JPH03112951A - Production of aromatic nitrogen compound containing fluoroalkyl group - Google Patents

Abstract

PURPOSE:To easily obtain the subject substance useful as a synthetic intermediate for pharmaceuticals and agricultural chemicals, a raw material for polymeric material, etc., in high yield by reacting a di(haloacyl) peroxide with an aromatic nitrogen compound using a specific carboxylic acid as a solvent. CONSTITUTION:The objective compound of formula IV or formula V can be produced by reacting a compound of formula I (X is F, Cl or H; n1 is integer of 1-10) with a compound of formula II or formula III [R1 and R2 are 1-10C (fluoro)acyl; R3 is 1-10C (fluoro)-alkyl; X1 is 0, sulfonyl, CO, dimethylmethine, methylene. etc.; n2 is 0 or 1; n3 is 0-3] in a solvent consisting of a compound of formula R4COOH (R4 is 1-8C alkyl or 1-3C perfluoroalkyl) (e.g. acetic acid or heptafluoro butyric acid) at 10-100 deg.C for 3-10hr. The amount of the carboxylic acid used as the solvent is preferably 100g to 10kg based on 1mol of the aromatic nitrogen compound.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for producing a fluoroalkyl group-containing aromatic nitrogen compound.

<Prior Art> Compounds containing a fluoroalkyl group among organic compounds have attracted attention in recent years as they exhibit useful properties such as physiological activity. In particular, a fluoroalkyl group-containing nitrogen compound in which a fluoroalkyl group is introduced into an aromatic nitrogen compound is considered to be useful as a raw material for synthetic intermediates and polymeric materials such as medicines, agricultural chemicals, and surfactants. However, at present, little is known about a manufacturing method for easily introducing a fluoroalkyl group into an aromatic nitrogen compound in a high yield and industrially effectively.

<Problems to be Solved by the Invention> The purpose of the present invention is to develop a fluoroalkyl group-containing nitrogen compound that can be used as a synthetic intermediate for water and oil repellents, medicines, agricultural chemicals, etc., and as a raw material for polymeric materials such as polyamide and polyimide. ,
The object of the present invention is to provide a method that can be easily manufactured industrially.

Means for Solving the Problems According to the present invention, the following general formula
nl represents an integer of 1 to 10); and a di(haloacyl)peroxide represented by the following general formula (II) or (III) (wherein R1 and R2 are an acyl group or a fluoroacyl group having 1 to 10 carbon atoms). and R1 has 1 to 10 carbon atoms.
represents an alkyl group or a fluoroalkyl group. Also X□
represents an oxygen atom, sulfonyl, carbonyl, dimethylmethine, methylene, ethylene, bis(trifluoromethyl)methine or -A-/-ゝ-A-Kichiゝ-+(〉-Haz-7A+llll. Here, A is oxygen atom, sulfonyl, carbonyl, dimethylmethine, methylene, ethylene, bis(trifluoromethyl)
It represents methine, and m represents an integer of O to 3. R2 represents 0 or 1, and n represents an integer of O to 3. ) is reacted with the aromatic nitrogen compound represented by the above general formula (n) or (Iff), and the aromatic ring in the aromatic nitrogen compound represented by the above general formula (n) or (Iff) is reacted with the di(haloacyl)peroxide shown by the above general formula (I). A method of introducing X(CFz)n of Number 1
Provided is a method for producing a fluoroalkyl group-containing aromatic nitrogen compound, which is characterized by using a carboxylic acid represented by the following (indicating a perfluoroalkyl group).

The present invention will be explained in more detail below.

In the method for producing a fluoroalkyl group-containing aromatic nitrogen compound of the present invention, a specific di(haloacyl)peroxide,
It is characterized by using a specific carboxylic acid as a solvent when reacting with a specific aromatic nitrogen compound.

The fluoroalkyl group-containing aromatic nitrogen compound obtained by the production method of the present invention can be represented by the following general formula (V) or (TV), where R and R2 are acetyl and propionyl.

It represents an acyl group or fluoroacyl group having 1 to 10 carbon atoms such as butyryl, heptanoyl, trifluoroacetyl, pentafluoropropionyl, heptafluorobutyryl, nonafluoroheptanoyl, etc., and R1 is methyl, ethyl, propyl, butyl, trifluoroacyl group, etc. It represents an alkyl group or fluoroalkyl group having 1 to 10 carbon atoms, such as fluoromethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl. In addition, Xl is an oxygen atom, sulfonyl, carbonyl, dimethylmethine, methylene, ethylene, bis(trifluoromethyl)methine or -A-
−A<2>−÷2>−A+. Here, A represents an oxygen atom, sulfonyl, carbonyl, dimethylmethine, methylene, ethylene, or bis(trifluoromethyl)methine, and m represents an integer of O to 3. Further, X represents a fluorine atom, a chlorine atom, or a hydrogen atom, nl represents an integer of 1 to 10, +n2 and R4 represent an integer of 0 to 1, and n represents an integer of O to 3. Examples of the fluoroalkyl group-containing aromatic nitrogen compound represented by the general formula (V) or (VI) include 1, for example, heptafluoropropyl-N,N'-diacetyl-
p-phenylenediamine, heptafluoropropyl-4
, 4'-bis(acetylamino)diphenyl ether,
Bis(heptafluoropropyl)-4,4'-bis(acetylamino)diphenyl ether, tridecafluorohexyl-4,4'-bis(acetylamino)diphenyl ether, bis(tridecafluorohexyl)-4,
4'-bis(acetylamino)diphenyl ether,
Pentadecafluoroheptyl-4,4'-bis-(acetylamino)diphenyl ether, bis(pentadecafluoroheptyl)-4,4'-bis(acetylamino)diphenyl ether, heptafluoropropyl-4,
4'-bis(acetylamino)diphenylsulfone,
Bis(heptafluoropropyl)-4,4'-bis(acetylamino)diphenylsulfone, 2-hebutafluoropropyl-3,5,3', 5'-tetramethyl-4,4'-bis(acetylamino) diphenyl ether, 2,2'-bis(heptafluoropropyl)-3,
5,3',5'-tetramethyl-4゜4'-bis(
acetylamino) Schiftyl ether, 2-(4-acetylamino-3-hebutafluoropropylphenyl)-
2-(4-acetylaminophenyl)hexafluoropropane, 2,2-bis(4-acetylamino-3-hebutafluoropropylphenyl)hexafluoropropane, 2-(4-(4-acetylamino-3) -hebutafluoropropylphenoxy)phenyl)-2-(4-(4
-acetylaminophenoxy)phenyl)hexafluoropropane, 2,2-bis(4-(4-acetylamino-3-hebutafluoropropylphenoxy)phenyl)
Preferred examples include hexafluoropropane.

The di(haloacyl)peroxide used in the production method of the present invention can be represented by the following general formula (I), where X represents a fluorine atom, a chlorine atom, or a hydrogen atom, and n
l represents an integer of 1 to 10. Fluoroalkyl group applicable in the general formula (I), i.e., X (CFz)
nx- is CF.

F (c Ft) 2-1F (CF2).

p (cF2)4-1F (c F2) 5F(CF
2) G-1” (CF2) ?F (CF2) *
F (CF2) *F (CF2) 5o-1CQC
F.

c Q (CF2) 2-1c n (c F2) 3
CQ (CF2) 4-1CQ (CF2) 5Cfl
(cFs)m-1C1(CF,)7CQ(CF2)
, -1CQ(CFz)sc a (c F2) z.

+, HCF2H (cps) 2+, H (CF, )3 H (CF2) 4-- H (CF2) 5H (CF2)
, -1H(CF2) t H(CF2) e-1H(CFz) 9H(CF2)
1. -, and can be appropriately selected and used from among these. At this time, if the number of carbon atoms in the fluoroalkyl group, that is, the number of carbon atoms, exceeds 10, it becomes difficult to produce a peroxide.

The specific aromatic nitrogen compound used in the production method of the present invention can be represented by the following general formula (If) or (m), where R1 and R2 are an acyl group having 1 to 10 carbon atoms or a fluoroacyl group. group, R3 represents an alkyl group or fluoroalkyl group having 1 to 10 carbon atoms, and X□ is an oxygen atom, sulfonyl, carbonyl, dimethylmethine,
Indicates methylene, ethylene, bis(trifluoromethyl)methine or -A-k2>-A-k2>-÷<2>A+w+. Here, A represents an oxygen atom, sulfonyl, carbonyl, dimethylmethine, methylene, ethylene, or bis(trifluoromethyl)methine, and m represents an integer of 0 to 3. R2
represents O or l, and n represents an integer of O to 3. In this case, if the acyl group or fluoroacyl group of R□ and R2 has R3 carbon atoms or the fluoroalkyl group has 11 or more carbon atoms, production becomes difficult. The general formula (
As the aromatic compound represented by n) or (m),
For example, N.

N'-Diacetyl-p-phenylenediamine, N.

N'-Diacetyl-m-phenylenediamine, N.

N'-bis(trifluoroacetyl)-p-phenylenediamine, N,N'-bis(trifluoroacetyl)-
m-phenylenediamine, N,N'-bis(heptafluoropropionyl)-p-phenylenediamine, N,N
'-bis(heptafluoropropionyl)-m-phenylenediamine.

4.4'-bis(acetylamino)diphenyl ether, 4.4'-bis(acetylamino)diphenyl sulfone, 4,4'-bis(acetylamino)diphenylketone, 4,4'-bis(acetylamino)diphenylmethane, 1,2-bis(4-acetylaminophenyl)ethane, 2,2-bis(4-acetylaminophenyl)propane, 4,4'-bis(acetylamino)biphenyl, 1.2-[4,4'- Bis(acetylamino)diphenylketone, 2,2-[4,4'-bis(acetylamino)diphenylcopropane, 4゜4'-bis(acetylamino)biphenyl-3゜5.3', 5'-tetra Methyl-4,4'-bis(acetylamino)diphenyl ether, 2,2-bis(4-acetylaminophenyl)hexafluoropropane, 2,2-bis(4-(
Examples include 4-acetylaminophenoxy)phenyl)hexafluoropropane.

The specific carboxylic acid used in the production method of the present invention can be represented by the following general formula (rV).

R4C0OH (IV) In the formula, R4 is an alkyl group having 1 to 8 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl, or trifluoromethyl.

Indicates a perfluoroalkyl group having 1 to 3 carbon atoms such as pentafluoroethyl and heptafluoropropyl.

Particularly preferred is a perfluoroalkyl group.

Preferred examples of the carboxylic acid represented by the general formula (I'/) include acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, pentafluoropropionic acid, and heptafluorobutyric acid.

In the production method of the present invention, when reacting the di(haloacyl)peroxide with the aromatic nitrogen compound represented by the general formula (II) or (III), a carboxylic acid represented by the general formula CIV) is added. By this,
Since the solubility of the aromatic nitrogen compound is increased, the fluoroalkyl group-containing aromatic nitrogen compound can be obtained in good yield and industrially effectively. The amount of the carboxylic acid and the aromatic nitrogen compound to be charged is preferably Log~5 of the carboxylic acid per 1 mon of the aromatic nitrogen compound.
It is desirable that the amount of catfish is 0 g, particularly preferably 100 g to 10 kg. If the amount of the carboxylic acid charged is less than 10 g, it is not preferable because there is no difference from the case where no carboxylic acid is added, and the effect of improving the yield cannot be obtained. Moreover, if it exceeds 50 kg, the decomposition of peroxide will be accelerated and the yield will decrease, which is not preferable. Further, the molar ratio of the di(haloacyl)berohaside and the aromatic nitrogen compound is 1:0.1 to 1:0.1.
The ratio is preferably 20, particularly 1:0.5 to 10. The charging molar ratio with the aromatic nitrogen compound is 0.
If it is less than 1, the yield of the fluoroalkyl group-containing aromatic nitrogen compound produced tends to decrease, and if it exceeds 20, unreacted aromatic nitrogen compounds will remain after the reaction is completed, making it difficult to isolate the desired product. This is not preferable because it becomes difficult. Furthermore, the reaction in the production method of the present invention can be carried out at normal pressure, and the reaction temperature is 0-150°C, preferably 1
The temperature is preferably in the range of 0 to 100°C. If the reaction temperature is less than 0°C, the reaction time tends to be long, whereas if it exceeds 150°C, the pressure during the reaction becomes high, making it difficult to carry out one reaction operation, which is not preferable.

Further, the reaction time can be generally carried out in the range of 30 minutes to 20 hours, but it is practically desirable to set the conditions so that the reaction time is 3 to 10 hours.

In the present invention, in order to handle and react the di(haloacyl)peroxide more efficiently, it is preferable to use a halogen-based solvent in addition to the carboxylic acid represented by the general formula (IV).

The solvent is particularly preferably a halogenated aliphatic solvent that does not contain a hydrogen atom, and specifically, for example, 2-chloro-
1,2-dibromo-1,1,2-trifluoroethane,
1,2-dibromohexafluoropropane, 1,2-dibromotetrafluoroethane, 1,1-difluorotetrachloroethane, 1,2-difluorotetrachloroethane, fluorotrichloromethane, heptafluoro-2,
3゜3-Trichlorobutane, 1,1,1,3-tetrachlorotetrafluoropropane, 1,1,1-trichloropentafluoropropane, 1,1,2-trichlorotrifluoroethane, etc. can be used, and especially Industrially, 1,1,2-trichlorotrifluoroethane is preferred. When using the above solvent, the concentration of the di(haloacyl)peroxide in the solvent is usually
The content is preferably about 2 to 30% by weight.

<Effects of the Invention> Since the method for producing a fluoroalkyl group-containing aromatic nitrogen compound of the present invention uses a specific carboxylic acid as a reaction solvent, the desired fluoroalkyl group-containing aromatic nitrogen compound can be easily produced in high yield. It can be effectively produced industrially. Further, the fluoroalkyl group-containing aromatic nitrogen compound obtained by the production method of the present invention can be used as a raw material for synthetic intermediates of water and oil repellents, medicines, agricultural chemicals, etc., and polymeric materials such as polyamides and polyimides.

<Examples> The present invention will be specifically explained below with reference to Examples and Comparative Examples, but the present invention is not limited to these.

"1"Y N,N'-diacetyl-P-phenylenediamine 0.
19g (ImmoQ) and 4g heptafluorobutyric acid (
0.43 g of bis(heptafluorobutyryl) peroxide (Immoll
8.5 g of a 1,1,2-trichlorotrifluoroethane solution containing ) was added and reacted for 5 hours at 40° C. under a nitrogen stream. After the reaction was completed, the reactants were mixed with 100 mQ of water, 1
After washing with 00 mQ of saturated sodium bicarbonate solution and 100 mQ of saturated brine and drying over magnesium sulfate, the reaction product was analyzed by gas chromatography, GC-MS, IR, and NMR1 elemental analysis. As a result, heptafluoropropyl-N,N'-diacetyl-p expressed by the following structural formula
-Phenylenediamine was obtained with a yield of 95%. The analysis results are shown below.

GC-MS IR (an-1) "H-NMR 360 (M"), 318,276.1573260 (MaNH), 1660 (MaCo), 1345 (MaCF, )
1225 (MaCF, ) (cocla) δ, 9.50 (I) 1. b).

8.75 (I1 (, b), 7.70-7.42 (3H,
m).

2.12 (3H, s), 2.10 (3t (, s) Elemental analysis Theoretical value C: 43.34% H: 3.08
% Actual value C: 43.44% H: 2.78% Japanff
i When the reaction was carried out in the same manner as in Example 1 except that heptafluorobutyric acid was not used, heptafluoropropyl-N,
N'-diacetyl-p-phenylenediamine was obtained with a yield of 56%.

1.4g trifluoroacetic acid instead of heptafluorobutyric acid
When the reaction was carried out in the same manner as in Example 1 except that (35mmoQ) was used, heptafluoropropyl-N, N'
-Diacetyl-p-phenylenediamine was obtained with a yield of 88%.

General idea■ And instead of heptafluorobutyric acid, 4g of acetic acid (67mmol1
When the reaction was carried out in the same manner as in Example 1 except that 2) was used, heptafluoropropyl-N was obtained.

N'-diacetyl-p-phenylenediamine was obtained with a yield of 80%.

4.4'-di(acetylamino)diphenyl ether 0
．． 28g (ImmoQ), 4g heptafluorobutyric acid
After dissolving in (I9mmoQ), bis(heptafluorobutyryl)peroxide Q, 43 g (Immof
Add 8.5 g of a 1,1.2-trichlorotrifluoroethane solution containing 2), and at 40°C under a nitrogen stream,
The reaction was allowed to proceed for 5 hours. After completion of the reaction, the reaction product was washed with 100 mQ of water, 100 mQ of saturated sodium bicarbonate solution, and 100 mQ of saturated brine, dried over magnesium sulfate, and the reaction product was analyzed by gas chromatography, GC-MS, IR, NMR1.
Analyzed by elemental analysis. As a result, bis(
Heptafluoropropyl)-4,4'-bis(acetylamino)diphenyl ether was obtained with a yield of 35%. The analysis results are shown below.

GC-MS IR (aI+-') "H-NMR Elemental analysis 452 (M"), 410, 368, 2493260 (MaN1 (), 1660 (MaCo), 1345 (MaCF3)
1225 (ICF2) (CDC13) δ=9.60 (I)! , b).

8.69(LH,b), 7.70-7.42(3)1
．． m).

7.20-6.84 (4H, m), 2.12 (611,
s) Theoretical value C: 50.44% H: 3.34% Actual value C: 50.21% H: 3.10c1C-MS IR((!!1-1) 'H-NMR Elemental analysis 620 (M+) , 578,536,4173260 (MaNH), 1670 (MaCo), 1340 (ycF, )1
220 (νCF2) (CDC1z) δ=9.60 (IH, b).

8.70 (LH, b), 7.70-7.42 (2H,
m).

7.20-6.85(4)1. ++), 2.15 (68
, s) Theoretical value c: 42-, sow H: 2.28
% Actual value C: 42.31% H: 2.16 vs. Japan u
1λ The reaction was carried out in the same manner as in Example 4 except that heptafluorobutyric acid was not used. Heptafluoropropyl-4,4
'-Bis(acetylamino)diphenyl ether is 31
% yield of bis(heptafluoropropyl)-4,4
'-Bis(acetylamino)diphenyl ether is 22
% yield.

The reaction was carried out in the same manner as in Example 4 except that trifluoroacetic acid was used instead of heptafluoropropyl-4,4'bis(acetylamino).
Bis(heptafluoropropyl)-4,4'-bis(acetylamino) with 58% yield of diphenyl ether.
Diphenyl ether was obtained with a yield of 33%.

The reaction was carried out in the same manner as in Example 4, except that bis(tridecafluoroheptanoyl) peroxide was used instead of bis(heptafluorobutyryl) peroxide, and analysis was conducted using the same analytical method. tridecafluorohexyl-4,4'-bis(acetylamino)diphenyl ether in 52% yield and bis(tridecafluorohexyl)-4,4'-bis(acetylamino)diphenyl ether in 32% yield. Obtained.

A reaction was carried out in the same manner as in Example 4, except that bis(pentadecafluorooctanoyl) peroxide was used instead of bis(heptafluorobutyryl) peroxide, and analysis was conducted using the same analytical method. Pentadecafluoroheptyl-4゜4'-bis(acetylamino)diphenyl ether in 48% yield, bis(pentadecafluoroheptyl)-4,4'-bis(acetylamino)
Diphenyl ether was obtained with a yield of 30%.

1" Broiled 4.4'-Bis(acetylamino)diphenylsulfone (0.33 g) (Immon) was mixed with heptafluorobutyric acid 4
g (I9mmo Q) and then 0.43 g of bis(heptafluorobutyryl) peroxide (I9mmo Q).
8.5 g of a 1,1.2-trichlorotrifluoroethane solution containing moQ) was added, and the mixture was reacted at 40° C. for 5 hours under a nitrogen stream. After the reaction is completed, the reactant is transferred to 100 mQ
of water, 100 mQ of saturated sodium bicarbonate solution, and 100 mQ of saturated saline solution.

After drying over magnesium sulfate, the reaction product was analyzed by gas chromatography, GC-MS, IR, and NMR1 elemental analysis. As a result, heptafluoropropyl-4゜4'-bis(acetylamino)diphenylsulfone represented by the following structural formula was obtained at a yield of 60%, and bis(heptafluoropropyl)-4,4'-bis(acetylamino)diphenyl Sulfone was obtained with a yield of 30%.

The analysis results are shown below.

GC-MS 500 (M”), 458,416,
297IR(an-1) H-NMR Elemental analysis 3260(yNH), 1660(wco), 1
345 (tcF, ) 1225 (ycFz), 1140
(MaSO□) (CDC1,) δ=9.60 (IH, b)
.

8.70 (LH, b), 7.70-7.40 (7H,
m).

2.12 (6H, s) Theoretical value C: 45.60% H: 3.02% Actual value C: 45.33Z H: 3.15xC-MS Ding R (CM-1) "H-NMR Elemental analysis 668 (M+), 626,584,4653260(t
NH), 1670 (yco), 1340 (tcF3)1
220 (γCF2), 1140 (MaSO,) (CDC1
3) δ, 9.60 (LH, b).

8.70 (IH, b), 7.70-7.40 (6H,
m).

2.15 (6H, s) Theoretical value C: 39.53% H: 2.11% Actual value
C: 39.31% H: 2.22% The reaction was carried out in the same manner as in Example 8 except that heptafluoropropyl-4,4 was not used.
'-bis(acetylamino)diphenylsulfone is 3
With a yield of 5%, bis(heptafluoropropyl)-4,
4'-bis(acetylamino)diphenylsulfone was obtained with a yield of 23%.

3,5,3',5'-tetramethyl- instead of 4,4'-bis(acetylamino)diphenylsulfone
The reaction was carried out in the same manner as in Example 8 except that 4,4'-bis(acetylamino)diphenyl ether was used, and analysis was performed using the same analytical method. As a result, 2-hebutafluoropropyl shown by the following structural formula was obtained. -3,5,3',5
'-Tetramethyl-4,4'-bis(acetylamino)diphenyl ether with a yield of 5o%, 2,2'-bis(heptafluoropropyl)-3,5,3'5'-tetramethyl-4, 4'-bis(acetylamino)diphenyl ether was obtained with a yield of 36%. The analysis results are shown below.

GC-MS IR (as-1) "H-NMR elemental analysis 508 (M"), 389 3260 (yNH), 1660 bco),
1345 (?CF,)1225(νCF2) (CDCI,)δ=9.60(LH,b).

8.69 (IH, b), 7.42 (IH, s).

7.20 (2N, s), 2.33 (6H, s).

2.30(3)1. s), 2.25 (3H, s).

2.12 (6H, s) Theoretical value C: 54.33% H: 4.561 Actual value C: 54.16% H: 4.72% C-MS IR (C!l-1) 676 (I4” ), 557 3260hNH), 1670(tcO), 13
40 (yCF, ) 1220 (maCF, ) 'H-NMR (CDCI3) δ = 9.60 (2H, b)
.

7.42 (2H, s), 2.28 (I2H, s).

2.12 (6H, s).

Elemental analysis Theoretical value C: 46.17% 113.
28 vs. measured value C: 46.05% H: 3.33%
The reaction was carried out in the same manner as in Example 8, except that 2,2-bis(4-acetylaminophenyl)hexafluoropropane was used instead of 4.4'-bis(acetylamino)diphenylsulfone. Analysis using the same analytical method revealed that 2-(4-acetylamino-3-hebutafluoropropylphenyl)-2-(
4-acetylaminophenyl)hexafluoropropane was obtained in a yield of 48%, and 2,2-bis(4-acetylamino-3-hebutafluoropyrlopylphenyl)hexafluoropropane was obtained in a yield of 34%. It was done. The analysis results are shown below.

GC-MS IR (C11-”) “H-NMR Elemental analysis 586 (H+), 467 3260 (yNH), 1660 (?CO),
1345 (tcF3) 1225 (MaCF2) (coct3) δ=9.60 (IH, b).

8.71 (IH, b), 7.70-7.45 (7H, m
).

2.18 (6H, s).

Theoretical value C: 45.07% H: 2.58% actual value
C: 44.90% H: 2.69% C-MS IR (all-') H-NMR Elemental analysis 754 (M"), 635 3260 (yNH), 1670 (yco), 1340 (
yCF, ) 1220 (MaCF2) (CDC1,) δ = 9.60 (2H, b).

7.25-7.45 (6H, m), 2.18 (68, s
).

Theoretical value C: 39.82% H: 1.871 Actual value
C: 39.65% H: 2.01% left 1■LL and 2,2-bis(4-(4-acetylaminophenoxy)phenyl) instead of 4,4'-bis(acetylamino)diphenylsulfone The reaction was carried out in the same manner as in Example 8, except that hexafluoropropane was used, and analysis was conducted using the same analytical method. As a result, 2-(4-(4-acetylamino-3- butafluoropropylphenoxy)phenyl) -2-(4-(4-
acetylaminophenoxy)phenyl)hexafluoropropane in 46% yield, 2,2-bis(4-(4-
Acetylamino-3-hebutafluoropropylphenoxy)phenyl)hexafluoropropane was obtained in a yield of 35%. The analysis results are shown below.

GC-MS IR(aI+-') “H-NMR Shir.

770 (M”), 651 3260 (sNH), 1660 (tco), 1345 (
yCF, ) 1225 (MaCF, ) (CDC1,) δ, 9.60 (IH, b).

Elemental analysis 8.71 (IH2b), 7.20-7.45 (I5H2
m) t2.12 (6H, s).

Theoretical value C: 53.00%) I: 3.01% Actual value C: 52.89% H: 3.15% 938 (M+
), 819 3260 (MaNH), 1670 (MaCo), 1340 (
MaCF, )1220 (MaCF2) (CDC13) δ=9.60 (2H, b).

7.25-7.45 (I4H, m).

2.12 (6H, s).

Claims (1)

[Claims] The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (In the formula, X represents a fluorine atom, a chlorine atom, a hydrogen atom,
n_1 is an integer from 1 to 10) and the following general formula (II) or (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) ▲Mathematical formulas, chemical formulas , tables, etc.▼...(III) (In the formula, R_1 and R_2 represent an acyl group or a fluoroacyl group having 1 to 10 carbon atoms, and R_3 represents an acyl group having 1 to 10 carbon atoms.
~10 alkyl or fluoroalkyl groups. In addition, X_1 represents an oxygen atom, sulfonyl, carbonyl, dimethylmethine, methylene, ethylene, bis(trifluoromethyl)methine, or ▲a mathematical formula, a chemical formula, a table, etc.▼. Here, A is an oxygen atom, sulfonyl, carbonyl, dimethylmethine, methylene, ethylene, bis(trifluoromethyl)
It represents methine, and m represents an integer of 0 to 3. n_2 represents 0 or 1, and n_3 represents an integer from 0 to 3. ) is reacted with an aromatic nitrogen compound represented by the general formula (I
A method for introducing X(CF_2)_n_1- in a di(haloacyl)peroxide represented by the general formula (I) into an aromatic ring in an aromatic nitrogen compound represented by I) or (III), the method comprising: As a solvent when carrying out, the following general formula (IV) R_4COOH...(IV) (wherein R_4 represents an alkyl group having 1 to 8 carbon atoms or a perfluoroalkyl group having 1 to 3 carbon atoms) is used. A method for producing a fluoroalkyl group-containing aromatic nitrogen compound, the method comprising using a carboxylic acid.