafter in the margins) [1] [I[] These compounds are chloromethylated salicylaldehyde represented by the formula is reacted with triphenylphosphine to form 3-formyl-2-hydroxy-5-nitrobenzyltriphenylphosphonium chloride or 3-formyl-4-
hydroxy-5-nitrobenzyltriphenylphosphonium chloride, and then reacted with a large excess (for example, 10 moles or more per mole of the phosphonium salt) of varapormaldehy in the presence of an alkali, It can be manufactured by vinylization. In this reaction, it is important to use a mixed solvent of an aprotic polar solvent and water as the solvent. Although there are no limitations to the reaction temperature and reaction time, generally a few hours of reaction under mild conditions at room temperature to about 40°C is sufficient. Formula [I] produced in this way or

The vinyl salicylaldehyde derivative [■] is a novel compound that has not been previously known, and is useful as an intermediate for vinyl spiropyran derivatives as described above. Furthermore, it is useful as an intermediate for useful vinyl salicylidene aniline derivatives that exhibit monobotochromism or thermochromism, and can be used alone to copolymerize with vinyl compounds such as styrene and methyl methacrylate. It is an extremely useful substance that can introduce salicylaldehyde derivative units containing highly reactive hydroxyl groups and aldehyde groups into molecules. The starting compounds of formulas (1) and (2) are known ones, such as mononitro-substituted salicylaldehyde (5
-nitro-3-chloromethylsalicylaldehyde or 3
-Nitro-5-chloromethylsalicylaldehyde) with chloromethyl methyl ether, or by reacting 5-chloromethylsalicylaldehyde with fuming nitric acid or the like. The reaction between the compound (1) or (2) above and triphenylphosphine can be easily carried out, for example, by refluxing in a benzene solvent. Next, the obtained phosphonium salt is homogeneously reacted with a large excess of paraformaldehyde in the presence of an alkali in a mixed solvent of an aprotic polar solvent such as dimethyl sulfoxide and water, under mild reaction conditions. The final product, a vinyl salicylaldehyde derivative, is obtained in good yield. The reaction formula is as follows. (1) (phosphonium salt) H in Hensen Next, the vinyl salicylaldehyde derivative of the above formula [I] or [II] is reacted with a quaternary iodide represented by the general formula in the presence of an alkali, or A vinyl spiropyran derivative represented by the general formula %) can be produced by reacting the quaternary iodide with an indoline compound represented by the general formula obtained by treating the quaternary iodide with an alkali. In the above general formula, R1 represents hydrogen, halogen, lower alkyl group or lower alkoxy group. The quaternary chloride represented by the general formula (3) is a known one, such as 2,3.3-trimethylindolenium methioiodide, 2.3゜3-trimethyl-5-
Chlorindolenium methioiodide, 2,3.3-
) Dimethyl-5-methyl-indolenium methioiodide, 2,3゜3-trimethyl-5-methoxyindolenium methioiodide, 2,3.3-)trimethyl-5
-Carpomethoxyindolenium methioiodide and the like can be used. This reaction is usually carried out using an aliphatic alcohol such as methanol or ethanol as a solvent, and equimolar amounts of compound [I] or [II] and compound (5) in the presence of an alkali of an organic amine such as triethylamine, piperidine, or pyridine. Indoline compound (4) obtained by stirring the compound (3) in an aqueous solution of an inorganic alkali such as caustic soda and the compound [+1 or [II]
This can be carried out by refluxing equimolar amounts of these in an aliphatic alcohol such as methanol or ethanol. The reaction is preferably carried out by adding a small amount of hydroquinone or the like as a polymerization inhibitor. The vinyl spiropyran derivative obtained in this way is a photochromic compound with a long color development life and excellent practicality, but it can also be combined with other vinyl monomers to produce a photochromic polymeric material. You can also. The thus obtained spiropyran compound itself is a useful photochromic compound with excellent practicality and long color development life, and can be further copolymerized with other vinyl monomers to produce useful photochromic compounds. It can also be used to produce molecular compounds. These can be used as color-forming species in a wide range of fields, including make-up cosmetics, textiles, decorative materials such as toys, image-forming materials, recording materials, photosensitive materials, optical filters, display materials, and masking materials. In the following, the present invention will be further explained with reference to Examples, but it goes without saying that the scope of the present invention is not limited to these Examples. V! 3-chloromethyl-5-nitrosalicylaldehyde 24
．． gr (0.11 mol) and triphenylphosphine 29 gr (0.11 mol) in benzene 280 c
The solution was dissolved in c and heated under reflux for 3 hours. After cooling, the precipitate was filtered and thoroughly washed with acetone to obtain 42 gr of 3-pormyl-2-hydroxy-5-nitrobenzyl) +7 phenylphosphonium chloride (yield: 80%).
) was obtained as white crystals. Elemental analysis results: HN calculated value (%) 65.34' 4.40
2.93 Actual value (%) 64.94. 4.56
．． 2.87 gr of paraformaldehyde (1 mol) was dissolved in 50 cc of distilled water with heating, and then 7.2 gr of 3-formyl-2-hydroxy-5-nitrobenzyltriphenylphosphonium chloride obtained in Example 1 ( 0,015
mol) dissolved in 100 cc of dimethyl sulfoxide was mixed with this. While stirring 12.5
Add 16 cc of N caustic soda aqueous solution and heat to 30°C to 40'°C.
The mixture was stirred at 1' for 5 hours. Next, add 200 cc of 0.5''N caustic soda aqueous solution, filter out the precipitated phenylphosphine oxide, and if there are fine precipitates in the filtrate, extract with benzene. Neutralize the filtrate with diluted hydrochloric acid. ,
The deposited precipitate was extracted with ether, the ether layer was washed with water, the solvent was distilled off, and the obtained crystals were recrystallized from chloroform. Thus, 27 gr (yield 94%) of 5-2L-rho-3-vinylsalicylaldehyde having a melting point of 135-137 DEG C. was obtained as pale yellow crystals. Elemental analysis results: - IIN calculated value (%) 55.93 3.63 7.2
5 Actual value (%) 55.89 3.82 7.
Resonance spectrum of vinyl group by 13NMR: 5.5
~7.3 P 8 bottles (CDCI3 solution) IIa = 5.5
11'p', 1lb=5.9LP+1lc=7.0
011'l''''Rule 2.3.3-) 3.01 g (0.01 mol) of lymethylindolenium methioiodide was dissolved in 50 cc of IN aqueous sodium hydroxide solution with stirring, and the floating oil was dissolved with ether. The ether layer was extracted and washed several times with water. Anhydrous sodium sulfate was added to this ether layer for dehydration, followed by filtration, and the filtrate was distilled off. The obtained indoline compound and the 5- 1.93g (0.01mol) of nitro-3-vinylsalicylaldehyde was dissolved in 50cc of absolute ethanol, a little hydroquinone was added, and the mixture was refluxed for 6 hours.After cooling, the solid was filtered off and recrystallized with ether. 2.5 g (yield 71%) of 6'-nitro-8'-vinyl-1,3,3) lyntylindolinobenzospiropyran having a melting point of 168-170°C was obtained as pale orange crystals. The infrared absorption spectrum of the compound is shown in Figure 1. Elemental analysis results: HN Calculated value (%) 72.41 5.75 8.0
5 Actual value (%) 71.51 5.92 7.
Absorption spectrum of pyran ring by 76TR: 1 (150
(C=C stretching vibration) 1280 (C-0 stretching vibration) 670 (C-H stretching vibration) Resonance spectrum of vinyl group by N M 'H 5.0 ~
6.811Pm 28 bottles (CDCI3 solution) 11a = 5
．． 15T? lI* 1Ib= 5.59) f・” +
1lc=6.55rf'Example 4 5-chloromethyl-3-nitrosalidylaldehyde 1' was reacted in the same manner as in Example 1 (!: 3-pormyl-
26 gr of white crystals of 4-hydroxy-5-nitrobenzyltriphenylbosphonium chloride (yield 76
%) was obtained. Elemental analysis results: CHN Calculated value (%) 65.34 4.40 2.9
3 Actual measurement value (%) 65.30 4.58 2.
80 (pl+ 5-) 3-formyl-4-hydroxy-5-nitrobenzyltriphenylphosphonium chloride obtained in Example 4 was reacted in the same manner as in Example 2, and the melting point was 93.5-94.5°C.
3-nitro-5-vinylsalicylaldehyde 2.3
gr (yield 79%) was obtained as pale yellow crystals. Elemental analysis results: Calculated value (%) -" 55,93 3.63 7.
25 Actual value (%)' 55.92 '3.71L
7. ', 14 NMR resonance spectra of vinyl groups 5.3-6.9R) 8 in 11 (CD C13,
Clear liquid) Ha=5.37ppm, ob=s, 13'7
1'F", Hc=6', 7711mExample" - 3-nitro-5-vinylsalicylaldehyde obtained in Example 5 was reacted in the same manner as in Example 3. Recrystallize with methanol, melting point 159-161℃
2.8 g (yield 79%) of 8'-nitro-6'-vinyl-1,3,3-trimedylindolinobenzosviropyran (8) was obtained as blue crystals (7). The infrared absorption spectrum is shown in Figure 2. Elemental analysis results: HN Calculated value (%) 72.41 5.75 8.05
. Actual value (%) 72.40 5.97 7.8
Absorption spectrum of pyran ring by 3IR 1650 (C=C stretching vibration) 1280' (, C-0 stretching vibration) 650 (C,''H stretching vibration) Resonance spectrum of vinyl group by NMR 5.0-6.9
8 bottles for P (CD C13 solution) 11a = 5.20K”
, IIb=5.591Pm, IIc=6.73PV
! Compound 6'-nitro8'-vinyl-1,3 obtained in Example 1
,3-=)limethylindolinobenzosbiropyran and conventional 6'-nitro-1,3,3-trimethylindolinobenzospiropyran were dissolved in benzene to form a benzene solution, and exposed to ultraviolet light for 10 minutes. When irradiated for a minute, the colors developed red and blue, respectively. however,
Conventional 6'-nitro-1,3,3-)lynchylindolinobenzospirobilane was rapidly decolored by irradiation, whereas 6'-nitro-8'-vinyl-1,3-) according to the present invention
, 3-) Lymphyl indolinobenzospiropyran did not show discoloration for a long time after irradiation.

[Brief explanation of drawings]

FIG. 1 is an infrared absorption spectrum of the compound obtained in Example 3. Figure 2 shows the infrared absorption spectra of the compound obtained in Example 6.
It is le. (Margin below)

Claims (1)

[Claims] 1. A vinyl salicylaldehyde derivative represented by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [I] or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II]. 2. Formulas ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) or ▲ Mathematical formulas,
There are chemical formulas, tables, etc. ▼ (2) The salicylaldehyde derivative represented by (2) is reacted with triphenylphosphine to form a phosphonium salt, and then reacted with formaldehyde in the presence of an alkali in a mixed solvent of an aprotic polar solvent and water. A method for producing a vinyl salicylaldehyde derivative represented by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [I] or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II].