JP2005343827A - Hydroxyalkyl-substituted 4,4'-dihydroxybenzophenones - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydroxyalkyl-substituted 4,4'-dihydroxybenzophenone useful as an intermediate or a raw material of a dyestuff, a synthetic resin, an ultraviolet absorber, a medicine, a photoresist of an electronic part, etc., or as a color-developing agent for a thermosensitive recording, etc. <P>SOLUTION: This hydroxyalkyl-substituted 4,4'-dihydroxybenzophenone is expressed by the formula [wherein, R is a 1-4C alkyl]. The hydroxyalkyl-substituted 4,4'-dihydroxybenzophenone is rich in reactivity by itself, and has a good anti-oxidation performance and heat resistance, and therefore, it is useful as an intermediate or a raw material of a functional chemical requiring a highly functional performance. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to novel hydroxyalkyl-substituted 4,4′-dihydroxybenzophenones, and more specifically, a compound having hydroxyalkyl groups at the 3- and 5-positions of two phenyl nuclei of 4,4′-dihydroxybenzophenone. It is. These compounds are useful as functional chemical intermediates or raw materials such as dyes, synthetic resins, ultraviolet absorbers, pharmaceuticals, and photoresists for electronic parts, or as color developers for thermal recording.

In recent years, the performance required for functional chemicals has been diversified and sophisticated, and high functional performance has been required for the raw material compounds. Among these, as for dihydroxybenzophenone derivatives, for example, Jour. Indian. Chem. Soc., Vol. 45, N05, 1968 describes 3,3′-diacetyl-4,4′-dihydroxybenzophenone.
JP-A-61-282335 discloses 2,3,4,4′-tetrahydroxybenzophenone, 2,3,4-trihydroxybenzophenone and 2,4-dihydroxybenzophenone. However, polyfunctional dihydroxybenzophenones in which a hydroxyalkyl group is substituted with two phenyl nuclei have not been known so far.

JP-A-61-282335 Jour.Indian.Chem.Soc., Vol.45, N05,1968

  Accordingly, the present invention has been made in view of the above-described situation in the conventional dihydroxybenzophenone derivatives, and in each of the two phenyl nuclei of 4,4′-dihydroxybenzophenone, It is an object of the present invention to provide novel polyfunctional 4,4′-dihydroxybenzophenones in which a hydroxyl group via a group is substituted by a nucleus.

  In view of the above situation, the inventor of the present invention has a highly functional compound in which two primary hydroxyl groups via alkyl groups are located at symmetrical positions of two phenyl nuclei of 4,4′-dihydroxybenzophenone. The present invention was completed by discovering that it is a novel compound having performance.

  The hydroxyalkyl-substituted 4,4′-dihydroxybenzophenones of the present invention have primary hydroxyl groups via alkyl groups at the 3,5 positions of the two phenyl nuclei of 4,4′-dihydroxybenzophenone, Such polyfunctional hydroxyalkyl group-substituted dihydroxybenzophenones having two primary hydroxyl groups in one molecule via two phenolic hydroxyl groups and a hydrophobic alkyl group are themselves highly reactive, In addition, it has good antioxidation performance and heat resistance performance, and is therefore useful as a functional chemical intermediate or raw material that requires high functional performance.

  EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

  The hydroxyalkyl-substituted 4,4′-dihydroxybenzophenones of the present invention are represented by the following general formula (1).

General formula (1)
(In the formula, R represents an alkyl group having 1 to 4 carbon atoms.)

In the general formula (1), R represents an alkyl group having 1 to 4 carbon atoms, and specifically includes, for example, a methyl group, an ethyl group, a linear or branched propyl group, and a butyl group. Etc.
In these, as R, a C1-C3 alkyl group is preferable and a methyl group is especially preferable.
In the compound represented by the general formula (1) of the present invention, the properties of the compound, for example, the hydrophobicity can be increased or decreased by arbitrarily selecting the number of carbon atoms of R.

  Accordingly, specific examples of the hydroxyalkyl-substituted 4,4′-dihydroxybenzophenones represented by the general formula (1) include 3,3 ′, 5,5′-tetrahydroxymethyl-4,4. '-Dihydroxybenzophenone, 3,3', 5,5'-tetrahydroxyethyl-4,4'-dihydroxybenzophenone, 3,3 ', 5,5'-tetrahydroxy n-propyl-4,4'-dihydroxybenzophenone 3,3 ′, 5,5′-tetrahydroxyisopropyl-4,4′-dihydroxybenzophenone, 3,3 ′, 5,5′-tetrahydroxy n-butyl-4,4′-dihydroxybenzophenone, 3,3 Examples include ', 5,5'-tetrahydroxy 2-butyl-4,4'-dihydroxybenzophenone.

  In such hydroxyalkyl-substituted 4,4′-dihydroxybenzophenones represented by the general formula (1) according to the present invention, the production method is not particularly limited, but for example, the following 4,4 ′ -It can manufacture by reacting the alkyl aldehyde represented by the dihydroxybenzophenone (Formula 1) and following General formula (2) in a solvent in presence of an alkali catalyst.

General formula (2)

Formula 1
(In the formula, R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)

In the alkyl aldehyde represented by the general formula (2), R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, and n -A propyl group, an isopropyl group, etc. can be mentioned.
Therefore, specific examples of the alkyl aldehyde represented by the general formula (2) include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, and isobutyraldehyde.

In the above reaction, the molar ratio of alkyl aldehyde to 1 mol of 4,4′-dihydroxybenzophenone is usually 5 to 30 mol, preferably 10 to 20 mol.
In this reaction, the alkyl aldehyde may be used as, for example, a 20 to 40% by weight aqueous solution from the viewpoint of ease of handling.

  Examples of the alkali catalyst include divalent metals such as alkali metal hydroxides and acetates such as sodium hydroxide, potassium hydroxide and lithium hydroxide, calcium hydroxide, zinc hydroxide and magnesium hydroxide, preferably And alkaline earth metal hydroxides and acetates, tertiary amines such as pyridine, trimethylamine, and tributylamine. Of these, sodium hydroxide and potassium hydroxide are particularly preferably used. Such an alkali catalyst may be used in this reaction as, for example, a 20 to 50% by weight aqueous solution from the viewpoint of ease of handling.

Such an alkali catalyst is used in an amount of 2 to 5 mol, preferably 3 to 4 mol, per 1 mol of the above 4,4′-dihydroxybenzophenone.
When the amount of alkali catalyst used exceeds the above range, the amount of alkali catalyst in the reaction system becomes unnecessarily excessive, and after completion of the reaction, the reaction system is acidified to precipitate and collect the reaction product. This is not preferable because an unnecessarily large amount of acid is required.

In the present invention, the reaction of 4,4′-dihydroxybenzophenone and an alkylaldehyde in the presence of an alkali catalyst is usually performed in a solvent, preferably an aqueous solvent or a mixed solvent of water and an organic solvent.
The solvent is usually used in a range of 1 to 5 times, preferably about 2 to 3 times by weight with respect to the 4,4′-dihydroxybenzophenone as a raw material.
All of these solvents may be used as a solvent for the alkyl aldehyde or alkali catalyst used in the reaction.
The organic solvent used by mixing with water is, for example, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, as long as the solubility in the alkali catalyst and the raw material alkyl aldehyde is not impaired. Alcohol solvents such as ethylene glycol, ethylene glycol monomethyl ether, diethylene glycol, and carbitol, and water-soluble organic solvents such as tetrahydrofuran, dioxane, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone are used.
The above reaction is usually performed at a temperature in the range of 30 to 70 ° C, preferably 40 to 60 ° C, usually for 1 to 72 hours, preferably about 4 to 16 hours.

In order to separate and recover the desired reaction product from the obtained reaction mixture after completion of the reaction, for example, after completion of the reaction, the obtained reaction mixture is cooled and used as an extraction solvent for aromatic hydrocarbons, fatty acids. After adding an organic solvent that does not mix with water, such as aliphatic alcohols, aliphatic ketones, and esters, or a mixture thereof to the reaction mixture, an acidic compound such as an organic acid or an inorganic acid, or an aqueous solution thereof is added thereto. In addition, the reaction mixture is neutralized, the aqueous layer is separated, and the reaction product is extracted into the organic layer. Next, the organic layer thus obtained is concentrated if necessary, then cooled, and the solid content thus precipitated is filtered to obtain the desired hydroxyalkyl-substituted 4,4′-dihydroxybenzophenone. Can be obtained.
Alternatively, after the reaction mixture has been neutralized, an extraction solvent may be added thereto.
Examples of the extraction solvent include aliphatic alcohols such as methanol and 1-butanol, aliphatic ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate and butyl acetate, aromatic hydrocarbons such as benzene, toluene and xylene. Can be mentioned. These extraction solvents can be used alone or as a mixture of two or more.
Among the acidic compounds used for the neutralization treatment, examples of the organic acid include formic acid, acetic acid, propionic acid, and oxalic acid. Examples of the inorganic acid include sulfuric acid, phosphoric acid, and phosphorous acid. Examples include acids, hypophosphorous acid, hydrochloric acid and the like. Among these, an aqueous hydrochloric acid solution or an aqueous sulfuric acid solution is most preferably used in terms of economy and operability.
By such a method, the hydroxyalkyl-substituted 4,4′-dihydroxybenzophenone of the present invention can be obtained as a crude product or a high-purity product as required.

(Production of 3,3 ′, 5,5′-tetrahydroxymethyl-4,4′-dihydroxybenzophenone)
4,4′-dihydroxybenzophenone 42.8 g (0.2 mol), 48% sodium hydroxide aqueous solution 66.7 g (0.8 mol) and pure water 66.7 g were charged into a 1 L four-necked flask, and at room temperature. Under stirring, 342.9 g (4.0 mol) of 35% aqueous formaldehyde solution was added dropwise over 1 hour to cause a reaction. Thereafter, the temperature was raised to 60 ° C., and the mixture was further reacted with stirring for 60 hours.
After completion of the reaction, 230.4 g of methyl ethyl ketone was added to the resulting reaction mixture, followed by neutralization by adding 104.4 g of 16% sulfuric acid, and then 123.6 of 1-butyl alcohol was added to dissolve the reaction product. I let you. Thereafter, the aqueous layer was separated, and methyl isobutyl ketone was added to the obtained oil layer, which was then cooled, and the precipitated crystals were separated by filtration to give crude crystals of the desired product (purity of 84% according to high performance liquid chromatography analysis). ) Was obtained as a pale yellow powder. A mixed solution of methanol and methyl isobutyl ketone was added to the obtained crude crystals and dissolved at a temperature of 50 ° C., then cooled, crystallized, then filtered and dried to obtain the desired 3, 3, 3 ′, 5, 5 28 g of '-tetrahydroxymethyl-4,4'-dihydroxybenzophenone was obtained as a pale yellow powder having a purity of 89.9% (according to high performance liquid chromatography analysis). The yield based on the raw material 4,4′-dihydroxybenzophenone was 41.9%.
Mass spectrometry (LC-MS / AP): 333.5 (M ^−H )
Proton nuclear magnetic resonance spectrum analysis (400 MHz, solvent DMSO)

Claims (1)

It is represented by the following general formula (1)

General formula (1)
(In the formula, R represents an alkyl group having 1 to 4 carbon atoms.)
Hydroxyalkyl-substituted 4,4'-dihydroxybenzophenones