JP2003089679A - Fluorine-containing amine compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new fluorine-containing amine compound. SOLUTION: This fluorine-containing amine compound is represented by the general formula R<1> -Ar-CH2 N(R<2> )2 (wherein, Ar denotes an aromatic hydrocarbon group substituted with at least one kind selected from fluorine atom and fluoroalkyl groups; R<1> denotes a hydrocarbon group or the hydrocarbon group substituted with a halogen group or hydroxy group; and R<2> s denote each independently hydrogen atom, a hydrocarbon group or the hydrocarbon group substituted with a halogen group or hydroxy group).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel fluorine-containing amine compound, a protonic acid salt thereof, and a process for producing these novel compounds.

[0002]

2. Description of the Related Art Parylene excellent in heat resistance, chemical resistance, water repellency, low dielectric property and low refractive index; p-xylene resin can be formed into a thin film by a vapor deposition method or the like.
In addition, since it can be a base material having various shapes, the parylene material can be ideally used for a similar coating in a wide range of fields such as electronics, automobile industry and medical industry. Among them, the following general formula

[0003]

[Chemical 4]

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, which is a dimer of the basic substance, is shown below.

[0005]

[Chemical 5]

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

[0007]

[Chemical 6]

[Scheme II

[0009]

[Chemical 7]

A synthesis 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.

[0011]

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 a derivative thereof, which is extremely useful as a low-toxic raw material that can be provided at a significantly lower cost than conventional ones, and a protonic acid salt thereof and a novel compound thereof. It is to provide a manufacturing method.

Another object of the present invention is that it can be synthesized at a low cost and in a high yield by a simple operation and has low toxicity.
It is an object of the present invention to provide a fluorine-containing amine compound and a protonic acid salt thereof which are extremely useful as a starting material for octafluoro- [2,2] paracyclophane or a derivative thereof, and a method for producing these novel compounds.

Another object of the present invention is, in addition to the above advantages,
Octafluoro-, which has a low impurity content and is easy to purify or can omit the purifying step, is suitable for mass production.
It is to provide a fluorine-containing amine compound and a protonic acid salt thereof which are extremely useful as a raw material for [2,2] paracyclophane or a derivative thereof, and a method for producing these novel compounds.

[0014]

Therefore, the present inventors have
In order to achieve the above-mentioned objects, a novel fluorine-containing amine compound, a protonic acid salt thereof and a method for producing these novel compounds have been earnestly studied, and as a result, the present invention has been completed.

That is, the present invention provides the following (1) to (1
It is achieved by 1).

(1) General formula (1)

[0017]

[Chemical 8]

(In the formula, Ar represents an aromatic hydrocarbon group substituted with at least one selected from a fluorine atom and a fluoroalkyl group. R ¹ is a hydrocarbon group, a halogen group or a hydroxyl group. Represents a substituted hydrocarbon group, and R ² each independently represents a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a halogen group or a hydroxyl group.) Amine compound.

(2) The fluorine-containing amine compound according to the above (1), wherein R ¹ is a hydrocarbon group.

(3) Ar is an aromatic monocyclic hydrocarbon group, and the total of the fluorine atom substituted by the Ar and the fluoroalkyl group is 4, the fluorine-containing amine according to the above (1) or (2). Compound.

(4) The fluorine-containing amine compound according to any one of the above (1) to (3), wherein R ¹ is a methyl group and R ² is a hydrogen atom.

(5) The fluorine-containing amine compound according to any one of (1) to (4) above, wherein Ar is a tetrafluorophenylene group.

(6) General formula (3)

[0024]

[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. R ² independently represents a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a halogen group or a hydroxyl group, and X ⁻ represents a counter ion). The protonic acid salt of the fluorine-containing amine compound according to any one of (1) to (6) above.

(7) General formula (2)

[0027]

[Chemical 10]

(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. The method for producing a proton acidic salt of a fluorine-containing amine compound according to claim 7, wherein a fluorine-containing cyano compound represented by the formula (1) is subjected to a hydrogenation reaction (by contact with hydrogen gas).

(8) The production method as described in (7) above, wherein the hydrogenation reaction is carried out in the presence of a carbon-supported palladium catalyst.

(9) The production method as described in (7) or (8) above, wherein the hydrogenation reaction is carried out under acidic conditions.

(10) The fluorine-containing amine compound according to any one of (1) to (6), which is characterized in that the protonic acid salt of the fluorine-containing amine compound described in (6) above is treated with an alkali. A method for producing an amine compound.

(11) The protonic acid salt is obtained by hydrogenating the fluorine-containing cyano compound represented by the general formula (2) described in (7) above (10).
Manufacturing method.

[0033]

BEST MODE FOR CARRYING OUT THE INVENTION The fluorine-containing amine compound of the present invention is characterized by being represented by the general formula (1).

R ¹ in the above 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) and 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 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 missyl group and a cumenyl group; a 1-naphthyl group, a 2-naphthyl group. Examples thereof include naphthyl group, benzyl group, phenethyl group, p-benzyl group and methylbenzyl group.

Further, 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
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 or a derivative thereof by using an existing production method,
A methyl group is more preferred.

R ^{2 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, the hydrocarbon group is not particularly limited and may be an unsubstituted monovalent hydrocarbon group, such as an aliphatic hydrocarbon group (chain hydrocarbon group) and 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 composed of a monovalent chain unsaturated hydrocarbon group having 2 to 20 carbon atoms, and a monovalent alicyclic hydrocarbon composed of a monovalent cycloalkyl group having 3 to 20 carbon atoms 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.

Specific examples of the above 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 phenyl group, naphthyl group, anthryl group, alkylphenyl group (tolyl group, xylyl group, missicyl group, cumenyl group, etc.), 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 fluorine atom, chlorine atom, bromine atom and iodine atom.

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.

The above R ^2's each independently represent the above-mentioned atom or group, 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.

Ar in the general formula (1) is at least 1
Represents an aromatic hydrocarbon group substituted with two fluoro groups or fluoroalkyl groups.

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 ² ) ₂ 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" means -R ¹ group and -CH ₂ N group).
The (R ²⁾ substituent which substitutes refers to non-bonding positions _{2 group} is bound) may be at least one of a fluorine atom or a fluoroalkyl group, but preferably, all Zan'i is a fluorine atom is there. 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.

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 10 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.

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, but 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 the fluorine atom and the fluoroalkyl group substituted on the above aromatic monocyclic hydrocarbon group may be the same or different in the case of plural, 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 from the viewpoint of steric hindrance, 2, 3,
The 5,6-tetrafluorophenylene group is more preferable.

As mentioned above, the fluorine-containing amine compound represented by the general formula (1) is most preferably 2,
It is 3,5,6-tetrafluoro-4-methylbenzylamine.

The fluorine-containing amine compound of the present invention is
A compound characterized by being obtained from the fluorine-containing cyano compound represented by the general formula (2) is preferable.

[0064] Here, with respect to Ar and R ¹ in the general formula (2) is the same as Ar and R ¹ in the general formula (1). Therefore, the fluorine-containing cyano compound represented by the general formula (2) is most preferably 2,3,5,6-tetrafluoro-4-methylbenzonitrile.

The reason why the fluorine-containing cyano compound of the above-mentioned general formula (2) is used is that the fluorine-containing cyano compound is already known and can be easily produced by those skilled in the art. A suitable fluorine-containing cyano compound can be obtained in high yield by the method. The production method obtained from the fluorine-containing cyano compound of the general formula (2) will be described later.

Next, the protonic acid salt of the fluorine-containing amine compound of the present invention is characterized by being represented by the general formula (3). Such a novel protonic acid salt of a fluorine-containing amine compound is one of intermediates produced in the process of producing the fluorine-containing amine compound of the present invention, and particularly, the fluorine-containing cyano compound represented by the general formula (2) is used. It can be provided at a low price, and further, by performing an ion exchange reaction using an ion exchange resin found by the present inventor, N, N, N-trimethyl-2,3,5,6-tetrafluoro It can also be a raw material for producing 4-methylbenzylammonium hydroxide.

Here, Ar and R ¹ in the above general formula (3) are
And R ² are the same as Ar, R ¹ and R ^{2 in} the general formula (1).

Further, X ⁻ in the above general formula (3) 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
OO ⁻ ) ₂ , CH ₃ COO ⁻ , organic anions such as CF ₃ COO ⁻ , Cl ⁻ , NO ₃ ⁻ , BF ₄ ⁻ , SO ₄ ²⁻ , Br ⁻ , P
Examples thereof include inorganic anions such as O ₄ ^{2 −} and ClO ₄ ⁻ . When the anion has a valence of 2 or more like SO ₄ ²⁻ , R ¹ —Ar— containing a number of cations (quaternary ammonium ion (N ⁺ )) corresponding to the valence of the anion. CH
₂ N ⁺ H (R ² ) ₂ ) to form a counter ion.

Next, the method for producing a protonic acid salt of a fluorine-containing amine compound of the present invention is characterized by hydrogenating a fluorine-containing cyano compound represented by the above general formula (2).

As the reaction conditions for the hydrogenation reaction, it is preferable to carry out the reaction under acidic conditions in a liquid phase (solution) using a catalyst.

The hydrogenation reaction is carried out in the liquid phase (solution). 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 (2) 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 general formula (2), 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, DMF (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 general formula (2) 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.

In order to dissolve the acidic substance in a suitable solvent, a gaseous acidic substance may be blown into the solvent to dissolve it, or a liquid or solid acidic substance may be added to the solvent. Then, they may be stirred and dissolved. Moreover, what was made to melt | dissolve in the solvent with high solubility of an acidic substance previously may be added to another solvent.

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 with 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.

Further, among the above-mentioned catalysts, the amount of the catalyst to be carried when the catalyst material is carried on the carrier cannot be uniquely defined because it depends on the catalytic activity of the catalyst material and the like, but it is suitable as a rough guide. As an example of the carbon-supported palladium catalyst, the amount of palladium supported is in the range of 1 to 20% by mass, preferably 2 to 10% by mass, based on the whole catalyst.

Further, the amount of the catalyst (which means the amount including the carrier) added to the reaction system cannot be uniquely defined because it depends on the amount supported on the carrier and the like, but in the general formula (2) above. 0.1 for the fluorinated cyano compound represented
-30% by mass, preferably 0.5-20% by mass. When the amount of catalyst added is less than 0.1% by mass, a sufficient reaction rate cannot be obtained, which is not preferable, while 30% by mass
If it exceeds, it is not preferable in terms of reaction control and economy. The catalyst may be added at one time (before the start of the reaction), but as in the example, it may be added intermittently (in several steps) from the viewpoint of reaction control. Good.

The particle size of the above catalyst is not particularly limited. Although the specific gravity and the shape are also involved, the size may be such that it does not easily settle or float even when hydrogen gas is introduced (blown) into the solution and is easily dispersed (suspended) uniformly by stirring.

The shape of the above catalyst is not particularly limited. Although the particle size and specific gravity are also related,
Any shape may be used as long as it does not easily settle or float and is easily suspended in a solution, and for example, may have a spherical shape, a cylindrical shape, a cylindrical shape (or a porous shape), a ring shape, or the like.

The hydrogenation reaction can be carried out by introducing hydrogen gas into the reaction system. For example, the fluorine-containing cyano compound represented by the general formula (2) 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 (2). 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 hydrogen gas may be introduced at any time from the start of the reaction to the end of the reaction (preferably at the start of the reaction), intermittently (in several steps) or continuously (at an appropriate flow rate). (Although the flow rate may be changed on the way), it is preferably introduced at a constant flow rate from the start of the reaction to the end of the reaction. In any case, undissolved hydrogen gas may be extracted from the reaction tank and circulated so as to be introduced again into the solution. The reaction is terminated when the fluorine-containing cyano compound represented by the general formula (2) in the solution has disappeared.

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.

The atmospheric pressure (reaction pressure) in the vessel during the hydrogenation reaction is not particularly limited, but by carrying out under pressure, vaporization (transpiration) of the acidic substance dissolved in the solution is suppressed. If the reaction can be speeded up and the overall production cost (running cost required for pressurization and equipment cost is included as part of the production cost as depreciation amount), it is usually normal. Pressure may be applied within the range of 100 to 100,000 Pa, but if such an effect cannot be obtained, it is necessary to use a pressure-resistant device in the reaction system and additionally attach a pressurizing device. It may be performed at atmospheric pressure (normal pressure).

The reaction time for the hydrogenation reaction is represented by the general formula (2) of the raw material, as long as the reaction of the fluorine-containing cyano compound represented by the general formula (2) in the solution is completed. It cannot be uniquely defined because it depends on the charged amount (supply amount) of the fluorinated cyano compound, the reaction temperature, the catalyst amount, and the like. In particular, when the catalyst activity is lowered during the reaction, the catalyst may be newly replenished to shorten the reaction time (see Examples).

Further, in the hydrogenation reaction, from the viewpoint of safety, hydrogen gas is introduced after the inside of the reaction system is replaced with an inert gas such as nitrogen gas or argon gas, preferably nitrogen gas in terms of cost. Preferably.

By the hydrogenation reaction described above, the target acidic protonic salt of the fluorine-containing amine compound represented by the above general formula (3) can be synthesized at a high yield and at a 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 method for producing the fluorine-containing amine compound represented by the general formula (1) of the present invention is to treat the proton acidic salt of the fluorine-containing amine compound represented by the above general formula (3) with an alkali. It is characterized by doing. 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, the one separated as an aqueous solution of the protonic acid salt of the fluorine-containing amine compound is used as it is,
It is preferable to add an alkali to the aqueous solution to make the solution alkaline and to process the solution.

Here, the protonic acid salt of the fluorine-containing amine compound is represented by the above general formula (3), and the description thereof is omitted here.

The protonic acid salt of the fluorine-containing amine compound is treated with alkali.

The above-mentioned alkali is not particularly limited, and includes alkali metal and alkaline earth metal element hydroxides, alkali metal carbonates, ammonia, amines and the like in a broad sense. For example, various conventionally known alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium phosphate, calcium hydroxide, barium hydroxide, calcium carbonate, 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 (the temperature of the solution) is not particularly limited, but is usually 0-10.
It is 0 ° C, preferably 0 to 50 ° C.

Then, the organic substance (product) released 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, it is possible to obtain the target fluorine-containing amine compound represented by the general formula (1).

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 (superheat 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 general formula (1) of the present invention can be obtained, and it has been described in the prior art using such an inexpensive fluorine-containing amine compound having low toxicity. Journal of Fl
uorine Chemistry, 30 (198
6) Scheme I described in 399-414.
1-Bromomethyl-4-methyl-2,3,5,6-tetrafluorobenzene was treated with anhydrous trimethylamine to give 4-methyl-2,3,5,6-tetrafluorobenzyltrimethylammonium bromide,
For example, the Scheme III shown below

[0108]

[Chemical 11]

As shown in, the fluorine-containing amine compound represented by the general formula (1) of the present invention has R such as methyl iodide.
A compound represented by the following general formula (4) is reacted with a compound represented by ³ X (alkylating agent).

[0110]

[Chemical 12]

(In the formula, Ar represents an aromatic hydrocarbon group substituted with at least one selected from a fluorine atom and a fluoroalkyl group. R ¹ is a hydrocarbon group, a halogen group or a hydroxyl group. Represents a substituted hydrocarbon 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, and X ⁻ represents an organic or inorganic anion. .) And then the same operation as Scheme I is performed, whereby octafluoro- [2,2] paracyclophane or a compound thereof can be obtained at a much lower cost than the conventional method. A derivative can be obtained. A typical example of such a synthesis method will be described in detail in Examples.

[0112]

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

Example 1 100 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 ).

[0117] The reaction scheme of this example (Scheme I
V) is shown below.

[0118]

[Chemical 13]

Reference Example 1 (Synthesis method of octafluoro- [2,2] paracyclophane; Scheme III) N, N, N-trimethyl-2,3,5,6-tetrafluoro-4-methylbenzylammonium io Synthesis of Zide In a 100 ml three-necked flask, 2.2 g (0.011 mol) of 2,3,5,6-tetrafluoro-4-methylbenzylamine obtained in Example 1 and ether 30 m
1, water 10 ml, methyl iodide 6.0 g (0.43 mo
l) was added. The reaction solution was stirred at room temperature, and 22 ml of 1000 mol / l (1N) sodium hydroxide aqueous solution
Was dripped. The aqueous layer was separated, neutralized with hydroiodic acid, and water was distilled off under reduced pressure. The residue is recrystallized from water, N, N, N
-Trimethyl-2,3,5,6-tetrafluoro-4-
2.8 g of methylbenzylammonium iodide was obtained. The yield was 69 mol%. The physical properties of the obtained compound were as follows.

¹ H-NMR (DMSO-d ₆ ) 2.32
_{(3H, CH 3), 3.14} (9H, NCH 3), 4.6
9 (2H, CH ₂₎ 3-necked flask octafluoro [2.2] paracyclophane synthetic 50ml, N, N, N- trimethyl-2,3,5,6-tetrafluoro-4-methylbenzyl 2.27 g (6.25 mmo) of ammonium iodide
l) and 8.5 ml of water were added, and 2.24 g of silver oxide was further added.
(9.5 mmol) was added. The precipitated silver iodide was filtered, the filter cake was washed with 6 ml of water, and combined with the filtrate. 100
Aqueous solution obtained in 3 ml flask with 3 necks, toluene 40
ml and 80 mg of phenothiazine were added. The solution was heated and the water was removed by Dean Stark. afterwards,
The mixture was reacted under reflux for 8 hours. 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. By sublimating (130 ° C., 10 mmHg) the obtained solid, octafluoro [2.
2] 0.36 g of paracyclophane was obtained. The yield was 33 mol%.

¹ H-NMR (CDCl ₃ ) 3.27 The reaction scheme (Scheme V) of this Reference Example is shown below.

[0122]

[Chemical 14]

[0123]

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. It is possible to provide a useful fluorine-containing amine compound that can be a low-cost raw material for paracyclophane, a protonic acid salt thereof, and these novel compounds. As a result, octafluoro- [2,2] paracyclophane, which can be manufactured safely compared to the case of using conventional pentafluorobenzonitrile (highly toxic) as a raw material, and is significantly cheaper,
Further, Parylene F can be provided, and it can be ideally used for a similar coating in a wide range of fields such as the next generation of semiconductors for use as an interlayer insulating film and the electronics industry, automobile industry, medical industry, and the like.

Claims (5)

[Claims] 1. A compound represented by the general formula (1): (In the formula, Ar represents an aromatic hydrocarbon group substituted with at least one selected from a fluorine atom and a fluoroalkyl group. R ¹ is substituted with a hydrocarbon group, a halogen group or a hydroxyl group. Represents a hydrocarbon group, and each R ² independently represents a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a halogen group or a hydroxyl group.). 2. A compound represented by the general formula (3): (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. Each R ² independently represents a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a halogen group or a hydroxyl group.
X ⁻ represents a counter ion. And a protonic acid salt of a fluorine-containing amine compound. 3. A compound represented by the general formula (2): (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. The hydrogenation reaction of the fluorine-containing cyano compound represented by the formula (1) is carried out, and the method for producing a protonic acid salt of a fluorine-containing amine compound according to claim 2, wherein. 4. The fluorine-containing amine compound according to claim 1, wherein the protonic acid salt of the fluorine-containing amine compound represented by the general formula (3) according to claim 2 is treated with an alkali. Production method. 5. The method according to claim 4, wherein the protonic acid salt is obtained by hydrogenating the fluorine-containing cyano compound represented by the general formula (2) according to claim 3.