JP2007332068A - New fluoroadamantane derivative and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a new fluoroadamantane derivative and to provide a method for producing the same. <P>SOLUTION: The method for producing a compound represented by formula (5) comprises reacting a compound represented by formula (6) with a compound represented by formula (R<SP>FA</SP>C(O))<SB>2</SB>O and then with a compound represented by formula (R<SP>FB</SP>CH<SB>2</SB>OH). The method for producing a compound represented by formula (1) comprises reacting a compound represented by formula (31) with a protonic nucleophilic species to give a compound represented by formula (2) and then reacting the compound represented by formula (2) with a basic compound represented by formula R-CHO in the presence of a basic compound. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

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

  Among the adamantane hydrogen atoms, a fluoroadamantane compound is known in which a hydrogen atom bonded to a tertiary carbon atom is substituted with a hydroxy group, a fluorocarbonyl group or a fluoroalkylcarbonyloxy group, and the remaining hydrogen atoms are substituted with fluorine atoms. (See Patent Document 1).

In Non-Patent Document 1 and Non-Patent Document 2, a compound represented by the following formula (Ad-H) and a reaction intermediate obtained by reacting CH ₃ Li with each other are represented by the following formula (Ad-I). It is described that a compound, a compound represented by the following formula (Ad-Br) or a compound represented by the following formula (Ad-Si) was obtained.

International Publication No. 2004/052832 Pamphlet J. et al. Org. Chem. 1992, 57, 4749 J. et al. Org. Chem. 1993, 58, 1999

However, the reactivity of a fluoroadamantane compound in which a fluorocarbonyl group is bonded to a tertiary carbon atom of adamantane has not been sufficiently studied. Moreover, the reactivity of the hydrogen atom in the compound represented by the formula (Ad-H) has not been studied except that the hydrogen atom reacts with CH ₃ Li.

  The present inventors examined the reactivity of fluoroadamantane having a hydrogen atom bonded to the tertiary carbon atom of adamantane. As a result, it was found that a hydrogen atom in the fluoroadamantane can be substituted with a 1-hydroxy hydrocarbon group. Furthermore, a novel fluoroadamantane derivative was found.

That is, the present invention provides the following inventions.
[1] A compound represented by the following formula (6) is reacted with a compound represented by the formula (R ^FA C (O)) ₂ O, and then a compound represented by the formula R ^FB CH ₂ OH is reacted. A method for producing a compound represented by the following formula (5):

However, the symbols in the formulas have the following meanings (the same applies hereinafter).
G: A halogen atom or a hydroxy group.
J: a hydrogen atom or a group represented by the formula —C (O) G, and two Js may be the same or different.
R ^FA and R ^FB : each independently a perfluoroalkyl group which may contain an etheric oxygen atom having 1 to 20 carbon atoms.
T: a group corresponding to each of J, T corresponding to J being a hydrogen atom is a hydrogen atom, and T corresponding to J being a group represented by the formula —C (O) G is represented by the formula —C (O ) groups represented by the group or the formula -OC ^{(O) R FA} represented by _OCH 2 ^{R FB.}

  [2] A compound represented by the following formula (31).

However, the symbols in the formulas have the following meanings (the same applies hereinafter).
Q: —CHF— or —CF ₂ —, wherein six Qs may be the same or different.
Z ^{1 is a} hydrogen atom, a fluorine atom, a hydroxy group or a fluorocarbonyl group, and two Z ^{1 s} may be the same or different.

  [3] A compound represented by the following formula (311).

However, the symbol in a formula shows the following meaning.
Z ^{11 is a} fluorine atom, a hydroxy group or a fluorocarbonyl group, and two Z ¹¹ may be the same or different.

  [4] A compound represented by the following formula (31) is reacted with a protic nucleophile to obtain a compound represented by the following formula (2), and then the compound represented by the formula and R—CHO. A method for producing a compound represented by the following formula (1), wherein: is reacted in the presence of a basic compound.

However, the symbols in the formulas have the following meanings (the same applies hereinafter).
Y: a group corresponding to each of Z ¹ , Y corresponding to a hydrogen atom Z ¹ corresponds to a hydrogen atom, and Y corresponding to a fluorine atom Z ¹ corresponds to a fluorine atom and a hydroxy group Z ¹ Y corresponding to Z ¹ which is a hydroxy group and a fluorocarbonyl group is a hydrogen atom.
R: A hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
X: a group corresponding to Y, X corresponding to Y being a hydrogen atom is a hydrogen atom or a group represented by the formula -CHROH, X corresponding to Y being a fluorine atom is a fluorine atom or a hydroxy group X corresponding to a certain Y is a hydroxy group.

  [5] A compound represented by the following formula (11).

However, the symbol in a formula shows the following meaning.
X ^{1 is a} hydrogen atom, a fluorine atom, a hydroxy group or a group represented by the formula —CHROH, and two X ^{1 s} may be the same or different.

  [6] A compound represented by the following formula (111).

However, the symbol in a formula shows the following meaning.
X ^{11 is a} fluorine atom, a hydroxy group or a hydroxymethyl group, and two X ^{11 s} may be the same or different.

  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 a material excellent in heat resistance, releasability, chemical resistance, transparency, light resistance, water repellency, oil repellency, low refractive index and the like.

  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. Further, symbols in the group are as defined above unless otherwise specified.

In the present invention, the following compound (6) is reacted with a compound represented by the formula (R ^FA C (O)) ₂ O, and then a compound represented by the formula R ^FB CH ₂ OH is reacted. The manufacturing method of 5) is provided.

  G in the compound (6) is preferably a hydroxy group.

  Specific examples of the compound (6) include the following compounds.

R ^FA and R ^FB are each independently CF _3- , CF ₃ CF _2- , (CF ₃ ) ₂ CF-, F (CF ₂ ) ₃ OCF (CF ₃ )-or F (CF ₂ ) ₃ OCF ( CF ₃ ) CF ₂ OCF (CF ₃ ) — is preferred.

Specific examples of the compound represented by the formula (R ^FA C (O)) ₂ O include (CF ₃ C (O)) ₂ O.

Specific examples of the compound represented by the formula R ^FB CH ₂ OH include CF ₃ CH ₂ OH, CF ₃ CF ₂ CH ₂ OH, (CF ₃ ) ₂ CFCH ₂ OH, and F (CF ₂ ) ₃ OCF (CF _{3 ) CH 2 OH, F (CF} 2) 3 OCF (CF 3) CF 2 OCF (CF 3) CH 2 OH and the like.

In the production method of the present invention, the compound represented by the formula (R ^FA C (O)) ₂ O is a compound (6) having a group represented by m formulas —C (O) G (provided that m represents an integer of 1 to 4. The same shall apply hereinafter.) The compound represented by the formula (R ^FA C (O)) ₂ O is preferably used in (2 to 3) m-fold mol.

The temperature during the reaction of the formula ^(R FA C _^(O)) compounds represented by ₂ O is preferably -80 ° C. ~0 ° C..
The reaction may be performed under pressure, reduced pressure, or atmospheric pressure.
The reaction may be performed in the presence of a solvent or in the absence of a solvent. From the viewpoint of volume efficiency, the reaction is preferably performed in the absence of a solvent.

In the production method of the present invention, the compound represented by the formula R ^FB CH ₂ OH represents the formula R ^FB CH with respect to the compound (6) having m groups represented by the formula —C (O) G. _The compound represented by ₂ OH is preferably used in a (2-3) m-fold mole.
The temperature during the reaction of compounds of the formula ^R FB _CH 2 OH is preferably -80 ℃ ~ + 40 ℃.
The reaction may be performed under pressure, reduced pressure, or atmospheric pressure.
The reaction may be performed in the presence of a solvent or in the absence of a solvent. From the viewpoint of volume efficiency, the reaction is preferably performed in the absence of a solvent.

The reason why the compound (5) is obtained in the production method of the present invention is not necessarily clear, but the compound (6) is produced by the reaction of the compound represented by the formula (R ^FA C (O)) ₂ O described below. It is considered that the compound (i1) undergoes a transfer reaction to produce the following compound (i2), and then the compound (i2) and the compound represented by the formula R ^FB CH ₂ OH react to produce a compound (5).

However, the symbol in a formula shows the following meaning.
J ^i1: a respectively a group corresponding to J, ^{J i1 J i1} is corresponding to J hydrogen atom, a group represented by the formula -C (O) G which corresponds to a hydrogen atom J is the formula - A group represented by C (O) OC (O) R ^FA .
J ^i2: a corresponding group ^{J i1, J i2} is a hydrogen atom corresponding to ^{J i1} is a hydrogen atom, a group represented by the formula ^{-C (O) OC (O)} R FA J i1 J ⁱ² corresponding to is a group represented by the formula —C (O) OC (O) R ^FA or a group represented by the formula —OC (O) R ^FA .

  The reaction product in the production method of the present invention is usually a mixture of the compound (5) and the following compound (5a).

However, the symbol in a formula shows the following meaning.
T ^a : a hydrogen atom or a group represented by the formula —C (O) OCH ₂ R ^FB , and two T ^a may be the same or different.

  In the production method of the present invention, the mixture (5) may be isolated by purifying the mixture (distillation method, purification method by chromatography, etc.), or the mixture without purification. You may use for the intended use.

  The compound (5) is preferably the following compound (51).

However, the symbol in a formula shows the following meaning.
T ^{1 is a} hydrogen atom, a group represented by the formula —C (O) OCH ₂ R ^FB or a group represented by the formula —OC (O) R ^FA , and two T ¹ may be the same May be different.

  Specific examples of the compound (5) include the following compounds.

  The following compound (4) can be produced by subjecting the compound (51) to a fluorination reaction to obtain the following compound (4) and then subjecting the compound (4) to a thermal decomposition reaction.

However, the symbol in a formula shows the following meaning.
T ^F: each ^{T 1} a corresponding group, ^{T F} is hydrogen atom or fluorine atom corresponding to ^{T 1} is a hydrogen atom, a ^{T 1} is a group represented by the formula -OC ^{(O) R FA} The corresponding T ^F is a group represented by the formula —OC (O) R ^FA group and the group represented by the formula —C (O) OCH ₂ R ^{FB. The} T ^F corresponding to T ¹ is the formula —C (O) OCF ₂ R ^FB. A group represented by

Z: a group corresponding to each of T ^F , wherein Z corresponding to T ^F corresponding to a hydrogen atom is a hydrogen atom or a fluorine atom, Z corresponding to ^TF being a fluorine atom is a fluorine atom, and a formula —OC (O ) Z corresponding to ^{T F} is a group represented by ^{R FA} is hydroxy group, Z is fluoro group corresponding to ^{T F} is a radical of the formula ^{_{-C (O) OCF 2 R FB}} .

  The fluorination reaction and the thermal decomposition reaction are preferably carried out according to the method described in International Publication No. 2004/052832.

Six Q in the compounds of the present invention, -CF ₂ - are preferred.

  The following compound (31) is preferable as the compound (3), and the following compound (311) is particularly preferable.

Z ¹ in the compound (31) is preferably a fluorine atom, a hydroxy group or a fluorocarbonyl group.
In the compound (311), two Z ¹¹ are preferably fluorine atoms.

  Specific examples of the compound (31) include the following compounds.

  Compound (3) is a novel fluoroadamantane derivative having a fluorocarbonyl group and a hydroxy group bonded to the tertiary carbon atom of fluoroadamantane. In the present invention, the compound (31) is reacted with a protic nucleophile to obtain the following compound (2). Next, the compound (2) and the compound represented by the formula R-CHO are converted in the presence of a basic compound. The production method of the following compound (1) to be reacted with is provided.

  In the compound of the present invention, R is preferably a hydrogen atom.

  In the compound (1), X corresponding to Y which is a hydrogen atom is preferably a group represented by the formula —CHROH.

  The protic nucleophilic species in the present invention refers to a compound having a proton and performing a nucleophilic reaction. The protic nucleophile is preferably ammonia, hydrogen sulfide or water, particularly preferably water.

  The compound represented by the formula R—CHO in the present invention is preferably H—CHO.

  Basic compounds in the present invention include alkali metal hydroxides (sodium hydroxide, potassium hydroxide, etc.), organic metal basic compounds (butyl lithium, methyl lithium, phenyl lithium, methyl magnesium iodide, ethyl magnesium bromide, phenyl Magnesium bromide etc.) is preferred, and alkali metal hydroxides are particularly preferred.

The reaction of the compound (31) and the protic nucleophile may be performed in the presence of an organic solvent. Examples of organic solvents include diethyl ether, acetone, tetrahydrofuran, dioxane, toluene, xylene, trichlorotrifluoroethane, dichloropentafluoropropane, Fluorinert FC-77 (Three M, trade name), and fluoroether E2 (Lancaster, trade name). , Perfluorooctane, perfluorodecalin and the like.
The temperature in the reaction is preferably 0 to 90 ° C, particularly preferably 0 to 50 ° C. The pressure in the reaction is not particularly limited.

  When the protic nucleophilic species in the reaction is water, the amount of water relative to the compound (31) having m fluorocarbonyl groups is preferably (1 to 100) m-fold mole, and (1 to 10) m. Double moles are particularly preferred.

When the basic compound is an alkali metal hydroxide, the reaction temperature in the reaction between the compound (2) and the compound represented by the formula R—CHO is preferably 50 to 120 ° C., particularly preferably 60 to 100 ° C. . Moreover, when a basic compound is an organometallic compound, -80-0 degreeC is preferable and -80--40 degreeC is especially preferable. The reaction pressure is not particularly limited.
The reaction is preferably performed in the presence of a polar solvent. The polar solvent is preferably an organic polar solvent or water. When the basic compound is an alkali metal hydroxide, methanol, ethanol, 2-propanol, dimethyl sulfoxide, or N, N-dimethylformamide is preferable. Moreover, you may use the mixed solvent of these organic solvents and water. When the basic compound is an organometallic compound, diethyl ether, tetrahydrofuran, or dioxane is preferred.

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

  Compound (1) is a novel fluoroadamantane derivative having a 1-hydroxy hydrocarbon group and a hydroxy group bonded to a tertiary carbon atom of fluoroadamantane. The compound (1) is preferably the following compound (11), particularly preferably the following compound (111).

X ¹ in the compound (11) is preferably a fluorine atom, a hydroxy group or a group represented by the formula —CHROH.
Two X ¹¹ in the compound (111) are preferably fluorine atoms.

  Specific examples of the compound (11) include the following compounds.

  By reacting the compound (11) with a compound having a functional group capable of reacting with a hydroxy group (carboxyl group, isocyanate group, etc.) and a polymerizable group (vinyloxy group, (meth) acryloyloxy group, etc.). A polymerizable fluoroadamantane can be produced. The fluoroadamantane is a useful compound as a monomer for producing a polymer having excellent physical properties such as heat resistance, releasability, chemical resistance, transparency, durable light resistance, and low refractive index.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

In the following, GC for gas chromatography analysis, GC-MS for gas chromatography mass analysis, IR for infrared absorption spectrum analysis, TMS for tetramethylsilane, R225 for CClF ₂ CF ₂ CHClF, and CCl ₂ FCClF ₂ R113. Each NMR data is shown as an apparent chemical shift range, and the integral value is expressed as a ratio.

[Example 1] Production Example of Compound (5-1) The following compound (6-1) (450 g) was placed in a flask, and (CF ₃ C (O)) ₂ O (927 g) was added while cooling the flask. Added dropwise over a period of minutes. After completion of the dropping, the inside of the flask was stirred at 25 ° C. for 4 hours, and then CF ₃ CH ₂ OH (442 g) was dropped into the flask over 2 hours while cooling the flask with ice water. After completion of dropping, the inside of the flask was stirred at 25 ° C. for 3 days.

  The liquid in the flask was concentrated under reduced pressure to obtain a crude product (777 g, light brown liquid). As a result of analyzing the crude product by GC, NMR and IR, the following compound (5-1) (reaction yield: 14.25%), the following compound (5a-1) (reaction yield: 83.7%) and the following compound: Formation of (5b-1) (reaction yield 1.6%) was confirmed.

The crude product (709 g) was placed in the flask, and (CF ₃ C (O)) ₂ O (70 g) was gradually added dropwise, followed by stirring at 25 ° C. for 1 hour. The reaction solution was obtained by concentrating the liquid in the flask under reduced pressure. As a result of GC analysis of the reaction product, the content of the compound (5b-1) was 0.5% or less.

The NMR data of the compound (5-1) are shown below.
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 1.8 to 2.4 (m, 14H), 4.46 (q, 2H)
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −74.1 (t, 6F).

The NMR data of the compound (5a-1) are shown below.
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 1.73 (s, 2H), 1.9 (dd, 8H), 2.1 (s, 2H) 2 .2 (s, 2H), 4.47 (q, 4H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): −74.4 (t, 6F).

The NMR data of the compound (5b-1) are shown below.
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 1.6 to 1.8 (m, 12H), 2.3 (s, 2H), 4.46 (q , 2H)
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −74.2 (t, 3F).
The ¹³ C-NMR data of the compound (5b-1) are shown below.
¹³ C-NMR (75.1 MHz, solvent: CDCl ₃ , standard: CDCl ₃ ) δ (ppm): 30.1 (s), 34.8 (s), 37.4 (s), 44.1 (s ), 44.2 (s), 45.9 (s), 60.2 (d), 68.2 (s), 123 (q), 174.6 (s).
IR data of the compound (5b-1) are shown below.
IR (cm < ^-1 >): 3370 (br), 2910, 1740, 1290, 1160.

[Example 2] Production Example of Compound (4-1) An autoclave (made of nickel, internal volume 500 mL) was prepared, and a NaF pellet packed layer was installed at the gas outlet of the autoclave. R113 (312 g) was added to the autoclave and stirred while maintaining at 25 ° C. As it was, nitrogen gas was blown into the autoclave for 1 hour, and then fluorine gas diluted to 20% volume with nitrogen gas (hereinafter referred to as 20% fluorine gas) was blown. A solution obtained by dissolving the reaction product (2 g) obtained in Example 1 in R113 (40 g) was introduced into an autoclave, and 20% fluorine gas was blown as it was.

  Next, after nitrogen gas was blown into the autoclave, the contents were collected and analyzed by NMR. As a result, it was confirmed that the following compound (4-1) and the following compound (4a-1) were produced.

The NMR data of the compound (4-1) are shown below.
¹⁹ F-NMR (282.7 MHz, solvent CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −76.0 (3F), −86.0 (3F), −91.0 (2F), −102. 0-104.0 (2F), -111.0-114.0 (8F), -121.0 (2F), -217.5 (2F).

The NMR data of the compound (4a-1) are shown below.
¹⁹ F-NMR (282.7 MHz, solvent CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −86.0 (6F), −91.0 (4F), −98.0 (2F), −110. 0 (8F), -121.0 (2F), -217.5 (2F).

[Example 3] Production example of compound (3-1) A mixture of compound (4-1) and compound (4a-1) (256.9 g) obtained in the same manner as in Example 2 in a flask under a nitrogen gas atmosphere. And KF (1.46 g) were added, and the inside of the flask was heated at 80 to 90 ° C. for 20 hours.

After allowing the flask to cool, the contents of the flask were collected to obtain a solid (157.6 g). As a result of analyzing solid matter by GC and ¹⁹ F-NMR, it was confirmed that the following compound (3a-1) and compound (3-1) were produced.

The NMR data of the compound (3-1) are shown below.
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): 55.2 (s, 1F), −102.4 (m, 6F), −113.6 (m, 6F), -217.5 (s, 2F).

The NMR data of the compound (3a-1) are shown below.
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): 55.6 (s, 2F), −97.9 (s, 2F), −109.9 (s, 8F), -120.6 (s, 2F), -217.7 (s, 2F).

[Example 4] Production Example of Compound (2-1) The solid matter (42 g) obtained in Example 3 was dissolved in acetone (207 g), NaF (20 g) and ice (8 g) were added, and then 12 ° C at 25 ° C. Stir for hours. The filtrate obtained by filtering the obtained product was concentrated to obtain a brown solid-liquid mixture (34.5 g). The formation of the following compound (2-1) and the following compound (2a-1) was confirmed by NMR and GC-MS analysis of the mixture. The mixture (34.5 g) was purified by column chromatography to obtain a highly pure compound (2-1) (6.76 g, colorless liquid).

The NMR data of the compound (2-1) are shown below.
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 3.79 (m, 1H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −107.6 (m, 6F), −118.9 to −121.2 (m, 6F), − 218.2 (s, 2F).
MS molecular ion peak of compound (2-1): 404.

The NMR data of the compound (2a-1) are shown below.
¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 3.78 (s, 2H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , standard: CFCl ₃ ) δ (ppm): −107.6 (m, 6F), −118.9 to −121.2 (m, 6F), − 218.2 (s, 2F).
MS molecular ion peak of compound (2a-1): 388.

[Example 5] Production Example of Compound (1-1) The flask was charged with the compound (2-1) (96 mg) obtained in Example 4, dimethyl sulfoxide (5 g), and 10% by mass KOH aqueous solution, and further a formalin aqueous solution. (1.2 g) was added, and the inside of the flask was heated at 70 ° C. for 10 hours. Next, water (50 mL) was put into the flask, and further 1 mol / L HCl aqueous solution was added to adjust the pH of the solution in the flask to 4. Then, the solution in the flask was extracted with R225 (30 mL × 2). The obtained extract was washed with water, dried over anhydrous magnesium sulfate, and concentrated to obtain the following compound (1-1) (50 mg).

¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 4.57 (s, 2H).
¹⁹ F-NMR (282.7 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): −113.5 to −114.1 (m, 6F), −121 (m, 6F), −219. 2 (s, 2F).

According to the production method of the present invention, a novel fluoroadamantane derivative excellent in heat resistance, releasability, chemical resistance, transparency, durable light resistance, low refractive index and the like and a production method thereof are provided. The fluoroadamantane derivative of the present invention is useful as an optical fiber material, a pellicle material, a lens material, a display surface protective film, and the like.

Claims (6)

A compound represented by the following formula (6) is reacted with a compound represented by the formula (R ^FA C (O)) ₂ O, and then a compound represented by the formula R ^FB CH ₂ OH is reacted. (5) The manufacturing method of the compound represented by.

However, the symbol in a formula shows the following meaning.
G: A halogen atom or a hydroxy group.
J: a hydrogen atom or a group represented by the formula —C (O) G, and two Js may be the same or different.
R ^FA and R ^FB : each independently a perfluoroalkyl group which may contain an etheric oxygen atom having 1 to 20 carbon atoms.
T: a group corresponding to each of J, T corresponding to J being a hydrogen atom is a hydrogen atom, and T corresponding to J being a group represented by the formula —C (O) G is represented by the formula —C (O ) groups represented by the group or the formula -OC ^{(O) R FA} represented by _OCH 2 ^{R FB.} A compound represented by the following formula (31):

However, the symbol in a formula shows the following meaning.
Q: —CHF— or —CF ₂ —, wherein six Qs may be the same or different.
Z ^{1 is a} hydrogen atom, a fluorine atom, a hydroxy group or a fluorocarbonyl group, and two Z ^{1 s} may be the same or different. A compound represented by the following formula (311):

However, the symbol in a formula shows the following meaning.
Z ^{11 is a} fluorine atom, a hydroxy group or a fluorocarbonyl group, and two Z ¹¹ may be the same or different. A compound represented by the following formula (31) is reacted with a protic nucleophilic species to obtain a compound represented by the following formula (2), and then the compound represented by the following formula and the formula R-CHO are made basic. The manufacturing method of the compound represented by the following Formula (1) made to react in presence of a compound.

However, the symbol in a formula shows the following meaning.
Q: —CHF— or —CF ₂ —, wherein six Qs may be the same or different.
Z ^{1 is a} hydrogen atom, a fluorine atom, a hydroxy group or a fluorocarbonyl group, and two Z ^{1 s} may be the same or different.
Y: a group corresponding to each of Z ¹ , Y corresponding to a hydrogen atom Z ¹ corresponds to a hydrogen atom, and Y corresponding to a fluorine atom Z ¹ corresponds to a fluorine atom and a hydroxy group Z ¹ Y corresponding to Z ¹ which is a hydroxy group and a fluorocarbonyl group is a hydrogen atom.
R: A hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
X: a group corresponding to Y, X corresponding to Y being a hydrogen atom is a hydrogen atom or a group represented by the formula -CHROH, X corresponding to Y being a fluorine atom is a fluorine atom or a hydroxy group X corresponding to a certain Y is a hydroxy group. A compound represented by the following formula (11):

However, the symbol in a formula shows the following meaning.
Q: —CHF— or —CF ₂ —, wherein six Qs may be the same or different.
R: A hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
X ^{1 is a} hydrogen atom, a fluorine atom, a hydroxy group or a group represented by the formula —CHROH, and two X ^{1 s} may be the same or different. A compound represented by the following formula (111):

However, the symbol in a formula shows the following meaning.
X ^{11 is a} fluorine atom, a hydroxy group or a hydroxymethyl group, and two X ^{11 s} may be the same or different.