JPH05271129A - @(3754/24)perfluorodecalin)alcoholic derivative - Google Patents

Abstract

PURPOSE:To obtain a new (perfluorodecalin)alcoholic derivative, excellent as a raw material for surfactants and water and oil repellents and further useful as a raw material, etc., for fluororesins and fluororubbers. CONSTITUTION:The objective (perfluorodecalin)alcoholic derivative is expressed by formula I (n, is 0 or 1), e.g. 1-hydroxymethyl-perfluorodecalin. This compound can be produced by fluorinating a naphthalene derivative expressed by formula II or III or formula IV or V (R<1> and R<3> are H or 1-6C alkyl) with a fluorinating agent such as fluorine gas or hydrogen fluoride, then reacting the resultant compound with a saturated aliphatic alcohol expressed by the formula R<2>-OH or R<4>-OH (R<2> and R<4> are 1-6C alkyl), providing a compound of formula VI or VII and subsequently reducing the obtained compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel (perfluorodecalin) alcohol compound, and more particularly, it is useful as a raw material for a surfactant, a water / oil repellent agent, a fluororesin or a fluororubber synthetic material (perfluorodecaline) Decalin) relating to alcoholic substances.

[0002]

2. Description of the Related Art Conventionally, a fluorine atom combines with most elements and has a large binding energy, and in addition to being a little larger than a hydrogen atom and about the same size as oxygen, it is different from other halogen atoms. It is known that hydrogen atoms of organic compounds can be sequentially replaced by fluorine atoms. Therefore, it is possible to produce various organic fluorine compounds having various excellent physical properties from low fluorinated compounds to highly fluorinated highly fluorinated compounds. In particular, high fluoride has a structure in which the carbon chain is surrounded by fluorine atoms, which makes it difficult to attack reagents and the like from the outside and weakens the interaction between molecules of the same species and molecules of other species. With the function. Such high fluorides are generally characterized by thermal and chemical stability, electrical properties, surface activity, surface properties and the like. On the other hand, low fluoride exhibits remarkable properties in terms of physiological activity. Therefore, the application fields of organic fluorine compounds include surfactants, water and oil repellents, release agents, fluorine oils, inert liquids, fluororesins, fluororubbers, fluororesins, fluorosilicones, and the like. Recently, it has been attracting attention as an agricultural / pharmaceutical intermediate and a medical material. As described above, since the field of application of the organic fluorine compound is extremely wide, research and development of new organic fluorine compounds are being actively conducted.

[0003]

DISCLOSURE OF THE INVENTION The present invention is to provide a novel organic fluorine compound which is excellent as a raw material for surfactants and water / oil repellents and is useful as a raw material for the synthesis of fluororesins and fluororubbers. It was done for the purpose.

[0004]

Means for Solving the Problems As a result of intensive studies to develop a novel organic fluorine compound having the above-mentioned properties, the present inventors found that a specific (perfluorodecalin) alcohol compound is suitable for the purpose. I found that The present invention has been completed based on such findings. That is, the present invention has the general formula (I)

[0005]

[Chemical 2]

[In the formula, n represents 0 or 1. ] It provides the (perfluorodecalin) alcohol body represented by this. The (perfluorodecalin) alcohol compound of the present invention is a novel compound that has not been published in the literature, and has the general formula (II) when n is 0 in the general formula (I).

[0007]

[Chemical 3]

Hydroxymethyl-perfluorodecalin represented by the general formula (III) in which n is 1

[0009]

[Chemical 4]

It can be classified into (2-hydroxy-1,1-difluoro) ethyl-perfluorodecalin represented by: Further, the bonding positions of the hydroxymethyl group in the general formula (II) and the (2-hydroxy-1,1-difluoro) ethyl group in the general formula (III) are at the 1-position and the 2-position of the perfluorodecalin ring, respectively. It may be. That is, the (perfluorodecalin) alcohol compound of the present invention includes 1-hydroxymethyl-perfluorodecalin, 2-hydroxyethyl-perfluorodecalin, 1- (2-hydroxy-1,1-difluoro) ethyl-perfluorodecalin and 2- ( 2-hydroxy-1,1-difluoro) ethyl-perfluorodecalin.

The method for producing the hydroxymethyl-perfluorodecalin represented by the above general formula (II) is not particularly limited and various methods can be used, but the following method is preferably used. First, the general formula (IV) or (IV ')

[0012]

[Chemical 5]

[Wherein R ¹ is a hydrogen atom or a carbon number of 1 to 6]
Represents an alkyl group of. ] The naphthalene derivative represented by the following formula is fluorinated using a fluorinating agent such as fluorine gas or hydrogen fluoride, and then represented by the general formula (V) R ² —OH (V) [wherein R ² is carbon. The alkyl groups of the numbers 1 to 6 are shown. ] By reacting a saturated aliphatic alcohol represented by the general formula (VI)

[0014]

[Chemical 6]

[In the formula, R ² has the same meaning as described above. ]
By obtaining an alkoxycarbonyl-perfluorodecalin represented by and then reducing this, the hydroxymethyl-perfluorodecalin represented by the general formula (II) can be obtained.

Examples of the naphthalene derivative represented by the above general formula (IV) include naphthylmethyl formate, naphthylmethyl acetate, naphthylmethyl propionate, naphthylmethyl butyrate and naphthylmethyl valerate. Examples of the naphthalene derivative represented by the general formula (IV ′) include naphthalenecarboxylic acid, methyl naphthalenecarboxylate, ethyl naphthalenecarboxylate, propyl naphthalenecarboxylate, butyl naphthalenecarboxylate, and amyl naphthalenecarboxylate. .. Further, examples of the saturated aliphatic alcohol represented by the general formula (V) include methanol, ethanol, n-propanol, isopropanol, various butanols, various pentanols, various hexanols, and cyclohexanols.

When the naphthalene derivative represented by the above general formula (IV) or (IV ') is fluorinated, no solvent may be used. For example, chloroform, carbon tetrachloride, methylene chloride, trifluoroacetic acid, chloro. It is advantageous to use a solvent containing a halogen atom in the molecule, such as fluoroether and freon-113 (1,1,2-trichloro-1,2,2-trifluoroethane). In particular, CFC-113 is preferably used in terms of reactivity and economy. The reaction temperature for fluorination is usually selected in the range of -50 ° C to 100 ° C, preferably -20 ° C to 30 ° C. This temperature is -50
Below ℃, the reaction rate is too slow to be practical,
When it exceeds, the decomposition of the reaction product becomes remarkable, which is not preferable.

In the reduction reaction of the alkoxycarbonyl-perfluorodecalin represented by the general formula (VI), lithium aluminum hydride, sodium borohydride, sodium bis (2-methoxyethoxy) aluminum hydride are used as reducing agents. Metal hydrides such as, especially lithium aluminum hydride are preferably used.
Hydrogen gas can also be used. When reducing with the metal hydride, usually in an ether solvent,
It is carried out at a temperature in the range of -80 to 20 ° C. On the other hand, the reduction using hydrogen gas is usually carried out in a suitable solvent in the presence of a hydrogenation catalyst such as ruthenium carbon, rhodium carbon, platinum carbon or palladium carbon.

The hydroxymethyl-perfluorodecalin represented by the general formula (II) can also be produced by the following method. First, a naphthalene derivative represented by the general formula (IV) or (IV ′) is fluorinated by the same method as described above, and then reacted with water, or an alkoxycarbonyl group represented by the general formula (VI). Hydrolyze perfluorodecalin to give a compound of general formula (VII)

[0020]

[Chemical 7]

By obtaining the perfluorodecalincarboxylic acid represented by the formula (1) and then reducing it in the same manner as described above, the hydroxymethyl-perfluorodecalin represented by the general formula (II) can be obtained. On the other hand, the above general formula (III)
The method for producing (2-hydroxy-1,1-difluoro) ethyl-perfluorodecalin represented by is not particularly limited and various methods can be used, but the following method is preferably used. First, the general formula (VIII) or (VIII ')

[0022]

[Chemical 8]

[Wherein R ³ is a hydrogen atom or a carbon number of 1 to 6]
Represents an alkyl group of. ] The naphthalene derivative represented by the following formula is fluorinated using a fluorinating agent such as fluorine gas or hydrogen fluoride, and then the general formula (IX) R ⁴ —OH (IX) [wherein R ⁴ is carbon The alkyl groups of the numbers 1 to 6 are shown. ] By reacting with a saturated aliphatic alcohol represented by the general formula (X)

[0024]

[Chemical 9]

[In the formula, R ⁴ has the same meaning as described above. ]
Alkoxycarbonyldifluoromethyl-perfluorodecalin represented by the following formula is obtained, and this is then reduced to give (2-hydroxy-
1,1-difluoro) ethyl-perfluorodecalin is obtained.

Examples of the naphthalene derivative represented by the general formula (VIII) include naphthyl acetic acid, methyl naphthyl acetate, ethyl naphthyl acetate, propyl naphthyl acetate, butyl naphthyl acetate, pentyl naphthyl acetate, and hexyl naphthyl acetate. Examples of the naphthalene derivative represented by the general formula (VIII ') include 2-naphthylethyl formate, 2-naphthylethyl acetate and propionic acid 2
-Naphthylethyl, 2-naphthylethyl butyrate, valeric acid 2
-Naphthylethyl, 2-naphthylethyl caproate and the like can be mentioned. Furthermore, examples of the saturated aliphatic alcohol represented by the general formula (IX) include methanol, ethanol, n-propanol, isopropanol, various butanols, various pentanols, various hexanols, and cyclohexanols.

Fluorination of the naphthalene derivative represented by the general formula (VIII) or (VIII ') and reduction of the alkoxycarbonyldifluoromethyl-perfluorodecalin represented by the general formula (X) are carried out by the above general formula (II). Can be carried out by a method similar to the method described in the production of hydroxymethyl-perfluorodecalin. In addition, (2-hydroxy-1, represented by the general formula (III)
1-Difluoro) ethyl-perfluorodecalin can also be produced by the method shown below. First, the naphthalene derivative represented by the general formula (VIII) or (VIII ') is fluorinated by the same method as described above, and then reacted with water, or by the alkoxycarbonyldifluoro represented by the general formula (X). By hydrolyzing methyl-perfluorodecalin, a compound of the general formula (XI)

[0028]

[Chemical 10]

The (perfluorodecalin) difluoroacetic acid represented by the formula (III) is obtained by reducing the difluoroacetic acid represented by the general formula (III).
1,1-difluoro) ethyl-perfluorodecalin is obtained.

[0030]

The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

Example 1 (1) Production of 1-methoxycarbonyl-perfluorodecalin In 450 g of Freon 113 solvent, 7 g of 1-naphthylmethyl acetate was put, and fluorine gas was blown into this at 0 ° C. to carry out a fluorination reaction. It was Next, when 30 g of methanol was added to this reaction system to carry out a reaction, 1-methoxycarbonyl-perfluorodecalin was obtained with a yield of 80%. The infrared (IR) spectrum of this product is shown in Fig. 1.
Fig. 2 shows the proton nuclear magnetic resonance ( ¹ H-NMR) spectrum.
FIG. 3 shows a nuclear magnetic resonance ( ¹⁹ F-NMR) spectrum using isotope fluorine, and FIG. 4 shows a gas chromatograph-mass spectrum (GC-MS) analysis result. Figure 1
From the IR spectrum, carbonyl group (C = O), confirmed the presence of a methyl group (CH ₃₎ and C-F bonds. Of FIG.
^{From the 1} H-NMR spectrum, a methoxycarbonyl group (-
The presence of H derived from COOCH ₃ ) was confirmed. ^{19 of} FIG.
From the F-NMR spectrum, it was confirmed that the abundance ratio (CF ₂ : CF) of the part in which two fluorines were bonded to carbon and the part in which one fluorine was bonded to carbon was approximately 14: 3. Furthermore, it was confirmed from GC-MS in FIG. 4 that the molecular weight was 502.

(2) Preparation of 1-hydroxymethyl-perfluorodecalin 0.69 g of lithium aluminum hydride (LiAlH ₄ ) was suspended in 10 ml of diethyl ether, and -7
Cooled to 8 ° C. To this, a solution prepared by diluting 3 g of 1-methoxycarbonyl-perfluorodecalin obtained in (1) above with 5 ml of diethyl ether was added dropwise over 10 minutes. After dropping, slowly at 20 ℃ for about 1 hour
The temperature was raised to. After the reaction, excess LiAlH ₄ was treated, acidified with sulfuric acid, and the ether layer was concentrated.
1-Hydroxymethyl-perfluorodecalin yield 7
Obtained at 0%. The infrared (IR) spectrum of this product is shown in FIG. 5, the proton nuclear magnetic resonance ( ¹ H-NMR) spectrum is shown in FIGS. 6 and 7 (D ₂ O added), and the nuclear magnetic resonance with isotope fluorine ( ¹⁹ F-NMR) is shown. The spectrum is shown in FIG. 8 and the gas chromatograph-mass spectrum (GC-MS) analysis result is shown in FIG. 9, respectively.

From the IR spectrum of FIG. 5, a methylene group (-
The presence of CH ₂ —) and hydroxyl group (—OH) was confirmed. From the ¹ H-NMR spectrum of FIG. 6, a methylene group (—CH ₂
It was confirmed that the abundance ratio of H derived from −) to H derived from the hydroxyl group (—OH) was approximately 2: 1 (that is, the ratio of methylene group to hydroxyl group was 1: 1). ¹ H-N in FIG.
From the MR spectrum (D ₂ O addition), it was confirmed that the hydroxyl group was an alcoholic hydroxyl group because the peak at 5.4 ppm disappeared (the alcoholic hydroxyl group is easily proton-exchanged, and addition of D ₂ O- The peak has disappeared because it became OD). From the ¹⁹ F-NMR spectrum in FIG. 8, the part where two fluorines are bonded to carbon and the carbon is 1
Abundance ratio with two fluorine-bonded parts (CF ₂ : CF)
Was about 14: 3. Furthermore, it was confirmed from GC-MS in FIG. 9 that the molecular weight was 474.

Example 2 (1) 1-methoxycarbonyldifluoromethyl-per
Production of fluorodecalin In 450 g of Freon 113 solvent, methyl 1-methylacetate was added.
Add 7g and blow fluorine gas into it at 0 ° C.
Fluorination reaction was performed. Next, methanol is added to this reaction system.
When 30 g was added and the reaction was carried out,
Lubonyldifluoromethyl-perfluorodecalin
It was obtained at a rate of 75%. Infrared (IR) spectrum of this thing
Toll is shown in Fig. 10, and proton nuclear magnetic resonance (¹H-NMR)
Fig. 11 shows the spectrum, and nuclear magnetic resonance (
¹⁹F-NMR) spectrum is shown in FIG.
The rough-mass spectrum (GC-MS) analysis results are shown in FIG.
Shown in. From the IR spectrum of FIG. 10, the carbonyl group
(C = O), methyl group (CH₃) And the presence of C—F bonds
confirmed. Of FIG.¹From the H-NMR spectrum,
Toxycarbonyl group (-COOCH ₃) Of hydrogen derived from
Existence was confirmed. Of FIG.¹³F-NMR spectrum
CF₂: CF was found to be 16: 3. It
In addition, the molecular weight is 552 according to GC-MS in FIG.
I understood it.

(2) Production of 1- (2-hydroxy-1,1-difluoro) ethyl-perfluorodecalin 0.41 g of lithium aluminum hydride (LiAlH ₄ ) was suspended in 10 ml of diethyl ether, and -7
Cooled to 8 ° C. To this, a solution prepared by diluting 3 g of 1-methoxycarbonyldifluoromethyl-perfluorodecalin obtained in (1) above with 5 ml of diethyl ether was added dropwise over 10 minutes. After the dropping, the temperature was slowly raised to 20 ° C. over about 1 hour. After the reaction, excess LiAl
After H ₄ was treated and acidified with sulfuric acid, the ether layer was concentrated to give 1 (2-hydroxy-1,1-difluoro) ethyl-perfluorodecalin in a yield of 75%. The infrared (IR) spectrum of this product is shown in FIG.
The proton nuclear magnetic resonance ⁽¹ H-NMR) spectra in FIGS. 15 and 16 (D ₂ O added), nuclear magnetic resonance with isotopes fluorine ⁽¹⁹ F-NMR) spectrum in Figure 17, gas chromatography - mass The results of the spectrum (GC-MS) analysis are shown in FIG. From the IR spectrum of FIG. 14, methylene group (—CH ₂ —), hydroxyl group (—OH) and C—F
The presence of the bond was confirmed. From the ¹ H-NMR spectrum of FIG. 15, a methylene group (—CH ₂ —) and a hydroxyl group (—O
The presence of H) was confirmed. From the ¹ H-NMR spectrum (D ₂ O added) in FIG. 16, it was confirmed that the hydroxyl group was an alcoholic hydroxyl group because the peak at 2.9 ppm disappeared. From the ¹⁹ F-NMR spectrum in FIG. 17, C
It was found that the F ₂ : CF was 16: 3. further,
From GC-MS in FIG. 18, it was found that the molecular weight was 524.

[0036]

INDUSTRIAL APPLICABILITY The (perfluorodecalin) alcohol body of the present invention can be widely and effectively used as a raw material for surfactants and water / oil repellents, and as a synthetic raw material for fluororesins and fluororubbers in various fields. , Industrial value is extremely large.

[Brief description of drawings]

1-methoxycarbonyl-obtained in Example 1
It is an IR spectrum figure of perfluorodecalin.

FIG. 2 1-methoxycarbonyl-obtained in Example 1
It is a < ¹ > H-NMR spectrum figure of perfluorodecalin.

FIG. 3 1-methoxycarbonyl-obtained in Example 1
It is a < ¹⁹ > F-NMR spectrum figure of perfluorodecalin.

FIG. 4 1-methoxycarbonyl-obtained in Example 1
It is a GC-MS figure of perfluorodecalin.

5 is an IR spectrum diagram of 1-hydroxymethyl-perfluorodecalin obtained in Example 1. FIG.

6 is a ¹ H-NMR spectrum diagram of ¹ -hydroxymethyl-perfluorodecalin obtained in Example 1. FIG.

FIG. 7 ¹ H-NMR spectrum (D ₂ O of ¹ -hydroxymethyl-perfluorodecalin obtained in Example 1)
FIG.

8 is a ¹⁹ F-NMR spectrum diagram of 1-hydroxymethyl-perfluorodecalin obtained in Example 1. FIG.

9 is a GC-MS diagram of 1-hydroxymethyl-perfluorodecalin obtained in Example 1. FIG.

10 is an IR spectrum diagram of 1-methoxycarbonyldifluoromethyl-perfluorodecalin obtained in Example 2. FIG.

FIG. 11 ¹ H-NM of 1-methoxycarbonyldifluoromethyl-perfluorodecalin obtained in Example 2.
It is an R spectrum figure.

12: ¹⁹ F-NM of 1-methoxycarbonyldifluoromethyl-perfluorodecalin obtained in Example 2 FIG.
It is an R spectrum figure.

FIG. 13: GC-MS of 1-methoxycarbonyldifluoromethyl-perfluorodecalin obtained in Example 2.
It is a figure.

FIG. 14: 1- (2-hydroxy-) obtained in Example 2
FIG. 3 is an IR spectrum diagram of 1,1-difluoro) ethyl-perfluorodecalin.

FIG. 15: 1- (2-hydroxy-) obtained in Example 2
Of 1,1-difluoro) ethyl-perfluorodecalin
^{It is a} < ¹ > H-NMR spectrum figure.

FIG. 16: 1- (2-hydroxy-obtained in Example 2)
Of 1,1-difluoro) ethyl-perfluorodecalin
¹ H-NMR spectrum (D ₂ O added) diagrams.

FIG. 17: 1- (2-hydroxy-obtained in Example 2)
Of 1,1-difluoro) ethyl-perfluorodecalin
^{It is a 19} F-NMR spectrum figure.

FIG. 18: 1- (2-hydroxy-) obtained in Example 2
FIG. 3 is a GC-MS diagram of 1,1-difluoro) ethyl-perfluorodecalin.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C09K 3/18 102 8318-4H

Claims (1)

[Claims] 1. A compound represented by the general formula (I): [In formula, n shows 0 or 1. ] (Perfluorodecalin) alcoholic body represented by