JPS603378B2 - Chalcone derivative and its manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a chalcone derivative useful as a raw material for producing photosensitive resins and a method for producing the same.

Until now, photosensitive resins having a diazo group, azide group, cinnamoyl group, or chalcone group as photosensitive groups have been known, but the methods for introducing these photosensitive groups are complicated, and the resulting photosensitive resin There are problems with refining etc.

As a result of various studies on methods for introducing photosensitive groups into polymers, the present inventors discovered that 3'-hydroxychalcone derivatives met the purpose, and thus completed the present invention.

That is, the present invention provides novel 3' -monohaloacetyloxychalcone derivatives.

This new chalcone conductor has a reaction formula (X in the formula), for example.
and R have the same meanings as above), it can be produced by reacting a 3'-hydroxychalcone derivative and monohaloacetyl chloride in the presence of a dehydrochlorination agent.

In this method, examples of 3'-hydroxychalcone derivatives used as starting materials include 3'-hydroxychalcone. 4-nitro-3'-hydroxychalcone,
4-cyano 3'-hydroxychalcone, 4-methyl-
Examples include 3'-hydroxychalcone, 4-isopropyl-3'-hydroxychalcone, and the like.

In addition, monohaloacetyl chloride includes monochloroacetyl chloride, monopromoacetyl chloride,
Monoiodoacetylc.

You can mention rides, etc. In addition, organic compounds such as triethylamine and pyridine, which are commonly used as dehydrochlorination agents in the present invention, are undesirable because they react with haloacetyl groups, and inorganic compounds that are immovable in organic solvents are desirable. Examples include potassium carbonate, sodium carbonate, sodium bicarbonate, and the like.

As the reaction solvent, a solvent inert to monohaloacetyl chloride is used.

Examples include benzene, toluene, xylene, carbon tetrachloride, ethane tetrachloride, acetonitrile, dimethylacetamide, and the like. The reaction temperature is 20qo to 1
The temperature is preferably 00°C, but is not limited thereto. The molar ratio of 3'-hydroxychalcone and monohaloacetyl chloride at this time is selected within the range of 1:1 to 1:3, but is not limited thereto. Further, the dehydrochlorination agent to be used may be used in a ratio of 1:1 or more with 3'-hydroxychalcone, but it is usually preferably 1:1 to 1:3. The reaction product is isolated and purified by conventional methods. The chalcone derivatives obtained according to the present invention have high activity in the haloacetyl group portion, and can be easily produced without a catalyst under mild conditions by the Menshutkin reaction with a polymer having a tertiary amino group in the main chain or side chain, for example. A photosensitive resin can be obtained simply by heating at 30qo to 60qo.

Moreover, since it has absorption in a longer wavelength region than the cinnamic acid derivatives conventionally used in photosensitive resins, the resulting photosensitive resin has high sensitivity. Next, the present invention will be explained in detail based on reference examples and examples.

Reference Example Synthesis of 13'-Hydroxy-4-cyanochalcone 1.8 hours of p-cyanobenzaldehyde and 1.7 hours of 3-hydroxyacetophenone were dispersed in 5 parts of ethanol, and 10 parts of a 10% aqueous solution of caustic soda was added to this. 5℃
I add this while worshiping the lights.

After rinsing at 5°C for 3 minutes, pouring into dilute hydrochloric acid gives a pale yellow precipitate.

This is washed with a 50% alcohol solution. This is recrystallized from aqueous ethanol. Yield 2.6 hours (yield 84%) Melting point 181-18〆0. Infrared absorption spectrum shows 2240 skin-1 absorption based on nitrile, 167
Absorption due to carbonyl groups was confirmed at Yamabashi-1, and absorption due to double bonds was confirmed at 1610-1. Elemental analysis also agreed with the theoretical values. Reference example 2 Synthesis of 3'-hydroxy-4-isopropyl chalcone p
Disperse 7.4 parts of isopropylbenzaldehyde and 6.8 parts of 3-hydroxyacetophenone in 15 parts of ethanol, and gradually add 4 parts of caustic soda and 30 parts of an aqueous solution.

Boil this mixture at 80°C for 4 hours. After finishing Takaazusa, cool and acidify with dilute hydrochloric acid. An oily product is obtained. If left at room temperature overnight, it will crystallize. When this is recrystallized from a mixture of dichloromethane and hexane, 6.8 cm crystals are obtained. Infrared absorption spectrum confirmed carbonyl absorption at 1670 arc-1, double bond absorption at 1610 arc-1, and phenol absorption at 3400 skin-1. The melting point of the crystals was 89.5-9ro. Example 1 Synthesis of 3-nitro-3'-monochloroacetyloxychalcone 1 day's worth of 3nitro-3'-hydroxychalcone and 0.67 days' worth of monochloroacetyl chloride were dissolved in 10 parts of dry acetonitrile, and 0.84 days' worth of monochloroacetyl chloride was dissolved therein. Add carbonated soda and light the lamp for 4 hours at 80:00, while vigorously worshiping the hawk.

After cooling, the first eluted portion is collected using a silica gel column using dichloromethane as the eluent, and the solvent is removed using an evaporator. When the obtained crystals are recrystallized from a mixed solution of benzene and hexane, crystals of 1.3 hours are obtained. Melting point 132
~133qo. The absorption maximum of 29 dishes m was confirmed by ultraviolet absorption spectrum. In addition, the infrared absorption spectrum shows that 1530 Hada-1 and 1350 Hada-1 have absorption by nitro groups, 1610 Hada-1 has absorption by double bonds, 1660 Hada-1 has absorption by ketone carbonyl, and 1770 Kay-1
Absorption of chloroacetyl group by carbonyl was confirmed. This ultraviolet absorption spectrum is shown in FIG. Example
2 Synthesis of 3'-monochloroacetyloxychalcone 1 night of 3'-hydroxychalcone and 0.6 nights of monochloroacetyl chloride were mixed with 50' of dry benzene and 1' of dry benzene.
Dissolve in a mixture of dry dimethylacetamide, add 0.5 ml of potassium carbonate, and reflux for 7 hours with worship.

After the reaction is complete, the solvent is removed using a rotary evaporator and the mixture is left to stand at room temperature to obtain crystals. When this is recrystallized from a mixture of benzene and hexane, 0.9 ta of crystals with a melting point of ~86°C are obtained. 17 by infrared absorption spectrum
Section 80-1 shows absorption of chloroacetyl group by carbonyl, 1610-1 shows absorption of ketone by carbonyl, 1
Absorption due to double bonds was confirmed in 610-1. Also,
Ultraviolet absorption spectra confirmed an absorption maximum in 31 plates. Example 3 Synthesis of 4-cyano-3'-monochloroacetyloxychalcone Drying of 2'-hydroxy-4-cya/rucon for 1 night and monochloroacetyl chloride for 0.45 days with 40 parts of acetonitrile and 5 parts of dimethylacetamide Dissolve it in a mixed solution, add 0.85 g of carbonated soda to it,
Reflux for two hours while vigorously worshiping.

After the reaction is complete, the second eluting component is bridged in a silica gel column using a 1:1 mixture of dichloromethane and benzene as the eluent. When recrystallized from a mixture of benzene and hexane, one crystal with a melting point of 117 to 118 degrees Celsius is obtained.
Infrared absorption spectra confirmed absorption by nitrile in 2240 Ka-1 and absorption by double bonds in 1610 Hada-1. Furthermore, an absorption maximum at 30 m was confirmed by ultraviolet absorption spectrum. Example 44-Isopropyru-3'
-Synthesis of monochloroacetyloxychalcone.

Disperse 1.5 g of 4-isopropyl-3'-hydroxychalcone and 1.5 g of potassium carbonate in 15 g of dry acetonitrile, and add 0.96 g of monochloroacetyl chloride while stirring at room temperature.

After reacting for 4 hours at room temperature, the mixture is filtered and the filtrate is concentrated using a rotary evaporator to obtain an oil. This is dissolved in dichloromethane, passed through a silica gel column chromatography, and the first eluted portion is collected. The resulting solution is concentrated on a rotary evaporator to give an oil. When this is left at room temperature, it crystallizes. Absorption 1.3
evening. Melting point is ~86qo. Infrared absorption spectrum shows absorption based on isopropyl group at 2950c, 1780
Absorption based on monochloroacetyl group in Ka-1, 1610
Absorption based on double bonds was confirmed in Skin-1. Furthermore, an ultraviolet absorption spectrum confirmed an absorption maximum of 32 m'. Example 5 Synthesis of 4-cyano-3'-monochloroacetyloxychalcone 1.3 hours of 4-cyano-3'-hydroxychalcone and 0.88 hours of monochloroacetyl chloride were dispersed in 15 hours of dry acetonitrile,
Add 1.11 tablespoons of carbonated soda to this.

The mixture was refluxed for 4 hours while being vigorously stirred. After cooling the reaction solution to room temperature, it was filtered through a furnace, and the furnace solution was concentrated under reduced pressure.
The obtained solid was recrystallized from a mixture of benzene and hexane to obtain 1.1 crystals with a melting point of 141.5-142°C. Infrared absorption spectra confirmed nitrile absorption at 2240ka-1, chloroacetyl group-based absorption at 178n-1, and double bond-based absorption at 1610ka-1. The infrared absorption spectrum of 4-cyano-3'-monochloroacetyloxychalcone thus obtained is shown in FIG. Also, according to the ultraviolet absorption spectrum, 30
The absorption maximum of .m was confirmed.

[Brief explanation of the drawing]

Figure 1 shows the ultraviolet absorption spectrum of 3-nitro-3'-monochloroacetyloxychalcone of the present invention;
The figure shows an infrared absorption spectrum of 4-cyano-3'-monochloroacetyloxychalcone. Figure 1 Figure 2

Claims (1)

[Claims] 1 General formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ A 3'-monohaloacetyloxychalcone derivative represented by 2. 3'-hydroxy represented by the general formula ▲ Numerical formulas, chemical formulas, tables, etc. chalcone derivative,
A monohaloacetyl chloride represented by the general formula X-CH_2COCl (X in the formula is a halogen atom) is reacted. A method for producing the 3'-monohaloacetyloxychalcone derivative. 3. The manufacturing method according to claim 2, wherein the reaction is carried out in the presence of a solid dehydrochlorination agent.