JP2014101302A - Quinic acid derivative compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel quinic acid derivative compound which is derived from plants and potentially applicable to chemical products or the like.SOLUTION: The compound is represented by the specified general formula (I). In the general formula (I), Rrepresents a single bond, an alkylene group, an arylene group, or the like; and Rand Reach independently represent a hydrogen atom, an alkyl group, an aryl group, or the like, where Rand Rmay be linked to each other to form a ring structure together with the carbon atoms bonded thereto and with R.

Description

  The present invention relates to a novel quinic acid derivative compound.

In recent years, compounds that do not originate from petroleum resources, which are said to be limited, have attracted attention, and among them, research and development of organic compounds, plastics, pharmaceuticals, etc. that make use of plant resources have been actively conducted.
As a plant-derived useful compound, polyphenols have been produced and developed in various ways. For example, coffee beans, sweet potato leaves, mugwort, and the like contain many polyphenols called chlorogenic acid. Various studies have been conducted to develop quinic acid (1,3,4,5-tetraoxycyclohexane-1-carboxylic acid) obtained by hydrolyzing chlorogenic acid into pharmaceuticals and the like.
As the use of quinic acid itself as a chemical product, for example, a technique using quinic acid as a complex-forming compound has been disclosed (for example, see Patent Documents 1 and 2).

Special Table 2000-507154 JP 2005-506423 A

  However, the quinic acid used in the above-mentioned patent documents is only listed as one embodiment of tannin, and does not focus on the characteristics of the quinic acid compound itself. In this way, studies on the use of quinic acid compounds are limited to high-value-added products such as pharmaceuticals, and studies on the induction of compounds that can be used for cheap and highly versatile chemical products are sufficiently conducted. The current situation is not.

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a novel quinic acid derivative compound that is a plant-derived compound and can be expected to be used for chemical products.

  As a result of intensive studies in view of the above problems, the inventors have found that a quinic acid derivative having a specific structure is a novel compound and can be expected to be used as a precursor of a polymer compound raw material or a polymerizable compound. completed.

That is, the configuration of the present invention is as follows.
<1> A compound represented by the following general formula (I).

(In the general formula (I), ^{R 1} is a single bond, each .R ² and ^{R 3} independently represents an alkylene group or an arylene group, a hydrogen atom, an alkyl group, or an aryl group, ^{R 2} and R ³ may be linked to each other to form a ring structure together with the carbon atom to which each is bonded and R ¹ .

  Since the compound of the present invention has a rigid ring skeleton and two hydroxyl groups in the molecule as represented by the general formula (I), it is a raw material for a resin having a relatively high glass transition temperature. Useful as. In addition, since the resin has an acetal group that is easily cleaved by an acid in the molecule, the resin synthesized containing the compound of the present invention can be given a property of being easily decomposed by an acid. It is useful for the synthesis of resins used in pattern-forming resin compositions such as resist materials, and the obtained resin has a high Tg in the absence of acid, and is known biodegradable resin by adding acid. It also has the advantage of being easier to disassemble.

  According to the present invention, it is possible to provide a novel quinic acid derivative compound which is a plant-derived compound and can be expected to be used for chemical products.

2 is an NMR chart of exemplary compound M-1 obtained in Example 1. FIG.

  DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail. However, the description of constituent elements described below is an example (representative example) of an embodiment of the present invention, and is not specified by these contents. Various modifications can be made within the scope of the gist.

  In addition, the numerical value range shown using "to" in this specification shows the range which includes the numerical value described before and behind "to" as a minimum value and a maximum value, respectively. In addition, unless otherwise specified, the term “substituent” is used in the sense of including an unsubstituted one and those further having a substituent. For example, when the term “alkyl group” is used, an unsubstituted alkyl group is used. And an alkyl group further having a substituent. The same applies to other substituents.

  The compound of the present invention is a compound synthesized from quinic acid as a raw material, and is a compound represented by the following general formula (I).

In the general formula (I), R ¹ represents a single bond, an alkylene group, or an arylene group.
Examples of the alkylene group in R ¹ include an alkylene group having 1 to 6 carbon atoms, and more specifically, a methylene group, an ethylene group, a propylene group, an i-propylene group, an n-butylene group, a t-butylene group, and the like. Is mentioned.
Examples of the arylene group for R ¹ include an arylene group having 6 to 12 carbon atoms, and more specific examples include a phenylene group and a naphthylene group.
R ¹ is preferably an ethylene group, an n-butylene group, a phenylene group or the like.

R ² and R ³ each independently represent a hydrogen atom, an alkyl group, or an aryl group, and examples of the alkyl group include an alkyl group having 1 to 6 carbon atoms.
Among them, both R ² and R ³ is a hydrogen atom, a methyl group, or ethyl group.
The aryl group in R ² and R ^3, include an aryl group having 6 to 12 carbon atoms, more specifically, a phenyl group, a naphthyl group, and the like.
Among them, both R ² and R ³ is a hydrogen atom, a methyl group, or ethyl group.

R ² and R ³ may be connected to each other to form a ring structure together with the carbon atom to which they are bonded and R ^{1. When} these form a ring structure, the ring formed is 3 to 7 It is preferably a membered alicyclic ring, for example, a 5-membered to 6-membered alicyclic ring, more preferably a cycloheptyl ring or a cyclohexane ring. Moreover, you may have 2 or more rings, such as what condensed 2 or more rings.

The compound represented by the general formula (I) is not particularly limited as long as it is a compound having a structure represented by the general formula (I).
Although the exemplary compounds (M-1) to (M-10) of the quinic acid derivative compound of the present invention are listed below, the present invention is not limited to these.

  As described above, the novel quinic acid derivative compound of the present invention is useful as a raw material for a resin (polymer compound), a precursor for a bifunctional acrylate monomer, and the like. As is clear from the above structure, all of the novel compounds of the present invention are diol compounds, and therefore are easily polymerized by a condensation reaction, and can also be used as raw materials for polyesters and polyurethane resins.

The novel quinic acid derivative compound of the present invention can be obtained, for example, by the following scheme.
Quinic acid (1,3,4,5-tetraoxycyclohexane-1-carboxylic acid) as a starting material for producing the compound of the present invention is, for example, from plants such as coffee beans, sweet potato leaves, mugwort, etc. It is obtained by hydrolyzing chlorogenic acid, which is a polyphenol extracted by means such as boiling with water or boiling with alcohol.
Quinic acid is also available as a commercial product, and examples thereof include (1R, 3R, 4R, 5R)-(−)-quinic acid (trade name) manufactured by Aldrich.

As shown below, quinic acid is a pentafunctional compound in which four hydroxyl groups and one carboxyl group are bonded to a cyclohexane ring. In the presence of a catalyst such as an acid catalyst, the 3- and 4-position hydroxyl groups on the ring are acetalized. It is known that the 1-position carboxyl group and the 5-position hydroxyl group can be easily converted into the following polyalicyclic compounds by esterification (lactonization). As described in detail below, the compound of the present invention can be synthesized using the following polyalicyclic compound.
For example, it is a compound synthesized by mixing quinic acid and acetone and reacting them in the presence of a catalyst such as sulfuric acid. After the reaction, neutralization was performed, and acetone was distilled off. By separating and purifying, an alicyclic compound having the following structure used for the synthesis of the compound of the present invention can be obtained.

(Synthesis scheme)
Since the polyalicyclic compound repeats decomposition and ring closure in the presence of an acid catalyst, the substituent can be converted by using an aldehyde compound or a ketone compound that can easily form an acetal ring with the alcohols at positions 3 and 4. This is a so-called transacetalization reaction.
Below, the example of the synthetic scheme using the compound X which is a typical polyalicyclic compound is shown.

R ^Xa and R ^Xb in the compound X each independently represent a hydrogen atom, an alkyl group or an aryl group, and the hydrogen atom, alkyl group or aryl represented by R ² and R ³ in the general formula (I) described above It is synonymous with group, and a preferable aspect is also the same. R ¹ in the compound (A) has the same meaning as R ¹ in aforementioned formula (I), preferable embodiments thereof are also the same.
Further, R ^A and R ^B in the compound (A) each independently represent a hydrogen atom, an alkyl group (eg, methyl group, ethyl group, etc.), an aryl group (eg, phenyl group, etc.), etc. ^A and R ^B may be the same or different.
Examples of the compound (A) include dialdehyde and diketone compounds. Examples of the dialdehyde that is an example of the compound (A) include terephthalaldehyde, glutaraldehyde, and the like. Examples of the diketone compound that is another example of the compound (A) include cyclohexane-1,6-dione, dibenzoylpropane, hexane-2,5-dione, and the like.
In the transacetalization reaction, it is preferable to use an acid catalyst such as paratoluenesulfonic acid, methanesulfonic acid, or sulfuric acid as the catalyst. This reaction is preferably carried out in an inert solvent such as ethyl acetate, pyridine, dimethylacetamide, xylene, toluene, benzene, octane, isooctane, hexane, cyclohexane, sulfolane, chlorobenzene, dichlorobenzene, or a mixed solution thereof, preferably 30 It is preferable to carry out in a temperature range of from ° C to 250 ° C, more preferably from 60 ° C to 200 ° C.

In addition, as an application of the novel compound, for example, the exemplified compound M-2 and the following compound (B) can be reacted to obtain a polymer compound having a repeating unit as shown in the following (P-2). In the following compound (B), R ^A and R ^B each independently represent a hydroxyl group, a halogen atom (eg, chlorine atom, bromine atom) or an alkoxy group, and R ^C represents an alkylene group, a cycloalkylene group or R ^C in the compound (B) used for the synthesis of the polymer compound having an arylene group and having a repeating unit shown in the following (P-2) is a phenylene group.

  Thus, it can be seen that the novel quinic acid derivative compound of the present invention is useful as a resin raw material.

Examples of the present invention will be described below, but the present invention is not limited to these examples.
[Example 1]
<Synthesis of polyalicyclic compound C>
After putting 100 g of quinic acid (manufactured by Aldrich) and 2.5 L of acetone into a 3 L reaction vessel, 5 mL of sulfuric acid was added dropwise over 1 minute, then 400 g of sodium sulfate was added in portions, and heated at 55 ° C. for 4 hours. The reaction was carried out at reflux.
Thereafter, 100 g of sodium sulfate was added, and the reaction was further performed for 1 hour.
After the temperature was lowered to room temperature (25 ° C.), 200 mL of 9% by mass of sodium bicarbonate water was added, stirred for 15 minutes, and filtered. All the solvents were distilled off by depressurizing the filtrate. Further, the mixture was separated with ethyl acetate and brine, and the ethyl acetate layer was dried over magnesium sulfate, and then the solvent was distilled off again under reduced pressure to obtain 85 g of Compound C having the following structure. (Yield 77%)

<Synthesis of Compound M-1>
4.3 g of the compound C obtained above, 1.3 g of terephthalaldehyde, 40 mL of toluene, and 0.1 g of paratoluenesulfonic acid were added to the reaction vessel and reacted at 100 ° C. The reaction solution became cloudy in about 1 hour. After the reaction solution became cloudy, it was further stirred for 1 hour, allowed to cool to room temperature, and filtered. Solid content was filtered and 4.0g of exemplary compound M-1 of the following structure was obtained.
The structure of exemplary compound M-1 was confirmed by NMR (deuterated solvent: N, N-dimethyl sulfoxide: DMSO). The NMR chart of exemplary compound M-1 is shown in FIG.

As an application example of M-1 which is the obtained compound of the present invention, a synthesis example of a polyester resin using Compound M-1 is shown below.
<Synthesis of Resin P-1>
Compound G-1 (4.5 g) obtained in Example 1 and pyridine (10 mL) were added to a reaction vessel and dissolved, and then a dimethylacetamide (DMAc) solution in which 2.0 g of terephthalic acid chloride was dissolved was added. After reacting at 110 ° C. for 9 hours, it was reprecipitated with methanol and filtered. The solid content separated by filtration was dried under reduced pressure to obtain 5.0 g of a resin P-1 composed of repeating units having the following structure.
As a result of measuring the molecular weight by GPC method using tetrahydrofuran (THF) as a solvent, the weight average molecular weight (Mw) of the obtained resin P-1 was 20,000.

  Thus, the novel quinic acid derivative compound of the present invention is useful for the synthesis of a polymer resin having a rigid skeleton in the main chain.

Claims (1)

The compound represented by the following general formula (I).

(In the general formula (I), ^{R 1} is a single bond, each .R ² and ^{R 3} independently represents an alkylene group or an arylene group, a hydrogen atom, an alkyl group, or an aryl group, ^{R 2} and R ³ may be linked to each other to form a ring structure together with the carbon atom to which each is bonded and R ¹ ).