JP2006137798A - Method for producing new adamantane reaction product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a new adamantane reaction product having a fluoroadamantane structure. <P>SOLUTION: This method for producing an adamantane reaction product is characterized by reacting an adamantane compound in which two to four hydrogen atoms of adamantane are substituted with reactive group (Y)-containing groups and one or more of the remaining hydrogen atoms are substituted with one or more fluorine atoms, with a multi-functional compound having two or more groups (Z) each capable of reacting with Y. For example, a compound (a-1F) and a compound represented by the formula: ClCO-Ph<SP>2</SP>-COCl (Ph<SP>2</SP>is 1,3-phenylene group) are subjected to a polycondensation reaction to produce a polyester having units in whose each unit a perfluoroadamantane structure is connected to a 1,4-diphenylene group through an ester bond. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a novel adamantane reactant.

  As a compound in which a fluorine atom is bonded to a carbon atom of adamantane, 1 to 4 hydrogen atoms of adamantane are substituted with a hydroxyl group, a fluorocarbonyl group or a fluoroalkylcarbonyloxy group, and one or more of the remaining hydrogen atoms are converted to fluorine atoms Substituted compounds are known (see Patent Document 1). In addition, the compound represented by the following formula (y) obtained by reacting the compound represented by the following formula (x) with methacrylic acid among the compounds is a polymer excellent in transparency to short wavelength light and etching resistance. It is described in Patent Document 1 as a monomer of.

International Publication No. 04/052832 Pamphlet

  An object of the present invention is to provide a method for producing a novel and useful compound containing a fluoroadamantane structure by reacting a polyfunctional compound capable of reacting with fluoroadamantane having a reactive group.

  The inventors of the present invention provide an adamantane compound in which 2 to 4 hydrogen atoms of adamantane are substituted with a group containing a reactive group (Y) and one or more of the remaining hydrogen atoms are substituted with fluorine atoms, and the reaction It has been found that a novel and useful adamantane reactant can be obtained by reacting a polyfunctional compound having two or more groups (Z) capable of reacting with the sex group (Y).

That is, the present invention provides the following inventions.
<1>: an adamantane compound in which 2 to 4 hydrogen atoms of adamantane are substituted with a group containing a reactive group (Y) and one or more of the remaining hydrogen atoms are substituted with fluorine atoms, and the reactive group A method for producing an adamantane reactant, which comprises reacting a polyfunctional compound having two or more groups (Z) capable of reacting with (Y).

<2>: The group containing the reactive group (Y) is a hydroxyl group or a hydroxylmethyl group, and the group (Z) capable of reacting with the reactive group (Y) is represented by the formula —C (O) X ^1. Wherein X ¹ is a hydroxyl group, a halogen atom or a group represented by the formula —OR ¹ (where R ¹ contains an alkyl group having 1 to 10 carbon atoms or an etheric oxygen atom between carbon-carbon bonds). And a method for producing an adamantane reactant of <1> which is an isocyanate group.

  <3>: The method for producing an adamantane reactant according to <1>, wherein the adamantane compound is a compound represented by the following formula (a), and the polyfunctional compound is a compound having two or more groups capable of reacting with a hydroxyl group.

However, the symbol in a formula shows the following meaning.
Y ¹ may be the same or different and each independently represents a hydrogen atom, a fluorine atom, a hydroxyl group or a hydroxylmethyl group, and 2 to 4 groups selected from four Y ¹ are a hydroxyl group or a hydroxyl group Methyl group.
Q ¹ may be the same or different and each independently represents —CHF— or —CF ₂ —.

<4>: A group containing a reactive group (Y) is represented by the formula —C (O) X ² (where X ² is a hydroxyl group, a halogen atom, or a group represented by the formula —OR ² (where R ² is carbon). An alkyl group having 1 to 10 carbon atoms, an alkyl group having 2 to 10 carbon atoms which may contain an etheric oxygen atom between carbon-carbon bonds, or a phenyl group. The method for producing an adamantane reactant according to <1>, wherein the group (Z) capable of reacting with the reactive group (Y) is a hydroxyl group or an amino group.

<5>: The adamantane compound is a compound represented by the following formula (b), and the polyfunctional compound is represented by the formula —C (O) X ² (where X ² is represented by a hydroxyl group, a halogen atom or the formula —OR ^2). Wherein R ² represents an alkyl group having 1 to 10 carbon atoms, an alkyl group having 2 to 10 carbon atoms which may contain an etheric oxygen atom between carbon-carbon bonds, or a phenyl group. The method for producing an adamantane reactant according to <1>, which is a compound having two or more groups capable of reacting with.

However, the symbol in a formula shows the following meaning.
Y ² may be the same or different, and each independently represents a hydrogen atom, a fluorine atom or a group represented by the formula —C (O) X ² , and ² to ² selected from 4 Y 2 four groups of the group represented by the formula -C (O) ^{X 2.} However, X ² are as defined above.
Q ² may be the same or different and each independently represents —CHF— or —CF ₂ —.

<6>: Any one of <1> to <5>, wherein the reaction between the group containing the reactive group (Y) and the group (Z) capable of reacting with the reactive group (Y) is a polycondensation reaction. A process for producing an adamantane reaction product.
<7>: The method for producing an adamantane reactant according to any one of <1> to <6>, wherein the number average molecular weight of the adamantane reactant is 600 to 10000000.

  According to the production method of the present invention, a new and useful compound containing a fluoroadamantane structure can be produced. The adamantane reactant obtained by the production method of the present invention is a compound excellent in heat resistance, mold release, chemical resistance, transparency, light resistance, water repellency, oil repellency and low refractive index.

  In the present specification, a compound represented by the formula (1) is referred to as a compound (1). Compounds represented by other formulas are also shown in the same manner.

  Adamantane refers to a compound represented by the following formula (Ad). The adamantane compound in the present invention means that 2 to 4 hydrogen atoms bonded to carbon atoms of adamantane are substituted with a group containing a reactive group (Y) (hereinafter simply referred to as Y), and 1 of the remaining hydrogen atoms. A compound in which more than one is substituted with fluorine atoms.

Y represents a hydroxyl group, a group represented by the formula —C (O) X ² (wherein X ² has the same meaning as described above, and the same shall apply hereinafter) (hereinafter, the group is simply referred to as —COX ² ); an amino group, an isocyanato group, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, -COX ² is preferred.

When X ² is a group represented by the formula —OR ² , R ² is an alkyl group having 1 to 4 carbon atoms and an alkyl group having 2 to 4 carbon atoms which may contain an etheric oxygen atom between carbon-carbon bonds. An alkyl group or a phenyl group is preferable, and a methyl group, a methoxymethyl group, or a phenyl group is particularly preferable.
X ² is preferably a hydroxyl group, a halogen atom, a methoxy group or a phenoxy group, more preferably a hydroxyl group, a fluorine atom, a chlorine atom or a methoxy group, and particularly preferably a fluorine atom or a chlorine atom.

The group containing Y is represented by Y itself, a group in which Y is bonded to a methylene group (for example, a hydroxymethyl group, a group represented by the formula —CH ₂ C (O) X ² , a formula —CH ₂ NCO). Group, a group represented by the formula —CH ₂ NH ₂ , etc.), and a hydroxyl group, a hydroxymethyl group or —COX ² is preferable.

  The carbon atom of the adamantane to which the group containing Y is bonded may be a secondary carbon atom or a tertiary carbon atom, and is preferably a tertiary carbon atom. The number of Y in the adamantane compound is preferably 2. 2 to 4 Y in one molecule may be the same group or different groups, and are preferably the same group from the viewpoint of availability. In the adamantane compound, the remaining hydrogen atoms that are not substituted with the group containing Y may be partially substituted with fluorine atoms, or all may be substituted with fluorine atoms, and all may be replaced with fluorine atoms. It is preferably substituted.

  When the remaining hydrogen atom is present in the adamantane compound without being replaced by a fluorine atom, the hydrogen atom is preferably bonded to a carbon atom adjacent to the carbon atom to which the group containing Y is bonded, When there is a carbon atom sandwiched between carbon atoms to which the contained group is bonded, it is preferably bonded to the carbon atom.

A method in which an adamantane compound in which a group containing Y is a hydroxylmethyl group is subjected to a reduction reaction of an adamantane compound in which a group containing Y is —COX ² in the presence of a reducing agent (for example, LiAlH ₄ , NaBH _4, etc.). Can be manufactured.

As the adamantane compound in which the group containing Y is a hydroxyl group or a hydroxylmethyl group, the following compound (a) is preferred (provided that Q ¹ and Y ¹ have the same meanings as described above; the same shall apply hereinafter).

Specific examples of the compound (a) in which Y ¹ is a hydroxyl group include the following compounds. Specific examples of the compound (a) in which Y ¹ is a hydroxymethyl group include compounds in which the hydroxyl group in the following formula is substituted with a hydroxymethyl group.

As the adamantane compound in which the group containing Y is —COX ² , the following compound (b) is preferable (provided that Q ² and Y ² have the same meaning as described above; the same applies hereinafter).

Specific examples of the compound (b) in which Y ² is a group represented by the formula —C (O) Cl include the following compounds. Specific examples of the compound (b) when Y ² is a group other than the group represented by the formula —C (O) Cl include a group represented by the formula —C (O) Cl in the following formula: _{-COOH, -COBr, -COF, -COOCH 3} , include compounds obtained by replacing the groups such as -COOCH ₂ OCH _3.

  The polyfunctional compound in the present invention is a compound having two or more reactive groups (Z) (hereinafter referred to simply as Z) capable of reacting with Y of the adamantane compound. The number of Z in the polyfunctional compound is preferably 2 to 4 and particularly preferably 2 from the viewpoint of reactivity with the adamantane compound.

Z of the polyfunctional compound is selected according to Y type, reactivity, etc. of the adamantane compound. Z in the case where Y is a hydroxyl group is a group represented by the formula —C (O) X ¹ (where X ¹ has the same meaning as described above; the same shall apply hereinafter) (hereinafter, the group is simply referred to as —COX ^1). Or an isocyanate group is preferred.
When X ¹ is a group represented by the formula —OR ¹ , R ¹ is an alkyl group having 1 to 4 carbon atoms or an alkyl group having 2 to 4 carbon atoms which may contain an etheric oxygen atom between carbon-carbon bonds. An alkyl group is preferred, and a methyl group is particularly preferred.
X ¹ is preferably a hydroxyl group, a halogen atom or a methoxy group, particularly preferably a chlorine atom or a methoxy group. When the combination of Z and Y is the above group, there is an advantage that the polycondensation reaction between the adamantane compound and the polyfunctional compound can be carried out efficiently.

Z in the case where Y is —COX ² is preferably a hydroxyl group or an amino group.

Among the polyfunctional compounds, those in which Z is —COX ¹ include compounds having two —COX ¹ such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, and fumaric acid. And aliphatic dicarboxylic acids such as maleic acid and itaconic acid; acid chlorides of the aliphatic dicarboxylic acids; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid; and acid chlorides of the aromatic dicarboxylic acids.

  When dicarboxylic acid is used as the polyfunctional compound, an acid anhydride corresponding to the dicarboxylic acid may be reacted. Examples of acid anhydrides include saturated aliphatic dicarboxylic acid anhydrides, unsaturated aliphatic dicarboxylic acid anhydrides, saturated alicyclic polycarboxylic acid anhydrides, unsaturated alicyclic polycarboxylic acid anhydrides, and aromatic polyvalent anhydrides. Carboxylic anhydride is preferred.

  Specific examples of the acid anhydride include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride (1,2-cyclohexanedicarboxylic anhydride), 1,2,3,4-cyclohexanetetracarboxylic acid. -1,2-anhydride, methylcyclohexenylcarboxylic anhydride, het anhydride, hymic anhydride, phthalic anhydride, tetrabromophthalic anhydride, tetrachlorophthalic anhydride, nitrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride Examples thereof include acid and merit anhydride.

  As the polyfunctional compound in which Z is a hydroxyl group, a compound having 2 to 4 hydroxyl groups is preferable, and a compound having 2 or 3 hydroxyl groups is particularly preferable. Specific examples of the compound include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6 -Hexanediol, glycerin, trimethylolpropane, pentaerythritol, diglycerin, 1,4-bis (2-hydroxyethoxy) benzene and the like.

  As the polyfunctional compound in which Z is an isocyanate group, a compound having 2 to 4 isocyanate groups is preferable, and a compound having two isocyanate groups is particularly preferable. The compound is preferably a chain aliphatic diisocyanate, a cycloaliphatic diisocyanate, or an aromatic diisocyanate.

Specific examples of the chain aliphatic diisocyanate include 1,3-propane diisocyanate, 1,4-butane diisocyanate, 1,5-pentane diisocyanate, 1,6-hexane diisocyanate, 3 -Methylhexane-1,6-diisocyanate, 3,3-dimethylpentane-1,5-diisocyanate and the like.
Specific examples of cycloaliphatic diisocyanates include 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), and isophorone diisocyanate. Is mentioned.

  Specific examples of the aromatic diisocyanate include m-xylylene diisocyanate, p-xylylene diisocyanate, α, α, α ′, α′-tetramethyl-p-xylylene diisocyanate, 1,4-pheny Range isocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, 1,5-naphthalene diisocyanate, 2,6-naphthalene diisocyanate, tolidine diisocyanate, and tolylene An isocyanate etc. are mentioned.

  The polyfunctional compound in which Z is an amino group is preferably a compound having 2 to 4 amino groups, particularly preferably a compound having 2 amino groups, and particularly preferably an aliphatic diamine or an aromatic diamine. As the aromatic diamine, a compound in which an amino group is directly bonded to the aromatic ring, or a compound in which an amino group is bonded to the aromatic ring via an alkylene group is preferable.

Specific examples of the aliphatic diamine include ethylene diamine, propylene diamine, hexamethylene diamine, isophorone diamine, 1,4-cyclohexane diamine, piperazine, and piperazine derivatives.
Specific examples of the aromatic diamine having an amino group directly bonded to the aromatic ring include diaminobenzene, 2,4-diaminotoluene, 2,6-diaminotoluene, 4,4′-diaminodiphenylmethane, 3,3′-dimethyl- 4,4′-diaminodiphenylmethane, 3,3′-diethyl-4,4′-diaminodiphenylmethane, 3,5-diethyl-2,4-diaminotoluene, 3,5-diethyl-2,6-diaminotoluene, m -Xylylenediamine, p-xylylenediamine, etc. are mentioned.

  The adamantane reactant in the present invention refers to a compound produced by a reaction between Y of an adamantane compound and Z of a polyfunctional compound.

  Various reaction conditions (temperature, pressure, time, etc.) in the production method of the present invention are not particularly limited, and a known method can be applied according to the combination of Y of the adamantane compound and Z of the polyfunctional compound. The amount of the adamantane compound and polyfunctional compound used is preferably (1-5) n / m-fold mole of the adamantane compound relative to the polyfunctional compound (where n is the number of Y present in the adamantane compound). M represents the number of Z present in the polyfunctional compound, and each independently represents an integer of 2, 3 or 4. The same shall apply hereinafter.

  Since the adamantane compound of the present invention has two or more Y and the polyfunctional compound has two or more Z, the adamantane product produced by reacting them can be a polymer compound. The number average molecular weight of the adamantane reactant is preferably 600 to 10000000.

According to the production method of the present invention, various adamantane reactants can be produced by combining Y of an adamantane compound and Z of a polyfunctional compound. Among these, in the production method of the present invention, the following compound (a-1) having two hydroxyl groups or the following compound (b-1) having two -COX ¹ is used as an adamantane compound, and Z is 2 as a polyfunctional compound. It is preferable to obtain an adamantane reactant by using a compound having a number of compounds and subjecting them to a polycondensation reaction. However, Q ¹ , Q ² , and X ¹ in the following formula have the same meaning as described above.

As an example of the polycondensation reaction, for example, in the polycondensation reaction of an adamantane compound in which Y is a hydroxyl group and a polyfunctional compound in which Z is —COX ¹ , a polyester is generated.
An adamantane reaction product obtained when a polycondensation reaction between the compound (a-1) and a polyfunctional compound represented by the formula X ¹ (O) CE ¹ -C (O) X ¹ having two —COX ¹ Is a polyester composed of a repeating unit represented by the following formula (A1) (wherein Q ¹ represents the same meaning as described above, and E ¹ was obtained by removing two —COX ¹ from the polyfunctional compound) Showing residues).

The adamantane reaction product obtained by polycondensation reaction between the compound (b-1) and a polyfunctional compound represented by the formula HO—E ² —OH having two hydroxyl groups is a repeating compound represented by the following formula (B1) It is a polyester composed of units (wherein Q ² represents the same meaning as described above, and E ² represents a residue obtained by removing two hydroxyl groups from the polyfunctional compound).

  In the method for producing polyester, a polycondensation reaction may be performed in the presence of an acid acceptor and / or an activator in order to neutralize the acid. The acid acceptor is preferably a basic compound such as pyridine, triethylamine, dimethylaniline. The acid acceptor is preferably used in an amount of (0.8-3) n-fold mol, particularly preferably (1-1.5) n-fold mol, based on the adamantane compound having n hydroxyl groups. As the activator, dicyclohexylcarbodiimide, polyphosphoric acid, or imidazole is preferred.

In the reaction of an adamantane compound in which Y is a hydroxyl group and a polyfunctional compound in which Z is an isocyanate group, polyurethane is produced by a polycondensation reaction between the hydroxyl group and the isocyanate group. The adamantane reactant produced by polycondensation reaction between the compound (a-1) and a diisocyanate compound represented by the formula OCN-E ³ -NCO having two isocyanate groups is represented by the following formula (A2): It is a polyurethane composed of repeating units (wherein Q ^{1 in} the formula represents the same meaning as described above, and E ³ represents a residue obtained by removing two isocyanate groups from a diisocyanate compound).

  The reaction may be performed in the presence of a catalyst. The catalyst is preferably dibutyltin dilaurate, tin octanoate, cobalt naphthenate, vanadium acetylacetonate, dimethyltin diethylhexanoate, triethylenediamine, tetramethylguanidine or dimethylcyclohexylamine. A catalyst may use 1 type or may use 2 or more types. The reaction temperature in the polycondensation reaction is preferably 50 to 90 ° C. The reaction pressure is not particularly limited.

In the polycondensation reaction between the adamantane compound in which Y is —COX ² and the polyfunctional compound in which Z is an amino group, polyamide is generated. The adamantane reactant obtained by polycondensation reaction of the compound (b-1) having two —COX ² and the diamino compound represented by the formula H ₂ NE ⁴ —NH ₂ having two amino groups is It is a polyamide comprising a repeating unit represented by the following formula (B2) (wherein Q ² represents the same meaning as described above, and E ⁴ represents a residue obtained by removing two amino groups from a diamino compound). ).

  The reaction may be performed in the presence of a condensing agent. As the condensing agent, anhydrous sulfuric acid, thionyl chloride, sulfite ester, picryl chloride, phosphorus pentoxide, phosphorus oxychloride, phosphite-pyridine condensing agent, triphenylphosphine-hexachloroethane condensing agent, or propylphosphoric anhydride A product-N-methyl-2-pyrrolidone-based condensing agent is preferable. The reaction temperature and reaction pressure in the polycondensation reaction are not particularly limited.

In a polycondensation reaction between an adamantane compound in which Y is a hydroxyl group and phosgene or triphosgene ((CCl ₃ O) ₂ CO), a polycarbonate is formed. The adamantane reactant produced by the polycondensation reaction between the compound (a-1) and phosgene or triphosgene is a polycarbonate composed of a repeating unit represented by the following formula (A3) (provided that Q ¹ in the following formula is It has the same meaning as above.)

  In the method for producing polycarbonate, a polycondensation reaction may be performed in the presence of an acid acceptor in order to neutralize the acid. The acid acceptor is preferably a basic compound such as pyridine, triethylamine, dimethylaniline. The acid acceptor is preferably used in an amount of (0.8-3) n-fold mol, particularly preferably (1-1.5) n-fold mol, based on the adamantane compound having n hydroxyl groups.

The present invention will be described in detail with reference to examples, but the present invention is not limited thereto.
In Examples, CFCl ₂ CF ₂ Cl is denoted as R-113, dichloropentafluoropropane as R-225, and tetramethylsilane as TMS. As R-225, a mixture of CF ₃ CF ₂ CHCl ₂ and CF ₂ ClCF ₂ CHFCl was used. Gas chromatography-mass spectrometry is referred to as GC-MS analysis.

The yield of the reaction was determined from ¹⁹ F-NMR measurement using hexafluorobenzene as an internal standard, and the selectivity of the reaction was determined from the peak area ratio of GC analysis. The number average molecular weight was determined using a gel permeation chromatography method. The pressure is indicated by gauge pressure.
R ^F1 in the formula represents a group represented by the formula —CF (CF ₃ ) OCF ₂ CF (CF ₃ ) O (CF ₂ ) ₃ F, and R ^F2 represents a formula —CF (CF ₃ ) O (CF ₂ ) ₃ The group represented by F is shown.

  [Example 1] Production Examples of Compound (a-1F) and Compound (a-1H)

[Example 1-1] Production example of compound (a-11) The above compound (a-12) (2.01 g) and sodium fluoride (1.51 g) were placed in a round bottom flask (internal volume 50 mL), and R- 225 was added and stirred in suspension. While continuing stirring, the compound represented by the formula R ^F2 —COF (11.23 g) was added dropwise at 25 ° C. After completion of dropping, the mixture was stirred while raising the temperature to 70 ° C., and stirring was continued for 12 hours while maintaining the internal temperature at 60 to 65 ° C. After adding and diluting with R-225, sodium fluoride was removed with a filter paper, and the resulting solution was concentrated with an evaporator to remove R-225 and an excess of the compound represented by the formula R ^F2 -COF. . The concentrated solution was subjected to liquid separation treatment with sodium bicarbonate water and R-225 twice. The obtained organic layer was washed twice with water, magnesium sulfate was added, and the mixture was allowed to stand for 12 hours. Magnesium sulfate was filtered and concentrated with an evaporator and a vacuum pump to obtain a colorless solution (8.28 g). As a result of analysis by GC and NMR, it was confirmed that the compound (a-11) was produced (selectivity 95.4%, yield 83.4%).

[Example 1-2] Production Example of Compound (a-10F) and Compound (a-10H) After adding R-113 (312 g) to an autoclave (internal volume: 500 mL, made of nickel), the mixture was stirred and kept at 25 ° C. It was. At the autoclave gas outlet, a cooler maintained at 20 ° C., a packed bed of NaF pellets, and a cooler maintained at −10 ° C. were installed in series. In addition, a liquid return line for returning the agglomerated liquid to the autoclave was installed from the cooler maintained at −10 ° C. After blowing nitrogen gas into the autoclave at 25 ° C. for 1 hour, fluorine gas diluted to 20% with nitrogen gas (hereinafter referred to as 20% diluted fluorine gas) is heated at 25 ° C. at a flow rate of 10.6 L / h for 30 minutes. After blowing, the pressure inside the autoclave was increased to 0.15 MPa (gauge pressure) and then blown for another 30 minutes. Next, while maintaining the reactor internal pressure at 0.15 MPa (gauge pressure), 20% diluted fluorine gas was blown at the same flow rate, and the product (4.7 g) obtained in Example 1-1 was R-113 ( A solution dissolved in 94.3 g) was injected over 2.6 hours.

  Next, the pressure inside the autoclave is maintained at 0.15 MPa (gauge pressure) while blowing 20% diluted fluorine gas at the same flow rate, and the R-113 solution having a benzene concentration of 0.01 g / mL is changed from 25 ° C. to 40 ° C. 9 mL was injected while raising the temperature until the benzene solution inlet of the autoclave was closed, and stirring was continued for 0.3 hours. While maintaining the reactor pressure at 0.15 MPa (gauge pressure) and maintaining the reactor temperature at 40 ° C., the benzene solution (6 mL) was injected, the benzene solution inlet of the autoclave was closed, and stirring was continued for 0.3 hours. Continued. Furthermore, the same operation was repeated 3 times. The total amount of benzene injected was 0.34 g, and the total amount of R-113 injected was 33 mL.

Further, stirring was continued for 1 hour while blowing 20% diluted fluorine gas at the same flow rate. Next, nitrogen pressure was blown in for 1 hour with the pressure inside the reactor at normal pressure. As a result of analyzing the product by GC-MS, ¹ H-NMR, and ¹⁹ F-NMR, it was confirmed that the compound (a-10F) was contained in a yield of 55%. In addition, the compound (a-10H) was contained in a yield of 27%. The main component in the other components was a compound having two or more hydrogen atoms in the adamantane skeleton.

[Example 1-3] Production Example of Compound (a-1F) and Compound (a-1H) A solution (11.8 g) of the product obtained in Example 1-2 was charged into a round bottom flask (internal volume 100 mL). A 15% by mass methanol solution (24 g) of sodium hydroxide was added dropwise. The mixture was heated while stirring, refluxed for 11 hours, and allowed to cool. Diluted aqueous HCl was slowly added dropwise until the liquid became neutral, and t-butyl methyl ether was added to perform extraction three times. The obtained organic layer was concentrated by an evaporator and then sufficiently dried by a vacuum pump to recover a pale yellow powder (3.8 g). As a result of analysis by ¹⁹ F-NMR, the compound (a-1F) and the compound (a-1H) were contained.

  The reaction was carried out in the same manner as in Example 1-1 to Example 1-3 to obtain a product containing the compound (a-1F) and the compound (a-1H) in 2: 3 (molar ratio). The product was used in the following reaction.

¹⁹ F-NMR (282.7 MHz, solvent: CD ₃ OD, standard: CFCl ₃ ) δ (ppm) of compound (a-1F): −117.6 to −124.4, −221.5 to −224. 5.
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm) of compound (a-1H): 4.95 (dm, J _HF = 47.8 Hz, 1H).
¹⁹ F-NMR (282.7 MHz, solvent: CD ₃ OD, standard: CFCl ₃ ) δ (ppm) of compound (a-1H): −118.1 to −123.9 (10F), −221.6 ( 1F), −222.5 (1F), −223.5 (dm, J = 48 Hz, 1F).

  [Example 2] Production example of compound (b-1F) and compound (b-1H)

Example 2-1 Production Example of Compound (b-11) Compound (b-12) (0.78 g) and NaF (0.83 g) were placed in a round bottom flask (internal volume 50 mL), and R-225 was added. The mixture was stirred in a suspended state. The mixture was stirred while maintaining the temperature in the flask at 25 ° C., and a compound represented by the formula R ^F1 —COF (5.74 g) was added dropwise. After completion of the dropwise addition, the temperature in the flask was heated to 65 to 70 ° C. while stirring, and stirred as it was for 3 hours.

  Next, the reaction solution in which NaF was removed by filtering the solution in the flask obtained by adding R-225 to the flask was obtained. The reaction crude liquid was washed 3 times with a saturated aqueous sodium hydrogen carbonate solution and saturated brine. Further, after washing twice with ion-exchanged water, magnesium sulfate was added and the mixture was allowed to stand for 1 hour. Next, the filtrate obtained by removing magnesium sulfate by filtration was concentrated with an evaporator, and further concentrated under reduced pressure with a vacuum pump to obtain a concentrate (2.46 g). As a result of analyzing the concentrate by GC and NMR, it was confirmed that the compound (b-11) was formed (selectivity 99.7%, yield 46%).

Example 2-2 Production Example of Compound (b-10F) and Compound (b-10H) R-113 (312 g) was added to an autoclave (internal volume: 500 mL, made of nickel) and kept at 25 ° C. while stirring. did. At the autoclave gas outlet, a cooler maintained at 20 ° C., a NaF pellet packed bed, and a cooler maintained at 10 ° C. were installed in series. A liquid return line for returning the agglomerated liquid to the autoclave was installed from the cooler maintained at −10 ° C. After nitrogen gas was blown for 1.0 hour, fluorine gas diluted to 20% by volume with nitrogen gas (hereinafter referred to as 20% fluorine gas) was blown for 30 minutes at a flow rate of 9.05 L / h, and then inside the autoclave. The pressure was increased to 0.15 MPa and then blown for another 30 minutes. Next, while blowing 20% fluorine gas at the same flow rate, a solution obtained by dissolving the compound (b-11) (2.46 g) obtained in Example 2-1 in R-113 (49.03 g) was added over 1.3 hours. And injected.

  Next, while blowing 20% fluorine gas at the same flow rate, the autoclave pressure was maintained at 0.15 MPa, and an R-113 solution having a benzene concentration of 0.01 g / mL (hereinafter referred to as a benzene solution) was added to the autoclave temperature. While heating from 25 ° C. to 40 ° C., 9 mL was injected, the benzene inlet of the autoclave was closed, and stirring was continued for 0.3 hours.

  Next, a benzene solution (6 mL) was injected while maintaining the pressure in the autoclave at 0.15 MPa and the temperature in the autoclave at 40 ° C., and stirring was continued for another 0.3 hours. Next, while maintaining the pressure in the autoclave at 0.15 MPa and the temperature in the autoclave at 40 ° C., a benzene solution (8.5 mL) was injected, and stirring was further continued for 1.0 hour. The total amount of benzene injected was 0.24 g, and the total amount of R-113 injected was 23.5 mL. Subsequently, nitrogen gas was blown for 1.0 hour, and then the contents in the autoclave were recovered.

The contents were analyzed by GC-MS analysis and ¹⁹ F-NMR. As a result, the contents were fluorine bonded to the carbon atom of adamantane of the above compound (b-10F) (yield 76%) and compound (b-10F). It was confirmed that the mixture was a compound (yield 18%) in which one or more of the atoms were replaced with hydrogen atoms. Furthermore, as a result of analysis by ¹ H-NMR, it was confirmed that the compound (b-10H) was produced.

Example 2-3 Production Example of Compound (b-1F) and Compound (b-1H) The mixture (2.39 g) obtained in Example 2-2 was charged into a flask together with KF powder (0.08 g). At the top of the flask, a reflux condenser whose temperature was adjusted to 20 ° C. and a fluororesin film pack (manufactured by DuPont, trade name: Tedlar pack) were installed in series. While the inside of the flask was vigorously stirred, the flask was immersed in an oil bath at 117 to 120 ° C. and heated for 3 hours. Next, after cooling the flask, the KF powder was removed by filter filtration, and a liquid sample (2.00 g) was recovered. As a result of analyzing the liquid sample by ¹⁹ F-NMR, it was confirmed that the compound (b-1F) and the compound (b-1H) were produced.

  The reaction was carried out in the same manner as in Example 2-1 to Example 2-3 to obtain a product containing compound (b-1F) and compound (b-1H). The product was used in the following reaction.

¹⁹ F-NMR (283.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): 55.4 (2F), -97.9 (2F), -109.9 of compound (b-1F) (8F), -120.8 (2F), -217.8 (2F).
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm) of compound (b-1H): 5.95 (d, J _FH = 42.3 Hz, 1H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): 49.4 (2F), −107.4 to −112.0 (8F) of compound (b-1H) , -120.8 (2F), -204.7 (1F), -217.8 to -218.4 (2F).

[Example 3 (Example)] Production example of adamantane reactant (Part 1)
The product obtained in Example 1 (0.4 g) and 2,4-toluylene diisocyanate (2,4-TDI) (0.177 g) were mixed at 25 ° C. to obtain a mixture. The mixture was then stirred at 130 ° C. for 30 minutes to give a brown reaction product. Formation of polyurethane was confirmed by NMR of the reaction product. As a result of measuring the number average molecular weight of the reaction product, it was about 1500.

¹ H-NMR (300.4 MHz, solvent: CD ₃ SOCD ₃ , standard: TMS) ₄ ) δ (ppm): 5.19 (d, br), 6.5 to 9.6 (m) of the product.
¹⁹ F-NMR (282.7 MHz, CD ₃ SOCD ₃ , standard: CFCl ₃ ) δ (ppm) of the product: −116.8 to −122.9 (m), −220.5 (m), −221 .5 (m).

[Example 4 (Example)] Example of production of adamantane reactant (part 2)
The product obtained in Example 1 (0.25 g), N (CH ₂ CH ₃ ) ₃ (0.15 g), and a compound represented by the formula ClCO—Ph ¹ —COCl (where Ph ¹ is 1,4- A phenylene group is shown.) (0.124 g) dissolved in N, N-dimethylacetamide (3.8 g) was stirred at 25 ° C. for 24 hours. The solution was then poured into water (60 mL), and the resulting solid was collected by filtration and further dried at 200 ° C. for 1 hour to obtain a brown reaction product (0.23 g). Formation of polyester was confirmed from IR and NMR of the reaction product.

¹ H-NMR (300.4 MHz, solvent: CD ₃ SOCD ₃ , standard: TMS) δ (ppm): 5.23 (d, br), 6.65 (d, br), 6.9- 8.4 (m).
¹⁹ F-NMR (282.7 MHz, solvent: CD ₃ SOCD ₃ , standard: CFCl ₃ ) δ (ppm): −112.4 to −123.5 (m), −219.8 to −221. 7 (m).
IR (neat) of the reactant: 1230, 1330, 1680, 1790 cm ⁻¹ .
10 mass% reduction temperature of the reaction product: 236.1 ° C.

[Example 5 (Example)] Production example of adamantane reactant (part 3)
The product obtained in Example 1 (0.25 g), N (CH ₂ CH ₃ ) ₃ (0.15 g), and a compound represented by the formula ClCO—Ph ² —COCl (where Ph ² is 1,3- A phenylene group is shown.) A solution prepared by dissolving (0.128 g) in N, N-dimethylacetamide (3.8 g) was stirred at 25 ° C. for 24 hours. Next, the solution was poured into water, and the produced solid was collected by filtration and further dried to obtain a reaction product. Formation of polyester was confirmed by NMR of the reaction product. The number average molecular weight of the reaction product was 700 to 4000.

¹ H-NMR (300.4 MHz, solvent: CD ₃ SOCD ₃ , standard: TMS) δ (ppm): 6.74 (d, br), 7.8 to 8.7 (m) of the reaction product.
¹⁹ F-NMR (282.7 MHz, solvent: CD ₃ SOCD ₃ , standard: CFCl ₃ ) δ (ppm): −112.4 to −124.0 (m), −210.1 to −222. 1 (m).

[Example 6 (Example)] Production example of adamantane reactant (part 4)
A solution prepared by dissolving the product obtained in Example 2 (90 mg) and ethylenediamine (29 mg) in CDCl ₃ was stirred at 25 ° C. The solution was then dried to obtain a solid reaction product. Formation of polyamide was confirmed by NMR of the reaction product. The number average molecular weight of the reaction product was 1000 to 3000.

¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 1.26 (s, br), 2.6 to 4.2 (m, br), 6. 1 (dd, br).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm) of the reaction product: −80.5 to −1465.8 (m), −204.2 to −221.1 ( m).

[Example 7 (Example)] Production example of adamantane reactant (part 5)
The product (10.76 g) obtained in Example 2 was dissolved in R-225 (100 mL), and an excess amount of methanol was added with good stirring to obtain a reaction solution. After removing hydrogen fluoride and methanol produced by washing the reaction solution with water, R-225 in the reaction solution was distilled off to obtain a crude product (10.74 g). As a result of analyzing the crude product, the production of the following compound (c-1F) and the following compound (c-1H) was confirmed. The crude product was further purified by column chromatography to obtain a mixture (5.89 g) consisting of compound (c-1F) and compound (c-1H).

A solution in which the mixture (1.10 g) was dissolved in CHCl ₃ (30 mL) and a solution in which 1,8-octanediamine (0.31 g) was dissolved in CHCl ₃ (40 mL) were mixed. The mixture was stirred for 24 hours, and further stirred at 60 ° C. for 2 hours to obtain a reaction crude liquid. Next, the solid obtained by concentrating the reaction crude liquid was washed with water, filtered, and then vacuum-dried to obtain a brown reaction product (0.31 g). Formation of polyamide was confirmed from IR of the reaction product.

IR (neat) of the reactant: 1223, 1596, 1701, 2856, 2928 cm ⁻¹ .
5 mass% reduction temperature of the reaction product: 162.2 ° C.
10 mass% reduction temperature of the reaction product: 190.8 ° C.

[Example 8 (Example)] Production example of adamantane reactant (No. 6)
Pyridine (0.37 g) was added to a solution of 1,8-octanediol (0.32 g) dissolved in CHCl ₃ (30 mL) and stirred well. Further, a solution obtained by dissolving the product (1.03 g) obtained in Example 2 in CHCl ₃ (20 mL) was added, and the mixture was stirred at 25 ° C. for 24 hours. Next, the mixed solution was washed with water, and CHCl ₃ was distilled off to obtain a yellow reaction product (1.24 g). Formation of polyester was confirmed by NMR and IR of the reaction product.
IR (neat) of the reaction product: 1284, 1469, 1767, 2861, 2936, 3330 cm ⁻¹ .
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 1.3 to 1.8 (m, br), 4.47 (m) of the reaction product.
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −95.0 to −121.4 (m), −204.2 to −218.8 (reaction product) m).

[Example 9 (Example)] Production example of adamantane reactant (part 7)
The product obtained in Example 1 (0.25 g), N (CH ₂ CH ₃ ) ₃ (0.17 g), and Cl ₃ COC (O) OCCl ₃ (0.061 g) were combined with N, N-dimethylacetamide (3 The solution dissolved in 1 g) was stirred at 25 ° C. for 24 hours. The solid produced by pouring the solution into water was collected by filtration and dried to obtain a white reaction product. Formation of polycarbonate was confirmed by NMR of the reaction product.
¹ H-NMR (300.4 MHz, solvent: CD ₃ SOCD ₃ , standard: TMS) δ (ppm) of reaction: 7.2 (m, br).
¹⁹ F-NMR (282.7 MHz, solvent: CD ₃ SOCD ₃ , standard: CFCl ₃ ) δ (ppm): −119.2 to −121.2 (m, br), −220.3 to − 221.3 (m, br).

According to the present invention, a novel method for producing an adamantane reactant is provided. According to the production method of the present invention, various adamantane reactions excellent in heat resistance, releasability, chemical resistance, transparency, durable light resistance, and low refractive index, particularly excellent in transparency and low refractive index. Things can be manufactured efficiently. The adamantane reactant provided by the method of the present invention is an optical material such as an optical fiber material (optical fiber core material and cladding material), a pellicle material, a lens material (eyeglass lens, optical lens, optical cell, etc.), a display (PDP, LCD, It is useful as a surface protective film for CRT, FED).

Claims (7)

  An adamantane compound in which 2 to 4 hydrogen atoms of adamantane are substituted with a group containing a reactive group (Y) and at least one of the remaining hydrogen atoms is substituted with a fluorine atom; and the reactive group (Y) A method for producing an adamantane reactant, comprising reacting a polyfunctional compound having two or more groups (Z) capable of reacting. The group containing the reactive group (Y) is a hydroxyl group or a hydroxylmethyl group, and the group (Z) capable of reacting with the reactive group (Y) is a group represented by the formula —C (O) X ¹ (provided that , X ¹ is a hydroxyl group, a halogen atom, or a group represented by the formula —OR ¹ (wherein R ¹ is an alkyl group having 1 to 10 carbon atoms or carbon that may contain an etheric oxygen atom between carbon-carbon bonds). The method for producing an adamantane reactant according to claim 1, which represents an alkyl group of 2 to 10). The method for producing an adamantane reactant according to claim 1, wherein the adamantane compound is a compound represented by the following formula (a), and the polyfunctional compound is a compound having two or more groups capable of reacting with a hydroxyl group.

However, the symbol in a formula shows the following meaning.
Y ¹ may be the same or different and each independently represents a hydrogen atom, a fluorine atom, a hydroxyl group or a hydroxylmethyl group, and 2 to 4 groups selected from four Y ¹ are a hydroxyl group or a hydroxyl group Methyl group.
Q ¹ may be the same or different and each independently represents —CHF— or —CF ₂ —. The group containing the reactive group (Y) is represented by the formula —C (O) X ² (where X ² is a hydroxyl group, a halogen atom, or a group represented by the formula —OR ² (where R ² has 1 to 10 carbon atoms). An alkyl group having a carbon number of 2 to 10 which may contain an etheric oxygen atom between carbon-carbon bonds, or a phenyl group. The method for producing an adamantane reactant according to claim 1, wherein the group (Z) capable of reacting with the group (Y) is a hydroxyl group or an amino group. The adamantane compound is a compound represented by the following formula (b), and the polyfunctional compound is represented by the formula —C (O) X ² (where X ² is a hydroxyl group, a halogen atom or a group represented by the formula —OR ² (provided that , R ² represents an alkyl group having 1 to 10 carbon atoms, an alkyl group having 2 to 10 carbon atoms which may contain an etheric oxygen atom between carbon-carbon bonds, or a phenyl group. The method for producing an adamantane reactant according to claim 1, wherein the compound is a compound having two or more groups capable of forming an adamantane.

However, the symbol in a formula shows the following meaning.
Y ² may be the same or different, and each independently represents a hydrogen atom, a fluorine atom or a group represented by the formula —C (O) X ² , and ² to ² selected from 4 Y 2 four groups of the group represented by the formula -C (O) ^{X 2.} However, X ² are as defined above.
Q ² may be the same or different and each independently represents —CHF— or —CF ₂ —.   The adamantane reactant according to any one of claims 1 to 5, wherein the reaction between the group containing the reactive group (Y) and the group (Z) capable of reacting with the reactive group (Y) is a polycondensation reaction. Manufacturing method. The number average molecular weight of an adamantane reactant is 600 to 10000000. The method for producing an adamantane reactant according to any one of claims 1 to 6.