JP2003146947A - Method for producing organic ammonium hydroxide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an organic ammonium hydroxide from a fluorine-containing amine compound. SOLUTION: This method for producing the organic ammonium hydroxide of formula 2: [R<1> -Ar-CH2 N(R<3> )3 ]<+> -OH<-> (Ar is at least one fluoro- or fluoroalkyl- aryl; R<1> is an alkyl, or a halo- or hydroxy-alkyl; R<3> is independently a hydrogen atom, a hydrocarbon group or a hydrocarbon group substituted with a halogen group or a hydroxy group) comprises reacting a fluorine-containing amine compound of formula 3: R<1> -Ar-CH2 N(R<2> )2 (wherein, Ar is same as the one in formula 2; R<2> is independently H, an alkyl, or a halo- or hydroxy-alkyl) with a compound of formula 4: R<3> 2 SO4 (R<3> is same as the one in formula 2) to provide an organic ammonium sulfate of formula 1: [R<1> -Ar-CH2 N(R<3> )3 ]<+> -.R<3> SO4 <-> (Ar, R<1> and R<3> are same as the ones in formula 2 respectively), and further reacting the organic ammonium sulfate with a hydroxide/oxide of an alkaline earth metal.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a novel organic ammonium hydroxide.

[0002]

2. Description of the Related Art Parylene (p-xylene resin), which has excellent heat resistance, chemical resistance, water repellency, low dielectric properties and low refractive index, is
Since it can be formed into a thin film by vapor deposition method and can be used as a base material with various shapes, parylene materials are ideal for similar coatings in a wide range of fields such as electronics, automobile industry and medical industry. Can be used. Among them, the following general formula

[0003]

[Chemical 5]

Parylene F represented by: poly (α, α,
α ′, α′-tetrafluoro-p-xylene) has a low dielectric constant and can be used as an interlayer insulating film of a next-generation semiconductor. In addition, due to its high melting point and low dielectric constant, it is expected to be used in various fields including electronics.

However, at present, the chemical structural formula I shown below, which is a dimer of the basic substance, is shown.

[0006]

[Chemical 6]

The octafluoro- [2,2] paracyclophane represented by the formula is, for example, Journal of F
luorine Chemistry, 30 (198
6) Schema described in 399-414
I;

[0008]

[Chemical 7]

And Scheme II;

[0010]

[Chemical 8]

[0012] A synthesizing method and the like have been proposed (Sc
Heme I is more practical), but in any case, the starting material hexafluorobenzene is highly toxic and difficult to handle, and the production cost is very high by these methods. Since parylene F is also very expensive, there is a problem that its use is extremely limited, such as being used only as an extremely thin film or an adhesive layer.

[0012]

Therefore, the object of the present invention has been made in view of the above circumstances, and octafluoro, which is a dimer of the basic substance of parylene, preferably parylene F, of p-xylene resin. -[2,2] paracyclophane or an organoammonium hydroxide, which is an intermediate of fluorine-containing paracyclophane which is a derivative thereof, can be provided as a raw material with low toxicity, which can be provided at a much lower cost than before. It is an object of the present invention to provide a method for producing an extremely useful and novel fluorine-containing amine compound at a significantly low cost.

Another object of the present invention is that it can be synthesized with a simple operation at low cost and in high yield and has low toxicity.
From a novel fluorine-containing amine compound, which is extremely useful as a raw material of octafluoro- [2,2] paracyclophane or a fluorine-containing paracyclophane which is a derivative thereof, to an organic compound which is an intermediate of fluorine-containing paracyclophane at a significantly low cost. It is to provide a method for producing ammonium hydroxide.

Another object of the present invention is, in addition to the above advantages,
Octafluoro-, which has a low impurity content, is easy to purify, and can be omitted for mass production.
From a novel fluorine-containing amine compound, which is extremely useful as a raw material for [2,2] paracyclophane or a fluorine-containing paracyclophane which is a derivative thereof, an organic ammonium hydroxide which is an intermediate of fluorine-containing paracyclophane is remarkably inexpensive. It is to provide a method of manufacturing a side.

[0015]

Therefore, the present inventors have
In order to achieve the above-mentioned objects, as a result of diligent studies on fluorinated paracyclophane, in the process up to organic ammonium hydroxide, which is an intermediate of fluorinated paracyclophane, among the conventional synthetic methods from hexafluorobenzene. Since it has the above-mentioned problems (therefore, it was also found that the synthetic method from the intermediate to the fluorine-containing paracyclophane does not have the above-mentioned problems even if it is carried out in the same manner as in the conventional method), the production of such an intermediate is , Found a very useful and novel fluorine-containing amine compound as a low-toxicity raw material that can be provided much cheaper than the conventional synthesis method from hexafluorobenzene, and a new and simple synthetic method from such raw material After that, organic ammonium hydroxide, which is an intermediate of fluorine-containing paracyclophane, is much cheaper. Become known that it is possible to provide, in which the present invention has been completed.

That is, the present invention provides the following (1) to (7).
Achieved by

(1) A method for producing an organic ammonium hydroxide obtained by reacting an organic ammonium sulfate with a hydroxide of an alkaline earth metal and / or an oxide of an alkaline earth metal.

(2) Organic ammonium sulfate is represented by the following general formula (1)

[0019]

[Chemical 9]

(In the formula, Ar represents an aromatic hydrocarbon group substituted with at least one fluorine atom or a fluoroalkyl group. R ¹ is a hydrocarbon group or a hydrocarbon group substituted with a halogen group or a hydroxyl group. Represents a group.
R ^3's each independently represent a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a halogen group or a hydroxyl group. ), The organic ammonium hydroxide is represented by the following general formula (2)

[0021]

[Chemical 10]

[0022] (wherein, Ar, R ¹ and R ³ are the same as Ar, R ¹ and R ³ in the general formula (1).) The organic ammonium according to (1) represented by hydro key Side manufacturing method.

(3) The method for producing an organic ammonium hydroxide according to the above (2), wherein R ¹ and R ³ are each a hydrocarbon group.

(4) The organic ammonium hydro according to (2) or (3) above, wherein Ar is an aromatic monocyclic hydrocarbon group, and the sum of the fluorine source substituted with Ar and the fluoroalkyl group is 4. The manufacturing method of kid side.

(5) The method for producing an organic ammonium hydroxide according to any one of the above (2) to (4), wherein R ¹ and R ³ are both methyl groups.

(6) The method for producing an organic ammonium hydroxide according to any one of the above (2) to (5), wherein Ar is a tetrafluorophenylene group.

(7) The following general formula (3)

[0028]

[Chemical 11]

[0029] (.R ² wherein, Ar and R ¹ are the same as Ar and R ¹ in the general formula (1) are each independently replaced with hydrogen atom, a hydrocarbon group or a halogen group or a hydroxyl group To a fluorine-containing amine compound represented by the following general formula (4)

[0030]

[Chemical 12]

[0031] (wherein, R ³ is, R ³ is the same as. In formula (1)) by reacting a compound represented by, to obtain the organic ammonium sulfate, alkali organic ammonium sulfate A method for producing an organic ammonium hydroxide, which comprises reacting a hydroxide of an earth metal and / or an oxide of an alkaline earth metal.

[0032]

BEST MODE FOR CARRYING OUT THE INVENTION The method for producing organic ammonium hydroxide according to the present invention (the first production method) is a method in which an alkaline earth metal hydroxide and / or an alkaline earth metal oxide is added to organic ammonium sulfate. It is characterized by reacting. A method for producing organic ammonium hydroxide according to another invention of the present invention (second production method) is represented by the fluorine-containing amine compound represented by the general formula (3) and the general formula (4). Is obtained by reacting the compound with an organic ammonium sulfate, and the organic ammonium sulfate is reacted with a hydroxide of an alkaline earth metal and / or an oxide of an alkaline earth metal. .

Hereinafter, (I) the first production method of the present invention, (II)
The second manufacturing method of the present invention will be sequentially described.

(I) The first manufacturing method of the present invention will be described.

The first production method of the present invention is characterized by reacting an organic ammonium sulfate with a hydroxide of an alkaline earth metal and / or an oxide of an alkaline earth metal.

Here, the organic ammonium sulfate as a raw material is not particularly limited, and conventionally known ones can be used, but the one represented by the general formula (1) is preferable. Hereinafter, the general formula (1) will be mainly described.

Here, R ¹ in the general formula (1) represents a hydrocarbon group or a hydrocarbon group substituted with a halogen group or a hydroxyl group.

Here, the hydrocarbon group is not particularly limited and may be an unsubstituted monovalent hydrocarbon group, such as an aliphatic hydrocarbon group (chain hydrocarbon group) or an alicyclic group. It may be a formula hydrocarbon group or an aromatic hydrocarbon group, but is preferably a linear or branched monovalent alkyl group having 1 to 20 carbon atoms (saturated hydrocarbon group). , A monovalent aliphatic hydrocarbon group consisting of a monovalent chain unsaturated hydrocarbon group having 2 to 20 carbon atoms; a monovalent alicyclic hydrocarbon consisting of a monovalent cycloalkyl group having 3 to 20 carbon atoms Group; or a monovalent aromatic hydrocarbon group consisting of a monovalent aryl group having 6 to 20 carbon atoms and a monovalent aralkyl group having 7 to 20 carbon atoms, and more preferably a straight chain having 1 to 6 carbon atoms. Chain-like or branched monovalent lower alkyl group having a side chain, having 3 to 3 carbon atoms A lower cycloalkyl group, particularly preferably a methyl group.

Specific examples of the above-mentioned aliphatic hydrocarbon group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, te.
rt-butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, isohexyl group, heptyl group, methylhexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group,
Tridecyl group, tetradecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, vinyl group, 1-propenyl group, allyl group, isopropenyl group,
Examples thereof include a 1-butenyl group, a 2-butenyl group, a 2-methylallyl group, a 2-pentenyl group, an ethynyl group and a 1-propynyl group.

Specific examples of the alicyclic hydrocarbon group include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, Cyclododecyl group, cyclotridecyl group,
Examples thereof include a cyclotetradecyl group, a cyclopentadecyl group, a cyclohexadecyl group, a cycloheptadecyl group, a cyclooctadecyl group, cyclic terpenes, and a 1-cyclohexenyl group.

Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and an anthryl group; an alkylphenyl group such as a tolyl group, a xylyl group, a missicyl group, and a cumenyl group; 1-naphthyl group, 2- Examples thereof include naphthyl group, benzyl group, phenethyl group, p-benzyl group and methylbenzyl group.

The substituted halogen group of the hydrocarbon group in the hydrocarbon group substituted with a halogen group or a hydroxyl group is not particularly limited,
Examples thereof include a fluoro group, a chloro group, a bromo group, an iodo group, an iodosyl group and an iodoyl group, but a fluoro group is preferable.

The type of the substituted halogen group or the hydroxyl group of the hydrocarbon group may be one type or two or more types. Moreover, the number of the substituted halogen group of the hydrocarbon group or the substituent of the hydroxyl group may be within the range of the number of hydrogen atoms of the hydrocarbon group.

The hydrocarbon group obtained by substituting a halogen group or a hydroxyl group may be the same as the unsubstituted hydrocarbon group.

Hydrocarbon groups are preferable as R ¹ and, among them, one of the objects of the present invention is excellent in heat resistance, chemical resistance, water repellency, low dielectric property and low refractive index. Useful as a raw material for p-xylene resin
A fluorine-containing amine compound that can be a low-cost raw material suitable for inexpensively producing [2,2] paracyclophane or a derivative thereof through the organic ammonium hydroxide of the present invention using an existing production method is obtained. From the viewpoint, a methyl group is more preferable.

R ³ in the general formula (1) each independently represents a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a halogen group or a hydroxyl group.

Here, as the hydrocarbon group and the hydrocarbon group substituted with a halogen group or a hydroxyl group,
It is the same as the definition (explanation) of R ¹ described above.

The above R ^3's each independently represent an atom or a group shown above, and may be the same or different.
It may be different.

The above R ³ is preferably a hydrocarbon group, more preferably a methyl group, an ethyl group, a propyl group or a butyl group, and among them, a methyl group is particularly preferable, and the object of the present invention is particularly preferable. , Which is useful as a raw material for a resin having excellent heat resistance, chemical resistance, water repellency, low dielectric property and low refractive index, which is one of the From the viewpoint of obtaining an organic ammonium sulfate that can be a low-cost raw material suitable for, it is a case where all ^three R ³ in the general formula (1) are methyl groups.

Further, R ³ SO in the above general formula (1) is
₄ ⁻ represents a counter ion opposite to N ⁺ . That is, R ³ S
The anion of O ₄ ⁻ forms a counter ion with a cation (R ¹ —Ar—CH ₂ N ⁺ (R ³ ) ₃ containing a quaternary ammonium ion (N ⁺ )).

Ar in the general formula (1) is at least 1
It represents an aromatic hydrocarbon group substituted with one fluorine atom (fluoro group) or a fluoroalkyl group.

Here, the aromatic hydrocarbon group is not particularly limited, but preferably has 6 to 6 carbon atoms.
20 is a divalent aromatic hydrocarbon group, more preferably a phenylene group which is a divalent aromatic monocyclic hydrocarbon group, and particularly preferably a p-phenylene group (each of the para-position bonds is- R ¹ group and —CH ₂ N ⁺ (R ³ ) ₃ group are bonded).

Specific examples of the aromatic hydrocarbon group include a phenylene group, a naphthylene group and an anthrylene group.

Residue of the aromatic ring of the divalent aromatic hydrocarbon group (the term "residue" here means -R ¹ group and -CH ₂ N group).
^At least one of the substituents which can be substituted on ⁺ (R ³ ) ₃ other than the bonding position to which the group is bonded is a fluorine atom or a fluoroalkyl group, but preferably all the remaining residues are fluorine atoms. Is. This is because a fluorine atom can provide a low-cost raw material that can obtain octafluoro- [2,2] paracyclophane or a derivative thereof that is more excellent in heat resistance than a fluoroalkyl group. In addition, as the substituent that can be substituted on the residual position of the aromatic ring,
It is sufficient that at least one is a fluorine atom or a fluoroalkyl group, and the presence of other substituents is not excluded.

Here, the fluoroalkyl group capable of substituting at the residue of the aromatic ring of the divalent aromatic hydrocarbon group is not particularly limited, but preferably has 1 to 1 carbon atoms.
20 is a straight chain, branched or cyclic alkyl group having a side chain, part of which is fluorinated, preferably a straight chain having 1 to 10 carbon atoms, branched or cyclic having a side chain. Part of the alkyl group is fluorinated, and particularly preferably, part of the linear or branched alkyl group having 1 to 6 carbon atoms is fluorinated.

Specific examples of the fluoroalkyl group include mono-, di-, tri-fluoromethyl groups, mono-,
Di-, tri-, tetra-, penta-fluoroethyl groups,
Fluoropropyl group, fluorobutyl group, fluoropentyl group, fluorohexyl group, fluoroheptyl group, fluorooctyl group, fluorononyl group, fluorodecyl group, fluoroundecyl group, fluorododecyl group which are partially or wholly fluorinated. , Fluorotridecyl group, fluorotetradecyl group, fluorohexadecyl group, fluoroheptadecyl group, fluorooctadecyl group, fluorononadecyl group and the like.

Although the total sum of the fluorine atom substituted with the divalent aromatic hydrocarbon group and the fluoroalkyl group varies depending on the number of aromatic rings, in the case of a phenylene group which is a suitable aromatic hydrocarbon group, Usually 1 to 4, preferably 2 to 4
And more preferably four. This provides a raw material from which octafluoro- [2,2] paracyclophane or its derivative having excellent dielectric properties can be obtained when there is no hydrogen atom (that is, C—H bond) at the residue of the aromatic ring. Because you can.

The types of fluorine atom and fluoroalkyl group substituted on the above aromatic monocyclic hydrocarbon group may be the same or different in the case of plural types, depending on their numbers. However, from the viewpoint of providing a low cost raw material, it is preferable that all are the same species.

Therefore, as Ar, a tetrafluorophenylene group is preferable, and 2,3,3 from the viewpoint of steric hindrance.
The 5,6-tetrafluorophenylene group is more preferable.

As described above, the organic ammonium sulfate represented by the general formula (1) is most preferably N, N, N-trimethyl-2,3,5,6-tetrafluoro-4-methylbenzyl. It is ammonium sulfate (N, N, N-trimethyl-2,3,5,6-tetrafluoro-4-methylbenzylammonium monomethylsulfate).

Next, the alkaline earth metal hydroxide and / or the alkaline earth metal oxide to be reacted with the above-mentioned organic ammonium sulfate is not limited to a casting but is, for example, calcium hydroxide, as long as it is not particularly limited. Examples thereof include barium hydroxide, magnesium hydroxide, strontium hydroxide, beryllium hydroxide, calcium oxide, barium oxide, magnesium oxide, strontium oxide and beryllium oxide. These may be used alone or in combination of two or more. From the viewpoint of reactivity and cost, barium hydroxide is preferable.

In the first production method of the present invention, the above-mentioned organic ammonium sulfate is dissolved in water in an appropriate amount, and an alkaline earth metal hydroxide and / or an alkaline earth metal oxide is added thereto to obtain a solution. By stirring the obtained suspension at a predetermined temperature, the target organic ammonium hydroxide, preferably the organic ammonium hydroxide represented by the above general formula (2), is synthesized.

The amount of organic ammonium sulfate added to water is usually 0.01 to 5 mol / liter, preferably 0.1 to 1 mol / liter, and more preferably 0.5 to 1 mol / liter. To be prepared. The amount of organic ammonium sulfate added is 0.01 mol /
When it is less than 1 liter, productivity is lowered, which is not preferable, while when it exceeds 5 mol / liter, it is not preferable in terms of reaction control. In addition, "water" used in the present invention
May contain a substance that does not affect the reaction (may be in the form of a compound or an ion), and such water (aqueous solution) should be excluded from the range of water usable in the present invention. However, it is included in the technical scope of the present invention. The same applies to the use of other additives.

The amount of the alkaline earth metal hydroxide and / or the alkaline earth metal oxide added is such that the organic ammonium sulfate (preferably the above general formula (1)
1 to 100 moles of organic ammonium sulfate represented by the formula, usually 0.5 to 100 moles, preferably 0.5 to 50 moles.
The molar amount is more preferably 0.5 to 10 mol.
When the amount of the alkaline earth metal hydroxide and / or the alkaline earth metal oxide added is less than 0.5 mol, the reaction does not proceed sufficiently, while the alkaline earth metal water is added. If the added amount of the oxide and / or the alkaline earth metal oxide exceeds 100 mol, it is not preferable in terms of economy.

The alkaline earth metal hydroxide and / or the alkaline earth metal oxide may be added to the reaction system as they are, or may be added as an aqueous solution having an appropriate concentration. Although it is not particularly limited, it is preferably added as an aqueous solution in terms of diffusion rate into the entire reaction system and handleability. At this time, the amount of water used to form the aqueous solution is also a part of the amount of water used to dissolve the solid matter. The concentration of the alkaline earth metal hydroxide and / or the alkaline earth metal oxide in the case of forming an aqueous solution is not particularly limited. In addition, as a method for adding the hydroxide of an alkaline earth metal and / or the oxide of an alkaline earth metal, the whole amount may be added at once, or intermittently (stepwise) divided into several times. It may be added or may be added continuously and is not particularly limited.

The reaction is carried out while appropriately stirring the reaction solution obtained by adding these, and the reaction temperature (liquid temperature) is usually 0 to 100.
℃, preferably 10 to 50 ℃, more preferably 10 to 5
It is 0 ° C. If the reaction temperature is lower than 0 ° C, the reaction rate is lowered, which is not preferable. On the other hand, if the reaction temperature is higher than 100 ° C, an autoclave or the like is required, which is not preferable in terms of economy.

The reaction time cannot be uniquely defined because it varies depending on the concentration of the reaction solution, the liquid temperature, the liquid volume, etc., but it is usually 1 to 24 hours, preferably 1 to 12 hours. It is preferably 1 to 6 hours.

After the reaction (synthesis), a by-product precipitated (in addition, when a solid material containing organic ammonium sulfate is used as a raw material, a by-product contained therein is also included).
Is filtered, the filtered product is washed with water, and the washed water is combined with the filtrate to obtain an aqueous solution of the target organic ammonium hydroxide, preferably the organic ammonium hydroxide represented by the general formula (2). be able to. Although this solution may be further purified to isolate the desired product, it is preferably used for the production of octafluoro- [2,2] paracyclophane or a fluorine-containing paracyclophane which is a derivative thereof. This is advantageous because it leads to a reduction in product cost. The purification method after synthesis is not particularly limited, and an optimal method may be appropriately selected from various conventionally known purification methods.

As described above, the organic ammonium hydroxide (target product) of the present invention can be obtained by a simple method using an inexpensive and less toxic fluorine-containing amine compound.

Here, the organic ammonium hydroxide (target product) is not particularly limited, and conventionally known ones can be obtained by the above-mentioned production method, but preferably the general formula (2) It is an organic ammonium hydroxide represented by.

[0071] Here, Ar in formula (2), R ¹ and R ³ are the same as Ar, R ¹ and R ³ as described in the general formula (1).

HO ⁻ in the above general formula (2) is N ⁺
Represents a counterion opposite to. That is, the HO ⁻ anion is a cation (quaternary ammonium ion (N ⁺ )
A counter ion is formed with R ¹ —Ar—CH ₂ N ⁺ (R ³ ) ₃ ) containing R.

Therefore, the organic ammonium hydroxide represented by the general formula (2) is most preferably N, N, N-trimethyl-2,3,5,6-tetrafluoro-4-methylbenzylammonium hydrol. It's a side.

(II) The second manufacturing method of the present invention will be described.

As the second production method of the present invention, the fluorine-containing amine compound represented by the general formula (3) is reacted with the compound represented by the general formula (4) to obtain an organic ammonium sulfate, This organic ammonium sulfate is characterized by reacting an alkaline earth metal hydroxide and / or an alkaline earth metal oxide.

First, the fluorine-containing amine compound represented by the above general formula (3) as a raw material will be described.

Ar and R ¹ in the general formula (3) are the same as the definitions (explanation) of Ar and R ^{1 in} the general formula (1).

R ² in the general formula (3) each independently represents a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a halogen group or a hydroxyl group.

Here, as the hydrocarbon group and the hydrocarbon group substituted with a halogen group or a hydroxyl group,
It is the same as the definition (explanation) of R ¹ in the above-mentioned general formula (1).

The above R ^2's each independently represent an atom or group shown above, and may be the same or different.

Preferred as R ² is a hydrogen atom,
A straight-chain or branched monovalent lower alkyl group having 1 to 6 carbon atoms and a lower cycloalkyl group having 3 to 6 carbon atoms, more preferably one of the objects of the present invention. Octafluoro-, which is useful as a raw material for resins with excellent heat resistance, chemical resistance, water repellency, low dielectric properties and low refractive index
Both are cases of hydrogen atoms from the viewpoint of obtaining a fluorine-containing amine compound that can be a low-cost raw material suitable for inexpensively producing [2,2] paracyclophane. In the present invention, -R ² in the fluorine-containing amine compound represented by the general formula (3) is used.
Since the group is dissociated and a —R ³ group (which is usually a substituent different from the —R ² group) is bonded to form an organic ammonium sulfate of the general formula (1), R ² and R ³ are combined. The same content (range) is represented separately.

Therefore, the fluorine-containing amine compound represented by the general formula (3) is most preferably 2, 3,
It is 5,6-tetrafluoro-4-methylbenzylamine.

The fluorine-containing amine compound represented by the above general formula (3) has the following general formula (5)

[0084]

[Chemical 13]

(In the formula, Ar represents an aromatic hydrocarbon group substituted with at least one fluorine atom or a fluoroalkyl group. R ¹ is a hydrocarbon group or a hydrocarbon group substituted with a halogen group or a hydroxyl group. A compound obtained from a fluorine-containing cyano compound represented by the formula (1) is desirable.

Here, Ar and R ¹ in the general formula (5) are the same as the definitions (explanation) of Ar and R ^{1 in} the general formula (1). Therefore, the fluorine-containing cyano compound represented by the general formula (5) is most preferably 2, 3,
It is 5,6-tetrafluoro-4-methylbenzonitrile.

The reason why the fluorine-containing cyano compound represented by the general formula (5) is used is that the fluorine-containing cyano compound is already known, has low toxicity, and many methods for producing it at low cost have been developed. This is because those skilled in the art can easily produce it, and it can be easily obtained as a commercial product, and a suitable fluorine-containing cyano compound can be obtained in a high yield by the production method described below.

A new and suitable method for producing the fluorine-containing amine compound represented by the general formula (3) from the fluorine-containing cyano compound represented by the general formula (5) will be described below.

As a preferred method for producing the fluorine amine compound, for example, a fluorine-containing cyano compound represented by the above general formula (5) is subjected to hydrogenation reaction to give the following general formula (6).

[0090]

[Chemical 14]

(In the formula, Ar represents an aromatic hydrocarbon group substituted with at least one fluorine atom or a fluoroalkyl group. R ¹ is a hydrocarbon group or a hydrocarbon group substituted with a halogen group or a hydroxyl group. Represents a group.
R ^2's each independently represent a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a halogen group or a hydroxyl group. Y ⁻ represents a counter ion. ) Is obtained by synthesizing a protonic acid salt of a fluorine-containing amine compound represented by the formula (1) and treating it with an alkali.

Here, the fluorine-containing cyano compound represented by the above general formula (5) is as described above. Further, in the proton acidic salt of the fluorine-containing amine compound represented by the general formula (6), Ar and R in the general formula (6) are
With respect to ^1, the general formula (1) Ar and R ¹ defined in (description) is the same as, for R ² in the general formula (6), the general formula (3) Definition of R ² in (Description ) Is the same.

Further, Y ⁻ in the above general formula (6) represents a counter ion opposite to N ⁺ (an anion obtained by deprotonating an acid). The anion is not particularly limited and may be an organic or inorganic anion, but is preferably an inorganic anion.

As the above-mentioned anion, specifically, (C
Organic anions such as OO ⁻ ) ₂ , CH ₃ COO ⁻ , CF ₃ COO ⁻ , Cl ⁻ , NO ₃ ⁻ , BF ₄ ⁻ , 1 / 2SO ₄ ²⁻ , Br
^- , I ⁻ , 1 / 2PO ₄ ²⁻ , ClO ₄ ^−, and other inorganic anions. These anions are cations (R ¹ -Ar containing quaternary ammonium ion (N ⁺ )).
_{^{-CH 2 N + H (R 2}} ) 2) to form the counterions between.

The reaction conditions for the hydrogenation reaction for synthesizing the protonic acid salt of the fluorine-containing amine compound represented by the general formula (6) from the fluorine-containing cyano compound represented by the general formula (5) are as follows: It is preferable to use a catalyst in a liquid phase (solution) under acidic conditions.

The hydrogenation reaction is carried out in the liquid phase (solution). In order to carry out the reaction in a liquid phase (solution), a solution adjusted to desired conditions by, for example, dissolving the fluorine-containing cyano compound represented by the above general formula (5) and an acidic substance in a suitable solvent. Can be prepared.

The solvent is not particularly limited as long as it can dissolve the fluorine-containing cyano compound represented by the above general formula (5) and further the acidic substance. For example, methanol, Alcohols such as ethanol, 2-propanol, butanol, pentanol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether; toluene,
Aromatic hydrocarbons such as benzene and xylene; hexane,
Hydrocarbons such as cyclohexane, heptane and octane;
Acetates such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate; ethylphenol ether, propyl ether, tetrahydrofuran, dioxane, water, N, N-dimethylformamide and the like can be used. These may be used alone or in combination of two or more. Among them, ethanol is preferable because it is excellent in stability during the hydrogenation reaction and the effect of promoting the reaction.

The hydrogenation reaction is preferably carried out under acidic conditions from the viewpoint of the effect of promoting the reaction. For that purpose, the reaction system may be brought into an acidic state, but it is preferable to carry out the reaction in an acidic solution using an acidic substance which can be dissolved in a suitable solvent. As shown in the examples,
The fluorine-containing cyano compound represented by the above general formula (5) is dissolved in a suitable solvent, and an acidic substance-containing solvent whose acid concentration has been measured by previously dissolving the acidic substance in the solvent is added thereto in an appropriate amount. The acid concentration (acidic condition) of the reaction solution may be adjusted.

The acidic substance is not particularly limited, and examples thereof include gaseous acidic gases such as hydrogen chloride gas; hydrochloric acid, nitric acid, tetrafluoroboric acid, perchloric acid, phosphoric acid, hydrogen bromide. Acids, inorganic acids such as sulfuric acid; acetic acid,
Examples thereof include organic acids such as oxalic acid and trifluoroacetic acid. These may be used alone or in combination of two or more. Of these, hydrogen chloride gas is preferable.

The acid concentration of the reaction solution containing an acidic substance is 0.
The amount may be adjusted to 01 to 10 mol / liter, preferably 0.05 to 5 mol / liter, and more preferably 0.1 to 3 mol / liter. If the acid concentration is less than 0.01 mol / liter, the reaction promoting effect cannot be sufficiently obtained. On the other hand, if it exceeds 10 mol / liter, the effect corresponding to the added amount cannot be obtained, which is not preferable from the economical viewpoint.

The hydrogenation reaction is preferably carried out in the presence of a catalyst. Such a catalyst is suspended in the reaction solution,
The catalyst may be stirred appropriately so as not to settle or float so that it is uniformly dispersed (suspended) in the solution.

Any catalyst can be used as long as it can promote the hydrogenation reaction, and examples thereof include palladium catalysts such as carbon-supported palladium (hereinafter also simply referred to as Pd / C) catalysts and cobalt such as Raney cobalt and cobalt. -Based catalysts, nickel-based catalysts such as nickel and Raney nickel,
Platinum, platinum-based catalysts such as platinum on carbon, rhodium oxide,
Examples thereof include rhodium catalysts such as carbon-supported rhodium, ruthenium oxide, ruthenium catalysts such as carbon-supported ruthenium, and bimetal catalysts, but palladium-based catalysts and nickel-based catalysts are preferable. Here, the bimetallic catalyst is a catalyst having two or more kinds of metals, and in addition to the above-mentioned metals, a catalyst composed of copper, zinc, bismuth, molybdenum, silver, aluminum, titanium, chromium, etc. Say.

The hydrogenation reaction can be carried out by introducing hydrogen gas into the reaction system. For example, a fluorine-containing cyano compound represented by the general formula (5) in which a catalyst is suspended is used. And hydrogen gas is introduced into the upper space of the reaction tank (container) containing the acidic substance-containing solution, and the hydrogen gas may be dissolved in the solution by gas-liquid contact with the solution surface (by stirring, Hydrogen gas can be introduced into the solution from the bottom or side of the reaction tank so that the gas-liquid contact effect can be improved and the dissolution rate of hydrogen gas can be improved), and hydrogen gas can be introduced (blown) into the solution. Blow,
The hydrogen gas may be blistered with appropriate stirring to make the contact time with the solution longer, or the hydrogen gas may be injected (pressurized) into the solution through a pipe (hydrogen gas at the tip of the pipe). It is possible to appropriately use a conventionally known technique for introducing hydrogen gas during the hydrogenation reaction, such as installing the inlet so as to be located in the solution). Here, the gas pressure when hydrogen gas is blown into the solution is usually atmospheric pressure to 100,000 P.
The range is a.

The introduction amount (supply amount) of hydrogen gas is 2 to 50 mol, preferably 2 to 20 mol, and more preferably 2 to 10 mol, relative to 1 mol of the fluorine-containing cyano compound represented by the general formula (5). It is a mole. When the introduced amount (supply amount) of hydrogen gas is less than 2 mol, the reaction is not completed, which is not preferable.
On the other hand, when the introduced amount (supply amount) of hydrogen gas exceeds 50 mol, it is not preferable in terms of reaction control and economy.

The reaction temperature (liquid temperature) in the hydrogenation reaction is
The progress of the reaction largely depends on the state of the catalyst, but usually 0 to
The temperature is 350 ° C, preferably 20 to 350 ° C. When the reaction temperature (liquid temperature) is lower than 10 ° C, the catalyst activity is low and the reaction is slow, so that it takes a long time to complete the reaction and the manufacturing cost increases. Fluorine-containing amine compound that is a low-cost raw material suitable for inexpensively producing octafluoro- [2,2] paracyclophane or a derivative thereof, which is useful as a raw material of a resin excellent in water-based, low dielectric property and low refractive index It is against the object of the present invention to obtain. On the other hand, when the reaction temperature (liquid temperature) exceeds 350 ° C., it becomes difficult to control the reaction, which is not preferable.

By the above hydrogenation reaction, the protonic acid salt of the fluorine-containing amine compound represented by the above general formula (5) can be synthesized in high yield and at low cost.

The resulting solution containing the protonic acid salt of the fluorine-containing amine compound is then separated and purified by an appropriate operation, preferably a simple and inexpensive operation. Hereinafter, one example will be described, but the present invention is not limited thereto.

First, the solvent is completely distilled off from the reaction solution under reduced pressure. Such a solvent may be appropriately collected and recycled.

Next, the residue is dissolved in water and the catalyst is filtered.

Further, if necessary, the nonionic organic substance in the filtrate may be washed with an appropriate washing liquid, and then the liquid may be separated. In fact, there is almost no non-ionic organic matter, so such washing can be omitted. It should be noted that the washing liquid may be any liquid as long as it can solvent-extract the nonionic organic matter in the filtrate (aqueous layer), and examples thereof include organic solvents such as ether, ethyl acetate, methyl isobutyl ketone, and toluene (non-aqueous system). Solvent) can be used.

By the above operation, the protonic acid salt of the fluorine-containing amine compound can be separated and purified, but it may be separated and purified by other conventionally known operations.

Next, the fluorine-containing amine compound represented by the general formula (6) can be obtained by treating the proton acidic salt of the fluorine-containing amine compound represented by the general formula (6) with an alkali. it can. Preferably, after the separation and purification of the protonic acid salt of the above-mentioned fluorine-containing amine compound, the alkali treatment is subsequently performed. That is, it is preferable that the aqueous solution of the protonic acid salt of the fluorine-containing amine compound is used as it is, and alkali is added to the aqueous solution to make the solution alkaline.

The protonic acid salt of the fluorine-containing amine compound is represented by the above general formula (6).

The alkali that can be used when the protonic acid salt of the above-mentioned fluorine-containing amine compound is treated with alkali is not particularly limited, and hydroxides of alkali metals and alkaline earth metal elements, and Alkali metal carbonate, ammonia, refers to alkali in a broad sense including amines, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium phosphate, calcium hydroxide, barium hydroxide, calcium carbonate, Various conventionally known alkalis such as sodium carbonate, ammonium carbonate and sodium hydrogen carbonate can be used.

The amount of the alkali added may be adjusted so that the pH of the alkali treatment solution is 7 or more, preferably 8 or more.

The alkali treatment temperature (solution temperature) is not particularly limited, but is usually 0-10.
It is 0 ° C, preferably 0 to 50 ° C.

Subsequently, the organic substance (product) liberated from the aqueous layer by the alkali treatment is subjected to solvent extraction with a suitable organic solvent, dried with a suitable desiccant if necessary, and the organic layer is concentrated. However, the fluorine-containing amine compound represented by the general formula (3) can be obtained.

As the above organic solvent, for example, ether, ethyl acetate, methyl isobutyl ketone, toluene and the like can be used.

The desiccant is not particularly limited, and examples thereof include sodium sulfate, magnesium sulfate, calcium chloride, molecular sieve and the like.

The operation of concentrating the organic layer after drying is not particularly limited, and the solvent may be distilled off under normal pressure (superheated concentration), or the solvent may be distilled off under reduced pressure. Okay (concentration under reduced pressure), and by further distilling off the solvent using various conventionally known concentration operations such as ventilation concentration and spray concentration,
A target fluorine-containing amine compound can be obtained.

As described above, the fluorine-containing amine compound represented by the above general formula (3), which is a novel compound, can be obtained.

[0122] Next, in the general formula (3) above general formula to be reacted with the fluorine-containing amine compound represented by (4) a compound represented by, R ³ is, R ³ in the general formula (1) Is the same as.

Therefore, examples of the compound represented by the general formula (4); R ³ ₂ SO ₄ include alkyl sulfates such as dimethyl sulfate, diethyl sulfate and diamyl sulfate. Dimethyl sulfate is preferable from the viewpoint of obtaining organic ammonium sulfate that can be a low-cost raw material.

The amount of the compound represented by the general formula (4) added is 3 to 100 mol, preferably 3 to 5 mol, based on 1 mol of the fluorine-containing amine compound represented by the general formula (3).
It is 0 mol, more preferably 3 to 10 mol. When the addition amount of the alkylating agent which is the compound is less than 3 mol, the alkylation reaction does not proceed sufficiently, while the addition amount of the compound represented by the general formula (4) exceeds 100 mol. In that case, it is not preferable in terms of economy.

Next, in the above synthesis, the fluorine-containing amine compound represented by the general formula (3) as a raw material is soluble in an organic solvent and slightly soluble in water, and represented by the general formula (4). The organic ammonium sulfate obtained by reacting the compound described above (preferably the organic ammonium sulfate represented by the general formula (1). The same applies hereinafter) is a water-soluble typical salt. It has such properties and is hardly soluble in most organic solvents. Therefore, in the above synthesis, the two-layer system of the organic solvent and water was added to the general formula (3) of the raw material.
An appropriate amount of the fluorine-containing amine compound represented by the formula (4) is added, and further an appropriate amount of the compound represented by the general formula (4) is added. At this time, the desired organic ammonium sulfate can be obtained on the aqueous layer side by stirring and synthesizing while adding alkali so that the aqueous layer is always kept alkaline.

The organic solvent that can be used on the organic layer side of the above-mentioned two-layer system is an organic solvent which can dissolve the fluorine-containing amine compound represented by the general formula (3) and which is the target product. There is no particular limitation as long as it is insoluble or slightly soluble in ammonium sulfate.

Therefore, as the organic solvent which can be used on the organic layer side, for example, methyl ether, ethyl ether, n-butyl ether, isopropyl ether,
Phenyl ether, 2-methoxyethyl ether (diglyme ether), tetrahydrofuran, paradioxane, 1,2-propylene oxide, vinyl ether, allyl ether, methyl ethyl ether, methyl-n-propyl ether, methyl isopropyl ether, methyl-t- Butyl ether, methyl-n-butyl ether,
Examples thereof include ethers such as methylphenyl ether, ethylphenyl ether, ethylphenol ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and triethylene glycol monomethyl ether; aromatic hydrocarbons such as toluene, benzene, and xylene. These may be used alone or in combination of two or more.
Preferred is ethyl ether.

The amount of the organic solvent used in the organic layer may be such that the fluorine-containing amine compound represented by the general formula (3) can be sufficiently dissolved. ) 100 to 10,000 parts by mass, preferably 500 to 100 parts by mass, relative to 100 parts by mass of the fluorine-containing amine compound represented by
The amount is 10000 parts by mass, more preferably 500 to 5000 parts by mass. When the amount of the organic solvent used is less than 100 parts by mass, it becomes difficult to control the reaction. On the other hand, when the amount of the organic solvent used exceeds 10,000 parts by mass, productivity is lowered, which is not preferable.

The amount of water used on the water layer side of the two-layer system may be such that the synthesized organic ammonium sulfate can be sufficiently dissolved, and 100 parts by mass of the organic solvent for the organic layer is used. The amount is usually 50 to 10000 parts by mass, preferably 100 to 5000 parts by mass, and more preferably 200 to 5000 parts by mass. The amount of water used is 5
If the amount is less than 0 parts by mass, organic ammonium sulfate may precipitate, while the amount of water used is 10
If it exceeds 000 parts by mass, the productivity is lowered, which is not preferable.

The alkali used for keeping the above aqueous layer alkaline is not particularly limited, and hydroxides of alkali metals and alkaline earth metal elements, carbonates of alkali metals, and ammonia. ,
Refers to alkali in a broad sense including amines, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium phosphate, calcium hydroxide, barium hydroxide, calcium carbonate, sodium carbonate, ammonium carbonate, hydrogen carbonate. Various conventionally known alkalis such as sodium can be used. These may be used alone or in combination of two or more. Sodium hydroxide is preferable from the viewpoint of reactivity and cost.

The above alkali is preferably added to the aqueous layer as an aqueous alkali solution prepared to have an appropriate concentration, from the viewpoints of diffusion rate into the entire aqueous layer and handleability. At this time, the amount of water added as the alkaline aqueous solution is also
It is a part of the amount of water used in the above water layer. Therefore, as the reaction progresses, the amount of water used may gradually increase within the above range. The alkali concentration in the case of using the alkaline aqueous solution is not particularly limited.

In the above reaction, the total amount of alkali is usually 10 to 200 parts by weight, preferably 10 parts by weight, relative to 100 parts by weight of the fluorine-containing amine compound represented by the general formula (3).
To 100 parts by weight, more preferably 20 to 100 parts by weight. When the total amount of alkalis is less than 10 parts by mass, the reaction does not proceed sufficiently, while when the total amount of alkalis exceeds 200 parts by mass, excess alkali is used, which is economically disadvantageous. Not preferable.

The liquid temperature of the two-layer system during the above reaction is not particularly limited, but is usually 0-10.
0 ° C, preferably 0 to 50 ° C, more preferably 10 to 5
It is 0 ° C. When the liquid temperature is lower than 0 ° C., the reaction rate decreases, which is not preferable. On the other hand, when the liquid temperature is higher than 100 ° C., an autoclave or the like is required, which is not economically preferable.

The reaction time is not particularly limited, but the end of the reaction can be easily known by the change in the alkali concentration as described above, and even if a certain time elapses, The time when the change in alkali concentration disappears can be regarded as the time when the synthesis (reaction) is completed.

Subsequently, the aqueous layer side in which the target product produced by the above-mentioned synthesis is dissolved is separated, the alkali is neutralized with an appropriate acidic substance, and water is distilled off by an appropriate method to dryness. .
By appropriately drying this, a solid product containing the target product, organic ammonium sulfate, can be obtained. In addition, in addition to the target substance in the obtained solid, by-products are mixed, so the target substance may be further purified to be isolated, but it is preferable to purify such a solid substance. Instead, it is advantageous to use it for the production (synthesis) of organic ammonium hydroxide as it is, because it leads to a reduction in product cost.

Here, the acidic substance that can be added to the aqueous solution after separation for the purpose of neutralization is not particularly limited, and a gaseous, liquid or solid acidic substance can be used. Usually, it is advantageous to use an acidic solution whose concentration is dissolved in water to adjust its handleability and ease of neutralization work. Examples of such acidic substances or acidic solutions thereof include inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid, hydroiodic acid and hydrobromic acid. These may be used alone or in combination of two or more. Among them, the separation of the target
From the point of purification, sulfuric acid is preferred.

Further, the method of distilling off water to dryness after neutralization is not particularly limited, and examples thereof include a method of distilling off water under reduced pressure to dryness, and a method of distilling water under normal pressure. A conventionally known method such as a method of removing and drying can be appropriately used.

Further, the dried solid matter may be dried by an appropriate method, and various conventionally known drying methods such as a high temperature reduced pressure drying method and a hot air drying method can be appropriately used.

If necessary, the solid matter after being dried and solidified is dissolved in the above-mentioned specific solvent such as acetone, and by-products such as inorganic salts produced by the neutralization are removed by filtration or the like, and the solvent of the filtrate is removed. May be distilled off, further, the residue may be recrystallized from water, for example, the purification method of the intended product should not be particularly limited, conventionally known purification From the technology, the optimal purification method may be appropriately selected in consideration of the manufacturing cost, but in reality, in addition to inorganic salts, organic salts are mixed, so purification here is not easy. However, it is more advantageous to remove it in the subsequent production process of organic ammonium hydroxide.

Next, an organic ammonium hydroxide can be produced by reacting the organic ammonium sulfate obtained by the above synthesis with an alkaline earth metal hydroxide and / or an alkaline earth metal oxide. it can. This manufacturing method can be performed in the same manner as the first manufacturing method of the present invention, and the description thereof is omitted here.

The organic ammonium hydroxide obtained by the first or second production method of the present invention is then subjected to a conventionally known method, for example, the following general formula (7)

[0142]

[Chemical 15]

(In the formula, Ar is A in the general formula (1) above.
same as r. ) Fluorine-containing paracyclophane represented by the formula (1) can be produced. The method for producing the fluorine-containing paracyclophane will be briefly described below.

The method for synthesizing the fluorine-containing paracyclophane represented by the above general formula (7) is not particularly limited, and for example, octafluoro- [2 which is one of fluorine-containing paracyclophane is used. , 2] Paracyclophane or its derivatives are described in Journa described in the prior art.
l of Fluorine Chemistry, 3
0 (1986) 399-414, a heating operation similar to that of Scheme I (specifically, the experimental operation on page 406) can be obtained at a much lower cost than the conventional method. The manufacturing method will be briefly described below.

The organic ammonium hydroxide obtained by the above-mentioned first or second production method of the present invention (preferably the organic ammonium hydroxide represented by the above general formula (2). The same applies hereinafter. A solvent, and if necessary, a polymerization inhibitor, is heated to remove the water from the solution, and then the reaction is carried out under heating and refluxing to give a fluorine-containing paracyclophane. Can be obtained. After completion of the reaction, the solution is cooled, the solid matter is filtered to obtain a filtrate, and the filtered solid matter is also extracted with a solvent. Fluorine-containing paracyclophane can be purified by distilling the solvent from the solution obtained by combining the filtrate and the extract with the filtrate and the extract to dryness and sublimating the obtained solid. Further, if necessary, high-purity fluorine-containing paracyclophane can be obtained by recrystallization.

The concentration of the organic ammonium hydroxide in the aqueous solution is not particularly limited, and as described above, the organic ammonium hydroxide obtained by the first or second production method of the present invention. It is possible to use an aqueous solution of
˜2 mol / liter, preferably 0.1 to 2 mol / liter, more preferably 0.1 to 1 mol / liter. When the concentration is less than 0.01 mol / liter, productivity is lowered, which is not preferable. On the other hand, when the concentration exceeds 2 mol / liter, precipitation may occur, which is not preferable.

The solvent added to the above aqueous solution is one which can dissolve the products (intermediate product and final target product), and more preferably, the solvent is distilled off thereafter to obtain the target product. There is no particular limitation as long as it can be easily purified. As such a solvent,
For example, aromatic hydrocarbons such as toluene, benzene, and xylene; hydrocarbons such as hexane, cyclohexane, methylcyclohexane, heptane, and octane; acetates such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate; ethyl phenol ether , Propyl ether, etc. They are,
One kind may be used alone, or two or more kinds may be mixed and used.

The amount of the solvent added to the above aqueous solution is
The amount is usually 1 to 10000 parts by mass, preferably 10 to 5000 parts by mass, and more preferably 100 to 1000 parts by mass with respect to 100 parts by mass of the aqueous solution. If the amount of the solvent added is less than 1 part by mass, the target product may precipitate, while if it exceeds 10,000 parts by mass, it is not preferable in terms of productivity.

As the polymerization inhibitor added to the above-mentioned aqueous solution as needed, the above-mentioned organic ammonium hydroxide and the products (the intermediate product and the target product, fluorinated paracyclophane), which are not planned, are polymerized. It is added for the purpose of prevention, and is not particularly limited as long as it can achieve the purpose of preventing polymerization, and examples thereof include phenothiazine.

The amount of the polymerization inhibitor added to the aqueous solution is usually 0.01 to 100 parts by weight of the aqueous solution.
5 parts by mass, preferably 0.01 to 1 part by mass, more preferably 0.1 to 1 part by mass. When the amount of the above-mentioned polymerization inhibitor added is less than 0.01 parts by mass, the polymerization cannot be sufficiently prevented, while when it exceeds 5 parts by mass, it is not preferable in terms of economy.

Next, the temperature for heating the obtained solution is usually 30 to 300 ° C., preferably 50 to 200.
C., more preferably 80 to 150.degree. If the heating temperature is lower than 30 ° C., the reaction does not proceed sufficiently, while if it exceeds 300 ° C., it is difficult to control the reaction, which is not preferable.

Further, water is removed from the solution by the above heating until no water is distilled off. The removal of such water is not particularly limited, and conventionally known various low-boiling compound (liquid) removal devices and distillation devices can be used, and specifically, for example,
Devices such as the Dean-Stark device can be used.

Furthermore, the final desired product can be obtained by carrying out the reaction while heating and refluxing the solution for a predetermined time after the water is no longer distilled off.

[0154] For example, when the method is carried out in a batch system, it cannot be defined uniquely because it varies depending on the amount of treatment and the temperature condition at one time, but it is usually 1 to 48 hours, preferably 1 to 2 hours.
It is 4 hours, more preferably 1 to 12 hours. When the reaction time is less than 1 hour, the progress of the reaction is insufficient, while when it exceeds 48 hours, it is not preferable in terms of productivity.

Next, after completion of the reaction, the solution is cooled, the solid matter is filtered to obtain a filtrate, and the filtered solid matter is also extracted with a solvent.

By cooling the solution, the object of the present invention remains dissolved in the solution after cooling, but is effective only for the polymer compound which becomes insoluble in the low temperature solution after cooling. It can be solidified and can be easily separated by filtration as a solid to obtain a filtrate containing the desired product.
In addition, in the present invention, since the polymerization inhibitor is added, it is possible to suppress the generation of such solid matter, so that the reaction yield of the target product can be improved. Further, the amount of the target product incorporated into the solid product whose generation is suppressed can be reduced and can be easily recovered from the solid product, so that the yield of the target product after the final purification can be improved. Also contributes greatly.

Further, the target product incorporated in the residual solid is also extracted with a solvent and effectively recovered as an extract. The method for recovering the desired product from the solid residue is not particularly limited, and various conventionally known purification methods can be applied. For example, soxhlet may be used for solvent extraction. The solvent used for solvent extraction is the same as the solvent added to the aqueous solution of the above organic ammonium hydroxide, but it is treated as a mixed solvent in removing the solvent together with the filtrate later. Is advantageous in that it is simple,
It does not limit the use of other solvents, and it should not be particularly limited as long as it can dissolve the target product, as a solvent that can be added to the aqueous solution of the organic ammonium hydroxide The various solvents exemplified above can be used.

Next, the solvent is distilled off from the combined solution of the filtrate and the extract to dryness, and the obtained solid is sublimated, whereby the target product fluorinated paracyclophane can be purified. it can.

As a method of distilling the solvent from the combined solution of the filtrate and the extract, the solvent may be distilled off under reduced pressure (distillation under reduced pressure), or the solvent may be distilled off under normal pressure. Good, etc., should not be particularly limited.

The desired fluorinated paracyclophane can be purified by the above-mentioned purification operation, and if necessary, the solid obtained by sublimation can be recrystallized with a suitable solvent to give a purified product. Further, highly pure fluorine-containing paracyclophane can be obtained. However, the present invention should not be limited to the above-mentioned purification method by recrystallization, and various conventionally known purification methods can be appropriately used.

[0161]

EXAMPLES The present invention will be specifically described below with reference to examples.

Example 1 (1) Starting material 2,3,5,6-tetrafluoro-4-
Synthesis of methylbenzylamine 100 ml of ethanol was added to a 200 ml three-necked flask and hydrogen chloride gas was introduced to prepare an ethanol solution of hydrogen chloride. The acid concentration of hydrogen chloride in ethanol is
It was 2.04 mol / liter.

In another 200 ml three-necked flask, 50 ml of ethanol and 2,3,5,6-tetrafluoro-4 were added.
-Methylbenzonitrile 10.5 g (0.053 mol)
Was added to dissolve 2,3,5,6-tetrafluoro-4-methylbenzonitrile in ethanol, and then 31 ml of an ethanol solution of hydrogen chloride prepared above and a palladium catalyst supported on carbon (palladium supported amount; 5% by mass). 0.5 g
Was added and the inside of the flask was replaced with nitrogen, and then hydrogen gas was added to 2.
4 liters were introduced and stirred at room temperature for 70 hours. Carbon supported palladium catalyst (palladium supported: 5% by mass) 0.4
g was added, and the mixture was further stirred for 100 hours. Then, ethanol was distilled off under reduced pressure, 150 ml of water was added to the residue, and the mixture was filtered. After adding 50 ml of ether to the filtrate, the layers were separated.

Next, the separated aqueous layer was adjusted to pH 8 with sodium hydroxide and then extracted with 100 ml of ether. The ether layer is concentrated to give 2,3,5,6-tetrafluoro-4.
-9.6 g of methylbenzylamine were obtained. The yield was 94 mol%. The physical properties of the obtained compound were as follows.

B. p. 49 ° C. (4 mmHg) ¹ H-NMR (CDCl ₃ ) 1.54 (2H, N
H ₂ ), 2.22 (3H, CH ₃ ), 3.92 (2H, C
H ₂ ).

The reaction scheme up to this point (Scheme I
V) is shown below.

[0167]

[Chemical 16]

(2) N, N, N-trimethyl-2,3,5,6-tetrafluoro-4-methylbenzylammonium sulfate (N, N, N) using the compound synthesized in (1) above -Trimethyl-2,3,5,6-tetrafluoro-4-methylbenzylammonium monomethylsulfate) 40 ml of ether and 10 ml of water were added to a 100 ml three-necked flask, and the solution of this two-layer system was added to Above (1)
2,3,5,6-tetrafluoro-4 obtained by the synthesis of
Methylbenzylamine (1.92 g, 9.94 mmol) was added, and dimethyl sulfate (3.8 g, 30 mmol) was further added. 1N so that the water layer is always alkaline
The reaction solution was stirred at room temperature while adding an aqueous sodium hydroxide solution. The total amount of 1N sodium hydroxide aqueous solution is 28 ml
When the mixture was added to the above, the aqueous layer was separated, neutralized with sulfuric acid, and water was distilled off under reduced pressure to dryness. Further, by drying under reduced pressure at 50 ° C., 5.74 g of a solid matter was obtained. The solid contains the target N, N, N-trimethyl-2,3,3.
In addition to 2.8 g of 5,6-tetrafluoro-4-methylbenzylammonium monomethyl sulfate, sodium monomethyl sulfate and sodium sulfate were mixed. The target yield of N, N, N-trimethyl-2,3,5,6-tetrafluoro-4-methylbenzylammonium monomethylsulfate was 81 mol%.

The reaction scheme up to here (Scheme
V) is shown below.

[0170]

[Chemical 17]

(3) N, N, N-trimethyl-2,
Synthesis of 3,5,6-tetrafluoro-4-methylbenzylammonium hydroxide In a 50 ml three-necked flask, N, N, N-trimethyl-2,3,5 obtained by the synthesis of (2) above was obtained. 5.47 g of solid containing monomethyl sulfate of 6-tetrafluoro-4-methylbenzylammonium salt and 10 ml of water
Was added, the solid was dissolved in water, and 6.17 g (36 mmol) of barium hydroxide was added thereto, and N, N, N-trimethyl-2,3,5,6-tetrafluoro-4-methylbenzyl was added. A solution containing ammonium hydroxide was obtained.

The reaction scheme up to this point (Scheme V
I) is shown below.

[0173]

[Chemical 18]

Reference Example: Method for synthesizing octafluoro- [2,2] paracyclophane N, N, N-trimethyl-2,3,5,6 synthesized in (3) above in a 100 ml three-necked flask. -A reaction solution containing tetrafluoro-4-methylbenzylammonium hydroxide and 60 ml of toluene were added, and further 100 mg of phenothiazine was added for the purpose of preventing polymerization.
The solution was heated and the water was removed with Dean Stark and refluxed for 8 hours after no water distilled. After cooling, the solid matter was filtered, and the obtained solid matter was Soxhlet extracted with toluene. The filtrate and Soxhlet extract were combined and evaporated to dryness. The yield was 17 mol% as a result of determination by gas chromatography using tetralin as an internal standard.

¹ H-NMR (CDCl ₃ ) 3.27 The final reaction scheme (Scheme VII) is shown below.

[0176]

[Chemical 19]

[0177]

According to the present invention, octafluoro- [2,2], which is a dimer of the basic substance of parylene F, is excellent in heat resistance, chemical resistance, water repellency, low dielectric properties and low refractive index. A useful and novel organic ammonium hydroxide obtained from a fluorine-containing amine compound having low toxicity, which can be a low-cost raw material of paracyclophane, can be produced at a significantly low cost. As a result, the obtained organic ammonium hydroxide is heated in the same manner as a conventionally known method, so that it is produced safely as compared with the case where a conventional pentafluorobenzonitrile (highly toxic) is used as a raw material. And much cheaper octafluoro- [2,2]
Paracyclophane and further fluorine-containing paracyclophane such as parylene F can be synthesized, and it is used in a wide range of fields including electronics industry, automobile industry, medical industry, including the use of next-generation semiconductors for interlayer insulating films. Can be ideally used for conformal coating.

Claims (3)

[Claims] 1. A method for producing organic ammonium hydroxide, which comprises reacting an organic ammonium sulfate with a hydroxide of an alkaline earth metal and / or an oxide of an alkaline earth metal. 2. An organic ammonium sulfate is represented by the following general formula (1): (In the formula, Ar represents an aromatic hydrocarbon group substituted with at least one fluorine atom or a fluoroalkyl group. R ¹ represents a hydrocarbon group or a hydrocarbon group substituted with a halogen group or a hydroxyl group. R ³ each independently represents a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a halogen group or a hydroxyl group.), And the organic ammonium hydroxide has the following general formula (2): Chemical 2] (In the formula, Ar, R ¹ and R ³ are the same as A in the general formula (1).
same as r, R ¹ and R ³ . ) Claim 1 represented by
The method for producing an organic ammonium hydroxide according to 1. 3. The following general formula (3): [Chemical 3] (In the formula, Ar and R¹Is Ar of the general formula (1)
And R¹Is the same as. R ²Are independently hydrogen
Child, hydrocarbon group or halogen group or hydroxyl
Represents a hydrocarbon group substituted with a group. )
The following general formula (4) [Chemical 4] (In the formula, R³Is R in the general formula (1)³Same as
It ) Reacting the compound represented by
Mussulfate is obtained, said organic ammonium sulfate
Alkaline earth metal hydroxide and / or alkali
Organic acid characterized by reacting an oxide of an earth metal
Method for producing ammonium hydroxide.