JP2000229911A - Production of 2-alkyl-2-adamantyl (meth)acrylates - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce the subject compounds useful as a raw material for a coating material, an adhesive, etc., in high yield, at high rate of reaction in a simple step by reacting (meth)acryloyl chloride with alkyladamantanols. SOLUTION: (A) Benzoyl chloride or phosphorus trichloride is reacted with (meth)acrylic acid to provide (meth)acryloyl chloride, which is then reacted with (B) 2-alkyl-2-adamantanols represented by formula I (R2 is an alkyl, and R3 to R6 are each H or an alkyl) to produce (C) 2-alkyl-2-adamantyl (meth) acrylates represented by formula II (R1 is H or methyl). Furthermore, the component A can be reacted with (D) a 2-adamantanone represented by formula III in the presence of an organometallic compound containing R2 [preferably a Grignard reagent, etc., represented by R2MgX (X is a halogen)] to provide the compounds of the component C. Thereby, the compounds of the component C which are conventionally difficult to synthesize are produced in high yield in a simple step, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to 2-alkyl-2-alkyl-2-alkyl-2-phenyl-2-alkyl
The present invention relates to a method for producing adamantyl (meth) acrylates.

[0002]

2. Description of the Related Art 2-Alkyl-2-adamantyl (meth) acrylates have a polymer of Al, Si, F
Because of its excellent coating performance and patterning properties on metal surfaces such as e and Cu, it is useful as a raw material for paints, adhesives, adhesives, resins for inks, resists, etc., and is industrially simple to manufacture A method is needed.

[0003] In general, ester synthesis methods include a transesterification method using a catalyst such as an alkali metal, titanium and tin, an esterification method using an acid catalyst such as sulfuric acid, methanesulfonic acid and paratoluenesulfonic acid, and an esterification method using a fatty acid chloride. (Hereinafter, referred to as an acid chromatography method) and an esterification method using a dehydrating condensing agent such as dicyclohexylcarbodiimide (DCC).

However, for the synthesis of bulky esters such as 2-alkyl-2-adamantyl (meth) acrylates, a transesterification method or a method using a dehydrating condensing agent can provide a sufficient reaction rate due to steric hindrance. I can't. In addition, 2-alkyl-2-adamantanols and 2-alkyl-2-adamantyl (meth) acrylates are acid-decomposable, and in the esterification method using an acid catalyst, the raw materials and products are dehydrated and decomposed, so that high yield is obtained. It is difficult to obtain the target.

In the case of the acid chromatography method using a highly reactive acid chloride, such a bulky ester which is difficult to synthesize can be synthesized. Nozaki et a
l. , Jpn. J. Appl. Phys. 35,528
(1996) describes that 2-methyl-2-adamantyl methacrylate (177080-67-0) was synthesized by an esterification reaction using methacryloyl chloride. JP-A-10-182552 describes that 2-methyl-2-adamantyl methacrylate was synthesized from methacryloyl chloride and 2-adamantanone.

Generally, to synthesize fatty acid chloride, thionyl chloride (B. Helferich, Org. Synth. I, 147 (1941)),
Phosphorus pentachloride (Burcher, Ann.chim.phys. (5) 26,468 (188
2).), Phosgene (F. Reber et al., Helv. Chem. Acta., 37, 4
5 (1954).) Is often used. However, according to the study of the present inventors, fatty acid chloride synthesized by such a method contains an acidic component which is difficult to remove by a simple operation such as distillation. Therefore, 2-alkyl-2-adamantyl (meth) acrylate is used. When used in the synthesis of the compounds, 2-alkyl-2-adamantanol as the raw material or the product 2
-Alkyl-2-adamantyl (meth) acrylates were found to be preferentially dehydrated and decomposed, making it difficult to obtain the desired product. In addition, the said Jpn. J. App
l. Phys and JP-A-10-182552 do not disclose a method for synthesizing methacryloyl chloride used.

As described above, 2-alkyl-2-adamantyl (meth) acrylates have a bulky molecular structure, and no efficient synthesis method has been known because of acid-decomposability.

[0008]

DISCLOSURE OF THE INVENTION The present invention has been made in view of such conventional problems, and is intended to provide 2-alkyl-2-adamantyl (meth) acrylates with a high yield and a high reaction rate. It is an object of the present invention to provide a method of manufacturing with simple steps.

[0009]

The present invention relates to (meth) acryloyl chloride synthesized by reacting benzoyl chloride or phosphorus trichloride with (meth) acrylic acid, and 2-alkyl represented by the following formula (I). The present invention relates to a method for producing a 2-alkyl-2-adamantyl (meth) acrylate represented by the following formula (II), which comprises reacting -2-adamantanol.

[0010]

Embedded image (In the formula, R ² represents an alkyl group, and R ^{3 to} R ⁶ independently represent a hydrogen or an alkyl group.)

[0011]

Embedded image (Wherein R ¹ represents hydrogen or a methyl group, and R ² and R
^{3 to} R ⁶ are as defined above. In addition, the present invention relates to a method in which a (meth) acryloyl chloride synthesized by reacting benzoyl chloride or phosphorus trichloride with (meth) acrylic acid and 2-adamantanone represented by the formula (III) are represented by R ² (R ² has the same meaning as defined above), and a method for producing a 2-alkyl-2-adamantyl (meth) acrylate represented by the formula (II), characterized in that:

[0012]

Embedded image (Wherein, R ^{3 to} R ⁶ have the same meanings as described above.) The present inventor uses (meth) acryloyl chloride obtained by reacting benzoyl chloride or phosphorus trichloride with (meth) acrylic acid. The present invention was found to be able to effectively prevent the dehydration decomposition reaction of 2-alkyl-2-adamantanol as a raw material and / or 2-alkyl-2-adamantyl (meth) acrylate as a product. is there. That is, by reacting benzoyl chloride or phosphorus trichloride with (meth) acrylic acid, (meth) acryloyl chloride having a small amount of acidic components can be easily obtained without requiring a large number of steps or time for purification or the like. By using the (meth) acryloyl chloride thus obtained, 2-alkyl-2-adamantyl (meth), which has been conventionally difficult to produce, is used.
Acrylates can be produced in a simple process with a high yield and a high reaction rate.

[0013]

DETAILED DESCRIPTION OF THE INVENTION In the present invention, 2-alkyl-
2-Adamantyl (meth) acrylates are produced by the following chemical reaction formula (IV) or (V).

[0014]

Embedded image

(In the formula, X represents a halogen, and R ^{1 to} R ⁶ have the same meanings as described above.) First, in the present invention, to produce 2-alkyl-2-adamantyl (meth) acrylates, (Meta)
(Meth) acryloyl chloride is synthesized by reacting acrylic acid with benzoyl chloride or phosphorus trichloride.

The reaction temperature at this time is -20 ° C to 150 ° C.
The reaction temperature is more preferably 30 ° C. to 120 ° C., because the higher the temperature, the faster the reaction rate, and the lower the temperature, the more the side reaction can be suppressed. The reaction is carried out under reduced pressure while removing (meth) acryloyl chloride generated outside the system. This reaction can be carried out without a solvent, but if necessary, an inert solvent may be used. The obtained (meth) acryloyl chloride is preferably purified by distillation under reduced pressure. The boiling point of (meth) acryloyl chloride is 50 ° C to 60 ° C / 1.
It is 8.6 to 20.0 kPa.

Next, the obtained (meth) acryloyl chloride is reacted with a 2-alkyl-2-adamantanol represented by the formula (I) or a 2-adamantanone represented by the formula (III). (Ester synthesis reaction) to obtain 2-alkyl-2-adamantyl (meth) acrylates.

When synthesizing from 2-adamantanones represented by the formula (III), an organometallic compound containing R ² is used. As such an organometallic compound, a Grignard reagent represented by R ² MgX (X represents a halogen) and an alkyllithium compound represented by R ² Li are preferable because of their reactivity and low cost.

In the present invention, the compound represented by the formula (I) 2
In the -alkyl-2-adamantanols and organometallic compounds, the number of carbon atoms of the alkyl group R ² is not particularly limited, but is preferably 1 to 5 carbon atoms from the viewpoint of reactivity, ease of purification, polymerizability, and the like. Also, R ² is preferably linear. In particular, methyl, ethyl, n-propyl,
n-Butyl is preferred.

Further, 2-alkyl- represented by the formula (I)
In the 2-adamantanols and the 2-adamantanones represented by the formula (III), R ^{3 to} R ⁶ represent a group represented by the following formula:
From the viewpoint of purification and the like, hydrogen or an alkyl group having 1 to 5 carbon atoms is preferable, and hydrogen or a linear alkyl group having 1 to 5 carbon atoms is particularly preferable. Specifically, hydrogen, methyl, and ethyl are preferred.

In the ester synthesis reaction using the 2-alkyl-2-adamantanol represented by the formula (I), a base catalyst is used. The base catalyst is not particularly limited as long as it neutralizes the generated acid, and examples thereof include base catalysts used in ordinary acid chromatography such as triethylamine, pyridine and sodium hydrogen carbonate.

The reaction temperature for the ester synthesis reaction is usually -50.
C. to 100.degree. C., preferably 10.degree. As the reaction temperature is lower, side reactions are suppressed. The reaction time is usually 5
It is 40 hours, preferably 10 to 30 hours. As the reaction time is shorter, side reactions are suppressed. If necessary, a solvent inert to the reaction, such as a halogenated hydrocarbon or ether, may be used.

By such a reaction, 2-alkyl-2-adamantyl (meth) acrylates represented by the formula (II) are obtained. This can be further purified by a conventional method such as column chromatography.

[0024]

The present invention will be described below in detail with reference to Examples, but it should not be construed that the invention is limited thereto. The analysis in the examples was performed by gas chromatography (hereinafter referred to as GC) and NMR.

The purity of the product was calculated from the peak area of GC according to the following equation.

Purity (%) = (A / B) × 100 where A is the peak area of the desired product, 2-alkyl-2-adamantyl (meth) acrylates, and B is the sum of the areas of all the peaks. Represent.

The actual yield was calculated by the following equation.

Actual yield (%) = (C / D) × 100 where C is the number of moles of the desired product (calculated by multiplying the weight of the product by the purity and dividing by the molecular weight of the desired product) , D represents the number of moles of the starting material, 2-alkyl-2-adamantanols or (meth) acrylic acid.

Example 1 (Synthesis of methacryloyl chloride) 500 g of methacrylic acid was placed in a glass flask equipped with a stirrer, a dropping funnel, a thermometer, a Liebig condenser, and a receiver under a nitrogen stream.
(5.8 mol), 917 g of benzoyl chloride (6.5 mol)
The mixture was dropped in the order of l). The temperature was raised to 60 ° C. over 1.5 hours, and then the reaction was proceeded under reduced pressure while distilling off the generated methacryloyl chloride. Internal pressure is 17-20kP
a, The internal temperature was controlled at 60 to 100 ° C. After 3 hours, 1000 ppm of MEHQ (hydroquinone monomethyl ether) was added to the distilled methacryloyl chloride, and the mixture was distilled again at 50 to 55 ° C / 18.5 to 20.0 kPa to obtain 308 g of methacryloyl chloride.

(Synthesis of 2-methyl-2-adamantyl methacrylate) In a glass flask equipped with a stirrer, two dropping funnels, a thermometer, and a Dimroth condenser, 400 g of 2-methyl-2-adamantanol (2 .
4 mol) and 1600 ml of methylene chloride, 300 g (2.9 mol) of methacryloyl chloride obtained by the above method was charged into one of the dropping funnels, and 313 g (3.1 mol) of triethylamine was charged into the other. While stirring the inside of the glass flask, triethylamine and methacryloyl chloride were added dropwise over 1 hour while adjusting the amount of triethylamine to methacryloyl chloride so as to be in a small excess. At this time, a slight exotherm was observed. After dropping, 5.8 g of dimethylaminopyridine was added, and 2
Stirring was continued at 0-24 ° C for 20 hours. After washing the reaction solution with 2 L of water, ₃ L of 5% NaHCO ₃ aqueous solution and 10% NaCl
After successively washing with 3 L of an aqueous solution, 30 g of magnesium sulfate was added thereto, followed by drying.
520 g of methyl-2-adamantyl methacrylate were obtained. This was purified by column chromatography on silica gel to give 2-methyl-2-adamantyl methacrylate 4
86 g (2.07 mol) were obtained.

The purity of the obtained 2-methyl-2-adamantyl methacrylate is 98%, and the actual yield is 86% (2-
Methyl-2-adamantanol) and 36% (based on methacrylic acid). The ¹ H-NMR spectrum data of the product was as follows.

¹ H-NMR (CDCl ₃ ) 1.6-2.4 (20H, m), 5.5 (1H, s), 6.1 (1H, s) [Example 2] (Synthesis of methacryloyl chloride) Stirrer, dropping funnel, temperature A glass flask equipped with a total, a Liebig condenser and a receiver was charged with 25 g (0.18 mol) of phosphorus trichloride under a nitrogen stream, and 23.2 g (0.27 mol) of methacrylic acid was added dropwise. The temperature was raised to 60 ° C. over 2 hours, and then, under reduced pressure,
The reaction proceeded while distilling off the methacryloyl chloride produced. Internal pressure is 12-15kPa, internal temperature is 35-40
° C. Methacryloyl chloride 8.8
g was obtained.

(Synthesis of 2-methyl-2-adamantyl methacrylate) A glass flask equipped with a stirrer, a thermometer and a Dimroth condenser was placed in a nitrogen flask under a nitrogen stream.
6.6 g (0.04 mol) of adamantanol, methylene chloride 4
0 ml, and 5 g of methacryloyl chloride (0.048mo
l) and 5.3 g (0.052 mol) of triethylamine were added. While stirring at room temperature, 0.1 g of dimethylaminopyridine was added, and stirring was continued at 20 to 24 ° C for 20 hours. The reaction solution was mixed with 40 ml of water, 40 ml of a saturated aqueous solution of NaHCO ₃ ,
After washing with an aCl aqueous solution (40 ml), 1 g of magnesium sulfate was added and dried, and the filtrate was concentrated to obtain 9.1 g of crude 2-methyl-2-adamantyl methacrylate. This was purified by silica gel column chromatography to obtain 7.5 g (0.032 mol) of 2-methyl-2-adamantyl methacrylate.

The purity of the obtained 2-methyl-2-adamantyl methacrylate is 98%, and the actual yield is 80% (2-
Methyl-2-adamantanol) and 21% (methacrylic acid basis). The ¹ H-NMR spectrum data of the product was as follows.

¹ H-NMR (CDCl ₃ ) 1.6-2.4 (20 H, m), 5.5 (1 H, s), 6.1 (1 H, s)

Example 3 (Synthesis of Methacryloyl Chloride) In a glass flask equipped with a stirrer, a dropping funnel, a thermometer, a Liebig condenser, and a receiver, under a nitrogen stream, 500 g (5.8 mol) of methacrylic acid was added.
l) and 917 g (6.5 mol) of benzoyl chloride were added dropwise in this order.
The temperature was raised to 60 ° C. over 1.5 hours, and then, under reduced pressure,
The reaction proceeded while distilling off the methacryloyl chloride produced. Internal pressure is 17-20 kPa, internal temperature is 60-10
The temperature was controlled at 0 ° C. After 3 hours, 1000 ppm of MEHQ (hydroquinone monomethyl ether) was added to the distilled methacryloyl chloride, and 50 to 55 ° C / 18.
Distillation was again performed at 5-20.0 kPa to obtain 308 g of methacryloyl chloride.

(Synthesis of 2-methyl-2-adamantyl methacrylate) A glass flask equipped with a stirrer, two dropping funnels, a thermometer and a Dimroth condenser was charged with 62 g (2.6 mol) of magnesium and 300 ml of THF under a nitrogen stream. 369 g (2.6 mol) of methyl iodide from the dropping funnel
The THF solution (300 ml of THF) was slowly dropped at a rate keeping the internal temperature at about 40 ° C. After stirring for about 1 hour, a THF solution of 360 g (2.4 mol) of 2-adamantanone (THF 15
00 ml) was added dropwise. 300 g (2.9 mol) of methacryloyl chloride obtained by the above method on one of the dropping funnels,
The other was charged with 313 g (3.1 mol) of triethylamine. While stirring the inside of the glass flask, triethylamine and methacryloyl chloride were added dropwise over 1 hour while adjusting the amount of triethylamine to methacryloyl chloride so as to be in a small excess. At this time, a slight exotherm was observed. After dropping, dimethylaminopyridine 5.8
g was added and stirring was continued at 20-24 ° C for 20 hours. The reaction solution was washed with 2 L of water, 3 L of a 5% NaHCO ₃ aqueous solution,
After washing with 3 L of 0% NaCl aqueous solution, 30 g of magnesium sulfate was added and dried, and the filtrate was concentrated to give crude 2
532 g of -methyl-2-adamantyl methacrylate were obtained. This was purified by silica gel column chromatography to obtain 476 g (2.03 mol) of 2-methyl-2-adamantyl methacrylate.

The purity of the obtained 2-methyl-2-adamantyl methacrylate is 99%, and the actual yield is 85% (2-
Adamantanone standard) and 36% (methacrylic acid standard). The ¹ H-NMR spectrum data of the product was as follows.

¹ H-NMR (CDCl ₃ ) 1.6-2.4 (20 H, m), 5.5 (1 H, s), 6.1 (1 H, s)

Comparative Example 1 (Synthesis of Methacryloyl Chloride) 60.2 g of methacrylic acid was placed in a glass flask equipped with a stirrer, a dropping funnel, a thermometer, a Liebig condenser, and a receiver under a nitrogen stream.
(0.70 mol) and 91.6 g (0.77 mol) of thionyl chloride were added dropwise in this order. After reacting at 50 ° C. for 3 hours, the mixture was allowed to cool to room temperature, and acidic gases such as by-produced hydrogen chloride and sulfur dioxide were removed under reduced pressure at 13 kPa to 26 kPa. In addition, 5
Distillation under reduced pressure at 0-60 ° C / 18.6-20.0 kPa,
34.5 g of methacryloyl chloride were obtained. The actual yield of the obtained methacryloyl chloride was 47% (based on methacrylic acid).

(Synthesis of 2-methyl-2-adamantyl methacrylate) In a glass flask equipped with a stirrer, two dropping funnels, a thermometer, and a Dimroth condenser, 36 g of 2-methyl-2-adamantanol (0.22 g) was placed under a nitrogen stream. mo
l), 150 ml of methylene chloride was charged, and methacryloyl chloride 2 obtained by the above method was added to one of the dropping funnels.
7.2 g (0.26 mol) of triethylamine 2
8.5 g (0.28 mol) were charged. While stirring the inside of the glass flask, triethylamine and methacryloyl chloride were added dropwise over 30 minutes while adjusting the amount of triethylamine to methacryloyl chloride in a small excess. After completion of the dropwise addition, 0.53 g of dimethylaminopyridine was added, and stirring was continued at 20 to 24 ° C for 20 hours. After the reaction solution was washed with 150 ml of water, a saturated aqueous solution of NaHCO _{3 was} added.
After successively washing with 0 ml and 150 ml of a saturated aqueous solution of NaCl, 10 g of magnesium sulfate was added thereto, followed by drying. The filtrate was concentrated to obtain 32 g of a yellow oil.

The oil was analyzed by GC and ¹ H-NMR. As a result, it was found that the starting material was not 2-methyl-2-adamantyl methacrylate, but 2-methyl-2-adamantanol as a starting material and 2-methylene adamantane as a dehydrated product. Was confirmed.

Comparative Example 2 (Synthesis of 2-methyl-2-adamantyl methacrylate) 83 g of 2-methyl-2-adamantanol was placed in a glass flask equipped with a stirrer, thermometer, 10-stage Oldershaw and condenser. 0.5 mol), 500 g of dehydrated MMA (5 mol
l) and 24.9 g (0.1 mol) of dibutyltin oxide were charged. While stirring the inside of the glass flask, the internal temperature is 97-99.
Stirring was continued at 22 ° C. for 22 hours. Upon cooling to room temperature, a large amount of crystals precipitated.

The crystals were analyzed by GC and ¹ H-NMR. As a result, it was confirmed that the crystals were not 2-methyl-2-adamantyl methacrylate, but 2-methyl-2-adamantanol as a raw material.

Comparative Example 3 (Synthesis of Methacryloyl Chloride) A glass flask equipped with a stirrer, a dropping funnel, a thermometer, a Liebig condenser, and a receiver was charged with 25 g (0.12 mol) of phosphorus pentachloride under a nitrogen stream. 10.3 g (0.12 mol) of methacrylic acid was added dropwise. It exothermed to about 40 ° C. After heating at 60 ° C. for 30 minutes, the reaction was allowed to proceed while distilling off the generated methacryloyl chloride under reduced pressure. The internal pressure was controlled at 12 to 15 kPa, and the internal temperature was controlled at 25 to 40 ° C. 12 g of methacryloyl chloride were obtained.

(Synthesis of 2-methyl-2-adamantyl methacrylate) In a glass flask equipped with a stirrer, a thermometer, and a Dimroth condenser, 2-methyl-2-amide was placed under a nitrogen stream.
6.6 g (0.04 mol) of adamantanol, methylene chloride 4
0 ml, and 5 g of methacryloyl chloride (0.048mo
l) and 5.3 g (0.052 mol) of triethylamine were added. While stirring at room temperature, 0.1 g of dimethylaminopyridine was added, and stirring was continued at 20 to 24 ° C for 20 hours. The reaction turned black-brown. When 40 ml of water was added to the reaction solution, heat and smoke were generated. After washing with 40 ml of a saturated aqueous solution of NaHCO _{3 and} 40 ml of a saturated aqueous solution of NaCl, 1 g of magnesium sulfate was added thereto, followed by drying.
7.1 g of oil were obtained. From GC and ¹ H-NMR, it was confirmed that the starting material was 2-methyl-2-adamantanol and the dehydrated product was 2-methylene adamantane.

[0047]

According to the present invention, 2-alkyl-alkyl is useful as a raw material for materials such as paints, adhesives, pressure-sensitive adhesives, ink resins and resists, but has been difficult to produce.
2-adamantyl (meth) acrylates can be produced in a simple process with a high yield and a high reaction rate.

Claims (2)

[Claims] 1. A method of reacting (meth) acryloyl chloride synthesized by reacting benzoyl chloride or phosphorus trichloride with (meth) acrylic acid and a 2-alkyl-2-adamantanol represented by the following formula (I): 2-alkyl-2 represented by the following formula (II):
-A method for producing adamantyl (meth) acrylates. Embedded image (In the formula, R ² represents an alkyl group, and R ^{3 to} R ⁶ independently represent hydrogen or an alkyl group.) (Wherein R ¹ represents hydrogen or a methyl group, and R ² and R
^{3 to} R ⁶ are as defined above. ) 2. A method according to claim 1, wherein (meth) acryloyl chloride synthesized by reacting benzoyl chloride or phosphorus trichloride with (meth) acrylic acid and 2-adamantanone represented by the formula (III) are represented by R ² (R ² Has the same meaning as defined above.). A method for producing 2-alkyl-2-adamantyl (meth) acrylates represented by the formula (II), wherein the reaction is carried out in the presence of an organometallic compound containing Embedded image (In the formula, R ^{3 to} R ⁶ are as defined above.)