JP2001288129A - Perfluoroisopropylbenzene derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound which is useful as an intermediate or a raw material for agrochemicals, medicines, and other various industrial materials such as surfactants. SOLUTION: The perfluoroisopropylbenzene derivative represented by the general formula (1) X1 is H, a halogen, formyl, halogenated a 1 to 6C alkyl, a 1 to 6C alkoxy, a 1 to 6C alkylthio or the like; X2 is H, a halogen, formyl, hydroxy, a 1 to 6C alkyl, a 1 to 6C alkylthio, C(=0)-R1 [R1 is H, a halogen, hydroxy, a 1 to 6C alkyl, NR2R3 (R2 and R3 are each H, a 1 to 6C alkyl or the like)]; X3 is H, a halogen, hydroxy, cyano, isocyanate, isothiocyanato, hydrazino, diazo-C(=0)-R1, SO2-R4 [R4 is a halogen, hydroxy, a 1 to 6C alkyl, NR5R6 (R5 and R6 are each H or a 1 to 6C alkyl)]; X4 is H, a halogen, a 1 to 6C alkyl or a 1 to 6C alkoxy. But known compounds are excluded} or its salt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel perfluoroisopropylbenzene derivative or a salt thereof.

[0002]

2. Description of the Related Art Perfluoroisopropylbenzenes mainly have a perfluoroalkyl group exhibiting physicochemically distinctive properties, so that they are pesticides, pharmaceuticals, dyes, surfactants, wetting agents, dispersants, rubbers. Materials, release agents, water and oil repellents, optical materials, gas separation membrane materials, resist materials, antifouling paints, weather-resistant paints, paper processing agents, fiber treatment agents, functionality with features such as heat resistance and weather resistance It is useful as a synthetic intermediate or raw material such as a resin, an antistatic agent, a photographic toner, a liquid crystal material, and a solvent (for example, “CMC, a leading-edge technology of halogen chemicals”).

Heretofore, there have been few reports on the production of perfluoroisopropylbenzenes. As a method of introducing a perfluoroisopropyl group into a benzene ring, which is conventionally known in the literature, for example, (a). A method of substituting halogens of halogenated benzenes with 2-iodoheptafluoropropane in the presence of metallic copper, for example, (1) Tetrahedron, 2
5 , 5921 (1969), (2) German Published Patent No. 2
No. 606982, (3) Journal of the Chemical Society of Japan, 1876
(1972), (4) J.I. Chem. Soc. Perk
in Trans. 1,661 (1980), (5) B
ull. Chem. Soc. Jpn. , 65 . 2141
(1992). However, these methods have industrial disadvantages such as the need to introduce a halogen atom at an appropriate position of benzenes in advance, the need for excess copper, and the high reaction conditions. It is. Further, depending on the kind of the substituent of the benzene, the yield is low and it is not an effective method.

(B). A method of reacting hexafluoropropene with fluoronitrobenzene in the presence of a fluorine anion; Chem. Soc.
C, 2221 (1968), (2) Journal of Organic Synthesis Chemistry,
27 , 993 (1969), (3) Journal of the Chemical Society of Japan, 1,
98 (1976), (4) Tetrahedron, 5
1 , 13167 (1995). However, in these methods, since the substrate is limited to those strongly activated by an electron-withdrawing group such as perfluoronitrobenzenes and dinitrofluorobenzenes, the substituents, structures, and the like of the compounds that can be produced are limited.

(C). 1-hydroxy-1-trifluoromethyl-2,2,2 which can be produced by reacting an unsubstituted or substituted phenyl Grignard reagent with hexafluoroacetone.
A method of reacting 2-trifluoroethylbenzenes with a suitable fluorinating agent, for example, Canadian Patent 1,022,
No. 573 discloses a method. However, this method is not always economical due to reaction conditions such as using a reagent which is industrially difficult to handle such as hydrofluoric acid or SF ₄ as a fluorinating agent. (D). A method for obtaining perfluoroisopropylphenols by reacting phenols with (heptafluoroisopropyl) phenyltodonium trifluoromethanesulfonate is described in Bull. Chem. Soc. Jp
n. , 57 , 3361 (1984).
However, this method cannot be expected to be industrially practical due to the use of expensive reagents and low selectivity with respect to the resulting perfluoroisopropylated position.

(E). A method for obtaining perfluoroisopropylbenzenes by reacting iodobenzenes with a perfluoroisopropylzinc compound prepared in situ from 2-iodoheptafluoropropane and zinc in the presence of a palladium catalyst is described in Chemistry Letters, 137.
(1982). However, in this method, in addition to using zinc, reaction conditions such as a need to react under ultrasonic waves are not industrially advantageous. As a method for producing perfluoroisopropylbenzenes, a perfluoroisopropyl group is introduced into a target benzene by the above-mentioned method, or a perfluoroisopropylbenzene produced by the above-mentioned method is subjected to a structural conversion to obtain a target compound. Are not practical. As described above, since the conventional production method is not practical, there are few production examples of perfluoroisopropylbenzenes.However, the perfluoroisopropyl group is a substituent that is physically and biochemically characteristic. Thus, the utility of benzenes having a perfluoroisopropyl group introduced in some fields has been described.

Benzoic acids having a perfluoroisopropyl group as a substituent are described, for example, in JP-A-9-3191.
No. 47 describes that phthalic acids having a perfluoroisopropyl group on a benzene ring are useful as a positively chargeable charge control agent and a toner for electrostatic image development.
JP-A-59-69755 describes that benzoic acid amides having some perfluoroisopropyl groups are useful as photographic cyan couplers. or,
As perfluoroisopropylbenzenesulfonic acids, for example, US Pat. No. 3,501,522 describes that some sulfonic acids and salts thereof are useful as wetting agents and dispersants, and that 1-methyl- Starting from 4- (1-trifluoromethyl-1-hydroxy-2,2,2-trifluoroethyl) benzene, 1-methyl-4
-A process for producing 4-heptafluorobenzoic acid via heptafluoroisopropylbenzene is disclosed. However, this manufacturing method is industrially disadvantageous due to the high cost of manufacturing equipment and waste treatment because it is manufactured using highly toxic reagents such as SF ₄ and chromic acid.

[0008]

In the conventional methods, generally, a halogen atom is required in advance at a position where a perfluoroisopropyl group is introduced, or a perfluoroisopropyl group can be introduced, such as phenol and nitrobenzene. Since it was necessary to use benzenes having a certain substituent, the types of substituents of perfluoroisopropylbenzenes produced in the past were few. In addition, there is a problem that none of these methods is effective for mass production. For this reason, although perfluoroisopropyl groups have physical characteristics and are expected to be useful in various fields, perfluoroisopropylbenzenes have not been produced so far.

The present invention provides a novel and useful perfluoroisopropylbenzene derivative or a salt thereof,
A method for easily producing various perfluoroisopropylbenzene derivatives in good yield using perfluoroisopropylanilines which can be easily produced as raw materials according to the method described in Japanese Patent Application No. 11-229304. And to provide various novel perfluoroisopropylbenzene derivatives.

[0010]

The present invention provides a compound of the general formula (I)

Embedded image Ｘwherein X ₁ is a hydrogen atom, a halogen atom, a formyl group,
(C ₁ -C ₆ ) alkyl group, halo (C ₁ -C ₆ ) alkyl group, (C _1-
C ₆ ) alkoxy, (C ₁ -C ₆ ) alkylthio, hydroxy (C ₁ -C ₆ ) alkyl or (C ₁ -C ₆ ) alkylcarbonyloxy (C ₁ -C ₆ ) alkyl; ₂ is a hydrogen atom, a halogen atom, a formyl group, a hydroxy group, a (C ₁ -C ₆ ) alkyl group, a halo (C ₁ -C ₆ ) alkyl group, a (C ₁ -C ₆ ) alkoxy group, a (C ₁ -C 6 ₆ ) alkylthio group, (C ₁ -C ₆ ) alkylsulfinyl group, (C ₁ -C ₆ ) alkylsulfonyl group, hydroxy
(C ₁ -C ₆ ) alkyl group or —C (＝ O) —R ₁ (wherein R
₁ is a hydrogen atom, a halogen atom, a hydroxy group, (C ₁ -C ₆ )
An alkyl group, a (C ₁ -C ₆ ) alkoxy group or NR ₂ R ₃ (wherein R ₂ and R ₃ may be the same or different, a hydrogen atom, a (C ₁ -C ₆ ) alkyl group or a (C ₁ -C ₆ ) represents an alkoxy group. X ₃ represents a hydrogen atom, a halogen atom, a hydroxy group, a cyano group,

Isocyanate group, isothiocyanate group, hydrazino group, diazo group, mercapto group, (C ₁ -C ₆ )
Alkoxy group, (C ₁ -C ₆ ) alkylthio group, —C (＝ O)
—R ₁ (wherein R ₁ is as defined above) or —SO ₂ —R ₄
(Wherein R ₄ is a halogen atom, a hydroxy group, (C ₁ -C ₆ )
And an alkyl group or NR ₅ R ₆ (wherein R ₅ and R ₆ may be the same or different and represent a hydrogen atom or a (C ₁ -C ₆ ) alkyl group). X ₄ represents a hydrogen atom, a halogen atom, a (C ₁ -C ₆ ) alkyl group or a (C ₁ -C ₆ ) alkoxy group. However, (1) when X ₁ , X ₂ and X ₄ represent a hydrogen atom, X ₃
Excludes a hydroxycarbonyl group or a methoxycarbonyl group. (2) When X ₁ and X ₄ represent a hydrogen atom and X ₂ represents a formyl group, the case where X ₃ is a methoxy group is excluded. (3) X _1, of the X ₂ or X _3, if any one is showing a methoxy group and the remainder of X _1, X ₂ or X ₃ and X ₄
Excludes hydrogen atoms.

(4) X_TwoAnd X_ThreeAny one of
Represents a hydroxy group, the remaining X _TwoOr X_Three, X₁
And X_FourExcludes hydrogen atoms. (5) X₁, X_Two, X_ThreeOr X_FourAny one of
When it represents a fluorine atom, the remaining X₁, X_Two, X_ThreeOr X
_FourExcludes hydrogen atoms. (6) X₁, X_TwoAnd X_FourRepresents a hydrogen atom, X_Three
Excludes a chlorine atom, a bromine atom or an iodine atom. (7) X₁, X_Two, X_ThreeOr X_FourAny one of
Is a methyl group, the remaining X₁, X_Two, X_ThreeOr X
_FourExcludes hydrogen atoms. (8) X₁, X_TwoAnd X_FourRepresents a hydrogen atom, X_Three
Excludes an isopropyl group or a chloromethyl group. (9) X₁, X_ThreeAnd X_FourRepresents a hydrogen atom, X_Two
Excludes a trifluoromethyl group. (10) X₁And X_FourRepresents a methyl group, and X_TwoIs a hydrogen source
X to indicate a child_ThreeIs a hydrogen atom or heptafluoroiso
Excludes propyl group. Perfluoroisopro represented by｝
It relates to a pyrbenzene derivative or a salt thereof.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The general formula of the perfluoroisopropylbenzene derivative represented by the general formula (I) in the present invention
In the definition of (I), "i-"
Is iso, "sec-" is secondary, "t-" is tertiary, "alkyl" or "alkyl" indicating an alkyl moiety may be linear or branched, (C ₁ -C ₆ ) alkyl group ”means an alkyl group having 1 to 6 carbon atoms, for example, a methyl group, an ethyl group,
Examples thereof include a propyl group, an i-propyl group, a butyl group, a sec-butyl group, a t-butyl group, a neopentyl group, a 1,2-dimethylpropyl group, a hexyl group, and a heptyl group.

"Halogen atom" means a chlorine atom, bromine atom, iodine atom or fluorine atom, and "halo (C ₁ -C ₆ )
`` Alkyl group '' may be the same or different, and represents a linear or branched alkyl group having 1 to 6 carbon atoms in which one or more hydrogen atoms are substituted with a halogen atom, For example, difluoromethyl group, trifluoromethyl group, chloromethyl group, bromomethyl group, 1-fluoroethyl group, 1-chloroethyl group, 1-bromoethyl group,
2-chloroethyl group, 2-bromoethyl group, 2,2,2
-Trifluoroethyl group, 3-chlorobutyl group, 3-bromobutyl group, 1-chloropentyl group, 1-chlorohexyl group, 6-bromohexyl group and the like.

When it contains an "alkoxy group" or an "alkoxy" moiety, it means a linear or branched alkoxy group, and "(C ₁ -C ₆ ) alkoxy group" means, for example, a methoxy group, an ethoxy group I-propoxy group, sec-butoxy group, t-butoxy group, 1,2-dimethylpropoxy group,
Hexyloxy group and the like. The “halo (C ₁ -C ₆ ) alkoxy group” may be the same or different, and may have 1 to 6 carbon atoms in which one or more hydrogen atoms are substituted with a halogen atom. A branched alkoxy group, for example, difluoromethoxy, trifluoromethoxy, 2-chloroethoxy, 2-bromoethoxy, 2,2,2-trifluoroethoxy, pentafluoroethoxy, 1,1,2; , 2, -tetrafluoroethoxy group, 3-chlorobutoxy group, 3-bromobutoxy group, 1-chloropentyloxy group, 1-chlorohexyloxy group, 6-bromohexyloxy group and the like.

"(C ₁ -C ₆ ) alkylthio group" refers to a linear or branched alkylthio group having 1 to 6 carbon atoms, such as methylthio, ethylthio, i-propylthio, sec-butylthio group, t-butylthio group,
Hexylthio group and the like. The “halo (C ₁ -C ₆ ) alkylthio group” may be the same or different, and may have 1 to 6 carbon atoms in which one or more hydrogen atoms are substituted with a halogen atom. A branched alkylthio group, for example, a difluoromethylthio group, a trifluoromethylthio group, a 2,2,2-trifluoroethylthio group, a 1,1,2,2-tetrafluoroethylthio group,
-Chloroethylthio group, 3-bromoethylthio group and the like. "Hydroxy (C ₁ -C ₆ ) alkyl group" may be the same or different, and may have 1 to 6 carbon atoms in which one or more of its hydrogen atoms is substituted with a hydroxy group. It represents a branched alkyl group, for example, a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group and the like.

Hereinafter, typical production methods of the perfluoroisopropylbenzene derivative represented by the general formula (I) of the present invention will be exemplified, but the present invention is not limited thereto. [Manufacturing method 1]

Embedded image (Wherein, Y _1, Y ₂ and Y ₃ may be the same or different, a hydrogen atom, a hydroxyl group, a chlorine atom, a bromine atom, a fluorine atom, (C ₁ -C ₆₎ alkyl group, (C ₁ -C ₆ ) represents an alkoxy group or a hydroxy (C ₁ -C ₆ ) alkyl group, and W represents an oxygen atom or a sulfur atom.

An aniline represented by the general formula (II) is combined with phosgene, TCF (trichlorochloroformate) and the like in the presence or absence of an inert solvent to form a catalyst such as DMAP (4-dimethylaminopyridine). By reacting in the presence or absence, a perfluoroisopropylbenzene derivative represented by the general formula (Ia) can be produced.
In the perfluoroisopropylbenzene derivative represented by the general formula (Ia), a compound in which W represents an oxygen atom is described, for example, in J. Am. Am. Chem. Soc. , (1937) 7
9, p. 1236, Org. Synth. II, (194
3) p. 453; Org. Chem. , (196
6) 31, p. 596, Angew. Chem. In
t. Ed. Engl (1987), 26 (9), p. 8
94, Angew. Chem. Int. Ed. Engl
(1995), 34 (22), p. The compound can be produced according to the method described in No. 2497.

Compounds in which W represents a sulfur atom are described, for example, in J. Am. Chem. Soc. (1942) p. 374,
J. Am. Chem. Soc. (1946) 68, p.
2506, Liebigs Ann. Chem. (19
62) 657, 98, Bull. Cem. Soc. Jp
n. (1975) 48, p. It can be produced according to the method described in No. 2981. General formula (II) as starting material
Can be produced according to the method described in Japanese Patent Application No. 11-338707.

[Production method 2]

Embedded image (In the formula, Y ₁ , Y ₂ and Y ₃ are the same as above, and Y ₄ represents a hydrogen atom, a halogen atom, a hydroxy group, a sulfonyl halide group, a hydrazino group or a salt thereof.) Aniline is reacted with sodium nitrite or the like using an acidic solvent to react a diazonium salt of aniline and a metal halide in the presence or absence of a metal catalyst such as copper. , General formula
The perfluoroisopropylbenzene derivative represented by (Ib) can be produced.

According to the present production method, among the perfluoroisopropylbenzene derivatives represented by the general formula (Ib), compounds in which Y ₄ represents a hydrogen atom are described, for example, in J. Am. Chem. So
c. , P. 2095 (1949): Org. Reac
t. , 2, p. 262 (1944), Org. Synt
h. , (1955) III, 295; Am. Che
m. , 83 , p. 1251 (1961), etc., when Y ₄ is a fluorine atom, see, for example, Org. Reac
t. , 5 , p. 193 (1949); Org. Ch
em. , 36 , p. 63 (1971), when Y ₄ is a chlorine atom, see, for example, Org, Synth. ,
I, p. 170, (1941); Chem. So
c. , P. 819 (1945), for the case where Y ₄ is a bromine atom, see, for example, Org. Synth. III,
p. 185 (1955); Org. Chem. , 2
3 , p. 1139 (1958) and those in which Y ₄ is an iodine atom are described, for example, in J. Am. Org. Chem.
3 , p. 55 (1938); Am. Chem. So
c. 70 , p. 157 (1948); Am. Che
m. Soc. 92 , p. 2175 (1970); A
m. Chem. Soc. 93 , p. 4845 (197
It can be produced by the method described in 1) and the like.

Also, Y_FourIs a compound showing a hydroxy group,
For example, Org. Synth. , I, p. 404 (194
1), Org. Synth. , III, p. 130 (19
55), Can. J. Chem. , 41, p. 1653
(1963); Org. Chem. ,32, P. 3
844 (1967), Y_FourIs a sulfonyl halide group
The compounds shown are described, for example, in J. Am. Prakt. Che
m. [2]152, P. 251 (1939), Rec
l. Trav. Chim. Pays-Bas. ,84,
p. 22 (1965), Y_FourIs a hydrazino group or
For compounds showing salts, see, for example, Org. Synt
h. , I, p. 442 (1941)
Thus, each compound can be produced. Again
Perfluoroisopropylbenzene represented by the general formula (I-b)
Derivative, Y _FourIs a compound showing an aldehyde group,
Y obtained by the manufacturing method_FourIs a compound showing a hydroxy group
And can be produced by oxidation.

[Manufacturing method 3]

Embedded image (In the formula, Y ₁ , Y ₂ and Y ₃ are as defined above, Y ₅ represents a chlorine atom, an iodine atom or a bromine atom, and R represents a hydrogen atom or a (C ₁ -C ₁₂ ) alkyl group.) A halogenated benzene represented by the general formula (III) as a base,
Triphenylphosphine, an organic phosphorus compound such as bisdiphenylphosphinobutane, palladium, nickel, a transition metal such as cobalt or a complex thereof and reacted with carbon monoxide in the presence of an inert solvent to obtain a compound of the general formula (Ic)
Can be produced. This manufacturing method is, for example,
l. Chem. Soc. Jpn. , 48 , p. 2075
(1975); Am. Chem. Soc. 111 ,
p. 8742 (1989).

From the perfluoroisopropylbenzene derivative represented by the general formula (Ic), the following method is used.
(Id), general formula (Ie), general formula (If) and general formula (Ig)
Can be produced.

Embedded image (Wherein Y ₁ , Y ₂ , Y ₃ and R are the same as above,
al represents a halogen atom. This reaction can be carried out by a conventional method.

[0025]

The present invention will be described in more detail with reference to the following Examples, which by no means limit the present invention. 1. Production of halobenzenes. Example 1.1 Preparation of 1-chloro-4-heptafluoroisopropylbenzene.

Embedded image Concentrated hydrochloric acid (30 ml) was diluted with water (10 ml).
-Heptafluoroisopropylaniline (10 g, 3
8.3 mmol) to give a suspension. Then, sodium nitrite (2.9) was added such that the reaction temperature was 10 ° C. or less.
g, 42 mmol) aqueous solution (10 ml) was added slowly. After the addition was completed, the mixture was further stirred for 20 minutes. The diazonium salt solution was prepared separately from copper (I) chloride (5.7 g, 57
(Mmol) hydrochloric acid (25 ml) solution at room temperature. Then, the mixture was stirred at room temperature for 30 minutes, heated for 1 hour, cooled to room temperature, and hexane was added to separate an organic layer.
The organic layer once with water, twice with aqueous sodium thiosulfate,
The extract was washed once with a saturated saline solution, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a crude product of the desired product (8.6 g, crude yield: 80%). Physical properties: ¹ H-NMR δ (CDCl ₃ ); 7.49 (d.2H), 8.07 (d.2H).

Example 2.1 1-Bromo-2-fluoro-4
-Production of heptafluoroisopropylbenzene.

Embedded image 2-Fluoro-4-heptafluoroisopropylaniline (15.7 g, 56 mmol) was added to a 47% aqueous solution of hydrogen bromide (50 ml) diluted with water (15 ml). Then, an aqueous solution (20 ml) of sodium nitrite (4.1 g, 59 mmol) was gradually added so that the reaction temperature became 10 ° C. or lower. After the addition was completed, the mixture was further stirred for 20 minutes. The diazonium salt solution was separately prepared with copper (I) bromide (4.0 g,
26 mmol) in a 47% aqueous solution of hydrogen bromide (40 ml) at 65 ° C. in one portion, and stirred at 60-80 ° C. for 2 hours, cooled to room temperature, and added with hexane to separate an organic layer. The layer was washed once with water, twice with an aqueous solution of sodium thiosulfate, and once with a saturated saline solution. After drying over anhydrous sodium sulfate, the mixture was concentrated under reduced pressure to obtain the desired crude product (15 g, crude yield 78%). Physical properties: ¹ H-NMR δ (CDCl ₃ ); 7.294 (d.1H), 7.39 (d.1H),
7.72 (t.1H). ND 1.4318 (21.3 ° C.)

Example 3 Preparation of 1-bromo-3-heptafluoroisopropylbenzene

Embedded image Hydrochloric acid water (60 ml) was diluted with water (20 ml).
2-Bromo-4-heptafluoroisopropylaniline (20 g, 59 mmol) was added to form a suspension. Then, sodium nitrite (4.
(3 g, 62 mmol) aqueous solution (15 ml) was slowly added dropwise. After the addition, the mixture was further stirred for 30 minutes. Diphosphorous acid (35 ml) was added to the diazonium salt solution at 5 to 10 ° C,
The solution was dropped over several hours over one hour. After completion of the dropwise addition, the mixture was further stirred at room temperature for 3 hours, hexane was added to separate the organic layer, and the organic layer was washed once with water and once with a saturated saline solution.
After drying over anhydrous sodium sulfate, the residue obtained by concentration under reduced pressure was purified by column chromatography to obtain the desired product (17.2 g, crude yield 90%). Physical properties: ¹ H-NMR δ (CDCl ₃ ); 7.39 (t.1H), 7.554 (d.1H),
7.69 (m.1H), 7.76 (s.1H).

Example 4. Preparation of 4-heptafluoroisopropyl-iodobenzene.

Embedded image Under an ice bath, concentrated sulfuric acid (7.5 g, 76.6 mmol) was diluted with water (30 ml), and 4-heptafluoroisopropylaniline (10 g, 38.3 mmol) was added. Then, an aqueous solution of sodium nitrite (2.9 g, 42 mmol) (20 ml) was gradually added so that the reaction temperature was 0 ° C. or lower, and the mixture was further stirred for 20 minutes, and then concentrated sulfuric acid (3.8 g).
Was added. An aqueous solution of potassium iodide (9.5 g, 57.5 mmol) prepared separately from the diazonium salt solution (20 g)
ml) at room temperature. Then, after heating under reflux for 1 hour, cooling to room temperature, adding hexane and separating an organic layer, washing the organic layer once with water, twice with an aqueous solution of sodium thiosulfate and once with a saturated saline solution, After drying over anhydrous sodium sulfate, the mixture was concentrated under reduced pressure to obtain the desired crude product (13 g, crude yield 87%).

In the same manner, the following perfluoroisopropylbenzene derivative was obtained. 1-chloro-3-fluoro-4-heptafluoroisopropylbenzene Physical properties: ¹ H-NMR δ (CDCl ₃ ); 7.23-7.33 (m.2H), 7.56 (t.1H). ¹⁹ F-NMR δ (CDCl ₃ ) -75.82 (6F), -106.73 (1F), -178.6 (1F). 1-Chloro-2,6-dimethyl-4-heptafluoroisopropylbenzene Physical properties: ¹ H-NMR δ (CDCl ₃ ); 2.44 (s. 6H), 7.305 (s.2H). 1-chloro-4-heptafluoroisopropyl-2-methylbenzene Physical properties: ¹ H-NMR δ (CDCl ₃ ); 2.45 (s.3H), 7.38 (d.1H), 7.46 (m.2H). 1-chloro-4-heptafluoroisopropyl-2-methoxybenzene Physical properties: ¹ H-NMR δ (CDCl ₃ ); 3.95 (s.3H), 7.12 (s.1H), 7.14 (d .1H), 7.50 (d, 1H).

1-bromo-4-heptafluoroisopropyl-2-methylbenzene Physical properties: ¹ H-NMR δ (CDCl ₃ ); 2.48 (s.3H), 7.27 (d.1H), 7.45 (s.1H), 7.66 (d, 1H). 1-bromo-4-heptafluoroisopropyl-3-methylbenzene Physical properties: ¹ H-NMR δ (CDCl ₃ ); 2.50 (d.3H), 7.34 (d.1H), 7.42 (d .1H), 7.46 (s, 1H). 1-bromo-2,6-dimethyl-4-heptafluoroisopropylbenzene Physical properties: ¹ H-NMR δ (CDCl ₃ ); 2.48 (s.6H), 7.29 (s.2H) 1-bromo-4-heptafluoroisopropyl-2-methoxybenzene Physical properties: ¹ H-NMR δ (CDCl ₃ ); 3.944 (s.3H), 7.08 (brs.2H), 7.67 (d.1H). -Bromo-3-fluoro-4-heptafluoroisopropylbenzene Physical properties: ¹ H-NMR δ (CDCl ₃ ); 7.39-7.52 (m.3H). ¹⁹ F-NMR δ (CDCl ₃ ); -75.77 (6F),- 106.64 (1F), -178.61 (1F).

1-bromo-4-heptafluoroisopropyl-2-methylthiobenzene Physical properties: ¹ H-NMR δ (CDCl ₃ ); 2.51 (s.3H), 7.21 (m.1H), 7.285 (s.1H), 7.645 (d.1H). 1-bromo-2,6-dichloro-4-heptafluoroisopropylbenzene Physical properties: ¹ H-NMR δ (CDCl ₃ ); 7.604 (s, 2H). ¹⁹ F-NMR δ (CDCl ₃ ) -75.98 (6F), -182.61 (1F). 1-iodo-4-heptafluoroisopropyl-3-methylbenzene Physical properties: ¹ H-NMR δ (CDCl ₃ ); 2.47 (d.3H), 7.18 (d. 1H), 7.62 (d.1H), 7.68 (s.1). ND 1.4142 (24.2 ° C.) 1-iodo-4-heptafluoroisopropyl-2-methylbenzene Physical properties: ¹ H-NMR δ (CDCl ₃ ); 2.504 (s.3H), 7.10 (d.1H), 7.44 (s.1H), 7.94 (d, 1H).

1-Iodo 2,6-dimethyl-4-heptafluoroisopropylbenzene Physical properties: ¹ H-NMR δ (CDCl ₃ ); 2.54 (s.6H), 7.26 (s.2H). ¹⁹ F-NMR δ ( _{CDCl 3); -76.15 (d,} 7F), -183.28 (m, 1F) 1- iodo-4-heptafluoro-isopropyl-2-methylbenzene physical ^{properties:. 1 H-NMR δ (} CDCl 3); 2.51 (s. 3H), 7.10 (d.1H), 7.444 (s.1H), 7.94 (d.1H). 1-iodo-4-heptafluoroisopropyl-2-methylthiobenzene Physical property: ¹ H-NMR δ (CDCl ₃ ); 2.50 (s.3H), 7.06 (d.1H), 7.235 (s.1H), 7.91 (d.1H) 1-iodo-4-heptafluoroisopropyl-2-methoxybenzene Physical properties: ¹ H-NMR δ (CDCl ₃ ); 3.93 (s.3H), 6.94 (d.1H), 6.98 (s.1H), 7.90 (d.1H).

2. Production of alkylbenzenes Example 5. Production of 1-methyl-2-heptafluoroisopropylbenzene.

Embedded image In an ice bath, concentrated hydrochloric acid (90 ml) was diluted with water (30 ml), and 4-heptafluoroisopropyl-3-methylaniline (30 g, 109 mmol) was added to glacial acetic acid (30 ml).
l) The solution was added. Then, an aqueous solution (15 ml) of sodium nitrite (8 g, 115 mmol) was gradually added so that the reaction temperature was 5 ° C. or lower. After adding, 1 more
The mixture was stirred for a while, and diphosphorous acid (50 ml) was added thereto, and the temperature was gradually raised, followed by stirring at room temperature for 15 hours. Then, hexane is added to separate the organic layer, and the organic layer is washed twice with water, once with a saturated aqueous solution of sodium hydrogencarbonate, once with a saturated saline solution, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. As a result, an intended crude product (19 g) was obtained.

By the same reaction, the following compounds were produced. 1-Methyl-3-heptafluoroisopropylbenzene Physical properties: ¹ H-NMR δ (CDCl ₃ ); 2.42 (s.3H), 7.35-7.41 (m.4H). 1,2-Dimethyl-3-heptafluoroisopropylbenzene _{^{1 H-NMR δ (CDCl 3}} );. 2.35 (s.3H), 2.40 (d.3H), 7.13-7.19 (m.1H), 7.29-7.63 (m.2H) 1- ethyl-3 over heptafluoroisopropyl Benzene properties: ¹ H-NMR δ (CDCl ₃ ); 1.27 (t.3H), 2.73 (dd.2H), 7.37-7.48 (m.4H). ¹⁹ F-NMR δ (CDCl ₃ ); -76.23 (d .7F), -183.08 (m.1F). 1-chloromethyl-2-heptafluoroisopropylbenzene Physical properties: ¹ H-NMR δ (CDCl ₃ ); 4.79 (d.2H), 7.44 (m.1H), 7.52-7.63 (m.3H). 1-methyl-2-heptafluoroisopropyl-5-methylthiobenzene Physical properties: ¹ H-NMR δ (CDCl ₃ ); 2.49 (d.3H), 2.495 (s.3H), 7.09 (s.1H) ), 7.11 (d.1H), 7.37 (d.1H).

2-Heptafluoroisopropylbenzyl alcohol Physical properties: ¹ H-NMR δ (CDCl ₃ ); 4.925 (d.2H), 7.41 (d.1H), 7.51-7.59 (m.2H), 7.81 (d.1H) 1-Methyl-2-heptafluoroisopropyl-5-methoxybenzene Physical properties: ¹ H-NMR δ (CDCl ₃ ); 2.49 (d.3H), 3.824 (s.3H), 6.78 (s.1H), 6.79 () d.1H), 7.40 (d.1H). nD 1.4114 (24.2 ° C.) 2′-heptafluoroisopropylbenzyl acetate Physical properties: ¹ H-NMR δ (CDCl ₃ ); 2.125 (s.3H), 5.32 (d.2H), 7.44 (m.1H), 7.51-7.59 (m.3H). 1-bromomethyl-2-heptafluoroisopropylbenzene Physical properties: ¹ H-NMR δ (CDCl ₃ ); 4.68 (d.2H), 7.40-7.45 (m.1H), 7.50-7.58 (m.3H).

3. Manufacture of benzoic acids. Example 7. Methyl 4-heptafluoroisopropyl-
Production of 3-methylbenzoate.

Embedded image In an autoclave, 1-iodo-4-heptafluoroisopropyl-3-methylbenzene (1.0 g, 2.6 mmol), palladium chloride (10 ml, 2 mol%), triphenylphosphine (54 g, 8 mol%) and triethylamine (0.52 g, 5.2 mmol) were suspended in methanol (10 ml). Next, the inside of the autoclave was replaced with carbon monoxide, and the pressure in the vessel was adjusted to about 14 atm. This was heated to about 120 ° C. and stirred for 8 hours. Then, after cooling to room temperature, insolubles were removed by filtration, and the filtrate was concentrated.
Purification by silica gel column chromatography (hexane: ethyl acetate = 9: 1) gave the desired product (0.7%).
7 g, 94% yield).

Embodiment 8 FIG. Preparation of ethyl 2-fluoro-4-heptafluoroisopropylbenzoate.

Embedded image In an autoclave, 1-bromo-2-fluoro-4-heptafluoroisopropylbenzene (10.0 g, 29 g
Mmol), dichlorobis (triphenylphosphine)
Palladium (1.0 g, 5 mol%) and triethylamine (3.5 g, 35 mmol) were added to ethanol (60 m
l). Next, the inside of the autoclave was replaced with carbon monoxide, and the pressure in the vessel was adjusted to about 14 atm. This was heated to about 120 ° C. and stirred for 8 hours. Then, after cooling to room temperature, insolubles were removed by filtration, and the filtrate was concentrated and concentrated on silica gel column chromatography (hexane: ethyl acetate = 9: 9).
The desired product (7.4 g, yield 75) was obtained by purification in 1).
%).

Embodiment 9 FIG. Preparation of methyl 4-heptafluoroisopropylbenzoate.

Embedded image 1-bromo-4-heptafluoroisopropylbenzene (11.8 g, 31.7 mmol) in an autoclave
And dichlorobis (triphenylphosphine) palladium (1.1 g, 5 mol%) and potassium carbonate (3.2 g,
31.7 mmol) were suspended in methanol (50 ml). Next, the inside of the autoclave was replaced with carbon monoxide, and the pressure in the vessel was adjusted to about 14 atm. This was heated to about 110 ° C. and stirred for 6 hours. Then, after cooling to room temperature, insolubles were separated by filtration, and the filtrate was concentrated and purified by silica gel column chromatography (hexane: ethyl acetate = 9: 1) to obtain the desired product (7.4 g, yield 75%). Obtained.

The following compounds were prepared in the same manner. Methyl 2,6-dimethyl-4-heptafluoroisopropylbenzoate Physical properties: ¹ H-NMR δ (CDCl ₃ ); 2.37 (s.6H), 3.94 (s.3H), 7.27 (s.2H). Methyl 4-hepta Fluoroisopropyl-2-methoxybenzoate Physical properties: ¹ H-NMR δ (CDCl ₃ ); 3.92 (s.3H), 3.95 (s.3H), 7.19 (s.1H), 7.21 (d.1H), 7.87 (d .1H). Methyl 4-heptafluoroisopropyl-2-methylbenzoate Physical properties: m.p. p. 39-40 ° C Ethyl 2,6-dimethyl-4-heptafluoroisopropylbenzoate Physical properties: ¹ H-NMR δ (CDCl ₃ ); 1.41 (t.3H), 2.38 (s.6H), 4.43 (dd.2H), 7.33 (s.2H).

Methyl 3-fluoro-4-heptafluoroisopropylbenzoate Physical properties: ¹ H-NMR δ (CDCl ₃ ); 3.965 (s.3H), 7.72 (t.1H), 7.86 (m.1H), 7.96 (m .1H). Methyl 4-heptafluoroisopropyl-3-methylbenzoate Physical Properties: ¹ H-NMR δ (CDCl ₃ ); 2.59 (d.3H), 3.94 (s.3H), 7.56 (d.1H), 7.914 ( d.1H), 7.955 (s.1H). Methyl 4-heptafluoroisopropyl-2-methylsulfonylbenzoate Physical Properties: ¹ H-NMR δ (CDCl ₃ ); 3.38 (s.3H), 4.014 (s.3H), 7.86 (d.1H), 7.945 (d.1H), 8.38 (s.1H). ND 1.4450 (27.2 ° C.)

Comparison with Prior Art of Benzoic Acids US Pat. No. 3,462,482 discloses benzoic anilides having some heptafluoroisopropyl groups, for example, 4- (heptafluoroisopropyl) benz-4-.
Chloroanilide is described as being useful as a herbicide, insecticide and acaricide. A method for producing 4-heptafluoroisopropyl benzoic acid as the starting material is also disclosed, which discloses the production of 1-methyl-4- (1-trifluoromethyl-1-hydroxy-2,2,2-trifluoroethyl) benzene. As a raw material, 4-heptafluorobenzoic acid is obtained via 1-methyl-4-heptafluoroisopropylbenzene, but is produced using a highly toxic compound such as SF ₄ or chromic acid, and is a practical production method. It can not be said.

According to the method of the present invention, 4-cytafluoroisopropylaniline is used as a raw material to prepare 1-cyano-
4-heptafluoroisopropylbenzene or 1-halo-4-heptafluoroisopropylbenzene ("halo")
Represents a chlorine, bromine or iodine atom)
4-Heptafluoroisopropylbenzoic acid can be produced and is more practical.

Example 10. Preparation of 4-heptafluoroisopropylbenzoic acid.

Embedded image In an ice bath, methyl 4-heptafluoroisopropylbenzoate (0.5 g, 1.5 mmol) in ethanol (4
ml) solution, a solution of sodium hydroxide (0.1 g, 2.5 mmol) dissolved in water (4 ml) was added dropwise. About 2
After stirring for an hour, hexane and water were added, and the aqueous layer was separated. The aqueous layer was acidified by adding 3N-hydrochloric acid, and then ethyl acetate was added to separate the organic layer. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain the desired product (9.0 g, yield 93%).

Example 11 Preparation of 4-heptafluoroisopropyl-3-methylbenzoic acid

Embedded image Methyl 4-heptafluoroisopropyl-3 in an ice bath
-A solution of sodium hydroxide (0.1 g, 2.5 mmol) in water (4 ml) was added dropwise to a solution of methyl benzoate (0.4 g, 1.3 mmol) in methanol (4 ml). After stirring for about 2 hours, hexane and water were added, and the aqueous layer was separated. The aqueous layer was acidified by adding 3N-hydrochloric acid, and then ethyl acetate was added to separate the organic layer.
The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain the desired product (0.32 g, yield: 84%).

Example 12. Preparation of 2-fluoro-4-heptafluoroisopropylbenzoic acid.

Embedded image Ethyl 2-fluoro-4-heptafluoroisopropylbenzoate (0.5 g, 1.5 mmol) in an ice bath
Was dissolved in ethanol (4 ml), and a solution of sodium hydroxide (0.1 g, 2.5 mmol) dissolved in water (4 ml) was added dropwise. After stirring for about 2 hours, hexane and water were added, and the aqueous layer was separated. The aqueous layer was acidified by adding 3N-hydrochloric acid, and then ethyl acetate was added to separate the organic layer. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain the desired product (0.38 g, yield 83%).

Similarly, the following compound was prepared: 2-fluoro-4-heptafluoroisopropylbenzoic acid Physical properties: ¹ H-NMR δ (CDCl ₃ ); 7.484 (d.1H), 7.52 (d.1H), 8.18 (t.1H), 10.55 (brs.1H). 4-Heptafluoroisopropyl-2-methoxybenzoic acid Physical properties: ¹ H-NMR δ (CDCl ₃ ); 4.124 (s.3H), 7.28 (s.1H) ), 7.37 (m.1H), 8.27 (d.1H). p. 96-97 ° C

4-Heptafluoroisopropyl-2-methylbenzoic acid Physical properties: ¹ H-NMR δ (CDCl ₃ ); 2.72 (s.3H), 7.53 (s.1H), 7.54 (d.1H), 8.18 ( d.1H). m. p. 108-109 ° C 2,6-Dimethyl-4-heptafluoroisopropylbenzoic acid Physical properties: ¹ H-NMR δ (CDCl ₃ ); 2.505 (s.6H), 7.34 (s.2H). p. 80-81 ° C. 3-Fluoro-4-heptafluoroisopropylbenzoic acid Physical properties: ¹ H-NMR δ (CDCl ₃ ); 7.784 (t.1H), 7.94 (d.1H), 8.05 (m.1H), 11.40 (brs.1H). ¹⁹ F-NMR δ (CDCl ₃ ); -75.49 (6F), -107.54 (1F), -178.29 (1F). p. 54-58 ° C

4-Heptafluoroisopropyl-3-methylbenzoic acid Physical properties: ¹ H-NMR δ (CDCl ₃ ); 2.62 (d.3H), 7.62 (d.1H), 8.00 (d.1H), 8.03 ( s.1H). m. p. 129-130 ° C 4-heptafluoroisopropyl-2-methylsulfonylbenzoic acid Physical properties: ¹ H-NMR δ (CDCl ₃ ); 3.45 (s.3H), 7.99 (m.2H), 8.41 (s.1H), 9.42 (brs. 1H). Production of benzoic acid halides.

Example 13 Preparation of 4-heptafluoroisopropyl-3-methylbenzoyl chloride

Embedded image 4-Heptafluoroisopropyl-3-methylbenzoic acid (0.32 g, 1.0 mmol) was converted to thionyl chloride (3 m
1), added with a drop of dimethylformamide (DMF) and heated under reflux for 3 hours. After completion of the reaction, the mixture was cooled to room temperature, and thionyl chloride was distilled off under reduced pressure to obtain a crude product of the intended product.

The following compounds were prepared in the same manner. 3-heptafluoroisopropyl benzoyl chloride ^{properties:. 1 H-NMR δ (} CDCl 3); 7.71 (s.1H), 7.94 (d.1H), 8.33 (d.1H), 8.37 (s.1H) 19 F- NMR δ (CDCl ₃ ); -76.04 (6F), -182.83 (1F), 4-heptafluoroisopropyl-2-methylbenzoyl chloride Physical properties: ¹ H-NMR δ (CDCl ₃ ); 2.65 (s.3H), 7.555 (s.1H), 7.615 (d.1H), 8.31 (d.1H). 4-Heptafluoroisopropyl-2-methoxybenzoyl chloride Physical properties: ¹ H-NMR δ (CDCl ₃ ); 3.984 (s.3H), 7.22 (s.1H), 7.30 (d.1H), 8.15 (d.1H). 4-Heptafluoroisopropyl-2-methylthiobenzoyl chloride Physical properties: ¹ H-NMR δ (CDCl ₃ ); 3.34 (s.3H) , 8.04 (d.1H), 8.40 (d.1H), 4-heptafluoroisopropyl-2-methylsulfonylbenzoyl chloride Physical properties: ¹ H-NMR δ (CDCl ₃ ); 3.34 (s.3H), 8.04 (s. 2H), 8.40 (s.1H). 4-Heptafluoroisopropyl-3-methylbenzoyl chloride _{^{1 H-NMR δ (CDCl 3}} ); 2.64 (d.3H), 7.66 (d.1H), 8.00-8.05 (m.2H).

5. Production of benzoic acid amides. Example 14. Preparation of 4-heptafluoroisopropyl-3-methylbenzoic acid amide.

Embedded image Aqueous ammonia (5 ml) was added to a crude product of 4-heptafluoroisopropyl-3-methylbenzoyl chloride (0.4 g) in an ice bath, and the mixture was stirred for about 30 minutes. Ethyl acetate was added to separate the organic layer, and the organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain the desired product (0.3 g, crude yield: 98%).

The following compounds were prepared in the same manner. 4-Heptafluoroisopropyl-2-methylbenzamide Physical properties: ¹ H-NMR δ (CDCl ₃ ); 4.03 (s.3H), 7.20 (s.1H), 7.32 (d.1H), 8.32 (d, 1H). m. p. 104-105 ° C 3-Fluoro-4-heptafluoroisopropylbenzamide Physical properties: ¹ H-NMR δ (CDCl ₃ ); 6.47 (brs.2H), 7.66-7.71 (m.3H). ¹⁹ F-NMR δ (CDCl ₃ ); -75.64 (6F), -107.53 (1F), -178.44 (1F). M. p. 85-86 ° C 4-heptafluoroisopropyl-3-methylbenzamide Physical properties: ¹ H-NMR δ (DMSO-d ₆ ); 2.53 (d.3H), 7.59 (d.1H), 7.86 (d.1H), 7.90 (s.1H). m. p. 66-68 ° C

6. Production of cyanobenzenes. Example 15. Preparation of 1-cyano-4-heptafluoroisopropyl-3-methylbenzene.

Embedded image 4-heptafluoroisopropyl-3-methylbenzamide (0.3 g, 1 mmol) was converted to thionyl chloride (4 m
1) and heated under reflux for 1 hour. After cooling to room temperature,
Thionyl chloride was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (hexane: ethyl acetate = 9: 1) to give the desired product (0.22 g, yield 78%).
I got

The following compounds were prepared in the same manner. 1-cyano-4-heptafluoroisopropyl-2-methylbenzene Physical properties: ¹ H-NMR δ (CDCl ₃ ); 2.41 (s.3H), 7.33-7.41 (m.3H). 1-cyano-4-heptafluoro Isopropyl-2-methoxybenzene 1-cyano 3-fluoro-4-heptafluoroisopropylbenzene Physical properties: ¹ H-NMR δ (CDCl ₃ ); 7.55 (d.1H), 7.63 (d.1H), 7.79 (t.1H) 1-cyano-4-heptafluoroisopropyl-3-methylbenzene Physical properties: ¹ H-NMR δ (CDCl ₃ ); 2.59 (d.3H), 7.60 (brs.3H).

7. Production of phenols. Example 16. Production of 4-heptafluoroisopropyl-3-methylphenol.

Embedded image 4-Heptafluoroisopropyl-3-methylaniline (5 g, 18 mmol) was added to glacial acetic acid (25 ml) in an ice bath.
And concentrated sulfuric acid (3.6 g) was added. Then, sodium nitrite (1.4 g,
20 mmol) in water (3 ml) was added slowly. After the addition was completed, the mixture was further stirred for 30 minutes, and then added with water (3 ml), heated to about 80 ° C., and stirred for 5 hours.
After completion of the reaction, the reaction mixture was cooled to room temperature, hexane was added to separate the organic layer, and the organic layer was washed twice with water, once with a saturated aqueous solution of sodium hydrogen carbonate, once with a saturated saline solution, and dried over anhydrous sodium sulfate. Thereafter, the mixture was concentrated under reduced pressure, and purified by silica gel column chromatography (hexane: ethyl acetate = 3: 1) to obtain the desired product (4.0 g, yield 81%).

Similarly, the following compound was produced: 4-Heptafluoroisopropyl-2-methylphenol Physical properties: ¹ H-NMR δ (CDCl ₃ ); 3.26 (s.3H), 5.80 (brs. 1H), 6.84 ( d.1H), 7.30 (d.1H), 7.33 (s.1H). 4-Heptafluoroisopropyl-2-methoxyphenol Physical Properties: ¹ H-NMR δ (CDCl ₃ ); 3.88 (s.3H), 6.74 ( d.1H), 6.94 (s.1H), 6.96 (d.1H), 4-heptafluoroisopropyl-3-methylphenol Physical properties: ¹ H-NMR δ (CDCl ₃ ); 2.46 (s.1H), 5.19 ( s.1H), 6.74 (brs.2H), 7.44 (d, 1H). nD 1.4242 (24.1 ° C.) 2,6-dimethoxy-4-heptafluoroisopropylphenol Physical properties: ¹ H-NMR δ (CDCl ₃ ); 3.89 (s.3H), 3.94 (s.6H), 5.82 (s.1H), 6.785 (s, 2H). 2,6-dimethyl-4-heptafluoroisopropylphenol Physical properties: ¹ H-NMR δ _{(CDCl 3); 2.26 (s.6H} ), 5.3 (brs.1H), 7.19 (s.2H).

8. Production of benzenesulfonyl halides. Example 17. Preparation of 4-heptafluoroisopropyl-3-methylbenzenesulfonyl chloride.

Embedded image 4-Heptafluoroisopropyl-3-methylaniline (5 g, 18.2 mmol) was added to glacial acetic acid (5 m
1) and concentrated hydrochloric acid (15 ml) was further added. Then, a solution of sodium nitrite (1.4 g, 20 mmol) dissolved in water (3 ml) was gradually added so that the reaction temperature was 0 ° C. or lower. After the addition was completed, the mixture was further stirred for 20 minutes. The diazonium salt solution was separately prepared with sodium bisulfite (5.3 g, 51 mmol), copper chloride (0.35 g, 3.5 mmol), glacial acetic acid (34 ml)
And concentrated hydrochloric acid (7 ml) at room temperature. After stirring at room temperature for 2.5 hours, hexane was added to separate the organic layer, and the organic layer was dried over anhydrous sodium sulfate.
By concentrating under reduced pressure, the target compound (4.4 g, yield 6)
7%).

The following compounds were prepared in the same manner. 4-Heptafluoroisopropyl-2-methylbenzenesulfonyl chloride Physical properties: ¹ H-NMR δ (CDCl ₃ ); 2.88 (s.3H), 7.69 (brs.2H), 8.21 (d.1H). 4-Heptafluoroisopropyl -2-methoxybenzenesulfonyl chloride Physical properties: ¹ H-NMR δ (CDCl ₃ ); 4.125 (s.3H), 7.34 (s.1H), 7.35 (d.1H), 8.10 (d.1H). 3-Fluoro -4-heptafluoroisopropylbenzenesulfonyl chloride Physical properties: ¹ H-NMR δ (CDCl ₃ ); 7.89-8.03 (m.3H). ¹⁹ F-NMR δ (CDCl ₃ ); -75.23 (6F), -177.9 (1F 4-Heptafluoroisopropyl-3-methylbenzenesulfonyl chloride Physical properties: ¹ H-NMR δ (CDCl ₃ ); 2.69 (d.3H), 7.77 (d.1H), 7.95 (d.1H), 7.97 (s) .1H). 2,6-dimethyl-4-heptafluoroisopropylbenzenesulfonyl chloride Physical properties: ¹ H-NMR δ (CDCl ₃ ); 2.09 (s.6H), 7.32 (d.2H),

9. Production of sulfonamides. Example 18. Preparation of 3-fluoro-4-heptafluoroisopropylbenzenesulfonamide.

Embedded image In 20 ml of tetrahydrofuran (THF) containing 1.0 g of 28% aqueous ammonia, 3-fluoro-4-
2 ml of a THF solution of 0.6 g (1.65 mmol) of heptafluoroisopropylbenzenesulfonyl chloride
Was added dropwise. After stirring at room mark for 2 hours, the solution was poured into water, and the desired product was extracted with ethyl acetate. The extract was washed with saturated saline and dried, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 0.5 g of the desired product. Physical properties: ¹ H-NMR δ (DMSO-d ₆ ); 7.76 (brs.2H), 7.91-7.95 (m.2H), 8.06 (t.1H). 4-Heptafluoroisopropyl-3-methylbenzenesulfonamide Physical properties: ¹ H NMR δ (CDCl ₃ ); 2.62 (d.3H), 4.87 (brs. 2H), 7.65 (d.1H), 7.83 (d.1H), 7.86 (d.1H). M. p. 130 ° C

10. Production of phenylhydrazines. Example 18. Production of 2,6-dimethyl-4-heptafluoroisopropylphenylhydrazine hydrochloride

Embedded image An aqueous solution (24 ml) of sodium nitrite (2.6 g, 2 mmol) was added to 2,6-dimethyl-4-heptafluoroisopropylaniline (10 g, 34.7 mmol) in hydrochloric acid (30 ml). The solution was added dropwise at a temperature not higher than ° C.
After further stirring for 15 minutes, the diazonium salt solution was added dropwise to a hydrochloric acid aqueous solution (85 ml) containing anhydrous tin chloride (20.4 g, 108 mmol) at room temperature. The precipitated cake-like solid was collected by filtration and washed successively with water and hexane to obtain the desired product (8.5 g, yield 72%). Physical properties: ¹ H-NMR δ (CDCl ₃ ); 2.474 (s.6H), 7.37 (s.2H), 9.99 (brs.2H). ¹⁹ F.NMR δ (CDCl ₃ );-70.81 (d.7F) , -177.36 (m.1F).

The following compounds were obtained in the same manner. 4-Heptafluoroisopropyl-2-methylphenylhydrazine Physical properties: ¹ H-NMR δ (CDCl ₃ ); 2.13 (s.3H), 3.41 (brs.2H), 5.30 (brs.1H), 7.04 (d.1H) , 7.23 (s.1H), 7.59 (d.1H). 2,6-dichloro-4-heptafluoroisopropylphenylhydrazine Physical properties: ¹ H-NMR δ (CDCl ₃ ); 4.06 (brs.2H), 5.83 (brs .1H), 7.47 (s.2H). ¹⁹ F-NMR δ (CDCl ₃ ); -76.23 (6F), -182.45 (1F). Production of isocyanates.

Example 1 Preparation of 4-heptafluoroisopropylphenylisocyanate

Embedded image A toluene solution (5 ml) containing 4-heptafluoroisopropylaniline (3 g, 10.9 mmol) was dropped into a toluene solution (70 ml) containing triphosgene (1.1 g, 3.6 mmol) while heating. After dropping,
The reaction solution was heated under reflux for 4 hours, the solvent was distilled off under reduced pressure, hexane was added to the residue, and the suspension was filtered. The obtained filtrate was concentrated to give the desired product (3 g). The following compounds were obtained in the same manner. 4-Heptafluoroisopropyl-2-methoxyisocyanate Physical properties: ¹ H-NMR δ (CDCl ₃ ); 3.895 (s.3H), 7.07 (s.1H), 7.10-7.16 (m.2H). p. 38-39 ° C 12. Production of benzaldehydes. 2-Heptafluoroisopropylbenzaldehyde Physical properties: ¹ H-NMR δ (CDCl ₃ ); 7.68 (m.3H), 8.04 (m.1H), 10.48 (d.1H).

13. Isothiocyanates Example 2 Preparation of 0.4-heptafluoroisopropyl-2-methoxyphenylisothiocyanate.

Embedded image 1.3 g (11.5 g) of 4-heptafluoroisopropyl-2-methoxyaniline dissolved in 100 ml of toluene
Mmol) at room temperature in 1.3 g of thiophosgene (11.
(5 mmol) was added dropwise, and the mixture was heated under reflux for 2 hours, then returned to room temperature, and the solvent was distilled off under reduced pressure to obtain 3.3 g (10.9 mmol) of the desired product. Physical properties: ¹ H-NMR δ (CDCl ₃ ); 3.96 (s.3H), 7.10 (s.1H), 7.11-7.22 (m.2H).

14. Production of acetophenones. Example 2 Preparation of 4-heptafluoroisopropylacetophenone

Embedded image 1-Bromo-4-heptafluoroisopropylbenzene (8.0 g, 24.6 mmol), n-butyl vinyl ether (11.1 mmol), sodium carbonate (11.7 g, 111 mmol) in n-butanol (50 ml), dppp (1,3-bis (diphenylphosphino) propane, 0.87 g, 1.8 mmol) and palladium acetate (0.28 g, 17.4 mmol) were added, and the mixture was heated under reflux for 11 hours. The solution was returned to room temperature and filtered,
The obtained filtrate was concentrated, and 3N-hydrochloric acid aqueous solution (40 m
l) was added and stirred vigorously for 30 minutes, then extracted with hexane, the organic layer was washed with saturated saline, the solvent was distilled off under reduced pressure, and the obtained residue was purified by column chromatography to give the desired compound. (5.6 g, yield 79%). Physical properties: ¹ H-NMR δ (CDCl ₃ ); 2.65 (s.3H), 7.74 (d.2H), 8.08 (d.2H). ND 1.4341 (21.5 ° C.)

The following compounds were obtained in the same manner. 2,6-Dimethyl-4-heptafluoroisopropylacetophenone Physical properties: ¹ H-NMR δ (CDCl ₃ ); 2.31 (s.6H), 2.50 (s.3H), 7.25 (s.2H). ¹⁹ F-NMR δ (CDCl ₃ ); -76.06 (6F), -183.33 (1F). 3-Fluoro-4-heptafluoroisopropylacetophenone Physical properties: ¹ H-NMR δ (CDCl ₃ ); 2.64 (s.3H), 7.73-7.79 ( 4-Heptafluoroisopropyl-3-methylacetophenone Physical properties: ¹ H-NMR δ (CDCl ₃ ); 2.61 (d.3H), 2.624 (s.3H), 7.60 (m.2H), 7.86 (m.1H). d.1H), 7.83 (d.1H), 7.85 (s.1H). 4-Heptafluoroisopropyl-2-methylacetophenone Physical properties: ¹ H-NMR δ (CDCl ₃ ); 2.565 (s.3H), 2.60 ( s.3H), 7.49 (s.1H), 7.504 (d.1H), 7.76 (d, 1H).

15. Production of diazonium salts. 4-Heptafluoroisopropyl-3-methyl-phenyldiazonium tetrafluoroborate Physical properties: ¹ H-NMR δ (CDCl ₃ ); 2.675 (d.3H), 8.25 (d.1H), 8.74 (d.1H), 8.81 ( ^{. s.1H) 19 F-NMR δ} (CDCl 3); -69.40 (6F), -143.99 (4F), -174.51 (1F).

The perfluoroisopropylbenzene derivative of the present invention can be used, for example, for producing the following compounds having pesticidal activity. Reference Example Production of 1,1-dimethyl-3- (4-heptafluoroisopropylphenyl) urea. 4 in tetrahydrofuran (15 ml) containing dimethylamine (50% aq. 0.38 g, 4.2 mmol).
-A tetrahydrofuran solution (2 ml) containing heptafluoroisopropylphenyl isocyanate (1 g, 3.5 mmol) was added at room temperature. After further stirring for 2 hours, the mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with saturated saline, and the solvent was distilled off under reduced pressure. (0.84 g, yield 75%) was obtained. Physical properties: m. p. 151.4 to 154.2 ° C

Reference Example 2 Herbicidal effect test on paddy field weeds after germination A 1 / 10,000 aret pot is filled with soil to make a paddy field,
The seeds of the rice paddy weed and the firefly were prepared before emergence. To this, a drug containing the compound obtained in Reference Example 1 as an active ingredient was treated as a drug solution of a predetermined dose. Processing 2
One day later, the herbicidal effect was investigated, and the herbicidal rate was calculated by comparing the herbicidal effect with that of no treatment. Criteria for herbicidal activity. 5 ... 100% weeding rate. 4 ... Weeding rate of 90% to 99%. 3 ... Weeding rate of 70% to 89%. 2 ... Weeding rate of 40% to 69%. 1 ... Weeding rate of 1% to 39%. 0 ... 0% weeding rate.

At the same time, phytotoxicity to rice was investigated, and the evaluation was made according to the following criteria. Criteria for phytotoxicity. 5 ... 100% weeding rate. 4 ... Weeding rate of 90% to 99%. 3 ... Weeding rate of 70% to 89%. 2 ... Weeding rate of 40% to 69%. 1 ... Weeding rate of 21% to 39%. 0: 0% to 20% herbicidal rate (no phytotoxicity). As a result, at a dose of 5 kg / ha, 4
The herbicidal activity against firefly was 2 and the phytotoxicity of rice was 0.

Test Example 2 Herbicidal Effect on Upland Weeds before Emergence A polyethylene vat having a size of 10 cm × 20 cm × 5 cm in height was filled with soil, and seeds of Arabidopsis, bentgrass, onion, and wheat and soybean as field crops were sown. Covered soil. A chemical solution containing the compound obtained in Reference Example 1 as an active ingredient was treated as a spray solution having a predetermined concentration. Fourteen days after the treatment, the herbicidal effect was investigated, and the herbicidal rate was calculated and determined in the same manner as in Test Example 1. At the same time, phytotoxicity to soybean and wheat was investigated, and judgment was made according to Test Example 1. As a result, a herbicidal activity of 5 against Arabidopsis and corn and 4 against bentgrass was shown at a dose of 5 kg / ha. At this time, the chemical damage to wheat and soybean was 0.

Test Example 3 Herbicidal effect on field weeds after emergence. The soil was packed into a polyethylene vat having a length of 10 cm x a width of 20 cm x a height of 5 cm, and seeds of the field weeds shown below were sown and covered with the soil, and each was grown until the 1-2 leaf stage, and obtained in Reference Example 1. A spray solution having a predetermined concentration of a drug containing a compound as an active ingredient was treated. Fourteen days after the treatment, the herbicidal effect was investigated, and the herbicidal rate was calculated and determined in the same manner as in Test Example 1. At the same time, phytotoxicity to soybean and wheat was investigated, and judgment was made according to Test Example 1. As a result, 5kg
The herbicidal activity was 5 against Arabidopsis and 3 against bentgrass and corn at a dose of / ha. No phytotoxicity was observed on soybean and wheat.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07C 233/65 C07C 233/65 243/22 243/22 255/50 255/50 265/12 265/12 309 / 86 309/86 311/16 311/16 F term (reference) 4H006 AA01 AB84 BJ50 BM10 BM71 BR30 BS30 BS90 BV71 FC52 FE13

Claims (21)

[Claims] 1. A compound of the general formula (I)中 where X₁Is a hydrogen atom, a halogen atom, a formyl group,
 (C₁-C₆) Alkyl group, halo (C₁-C₆) Alkyl group, (C₁-
C₆) Alkoxy group, (C₁-C₆) Alkylthio group, hydroxy
(C₁-C₆) Alkyl group or (C₁-C₆) Alkylcarbonyl
Oxy (C₁-C₆) Represents an alkyl group;_TwoIs a hydrogen atom,
Logen atom, formyl group, hydroxy group, (C₁-C₆) Al
Kill group, halo (C₁-C₆) Alkyl group, (C₁-C₆) Alkoxy
Group, (C₁-C₆) Alkylthio group, (C₁-C₆) Alkylsulf
Ynyl group, (C₁-C₆) Alkylsulfonyl group, hydroxy
 (C₁-C₆) Alkyl group or —C (＝ O) —R₁(Where R
₁Is a hydrogen atom, a halogen atom, a hydroxy group, (C₁-C₆)
Alkyl group, (C₁-C₆) Alkoxy or NR_TwoR_Three(formula
Medium, R_TwoAnd R_ThreeMay be the same or different, and
Child, (C₁-C₆) Alkyl group or (C₁-C₆) Represents an alkoxy group
You. ). ) And X_ThreeIs a hydrogen atom, a halogen atom
, Hydroxy, cyano, isocyanate, iso
Thiocyanate group, hydrazino group, diazo group, mercap
Group, (C₁-C₆) Alkoxy group, (C₁-C₆) Alkylthio
Group, -C (= O) -R₁(Where R₁Is the same as above. )
Or -SO_Two-R_Four(Where R_FourIs a halogen atom, hydro
A xy group, (C₁-C₆) Alkyl group or NR_FiveR₆(Where R
_FiveAnd R₆May be the same or different, a hydrogen atom or
(C₁-C₆) Represents an alkyl group. ). ) And X_Four
Is a hydrogen atom, a halogen atom, (C₁-C₆) Alkyl group or
(C₁-C₆) Represents an alkoxy group. However, (1) X₁, X_TwoAnd X_FourRepresents a hydrogen atom, X_Three
Represents a hydroxycarbonyl group or a methoxycarbonyl group
except. (2) X₁And X_FourRepresents a hydrogen atom, and X_TwoIs formyl
X represents a group_ThreeExcludes the case where is a methoxy group. (3) X₁, X_TwoOr X_ThreeOne of them is met
When it represents a xy group, the remaining X₁, X_TwoOr X_ThreeAnd X_Four
Excludes hydrogen atoms. (4) X_TwoAnd X_ThreeAny one of which is hydroxy
When a group is represented, the remaining X _TwoOr X_Three, X₁And X_FourIs water
Excludes elementary atoms. (5) X₁, X_Two, X_ThreeOr X_FourAny one of
When it represents a fluorine atom, the remaining X₁, X_Two, X_ThreeOr X
_FourExcludes hydrogen atoms. (6) X₁, X_TwoAnd X_FourRepresents a hydrogen atom, X_Three
Excludes a chlorine atom, a bromine atom or an iodine atom. (7) X₁, X_Two, X_ThreeOr X_FourAny one of
Is a methyl group, the remaining X₁, X_Two, X_ThreeOr X
_FourExcludes hydrogen atoms. (8) X₁, X_TwoAnd X_FourRepresents a hydrogen atom, X_Three
Excludes an isopropyl group or a chloromethyl group. (9) X₁, X_ThreeAnd X_FourRepresents a hydrogen atom, X_Two
Excludes a trifluoromethyl group. (10) X₁And X_FourRepresents a methyl group, and X_TwoIs a hydrogen source
X to indicate a child_ThreeIs a hydrogen atom or heptafluoroiso
Excludes propyl group. Perfluoroisopro represented by｝
Pyrbenzene derivatives or salts thereof. 2. X ₁ is a formyl group, a (C ₁ -C ₆ ) alkyl group, a halo (C ₁ -C ₆ ) alkyl group, a hydroxy (C ₁ -C ₆ ) alkyl group or a (C ₁ -C ₆ ) alkyl group. Alkylcarbonyloxy (C ₁ -C ₆ )
_2. The perfluoroisopropylbenzene derivative or a salt thereof according to claim 1, which represents an alkyl group, and wherein X ₂ , X ₃ and X ₄ represent a hydrogen atom. 3. X₁, X_ThreeAnd X_FourRepresents a hydrogen atom,
X_TwoIs (C₁-C₆) Alkyl group, halo (C₁-C₆) Alkyl group,
Hydroxy (C₁-C₆) Alkyl group, (C₁-C₆) Alkyl cal
Bonyl group or -C (= O) -R₁(Where R₁Is hydrogen field
Atom, hydroxy group, halogen atom, (C₁-C₆) Alkyl
Group, (C₁-C₆) Alkoxy or NR_TwoR _Three(Where R_Two
And R_ThreeMay be the same or different and represent a hydrogen atom, (C₁-C
₆) Alkyl group or (C₁-C₆) Represents an alkoxy group. )
You. 2. The perfluoroisopropyl according to claim 1, wherein
Benzene derivatives or salts thereof. 4. X ₁ , X ₂ and X ₄ each represent a hydrogen atom;
X ₃ is an isocyanate group, an isothiocyanate group or
The perfluoroisopropylbenzene derivative or a salt thereof according to claim 1, which represents a (C ₁ -C ₆ ) alkylcarbonyl group. 5. X ₁ and X _{4 each} represent a hydrogen atom, X ₂ represents a hydroxy group, a (C ₁ -C ₆ ) alkyl group or a (C ₁ -C ₆ ) alkoxy group, X ₃ represents a halogen atom, Hydroxy, cyano, isocyanate, isothiocyanate, hydrazino, —C (＝ O) —R ₁ (wherein R ₁ is a hydrogen atom, a hydroxy group, a halogen atom, a (C ₁ -C ₆ ) alkyl group , A (C ₁ -C ₆ ) alkoxy group or NR ₂ R ₃ (wherein R ₂
And R ₃ may be the same or different, and represent a hydrogen atom, (C _1-
And a C ₆ ) alkyl group or a (C ₁ -C ₆ ) alkoxy group. ). ) Or -SO ₂ -R ₄ (wherein, R ₄ is a halogen atom, in the hydroxy group, or NR ₅ R ₆ (wherein, R ₅ and R ₆
May be the same or different and represent a hydrogen atom or a (C ₁ -C ₆ ) alkyl group. ). 2. The perfluoroisopropylbenzene derivative according to claim 1 or a salt thereof. 6. X ₁ and X _{4 each} represent a hydrogen atom, X ₂ represents a halogen atom, and X ₃ represents a halogen atom or —C (=
O) -R ₁ (wherein R ₁ is a halogen atom, a hydroxy group, a (C ₁ -C ₆ ) alkyl group, a (C ₁ -C ₆ ) alkoxy group or N
R ₂ R ₃ (wherein, R ₂ and R ₃ may be the same or different and represent a hydrogen atom or a (C ₁ -C ₆ ) alkyl group). 2. The perfluoroisopropylbenzene derivative according to claim 1 or a salt thereof. 7. X₁Is a halogen atom or (C₁-C₆) Archi
X represents_TwoAnd X_FourRepresents a hydrogen atom, and X_ThreeBut c
Logen atom, hydroxy group, cyano group, diazo group, -C
(= O) -R₁(Where R₁Is a halogen atom, hydroxy
Group, (C₁-C ₆) Alkyl group, (C₁-C₆) Alkoxy group or
NR_TwoR_Three(Where R_TwoAnd R_ThreeMay be the same or different
Well, hydrogen atom or (C₁-C₆) Represents an alkyl group. )
You. ) Or SO_Two-R_Four(Where R_FourIs a halogen atom,
Droxy group or NR_FiveR₆(Where R_FiveAnd R₆Are the same
Or may be different, a hydrogen atom or (C₁-C₆) Alkyl group
Is shown. ). 2. The perfluo according to claim 1, wherein
Loisopropylbenzene derivatives or salts thereof. 8. X ₂ and X ₄ each represent a hydrogen atom, and X ₁ represents
A (C ₁ -C ₆ ) alkylthio group, wherein X ₃ is a halogen atom or —C (＝ O) —R ₁ (wherein R ₁ is a halogen atom, a hydroxyl group or a (C ₁ -C ₆ ) alkoxy group; The perfluoroisopropylbenzene derivative according to claim 1 or a salt thereof. 9. X ₁ represents a hydrogen atom, and X ₂ and X ₄ represent
X represents a (C ₁ -C ₆ ) alkyl group, X ₃ represents a halogen atom, a hydrazino group, —C (＝ O) —R ₁ (wherein R ₁ is a halogen atom, a hydroxy group, (C ₁ -C ₆ ) An alkyl group, a (C ₁ -C ₆ ) alkoxy group or NR ₂ R ₃ (wherein R ₂ and R ₃ may be the same or different and represent a hydrogen atom or a (C ₁ -C ₆ ) alkyl group) Or —SO ₂ —R ₄ (wherein R ₄ is a halogen atom, a hydroxy group or NR ₅ R ₆ (wherein R
₅ and R ₆ are the same as above. ). Claim 1)
Or a salt thereof. 10. X ₁ represents a hydrogen atom, and X ₂ and X ₄
2 represents a methoxy group, and X ₃ represents a hydroxy group. 11. The par according to claim 1, wherein X ₂ , X ₃ and X ₄ represent a hydrogen atom, and X ₁ represents a formyl group, a methyl group, a hydroxymethyl group, a chloromethyl group, a bromomethyl group or an acetoxymethyl group. Fluoroisopropylbenzene derivatives or salts thereof. 12. X ₁ , X ₃ and X _{4 each} represent a hydrogen atom, and X ₂ represents a formyl group, ethyl group, chloromethyl group, hydroxylmethyl group, acetyl group or N-methoxy-N
2. The perfluoroisopropylbenzene derivative or a salt thereof according to claim 1, which represents a -methylaminocarbonyl group. 13. The perfluoroisopropylbenzene derivative or a salt thereof according to claim ₁ , wherein X ₁ , X ₂ and X ₄ represent a hydrogen atom, and X ₃ represents an isocyanate group or an acetyl group. 14. X ₁ and X ₄ is a hydrogen atom, X ₂
Represents a methyl group, X ₃ represents a chlorine atom, a bromine atom, an iodine atom, a hydroxy group, a cyano group, an isothiocyanate group, a hydrazino group, —C (＝ O) —R ₁ (wherein R ₁ is a hydrogen atom, chlorine atom, hydroxy group, a methoxy group or an amino group.) or -SO ₂ -R ₄ (wherein, R ₄ is perfluoro isopropyl benzene derivatives according to claim 1, wherein indicating a.) that represents a chlorine atom or an amino group Or salts thereof. 15. X ₁ and X ₄ is a hydrogen atom, X ₂
Represents a methoxy group, and X ₃ represents a chlorine atom, a bromine atom, an iodine atom, a cyano group, a hydroxy group, a mercapto group, an isocyanate group, an isothiocyanate group, and —C (＝ O).
—R ₁ (wherein, R ₁ represents a hydrogen atom, a chlorine atom, a methoxy group, a hydroxyl group or an amino group) or —SO
_2- R ₄ (wherein R ₄ represents a chlorine atom or an amino group)
The perfluoroisopropylbenzene derivative or a salt thereof according to claim 1, wherein 16. X ₁ and X ₄ is a hydrogen atom, X ₂
Represents a fluorine atom, X ₃ represents a bromine atom or —C (（O)
-R ₁ (wherein, R ₁ represents a chlorine atom, a hydroxyl group,. Showing a methoxy group or an ethoxy group) perfluoro isopropylbenzene derivative or a salt thereof according to claim 1, wherein indicating a. 17. X ₂ and X ₄ each represent a hydrogen atom, and X ₁
Represents a methyl group, X ₃ represents a bromine atom, a hydroxy group, a cyano group, a diazo group, —C (＝ O) —R ₁ (wherein R ₁ is a chlorine atom, a hydroxyl group, a methyl group, a methoxy group or an amino group. represents a group.) or -SO ₂ -R ₄ (wherein, R ₄ is perfluoro isopropyl benzene derivative or a salt thereof according to claim 1, wherein indicating a.) that represents a chlorine atom or an amino group. 18. X ₂ and X ₄ is a hydrogen atom, X ₁
Represents a fluorine atom, X ₃ represents a chlorine atom, a bromine atom, a cyano group, —C (＝ O) —R ₁ (wherein, R ₁ represents a chlorine atom, a hydroxy group, a methyl group, a methoxy group or an amino group. .) or -SO ₂ -R ₄ (wherein, R ₄ is perfluoro isopropyl benzene derivative or a salt thereof according to claim 1, wherein indicating a.) that represents a chlorine atom or an amino group. 19. X ₂ and X ₄ each represent a hydrogen atom, and X ₁
Represents a methylthio group, X ₃ represents a bromine atom, an iodine atom,
The perfluoroisopropylbenzene derivative or a salt thereof according to claim 1, which represents ─C (誘導 体 O) -R ₁ (wherein, R ₁ represents a chlorine atom, a hydroxy group or a methoxy group). 20. X ₁ represents a hydrogen atom, and X ₂ and X ₄
Represents a methyl group, X ₃ represents a chlorine atom, bromine atom, iodine atom, carboxyl group, methoxycarbonyl group, acetyl group, hydrazino group or —SO ₂ —R ₄ (wherein R ₄ represents a chlorine atom or an amino group. The perfluoroisopropylbenzene derivative according to claim 1 or a salt thereof. 21. X ₁ represents a hydrogen atom, and X ₂ and X ₄
The perfluoroisopropylbenzene derivative or a salt thereof according to claim 1, wherein represents a methoxy group and X ₃ represents a hydroxy group.