JP2001031598A - Production of fluorine-containing aromatic compound and intermediate therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce the subject compound useful as a raw material for a resin excellent in heat resistance, chemical resistance, water repellency, low dielectric properties and low refraction ratio by reacting a specific di(thio)acetal compound derivative with a fluorine compound, or the like. SOLUTION: A compound of formula I [R1 and R2 are each a (substituted) aromatic ring; X1 to X4 are each O or S; (p) and (q) are each 2 or 3], [e.g. 1,9-diketo[2,2]paracyclophane-bis(ethylene-dithioketal)] is reacted with a fluorine compound (e.g. HF-pyridine) in the presence of a bromine compound (e.g. N- bromosuccinimide) to provide the objective compound of formula II. The compound of formula I is obtained by reacting a diketone compound of formula III with compounds of the formula X5-CpH2p-X6 (X5 and X6 are each OH or SH) and the formula X7-CqH2q-X8 (X7 and X8 are each OH or SH), (e.g. 1,2- ethanedithiol) in an organic solvent in the presence of a Broensted acid).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a novel fluorine-containing aromatic compound and a method for producing a di (thio) acetal compound derivative as an intermediate thereof. More particularly, the present invention relates to a method for producing a fluorine-containing aromatic compound and a di (thio) acetal compound derivative as an intermediate thereof by a simple operation and at low cost. The fluorine-containing aromatic compound thus obtained is useful as a raw material for a resin having excellent heat resistance, chemical resistance, water repellency, low dielectric properties and low refractive index.

[0002]

2. Description of the Related Art Fluorine-containing aromatic compounds are heat-resistant fluorine compounds.
It is widely known that it is useful as a raw material for resins.
For example, tetrafluoro- [2,2] paracyclophane
Is used as a raw material for heat resistance, chemical resistance and water repellency
Synthesizes excellent poly-α, α-difluoro-paraxylylene
Can be achieved. This tetrafluoro- [2,2]
As a method for producing lacyclophane, 1,9-dike
G [2,2] paracyclophane with 1,2-ethanedithio-
And boron trifluoride diethyl ether complex (boron trifl
uoride ethyl ehterate) [(C_TwoH_Five)_TwoO ・ BF_Three](Book
In the description, "BF _Three: Et_TwoO ")
After dithioacetalization by reacting with
1,9-diketo [2,2] paracyclophanbis
(Ethylenedithioketal) with 1,3-dibromo-5,
5-dimethylhydantoin (herein "DMH"
Poly (hydrogen fluoride) pyridini in the presence of
Um [pyridinium poly (hydrogen fluoride)] (this specification
Then, it is also referred to as "HF-pyridine").
And fluoridation (T. Itoh et a
l., Journal of Polymer Science: Part A: Polymer Ch
emistry, Vol. 33, 359-363 (1995)), and 1,9-di
Keto [2,2] paracyclophane with sulfur tetrafluoride or
Such as diethylaminosulfur trifluoride (DAST)
Manufactured by fluorination in the presence of a fluorinating agent
Method (Japanese Patent Application Laid-Open Nos. 9-25 and 252, 9-5
9,187 and JP-A-10-195,181
Information) is known.

However, of these methods, the latter method, that is, the method of performing fluorination using sulfur tetrafluoride or DAST, is highly toxic and corrosive, and expensive. Above, the reaction conditions were 150 ° C, 8M
Due to severe conditions such as pa, equipment such as a special reaction vessel using Hastelloy or the like, which is a stainless alloy (Ni-Mo type) having excellent corrosion resistance, is required, which increases the production cost and is economically preferable. There is no problem. Also,
The method using DAST has a problem that, despite the fact that DAST is very expensive, the amount of DAST used is almost as large as the amount of the raw material, which is uneconomical.

In the former method, that is, in the method of dithioacetalization and then fluorination with HF-pyridine, the amount of BF ₃ : Et ₂ O used in the dithioacetalization is 1,9-diketo as a raw material. [2.2] Paracyclophane 0.2
It is uneconomical because a very large amount of 4.0 mmol per 4 mmol is required, and the step of neutralizing unreacted BF ₃ : Et ₂ O with aqueous sodium bicarbonate or sodium hydroxide is further required. Necessary, and therefore, washing of the produced dithioacetal compound is troublesome and inefficient. Further, in the above method, DMH is used as a catalyst for fluorination. However, since this DMH has poor thermal stability, the fluorination reaction must be performed at an extremely low temperature of -78 ° C, and after the dithioacetalization reaction. B remaining
F ₃ : Et ₂ O has many disadvantages, such as decomposing HF-pyridine in the subsequent fluorination step.

[0005] For this reason, there is still a high demand for a method by which tetrafluoro- [2,2] paracyclophane and its derivatives and intermediates thereof can be produced easily and at low cost without requiring special equipment. Was something.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention has been made in view of the above circumstances, and provides a novel method for producing a fluorine-containing aromatic compound and a di (thio) acetal compound derivative as an intermediate thereof. That is.

Another object of the present invention is to provide a method for producing a fluorine-containing aromatic compound and a di (thio) acetal compound derivative as an intermediate thereof at a low cost by a simple operation without requiring special equipment. It is to be.

Still another object of the present invention is to provide a fluorine-containing aromatic compound and a di (thio) acetal compound derivative as an intermediate thereof at a low cost and in a high yield by a simple operation without special equipment. Is to provide a method for producing the same.

[0009]

Means for Solving the Problems The present inventors have made intensive studies in view of the above circumstances, and as a result, the following formula (5):

[0010]

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However, R ₁ and R ₂ each independently represent a divalent aromatic ring which may have a substituent other than a phenylene group. Or "diketone compound") or the following formula (6):

[0012]

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Wherein R ₃ represents a divalent aromatic ring which may have a substituent, wherein a dialdehyde compound represented by the following formula (hereinafter simply referred to as “dialdehyde compound”) is converted to a dithioacetal. Alternatively, in a method for producing a fluorine-containing aromatic compound by fluorinating a di (thio) acetal compound derivative obtained by diacetalization, using a Bronsted acid such as paratoluenesulfonic acid as a catalyst for dithioacetalization or diacetalization. As a result, it has been found that the amount of the catalyst used can be remarkably suppressed, and the step of removing (neutralizing) the catalyst is not required. In addition, the present inventors can improve the productivity of a di (thio) acetal compound derivative as an intermediate by simplifying the washing step, in addition to the above advantage that the amount of catalyst added can be significantly reduced, As a result, they have also found that the productivity of fluorine-containing aromatic compounds can be improved.

[0014] In addition to the above findings, the present inventors also carried out the fluorination reaction of the thus obtained di (thio) acetal compound derivative with a highly thermally stable bromine-containing compound such as N-bromosuccinimide. By performing the reaction in the presence, the temperature range applicable to the reaction can be extended, and it is not necessary to produce under a special condition of a very low temperature of -78 ° C as in the conventional method, and it is possible to produce a fluorine-containing aromatic compound at low cost. I also found it possible.

Based on the above findings, the present invention has been completed.

That is, the above objects are achieved by the following (A) to (T).

(A) The following formula (1):

[0018]

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Wherein R ₁ and R ₂ each independently represent a divalent aromatic ring which may have a substituent other than a phenylene group; X ₁ , X ₂ , X ₃ and X ₄ are And each independently represents an oxygen or sulfur atom; and p and q are each independently 2 or 3, in the presence of a fluorine compound and a bromine-containing compound. The following formula (2) comprising reacting:

[0020]

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Wherein R ₁ and R ₂ are the same as defined in the above formula (1).

(A) The following equation (3):

[0023]

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However, R ₃ is a group which may have a substituent.
X ₁ , X ₂ , X ₃ and X ₄ each independently represent an oxygen or sulfur atom; and p and q are each independently 2 or 3; Reacting a di (thio) acetal compound derivative represented by the following formula in the presence of a fluorine compound and a bromine-containing compound:

[0025]

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Wherein R ₃ is the same as defined in the above formula (3).

(C) The following formula (5):

[0028]

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Wherein R ₁ and R ₂ each independently represent a divalent aromatic ring which may have a substituent other than a phenylene group, and a diketone compound represented by the following formula (7):

[0030]

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Wherein X ₅ and X ₆ each independently represent a hydroxyl group or a mercapto group, and p is 2
Or 3, a compound (B1) represented by the following formula (8):

[0032]

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Wherein X ₇ and X ₈ each independently represent a hydroxyl group or a mercapto group, and q represents 2
Or 3, by reacting the compound (B2) represented by the formula (1) with an organic solvent in the presence of a Brönsted acid:

[0034]

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However, R ₁ , R ₂ , p and q are represented by the formula (5):
And the same as defined in (7) and (8); and wherein X ₁ , X ₂ , X ₃ and X ₄ each independently represent an oxygen or sulfur atom. Obtaining a derivative, and further reacting the thus obtained di (thio) acetal compound derivative in the presence of a fluorine compound and a bromine-containing compound:

[0036]

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Wherein R ₁ and R ₂ are the same as defined in the above formula (5).

(D) The following formula (6):

[0039]

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Wherein R ₃ represents a divalent aromatic ring which may have a substituent, and a dialdehyde compound represented by the following formula (7):

[0041]

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Wherein X ₅ and X ₆ each independently represent a hydroxyl group or a mercapto group, and p is 2
Or 3, a compound (B1) represented by the following formula (8):

[0043]

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Wherein X ₇ and X ₈ each independently represent a hydroxyl group or a mercapto group, and q represents 2
Or 3 in the presence of a Brönsted acid in an organic solvent with a compound (B2) of the following formula (3):

[0045]

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Where R ₃ , p and q are represented by the formula (6):
And the same as defined in (7) and (8); and wherein X ₁ , X ₂ , X ₃ and X ₄ each independently represent an oxygen or sulfur atom. Obtaining a derivative, and further reacting the thus obtained di (thio) acetal compound derivative in the presence of a fluorine compound and a bromine-containing compound:

[0047]

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Wherein R ₃ is the same as defined in the above formula (6).

(E) The following formula (5):

[0050]

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However, R ₁ and R ₂ each independently represent a divalent aromatic ring which may have a substituent other than a phenylene group. A diketone compound represented by the following formula (7):

[0052]

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Wherein X ₅ and X ₆ each independently represent a hydroxyl group or a mercapto group, and p is 2
Or 3, a compound (B1) represented by the following formula (8):

[0054]

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However, X ₇ and X ₈ each independently represent a hydroxyl group or a mercapto group, and q represents 2
Or reacting a compound (B2) of the formula (3) with an organic solvent in the presence of a Bronsted acid in the following formula (1):

[0056]

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However, R ₁ , R ₂ , p and q are represented by the formula (5):
And the same as defined in (7) and (8); and wherein X ₁ , X ₂ , X ₃ and X ₄ each independently represent an oxygen or sulfur atom. A method for producing a derivative.

(F) The following formula (6):

[0059]

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Wherein R ₃ represents a divalent aromatic ring which may have a substituent, and a dialdehyde compound represented by the following formula (7):

[0061]

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Wherein X ₅ and X ₆ each independently represent a hydroxyl group or a mercapto group, and p is 2
Or 3, a compound (B1) represented by the following formula (8):

[0063]

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Wherein X ₇ and X ₈ each independently represent a hydroxyl group or a mercapto group, and q represents 2
Or a compound (B2) represented by the formula (3), which is reacted in an organic solvent in the presence of a Bronsted acid:

[0065]

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Here, R ₃ , p and q are represented by the following formula (6):
And the same as defined in (7) and (8); and wherein X ₁ , X ₂ , X ₃ and X ₄ each independently represent an oxygen or sulfur atom. A method for producing a derivative.

(G) The following formula (5):

[0068]

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However, R ₁ and R ₂ each independently represent a divalent aromatic ring which may have a substituent other than a phenylene group. A diketone compound represented by the following formula (7):

[0070]

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Wherein X ₅ and X ₆ each independently represent a hydroxyl group or a mercapto group, and p is 2
Or 3, a compound (B1) represented by the following formula (8):

[0072]

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Wherein X ₇ and X ₈ each independently represent a hydroxyl group or a mercapto group, and q represents 2
Or 3 in the presence of a compound (B2) represented by the following formula (1):

[0074]

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Here, R ₁ , R ₂ , p and q are represented by the following formula (5):
And the same as defined in (7) and (8); and wherein X ₁ , X ₂ , X ₃ and X ₄ each independently represent an oxygen or sulfur atom. Derivative, and the di (thio) acetal compound derivative thus obtained is combined with a fluorine compound and N
The following formula (2) comprising reacting in the presence of halosuccinimide:

[0076]

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Provided that R ₁ and R ₂ are the same as defined in the above formula (5).

(H) The following formula (6):

[0079]

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Wherein R ₃ represents a divalent aromatic ring which may have a substituent, and a dialdehyde compound represented by the following formula (7):

[0081]

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Wherein X ₅ and X ₆ each independently represent a hydroxyl group or a mercapto group, and p is 2
Or 3, a compound (B1) represented by the following formula (8):

[0083]

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X ₇ and X ₈ each independently represent a hydroxyl group or a mercapto group, and q represents 2
Or 3 in the presence of a compound (B2) represented by the following formula (3):

[0085]

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Where R ₃ , p and q are represented by the formula (6):
And the same as defined in (7) and (8); and wherein X ₁ , X ₂ , X ₃ and X ₄ each independently represent an oxygen or sulfur atom. Derivative, and the di (thio) acetal compound derivative thus obtained is combined with a fluorine compound and N
The following formula (4) comprising reacting in the presence of halosuccinimide:

[0087]

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Provided that R ₃ is the same as defined in the above formula (6).

(G) The following formula (9):

[0090]

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Wherein G and G ′ each independently represent a fluorine atom, a bromine atom, a chlorine atom or an iodine atom, and m and m ′ each independently represent
A di (thio) acetal compound derivative represented by the formula: which is an integer of 0 to 3.

(K) The following formula:

[0093]

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Wherein G and G ′ each independently represent a fluorine atom, a bromine atom, a chlorine atom or an iodine atom, and m and m ′ each independently represent
The di (thio) acetal compound derivative according to the above (1), which is an integer of 0 to 3.

(D) The di (thio) acetal compound derivative has the following formula:

[0096]

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The method according to any one of the above (a), (d) and (h), wherein

(D) The di (thio) acetal compound derivative has the following formula:

[0099]

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The method according to (a) above,

(S) The di (thio) acetal compound derivative has the following formula:

[0102]

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The method according to any one of the above (a), (d) and (h), wherein

(Se) The di (thio) acetal compound derivative has the following formula:

[0105]

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The method according to any one of the above (A), (C) and (G).

(So) The bromine-containing compound is N-bromosuccinimide and / or 1,3-dibromo-5,5
-The method according to any one of the above (A) to (D), which is dimethylhydantoin.

(T) The fluorine compound is at least one selected from the group consisting of poly (hydrogen fluoride) pyridinium, cesium fluoride, hydrofluoric acid and potassium fluoride. The method according to any of the above.

(H) The Bronsted acid is p-toluenesulfonic acid and / or benzenesulfonic acid, preferably p-toluenesulfonic acid.
(F) The method according to any of the above.

(T) The organic solvent is an aromatic hydrocarbon, preferably toluene or xylene.
(F) The method according to any of the above.

[0111]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in detail below.

According to a first concept, the present invention provides the following formula (1):

[0113]

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And / or the following formula (3):

[0115]

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Reacting a di (thio) acetal compound derivative represented by the formula (hereinafter also collectively referred to as a “di (thio) acetal compound derivative)” in the presence of a fluorine compound and a bromine-containing compound. By the following equation (2):

[0117]

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And / or the following formula (4):

[0119]

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The present invention provides a method for producing each of the fluorine-containing aromatic compounds represented by the formulas (hereinafter, these are also collectively referred to as “fluorine-containing aromatic compounds”). In the present invention, the di (thio) acetal compound derivative represented by the formula (1) is converted to the fluorine-containing aromatic compound represented by the formula (2) and the di (thio) compound represented by the formula (3). The fluorine-containing aromatic compound represented by the above formula (4) is produced from the acetal compound derivative.

In the above formulas (1) and (3), X ₁ ,
X ₂ , X ₃ and X ₄ represent an oxygen or sulfur atom, preferably a sulfur atom, wherein X _{1 to} X ₄ may represent the same or different atoms. Also,
p and q are 2 or 3, and are appropriately selected according to the reactivity between the di (thio) acetal compound derivative and the fluorine compound, but are preferably 2, and at this time, p and q are the same. Or different.

In the above formula (1), R ₁ and R ₂
Represents a divalent aromatic ring which may have a substituent other than a phenylene group, wherein R ₁ and R ₂ may be the same or different. As is clear from the above description, R ₁ and R ₂ need not be phenylene groups and include, for example, a phenylene group having a substituent such as toluene. In the present invention, these divalent aromatic rings when R ₁ and R ₂ are unsubstituted are not particularly limited as long as they are divalent aromatic rings other than a phenylene group. The divalent aromatic ring having 6 to 16 atoms, more specifically, the following divalent aromatic ring is exemplified.

[0123]

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Among these, divalent naphthalene and biphenyl are preferably used. Further, the above equation (3)
In the above, R ₃ represents a divalent aromatic ring which may have a substituent. These divalent aromatic rings when R ₃ is unsubstituted are the same as R ₁ and R ₂ except that they contain phenylene. Of these, phenylene, divalent naphthalene and biphenyl are preferably used. Is done.

In the present invention, when R ₁ , R ₂ and R ₃ represent a divalent aromatic ring having a substituent, examples of the substituent that can be used include a halogen atom such as a fluorine atom, a bromine atom and a chlorine atom; A linear or branched alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group and isopropyl group; a linear or branched alkyl group having 1 to 4 carbon atoms such as trifluoromethyl group and pentafluoroethyl group; A branched-chain perfluoroalkyl group; a straight-chain or branched-chain alkoxy group having 1 to 4 carbon atoms such as a methoxy group and an ethoxy group;
And a linear or branched perfluoroalkoxy group having 1 to 4 carbon atoms such as a perfluoromethoxy group and a perfluoroethoxy group. Among these, a halogen atom such as a fluorine atom, a bromine atom and a chlorine atom, more preferably a fluorine atom or a chlorine atom, and most preferably a fluorine atom can be used as a substituent. At this time, when a plurality of substituents are present in the aromatic ring, the substituents may be the same or different, respectively. The number of bonds and bonding positions may be the same or different, and vary depending on the type of aromatic ring used. The number of substituents in each aromatic ring is usually 1 to 4 , Preferably an integer of 1-2. Further, the bonding position of the substituent in each aromatic ring varies depending on the type of the aromatic ring and the substituent to be used. For example, when R ₁ is represented by the following formula:

[0126]

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In the case represented by the above formula, a hydrogen atom of a methylene group (—CH ₂ —) in R ₁ is replaced by a fluorine atom.
That, -CF ₂ - substituted group represented by the divalent toluene, and methylene group (-CH ₂ -) is -CF ₂ - remaining four hydrogen atoms all fluorine atoms in the group and the benzene ring And divalent toluene substituted with.

The position of the carbon atom having a free valence of R ₁ , R ₂ and R ₃ is appropriately selected according to the reactivity between the di (thio) acetal compound derivative and the fluorine compound, and is not particularly limited. It is desirable that the positions are symmetrical in the cyclic skeleton. For example, in the case of divalent naphthalene, the positions are preferably (2, 6) and (1, 5). At this time, the positions of the carbon atoms having a free valence of R ₁ and R ₂ may be the same or different.

[0129] In view of these points, the R _1, R ₁ when R ₂ and R ₃ is a divalent aromatic ring which one have a methylene group as a substituent, R ₂ and R ₃ preferred examples Examples include the following.

[0130]

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Further, R₁, R_TwoAnd R_ThreeHas a substituent
R which is a divalent aromatic ring₁, R _TwoAnd R_ThreePreferred
Some examples are as follows.

[0132]

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That is, the di (thio) acetal compound derivatives preferably used in the present invention include the following.

[0134]

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Among these compounds, preferably, the following formula:

[0136]

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A di (thio) acetal compound derivative represented by the following formula:

[0138]

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The 1,9-diketo [2,2] paracyclophanbis (ethylene dithioketal) represented by the formula (1) is used in the present invention.

The following formula:

[0141]

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The di (thio) acetal compound derivative represented by is a novel compound and therefore constitutes another concept of the present invention. That is, according to the above concept, the present invention provides the following formula (9):

[0143]

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And a di (thio) acetal compound derivative represented by the formula:

In the above formula (9), G and G ′ each independently represent a fluorine atom, a bromine atom, a chlorine atom or an iodine atom, preferably a fluorine atom or a chlorine atom;
Particularly preferably, it represents a fluorine atom, and m and m 'are each independently an integer of 0 to 3, particularly preferably 0 or 3.

The di (thio) acetal compound derivative can be obtained by adding the following formula to the arbitrary position of divalent naphthalene as R ₃ in the formula (3):

[0147]

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Is a compound having a structure in which two groups represented by the following formulas are bonded, preferably at symmetric positions [at positions (2,6) and (1,5)]. In other words, in particular the following two equations:

[0149]

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The di (thio) acetal compound derivative represented by the following formula is preferably used, and more preferably, the following formula:

[0151]

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A di (thio) acetal compound derivative represented by the following formula is used.

In the present invention, as the fluorine compound,
Although not particularly limited, poly (hydrogen fluoride) pyridinium is preferably used as the fluorine compound.
[pyridinium poly (hydrogen fluoride)] (HF-pyridine), ammonium hydrogen fluoride, potassium hydrogen fluoride,
Potassium fluoride, hydrofluoric acid, sodium hydrogen fluoride, ammonium fluoride, antimony fluoride (II
I), antimony (V) fluoride, and cesium fluoride. Of these, HF-pyridine, cesium fluoride, hydrofluoric acid and potassium fluoride are preferably used. In the present invention, the above-mentioned fluorine compounds may be used alone or in the form of a mixture of two or more.

In the present invention, a fluorine molecule (F ₂ ) or a fluorine ion may be used as the fluorine compound.
Any one of them is not particularly limited, but one supplied from the above-mentioned fluorine compound is preferable.

In the present invention, the amount of the fluorine compound to be used is not particularly limited, and is appropriately selected in consideration of the reaction yield and the production cost. However, the amount of the fluorine atom to be added to the di (thio) acetal compound derivative is not limited. In order to promote the introduction efficiently and to improve the yield of the target product, it is preferable that fluorine is present in an excess concentration with respect to the di (thio) acetal compound derivative. Specifically, the amount of the fluorine compound to be used is generally 4 mol or more, preferably 4 to 1 mol, per 1 mol of the di (thio) acetal compound derivative.
00 mole, more preferably 4 to 40 mole, most preferably 4 to 20 mole. At this time, the amount of the fluorine compound is 4
When the amount is less than the mole, introduction of a fluorine atom into the di (thio) acetal compound derivative cannot be sufficiently performed, and the yield of the target product is undesirably reduced. On the other hand, even if the amount of the fluorine compound exceeds 100 moles, the yield does not change and the yield is economically disadvantageous, and the treatment of the remaining fluorine compound is costly, which is not preferable.

In the present invention, in order to improve the reaction efficiency, it is essential that the reaction between the di (thio) acetal compound derivative and the fluorine compound is carried out in the presence of a bromine-containing compound.

In the present invention, the bromine-containing compound is not particularly limited as long as it contains a bromine atom, but a compound having many bromine atoms per molecule is preferable. More preferably, it is a compound capable of generating Br ⁺ . Specifically, N-bromosuccinimide, 1,3-dibromo-5,5-dimethylhydantoin, and 3-bromo-1-chloro-5,5-
Dimethylhydantoin is preferred. Of these,
N-bromosuccinimide and 1,3-dibromo-5,
5-Dimethylhydantoin is preferably used in the present invention, and considering thermal stability, N-bromosuccinimide is particularly preferably used in the present invention.

According to the present invention, the amount of the bromine-containing compound is not particularly limited as long as it is an amount that effectively catalyzes the reaction between the di (thio) acetal compound derivative and the fluorine compound. Usually, 1 to 3 equivalents, preferably 1 to 1 equivalent to the di (thio) acetal compound derivative.
It is twice equivalent. In this specification, the term “equivalent” means a value obtained by the following equation.

[0159]

(Equation 1)

In the present invention, the di (thio) acetal compound derivative and the fluorine compound used as the raw materials may be added in a batch or sequentially. It is preferable to put the (thio) acetal compound derivative last.

In the present invention, the reaction temperature between the di (thio) acetal compound derivative and the fluorine compound is to prevent the need for special equipment due to the high temperature reaction and to prevent the yield from being reduced by the decomposition of the reaction reagent. -60 to 8
It is preferably 0 ° C, more preferably -60 to 3 ° C.
0 ° C, most preferably -20 to 25 ° C. Such control of the reaction temperature is performed by a known method,
For example, the reaction solution is immersed in a refrigerant at a desired temperature, or an inert gas (for example, nitrogen, argon or helium) cooled by liquid nitrogen or the like is flowed into the reaction vessel or bubbled in the reaction solution. It is done by things. The reaction time varies depending on the type of di (thio) acetal compound derivative or fluorine compound, reaction conditions and the like, but is usually 1 to 24 hours, preferably 2 to 24 hours.
12 hours.

In the present invention, the reaction of the di (thio) acetal compound derivative with the fluorine compound may be carried out without a solvent, in an inorganic solvent or an organic solvent.
The dissolution of the di (thio) acetal compound derivative and the fluorine compound improves the reaction efficiency and facilitates the removal of heat. Therefore, the dissolution is preferably performed in an organic solvent.

In the above embodiment, the reaction of the di (thio) acetal compound derivative with the fluorine compound in the presence of the organic solvent is preferably performed by adding the di (thio) acetal compound derivative to an organic solvent containing a fluorine compound. Is carried out by adding gradually. As used herein, the term “organic solvent containing a fluorine compound” means a state in which the fluorine compound is uniformly dissolved or dispersed in the organic solvent. The organic solvent containing a fluorine compound can be specifically obtained by using a known technique such as adding a fluorine compound to an organic solvent shown below. At this time, the final concentration of the di (thio) acetal compound derivative in the organic solvent is 1 to 40% by weight, preferably 3 to 30% in consideration of the reaction yield and the production cost.
% By weight.

The organic solvent used in the present invention is not particularly limited as long as it is a solvent which is not fluorinated. Examples thereof include aliphatic or aromatic hydrocarbons such as pentane, hexane, cyclohexane, octane and xylene. , Dichloromethane, 1,2-dichloroethane, chloroform, 1,1,2,2-tetrachloroethane, carbon tetrachloride, halogen-containing aliphatic or aromatic hydrocarbons such as trichlorofluoromethane and chlorotoluene, diglyme, and tetrahydrofuran And the like. Among these, dichloromethane, chloroform, and 1,2-dichloroethane are preferably used in consideration of efficiently proceeding the reaction and improving the yield. Further, the organic solvent used in the present invention is Li
It is preferably used as a solvent dried with a known desiccant such as AlH ₄ , CaH ₂ or molecular sieve.

Alternatively, in the present invention, the reaction of a di (thio) acetal compound derivative with a fluorine compound in the presence of an organic solvent can be carried out in an organic solvent containing a di (thio) acetal compound derivative by using a fluorine-containing gas such as hydrogen fluoride gas. To react the di (thio) acetal compound derivative with the fluorine compound. At this time, the concentration of the di (thio) acetal compound derivative in the organic solvent is 1 to 40% by weight, preferably 3 to 30% by weight in consideration of the reaction yield and the production cost. May be introduced in an amount as described above, but is usually 5 to 200 ml / min, preferably 10 to 10 ml / min.
0 ml / min.

In the present invention, the reaction between the di (thio) acetal compound derivative and the fluorine compound is carried out when the water content in the gas phase of the reaction system is 100 volppm or less, more preferably 50 volppm or less, and most preferably 10 volppm or less.
It is preferable to carry out in an atmosphere of not more than vol ppm.
At this time, if the water content exceeds 100 volppm,
There are disadvantages such as a reduction in the efficiency of fluorine atom introduction and a corrosion of the reaction vessel. Therefore, when the water content is 1
Before charging the solvent containing the fluorine compound into the reaction vessel so as to be 00 vol ppm or less, an inert gas such as argon, helium, or nitrogen is passed through liquid nitrogen, for example, to dry the reaction vessel in the form of a dry gas. It is preferable to replace the inside.

The reaction vessel used in the present invention is not particularly limited as long as it is not fluorinated. For example, a vessel coated with glass, polyethylene, polypropylene, fluororesin, or fluororesin is used. No. Of these coating materials,
In order to avoid contamination due to elution of alkali metal ions and heavy metal ions, polyethylene, polypropylene and fluorine resin are preferably used as the coating material.

Next, after the reaction between the di (thio) acetal compound derivative and the fluorine compound is completed in this way, the reaction-terminated liquid is subjected to silica column chromatography,
Alternatively, the desired fluorine-containing aromatic compound can be isolated by separation and purification by known means such as distillation and recrystallization.

The method for producing the di (thio) acetal compound derivative according to the present invention will be described below.

First, the first embodiment of the method for producing a di (thio) acetal compound derivative according to the present invention will be described below. In the first embodiment, considering that the amount of the catalyst used is smaller than in the conventional case, the step of removing (neutralizing) the remaining catalyst is unnecessary, and the yield of the target product, Since it is preferably used in the present invention and such a method was not previously known, the above-mentioned embodiment forms the second concept of the present invention.

That is, according to the second concept, the present invention provides the following formula (5):

[0172]

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And / or a diketone compound represented by the following formula (6):

[0174]

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The dialdehyde compound represented by the following formula (7):

[0176]

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A compound (B1) represented by the following formula (hereinafter also referred to simply as “compound (B1)”) and the following formula (8):

[0178]

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Comprising reacting a compound (B2) represented by the formula (hereinafter simply referred to as “compound (B2)”) in an organic solvent in the presence of a Brönsted acid, represented by the following formula (1):

[0180]

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And / or the following formula (3):

[0182]

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The present invention also provides a method for producing a di (thio) acetal compound derivative represented by the following formula: In the above concept, a di (thio) acetal compound derivative represented by the above formula (1) is derived from the diketone compound represented by the above formula (5), and a dialdehyde compound represented by the above formula (6) is derived from the dialdehyde compound represented by the above formula (6). The di (thio) acetal compound derivative shown in 3) is produced respectively. In the above formulas (1), (3) and (5) to (7), R ₁ ,
The definitions of R ₂ , R ₃ , X _{1 to} X ₄ , p and q are the same as described above, and X ₅ , X ₆ , X ₇ and X ₈ each independently represent a hydroxyl group or a mercapto group. In addition, with respect to terms and the like described in this specification, the same terms have the same definitions.

In the above embodiment, first, a diketone compound and / or a dialdehyde compound are dissolved in an organic solvent, and the compound (B1) and the compound (B2) are added to this solution.
Is added, the di (thio) acetal compound derivative can be efficiently prepared by reacting the compound (B1) and the compound (B2) with the diketone compound and / or the dialdehyde compound while removing water by further heating. . At this time, the diketone compound and the dialdehyde compound are each used alone to form a single type of di (thio) compound.
The acetal compound derivative may be produced, or the corresponding di (thio) acetal compound derivative may be produced as a mixture by using it in the form of a mixture of two or more.

In the present invention, the compound (B1) and the compound (B2) may be the same or different as long as they are compounds represented by the formulas (7) and (8), respectively. , The ratio of which is the desired product di (thio)
It is determined by the structure of the acetal compound derivative. Specific examples of the compound (B1) and the compound (B2) include:
1,2-ethanedithiol, 1,3-propanedithiol, ethylene glycol, 1,3-propanediol,
And 2-mercaptoethanol, among which 1,2-ethanedithiol and 1,3-propanedithiol are preferably used.

In the present invention, the abundance ratio of the diketone compound and / or dialdehyde compound, the compound (B1) and the compound (B2) as raw materials is such that the diketone compound and / or the dialdehyde compound are the compounds (B1) and (B2) ), The di (thio) acetal compound derivative having the desired structure can be obtained as long as the value is such that the ratio of the total amount of the compound (B1) and the compound (B2) is , 1 to 4 moles per mole of the diketone compound and / or dialdehyde compound.
Mole, preferably 1-2 moles. At this time, when the ratio of the total amount of the compound (B1) and the compound (B2) is less than 1 mol, the compound (B1) and the compound (B2) can sufficiently bind to the diketone compound and / or the dialdehyde compound. Therefore, the yield of the di (thio) acetal compound derivative as the target product is lowered, which is not preferable.
Conversely, even if the ratio of the total amount of the compound (B1) and the compound (B2) exceeds 4 mol, no corresponding improvement in the yield is observed, which is economically unfavorable and the remaining compound (B
Since the treatment of 1) and the compound (B2) is costly,
After all it is not desirable.

The Bronsted acid used in the present invention is not particularly limited as long as it can efficiently catalyze the reaction of the diketone compound and / or dialdehyde compound with the compounds (B1) and (B2). Examples include paratoluenesulfonic acid, benzenesulfonic acid, nitric acid, trifluoroacetic acid, 2,4,6-trinitrophenol, and formic acid. Of these, paratoluenesulfonic acid and benzenesulfonic acid, Particularly, paratoluenesulfonic acid is preferred. In addition,
In the present invention, the above Bronsted acids may be used alone or in the form of a mixture of two or more.

In the present invention, the amount of the Brönsted acid present is not particularly limited as long as it can catalyze the reaction of the diketone compound and / or dialdehyde compound with the compounds (B1) and (B2). And / or 1 to 5 mol%, preferably 0.0 to 5 mol%, based on 1 mol of the dialdehyde compound used.
1 to 0.5 mol%.

The organic solvent used in the present invention is not particularly limited as long as it does not inhibit the reaction of the diketone compound and / or dialdehyde compound with the compound (B1) and the compound (B2). Aliphatic hydrocarbons such as pentane; aromatic hydrocarbons such as toluene, xylene and benzene; halogen-containing aliphatic hydrocarbons such as dichloromethane and 1,2-dichloroethane; and halogen-containing aromatic hydrocarbons such as chlorotoluene. . Of these, aromatic hydrocarbons, more preferably toluene and xylene, are preferably used in the present invention in consideration of the solubility of the raw materials, the good reaction efficiency, the yield of the target product, and the like. Further, the organic solvent used in the present invention is preferably used as a solvent dried with a known drying agent such as LiAlH ₄ , CaH ₂ or molecular sieve.

As described above, the method for producing a di (thio) acetal compound derivative according to the second concept of the present invention and the method for producing a fluorinated aromatic compound according to the first concept of the present invention are novel. The process for preparing a fluorinated aromatic compound by using the thus prepared di (thio) acetal compound derivative in a process according to the first concept is also novel and therefore forms the third concept of the present invention. . Therefore, according to a third concept, the present invention provides a di (thio) compound by reacting a diketone compound and / or a dialdehyde compound with a compound (B1) and a compound (B2) in an organic solvent in the presence of a Bronsted acid. C) obtaining an acetal compound derivative and further reacting the di (thio) acetal compound derivative thus obtained in the presence of a fluorine compound and a bromine-containing compound. It is.

Alternatively, in the present invention, the di (thio) acetal compound derivative may be produced by a known method.

For example, as the second embodiment of the method for producing a di (thio) acetal compound derivative according to the present invention, T. Itoh et al., Journal of Polymer Science: Pa.
rt A: There is a method for producing a di (thio) acetal compound derivative according to the method described in Polymer Chemistry, Vol. 33, 359-363 (1995). Briefly, the diketone compound and / or dialdehyde compound is converted to a compound (B1)
And dithioacetalization or diacetalization reaction with compound (B2) in the presence of a Lewis acid,
A di (thio) acetal compound derivative is produced.

In the above second embodiment, the Lewis acids include the Bronsted acids listed above, and in addition thereto, for example, inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, oxalic acid, acetic acid, and the like. Paratoluenesulfonic acid, benzenesulfonic acid and boron trifluoride ethyl ether complex (boron trifluoride ethyl ehterate) (BF ₃ : Et ₂
Organic acids such as O) and aluminum (III) chloride; among these, boron trifluoride diethyl etherate, hydrochloric acid and acetic acid are preferably used. The amount of the Lewis acid can be determined by comparing the diketone compound and / or dialdehyde compound with the compound (B1) and the compound (B
The amount is not particularly limited as long as it can catalyze the reaction with 2), but is usually 20 to 100 mol%, based on 1 mol of the diketone compound and / or dialdehyde compound used.
Preferably it is 30 to 70 mol%.

The thus-obtained di (thio) acetal compound derivative thus obtained was referred to as a fluorine compound.
Since the method for producing a fluorine-containing aromatic compound comprising reacting in the presence of N-halosuccinimide such as N-bromosuccinimide, N-chlorosuccinimide and N-iodosuccinimide, preferably N-bromosuccinimide is novel, Such a method also forms the fourth concept of the present invention. Therefore, according to a fourth concept, the present invention provides a method for converting a diketone compound and / or a dialdehyde compound into a compound (B1) and a compound (B
2) and a dithioacetalization reaction or a diacetalization reaction in the presence of a Lewis acid to produce a di (thio) acetal compound derivative, and converting the thus produced di (thio) acetal compound derivative to a fluorine compound with N-
An object of the present invention is to provide a method for producing a fluorinated aromatic compound, which comprises reacting in the presence of halosuccinimide.

Alternatively, according to the third embodiment, the di (thio) acetal compound derivative according to the present invention is obtained by dissolving terephthalaldehyde in an organic solvent such as toluene, and adding compound (B1) and compound (B2) to this solution. After adding
By performing the reaction while further removing water by heating, the compound can be efficiently prepared. In the third embodiment, in order to improve the yield, the reaction is preferably performed in the presence of an acid catalyst. Examples of the acid catalyst that can be used at this time include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid; and organic acids such as oxalic acid, acetic acid, paratoluenesulfonic acid, benzenesulfonic acid, and boron trifluoride diethyl ether complex. Is mentioned. Of these, paratoluenesulfonic acid is preferred because of its excellent solubility. Also,
The amount of the acid catalyst is determined by comparing the amount of terephthalaldehyde
The amount is not particularly limited as long as it can catalyze the reaction with 1) and the compound (B2), but is usually 0.01 to 5 mol%, preferably 0.01 to 1 mol%, per 1 mol of the terephthalaldehyde used. Mol%.

The fluorine-containing aromatic compound thus produced is useful as a raw material for a resin having excellent heat resistance, chemical resistance, water repellency, low dielectric properties and low refractive index.

[0197]

The present invention will now be described more specifically with reference to examples. The yield of the target product is defined as the ratio (%) of the production amount (mol) of the target fluorine-containing aromatic compound based on 1 mol of the di (thio) acetal compound derivative used.
Expressed as

Reference Example 1 The Chemical Society of Japan, 1974, (3), pages 603-6
2,6-Naphthalenedicarbaldehyde (intermediate (1)) was synthesized according to the method described in J. No. 05.

Reference Example 2 T. Itoh et al. (Journal of Polymer Science: Part
A: Polymer Chemistry, Vol. 33, pp. 359-363 (1995))
1,9-diketo [2.2] according to the method described in
Paracyclophanbis (ethylene dithioketal) was synthesized.

Briefly, 6.0 g (25 mmol) of 1,9-diketo [2.2] paracyclophane was placed in a 100 ml three-neck glass flask equipped with a stirrer.
And 50 g of dichloromethane. Furthermore,
5.2 g (50 mmol) of ethanedithiol are added,
After stirring for 20 minutes at 25 ° C., 1.1 g (7.5 mmol) of boron trifluoride diethyl ether complex was added, and stirring was further continued for 2 hours at 25 ° C., whereby a white precipitate was formed. did. The resulting white precipitate was filtered off and 5%
Washing with an aqueous sodium hydrogen carbonate solution, a 15% aqueous sodium hydroxide solution and a saturated saline solution gave 6.4 g of 1,9-diketo [2.2] paracyclophanbis (ethylenedithioketal) (intermediate (2)). (90% yield).

Example 1 A stirrer and Dean-Stark trap
In a glass 300 ml three-necked flask equipped with ap), 17.5 g of toluene, 1.07 g (5.8 mmol) of the intermediate (1) synthesized in Reference Example 1, and 1,2-ethanedithiol 1 0.1 g (11.6 mmol) and 0.012 g (0.06 mmol) of paratoluenesulfonic acid monohydrate.
l) was charged and stirred. The temperature was further raised until the toluene was refluxed, and refluxed for 2 hours. After cooling to room temperature, the precipitated white solid was filtered, washed with methanol,
By drying with a vacuum dryer, 2,6-bis (ethylenedithioketal) naphthalene (compound (1))
1.75 g (90% yield) was obtained as a white solid.

The results of mass spectrometry and NMR of the compound (1) thus obtained are shown below.

NMR result: δ (in CDCl ₃ ) 3.4 (8H, m), 5.7 (2H, s), 7.7 (6H, m) Mass spectrometry result: 335 (M-1)

Example 2 14.0 g (78.6) of N-bromosuccinimide was placed in a 100 ml three-neck glass flask equipped with a stirrer.
mmol) and 50 g of dichloromethane were charged and completely dissolved by stirring. The three-necked flask was immersed in ice water while flowing argon gas (water content of 1 vol ppm or less) into the three-necked flask. 5. Hydrogen fluoride pyridine (HF-pyridine) (manufactured by Aldrich)
1 g (212 mmol) was added via syringe. 3.4 g of the compound (1) prepared in Example 1 while stirring at 0 ° C.
(10 mmol) was added in several portions.

After the reaction solution was neutralized with a 10% aqueous sodium hydroxide solution, the solid content was separated by filtration. After concentrating the organic layer, the residue was purified by column chromatography to obtain 1.2 g of 2,6-difluoromethylnaphthalene.

Example 3 In a 300 ml three-neck glass flask equipped with a stirrer, 175 g of toluene, 9.2 g (50 mmol) of the intermediate (1) synthesized in Reference Example 1, and 1,2-ethanedithiol 9.4 g (100 mmol) were charged and, while stirring, 3.5 g of boron trifluoride diethyl ether complex (2 g).
5 mmol) was added. The temperature was further raised until the toluene was refluxed, and refluxed for 2 hours. After cooling to room temperature, the precipitated white solid was filtered and washed with a 5% aqueous sodium hydrogen carbonate solution, a 15% aqueous sodium hydroxide solution and a saturated saline solution. The obtained white solid was dried with a vacuum drier to give 15.1 g of 2,6-bis (ethylenedithioketal) naphthalene (compound (2)) (yield 9).
0%) as a white solid.

N-bromosuccinimide (24.6) was placed in a 200 ml three-neck glass flask equipped with a stirrer.
g (140 mmol) and 90 g of dichloromethane were charged and completely dissolved by stirring. The three-necked flask was immersed in ice water while flowing argon gas (water content of 1 vol ppm or less) into the three-necked flask. Hydrogen fluoride pyridine (HF-pyridine) (Aldrich
11.0 g (382 mmol) was added via syringe. Compound (2) prepared above while stirring at 0 ° C.
6.0 g (17.9 mmol) were added in several portions.

After the reaction solution was neutralized with a 10% aqueous sodium hydroxide solution, the solid content was filtered off. After concentrating the organic layer, the residue was purified by column chromatography to obtain 1.6 g of 2,6-difluoromethylnaphthalene.

Example 4 8.6 g (30.0 mmol) of 1,3-dibromo-5,5-dimethylhydantoin and 5 ml of dichloromethane were placed in a 100 ml three-neck glass flask equipped with a stirrer.
0 g was charged and completely dissolved by stirring.
The three-necked flask was immersed in ice water while flowing argon gas (water content of 1 vol ppm or less) into the three-necked flask. Hydrogen fluoride pyridine (HF-pyridine) (Al
8.6 g (300 mmol) of Drich was added with a syringe. While stirring at 0 ° C., 5.0 g (14.9 mmol) of the compound (1) prepared in Example 1 was added in several portions.

After the reaction solution was neutralized with a 10% aqueous sodium hydroxide solution, the solid content was filtered off. After concentrating the organic layer, the residue was purified by column chromatography to obtain 1.8 g of 2,6-difluoromethylnaphthalene.

Example 5 First, 1,9-diketo [2.2] paracyclophane was
KC Dcwhirst et al (J. Am. Chem. Soc., 80, 3115
(1958)).

Stirrer and Dean-Stark trap (D
In a glass 100 ml three-necked flask equipped with ean-Stark Trap), 50 g of toluene and 2.0 g of 1,9-diketo [2.2] paracyclophane synthesized above.
(8.3 mmol), 1,2-ethanedithiol 1.6
0 g (17.0 mmol) and 0.002 g (0.008 mmol) of paratoluenesulfonic acid monohydrate were charged and stirred. Further raise the temperature until the toluene refluxes,
Refluxed for 2 hours. After cooling to room temperature, the precipitated white solid was filtered, washed with methanol, and dried with a vacuum drier to give 1,9-diketo [2.2] paracyclophane-bis (ethylenedithioketal). 1.9 g of naphthalene (compound (3)) was obtained as a white solid.

Example 6 A 100-ml three-neck glass flask equipped with a stirrer was charged with 3.5 g (19.5 m) of N-bromosuccinimide.
mol) and 50 g of dichloromethane, and completely dissolved by stirring. The three-necked flask was immersed in ice water while flowing argon gas (water content of 1 vol ppm or less) into the three-necked flask. Hydrogen fluoride pyridine (HF-pyridine) (manufactured by Aldrich) 1.7
g (57.6 mmol) was added via syringe. 1.0 g of the compound (3) prepared in Example 5 while stirring at 0 ° C.
(2.6 mmol) was added in several portions.

The reaction solution was neutralized with a 10% aqueous sodium hydroxide solution, and the solid content was separated by filtration. After concentrating the organic layer, the residue was purified by column chromatography to obtain 0.4 g of 1,9-tetrafluoro [2.2] paracyclophane.

[0215]

As described above, the method of the present invention is characterized in that a fluorine-containing aromatic compound is produced by reacting a di (thio) acetal compound derivative in the presence of a fluorine compound and a bromine-containing compound. Is what you do. Therefore, according to the method of the present invention, the bromine-containing compound used as the catalyst has a higher thermal stability than the conventional one, so that the reaction between the di (thio) acetal compound derivative and the fluorine compound is performed at a higher temperature than the conventional one. It can be carried out under normal pressure, the amount of bromine-containing compound used as a catalyst can be significantly suppressed, and the fluorine source is supplied relatively inexpensively, so that special equipment such as conventional equipment is used. Can be omitted, and the desired fluorine-containing aromatic compound can be produced at low cost.

Further, as described above, the method of the present invention
By reacting a diketone compound and / or a dialdehyde compound with the compound (B1) and the compound (B2) in an organic solvent in the presence of a Bronsted acid, di (thio)
It is characterized by producing an acetal compound derivative. Therefore, according to the method of the present invention, the amount of Bronsted acid used as a catalyst can be reduced to a very small amount as compared with a conventional catalyst (for example, BF ₃ : Et ₂ O), and the cost is significantly reduced. Since it can be suppressed, a di (thio) acetal compound derivative as an intermediate of a fluorine-containing aromatic compound can be produced at low cost and in high yield.

Further, the present invention is characterized in that a fluorine-containing aromatic compound of the formula (2) is produced by combining the above two methods of the present invention. Therefore, according to the method of the present invention, in addition to the above advantages,
Since the step of removing (washing / neutralizing) the catalyst required between the step of producing the di (thio) acetal compound derivative and the step of producing the fluorine-containing aromatic compound can be omitted,
It is possible to efficiently produce a di (thio) acetal compound derivative as an intermediate, and furthermore, a fluorine-containing aromatic compound as an intermediate by a simple operation as compared with the related art.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4C023 NA01 4C037 SA10 4C071 AA04 BB03 CC24 EE12 FF22 KK01 LL07 4H006 AA02 AC30 BA51 BB11 BB12 BB15 BB25 BB61 BB71 BC18 BC35 BE01 BE53 BJ50 BM10 BM71 FC54 FC56 FC56

Claims (9)

[Claims] 1. The following formula (1): Provided that R ₁ and R ₂ each independently represent a divalent aromatic ring which may have a substituent other than a phenylene group; X ₁ , X ₂ , X ₃ and X ₄ are each independently And represents an oxygen or sulfur atom; and p and q are each independently 2 or 3.
The following formula (2) comprising reacting an acetal compound derivative in the presence of a fluorine compound and a bromine-containing compound: Provided that R ₁ and R ₂ are the same as defined in the above formula (1). 2. The following formula (3): Wherein R ₃ represents a divalent aromatic ring which may have a substituent; X ₁ , X ₂ , X ₃ and X ₄ each independently represent an oxygen or sulfur atom; And q
Is independently reacted with a di (thio) acetal compound derivative represented by the following formula (4), which is 2 or 3, in the presence of a fluorine compound and a bromine-containing compound: Provided that R ₃ is the same as defined in the above formula (3). 3. The following formula (5): Provided that R ₁ and R ₂ each independently represent a divalent aromatic ring which may have a substituent other than a phenylene group, and a diketone compound represented by the following formula (7): ] Wherein X ₅ and X ₆ each independently represent a hydroxyl group or a mercapto group, and p is 2 or 3, and a compound (B1) represented by the following formula (8): Wherein X ₇ and X ₈ each independently represent a hydroxyl group or a mercapto group, and q is 2 or 3, and is reacted with an organic solvent in the presence of a Bronsted acid in an organic solvent. The following formula (1): However, R _1, R _2, p and q has the formula (5) are the same as defined in (7) and (8); and, X _1,
X ₂ , X ₃ and X ₄ each independently represent an oxygen or sulfur atom to obtain a di (thio) acetal compound derivative represented by the following formula, and further obtain the thus obtained di (thio) acetal compound derivative Is reacted with a fluorine compound and a bromine-containing compound in the presence of the following formula (2): Provided that R ₁ and R ₂ are the same as defined in the above formula (5). 4. The following formula (6): Wherein R ₃ represents a divalent aromatic ring which may have a substituent, and a dialdehyde compound represented by the following formula (7): Wherein X ₅ and X ₆ each independently represent a hydroxyl group or a mercapto group, and p is 2 or 3, and a compound (B1) represented by the following formula (8): Wherein X ₇ and X ₈ each independently represent a hydroxyl group or a mercapto group, and q is 2 or 3, and is reacted with an organic solvent in the presence of a Bronsted acid in an organic solvent. The following formula (3): Here, R ₃ , p and q are represented by formulas (6), (7) and (8)
And X ₁ , X ₂ , X ₃
And X ₄ each independently represent an oxygen or sulfur atom to obtain a di (thio) acetal compound derivative represented by the formula: and further converting the di (thio) acetal compound derivative thus obtained into a fluorine compound and a bromine compound. The following formula (4) comprising reacting in the presence of the containing compound: Here, R ₃ is the same as defined in the above formula (6), wherein R ₃ is a method for producing a fluorine-containing aromatic compound. 5. The following formula (5): However, R ₁ and R ₂ each independently represent a divalent aromatic ring which may have a substituent other than a phenylene group, and a diketone compound represented by the following formula (7): ] Wherein X ₅ and X ₆ each independently represent a hydroxyl group or a mercapto group, and p is 2 or 3, and a compound (B1) represented by the following formula (8): Wherein X ₇ and X ₈ each independently represent a hydroxyl group or a mercapto group, and q is 2 or 3, and is reacted with an organic solvent in the presence of a Bronsted acid in an organic solvent. The following formula (1) consisting of: However, R _1, R _2, p and q has the formula (5) are the same as defined in (7) and (8); and, X _1,
X ₂ , X _3, and X ₄ each independently represent an oxygen or sulfur atom, and a method for producing a di (thio) acetal compound derivative represented by the formula: 6. The following formula (6): Wherein R ₃ represents a divalent aromatic ring which may have a substituent, and a dialdehyde compound represented by the following formula (7): Wherein X ₅ and X ₆ each independently represent a hydroxyl group or a mercapto group, and p is 2 or 3, and a compound (B1) represented by the following formula (8): Wherein X ₇ and X ₈ each independently represent a hydroxyl group or a mercapto group, and q is 2 or 3, and is reacted with an organic solvent in the presence of a Bronsted acid in an organic solvent. The following formula (3) consisting of: Here, R ₃ , p and q are represented by formulas (6), (7) and (8)
And X ₁ , X ₂ , X ₃
And X ₄ each independently represents an oxygen or sulfur atom, and a method for producing a di (thio) acetal compound derivative represented by the formula: 7. The following formula (5): However, R ₁ and R ₂ each independently represent a divalent aromatic ring which may have a substituent other than a phenylene group. A diketone compound represented by the following formula (7): ] Wherein X ₅ and X ₆ each independently represent a hydroxyl group or a mercapto group, and p is 2 or 3, and a compound (B1) represented by the following formula (8): Wherein X ₇ and X ₈ each independently represent a hydroxyl group or a mercapto group, and q is 2 or 3, and the compound is reacted with a compound (B2) represented by the following formula in the presence of a Lewis acid. (1): embedded image However, R _1, R _2, p and q has the formula (5) are the same as defined in (7) and (8); and, X _1,
X ₂ , X ₃ and X ₄ each independently represent an oxygen or sulfur atom to obtain a di (thio) acetal compound derivative represented by the following formula, and further obtain the thus obtained di (thio) acetal compound derivative Is reacted with a fluorine compound in the presence of N-halosuccinimide to obtain the following formula (2): Provided that R ₁ and R ₂ are the same as defined in the above formula (5). 8. The following formula (6): Wherein R ₃ represents a divalent aromatic ring which may have a substituent, and a dialdehyde compound represented by the following formula (7): Wherein X ₅ and X ₆ each independently represent a hydroxyl group or a mercapto group, and p is 2 or 3, and a compound (B1) represented by the following formula (8): Wherein X ₇ and X ₈ each independently represent a hydroxyl group or a mercapto group, and q is 2 or 3, and the compound is reacted with a compound (B2) represented by the following formula in the presence of a Lewis acid. (3): embedded image Here, R ₃ , p and q are represented by formulas (6), (7) and (8)
And X ₁ , X ₂ , X ₃
And X ₄ each independently represent an oxygen or sulfur atom to obtain a di (thio) acetal compound derivative represented by the following formula. Further, the thus obtained di (thio) acetal compound derivative is converted to a fluorine compound and N 2 -Reacting in the presence of halosuccinimide, the following formula (4): Here, R ₃ is the same as defined in the above formula (6), wherein R ₃ is a method for producing a fluorine-containing aromatic compound. 9. The following formula (9): Wherein G and G ′ each independently represent a fluorine atom, a bromine atom, a chlorine atom or an iodine atom; and m and m ′ each independently represent an integer of 0 to 3. Di (thio) acetal compound derivatives.