JPH11335327A - Production of sesquiterpene acrylate or sesquiterpene methacrylate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce the subject (meth)acrylate from a sesquiterpene in high yield according to a one-stage reactional process by using a heteropoly acid as a catalyst. SOLUTION: (A) A sesquiterpene is reacted with (B) acrylic acid or methacrylic acid by using (C) a heteropoly acid as a catalyst. The component B is preferably a caryophyllene or a cedrene or a neoclovene. In the reaction, a polymerization inhibitor, e.g. hyroquinone is preferably used and the reaction is preferably carried out in an inert solvent such as n-butane in a molar ratio of the components B/A within the range of 0.1-100. Further, the component C is preferably used in an amount within the range of 0.01-100 wt.% based on the component B.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing sesquiterpene acrylate or sesquiterpene methacrylate, and more particularly, to a method for producing sesquiterpene represented by β-caryophyllene, cedrene, neocloben, etc. and acrylic acid or methacrylic acid as a heteropolyacid. To a sesquiterpene acrylate or sesquiterpene methacrylate by reacting the same with a catalyst.

Here, β-caryophyllene acrylate produced according to the present invention is represented by the following general formula (I):
Caryophyllene methacrylate has the general formula (II)
], Cedrene acrylate is represented by the following formula (III):
Cedrene methacrylate has a structure represented by the following formula (IV), neocloben acrylate has a structure represented by the following formula (V), and neocloben methacrylate has a structure represented by the following formula (VI). These are used not only as a photosensitive material as a photoresist used in microfabrication in a manufacturing process of a semiconductor device or the like, but also as a polymer material, an optical material, a paint, and the like.

[0003]

Embedded image

[0004]

Embedded image

[0005]

Embedded image

[0006]

Embedded image

[0007]

Embedded image

[0008]

Embedded image

[0009]

2. Description of the Related Art Conventionally, methods for producing sesquiterpene acrylate or sesquiterpene methacrylate include:
A method is known in which a desired sesquiterpene acrylate or sesquiterpene methacrylate is obtained from a sesquiterpene as a raw material by a two-stage reaction of a hydration reaction and an esterification reaction ("Perfume Chemical Directory", p. 627, Hirokawa Shoten Co., Ltd. Published on January 15, 1968, and as a reference, the fourth edition of Experimental Chemistry Lecture 22, "Organic Synthesis IV"-Acids, Amino Acids, and Peptides, pp. 50-51, Maruzen Co., Ltd., November 30, 1992 Issue).

As the esterification reaction, an esterification reaction between sesquiterpene alcohol and acrylic acid chloride or methacrylic acid chloride or a reaction between sesquiterpene alcohol and acrylic acid anhydride or methacrylic anhydride has been known for a long time. (For reference, 4th edition Experimental Chemistry Lecture 22 “Organic Synthesis IV”
Amino acids / peptides, pp. 50-51, Maruzen Co., Ltd.
Published November 30, 1992).

However, in these methods, sesquiterpene alcohol is used as a raw material. For example, β-caryophyllene alcohol is produced by a hydration reaction of β-caryophyllene, which is obtained only in an extremely low yield. There is a problem that it cannot be performed.

Furthermore, since β-caryophyllene alcohol and the like are tertiary alcohols, it is necessary to use acrylic acid chloride or methacrylic acid chloride for esterification. Acrylic acid chloride or methacrylic acid chloride is very expensive and has problems in handling due to unstable physical properties. In the method using acrylic acid anhydride or methacrylic acid anhydride, the acid anhydride used is expensive, and one molecule of acrylic acid or methacrylic acid is liberated as a by-product of the reaction. It has various disadvantages, such as being extremely difficult to convert to an anhydride for use.

[0013]

The object of the present invention is to provide a β-
Sesquiterpene acrylate or sesquiterpene methacrylate is converted from sesquiterpene to 1 by an addition reaction of sesquiterpene represented by caryophyllene, sedrene and neoclobene with acrylic acid or methacrylic acid.
It is an object of the present invention to provide a method for producing a high-yield reaction in a stepwise reaction process.

[0014]

Means for Solving the Problems The present inventors have studied an efficient method for producing sesquiterpene acrylate or sesquiterpene methacrylate, and have studied a method for producing an excellent addition reaction between sesquiterpene and acrylic acid or methacrylic acid. Focusing on that fact, as a result of intensive studies to solve the conventional problems, the inventors have found that the reaction proceeds efficiently by using a heteropolyacid as a catalyst, and have completed the method of the present invention.

That is, the present invention provides a method for producing sesquiterpene acrylate or sesquiterpene methacrylate, which comprises reacting sesquiterpene with acrylic acid or methacrylic acid using a heteropolyacid as a catalyst. In this case, the sesquiterpene
Each is preferably β-caryophyllene, cedrene or neoclobene.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Raw materials of sesquiterpene and acrylic acid or methacrylic acid used in the present invention do not need to be purified, and those having a general reagent purity can be used as they are.

Β-Caryophyllene, cedrene and neoclobene are represented by the general formula (VII), the general formula (VIII) and the general formula (VIII), respectively.
X)], which is called a sesquiterpene having 15 carbon atoms and is a raw material that can be industrially obtained as a component of plant essential oils and pine resin. Sesquiterpenes other than β-caryophyllene, sedrene and neocloben can also produce the corresponding acrylate or methacrylate by applying the method of the present invention.

[0018]

Embedded image

[0019]

Embedded image

[0020]

Embedded image

The heteropolyacid used in the present invention includes phosphotungstic acid, phosphomolybdic acid, silicotungstic acid, phosphotungstomolybdic acid, keitungstomolybdic acid, phosphovanadotungstic acid, phosphovanadomolybdic acid, and the like. However, the invention is not limited to only these heteropoly acids.

In the present invention, the reaction for synthesizing sesquiterpene acrylate or sesquiterpene methacrylate from sesquiterpene and acrylic acid or methacrylic acid proceeds as an addition reaction. At that time, the reaction is carried out as a homogeneous liquid phase system or a heterogeneous system of solid-liquid or solid-gas phase, and can be carried out under any conditions of normal pressure, reduced pressure, and increased pressure. is there. The reaction system is not particularly limited, but a continuous system is also a batch system,
Alternatively, it can be carried out by a semi-batch method.

In practicing the present invention, a polymerization inhibitor is added to the reaction system. Specifically, hydroquinone, hydroquinone monomethyl ether, methylhydroquinone,
Examples include phenothiazine, but the present invention is not limited to these polymerization inhibitors.

In carrying out the present invention, a solvent which is inert to the catalyst, the polymerization inhibitor, the starting materials and the reaction products can be added. Specifically, aliphatic saturated hydrocarbons such as n-butane, n-pentane, n-hexane, n-heptane, and n-octane, and aromatic hydrocarbons such as benzene, toluene, and xylene are solvent or diluted. Although it can be used as an agent, the present invention is not limited to these.

In carrying out the present invention, the charging ratio of sesquiterpene and acrylic acid or methacrylic acid to be subjected to the reaction is not particularly limited, but the molar ratio of acrylic acid (or methacrylic acid) / sesquiterpene is molar ratio. In the range of 0.1 to 100, but preferably in the range of 0.1 to 100.
It is in the range of 5 to 50. Charge ratio is 0.1 (molar ratio)
If it is less than 100, the reaction progresses slowly, while
If the molar ratio exceeds (mol ratio), the reaction proceeds sufficiently, but is not preferable from an economic viewpoint.

In carrying out the present invention, the amount of the catalyst to be added is 0.01 to 100 with respect to the sesquiterpene.
It is recommended that they be used in a percentage by weight, preferably between 0.1 and 50% by weight. When the amount of the catalyst is less than 0.01% by weight, the progress of the reaction is slow. On the other hand, when the amount exceeds 100% by weight, the reaction proceeds sufficiently but is not preferable from an economic viewpoint. Further, the amount of the polymerization inhibitor to be added is not particularly limited, but 0.01 to the sesquiterpene to be charged.
It is recommended to use 1% by weight, preferably 0.05-0.5% by weight. 0.01% by weight of polymerization inhibitor
If it is less than 1%, the effect of inhibiting polymerization is not obtained.
Even if it exceeds, there is no change in the effect of the inhibition of polymerization.

In carrying out the present invention, the method of charging the catalyst, the polymerization inhibitor and the raw materials is not particularly limited,
The catalyst, polymerization inhibitor, acrylic acid or methacrylic acid and sesquiterpene may be simultaneously charged, or the catalyst may be dissolved or suspended in another solvent and added. Further, before the reaction, acrylic acid or methacrylic acid, a catalyst and a polymerization inhibitor are mixed in advance, and then a sesquiterpene is added, or a sesquiterpene, a catalyst, and a polymerization inhibitor are mixed in advance, and then acrylic acid is added. Alternatively, a method such as adding methacrylic acid can also be performed.

In carrying out the present invention, the reaction temperature is not particularly limited, and the reaction can be carried out in a wide temperature range, preferably at a temperature of 0 to 300 ° C, more preferably at a temperature of 20 to 150 ° C. It is recommended to perform within the scope. When the reaction temperature is lower than 0 ° C., the reaction rate is reduced and the completion of the addition reaction is slowed. On the other hand, when the temperature is higher than 300 ° C., the thermal stability of the raw materials is reduced and polymerization is caused. Absent. The reaction time depends on the amount of the catalyst and the reaction temperature, but becomes extremely short when the amount of the catalyst is large and the temperature is high, and is long when the amount of the catalyst is small and the temperature is low. Usually, it is 5 to 15 hours at 60 to 80 ° C.
After the completion of the reaction, the reaction product is washed with a diluted alkaline aqueous solution,
The target product can be isolated by a separation operation such as distillation under reduced pressure.

The following three methods can be given as specific embodiments for carrying out the present invention. (1) A predetermined amount of a catalyst, a polymerization inhibitor, sesquiterpene and acrylic acid or methacrylic acid are put into a glass flask equipped with a stirrer and a reflux condenser together with a diluent such as a solvent, if necessary, and stirred. The method of reacting under heat. (2) A method in which a predetermined amount of a catalyst, a polymerization inhibitor, sesquiterpene and acrylic acid or methacrylic acid are charged into an autoclave together with an inert gas such as nitrogen or argon if necessary, and the mixture is heated and reacted under shaking or stirring. . (3) In a reactor maintained at a predetermined temperature and a predetermined pressure in advance,
A method in which a predetermined amount of a catalyst, a polymerization inhibitor, a sesquiterpene and acrylic acid or methacrylic acid are continuously introduced together with a diluent such as a solvent, if necessary, to cause a reaction.

After completion of the reaction, the desired product can be isolated from the reaction mixture, for example, as follows. That is, the reaction mixture is poured into n-hexane, and the polymer is removed by precipitation filtration. The recovered supernatant and filtrate are washed with tap water, washed with an aqueous alkali solution such as a 5% by weight aqueous sodium hydrogen carbonate solution, further washed with tap water, and then the low-boiling components are removed under reduced pressure to obtain high purity. A crude product is obtained in high yield. If necessary, the crude product is distilled under reduced pressure to obtain a product with higher purity.

In particular, since the obtained sesquiterpene acrylate or sesquiterpene methacrylate has high polymerizability, it is preferable to distill it in as short a time as possible. At this time, it is preferable to add a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, and phenothiazine, and these may be used alone or in combination of two or more.

The sesquiterpene acrylate or sesquiterpene methacrylate thus obtained is used for applications such as photoresists for KrF and ArF excimer lasers, UV inks, UV paints and coating agents.

[0033]

EXAMPLES The present invention will now be described more specifically with reference to examples, but the present invention is not limited thereto. The parts and percentages in the examples and comparative examples are:
Unless otherwise specified, weight is based.

Example 1 Internal volume of 2,000 equipped with a stirrer and a reflux condenser
In a 0 ml four-necked flask, 406.0 methacrylic acid was added.
g (4.6 mol, purity 98%), hydroquinone 0.1 g.
11 g, 11.6 g of silicomolybdic acid and 1,008.0 g of β-caryophyllene (4.1 mol, purity 82
%), And the mixture was heated and stirred at 70 ° C. for 8 hours to be reacted.
After cooling, the reaction mixture was poured into n-hexane, washed twice with an aqueous solution of 5% by weight of sodium hydrogencarbonate and twice with tap water, and distilled under reduced pressure to obtain 653 g of β-caryophyllene methacrylate (boiling point: 145 ° C. / 3mmHg, β-
The yield was 54% and the purity was 96% based on caryophyllene).

Example 2 Internal volume of 2,000 equipped with a stirrer and a reflux condenser
In a 0 ml four-necked flask, 406.0 methacrylic acid was added.
g (4.6 mol, purity 98%), hydroquinone monomethyl ether 0.12 g, phosphotungstic acid 11.
6 g and 1,008.0 g of β-caryophyllene (4.
(1 mol, purity: 82%), and the mixture was heated and stirred at 70 ° C. for 8 hours to be reacted. After cooling, the reaction mixture was poured into n-hexane, and added with an aqueous solution of 5% by weight of sodium hydrogen carbonate.
After washing twice with tap water and performing distillation under reduced pressure, β-
605 g of caryophyllene methacrylate (boiling point 145 ° C.
/ 3 mmHg, 50% yield based on β-caryophyllene,
(Purity 96%).

Example 3 Internal volume of 2,000 equipped with a stirrer and a reflux condenser
In a 0 ml four-necked flask, 340.0 g of acrylic acid
(4.6 mol, purity 98%), methylhydroquinone 0.11 g, silicotungstic acid 12.1 g and β-
1,008.0 g (4.1 mol, purity 82%) of caryophyllene was added, and the mixture was heated and stirred at 70 ° C. for 8 hours to be reacted. After cooling, the reaction mixture was poured into n-hexane,
After washing once with an aqueous solution of sodium hydrogencarbonate by weight and twice with tap water, distillation was performed under reduced pressure to obtain 599 g of β-caryophyllene acrylate (boiling point: 138 ° C./3 mmHg, β
-52% yield and 96% purity based on karyophyllene).

Example 4 Internal volume of 2,000 equipped with a stirrer and a reflux condenser
In a 0 ml four-necked flask, 340.0 g of acrylic acid
(4.6 mol, purity 98%), methylhydroquinone 0.12 g, phosphotungstic acid 12.3 g and β-
1,008.0 g (4.1 mol, purity 82%) of caryophyllene was added, and the mixture was heated and stirred at 70 ° C. for 8 hours to be reacted. After cooling, the reaction mixture was poured into n-hexane,
After washing once with an aqueous solution of sodium hydrogencarbonate by weight and twice with tap water, 576 g of β-caryophyllene acrylate (boiling point 138 ° C./3 mmHg, β
-Yield 50%, purity 96% based on caryophyllene).

Comparative Example 1 Internal volume of 2,000 equipped with a stirrer and a reflux condenser
In a 0 ml four-necked flask, 20 g of water, 10 g of p-toluenesulfonic acid, 300 g of toluene and 1,008.0 g of β-caryophyllene (4.1 mol, purity 82
%), And heated and stirred at 100 ° C. for 1 hour to cause a reaction. After cooling, the reaction mixture was washed once with an aqueous solution of 5% by weight of sodium hydrogen carbonate and once with tap water, and then distilled under reduced pressure to obtain crude β-caryophyllene alcohol, which was recrystallized with n-hexane. As a result, 117.0 g of β-caryophyllene alcohol was obtained as an intermediate material. Next, a stirrer and a reflux condenser were attached 2,
In a 000 ml four-necked flask, 117.0 g of this β-caryophyllene alcohol (0.5 mol, purity 96
%), 1,400 g of pyridine and 110.0 g (0.95 mol, purity 95%) of methacrylic acid chloride were added thereto, and the mixture was reacted by heating and stirring at 60 ° C. for 4 hours. After cooling, the reaction mixture was diluted with toluene, washed once with an aqueous solution of 5% by weight of sodium hydrogen carbonate and once with tap water, and then distilled under reduced pressure to obtain 72 g of β-caryophyllene methacrylate (boiling point 145 ° C./3 mmHg, β -6% yield and 96% purity based on caryophyllene).

Comparative Example 2 The same method as in Comparative Example 1 was used except that 96.0 g (0.95 mol, purity 95%) of acrylic acid chloride was used instead of methacrylic acid chloride. As a result, β
-Caryophyllene acrylate 69 g (boiling point 138 ° C /
3 mmHg, 6% yield and 96% purity based on β-caryophyllene).

COMPARATIVE EXAMPLE 3 Internal volume of 2,000 equipped with a stirrer and a reflux condenser
In a 0 ml four-necked flask, 406.0 methacrylic acid was added.
g (4.6 mol, purity 98%), hydroquinone 0.1 g.
11 g, sulfuric acid 15.0 g and β-caryophyllene 1,
008.0 g (4.1 mol, purity 82%)
The mixture was heated and stirred at 0 ° C. for 12 hours to be reacted. After cooling, the reaction mixture was poured into n-hexane, washed twice with an aqueous solution of 5% by weight of sodium hydrogen carbonate and twice with tap water, and distilled under reduced pressure to obtain β-caryophyllene methacrylate 2
66 g (boiling point 145 ° C./3 mmHg, yield 22% based on β-caryophyllene, purity 96%) were obtained.

Comparative Example 4 Internal volume of 2,000 equipped with a stirrer and a reflux condenser
In a 0 ml four-necked flask, 406.0 methacrylic acid was added.
g (4.6 mol, purity 98%), hydroquinone 0.1 g.
11 g, p-toluenesulfonic acid 18.0 g and β-
1,008.0 g (4.1 mol, purity 82%) of caryophyllene was added, and the mixture was heated and stirred at 70 ° C. for 24 hours to be reacted. After cooling, the reaction mixture was poured into n-hexane,
2 times with an aqueous solution of 5% by weight of sodium hydrogen carbonate and 2 times with tap water
After washing twice, vacuum distillation was performed to obtain 242 g of β-caryophyllene methacrylate (boiling point: 145 ° C./3 mmH
g, β-Caryophyllene, yield 20%, purity 96
%).

[0042]

According to the present invention, β-caryophyllene,
Sesquiterpene acrylate or sesquiterpene methacrylate can be produced in a single step from sesquiterpenes such as sedrene and neocloben in a high yield, and their industrial value is high.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // C07B 61/00 300 C07B 61/00 300

Claims (4)

[Claims] 1. A method for producing sesquiterpene acrylate or sesquiterpene methacrylate, comprising reacting sesquiterpene with acrylic acid or methacrylic acid using a heteropolyacid as a catalyst. 2. The method for producing sesquiterpene acrylate or sesquiterpene methacrylate according to claim 1, wherein the sesquiterpene is β-caryophyllene. 3. The method for producing sesquiterpene acrylate or sesquiterpene methacrylate according to claim 1, wherein the sesquiterpene is sedrene. 4. The method for producing sesquiterpene acrylate or sesquiterpene methacrylate according to claim 1, wherein the sesquiterpene is neocloben.