JPH0338548A - Adamantyl monocrotonate derivative - Google Patents

Abstract

NEW MATERIAL:A compound expressed by the formula (R<1> to R<3> are H, lower alkyl, halogen or OH). USE:A raw material for functional polymer materials etc. PREPARATION:Adamantane is reacted with anhydrous bromine in a nitrogen atmosphere to provide a monobrominated derivative or the adamantane is thermally reacted with the anhydrous bromine in the presence of a Lewis acid catalyst, such as AlBr3, to afford a di-, tri- or tetrabrominated derivative, which is subsequently reacted with concentrated sulfuric acid in the presence of silver sulfate or hydrolyzed with hydrochloric acid to afford a hydroxylated adamantane. The resultant hydroxylated adamantane is then dissolved in a solvent, such as toluene, and thermally reacted with crotonic acid in the presence of a catalyst, such as sulfuric acid or p-toluenesulfonic acid, to provide the subject substance.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel adamantyl monocrotonate derivative, which has polymerizability and is useful as a raw material for functional polymer materials and the like.

[Prior Art] Certain unsaturated adamantane ester derivatives are already known; for example, diallyl adamantane dicarboxylate is disclosed in JP-A-60-100537. Furthermore, JP-A-63-33350 discloses adamantyl mono(meth)acrylate derivatives developed by the present applicants. Polymers containing these derivatives as main monomer components have excellent heat resistance. It not only has high hardness and excellent impact resistance, but also has many characteristics such as a high optical refractive index, so it is used for heat-resistant plastic materials and glasses lenses. It is expected that it will be used as a variety of optical materials.

In other words, if we focus on applications for plastic lenses, for example, plastic lenses made of conventionally widely used acrylic resins, polycarbonate resins, allyl diglycol carbonate resins, polystyrene resins, etc. have poor heat resistance compared to glass lenses. Although they have the disadvantage of having a low optical refractive index, plastic lenses containing derivatives such as those mentioned above as main monomer components have extremely superior heat resistance compared to conventional plastic lenses. However, since it has a high level of light transmittance and a large optical refractive index, there are great expectations for improving the performance of plastic lenses.

On the other hand, most of the polymer materials currently used are 1,1-disubstituted ethylene type polymers represented by the following formula, and most of the adamantane unsaturated ester polymers are
．． It belongs to the 1-disubstituted ethylene type. On the other hand, the 1,2-disubstituted ethylene polymer represented by the following formula exhibits unique physical properties such as being more rigid and having a higher softening point than the 1,1-disubstituted ethylene polymer described above. , some research is underway. However, crotonic acid ester derivatives have poor reactivity compared to their corresponding methacrylic acid ester derivatives, which have radical polymerizability and are particularly the most versatile, and research on them has lagged considerably behind.

[Problems to be Solved by the Invention] Under these circumstances, the present inventors have been actively researching the practical use of crotonic acid ester derivatives and their polymers as C. The purpose of this study is to provide tM with a new industrially useful rotonate ester derivative.

[Means for Solving the Problems] The present invention provides an adamantyl monocrotonate derivative represented by the following formula [1].

[In the formula, R1, R2, and R3 are the same or different and hydrogen,
represents a lower alkyl group, halogen or hydroxyl group] [Function] Among the substituents represented by R1, R2, and R3 in the above formula [01], examples of the lower alkyl group include methyl, ethyl, propyl, butyl, etc. The most common is methyl. In addition, halogens include Br, C1, F, I
are mentioned, but the most preferred are Br and CI.

Representative examples of adamantyl monocrotonate derivatives represented by the above formula are as follows.

The adamantyl monocrotonate derivatives shown in (A) to (L) above are produced using, for example, adamantane or lower alkyl-substituted adamantane as a starting material, and the following (1)
It can be produced through the reactions shown in ~(3). As the lower alkyl-substituted adamantane, methyl-substituted adamantane will be described below as a representative example.

(1) Bromination of adamantane or methyl-substituted adamantane The monobromination reaction can be easily carried out, for example, by heating anhydrous bromine and adamantane (or its methyl-substituted product) in a nitrogen atmosphere. The reaction is carried out by heating anhydrous bromine and adamantane (or its methyl substituted product) in the presence of a Lewis acid catalyst such as aluminum bromide or boromine bromide (after the completion of the reaction, which can proceed more efficiently). After distilling off excess bromine, the product is extracted with carbon tetrachloride or the like, and further recrystallized with methanol or the like to obtain a highly pure brominated product.

(2) Brominated hydroxylated brominated adamantane (or its methyl substituted product) can be prepared by reacting it with concentrated sulfuric acid in the presence of silver sulfate or by hydrolyzing it with hydrochloric acid. Substituent) C can be changed.

Since the hydroxylated product usually precipitates as a solid in the reaction system, it can be obtained as a highly pure product by filtering it off after the reaction and recrystallizing it with n-hexane or the like.

(3) Esterification of hydroxylated product The hydroxylated product is dissolved in a solvent such as toluene, benzene, or cyclohexane, and heated to react with crotonic acid in the presence of a catalyst such as sulfuric acid or p-)luenesulfonic acid to dehydrate the theoretical amount. The adamantyl monocrotonate derivative can be obtained by terminating the reaction when the reaction reaches 0. After the reaction is completed, the adamantyl monocrotonate derivative is neutralized with an alkali, the formed precipitate is filtered off, and the solvent is distilled off under reduced pressure. A nate derivative (target product) is obtained.

Furthermore, when hydroxyadamantyl monocrotonate is reacted with phosphorus tribromide, the hydroxyl group is substituted with bromine, and bromoadamantyl monocrotonate (the target product) can be derived.

The adamantyl monocrotonate derivative of the present invention can be produced, for example, by the method described above, but since the production method itself is not limited at all in the present invention, in addition to the method described above, various known methods may be applied as appropriate. Of course, it is also possible to manufacture it by using the above-mentioned formula [I], and all of them are included in the technical scope of the present invention as long as they satisfy the constituent requirements of the above-mentioned formula [I].

The crotonyl group in the adamantyl monocrotonate derivative obtained in this way has polymerization activity, and the 10H and halogen introduced into the adamantane nucleus have reaction activity as normal hydroxyl and halogen groups. Therefore, it can be effectively used as a raw material for various organic syntheses such as polymer materials, agricultural chemicals, and medicines, but the most practical use is as a polymerizable monomer that utilizes the polymerization activity of the crotonyl group. It is. That is, this adamantyl monocrotonate derivative is polymerized in the presence of an anionic catalyst such as a Grignard reagent, a metal alkyl, or lithium sodium hydride to give a polymer exhibiting unique physical properties.

Moreover, this adamantyl monocrotonate derivative can be homopolymerized, and 2 ft! By copolymerizing the above, or copolymerizing with a copolymerizable monomer other than the derivative, a copolymer with further improved physical properties can be obtained depending on the use and purpose.

In other words, the above-mentioned adamantyl crotonate derivative alone or copolymer has a glass transition point that is extremely high compared to conventional optical plastic materials and compared to the aforementioned adamantyl methacrylate derivative alone or copolymer. It is colorless and transparent, has a high surface hardness, has a large optical refractive index, and has a very low polymerization shrinkage rate.As it has many physical properties, it is especially suitable for use in glasses, contact lenses, camera lenses, etc. Various lenses, prisms, photosensitive materials for recording, optical 1A fiber materials such as optical fibers, video discs, compact discs, etc.
It is extremely useful as a material for optical members that utilize reflection, gas separation membranes, etc. In particular, the optical properties (especially optical IFI suitability and optical refractive index) of polymers obtained using derivatives in which halogen is introduced into the adamantane nucleus as the main raw material are particularly excellent, and their suitability as optical materials is very (high). In addition, the heat resistance of this polymer varies depending on the degree of polymerization, etc., but it has a higher melting point and surface hardness than general vinyl polymers and acrylic polymers, and this melting point and hardness are due to a small amount of polyfunctionality. It can be further improved by copolymerizing a copolymerizable monomer.Therefore, the development of applications as a heat-resistant plastic material or a material for forming a heat-resistant film is also expected.

In addition, by selecting copolymerizable monomers that can be combined with adamantyl monocrotonate derivatives, paints, adhesives, pastes, hair styling products, plasticizers, varnishes, sizing agents for paper and fibers, wallpaper for building materials, and glue for bookbinding can be used. As mentioned earlier, it is expected to be widely developed as a food ingredient, and by utilizing the reactivity of the derivative, it can be used as a raw material for the production of agricultural chemicals, pharmaceuticals, etc.

[Example] LLLL (Manufacture of adamantyl monocrotonate) 400 g of cyclohexane IJZ and 1-hydroxyadamantane were placed in a one-sided glass colben equipped with an ice separator.
(2.63 mol), 500 g (5.81 mol) of crotonic acid, and 15 ml (260 main mol) of sulfuric acid (97%) were heated under reflux (70-115°C) and stirred to proceed with the esterification reaction. The reaction was terminated when the amount of water collected in the water separator reached the theoretical amount of dehydration (about 11 hours).

After neutralizing the reaction product with a 10% NaOH aqueous solution, the resulting precipitate was filtered off, and then cyclohexane was removed under reduced pressure. When the obtained liquid was distilled under reduced pressure to remove unreacted substances, a colorless transparent liquid adamantyl crotonate (target object) 484 was obtained.
g (2.20 mol) (boiling point: 95°C/1 amHg, yield 83.7%, specific gravity d 20 = 1.0581. Refractive index n
424=1.5062) was obtained.

The 1C-NMR spectrum of this product is shown in FIG.

13C-NMR (CDC1s, TMS standard δ) 17.4
(q), 30.6 (d), 36.0 (t)
, 41.1 (t) , 79.4 (S) , 124.4
(d), 142.3 (d), 164.9 (S
) The IR spectrum is as shown in Figure 2, with a peak derived from C=O of the ester group at 1720 cm-' and a peak derived from C-C at 970 cm-' and 16
It appears clearly at 50 cm-'.

d (Production of dimethyladamantyl monocrotonate) In a glass kolben equipped with a water separator, cyclohexane 250111.1-hydroxy-3,5-dimethyladamantane 150 g (0.64 mol), crotonic acid 121.3 g (1,41 mol), sulfuric acid (97%
) 3.7 ml (64 mmol) was heated under reflux and stirred (80-100°C) to advance the esterification reaction, and when the amount of water collected in the water separator reached the theoretical amount of dehydration ( The reaction was completed in about 7 hours).

After neutralizing the reaction product with a 10% NaOH aqueous solution, the resulting precipitate was filtered off, and then cyclohexane was removed under reduced pressure. The resulting liquid was distilled under reduced pressure to remove unreacted materials, yielding 127.2 g (0.51 mol) of 3.5-dimethyladamantyl monocrotonate (target product) as a colorless transparent liquid (boiling point: 123.5°C). 10.85 Hg, yield 80.1%
, ratio 1! d2゜÷1.0250, refractive index n d24=
1.4930) h'c get lale.

The 13C-NMR spectrum of this product is shown in FIG.

”C-NMR (CDCIs, TMS standard δ) 17.5
(Q), 29.8 (d), 30.1 (d),
33.6 (t) , 39.6 (t) , 42.5 (
d) , 47.1 (t) , 50.4 (t) , 8
0.8 (s).

124.4 (d), 142.4 (d), 16
5.1 (S) Also, the IR spectrum is as shown in Figure 4, and the peak derived from C←O of the ester group is at 175
0c"1, and the peak derived from C4C is 980-1
It clearly appears at 00100O' and 1700cm-'.

Togobanyu Org, 5ynth,, coll, vol, Is, 2
59 (1988), 50 g of 1-hydroxyadamantane was added to a 2It four-bottle flask.
(0,329 mol), a mixture of 1.5 mol/hexane solution of n-butyllithium 250 ml (0,4 mol) and ether 500a+1 and stirred in a water bath for 15 minutes. After adding diluted crotonic acid chloride (42 g (0.40 mol)) dropwise, the mixture was stirred at room temperature for 20 hours.

The resulting reaction solution was washed four times with 50 ml of saturated brine, the ether was distilled off under reduced pressure, and then distilled under reduced pressure to obtain a colorless transparent liquid adamantyl monochrome nate in a yield of about 50%.

1 1,3-dihydroxyadamantane 18.3g (109
mmol), 15 g (174 mmol) of crotonic acid, 150 ml of toluene. Ti! 0.5 ml of the acid was placed in a 50 C) ml glass colben equipped with a water separator and reacted for 5 hours at reflux temperature (110° C.).

After the reaction was completed, the reaction mixture was neutralized with a 10% aqueous NaOH solution, the generated precipitate was filtered off, and then toluene was removed under reduced pressure. The obtained liquid was purified by column chromatography using silica gel (developing agent: n-hexane-chloroform) for 11 minutes.
19.8 g (78.6 mmol) of 3-hydroxyadamantyl monocrotonate, a colorless and transparent viscous liquid (yield: 72
．． 1%) was obtained.

Further, 9.3 g (39.5 t mol) of this 3-hydroxyadamantyl monocrotonate was added to 150 ml of dehydrated methylene chloride solvent. After a zero reaction using 5.4 g (20 mmol) of phosphorus tribromide and reacting at room temperature under a nitrogen stream for 30 minutes,
The mixture was subjected to column chromatography using silica gel (developing agent: n-hexane-chloroform) to obtain 5.8 g (18.4 mmol) of 3-bromoadamantyl monocrotonate as a colorless transparent viscous liquid (yield 4B, 6%
) Force 5 was obtained.

The C-NMR spectra of these products are shown in Section 5.
Figure 6 shows the IR spectrum in Figure 7.8.

(5-1) Production of monocrotonate of trihydroxyadamantane H H Using 1,3,5-trihydroxyadamantane as a raw material and monoesterifying it with crotonic acid in the same manner as in Example 1, 3,5-dihydroxyadamantyl monochrome Tonate was obtained. The product was identified by IR spectrum and NMR spectrum analysis in the same manner as above.

(5-2) Conversion to bromine derivative 3,5-dibromoadamantyl crotonate was obtained in the same manner as in Example 4 using 3,5-dihydroxyadamantyl monocrotonate as a raw material. Identification of the object is “C-N”
Performed by MR and IR spectral analysis.

Example 6 (Production of 3,5,7-tribromoadamantylcrotonate) (6-1) Production of 3,5,7-trihydroxyadamantyl monocrotonate 1. Using 3,5,7-tetrahydroxyadamantane as a raw material Then, monoesterification with crotonic acid was carried out according to the method shown in Example 4 to obtain 3°5.7-trihydroxyadamantyl monocrotonate.

Identification of this compound was performed using IR and N
This was done by MR spectral analysis.

(6-2) Conversion to bromine derivative 3. Using 5.7-trihydroxyadamantyl monocrotonate as a raw material, bromine conversion of the hydroxyl group is performed according to (5-3) of Example 5, 3,5゜7-Dolipromoadamantyl monocrotonate was obtained. The product was identified by IR and NMR spectroscopy in accordance with (1-4) above.

and practice group (manufacture of 3-bromo-5,7-dimethyladamantyl monocrotonate) (7-1) Manufacture of 3.5-dimethyl-7-hydroxyadamantyl monocrotonate 1.3-dimethyl-5 , 7-dihydroxyadamantaf 40g (204 mmol), crotonic acid 21.1g
(245 mmol), toluene 400 a + 1° sulfuric acid 2
．． 1s+1 was placed in a 500a+1 glass colben equipped with a water separator and reacted at reflux temperature (110°C) for 7 hours. After the reaction was completed, it was neutralized with a 10% NaOH aqueous solution, and the formed precipitate was filtered out. The toluene was then removed under reduced pressure.

The resulting liquid was separated and purified by column chromatography using silica gel (developing agent: n-hexane-chloroform) to obtain 44.0 g (167 mmol) of 3.5 dimethyl-7-hydroxyadamantyl monocrotonate, a colorless and transparent viscous liquid. ) (yield 81.9%) was obtained.

(7-2) Conversion to bromine derivative 10 g (37.9 mmol) of 3.5-dimethyl-7-hydroxyadamantyl monocrotonate was dehydrated in 150 ml of methylene chloride solvent. Phosphorus tribromide 5.1 g (19
After the reaction, the mixture was subjected to column chromatography using silica gel (developing agent: n-hexane-chloroform).
5.0 g (15
, 3 mmol) (yield 40.4%).

The C-NMR spectra of these products are shown in Section 9.
See Figure 10! The R spectrum is shown in Figures 11 and 12.

Touhou Banhei (Production of 3-chloroadamantyl monocrotonate) Using 3-hydroxyadamantyl monocrotonate as a raw material, chlorination using phosphorus pentachloride in a nitrogen stream in 50 ml of dehydrated carbon tetrachloride produces 3-chloroadamantyl monocrotonate. Adamantyl monocrotonate was obtained.

In addition, the product identification is! Performed by R and NMR spectral analysis.

1 (Production of 3,5-dichloroadamantyl monocrotonate) Using 3.5-dihydroxyadamantyl monocrotonate as a raw material, chlorination with phosphorus pentachloride in the same manner as in Example 8 above yields 3.5- Dichloroadamantyl monocrotonate was obtained. The target object is identified using NM as described above.
Performed by R and IR spectral analysis.

Production of 3.5.7-trihydroxyadamantyl monocrotonate and phosphorus pentachloride in the same manner as in Example 8 above. After chlorination, 3,5°7-trichloroadamantyl monocrotonate was obtained. Identification of the object is
The analysis was carried out by NMR and IR spectroscopy as described above.

[Effects of the Invention] The present invention is constructed as described above, and since this derivative has excellent reaction activity, it can not only be widely used as a polymerizable monomer, but also used in various applications such as agricultural chemicals and medicines. It can be effectively used as a raw material for organic synthesis.

[Brief explanation of drawings]

Figure 1.3.5.7.9.10 is the NMR spectrum of the adamantyl monocrotonate derivative obtained in the example.
．． Figure 4.6.8.11.12 shows the IR spectrum of the same derivative.

Claims (1)

[Claims] (1) An adamantyl monocrotonate derivative represented by the following general formula [I]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] [In the formula, R^1, R^2, and R^3 are the same or different and represent hydrogen, a lower alkyl group, a halogen, or a hydroxyl group. ]