WO2007049656A1

WO2007049656A1 - Novel fluoroadamantane derivative and method for producing same

Info

Publication number: WO2007049656A1
Application number: PCT/JP2006/321297
Authority: WO
Inventors: Koichi Murata; Shu-Zhong Wang; Kazuya Oharu
Original assignee: Asahi Glass Company, Limited
Priority date: 2005-10-28
Filing date: 2006-10-25
Publication date: 2007-05-03
Also published as: JPWO2007049656A1

Abstract

Disclosed are a novel fluoroadamantane derivative and a method for producing the same. Specifically disclosed are a method for producing a compound (2) shown below wherein a compound (1) shown below is reacted with an azide and then subjected to a heat treatment; a compound (2a) shown below; a method for producing an adamantane derivative wherein the compound (2a) is addition-reacted with a hydroxy compound; a method for producing an adamantane derivative wherein the compound (2a) is addition-reacted with an amine compound; a method for producing a compound (3) shown below wherein the compound (2a) is hydrolyzed; and a compound (3a) shown below. In this connection, Q represents -CHF- or -CF2-; X represents H, F or COF; Y represents a group corresponding to X; Ya represents H, F or NCO; Z represents a group corresponding to Ya; and Za represents H, F or NH2.

Description

Specification

NOVEL FLUOROADAMANTANE DERIVATIVE AND METHOD FOR PRODUCING THE SAME

Technical field

[0001] The present invention relates to a novel fluoroadamantane derivative and a method for producing the same.

Background art

[0002] Of the hydrogen atoms of adamantane, the hydrogen atom bonded to the tertiary carbon atom is replaced with a hydroxy group, a fluorocarbon group, or a fluoroalkylcarboxyl group, and the remaining hydrogen atoms are replaced with fluorine atoms. Substituted fluoroadamantane compounds are known (see Patent Document 1).

[0003] Non-Patent Document 1 discloses a perfluoroalkylcarboxylic acid having a CF COC1 group.

2

Describes a method for chemically converting the CF COC1 group of chloride to —CF NCO group

twenty two

[0004] Patent Document 1: International Publication No. 04Z052832 Pamphlet

Non-Patent Literature 1: Synthesis of Fluoroorganic <Jompounds; Knunants, I. L., Yakobson, G. G., Eds .; Springer- Verlag: Berin, 1985; pp77-78.

Problems to be solved by the invention

However, the reactivity of a fluoroadamantany compound in which a fluorocarbon group bonded to a tertiary carbon atom of adamantane is bonded has been sufficiently studied. Means for solving the problem

[0006] The present inventors examined the reactivity of a fluorocarbonyl group of a fluoroadamantane compound having a fluorocarbon group at a tertiary carbon atom. As a result, it was found that the fluorocarbonyl group can be chemically converted into an isocyanato group, and the inventors succeeded in obtaining a fluoroadamantane compound having an isocyanato group at a tertiary carbon atom. Furthermore, as a result of examining the reactivity of the isocyanato group of the fluoradamantane compound, the fluoradamantany compound having a urethane bond, the fluoradamantany compound having a urea bond, and the amino group have Fluoroadamantani compound and its manufacturing method That is, the present invention has the following gist.

<1> A process for producing a compound represented by the following formula (2), which comprises reacting a compound represented by the following formula (1) with an azide and then heat-treating it.

[0008] [Chemical 1]

[0009] However, the symbols in the formula have the following meanings (the same shall apply hereinafter): o

Q: A monofluoromethylene group or a difluoromethylene group, and six Qs may be the same or different.

X: a hydrogen atom, a fluorine atom, or a fluorocarbon group, and the three Xs may be the same or different! / ヽ.

Y: groups corresponding to X, Υ corresponding to X being a hydrogen atom, hydrogen atom corresponding to X, Υ corresponding to X being a fluorine atom, corresponding to fluorine atom, X corresponding to fluorocarbon group Υ is a fluorocarbonyl group or an isocyanato group.

<0010> <2> A compound represented by the following formula (2a).

[0011] [Chemical 2]

However, the symbols in the formula have the following meanings (the same shall apply hereinafter): o

Y ^{3 is a} hydrogen atom, a fluorine atom, or an isocyanato group, and three Y ^a may be the same or different. [0013] <3> Isocyanato of compound (2a), characterized by addition reaction of a compound represented by formula (2a) and a hydroxy compound represented by formula R ^A (—OH) A method for producing a fluoradamantane derivative having an —NHC (O) 2 O bond formed by an addition reaction between a hydroxyl group and a hydroxy group of the hydroxy compound.

R ^A : ^A residue obtained by removing p hydroxy groups from the hydroxy compound.

p: An integer from 1 to 4.

<4> A compound represented by the formula (2a) and an amine compound represented by the formula R ^B (—NHR ^e )

q

An fluorinated group having an NHC (O) NR ^C bond formed by the addition reaction between the isocyanato group of the compound (2a) and a group represented by the formula NHR ^e of the amine compound. A method for producing a roadamantane derivative.

R ^B : a residue obtained by removing q groups — a group represented by NHR ^e from the amine compound.

R ^e : a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

q: An integer from 1 to 4.

<5> A process for producing a compound represented by the following formula (3), wherein the compound represented by the formula (2a) is hydrolyzed.

[0016] [Chemical 3]

[0017] However, the symbols in the formula have the following meanings (the same shall apply hereinafter): o

Z is a group corresponding to each of Y ^a, and Z corresponding to Y ³ which is a hydrogen atom is a hydrogen atom

, Z corresponding to a fluorine atom Y ^a corresponds to a fluorine atom, an isocyanato group Y ^a

Z is an isocyanato group or an amino group.

<0018><6> A compound represented by the following formula (3a): [0019] [Chemical 4]

[0020] However, the symbols in the formula have the following meanings (the same shall apply hereinafter): o

Z ^a : a hydrogen atom, a fluorine atom, or an amino group, and the three Z ^a may be the same or different.

The invention's effect

[0021] According to the present invention, a novel fluoroadamantane derivative and a method for producing the same are provided. The fluoroadamantane derivative of the present invention is excellent in heat resistance, releasability, chemical resistance, transparency, light resistance, water repellency, oil repellency, low refractive index and the like.

BEST MODE FOR CARRYING OUT THE INVENTION

In the present specification, a compound represented by the formula (1) will be referred to as a compound (1). The same applies to compounds represented by other formulas.

[0023] The present invention provides a process for producing the following compound (2) in which the following compound (1) is reacted with an azig compound and then heat-treated.

[0024] [Chemical 5]

Six Qs in the compound of the present invention may be the same or different, and it is preferable that four or more are difluoromethylene groups. All six Qs are difluoromethylene groups. It is particularly preferable (the same applies hereinafter) o

In the compound (1), three X's are each independently a fluorine atom or a fluorocarbo -It is preferred to be a group! /.

[0026] Specific examples of the compound (1) include the following compounds.

[0027] [Chemical 6]

[0028] Y in the compound (2) is a group corresponding to X. Isocyanato group is preferred as Y corresponding to X which is a fluorocarbonyl group. That is, in the method for producing the compound (2) of the present invention, it is preferable that all of the fluorocarbo- col groups of the compound (1) are substituted with isocyanato groups.

[0029] Specific examples of the compound (2) include the following compounds.

[0030] [Chemical 7]

[0031] The azide is preferably sodium azide. The amount of azide with respect to compound (1) having m fluorocarbon groups (1) (where m represents an integer of 1 to 4) is preferably 1 X m to 10 X m-fold mol. Xm to 2Xm times moles are particularly preferred. As reaction conditions (temperature, pressure, time, etc.), known reaction conditions can be applied. For example, the reaction conditions described in Sander, M. Monatsh. Chem. 1964, 95, 608 are preferably applied.

[0032] The temperature in the reaction is preferably 50 to + 50 ° C, particularly preferably 20 to + 20 ° C.

The pressure in the reaction is not particularly limited. The reaction is preferably carried out in the presence of a solvent. The solvent is particularly preferably an organic solvent having a boiling point of 90 to 140 ° C., preferably an organic solvent having a boiling point of 80 to 160 ° C. Moreover, you may use the mixed solvent of an organic solvent and water as a solvent. Specific examples of organic solvents include toluene, xylene, nitrobenzene, fluorinate FC-77 Examples include REM Co., Ltd. (trade name), Fluoroether E2 (Sleem KK, trade name), perfluorooctane, perfluorodecalin, and the like.

[0033] It is considered that the following compound (p2) is contained in the reaction product of compound (1) and azide.

[0034] [Chemical 8]

[0035] The symbols in the formula have the following meanings.

Y ^P: a corresponding group X, the Y ^P is hydrogen atom corresponding to X is a hydrogen atom, a Upsilon ^[rho fluorine atom corresponding to X is a fluorine atom, a full O b group Υ ^{対応} corresponding to X is a fluorocarbonyl group or an azidocarbonyl group.

[0036] In the production method of the compound (2) of the present invention, heat treatment is then performed. It is probable that compound (2) was formed because the Crutius reaction in which nitrogen molecules were released from the azidocarbonyl group of compound (ρ2) by the heat treatment proceeded.

[0037] In the heat treatment, the compound (p2) isolated from the reaction product may be heat-treated, or the compound (p2) may be heat-treated as it is without isolating the compound (p2) from the reaction product. From the viewpoint of reaction operation, the latter heat treatment is preferred. However, when the reaction between compound (1) and azide is carried out in the presence of water, it is preferable to remove the water before the heat treatment.

[0038] Known reaction conditions can be applied to the reaction conditions (temperature, pressure, time, etc.) in the heat treatment. For example, the reaction conditions described in Sander, M. Monatsh. Chem. 1964, 95, 608 are preferably applied. The temperature in the heat treatment is preferably 60 to 120 ° C, and 70 to 110 ° C is particularly preferred U. The heat treatment pressure is not particularly limited.

[0039] One preferred embodiment of the method for producing the compound (2) of the present invention is a method for producing the following compound (21), in which the following compound (11) is reacted with azido sodium and then heat-treated. It is done. [0040] [Chemical 9]

(11) (21)

[0041] According to the production method of the present invention, a fluoroadamantane derivative having an isocyanato group bonded to a tertiary carbon atom of adamantane can be produced. The present invention provides the following compound (2a).

[0042] [Chemical 10]

In the compound (2a), the three Y ³ are preferably each independently a fluorine atom or an isocyanato group.

[0044] As a preferred embodiment of the compound (2a), the following compound (21) may be mentioned.

[0045] [Chemical 11]

[0046] Compound (2a) is a novel compound having a characteristic structure having an isocyanato group bonded to the tertiary carbon atom of adamantane. Since the compound (2a) has a reactive isocyanato group, it can be derived into various fluoroadamantane derivatives by reacting with a compound having a group capable of reacting with the isocyanato group. [0047] Examples of the method for producing the fluoroadamantane derivative include the following production methods 1, 2, and 3.

[Production method 1]

Compound (2a) and a hydroxy compound represented by the formula R ^A (—OH) (hereinafter simply hydroxy)

P

Also called a compound. And a fluoroadamantane derivative having an —NHC (O) 2 O bond formed by the addition reaction of the isocyanato group of the compound (2a) and the hydroxy group of the hydroxy compound.

[0048] [Production method 2]

Compound (2a) and an amine compound represented by the formula R ^B (—NHR ^e ) (hereinafter, also simply referred to as an amin compound) are subjected to an addition reaction, and the isocyanate group of compound (2a) and the amine compound are combined. A method for producing a fluoroadamantane derivative having an —NHC (O) NR ^C — bond formed by an addition reaction with a group represented by the formula NHR ^e .

[0049] [Production method 3]

The manufacturing method of the following compound (3) which hydrolyzes a compound (2a).

[0050] [Chemical 12]

[0051] The hydroxy compound in production method 1 has 1 to 4 hydroxy groups. R ^{A in the} hydroxy compound is a group having 1 to 10 carbon atoms, and a 1 to 4 valent aliphatic hydrocarbon group, a 1 to 4 valent aromatic hydrocarbon group, and a 1 to 4 valent etheric oxygen Hydrocarbons containing atoms At least one group that is also chosen for its group power is preferred. Among them, carbon group 1 ~: LO group, monovalent to tetravalent saturated hydrocarbon group, phenol group, phenol group, benzenetriyl group, and benzenetetrayl group force are selected. At least one group, or a group having 2 to 10 carbon atoms, excluding a hydroxy group such as polyether monool, polyether diol, polyether triol, or polyether tetraol. Particularly preferred.

[0052] The monovalent R ^A is preferably an alkyl group having 1 to LO carbon atoms, an alkyl group having 2 to LO carbon atoms, an alkyl group containing an etheric oxygen atom between carbon bonds, or a phenyl group. Examples of monohydroxy compounds include methanol, ethanol, 1 propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert butyl alcohol, benzyl alcohol and the like.

[0053] The divalent ^RA is preferably an alkylene group having 1 to LO carbon atoms, an alkylene group having 2 to LO carbon atoms, an ethereal oxygen atom between carbon bonds, or a phenylene group. Dihydroxy compounds include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 2,2 dimethyl-1,3 propanediol, 1,4 butanediol, 1,5 pentanediol, 1,6 hexanediol, (2 hydroxy Ethoxy) Benzene and the like.

[0054] Examples of the trihydroxy compound or tetrahydroxy compound include glycerin, trimethylolpropane, pentaerythritol, and diglycerin.

[0055] In the production method 1, the reaction temperature in the addition reaction using the compound (2a) having one isocyanato group and the monohydroxy compound is preferably 50 to + 90 ° C. 20 ˜ + 40 ° C. is particularly preferred. The pressure in the addition reaction is not particularly limited. The addition reaction is preferably performed in the presence of a solvent. Solvents include jetyl ether, acetone, tetrahydrofuran, dioxane, toluene, xylene, trichlorodifluoroethane, dichloropentafluoropropane, Fluorinert FC-77 (manufactured by Slieem, trade name), fluoro ether Examples include E2 (trade name, manufactured by Lancaster), perfluorooctane, perfluorodephosphorus, etc.

[0056] In the production method 1! /, In the addition reaction of the compound (2) having 2 to 4 isocyanato groups with a dihydroxy compound, a trihydroxy compound, or a tetrahydroxy compound When a polyaddition reaction occurs between two or more isocyanato groups and two or more hydroxy groups, a polyurethane having two or more urethane bonds is formed. The amount of the hydroxy group of the hydroxy compound used for the polyaddition reaction is preferably 1 to 5 times the molar amount of the isocyanato group of the compound (2)! /. [0057] The temperature and pressure in the polyaddition reaction are not particularly limited. The polyaddition reaction may be performed in the presence of a catalyst. Examples of the catalyst include dibutyl-tin-dilaurate, tin-otatanoate, cobalt naphthenate, vanadium-acetylacetonate, dimethyl-tin-ethylhexanoate, triethylenediamine, tetramethyldazine, or dimethyl-cyclohexamine. It is done. Further, the catalyst may be one kind of catalyst or two or more kinds of catalysts.

[0058] The adamantane derivative obtained by Production Method 1 is excellent in heat resistance, releasability, chemical resistance, transparency, durability light resistance, low refractive index property and the like.

[0059] The amine compound in production method 2 is a compound having 1 to 4 groups represented by the formula NHR ^e . ^Re is preferably a hydrogen atom.

[0060] R ^B of Amin compound is a group having 1 to 10 carbon atoms having 1 to 10 carbon atoms, and 1-4 divalent aliphatic hydrocarbon group, 1-4 monovalent aromatic hydrocarbon group, And at least one group selected from a group power consisting of a hydrocarbon group including a monovalent to tetravalent etheric oxygen atom. Among them, a group having 1 to 10 carbon atoms, a monovalent to tetravalent saturated hydrocarbon group, a phenyl group, a phenyl group, a benzenetriyl group, and a benzenetetrayl group is selected. At least one group is particularly preferred.

[0061] The amine compound may be an aliphatic amine or an aromatic amine.

Aliphatic amines include methylamine, ethylamine, 1-propylamine, 2-propylamine, jetylamine, diisopropylamine, pyrrolidine, piperidine, morpholine, ethylenediamine, propylenediamine, hexamethylenediamine, isophorone diamine. And amine, 1, 4 cyclohexanediamine, piperazine and the like.

Aromatic amines include aline, benzylamine, 1-phenylethylamine, diaminobenzene, 2,4-diaminotoluene, 2,6 diaminotoluene, 4,4'-diaminodiphenylmethane, 3,3,1 dimethyl 4,4'-diaminodiphenylmethane, 3,3,1 jetyl-1,4,4'-diaminodiphenylmethane, 3,5 jetyl-2,4 diaminotoluene, 3,5 diethyl-2,6 diaminotoluene, m xylylenediamine Min, p-xylylenediamine and the like.

[0062] In production method 2, compound (2a) having one isocyanato group and one compound of formula NHR The reaction temperature in the addition reaction with a compound having a group represented by ^C is preferably is 50 to + 9 0 ° C instrument. 20 to + 40 ° C is particularly preferred. The pressure in the addition reaction is not particularly limited. The addition reaction is preferably performed in the presence of a solvent. Solvents include diethyl ether, acetone, tetrahydrofuran, dioxane, toluene, xylene, trichlorotetrafluoroethane, dichloropentafluoropropane, Fluorinert FC-77 (manufactured by Slieem, trade name), fluoroether E2 (Lancaster) Product, trade name), perfluorooctane, perfluorodecalin and the like.

[0063] In the production method 2, in the addition reaction of the compound (2a) having 2 to 4 isocyanato groups and the compound having two or more groups represented by the formula NHR ^e , 2 or more When a polyaddition reaction occurs between the isocyanato group of and the group represented by two or more formulas NHR ^e , a bond represented by two or more formulas — NHC (0) NR ^e is formed. Produced polyurea. The amount of the amino compound used in the polyaddition reaction is preferably 1 to 5 times the molar amount of the total amount of isocyanato groups in the compound (2). The polyaddition reaction may be performed in the presence of a catalyst.

[0064] The adamantane derivative obtained by the production method 2 is excellent in heat resistance, releasability, chemical resistance, transparency, durability light resistance, low refractive index property and the like.

[0065] For the hydrolysis reaction of compound (2a) in production method 3, known reaction conditions (temperature, pressure, time, etc.) can be applied. The amount of water relative to the total amount of isocyanato groups of compound (2) in the hydrolysis reaction is preferably 1 to: LOO times molar amount. The reaction temperature in the hydrolysis reaction is preferably 0 to 90 ° C, particularly preferably 0 to 40 ° C. The reaction pressure is not particularly limited. The hydrolysis reaction is preferably performed in the presence of a solvent. Solvents include jetyl ether, acetone, tetrahydrofuran, dioxane, toluene, xylene, trichlorodifluoroethane, dichloropentafluoropropane, Fluorinert FC-77 (manufactured by Seriem, product name), fluoroether E2 (manufactured by Lancaster, product) Name), perfluorooctane, perfluorodecalin and the like.

Z in [0066] Compound (3) is a corresponding group Y ^a. Z corresponding to Y ³ which is an isocyanato group is preferably an amino group. That is, in the production method 3, it is preferable that all of the isocyanato groups of the compound (2a) are chemically converted to amino groups. One preferred embodiment of the method for producing the compound (3) of the present invention includes a method for producing the following compound (31) in which the following compound (21) is hydrolyzed.

[0068] [Chemical 13]

[0069] According to Production Method 3, a fluoroadamantane derivative having an amino group bonded to a tertiary carbon atom of adamantane can be produced. The present invention provides the following compound (3a).

[0070] [Chemical 14]

[0071] 3 Z ^a in the compound (3a) are each independently preferably Ru fluorine atom or an amino group der.

[0072] As a preferred embodiment of the compound (3a), the following compound (31) may be mentioned.

[0073] [Chemical 15]

[0074] Specific examples of the compound (3a) include the following compounds.

[0075] [Chemical 16]

[0076] Compound (3a) is a novel compound having a characteristic structure having an amino group bonded to the tertiary carbon atom of adamantane. Since the compound (3a) has a reactive amino group, it can be derived into various fluoroadamantane derivatives by reacting with a compound having a group capable of reacting with an amino group. The adamantane derivative is excellent in heat resistance, releasability, chemical resistance, transparency, durability light resistance, low refractive index property and the like.

Example

[0077] The following is a description of the present invention with reference to examples. The present invention is not limited thereby. GC is gas chromatography, IR is IR spectrum, GC purity is determined by GC peak area ratio, tetramethylsilane is TMS, CF C1CF CHFC1 is R-225

twenty two

I write. FC-77 is a fluorine-containing organic solvent.

[0078] [Example 1 1] Production example of compound (2-1)

A mixture of activated sodium azide (3.25 g), water (8 mL) and FC-77 (20 mL) was added to the reaction vessel. Next, an FC-77 (2 OmL) solution containing the following compound (1-1) (18.13 g) was added dropwise to the reaction vessel. The temperature in the reaction vessel was kept at 5 ° C or lower and stirred for 1 hour as it was, and further stirred at 25 ° C for 4 hours. The FC-77 layer of the solution in the reaction vessel was separated and collected, and dried over magnesium sulfate. Next, when heated slowly, nitrogen generation was confirmed at around 80 ° C. The reaction was continued for 1 hour by heating to 95 ° C over 1 hour. Thereafter, FC-77 was distilled off to obtain the following compound (2-1) (15. 67 g, GC purity: 98%). The NMR data and IR data of the compound (2-1) are shown below.

[0079] ¹⁹ F— NMR data (282.7 MHz, CDC1, CFC1) δ (ppm): — 117. 1 (6F),-

3 3

121. 1 (6F),-220. 9 (3F).

IR (KBr) v: 2276 (N = C = 0), 1277cm ^_1 ₀

max

[0080] [Chemical 17] ,

)

[0081] [Example 1 2] Production example of the following compound (2-2)

The same conditions as in Example 1-1 except that compound (1-1) was changed to the following compound (1-2) (72g)

p

The following compound (2-2) (65 g) was obtained by performing the reaction. NMR of compound (2-2)

, IR, and mass spectrum (GC-MS) are shown below.

[0082] [Chemical 18]

[0083] F-NMR (282.7MHz, CDCl, CFCl) δ (ppm): — 110 (2F), — 117 (8F)

3 3

, -121 (2F), -218 (2F) ₀

IR (KBr) v: 2270 (N = C = O), 1280 cm ^_1 .

max

GC MS (EI) m / z: 470 (M) +.

[0084] [Example 1 3] Production example of the following compound (2-3)

The following compound (2-3) is obtained by reacting under the same conditions as in Example 11 except that the compound (11) is changed to the following compound (13).

[0085] [Chemical 19]

(2-3) [0086] [Example 1 4] Production example of following compound (2-4)

The following compound (2-4) is obtained by reacting under the same conditions as in Example 11 except that the compound (11) is changed to the following compound (14).

[0087] [Chemical 20]

[0088] [Example 2] Production example of adamantane derivative (Part 1)

The compound (2-1) (1.99 g) and R-225 (1 OmL) were placed in a flask maintained at 0 ° C. under a nitrogen atmosphere and stirred. Next, ethanol (0.22 g) was added dropwise over 5 minutes. After completion of the dropwise addition, the mixture was stirred for 5 hours at 25 ° C in the flask. The liquid in the flask was concentrated to obtain the following compound (Ad-1) (1.94 g) which is an adamantane derivative. The NMR data and IR data of the compound (Ad-1) are shown below.

[0089] 'H-NMROOO.4MHZ, CDCl, TMS) 6 (ppm): l.32 (t, J = 7.1 Hz, 3H),

Three

4.23 (q, J = 7.1Hz, 2H), 5.24 (b, 1H).

1 ⁹ F-NMR (282.7MHz; CDCl, CFC1) δ (ppm):-114.5 (6F), —121.1

3 3

(6F), -220.7 (3F).

IR (KBr) v: 3332, 1756 (C = 0), 1276 cm ^_1 .

max

[0090] [Chemical 21]

[Example 3] Production example of adamantane derivative (part 2)

Compound (2-1) (2. Olg) and R-225 (1 OmL) were placed in a flask maintained at 0 ° C. under a nitrogen atmosphere and stirred. Next, alin (0.42 g) was added dropwise over 3 minutes. After dropping The flask was stirred for 5 hours at a flask internal temperature of 25 ° C. The precipitated solid was collected by filtration, washed with R-225 and force-dried to obtain the following compound (Ad-2) (1.98 g) which is an adamantane derivative. The NMR data and IR data of the compound (— 2) are shown below.

[0092] 'H-NMROOO.4MHZ; Acetone d, TMS) δ (ppm): 3.79 (s, 2H), 7.06

6

(m, 1H), 7.31 (m, 2H), 7.48 (m, 2H).

1 ⁹ F-NMR (282.7 MHz; acetone-d, CFC1) δ (ppm): — 112.7 (6F), — 1

6 3

20.4 (6F), -220.0 (3F).

IR (KBr) v: 3346, 1693 (C = 0), 1565, 1274cm ^_1 ₀

max

[0093] [Chemical 22]

[0094] [Example 4] Production example of compound (3-1)

Into a reaction vessel, compound (2-1) (1.95 g) and tetrahydrofuran (10 mL) were added and stirred at 0 ° C. Next, water (0.086 g) was added dropwise over 5 minutes. After completion of dropping, the mixture was stirred at 25 ° C for 5.5 hours. The solution in the reaction vessel was concentrated to obtain the following compound (3-1) (1.65 g). The NMR data and IR data of compound (3-1) are shown below.

[0095] 'H-NMROOO.4MHZ, CDCl 2, TMS) δ (ppm): 2.15 (b).

Three

¹⁹ F-NMR (282.7 MHz; CDCl, CFC1) δ (ppm): — 120.1 (6F), —121.2

3 3

(6F), -221.1 (3F).

IR (KBr) v: 3430, 1272cm ^_1 .

max

[0096] [Chemical 23]

(3-1)

Industrial applicability

According to the present invention, a novel fluoroadamantane derivative excellent in heat resistance, releasability, chemical resistance, transparency, durability light resistance and low refractive index and a method for producing the same are provided. Loadamantane derivatives are composed of one optical fiber material (core material and clad material for one optical fiber), pellicle material, lens material (eyeglass lens, optical lens, optical cell, etc.), display (PDP, LCD, CRT, FED). Etc.) is useful as a surface protective film. The entire contents of the description, claims and abstract of Japanese Patent Application No. 2005-314800 filed on October 28, 2005 are incorporated herein by reference. Incorporate.

Claims

A process for producing a compound represented by the following formula (2), comprising reacting a compound represented by the following formula (1) with an azide and then heat-treating the compound.

[Chemical 1]

However, the symbol in a formula shows the following meaning.

A compound represented by the following formula (2a).

[Chemical 2]

However, the symbol in a formula shows the following meaning.

Y ³ : a hydrogen atom, a fluorine atom, or an isocyanato group, and three Y ^a are the same Or different.

^A compound represented by the following formula (2a) and a hydroxy compound represented by the formula R ^A (—OH) are subjected to an addition reaction, and the isocyanate group of the compound (2a) and the hydroxy group A method for producing a fluoroadamantane derivative having an NHC (O) 2 O-bond formed by an addition reaction with a hydroxy group of a compound.

[Chemical 3]

However, the symbol in a formula shows the following meaning.

Y ^{3 is a} hydrogen atom, a fluorine atom, or an isocyanato group, and three Y ^a may be the same or different.

p: An integer from 1 to 4.

A compound represented by the following formula (2a) and an amine compound represented by the formula R ^B (—NHR ^e ) are subjected to a caro reaction, and the isocyanate group of the compound (2a) and the amine compound A method for producing a fluoroadamantane derivative having an —NHC (0) NR ^e — bond formed by an addition reaction with a group represented by Formula 1 N HR ^e of a compound.

[Chemical 4]

However, the symbols in the formula have the following meanings: Q: A monofluoromethylene group or a difluoromethylene group, and the six Qs may be the same or different.

: A hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

q: An integer from 1 to 4.

A method for producing a compound represented by the following formula (3), wherein the compound represented by the following formula (2a) is hydrolyzed.

[Chemical 5]

However, the symbol in a formula shows the following meaning.

Q: A monofluoromethylene group or a difluoromethylene group, and the six Qs may be the same or different.

Z: a corresponding group Y ^a, and Z corresponding to Y ³ is a hydrogen atom Z which corresponds to Y ^a is a hydrogen atom, a fluorine atom corresponds to a fluorine atom, an isocyanato group Y ^a Z is an isocyanato group or an amino group.

A compound represented by the following formula (3a):

[Chemical 6]

However, the symbol in a formula shows the following meaning.