JP4817197B2 - Method for producing cyclopentanone compound - Google Patents

Description

  The present invention relates to a method for producing a novel cyclopentanone compound.

  With the advent of the information era, photochemical polymerization has been frequently used in a wide variety of fields. Now, its application goes beyond the field of synthetic resins to paints, printing plates, printed circuits, and integration. It has extended to the field of information recording such as circuits and electronic equipment. Photochemical polymerization is a technique for polymerizing a polymerizable compound by irradiating with light. Broadly speaking, photopolymerization that initiates polymerization by directly irradiating and activating a polymerizable compound, and photosensitization. There is photosensitization polymerization in which a polymerizable compound is polymerized by irradiating with light in the presence of an agent to generate an active species of a photosensitizer. In any photochemical polymerization, the start and stop of polymerization can be controlled by blinking of the exposure light source, and the polymerization degree and polymerization rate can be easily controlled by selecting the intensity and wavelength of the exposure light source. Moreover, photochemical polymerization can generally be initiated even at low temperatures because of the low energy of initiation of polymerization. In the field of information recording including printing plates for printing, such advantages of photochemical polymerization are bought, and visible light such as second harmonics of argon ion laser, helium neon laser, and Nd-YAG laser is obtained. There is a rapidly increasing demand for photopolymerizable compositions that can be polymerized by irradiation.

  Since most of the polymerizable compounds and polymerization initiators to be blended into the photopolymerizable composition absorb only ultraviolet rays, a photosensitizer is indispensable when attempting to polymerize the photopolymerizable composition with visible light. It becomes a technical element. The characteristics of the light-absorbing organic compound that is the main component of the photosensitizer include a large molecular extinction coefficient in the visible region, the ability to sensitize various polymerizable compounds and polymerization initiators, and sensitization efficiency. High solubility, excellent solubility in solvents and compatibility with other compounding components, and stability.

  Examples of typical light-absorbing organic compounds include coumarin compounds, cyanine dyes, cyclopentanone compounds, stilbene dyes, pyran compounds, methylene blue compounds, merocyanine dyes, and the like (see, for example, Patent Documents 1 to 7). ), All of which have advantages and disadvantages, and in a photopolymerizable composition composed of a plurality of materials such as a polymerizable compound and a binder resin, those that can always exhibit the characteristics as described above have not yet been found. Not. Therefore, in a new application field of photochemical polymerization, for example, in the field of information recording and electronic equipment, a combination of materials other than photosensitizers such as a polymerizable compound, a polymerization initiator, and a binder resin. The actual situation is that the combination is first determined, and then, a search is made for a suitable one of those polymerizable compounds and polymerization initiators from a variety of light-absorbing organic compounds by trial and error. Thus, recently, as the use of photochemical polymerization has expanded, an organic compound capable of absorbing visible light in a wider wavelength range has been demanded.

JP-A-54-151024 Japanese Patent Laid-Open No. 58-29803 JP 59-56403 A JP 63-23901 A JP-A 64-33104 JP-A-6-329654 Japanese Patent No. 3184319

  In view of such a situation, the present invention provides a novel organic compound capable of absorbing visible light in a wide wavelength range, thereby providing a range of light-absorbing organic compounds that can be selected in preparing a photopolymerizable composition and the like. It is a problem to widen.

  In order to solve this problem, the present inventor paid attention to the cyclopentanone compound, and intensively studied and searched. As a result, any cyclopentanone compound not described in the literature represented by the general formulas 1 to 3 is 500 nm. In addition to the absorption maximum wavelength in the visible region of longer wavelength, usually near 505 to 550 nm, and the large molecular extinction coefficient at the absorption maximum wavelength, the absorption maximum wavelength Since the half-value width of the molecular extinction coefficient at the center is significantly wide as 50 nm or more, it has been found that visible light near 500 nm frequently used for photochemical polymerization and the like can be efficiently absorbed.

(In General Formulas 1 to 3, R ^{1 to} R ⁸ represent a hydrogen atom or a substituent.)

That is, this invention solves the said subject by providing the cyclopentanone compound represented by either of General Formula 1 thru | or 3.

(In General Formulas 1 to 3, R ^{1 to} R ⁸ represent a hydrogen atom or a substituent.)

  As described above, the present invention is based on the creation of a novel cyclopentanone compound. The cyclopentanone compound according to the present invention has an absorption maximum in the visible region having a wavelength longer than 500 nm, and in addition to a large molecular extinction coefficient at the absorption maximum, a molecular extinction coefficient centered on the absorption maximum wavelength. Since the full width at half maximum is wide, visible light near 500 nm frequently used in photochemical polymerization and the like is efficiently absorbed. Therefore, the cyclopentanone compound of the present invention uses a visible light source near 500 nm as an exposure light source, for example, information display devices such as photographs, copying machines, printers, facsimiles, flexographic plate making, printing such as gravure printing, photoresists, It has a wide variety of uses including a photosensitizer in a printed circuit such as an integrated circuit, and a light absorber that constitutes a light absorbing layer of a write-once or rewritable high-density optical recording medium.

  It can be said that this invention having such remarkable effects is a very significant invention that contributes to the world.

  The embodiment of the present invention will be described. As described above, the present invention relates to a cyclopentanone compound represented by any one of the general formulas 1 to 3.

In General Formulas 1 to 3, R ^{1 to} R ⁸ each represent a hydrogen atom or a substituent. Examples of the substituent in R ¹ , R ² , R ⁴ , R ⁵ , R ⁷ and R ⁸ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an isopropenyl group, a 1-propenyl group, and a 2-propenyl group. 2-propynyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-butenyl group, 1,3-butadienyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1- Methylpentyl group, 2-methylpentyl group, 2-pentenyl group, 2-pentene-4-ynyl group, hexyl group, isohexyl group, 5-methylhexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group Aliphatic hydrocarbon group such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclohexenyl Group, cycloaliphatic hydrocarbon group such as cycloheptyl group, cyclooctyl group, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, mesityl group, o-cumenyl group, m-cumenyl Groups, p-cumenyl groups, aromatic hydrocarbon groups such as biphenylyl groups, and substituents in combination thereof.

Examples of the substituent in R ³ and R ⁶ include the same substituents as those in R ¹ , R ² , R ⁴ , R ⁵ , R ⁷ and R ⁸ , or a methoxy group, an ethoxy group, a propoxy group, Ether groups such as propoxy group, butoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, phenoxy group, ester groups such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, acetoxy group, benzoyloxy group, Amino such as methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, butylamino group, dibutylamino group, sec-butylamino group, tert-butylamino group, pentylamino group Group, fluoro group, chloro group, bromo group, iodo group, etc. Halogen group, hydroxy group, a carboxy group, a cyano group, a nitro group, further include a substituent by combination thereof.

  Specific examples of the cyclopentanone compound according to the present invention include those represented by chemical formulas 1 to 10. Each of these has an absorption maximum in the visible region longer than the wavelength of 500 nm, usually in the vicinity of 505 to 550 nm, and the molecular extinction coefficient at the absorption maximum wavelength (hereinafter, the molecular absorption coefficient at the absorption maximum wavelength is expressed as “ε In addition to being large, the full width at half maximum centering on the absorption maximum wavelength is as wide as 50 nm or more, so that it efficiently absorbs visible light around 500 nm frequently used for photochemical polymerization. It will be possible.

Although such a cyclopentanone compound can be prepared by various methods, a method using a dehydration condensation reaction between a ketone compound having an active methylene group and an aldehyde compound is preferable if the economy is important. When this method is used, for example, by reacting an aldehyde compound represented by any one of the general formulas 4 to 6 having R ^{1 to} R ⁸ corresponding to the general formulas 1 to 3 with cyclopentanone, Cyclopentanone compound is produced in good yield.

  That is, an appropriate amount of each of the aldehyde compound represented by any one of the general formulas 4 to 6 and cyclopentanone is taken in a reaction vessel (usually around 2: 1 in molar ratio), and dissolved in a solvent as needed. For example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, ammonia, triethylamine, piperidine, pyridine, pyrrolidine, aniline, N, N-dimethylaniline, N, N-diethylaniline, alkoxide, etc. Basic compounds, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, acetic anhydride, trifluoroacetic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, and other acidic compounds, aluminum chloride, zinc chloride, tin tetrachloride, tetrachloride After adding a Lewis acidic compound such as titanium, it is added by heating reflux or the like. Stirring the reaction at a temperature above ambient temperature or ambient temperature with.

  Examples of the solvent include hydrocarbons such as pentane, hexane, cyclohexane, octane, benzene, toluene, xylene, carbon tetrachloride, chloroform, 1,2-dichloroethane, 1,2-dibromoethane, trichloroethylene, tetrachloroethylene, chlorobenzene, Halogens such as bromobenzene and α-dichlorobenzene, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, isopentyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 2- Alcohols such as methoxyethanol, 2-ethoxyethanol, phenol, benzyl alcohol, cresol, diethylene glycol, triethylene glycol, glycerin And phenols, diethyl ether, diisopropyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, anisole, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, dicyclohexyl-18-crown-6, methyl carbitol, ethyl carbitol, etc. Ethers, acetic acid, acetic anhydride, trichloroacetic acid, trifluoroacetic acid, propionic anhydride, ethyl acetate, butyl carbonate, ethylene carbonate, propylene carbonate, formamide, N-methylformamide, N, N-dimethylformamide, N-methylacetamide, Acids and acid derivatives such as N, N-dimethylacetamide, hexamethylphosphoric triamide, trimethyl phosphate, acetonitrile, propionitrile, succinonitrile, benzonitrile, etc. Examples thereof include nitriles, nitro compounds such as nitromethane and nitrobenzene, sulfur-containing compounds such as dimethyl sulfoxide and sulfolane, water and the like, and these are used in combination as necessary.

  In the case of using a solvent, generally, when the amount of the solvent increases, the efficiency of the reaction decreases. On the other hand, when the amount of the solvent decreases, it becomes difficult to uniformly heat and stir or a side reaction easily occurs. Therefore, it is desirable that the amount of the solvent is up to 100 times the weight of the raw material compound, usually 5 to 50 times. Although depending on the type of raw material compound and reaction conditions, the reaction is completed within 24 hours, usually 1 to 10 hours. The progress of the reaction can be monitored by a general method such as thin layer chromatography, gas chromatography, high performance liquid chromatography and the like. A desired amount of the cyclopentanone compound of the present invention can be prepared by this method or according to this method. Any of the compounds represented by the general formulas 4 to 6 can be obtained in a desired amount by a known method.

  Although the cyclopentanone compound thus obtained may be used as the reaction compound depending on the application, it is usually prior to use, for example, dissolution, separation, gradient, filtration, extraction, concentration, thin layer chromatography. Can be purified by general-purpose methods for purifying similar compounds such as chromatography, gas chromatography, high performance liquid chromatography, distillation, sublimation, crystallization, etc., and these methods are applied in combination as needed .

  As described above, the cyclopentanone compound of the present invention has an absorption maximum in the visible region longer than 500 nm, usually in the vicinity of 505 to 550 nm, and has a large molecular extinction coefficient at the absorption maximum wavelength. Since the half-value width of the molecular extinction coefficient centered on the absorption maximum wavelength is wide, visible light having a wavelength of around 500 nm frequently used for photochemical polymerization is efficiently absorbed. Moreover, the cyclopentanone compound of the present invention is frequently used for photochemical polymerization and the like, for example, for various hydrophilic and hydrophobic solvents such as hydrocarbons, alcohols, ethers, ketones and esters. It exhibits solubility that does not interfere with practical use. Because of these properties, the cyclopentanone compound of the present invention is used in, for example, information display devices such as photographs, copying machines, printers, facsimiles, flexographic plate making, printing such as gravure printing, printed circuits such as photoresists, and integrated circuits. It has a wide variety of uses including a photosensitizer and a light-absorbing agent that constitutes a recording layer of a write-once or rewritable high-density optical recording medium.

  Furthermore, the cyclopentanone compound of the present invention is useful as a material for adjusting the chromaticity of an optical filter and a material for dyeing various types of clothing in addition to the above-described uses. In particular, the cyclopentanone compound of the present invention may be used in combination with one or more of other materials that absorb light in the ultraviolet region, visible region, or infrared region, if necessary, in general clothing, other than clothing, such as drape , Lace, casement, print, venetian blind, roll screen, shutter, goodwill, blanket, duvet, duvet cover, duvet cotton, sheets, cushion, pillow, pillowcase, cushion, mat, carpet, sleeping bag, tent Interior materials for vehicles including automobiles, bedding products such as window glass and window glass, paper diapers, diaper covers, health supplies such as glasses, monocles, lanets, insoles of shoes, linings of shoes, furrows, furoshiki , Umbrellas, parasols, plush toys, lighting devices, eg cathode ray tube displays, liquid crystal displays, electroluminescent displays , Optical filters for information display devices using plasma displays, panels and screens, sunglasses, sunroofs, sun visors, PET bottles, storage, greenhouses, cold weather, optical fibers, prepaid cards, microwave ovens, ovens, etc. When used for packaging materials, filling materials, containers, etc. for packaging, filling, or containing these articles in windows, obstacles and inconveniences caused by environmental light such as natural light and artificial light in living organisms and articles are prevented or reduced. In addition to being able to do this, there is an advantage that the color, color tone, texture, etc. of the article can be adjusted, and the light emitted from the article or transmitted can be adjusted to a desired color balance.

  Hereinafter, embodiments of the present invention will be described based on examples.

<Cyclopentanone compound>
Add an appropriate amount of ethanol to the reaction vessel, add 20 g of the aldehyde compound represented by Chemical Formula 11 and 8.4 ml of 0.1N sodium hydroxide aqueous solution while heating and stirring at 50 ° C., and add 4.8 g of cyclopentanone dropwise. After each addition, the reaction was allowed to proceed for 5 hours with heating and stirring at the same temperature. After the reaction mixture was cooled, the precipitated crystals were collected and recrystallized from methanol. As a result, 2.2 g of bright purple crystals of the cyclopentanone compound of the present invention represented by Chemical Formula 1 were obtained.

When a part of the crystal was taken and the melting point was measured by a conventional method, the melting point of the cyclopentanone compound represented by Chemical Formula 1 was 276 ° C. Furthermore, when a visible absorption spectrum in a methylene chloride solution was measured by a conventional method, an absorption maximum (ε = 7.94 × 10 ⁴ ) was observed near a wavelength of 506 nm. Further, when a ¹ H-nuclear magnetic resonance spectrum (hereinafter abbreviated as “ ¹ H-NMR spectrum”) in a chloroform-d solution was measured by a conventional method, the chemical shift (ppm, TMS) was 2.86. (S, 4H), 3.00 (s, 12H), 6.67 (d, 4H), 6.90 (d, 2H), 7.24 (d, 2H) and 7.39 (d, 4H) A peak was observed at the position of.

  The cyclopentanone compound of this example that efficiently absorbs visible light having a wavelength of around 500 nm is used for photosensitization in various fields including information display equipment, printing, printed circuits, integrated circuits, and optical recording media. It can be advantageously used as an agent or a light absorber.

  When the reaction was carried out in the same manner as in Example 1 except that the aldehyde compound represented by Chemical Formula 14 was used instead of the aldehyde compound represented by Chemical Formula 11, the cyclopentanone compound represented by Chemical Formula 2 represented by Chemical Formula 2 was reacted. Brown-brown crystals were obtained.

When a part of the crystal was taken and the melting point was measured by a conventional method, the melting point of the cyclopentanone compound represented by Chemical Formula 2 was 146 ° C. Furthermore, when a visible absorption spectrum in a methylene chloride solution was measured by a conventional method, an absorption maximum (ε = 8.02 × 10 ⁴ ) was observed near a wavelength of 520 nm. Further, when a ¹ H-nuclear magnetic resonance spectrum (hereinafter abbreviated as “ ¹ H-NMR spectrum”) in a chloroform-d solution was measured by a conventional method, the chemical shift (ppm, TMS) was 1.16. (T, 12H), 2.85 (s, 4H), 3.39 (q, 8H), 6.63 (d, 4H), 6.74 (dd, 2H), 6.88 (d, 2H) , 7.24 (d, 2H) and 7.36 (d, 4H) were observed at peaks.

  The cyclopentanone compound of this example that efficiently absorbs visible light having a wavelength of around 500 nm is used for photosensitization in various fields including information display equipment, printing, printed circuits, integrated circuits, and optical recording media. It can be advantageously used as an agent or a light absorber.

<Cyclopentanone compound>
Take an appropriate amount of tert-butanol in a reaction vessel, add 5 g of the aldehyde compound represented by Chemical Formula 12 and 2.1 g of potassium tert-butoxide, and drop 0.68 g of cyclopentanone while heating and stirring at 120 ° C. After each addition, the reaction was carried out by heating at reflux for 5 hours. After the reaction mixture was cooled, the precipitated crystals were collected and recrystallized with an acetone / methanol mixture to obtain 4.5 g of brown crystals of the cyclopentanone compound of the present invention represented by Chemical Formula 6.

When a part of the crystal was taken and the melting point was measured by a conventional method, the melting point of the cyclopentanone compound represented by Chemical Formula 6 was 210 ° C. Furthermore, when a visible absorption spectrum in a methylene chloride solution was measured by a conventional method, an absorption maximum (ε = 0.09 × 10 ⁴ ) was observed near a wavelength of 533 nm. Further, when a ¹ H-NMR spectrum in a chloroform-d solution was measured by a conventional method, the chemical shift (ppm, TMS) was 2.88 (s, 4H), 2.99 (s, 24H), 6.61. (D, 2H), 6.65 (d, 4H), 6.70 (d, 4H), 7.13 (d, 4H), 7.28 (d, 4H) and 7.29 (d, 2H) A peak was observed at the position of.

  The cyclopentanone compound of this example that efficiently absorbs visible light having a wavelength of around 500 nm is used for photosensitization in various fields including information display equipment, printing, printed circuits, integrated circuits, and optical recording media. It can be advantageously used as an agent or a light absorber.

<Cyclopentanone compound>
An appropriate amount of methanol is taken in a reaction vessel, and 1.55 g of an aldehyde compound represented by the chemical formula 13 and 0.5 g of potassium hydroxide are added thereto, and 0.2 g of cyclopentanone is added dropwise while stirring at 80 ° C. After the addition, the reaction was performed by heating under reflux for 3 hours. After the reaction mixture was cooled to room temperature, the precipitated crystals were collected and recrystallized from methanol. As a result, 0.43 g of dark green crystals of the cyclopentanone compound of the present invention represented by the chemical formula 10 was obtained.

When a part of the crystal was taken and the melting point was measured by a conventional method, the melting point of the cyclopentanone compound represented by Chemical Formula 10 was 336 ° C. Furthermore, when a visible absorption spectrum in a methylene chloride solution was measured by a conventional method, an absorption maximum (ε = 8.04 × 10 ⁴ ) was observed in the vicinity of a wavelength of 548 nm. Further, when a ¹ H-NMR spectrum in a chloroform-d solution was measured by a conventional method, the chemical shift (ppm, TMS) was 1.32 (s, 12H), 1.54 (s, 12H), 1.78. (Tt, 8H), 3.07 (s, 4H), 3.26 (t, 4H), 3.35 (t, 4H), 7.11 (s, 2H), 7.72 (s, 2H) And a peak at the position of 7.75 (s, 2H) was observed.

  The cyclopentanone compound of this example that efficiently absorbs visible light having a wavelength of around 500 nm is used for photosensitization in various fields including information display equipment, printing, printed circuits, integrated circuits, and optical recording media. It can be advantageously used as an agent or a light absorber.

Experimental example

<Absorptive power of cyclopentanone compound>
About the cyclopentanone compound of this invention shown in Table 1, the visible absorption spectrum in a thin film state was measured by a conventional method. Then, centering on the absorption maximum wavelength, a wavelength (A) where the molecular extinction coefficient is halved on the short wavelength side of the absorption maximum wavelength and a wavelength (B) where the molecular extinction coefficient is halved on the long wavelength side of the absorption maximum wavelength, respectively. The full width at half maximum (nm) obtained by substituting these wavelengths A and B into Equation 1 was calculated. At the same time, the visible absorption spectrum in the thin film state was measured in the same manner as described above for the known related compound represented by Chemical Formula 15 which is expected to be used as a photosensitizer, and the half width was calculated. As a control. The results are also shown in Table 1.

  As can be seen from the results in Table 1, the control analog compound represented by Formula 15 exhibited an absorption maximum at a wavelength of 484 nm, whereas all of the cyclopentanone compounds of the present invention have wavelengths longer than 500 nm. Absorption maximum was shown in the visible region near 506 to 550 nm. In addition, the half width of the control similar compound was about 42 nm, whereas the cyclopentanone compound of the present invention used for the experiment showed a half width of 50 to 59 nm, which is significantly higher than that. It was. This indicates that the cyclopentanone compound of the present invention can absorb visible light in a wider wavelength range than the related compounds in the visible region near 500 nm.

  The absorption wavelength of the cyclopentanone compound according to the present invention is frequently used for photochemical polymerization, such as argon ion laser, krypton ion laser, helium / cadmium laser, gas laser such as helium / neon laser, CdS laser, etc. It is close to the oscillation line or harmonic of a solid-state laser such as a semiconductor laser, distributed feedback type or Bragg reflection type Cd-YAG laser. Therefore, the cyclopentanone compound of the present invention can be used as a photosensitizer, a light absorber, etc., for such a laser light source, and for example, a sun lamp, a carbon arc, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp. Therefore, it has various uses in fields such as photochemical polymerization and optical recording using an ordinary light source such as a tungsten lamp as an exposure light source.

Claims (2)

The aldehyde compound represented by the general formula 6 and cyclopentanone are dissolved in a solvent of 5 to 50 times the total weight thereof , reacted with heating and stirring , the resulting reaction mixture is cooled, and precipitated crystals And cyclopentanone compound represented by the general formula 3 is collected by recrystallization from methanol.

(In General Formula 3 and General Formula 6, R ⁷ and R ⁸ are a hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, isopropenyl group, 1-propenyl group, 2-propenyl group, 2-propynyl group, Butyl, isobutyl, sec-butyl, tert-butyl, 2-butenyl, 1,3-butadienyl, pentyl, isopentyl, neopentyl, tert-pentyl, 1-methylpentyl, 2- Methylpentyl group, 2-pentenyl group, 2-pentene-4-ynyl group, hexyl group, isohexyl group, 5-methylhexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, cyclopropyl group, cyclobutyl Group, cyclopentyl group, cyclohexyl group, cyclohexenyl group, cycloheptyl group, cyclooctyl group It represents a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a xylyl group, a mesityl group, an o-cumenyl group, an m-cumenyl group, a p-cumenyl group, a biphenylyl group, or a combination thereof. ) The production method according to claim 1, wherein the cyclopentanone compound is a cyclopentanone compound represented by Chemical Formula 10 .