WO2001055063A1

WO2001055063A1 - Novel bisadamantane compounds, process for preparing the same, and novel biadamantane derivatives

Info

Publication number: WO2001055063A1
Application number: PCT/JP2001/000355
Authority: WO
Inventors: Shunji Katai; Shintaro Suzuki
Original assignee: Idemitsu Petrochemical Co., Ltd.
Priority date: 2000-01-25
Filing date: 2001-01-19
Publication date: 2001-08-02

Abstract

2-(2-Methyladamantyl)-2'-adamantylmethane compounds of the general formula (I) [wherein Y?1 and Y2¿ may be the same or different from each other and are each hydrogen, halogeno, hydrocarbyl, hydroxyl, hydrocarbyloxy, carboxyl, or hydrocarbyloxycarbonyl], and 3,3'-dialkoxycarbonyl-1,1'-biadamantane derivatives of the general formula (VI) [wherein R is alkyl having 2 to 8 carbon atoms]. The above novel bisadamantane compounds and the above novel biadamantane derivatives are excellent in heat resistance, water resistance and optical properties.

Description

Description New (bis) adamantane-based compound, process for producing the same, and new biadamantane derivative technical field

The present invention relates to a novel (bis) adamantane-based compound which is a novel 2- (2-methyladamantyl) -12'-adamantylmethane-based compound, a method for producing the same, and a method for producing 3,3, dialkoxycarbone. '—Relates to a new biadamantane derivative that is biadamantane. More specifically, a 2- (2-methyladamantyl) -12'-adamantyl methane compound, which has excellent heat resistance, water resistance and optical properties, and is useful as a component in coating materials and optical materials, etc. The present invention relates to a novel biadamantane derivative which is well-produced, and which has excellent solubility in various solvents while maintaining the properties of biadamantans. Landscape technology

Conventionally, adamantanes have a very stable carbon skeleton and exhibit a unique function, so that they can be used for various applications.In particular, due to their optical characteristics and heat resistance, optical disk substrates, optical fibers, It is used for lenses and the like (Japanese Unexamined Patent Publication No. Hei 9-310207, Japanese Unexamined Patent Publication No. Hei 6-304504).

However, the above-mentioned adamantane is mainly composed of a polymer having a monoadamantane compound as a monomer, and a substance having two or more adamantane skeletons and a derivative thereof are known, but the adamantane skeleton has a methylene group. As a matter of fact, little is known about asymmetric bis-adaman-based compounds linked via a bond.

In addition, biadamantanes having two or more adamantane skeletons are more expensive. Heat resistance and unique functions are expected.

However, conventionally known biadamantans, especially 3,3'-dimethoxycarbone and 1'-biadamantane (U.S. Pat. No. 3,342,880) are poorly soluble, It was a major constraint in developing various applications

Disclosure of the invention

Under such circumstances, the present invention provides a novel asymmetric bisadamanone-based compound having an adamantane skeleton bonded via a methylene group, which is excellent in heat resistance, water resistance, optical properties, and the like; An object of the present invention is to provide a novel biadamantane which is excellent in water resistance and optical properties and is excellent in solubility in various solvents.

The present inventors have conducted intensive studies to achieve the above object, and as a result, a 2- (2-methyladamantyl) -12′-adamantylmethane compound having a specific structure has not been published in the literature. It is a novel compound that has excellent heat resistance, water resistance, optical properties, etc., and that it can be efficiently produced by a specific process. Also, an alkoxycarbonyl group having 3 or more carbon atoms (carbon number Biadamantane having a specific structure having two or more alkoxy groups) is a novel compound that has not been published in the literature and has excellent heat resistance, water resistance, optical properties, etc., and excellent solubility in various solvents. Was found. The present invention has been completed based on such findings.

That is, the present invention

(1) General formula (I)

(Wherein, and Υ ² are each a hydrogen atom, a halogen atom, a hydrocarbyl group A hydroxyl group, a hydrocarbyloxy group, a carboxyl group or a hydrocarboxycarbonyl group, which may be the same or different.

)) 2-(2-methyladamantyl) 1 2 '-adamantyl methane compound,

(2) Method for producing 2- (2-methyladamantyl) -1′-adamantyl methane after dehydrating and dimerizing 2-methyl-2-adamantanol in the presence of an acid catalyst, followed by hydrogenation ,

(3) 2-(2-Methyladamantyl) — General formula (II) for halogenating adamantylmethane

(Wherein, at least one of X ¹ and X ² is a halogen atom and the remainder is a hydrogen atom.) A method for producing a 2- (2-methyladamantyl) -1′-adamantyl methyl halide , as well as

(4) Starting from 2- (2-methyladamantyl) -1 2'-adamantyl methane halide represented by the above general formula (Π), at least one halogen atom is converted to a hydrocarbyl group, a hydroxyl group or a hydroxyl group. A 2-, (2-methyladamantyl) _2'-adamantyl methane derivative, which is converted into a hydrocarbyloxy group, a carboxyl group or a hydrocarboxycarbonyl group;

(5) General formula (VI)

(Wherein, R represents an alkyl group having 2 to 8 carbon atoms.) Derivatives

Is provided. BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a 'Η-NMR spectrum chart of the compound obtained in Example 1 ₍ FIG. 2 is a' ³ C-NMR spectrum chart of the compound obtained in Example 1) ₍ FIG. 3 is an infrared analysis chart of the compound obtained in Example 1.

Figure 4 'is _t Figure 5 is .eta. NMR spectrum chart of the compound obtained in Example 2' of the compound obtained in Example 2 is ³ C-NMR spectrum chart ₍ FIG. 6 is an infrared analysis chart of the compound obtained in Example 1. BEST MODE FOR CARRYING OUT THE INVENTION

The 2- (2-methyladamantyl) -1 2'-adamantyl methane compound of the present invention has the following general formula (I)

This is a novel compound having a structure represented by the following, which has not been published in any literature.

In the above general formula (I), Y ¹ and Y ² each represent a hydrogen atom, a halogen atom, a hydrocarbyl group, a hydroxyl group, a hydrocarbyloxy group, a carboxy group or a hydrocarbylcarbonyl group. Here, preferred examples of the halogen atom include a chlorine atom, a bromine atom and an iodine atom.

Examples of the hydrocarbyl group include an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, and an aralkyl group having 7 to 15 carbon atoms. The alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various benzyl groups, various hexyl groups, various octyl groups, various decyl groups, cyclopentyl groups, cyclohexyl groups, methylcyclohexyl groups, etc. No. The aryl group having 6 to 15 carbon atoms and the aralkyl group having 7 to 15 carbon atoms may have a substituent such as a lower alkyl group on the ring, and examples thereof include a phenyl group, a tolyl group, Xylyl, naphthyl, methylnaphthyl, benzyl, methylbenzyl, phenethyl, naphthylmethyl and the like.

Examples of the hydrocarbyl group constituting the hydrocarbyloxy group and the hydrocarbyloxycarbonyl group include the same as those described above for the hydrocarbyl group.

Y ¹ and Y ² may be the same or different from each other. 2- (2-methyladamantyl) -12′-adamantylmethane represented by the above general formula (I) Among the compounds, particularly, in the general formula (I), 2- (2-methyladamantyl) -1′-adamantylmethane in which Y ¹ and Y ² are both hydrogen atoms, and the general formula (I) In which at least one of Y ¹ and Y ² is a hydroxyl group and the remainder is a hydrogen atom (that is, both are hydroxyl groups, or one is a hydroxyl group and the remainder is a hydrogen atom). Damantyl) — 1 '—a Damantimyl hydroxide is preferred.

The method for producing the 2- (2-methyladamantyl) -12'-adamantyl methane compound represented by the general formula (I) of the present invention is not particularly limited, but the method of the present invention shown below is provided. If it follows, it can manufacture efficiently.

First, a method for producing 2- (2-methyl adamantyl) -12'-adamantyl methane, which is a compound of the general formula (I) where Y '= Y ² = Η, will be described. According to the method of the present invention, the 2- (2-methyladamantyl) -1 -'- adamantyl methane can be obtained by the following reaction formula (a)

(IV)

(V)

It can be manufactured according to

That is, 2-methyl-2-adamantanol (111) is dehydrated and dimerized in the presence of an acid catalyst to obtain a compound (IV), and then hydrogenated to give 2- (2-methyladamantyl) One 2'-adamantylmethane (V) is obtained.

In the dehydration-dimerization reaction, the presence of a solvent is not essential, but a solvent can be used if necessary. The solvent is not particularly limited as long as it is inert to the reaction and is capable of dissolving the raw materials and products, and examples thereof include aliphatic hydrocarbon compounds such as hexane, heptane, and octane. Aromatic hydrocarbon compounds such as benzene, toluene and xylene are preferably used.

Examples of the acid catalyst include mineral acids such as sulfuric acid and hydrochloric acid, as well as heteropoly acids, zeolites, and ion exchange resins. These acid catalysts are based on 2-methyl-_ 2 Adaman evening Nord raw materials usually used in the proportion of ~ 1 0 weight ^_0/0.

The raw material concentration in the reaction system is not particularly limited, but the catalyst concentration is preferably about 0.1 to 5% by weight.

The temperature in the dehydration-dimerization reaction is selected in the range of usually room temperature to 150 ° C, preferably 50 to 10 ° C. The reaction time depends on the reaction temperature, type and amount of catalyst, etc. The time is usually 1 to 24 hours, preferably about 1 to 3 hours.

The compound (IV) thus dehydrated and dimerized is isolated according to a conventional method, and is subjected to the next hydrogenation reaction.

In this hydrogenation reaction, the presence of a solvent is not essential, but a solvent can be used if necessary. The solvent is not particularly limited as long as it is inert to the reaction and is capable of dissolving the raw material and the product. Examples thereof include aliphatic hydrocarbon compounds such as hexane, heptane, and octane; Aromatic hydrocarbon compounds such as benzene, toluene and xylene are preferably used.

In this hydrogenation reaction, a known hydrogenation catalyst represented by, for example, a Pt catalyst, Pd / C, Ru / C, Raney Ni or the like is used as a catalyst. These hydrogenation catalysts are usually used in an amount of about 1 to 10% by weight based on the raw materials.

The raw material concentration in the reaction system is not particularly limited, but the hydrogenation catalyst concentration is preferably about 0.1 to 5% by weight.

The temperature in the hydrogenation reaction is selected in the range of usually room temperature to 250 ° C, preferably 100 to 200 ° C. The hydrogen pressure is usually selected in the range of 0.5 to 5 MPa, preferably in the range of 2 to 3 MPa. Further, the reaction time depends on the reaction temperature, the hydrogen pressure, the type of the catalyst, and the like, and cannot be unconditionally determined, but is usually 1 to 1 hour, preferably about 1 to 6 hours.

The product hydrogenated in this manner is isolated according to a conventional method, and further purified to give the desired 2- (2-methyladamantyl) -12'-adamantyl monomer (V). can get.

Next, in the general formula (I), at least one of halogen atoms of Y 'and Y ^2, the remaining being a hydrogen atom (i.e., both a halogen atom or one remaining is a hydrogen atom with halo gen atom,) The method for producing 2- (2-methyladamantyl) -1′-adamantyl methane halide will be described. According to the method of the present invention, the 2- (2-methyladamantyl) -1′-adamantyl methane halide is represented by the following reaction formula (b)

(Wherein, at least ^one of X ¹ and X ² is a halogen atom and the remainder is a hydrogen atom).

That is, by halogenating 1- (2-methyladamantyl) -'- adamantylmethane (V), 2- (2-methyladamantyl) 1-2'-adamantylmethane halide (11) is obtained.

As the halogenation method, various methods can be used depending on the type of halogen. Here, the case where the halogen is bromine will be described.

In this bromination reaction, a solvent is not essential, but a solvent can be used if necessary. As the solvent, for example, a polar solvent such as methylene chloride or carbon tetrachloride is preferably used. If necessary, a Lewis acid such as aluminum trihalide or boron tribromide can be used as a catalyst. The temperature of the bromination reaction is usually from room temperature to about 60 ° C. A reaction time of about 1 to 10 hours is sufficient. The product brominated in this manner is isolated according to a conventional method. When this product is used as a raw material and a bromine atom in a molecule is converted to another group, it can be used as a crude product without purification. Purified according to the method. Thus, the desired 2- (2-methyladamantyl) -2′-adamantyl methane bromide [in the general formula (10, at least one of X ′ and X ² is a bromine atom and the remaining Are hydrogen atoms, that is, both are bromine atoms, or one is a bromine atom and the other is a hydrogen atom). Furthermore, according to the method of the present invention, 2_ (2-meth) represented by the general formula (Π) Ladamantyl) Starting from 1'2'-adamantyl methane halide, converting at least one halogen atom into a hydrocarbyl, hydroxyl, hydrocarbyloxy, carboxyl or hydrocarbyloxycarbonyl group, The 2- (2-methyladamantyl) -12'-adamantylmethane derivative of the present invention having the above-mentioned various groups in the molecule can be produced.

In this case, as the raw material halide, the bromide obtained as described above is preferable from the viewpoint of reactivity.

Next, as the compound represented by the general formula (11), 2- (2-methyladamantyl) -12′-adamantylmethane bromide (hereinafter sometimes simply referred to as a raw material bromide) is used. A method of converting at least one bromine atom into the above-described various groups and introducing the group will be described.

(1) Introduction of hydrocarbyl group and hydrocarbyloxy group

By reacting R, MgX, R'Li or R 'RLi (R' is a hydrocarbyl group and X is a halogen atom) with a raw bromide in the presence of a polar solvent such as tetrahydrofuran, 2- ( 2-methyl-adamantyl) 1 2'-adamantyl Can introduce a hydrocarbyl group or hydrocarbyloxy group into methane

(2) Introduction of hydroxyl group

Hydrolysis of the raw bromide in the presence of a hydrogen halide scavenger such as an organic base such as pyridine, triethylamine or dimethylformamide at a temperature of about 100 to 200 ° C for about 1 to 24 hours Thus, a hydroxyl group can be introduced into 2— (2-methyladamantyl) -1 2′-adamantylmethane.

(3) Introduction of carboxyl group

In the presence of a mineral acid such as sulfuric acid or hydrochloric acid, a heteropoly acid, zeolite, an acid catalyst such as an ion exchange resin, and a cocatalyst such as a Cu compound, the hydroxyl obtained in the above (2) is used. A compound having a carboxylic group is reacted with a carboxylating agent such as carbon monoxide and formic acid to carbonylate the hydroxyl group at the hydroxyl group to give 2- (2-methyladamantyl) -1 2'-adamantyl. Carboxyl groups can be introduced into methane.

In this carbonylation reaction, a solvent is not essential, but if necessary, a hydrocarbon solvent such as hexane can be used.

(4) Introduction of hydrocarbyloxycarbonyl group

In the presence of a mineral acid such as sulfuric acid or hydrochloric acid, a heteropoly acid, zeolite, an ion exchange resin or the like, an R'OH (R ' The esterification of the carboxyl group can introduce a hydrocarbyloxycarbonyl group into 2- (2-methyladamantyl) -1′-adamantylmethane.

In this esterification reaction, a solvent is not essential, but an appropriate solvent can be used if necessary.

The compound of the above (3) may be treated with thionyl chloride, phosphorus pentachloride or the like to synthesize acid chloride, and then reacted with R'OLi.

The biadamantane derivative of the present invention has the following general formula (VI)

In the above general formula (VI), R represents an alkyl group having 2 to 8 carbon atoms (linear or branched alkyl group), specifically, an ethyl group, an η-propyl group, an isopropyl group, an η-butyl group, an isobutyl group , Sec-butyl, tert-butyl, n-amyl, isoamyl, n-hexyl, n-heptyl, n-octyl or isooctyl. The two Rs in the general formula (VI) are usually the same, but may be different depending on the case.

The biadamantane derivative of the present invention is 3,3′-dialkoxycarbone-l-biadamantane represented by the general formula (VI), and specifically, 3,3′-diethoxycarbonyl_1, One viadamantane, 3, 3 'di η-propoxycarbone 1, one viadamantane, 3, 3' diisopropoxycarbone 2, 1, one viadamantane, 3, 3 '— di η-butoxycarbo Two-way 1 'one-viadamantane, 3, 3'-diisobutoxycarbone 1, 1, 1' one-viadamantane, 3, 3 'di-t-butoxycarbone two-one, one-viadamantane, 3, 3'- Diamiloxycarbone and one viadamantane.

The method for producing the biadamantane derivative of the present invention is not particularly limited.

A esterification reaction of 3,3'-dicarboxy-1,1-biadamantane represented by the formula and an alcohol represented by the general formula R〇H (where R is the same as described above) in the presence of an acid catalyst Or the formula (VIVI) in which the carboxyl group is changed to an acid halide in place of 3,3'-dicarboxy-biadamantane of the above formula (VI I)

(Wherein, X represents a halogen atom.) 3, 3'-dihalogenocarbon There is a method of reacting viadamantane with an alcohol represented by the above general formula ROH.

Examples of the acid catalyst include mineral acids such as sulfuric acid and hydrochloric acid; organic acids such as p-toluenesulfonic acid; and Lewis acids such as boron fluoride ether. Examples of reagents for converting (COOH) to acid halide (COX) include phosphoryl chloride, thionyl chloride, phosphorus pentachloride, and phosphorus trichloride.

The 3,3′-dicarboxy-1,1,1′-biadamantane represented by the formula (VII) used as a raw material here is biadamantane, 3,1,3′-biadamantane or 3,3′-dihydroxy It is synthesized by using 1,1'-biadamantane as a starting material and reacting it with formic acid in the presence of a strong acid such as fuming sulfuric acid, concentrated sulfuric acid or concentrated nitric acid, or in a carbon monoxide atmosphere. Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1

(1) Dehydration dimerization of 2-methyl-2-adamantanol

In a 200-milliliter four-necked flask equipped with a stirrer, condenser, and Dean-Stark trap, 2-methyl-1-adamantanol 41.5 g (250 millimoles), sulfuric acid 5. 0 g and 120 milliliters of n-heptane were charged and heated in an oil bath to reflux the solvent and react for 4 hours while dehydrating.

After the completion of the reaction, the reaction solution was poured into 100 g of water, neutralized with an aqueous solution of sodium carbonate, and the product was extracted with n-heptane. The oil layer was washed with water. Thereafter, n-heptane was distilled off with a dry evaporator to obtain 29.9 g of a crude product. Next, the crude product was passed through a silica gel column, recrystallized, and dried. 6.2 g of solid A1 were obtained.

(2) Hydrogenation

A 300 milliliter autoclave was charged with 15.0 g of the solid A obtained in (1) above, 3.0 g of 5% by weight Pd / C, and 150 milliliter of η-octane, and charged with 150 ml of hydrogen. It was pressurized to MPa and reacted at 20 ° C. for 5 hours.

After the completion of the reaction, the solvent was distilled off from the reaction solution from which the catalyst had been filtered off by means of a tally evaporator to obtain 15.0 g of a crude product. The crude product was recrystallized and dried to obtain 11.2 g of solid B.

(3) Identification of solid B

Various analyzes were performed on the solid B obtained in the above (2). The analysis results are as follows.

(A) Mass spectrometry by gas chromatography (CI method)

Molecular ion (M-1): 2 9 7

(Mouth) Mass spectrometry by gas chromatography (EI method)

m / e (spectral strength (%)): 149 (100), 107 (21.75), 93 (39.25), 79 (55.21) )

(C) Proton nuclear magnetic resonance (—NMR) analysis values measured using double-mouthed form as a solvent (see Figure 1)

δ (Ή / ρ pm): 0.907, 1.01 8, 1.29 2, 1.450, 1.573, 1.693, 1.746, 1.804, 1. 9 5 7, 2. 1 0 7

(2) Isotopic carbon nuclear magnetic resonance ( ¹³ C—N MR) analysis using double-mouthed form as a solvent (see Figure 2)

δ ( ¹³ C / p pm): 23.27, 27.88, 27.95, 28.12, 28.41, 32.33, 33.47, 3 3.55, 34.5 8, 36.27, 38.37, 38.76, 39.50, 39.65, 39.98, 42.20

(E) Infrared analysis (Fourier transform infrared absorption spectrum analysis (FT-IR), Diffuse reflection method) (See Fig. 3)

Absorption (cm- '): 2994. 4, 2902. 4, 2848. 8 (CH 3, CH 2, CH); 1 44 9. 1, 1 377. 4, 1 3 52. 0 (CH 3, CH 2 , CH)

From these analysis results, solid B

It was confirmed to be 2— (2-methyladamantyl) —2′-adamantylmethane represented by

Example 2

(1) Bromination, hydrolysis

In a 100 milliliter four-necked flask equipped with a cooling tube and a dropping funnel, 6.0 g (20 millimoles) of the solid B obtained in Example 1 was charged, and the mixture was added dropwise while stirring the inside with a stirrer. 25 g of bromine was slowly dropped from the funnel. After completion of the dropwise addition, the mixture was heated to 60 ° C. in an oil bath and reacted for 4 hours.

After the reaction was completed, the reaction solution was cooled, poured into a flask containing 100 g of ice and 50 milliliter of carbon tetrachloride, and excess bromine was treated with sodium hydrogen sulfite. After that, extraction with carbon tetrachloride, washing with water and evaporation of the solvent were performed to obtain 12.2 g of a crude bromide. Next, the crude bromide, 50 ml of pyridine and 18 ml of water were charged into a 100 ml autoclave and reacted at 150 ° C. for 6 hours. After completion of the reaction, sodium carbonate was added to the reaction solution to decompose pyridine monohydrobromide generated in the reaction. Then, after the solid was filtered off, pyridine and water were distilled off, then toluene was added and distilled off, and finally water was added and distilled off to obtain a crude product. Next, this crude product was passed through a silica gel column, the solvent was distilled off, and the residue was dried to obtain 4.1 g of solid C. (2) Identification of solid C

Various analyzes were performed on the solid C obtained in (1) above. The analysis results are as follows.

(A) Mass spectrometry by gas chromatography (CI method)

Molecular ion (M— 1): 3 1 3

(Mouth) Mass spectrometry by gas chromatography (EI method)

m / e (spectral strength ()): 312 (27.31), 165 (100), 95 (81.43), 79 (25.1 1), 4 1 (28.9.2)

(C) ¹ H-NMR analysis value measured with double-mouthed form as a solvent (see Fig. 4) δ (Ή / ρ pm): 0.946, 0.976, 1.374, 1.3 9 9, 1.5 80, 1.66 1, 1.17 17, 1.79 9, 1.994, 8.80 (OH, 1 1)

8.80 ppm disappears by adding D ₂₀

(2) ' ³ C-NMR analysis value measured using double-mouthed form as a solvent (see Fig. 5) δ ( ¹³ C / p pm): Not displayed because there are many peaks.

(E) Infrared analysis (FT-IR, diffuse reflection method) (See Fig. 6)

Absorption (cm- Li: 33 7 0.8 (hydroxyl), 2 9 1 2. 8, 2 8 54. 2, 1 4 5 1. 5, 1 3 5 1. 8 (CH 3, CH 2, CH)

From these analysis results, solid C

It is presumed to be a mixture of isomers of 2- (2-methyladamantyl) -1 2'-adamantyl methane hydroxide represented by

Example 3 (1) Synthesis of 3, 3'-n-propoxycarbone 1'-biadamantane

Dissolve 0.5 g (1.65 millimoles) of 3,3'-dihydroxy-dihydroxy-1-biadamantane in 5 milliliters of concentrated sulfuric acid and slowly add 1 milliliter of formic acid at 20 ° C. It was dropped. Thereafter, the mixture was further stirred for 2 hours. The reaction solution was poured into ice, the precipitate was collected by filtration, dissolved in an aqueous sodium hydroxide solution, and filtered to remove insoluble components. The filtrate was again made strongly acidic with hydrochloric acid to precipitate a carboxylic acid, which was collected by filtration, washed with water until the washing solution became neutral, then washed with methanol, and further dried under vacuum. To the 3,3'-dicarboxy-one-viadamantane obtained above, add 10 milliliters of thionyl chloride, reflux for 3 hours to form a homogeneous solution, and then distill off excess thionyl chloride under reduced pressure. Then, 10 milliliters of dehydrated n-propanol was added thereto, and the mixture was refluxed for 1 hour. Thereafter, methanol was added to the reaction solution, followed by filtration. The filtrate was concentrated, hexane was further added, and the insoluble matter was filtered. The mixture was concentrated, acetone was added thereto, and the insoluble matter was filtered, followed by concentration. The yield of the obtained product was 0.6 g, and the purity by gas chromatography was 99.7%.

The product was analyzed as follows. The results are as follows.

① Mass spectrometry by gas chromatography (CI method)

Molecular ion (M-1): 4 4 3

② Mass spectrometry by gas chromatography (EI method)

m / e (spectral strength (%)): 442 (10.2), 355 (18.40), 221 (100), 179 (48.31) ), 1 3 3 (4 1.5 3)

(3) Proton nuclear magnetic resonance analysis (II—NMR) (solvent: double-mouthed form)

δ CH / p pm): 0.869 (t, 6 H), 1.4 to 90 (m, 28 H), 2.0 25 (m, 4 H), 3.943 (t , 4H)

④ Isotopic carbon nuclear magnetic resonance analysis ( ¹³ C-NMR) (solvent: heavy-mouthed form) 5 ¹³ C / p pm): 1 0.34 1, 2 2. 0 3 8, 28. 6 0 7, 3 4. 3 85, 3 6.90, 36. 9 49, 3 8. 6 7 1, 4 1.71 3, 6 5.6.2 5, 1 78.2 1 0

一 Fourier transform infrared absorption analysis (FT-IR, diffuse reflection method)

Absorption (cm— '): 1 726.6 Carbonyl compound (ester)

As a result of the above analysis, the obtained product was identified to be 3,3'-di-n-open-mouthed oxycarbone-1,1-biadamantane represented by the following formula (IX).

(2) Solubility of 3,3, di-n-propoxycarbone-one viadamantane

0.5 g of 3,3, -di-n-propoxycarbone 1,1'-biadamantane obtained in the above (1) was mixed with 1 milliliter of 1-heptanone and 1 milliliter of 2-hexanone. Toluene, 1 milliliter of methyl lactate, 1 milliliter of ethyl lactate, 1 milliliter of ethylene glycol methyl ether acetate, or 1 milliliter of propylene glycol methyl acetate, all of which were easily added. Dissolved.

Comparative Example 1

(1) Synthesis of 3,3, dimethoxycarbone 1'-biadamantane In Example 3, methanol was used in place of n-propanol, methanol was added to the reaction solution, and the filtrate was filtered. Except for concentrating and recrystallizing with methanol, the same procedure as in Example 3 was carried out to obtain 0.35 g, 98.5% purity of 3,3'-dimethoxycarbone and 1'-biadamantane. I got

(2) Solubility of 3,3'-dimethoxycarbone 1,1,1-biadamantane 0.1 g of 3,3'-dimethoxycarbone 1,1'-biadamantane obtained in (1) above, 1-milliliter of 2-hexanone, 1-milliliter of methyl lactate, and lactic acid When added to 1 milliliter of ethylene glycol, 1 milliliter of ethylene glycol methyl ether acetate, or 1 milliliter of propylene glycol methyl ether acetate, none of them was dissolved. Industrial applicability

The 2- (2-methyladamantyl) -adamantyl methane compound of the present invention is a novel asymmetric bisadamantane compound having an adamantane skeleton bonded through a methylene group, and has heat resistance and water resistance. It has excellent properties and optical properties, and is useful as a component of coating materials and optical materials. This can be efficiently produced by the method of the present invention.

In addition, 3,3′-dialkoxy force 1′-biadamantane, a novel biadamantane derivative of the present invention, is excellent in heat resistance, water resistance, optical properties, etc., and is excellent in solubility in various solvents. It is something. Therefore, it can be used in a variety of applications, and can be widely used as optical materials such as optical disc substrates, optical fibers, lenses, and intermediates of organic chemicals.

Claims

Claims General formula (I)

(In the formula, Y ¹ and Y ² each represent a hydrogen atom, a halogen atom, a hydrocarbyl group, a hydroxyl group, a hydrocarbyloxy group, a carboxyl group, or a hydrocarboxycarbonyl group, and they may be the same or different. Good.

2) (2-methyladamantyl) — adamantyl methane compound represented by).

2. The 2- (2-methyladamantyl) -12'-adamantylmethane compound according to claim 1, which is 2- 2- (2-methyladamantyl) — —adamantylmethane.

3. —In the general formula (I), at least one of Y ¹ and 丫² is a hydroxyl group, and the rest is a hydrogen atom, 2- (2-methyladamantyl) —2′-adamantyl methane hydroxide. 2. The 2- (2-methyladamantyl) -1-2'-adamantyl methane compound according to claim 1.

4. A method for producing 2- (2-methyladamantyl) -1'-adamantylmethane, in which 2-methyl-2-adamantyl is dehydrated and dimerized in the presence of an acid catalyst, and then hydrogenated.

5. The 2- (2-methyladamantyl) 1-2 'according to claim 4, wherein the acid catalyst is used in a proportion of 1 to 10% by weight based on 2-methyl_2-adamantanol. Production method of adamantyl methane.

6. 2- (2-Methyladamantyl) — 2'-adamantyl Halogenation of methane, general formula (Π)

(Wherein at least one of X ¹ and X ² is a halogen atom and the remainder is a hydrogen atom.) Production of 2 _ (2-methyladamantyl) -1 2'-adamantyl methyl halide Method.

7. Starting from 2- (2-methyladamantyl) -2′-adamantyl methane halide represented by the general formula (11) according to claim 6, at least one halogen atom is A method for producing a 2- (2-methyl adamantyl) -1,2'-adamantyl methane derivative which is converted into a hydrocarbyl group, a hydroxyl group, a hydrocarbyloxy group, a carboxyl group or a hydrocarbyloxycarbonyl group.

8. General formula (VI)

(In the formula, R represents an alkyl group having 2 to 8 carbon atoms.) A novel biadamantan derivative represented by the following formula:

9. In the general formula (VI), R is ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-amyl, isoamyl, n 9. The novel biadaman derivative according to claim 8, which is —hexyl group, n-heptyl group, n-octyl group or isooctyl group.

10. The novel biadamantane derivative according to δ, wherein the derivative is 1 0.3,3'-di-n-propoxycarbone 1'-biadamantane.