JP2923316B2 - Adamantyl dicrotonate derivative - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel adamantyl dicrotonate derivative, which has cross-linking polymerizability and is useful as a raw material for functional polymer materials and the like. .

2. Description of the Related Art Certain adamantane unsaturated ester derivatives are already known. For example, Japanese Patent Application Laid-Open No. Sho 60-1000053 discloses diallyl adamantanedicarboxylate. JP-A-63-33350 discloses an adamantyl mono (meth) acrylate derivative developed by the present applicants. Polymers containing these derivatives as main monomer components not only have excellent heat resistance, but also have high hardness, excellent impact resistance, and many characteristics such as a large light refractive index. Therefore, it is expected to be used as various optical materials including heat-resistant plastic materials and lenses for glasses.

That is, for example, when attention is paid to the use as a plastic lens, an acrylic resin that has been widely used conventionally,
Plastic lenses made of polycarbonate resin, allyl diglycol carbonate resin, polystyrene resin, etc. have the disadvantages that they have poor heat resistance and low light refractive index compared to glass lenses, The plastic lens used as a component not only has extremely high heat resistance than conventional plastic lenses, but also has a high level of light transmittance and a large light refractive index. There are great expectations for improving performance.

On the other hand, most of the polymer materials currently used are 1,1-disubstituted ethyl-type polymers represented by the following formula, Most of the adamantane unsaturated ester polymer is also
It belongs to the 1,1-disubstituted ethylene type. In contrast, a 1,2-disubstituted ethylene polymer represented by the following formula is Studies have been made in some parts because of its unique physical properties such as higher rigidity and higher softening point than the 1,1-disubstituted ethylene polymer. However, crotonic acid ester derivatives have poor reactivity compared to methacrylic acid ester derivatives corresponding to this derivative, particularly having versatile radical polymerizability, and the study thereof is far behind.

[Problems to be Solved by the Invention] Under these circumstances, the present inventors have been actively developing research for practical use mainly of crotonic acid ester derivatives and polymers thereof. As one of the achievements, an adamantyl monocrotonate derivative represented by the following general formula [A], which is a novel industrially useful crotonic acid ester derivative, has been developed, and a patent application has already been filed (Japanese Patent Application No. Hei. 175021: Unpublished).

[In the formula, R ³ , R ⁴ and R ⁵ are the same or different and represent hydrogen, lower alkyl group, halogen or hydroxyl group. The present invention aims to provide industrially useful derivatives such as crotonic acid esters by applying the technology of the invention of the prior application.

[Means for Solving the Problems] The present invention provides an adamantyl dicrotonate derivative represented by the following general formula [I].

[Wherein R ¹ and R ² are the same or different and represent hydrogen, a lower alkyl group, a halogen or a hydroxyl group. [Action] In the above formula [I], the lower alkyl group among the substituents represented by R ¹ and R ² includes methyl, ethyl, propyl,
Butyl is the most common, and methyl is the most common. Examples of the halogen include Br, Cl, F, and I.
Most preferred is Br, Cl.

Representative examples of the adamantyl dicrotonate derivative represented by the above general formula are as follows.

The adamantyl dicrotonate derivatives as shown in the above (A) to (F) are prepared by using, for example, adamantane or lower alkyl-substituted adamantane as a starting material and the following (1)
It can be produced through a reaction as shown in (3).
The lower alkyl-substituted adamantane will be described below by taking methyl-substituted adamantane as a representative.

(1) Bromination of adamantane or methyl-substituted adamantane The monobromination reaction can be easily carried out, for example, by heating and reacting anhydrous bromine with adamantane (or a methyl-substituted product thereof) in a nitrogen atmosphere.
The tri- or tetrabromination reaction can be efficiently carried out by heating and reacting anhydrous bromine with adamantane (or a methyl-substituted product thereof) in the presence of a Lewis acid catalyst such as aluminum bromide or boron bromide. After completion of the reaction, excess bromine is distilled off, followed by extraction with carbon tetrachloride or the like, and recrystallization with methanol or the like to obtain a high-purity brominated product.

(2) Hydroxylation of brominated product Di, tri- or tetrabrominated adamantane (or a methyl-substituted product thereof) is reacted with concentrated sulfuric acid in the presence of silver sulfate or hydrolyzed with hydrochloric acid, for example.
It can be changed to di-, tri- or tetrahydroxylated adamantane (or its methyl substitution).

Since these hydroxylated compounds usually precipitate as solids in the reaction system, they can be obtained as high-purity substances by filtering off after the reaction and recrystallizing with n-hexane or the like.

(3) Esterification of di-, tri- or tetra-hydroxylated product Di-, tri- or tetra-hydroxylated product is converted to sulfuric acid or p-
An adamantyl dicrotonate derivative can be obtained by heating and reacting the hydroxylated product with an equimolar amount or more of crotonic anhydride in the presence of a catalyst such as toluenesulfonic acid. This reaction proceeds without a solvent since crotonic anhydride is in a liquid state, but it is of course possible to carry out the reaction in a solvent such as toluene, benzene or cyclohexane. After completion of the reaction, the reaction mixture is neutralized with an alkali, and the resulting precipitate is removed by filtration and the solvent is distilled off under reduced pressure to obtain an adamantyl dicrotonate derivative (target substance).

Also, when hydroxyadamantyl dicrotonate is reacted with phosphorus tribromide, the hydroxyl group is substituted with bromo, and it can be derived to bromoadamantyl dicrotonate (the target substance).

The adamantyl dicrotonate derivative of the present invention can be produced, for example, by the method as described above. However, in the present invention, the production method itself is not limited at all, and in addition to the above method, various known methods are appropriately applied. Of course, they can also be produced, and they are all included in the technical scope of the present invention as long as they satisfy the constitutional requirements of the general formula [I].

The two crotonyl groups in the adamantyl dicrotonate derivative thus obtained have a three-dimensional polymerization activity, and the -OH and halogen introduced into the adamantane nucleus have the usual reaction activity as a hydroxyl group and a halogen group. It can be effectively used as a raw material for various organic synthesis such as polymer materials, agricultural chemicals, pharmaceuticals, etc., but the most practical is the polymerizable monomer utilizing the polymerization activity of the crotonyl group. It is a use as. That is, the adamantyl dicrotonate derivative is polymerized in the presence of an anion catalyst such as Grignard reagent, metal alkyl, lithium sodium hydride or the like to give a polymer having specific physical properties. This adamantyl dicrotonate derivative can be homopolymerized, but the polymer usually has a three-dimensional structure and becomes a high molecular substance insoluble in a solvent, which makes it difficult to form a film or sheet. The most effective method is a method in which a small amount is copolymerized with another copolymerizable monomer as a crosslinkable copolymer component. And when this adamantyl dicrotonate derivative is copolymerized, the glass transition point of the copolymer rises and becomes harder, and properties such as lowering the polymerization shrinkage and increasing the photorefractive index are given. Various lenses for contact lenses, camera lenses, etc., prisms, photosensitive materials for recording, optical fiber materials such as optical fibers, materials for optical members such as video discs and compact discs that use transmission and reflection of light, gas separation This is extremely useful as a film or the like. Particularly, the effect of improving the optical properties (especially light transmittance and light refractive index) of a polymer obtained by using a derivative in which a halogen is introduced into an adamantane nucleus as a main raw material is particularly excellent, and is excellent in suitability for use as an optical material. A copolymer can be obtained. Although the heat resistance of the copolymer varies depending on the degree of polymerization and the copolymerization ratio of the adamantyl dicrotonate derivative, the melting point and the surface hardness are higher than those of general vinyl polymers and acrylic polymers. It is also expected to develop applications as a conductive plastic material or a heat-resistant film forming material.

In addition, by selecting a copolymerizable monomer to be combined with the adamantyl dicrotonate derivative, paints, adhesives, pastes, hair styling, plasticizers, varnishes, paper and fiber sizing agents, building material wallpaper and bookbinding paste It has been described earlier that a wide range of development is expected as a raw material and the like, and that the derivative can be used as a raw material for producing agrochemicals and pharmaceuticals by utilizing the reactivity of the derivative.

[Example] Example 1 (Production of adamantyl dicrotonate) One glass corvette with a water separator has 1,3-
80 g (0.476 mol) of dihydroxyadamantane, 200 g (1.30 mol) of crotonic anhydride, 2.6 ml (0.048 mol) of sulfuric acid (97%) were added, and the mixture was heated under reflux (100 → 115 ° C.) and stirred to advance the esterification reaction. The reaction was completed in about 30 minutes.

The reaction product is neutralized with a 10% aqueous NaOH solution, and the precipitate is separated by filtration. Then, the aqueous layer and the oil layer are separated, and the oil layer is developed by column chromatography (eluent: n-hexane / chloroform) packed with silica gel. Adamantyl dicrotonate (target substance) in the form of a colorless and transparent liquid (116 g (0.38
2 mol) (yield 80.4%, specific gravity d ₂₀ = 1.1144, refractive index n _d ²⁴ =
1.5142) was obtained.

NMR spectrum: ¹³ C-NMR (CDCl ₃ , TMS standard δ) 17.7 (q), 31.2 (d), 34.8 (t), 40.1 (t), 45.4
(T), 124.1 (d), 143.3 (d), 165.2 (s) IR spectrum: As shown in FIG.
Peak derived from O to 1715 cm ^-1, a peak derived from the CO-O-C is in 1180 cm ^-1, also peaks derived from C = C is 97
It clearly appears at 0 cm ^-1 and 1650 cm ^-1 .

Example 2 (Production of dimethyl adamantyl dicrotonate) One glass corvette with a water separator has 1,3-
150 g of dimethyl-5,7-dihydroxy-adamantane (0.7 g
65 mol), 353 g of crotonic anhydride (2.29 mol), sulfuric acid (97
%) Of 3.1 ml (0.057 mol), and the mixture was reacted for about 4 hours while stirring under heating (70 → 99 ° C.) to carry out an esterification reaction.

After neutralizing the reaction product with a 10% aqueous NaOH solution, the resulting precipitate is filtered off, then the aqueous layer and the oil layer are separated, and the oil layer is developed by column chromatography packed with silica gel (developing agent: n-hexane). / Chloroform) to separate and purify the target substance. 195 g (0.587 mol) of dimethyl adamantyl dicrotonate (target substance) as a colorless transparent viscous liquid (yield 76.7
%, Specific gravity d ₂₀ = 1.0551, and refractive index n _d ²⁴ = 1.5031).

NMR spectrum: ¹³ C-NMR (CDCl ₃ , TMS standard δ) 17.7 (q), 29.0 (d), 34.6 (s), 43.9 (t), 46.2
(T), 49.4 (t), 81.0 (s), 124.0 (d), 143.3
(D), 165.2 (s) IR spectrum: As shown in FIG.
The peak derived from O is 1715 cm ^-1 , the peak derived from CO-OC is 1175 cm ^-1 , and the peak derived from C = C is 97
It clearly appears at 0 cm ^-1 and 1660 cm ^-1 .

Example 3 Production of 5-hydroxyadamantyl dicrotonate 20 g (0.109 mol) of 1,3,5-trihydroxyadamantane, 39 g (0.253 mol) of crotonic anhydride, 0.4 ml (7.3 mmol) of sulfuric acid (97%) were placed in the same kolben used in Example 1. The esterification reaction was carried out by heating (100 → 135 ° C.) with stirring, and the reaction was completed in about 45 minutes. When this product is treated in the same manner as in Example 1, a colorless transparent viscous liquid 5
-17.6 g of hydroxyadamantyl dicrotonate (0.055
Mol) (50.5% yield).

NMR spectrum: ¹³ C-NMR (CDCl ₃ , TMS standard δ) 17.7 (q), 29.5 (d), 38.8 (t), 42.7 (t), 44.3
(T), 47.9 (t), 70.2 (s), 80.2 (d), 123.7
(S), 143.9 (d), 165.2 (s) IR spectrum: As shown in FIG.
Peak derived from O to 1715 cm ^-1, a peak derived from the CO-O-C is in 1180 cm ^-1, also peaks derived from C = C is 97
0cm ^-1, 1655cm ^-1, OH group has appeared clearly in the vicinity of 3450 cm ^-1.

Example 4 (Production of 5,7-dibromoadamantyl dicrotonate) (4-1) Production of 5,7-dihydroxyadamantyl dicrotonate In a flask similar to that used in Example 1, 10 g (0.05 mol) of 1,3,5,7-tetrahydroxyadamantane, 23 g (0.149 mol) of crotonic anhydride, 0.2 ml (3.7 mmol) of sulfuric acid (97%) were added. Then, the mixture was heated and stirred (100 → 150 ° C.) to advance the esterification reaction, and the reaction was completed in about 110 minutes. After the reaction product is neutralized with a 10% aqueous NaOH solution, a precipitate formed is filtered off, and the aqueous layer is extracted with a mixed solvent of ethyl acetate / tertiary butyl alcohol, and subjected to column chromatography packed with silica gel (developing agent = Separation and purification with ethyl acetate / tertiary butyl alcohol) yielded 5,7-dihydroxyadamantyl dicrotonate.

This compound was identified by IR and NMR spectrum analysis as in (1) above.

(4-2) Conversion to bromo derivative 5,7-dihydroxyadamantyl dicrotonate 5g
(0.015 mol), 120 ml of dehydrated methylene chloride solvent and 2.0 g (7.4 mmol) of phosphorus tribromide at room temperature under nitrogen stream.
Allowed to react for minutes.

After the reaction, the mixture was subjected to column chromatography packed with silica gel (developing agent: n-hexane / chloroform).
Purification using 5,7-dibromoadamantyl dicrotonate, a colorless transparent viscous liquid, 3.8 g (8.2 mmol)
(54.7% yield).

NMR spectrum: ¹³ C-NMR (CDCl ₃ , TMS standard δ) 17.8 (q), 42.4 (t), 49.3 (t), 54.0 (s), 56.2
(T), 78.3 (s), 122.9 (d), 145.0 (d), 164.6
(S) IR spectrum: As shown in FIG.
The peak derived from O is 1720 cm ^-1 , the peak derived from CO-OC is 1170 cm ^-1 , and the peak derived from C = C is 97
0cm ^-1, clearly appeared to 1655cm ^-1.

Example 5 (Production of 5,7-dichloroadamantyl dicrotonate) Using 5,7-dihydroxyadamantyl dicrotonate as a raw material, chlorination using phosphorus pentachloride under a nitrogen stream in 50 ml of dehydrated carbon tetrachloride gives 5 , 7-Dichloroadamantyl dicrotonate was obtained. Identification of the target is the same as above
Performed by NMR and IR spectral analysis.

[Effects of the Invention] The present invention is constituted as described above. Since this derivative has excellent reaction activity, it can be widely used as a cross-linkable polymerizable monomer, and can be used in various fields such as agricultural chemicals and pharmaceuticals. Can be effectively used as a raw material for organic synthesis.

[Brief description of the drawings]

1 to 4 are IR spectra of the adamantyl dicrotonate derivative obtained in the example.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C07C 69/56 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] An adamantyl dicrotonate derivative represented by the following general formula [I]: [Wherein R ¹ and R ² are the same or different and represent hydrogen, a lower alkyl group, a halogen or a hydroxyl group. ]