JPS603376B2 - 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 a photosensitive group 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 investigating various methods of introducing photosensitive groups into polymers, we found that 4
The present inventors have discovered that a chalcone derivative obtained by reacting a '-hydroxychalcone derivative with monohaloacetyl chloride meets the purpose, and has completed the present invention.

That is, the present invention provides a novel compound represented by the general formula (wherein X is a halogen atom and R is an unsubstituted phenyl group, a nitro group, a lower alkyl group, an alkoxy group, or a phenyl group substituted with a halogen atom). The present invention provides chalcone derivatives that are

This chalcone derivative can be prepared, for example, according to the reaction formula (in the formula, x and R have the same meanings as above)
It can be produced by reacting a '-hydroxychalcone derivative and monohaloacetyl chloride in the presence of a dehydrochlorination agent.

In this production method, the 4'
Examples of -hydroxychalcone derivatives include 4'-hydroxychalcone, 4-chloro-4'-hydroxychalcone, 4-methyl-4'-hydroxychalcone, 4-isopropyl-4'-hydroxychalcone, 4-methoxy4'-hydroxychalcone, Examples include 4-nitro-4'-hydroxychalcone.

In addition, monohaloacetyl chloride includes monochloroacetyl chloride, monobromoacetyl chloride,
Examples include monoiodoacetyl chloride.

Furthermore, organic compounds such as triethylamine and pyridine, which are commonly used as dehydrochlorination agents used in the present invention, are undesirable because they react with haloacetyl groups, and inorganic compounds that are insoluble in organic solvents are preferable. Examples include potassium carbonate, sodium carbonate, and sodium hydrogen carbonate. As the reaction solvent, a solvent inert to monohaloacetyl chloride is used.
Examples include solvents such as benzene, toluene, xylene, carbon tetrachloride, ethane tetrachloride, dichloromethane, acetone, acetonitrile, and dimethylacetamide. The reaction temperature is preferably from 20 to about the boiling point of the solvent used, but if the boiling point of the solvent is too high, it is preferably 100 qo or less. At this time, the molar ratio of 4'-hydroxychalcone and monohaloacetyl chloride was 1:
The ratio is selected within the range of 1 to 1:3, but is not limited thereto.

In addition, the dehydrohalogenating agent used should be in a ratio of 1:1 or more with 4'-hydroxychalcone, but usually 1:1 to 1:1.
A ratio of 1:3 is desirable. The reaction product is isolated and purified by conventional methods. The chalcone conductor obtained by the present invention has high activity at the haloacetyl group site, 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 primary mirror or side chain. For example 3
A photosensitive resin can be obtained simply by heating at 0 to 60 qo. Wrinkle also has absorption in a longer wavelength region than the cinnamic acid converter used in the secondary photosensitive resin, so the sensitivity of the resulting photosensitive resin is high. Next, the present invention will be explained in detail based on reference examples and examples.

Reference example Synthesis of 14'-hydroxy-4-chlorochalcone.

24 and 3 days of p-acetylphenol, 25 days of p-chlorobenzaldehyde, and 15 days of caustic soda are refluxed in a mixture of 150 degrees of water and 75 degrees of ethanol for 2 hours at sea.

After cooling the reaction solution to room temperature, it is left to stand overnight. Dilute the yellow reaction solution with the same amount of water. Further acidify with dilute hydrochloric acid. The pale yellow crystals obtained are collected and washed with 50% ethanol. Recrystallization from ethanol yields yellow crystals 3
1.5 evenings were obtained. 164 according to infrared absorption spectrum
A ketone in 0 skin-1 and a double bond in 1600 skin-1 were confirmed. The melting point of the crystal is 1935-195 qo. Reference example Synthesis of 24'-hydroxychalcone.

23.3 days of penzaldehyde, 27.2 days of p-acetylphenol and 152 hours of caustic soda are refluxed for 3 hours in a mixture of 100 parts of ethanol and 200 parts of water.

After cooling the reaction solution to room temperature, it is left to stand overnight. Then, add 300 ml of water to this solution and make it acidic with dilute hydrochloric acid.
The pale yellow precipitate obtained is collected by filtration and washed three times with 50% ethanol. The yield was 32 days. Recrystallization from ethanol gives pale yellow crystals with a melting point of 1770-178.5°C. From infrared absorption spectrum 3150 k-1
A wide range of phenol absorptions, 1645ka-1 ketone absorption, and 1610ka-1 double bond absorption were confirmed. Reference Example 3 Synthesis of 4'-hydroxy-4-isopropyl chalcone.

29,6 p-isopropylbenzaldehyde and 27
, 2 hours of p-acetylphenol and 15 hours of caustic soda were refluxed for 3 hours in a mixture of 70 degrees of ethanol and 150 degrees of water. After cooling the reaction solution to room temperature, 2
Add 00 [ of water and make acidic with dilute hydrochloric acid. The deposited precipitate is collected in a furnace and washed with a small amount of aqueous ethanol. When recrystallized from aqueous ethanol, 30.4-day crystals are obtained. Melting point is 156 qo to 157,500. 3300 skin-1 wide phenol absorption from infrared absorption spectrum, 1
We confirmed the absorption of ketones at 650 skin-1 and the absorption of double bonds at 1600 arc-1. Reference example 44'-hydroxy-4
-Synthesis of methoxychalcone.

25 2 p-anisaldehyde and 27, 2 p-
Acetylphenol 27.2 hours and 15 hours of caustic soda are refluxed for 1 hour in a mixed solution of 100 parts water and 100 parts ethanol.

After cooling the reaction solution to room temperature, it is poured into dilute hydrochloric acid. The yellow precipitate obtained is collected in a furnace, washed with a large amount of water, and recrystallized from aqueous ethanol. The gross yield is 339 yen. Melting point is 19yo
~194°C. Infrared absorption spectrum shows absorption of 315 melon-1 phenol, 164 melon-1 ketone,
Absorption of the 1600 arc-1 double bond was confirmed. Example
1 Synthesis of 4nitro-4'-monochloroacetyloxychalcone.

1,4 4-nitro-4'-hydroxychalcone and 1
Disperse 1-2 days of potassium carbonate in 80 volumes of dry acetonitrile, add 1-2 nights of monochloroacetic acid chloride, and reflux for 4 hours while praying.

Thereafter, it is cooled to room temperature, and the precipitate is removed by filtration to obtain a filtrate. This liquid is evaporated to dryness under reduced pressure. It was confirmed to be almost pure by thin layer chromatography.
The yield is 1.8 days. 17 by infrared absorption spectrum
Absorption of ester at 80-1, ketone at 1670-1, and double bond absorption at 1610-1 were confirmed. When recrystallized from a mixture of benzene and n-hexane, the melting point is 135.
qo~1305°C. Further, according to the ultraviolet absorption spectrum, the absorption maximum (input maX) was 317 mm.
Furthermore, olefin protons were confirmed by nuclear magnetic resonance spectroscopy. Example 2 Synthesis of 4'-monochloroacetyloxychalcone.

4'-Hydroxychalcone (1, 1) and potassium carbonate (0,8) were dispersed in 40' (40) dry benzene, and monochloroacetyl chloride (0,9) was added to this to generate carbon dioxide gas while bowing. Reflux until it stops.

It usually takes 2 to 3 hours. After the reaction is completed, cool to room temperature,
Solids are removed by filtration. The resulting benzene solution was evaporated to dryness under reduced pressure, and the pale yellow residue was washed with n-hexane. When recrystallized with a mixture of benzene and n-hexane, crystals 1 and 2 with points 11 and 1170 are obtained. Infrared absorption spectrum shows absorption of ester at 1780 arc-1, absorption of ketone at 1660 arc-1, 161
Absorption of the double bond of 0ka-1 was confirmed. 13 of the 4-monochloroacetyloxychalcone thus obtained
The nuclear magnetic resonance spectrum of C is shown in FIG. In addition, the absorption maximum of the 31 phantom plate was confirmed by ultraviolet absorption spectrum. The presence of olefin broton was also confirmed by nuclear magnetic resonance spectroscopy. Example 3 Synthesis of 4-isopropyl-4'-monochloroacetyloxychalcone.

Disperse 2,3 days of sodium carbonate in 40 degrees of dry acetonitrile, 2,76 degrees of 4-isopropyl-4'-hydroxychalcone, and add 2,4 days of monochloroacetyl chloride to this, and stir for 4 hours while praying. Reflux.

After the reaction is complete, the mixture is cooled to room temperature. The solid matter is removed in a furnace and concentrated in a furnace liquid evaporator to obtain crystals, which are recrystallized from benzene and n-hexane to obtain 2,59 crystals with a melting point of 119°C to 120.5°C. Isof of 2960 arc-1 by infrared absorption spectrum. Absorption based on lopil group, 1780 skin [1 ester absorption, 1660 skin - 1 ketone absorption, 1600 skin]
Absorption of the single bond of No. 1 was confirmed. This infrared absorption spectrum is shown in FIG. The absorption maximum of 34 carp m was confirmed by ultraviolet absorption spectrum. Additionally, the presence of olefin protons was confirmed by nuclear magnetic resonance. Example 4 Synthesis of 4-methoxy-4'-monochloroacetyloxychalcone.

4-Methoxy-4'-hydroxychalcone for 2.4 days, potassium carbonate for 1.5 days and monoacetyl chloride for 2.0 days were mixed in 40 minutes of dry acetonitrile and lit. Reflux for 5 hours.

After the reaction is completed, the mixture is cooled to room temperature, solids are removed by filtration, and the resulting filtrate is concentrated using an evaporator to obtain a pale yellow oil. When this is cooled in ice water, it crystallizes. When this is recrystallized with n-hexane, the melting point is 90CO ~
Crystals of 9〆○ were obtained in 2.6 days (78%). Infrared absorption spectra confirmed absorption of estel at 178 ratio S-1, ketone absorption at 166 mountains-1, and double bond absorption at 1600 ratio -1. Moreover, maximum absorption based on olefin at 344 nm was confirmed by ultraviolet absorption spectrum. Example 5 Synthesis of 4-chloro-4'-monochloroacetyloxychalcone.

4-chloro-4'-hydroxychalcone and 0
Disperse 1,6 days of sodium carbonate in 40 ships' worth of dry acetonitrile, add 1,0 days of monochloroacetic chloride, and reflux for 5 hours with stirring.

Thereafter, the mixture is cooled to room temperature, solids are removed by filtration, and the filtrate is concentrated to obtain pale yellow crystals. When this is recrystallized from a mixture of n-hexane and benzene, the melting point is 1.
1,42 tons of 4-chloro-4'-monochloroacetyloxychalcone having a temperature of 65.5 DEG C. to 160.5 DEG C. was obtained. The infrared absorption spectrum confirmed absorption of ester at 1780 cm-1, ketone at 1660 arc-1, and double bond absorption at 1600 skin-1. In addition, maximum absorption at 31 m was confirmed by ultraviolet absorption spectrum.

[Brief explanation of drawings]

Figure 1 shows the 13C nuclear magnetic resonance spectrum of 4'-monochloroacetyloxychalcone of the present invention, and Figure 2 shows the 4'-monochloroacetyloxychalcone spectrum.
-Isopropyl-4'-monochloroacetyloxychalcone shows an infrared absorption spectrum. Figure 2

Claims (1)

[Claims] 1 General formula ▲ Numerical formula, chemical formula, table, etc. A chalcone derivative represented by (which is a phenyl group). 2 General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R in the formula is an unsubstituted phenyl group, a nitro group, a lower alkyl group, an alkoxy group, or a phenyl group substituted with a halogen atom) 4 There are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ (formula A method for producing a chalcone derivative represented by (R and X have the same meanings as above). 3. The manufacturing method according to claim 2, wherein the reaction is carried out in the presence of a solid dehydrochlorination agent.