Title of Invention	PERFLUOROISOPROPYLBENZENE DERIVATIVES
Abstract	Perfluoroisopropylbenzene derivatives of the general formula (I) or salts thereof, useful as intermediates or raw materials in the synthesis of various industrial materials including agricultural chemicals, drugs and surfactants, wherein X<sub>1</sub> is H, halogeno, formyl, optionally halogenated C<sub>1</sub>-C<sub>6</sub> alkyl, C<sub>1</sub>-C<sub>6</sub> alkylthio, or the like; X is H, halogeno, formyl, hydroxyl, C<sub>1</sub>-C<sub>6</sub> alkyl, -C(=O)-R<sub>1</sub> (wherein R<sub>1</sub> is H, halogeno, hydroxyl, C<sub>1</sub>-C<sub>6</sub> alkyl, or NR<sub>2</sub>R<sub>3</sub>, with R<sub>2</sub> and R<sub>3</sub> being each H, C<sub>1</sub>-C<sub>6</sub> alkyl, or the like), or the like; X<sub>3</sub> is H, halogeno, hydroxyl, cyano, isocyanato, hydrazino, diazo, -C(=O)-R<sub>1</sub>, -SO<sub>2</sub>-R<sub>4</sub> (wherein R<sub>4</sub> is halogeno, hydroxyl, C<sub>1</sub>-C<sub>6</sub> alkyl, or NR<sub>5</sub>R<sub>6</sub>, with R<sub>5</sub> and R<sub>6</sub> being each H or C<sub>1</sub>-C<sub>6</sub> alkyl), or the like; and X<sub>4</sub> is H, halogeno, C<sub>1</sub>-C<sub>6</sub> alkyl, or C<sub>1</sub>-C<sub>6</sub> alkoxy, with publicly known compounds being excepted.

Title of Invention

PERFLUOROISOPROPYLBENZENE DERIVATIVES

Abstract

Perfluoroisopropylbenzene derivatives of the general formula (I) or salts thereof, useful as intermediates or raw materials in the synthesis of various industrial materials including agricultural chemicals, drugs and surfactants, wherein X1 is H, halogeno, formyl, optionally halogenated C1-C6 alkyl, C1-C6 alkylthio, or the like; X is H, halogeno, formyl, hydroxyl, C1-C6 alkyl, -C(=O)-R1 (wherein R1 is H, halogeno, hydroxyl, C1-C6 alkyl, or NR2R3, with R2 and R3 being each H, C1-C6 alkyl, or the like), or the like; X3 is H, halogeno, hydroxyl, cyano, isocyanato, hydrazino, diazo, -C(=O)-R1, -SO2-R4 (wherein R4 is halogeno, hydroxyl, C1-C6 alkyl, or NR5R6, with R5 and R6 being each H or C1-C6 alkyl), or the like; and X4 is H, halogeno, C1-C6 alkyl, or C1-C6 alkoxy, with publicly known compounds being excepted.

Full Text	DESCRIPTION PERFLUOROISOPROPYLBENZEN DERIVATIVE TECHNICAL FIELD This invention relates to a novel perfluoro-isopropylbenzene derivative or salts thereof. BACKGROUND ART Since perfluoroisopropylbenzenes have a perfluoroalkyl group, which exhibits mainly physicochemically distinctive features, they are useful as intermediates or raw materials for synthesizing agricultural chemicals, medicines, dye stuffs surface active agents, wetting agents, dispersing agents, rubber materials, releasing agents, water and oil repelling agents, optical materials, gas separation membrane materials, resist materials, antifouling paints, weather-proofing paints,- paper-converting agents, textile-treating agents, functional resins having such characteristics as heat resistance and weather resistance, antistatic agents, photographic toners, liquid crystal materials and solvents (refer, for example, to "Advanced Technology of Halogen Chemicals" published by CMC). Heretofore,' not many reports have been made on examples of production of perfluosoisopropyl-benzenes. Previously known methods in the literature for introducing a perfluoroisopropyl group into a benzene ring are, for example: (a) a method of replacing a halogen in a halogenated benzenes by using 2-iodoheptafluoropropane in the presence of metallic copper, for example, methods described in (1) Tetrahedron, £5, 5921 (1969), (2) German Patent publication No. 2606982, (3) Journal Chem. Soc. Jpn., 1876 (1972), (4) J. Chem. Soc. Perkin Trans. 1, 661 (1980), and (5) Bull. Chem. Soc. Jpn., 65, 2141 (1992). These methods, however, are industrially disadvantageous in that prior introduction of a halogen atom to the appropriate position of benzenes is necessary, excess of copper is required and the reaction temperature is high. Moreover, depending on the kind of substituents of benzenes, the yield is low and good results are not obtained. (b) a method of reacting hexafluoropropene on fluoronitrobenzenes in the presence of a fluorine anion, for example, the methods described in (1) J. Chem. Soc. C, 2221 (1968), (2) J. Soc' Org. Synth. Chem., Jpn., 21, 993 (1969), (3) J. Chem. Soc. Jpn., 198 (1976) and (4) Tetrahedron, 51, 13167 (1995). In these methods, however, the substrateis which can be used are restricted to those which have been strongly activated by electron withdrawing groups, e.g., perfluoronitrobenzenes and dinitrofluorobenzenes, so that the methods are limited as to the substituent, structure, etc. of obtainable compounds. (c) a method of reacting an unsubstituted or substituted phenyl Grignard reagent with hexafluoroacetone and then reacting 1-hydroxy-l-trifluoromethyl-2,2,2-trifluoroethylbenzenes thus obtained with an appropriate fluorinating agent, for example, the method described in Canadian Pat. No, 1,022,573. This method, however, is not always economically advantageous because it uses in the reaction industrially difficult-to-handle reagents, such as hydrofluoric acid and SF4. (d) a method of reacting (heptafluoroisopropyl) phenyliodonium trifluoromethanesulfonate with phenols to obtain perfluoroisopropylphenols, described in Bull. Chem. Soc. Jpn., .57., 3361 (1984). This method, however, is not promising for industrial practice owing to the use of expensive reagent and low selectivity as to the perfluoroisopropylated position of the compound obtained. (e) a method of reacting iodobenzenes, in the presence of palladium catalyst, with a perfluoroisopropylzinc compound prepared from 2-iodoheptafluoropropane and zinc in the system, to obtain perfluoroisopropylbenzenes, described in Chemistry Letters, 137 (1982). This method, however, is not industrially advantageous owing to its reaction conditions wherein zinc is to be used and the reaction needs to be conducted under ultrasonic waves. In the prior processes for producing perfluoroisopropylbenzenes, the intended compounds are produced by introducing a perfluoroisopropyl group into intended benzenes by the above-mentioned methods or by subjecting the perfluoroisopropylbenzenes produced'by the above-mentioned methods to structural transformation. Both processes are not satisfactory in practice. Since previous processes are thus not suited to practical use, few examples are known of the production of perfluoroisopropylbenzenes. However, since the perfluoroisopropyl group is a substituent having distinctive features both physically and biochemically, the literature in several fields describes the. usefulness of benzenes having a perfluoroisopropyl group introduced thereinto. As to benzoic acids having a perf luoroisopropyl group as a subs-ituent/ for example, JP-A-9-319147 discloses that phthalic acids having a perfluoroisopropyl group on the benzene ring is useful as a positively chargeable charge-controlling agent and as a toner for electrostatic image developing, and JP-A-59-69755 discloses that some of -he benzoic amides having a perfluoroisopropyl group are useful as a photographic cyan coupler. As to 'perfluoroisopropylber.zenesulfomc acids, for exmaple, U.S.P. No. 35C1322 describes that some of the sulfonic acids and their salts are useful as a wetting agent and dispersing agent and discloses a method of producing 4-heptafluorobenzoic acid from 1-methyl-4-(l-trifluoromethyl-l-hydroxy-2,2,2-trifluoroethyl)benzene as the starting material via 1-methyl-4-heptafluoroisopropylbenzene. This method, however, is industrially disadvantageous because it uses highly toxic reagent as SF4 and chromic acid and hence results in high cost of production facilities and waste proposal. In the previous known methods, in general, it is necessary to introduce a halogen atom beforehand to the position into which a perfluoroisopropyl group is to be introduced, or the benzenes to which a perfluoroisopropyl group can be introduced are limited to those having a certain substituent, such as phenols and nitrobenzenes. Consequently, the kinds of substituents of perfluoroisopropylbenzenes produced in the past are small in number. Furthermore, all of the methods described aboye are not suited to mass production. Therefore, in spite of the perfluoroisopropyl group being a substituent which has physically distinctive features and is promising for its usefulness in various fields, not much perfluoroisopropylbenzenes have hitherto been produced. DISCLOSURE OF THE INVENTION The objects of this invention are to provide a novel and useful perfluoroisopropylbenzene derivative or the salts thereof, and to provide a process for producing, in the manner described in JP-11-229304, various perfluoroisopropylbenzene derivatives in a simple manner and with good yield by using easily producible perfluoroisopropylanilines, and various novel perfluoroisopropylbenzene derivatives. According to this invention, there are provided a perfluoroisopropylbenzene derivative represented by the formula (I) or salts thereof: i-CtF, ( ) X, 0) -3r7 wherein Xx is a hydrogen atom, halogen atom, formyl group, (C^-Cg) alkyl group, halo (C^-Cg) alkyl group, (Ct-C6)alkoxy group, (C^-Cg) alkylthio group, hydroxy (C:-C6) alkyl group or (Cx-C6) alkylcarbonyloxy (Cx-Ce) alkyl group; X2 is a hydrogen atom, halogen atom, formyl group, hydroxy group, (C^-Cg) alkyl group, halolC^-C6) alkyl group, (C^-Cg) alkoxy group, "(C^Cg) alkylthio group, (Cj^-Cg) alkylsulfinyl group, (C^-Cg) alkylsulfonyl group, hydroxy (C1-C6) alkyl group or -C(=0)-R1 (wherein RX is a hydrogen atom, halogen atom, hydroxy group, (Cx-C6) alkyl group, (C^Cg) alkoxy group or NR2R3 (wherein R2 and R3 may be the same or different and are each a hydrogen atom, (C1-C6)alkyl group or (d-CJ alkoxy group)); X3 is a hydrogen atom, halogen atom, hydroxy group, cyano group, isocyanate group, isothiocyanate group, hydrazino group, diazo group, mercapto group, (C^-Cs) alkoxy group, (Ci-CJ alkylthio group, -c (=0) -R1 (wherein Rx is the same as defined above) or -S02-R4 (wherein R4 is a halogen atom, hydroxy group, (C^-CJalkyl group or NR5R6 (wherein R5 and R6 may be the same or different and are each a hydrogen atom or (Cx~ C6)alkyl group)); and X4 is a hydrogen atom, halogen atom, (Ci-C^alkyl group or (C^Cg) alkoxy group; provided that (1) when Xx, X2 and X4 are each a hydrogen atom, then X3 is not a hydroxycarbonyl group or methoxycarboxyl group, (2) when Xx and X4 are each a hydrogen atom and X2 is a formyl group, then X3 is not a inethoxy group, (3) when any one of Xl7 X2 and X3 is a methoxy group, then X4 and the remaining two of Xx/ X2 and X3 are not each a hydrogen atom, (4) when any one of X2 and X3 is a hydroxyl group, then Xx, X4 and the remaining one of X2 and X3 are not each a hydrogen atom, (5) when any one of X17 X2, X3 and X4 is a fluorine atom, then the remaining three of Xx, X2, X3 and X4 are not each a hydrogen atom, (6) when Xx, X2 and X4 are each a hydrogen atom, then X3 is not a chlorine atom, bromine atom or iodine atom, (7) when any one of X:, X2, X, and X4 is a methyl group, then the remaining three of X^ X2, X3 and X4 are not each a hydrogen atom, (8) when xlf X2 and X4 are each a hydrogen atom, then X3 is not an isopropyl group or chloromethyl group, (9) when Xx, X3 and X4 are each a hydrogen atom, then X2 is not a trifluoromethyl group, and (10) when X1 and X4 are each a methyl group and X, is a hydrogen atom, then X3 is not a hydrogen atom or heptafluoroisopropyl group. MODE FOR CARRYING OUT THE INVENTICM . As to the definition of the formula (I), which represents the perfluoroisopropylbenzene derivative of this invention, in the definition of its respective substituents, "i" means iso, "sec-" means secondary and "t" means tertiary, an "alkyl group" or "alkyl", which indicates an alkyl moiety, may be both of a straight chain or a branched chain, and a " (C\-C6)alkyl group" refers to an alkyl group having 1-6 carbon atoms, which may be, for example, a methyl group, ethyl group, propyl group, i-propyl group, butyl group, sec-butyl group, t-butyl group, neopentyl group., 1,2-dimethylpropyl group, hexyl group and heptyl group. A "halogen atom" indicates a chlorine atom, bromine atom, iodine atom or fluorine atom; a "halo [C^ C6) alkyl group, which may be the s^r.e or different, indicates a straight or branched chain alkyl group having 1-6 carbon atoms wherein at least one of the hydrogen atoms has been substituted with a halogen atom, and may be, for example, a 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 and 6-bromohexyl group. An "alkoxy group" or "alkoxy" moiety means a straight or branched chain alkoxy group, and a "{Cx-C6)alkoxy group" refers, for example, to a methoxy group, ethoxy group, i-propoxy group, sec-butoxy group, t-butoxy group, 1,2-dimethylpropoxy group and hexyloxy group. A "halo (C^-Cg) alkoxy group", which may be the same or -different, indicates a straight or branched chain alkoxy group having 1-6 carbon atoms wherein at least one of the hydrogen atoms has been substituted with a halogen atom, and may be, for example, a difluoromethoxy group, trifluoromethoxy group, 2-chloroethoxy group, 2-bromoethoxy group, 2,2,2-trifluoroethoxy-group, pentafluoroethoxy group, .1,1, 2, 2-tetraf luoroethoxy group, 3-chlorobutoxy group, 3-bromobutoxy group, 1-chloropentyloxy group, 1-chlorohexyloxy group and 6-bromohexyloxy group. A " (Ct-C6) alkylthio group" refers to a straight or branched chain alkylthio gioup having 1-6 carbon atoms and may be, for example, • • methylthio group, ethylthio group, i-propylthio gioup, sec-butyl thio group, t-butylthio group and hexylthio group. A "halo(Ci-CJ alkylthio group", which may be the same or different, refers to a str-ilght or branched chain alkylthio group having 1-6 carbon atoms wherein at least one of the hydrogen atoms has been substituted with a halogen atom, and may be, for example, a difluoromethylthio group, trifluoromethylthio group, 2,2,2-trifluoroethylthio group, 1,1,2,X-tetrafluoroethylthio group, 2-chloroeth'/lthio group and 3-bromoethylthio group. A "hydroxy (Ci-CJalkyl group", which may be the same or different, refers to a straight or branched chain alkyl group having 1-6 carbon at/>.'ns wherein at least one of the hydrogen atoms has be';-'- substituted with a hydroxy group, and may be, for example, a hydroxymethyl group, 1-hydroxyethyl gro -P anci hydroxyethyl group. Some examples of the represer.native processes for producing the perfluoroisopropylber.zene derivative represented by the formula (I) of this invention are described below,- but the invention is r.ot limited thereby- p. 2497. The compounds wherein W is a sulfur atom may be produced, for example, according to the methods described in J. Chem. Soc. (1942) p. 374, J. Am. Chem. Soc. (1946) 68, p. 2506, Liebigs Ann. Chem. (1962) 657, 98 and Bull. Chem. Soc. Jpn. (1975) 48, p. 2981. The anilines represented by the formula (II), a starting material, may be produced according to the method described in JP-11-338707. wherein Yx, Y2 and Y3 are the same as defined above, and Y4 is a hydrogen atom, halogen* atom, hydroxy .group, sulfonyl halide group or hydrazino g^oup or the salt thereof. / By reacting a diazonium salt of an aniline, obtained by reacting an aniline represented by the formula (II) with sodium nitrite, etc. by using an acidic solvent, and a metal halide with each other in the presence or absence of a metal catalyst, such as copper, the perfluoroisopropylbenzene derivative represented by the formula (I-b) can be produced. In the present process, among the perfluoroisopropylbenzene derivatives represented by the formula (I-b), the compounds wherein Y4 is a hydrogen atom may be produced, for example, according to the methods described in J. Chem. Soc, p. 2095 (1949): Org. React., 2, p.262 (1944), Org. Synth., (1955) III, 295 and J. Am. Chem., £2, p.1251 (1961), those wherein Y4 is a fluorine atom according to the method described in Org. React., 5, p.193 (1949) and J. Org. Chem., JI6, p. 63 (1971), those wherein Y4 is a chlorine atom according to the method described in Org. Synth., I. p.170 (1941) and J. Chem. Soc, p.819 (1945), those wherein Y4 is a bromine atom according to the method described in Org. Synth. Ill, p.185 (1955) and J. Org. Chem., 23, p.1139 (1958) and those wherein Y4 is an iodine atom according to the method described in J. Org. Chem. 3, p.55 (1938), J. Am. Chem. Soc. 7_Q, p.157 (1948), J. Am. Chem. Soc. 92, p.2175 (1970) and J. Am. Chem. Soc. .93, p.4845 (1971). The compounds wherein Y4 is a hydroxy group may be produced-, for example, according to the methods described in Org. Synth., I, p.404 (1941), Org. Synth., Ill, p.130 (1955), Can. J. Chem, 11, p.1653 (1963) and J. Org. Chem., 32, p.3844 (1967), those wherein Y4 is a sulfonyl halide group according to the methods described in J. Prakt. Chem. [2]152, p.251 (1939) and Reel. Trav. Chiiru Pays-Bas., £1/ p.22 (1965), and those wherein Y4 is a hydrazine) group or its salt according to the method described in Org. Synth., I, p.442 (1941)'. In the perfluoroisopropylbenzene derivatives, the compounds wherein Y4 is an aldehyde group may be produced by oxidizing the compounds wherein Y4 is a hydroxy group obtained by the above-mentioned methods, according to a conventional method. wherein Ylf Y2 and Y3 are the same as defined above, Y5 is a chlorine atom, iodine atom or bromine atom, and R is a hydrogen atom or (C^-C^)alkyl grdup. By reacting the halogenated benzenes represented by the formula (III) with carbon monoxide in the presence of a base, organic phosphorus compound, such as triphenylphosphine and bisdiphenyl-phosphinobutane, transition metal, such as palladium, nickel and cobalt, or its complex, and an inert solvent, the perfluoroisopropylbenzene derivatives represented by the formula (I-c) can be produced. This process can be conducted, for example, according to the methods described in Bull. Chem. Soc. Jpn., I£, p.2075 (1975) and J. Am, Chem. Soc. Ill, p.8742 (1989). By starting from the perfluoro-isopropylbenzene derivatives represented by the formula (I-c) and through the method described below, ^erfluoroisopropylbenzene derivatives represented by :he formulas (I-d), (I-e), (I-f) and (I-g) can be produced. wherein Y17 Y2, Y, and R are the same as defined above, and Hal is a halogen atom. shown above may be conducted by conventional metr-^ds . EXAMPLES Some representative examples of this invention are described below with reference to Examples, but the invention is not limited thereto. 1. Preparation of halobenzenes Example 1 Preparation of l-chloro-4-heptafluoro- isopropylbenzene Concentrated hydrochloric acid (30 ml) was diluted with water (10 ml), and 4-heptafluoro-isopropylaniline (10 g, 38.3 mmols) was added thereto to form a suspension. Th'en, aqueous sodium nitrite (2.9 g, 42 mmols) solution (10 ml) was slowly added thereto so that the reaction temperature might be not higher than 10°C. After completion of the addition, the reaction mixture was stirred for further 20 minutes. The resulting diazonium salt solution was slowly added at room temperature to a solution of copper chloride (I) (5.7 g, 57 mmols) in hydrochloric acid (25 ml) prepared separately. Then the reaction mixture was stirred at room-temperature for 30 minutes, heated for 1 hour, then cooled to room temperature, hexane was added to the reaction mixture to separate an organic layer, the organic layer was washed once with water, twice with an aqueous sodium thiosulfate solution and once with a saturated aqueous sodium chloride solution, dried with anhydrous sodium sulfate, and then concentrated under reduced pressure to obtain a crude product (8.6 g, yield (crude) 80%) of the intended compound. Physical property: ^-NMR 5(CDC13): 7.49(d, 2H) , 8.07(d, 2H). Example 2 Preparation of l-bromo-2-fluoro-4-heptafluoroisopropylbenzene An aqueous 47% hydrogen bromide solution (50 ml) was diluted with water (15 ml), and 2-flnoro-4-heptafluoroisopropylaniline (15,7 g, 56 mmol."t a time at 65°C to a separately prepared solution of copper bromide (I) (4.0 g, 26 mmols) in an aqueous 47% hydrogen bromide solution (40 ml) , the resul1 i-n(3 reaction mixture was stirred at 60-80°C for '/ hours, then cooled to room temperature, hexane was odded thereto to separate an organic layer, the organic layer was washed once.with water, twice with an aq~;eous sodium thiosulfate solution and once with a saturated aqueous sodium chloride solution. Then the organic layer was dried with anhydrous sodium sulfate and concentrated under reduced pressure to obtai'- a crude product (15 g, yield (crude) 78%) of the intended compound. Physical property: ^-NMR 5(CDC1,): 7.294(d, 1H) , 7.39(d, 1H), 7.72 (t, 1H) . nD 1.4318 (21.3°C) Example 3 Preparation of l-bromo-3-heptafluoro-isopropylbenzene An aqueous hydrochloric acid solution (60 ml) was diluted with water (20 ml), and 2-bromo-4-heptafiuoroisopropylaniline (20 g, 59 mmols) was added thereto to form a suspension. Then an aqueous sodium nitrite (4.3 g, 62 mmols) solution (15 ml) was slowly added to the suspension so that the reaction temperature might be 5°C. After completion of the addition, the reaction mixture was stirred for further 30 minutes. To the resulting diazonium salt solution was added dropwise at 5-10°C hypophosphorous acid (35 ml) in several portions over 1 hour. After completion of the addition, the reaction mixture was further stirred at room temperature for 3 hours, then hexane was added thereto to separate an organic layer, the organic layer was washed once with water and once with an aqueous saturated sodium chloride solution, dried with anhydrous sodium sulfate, then concentrated under reduced pressure, and the resulting residue was purified by column chromatography to obtain the intended product (17.2 g, yield (crude) 90%). Physical property: XH-NMR 5(CDC13): 7.39 (t, 1H) , 7.554(d, 1H) , 7.69 (m, 1H) , 7.76(s, 1H) . Example 4 Preparation of 4-heptafluoroisopropyl-iodobenzene In an ice bath, concentrated sulfuric acid (7.5 g, 76.6 mmols) was diluted with water (30 ml), and 4-heptafluoroisopropylaniline (10 g, 38.3 mmols) was added thereto. Then an aqueous sodium nitrite (2.9 g, 42 mmols) solution (20 ml) was slowly added so that the reaction temperature might be not higher than 0°C, the reaction mixture was further stirred for 20 minutes, and then concentrated sulfuric acid (3.8 g) was added. The resulting diazonium salt solution was slowly added at room temperature to a separately prepared aqueous potassium iodide (9.5 g, 57.5 mmols) ■ solution (20 ml). Then the resulting mixture was heated under reflux for 1 hour, then cooled to room- temperature, hexane was added thereto to separate an organic layer, the organic layer was washed once with water, twice with an aqueous sodium thiosulfate solution and once with an aqueous saturated sodium chloride solution, dried with anhydrous sodium sulfate, and then concentrated under reduced pressure to obtain a crude product (13 g, yield (crude) 87%) of the intended compound. In the same manner as above, the following perfluoroisopropylbenzene derivatives were obtained. l-chloro-3-fluoro-4-heptafluoroisopropylbenzene Physical property: XH-NMR 5(CDC13); 7.23-7.33(m, 2H), 7.56(t, 1H), 19F-NMR 5(CDC13) ; -75.82(6F), -106.73 (IF), -178.6(1F). l-chloro-2,6-dimethyl-4-heptafluoroisopropylbenzene Physical property: ^I-NMR 5(CDC13); 2.44 (s, 6H) , 7.305(s, 2H). l-chloro-4-heptafluoroisopropyl-2-methylbenzene Physical property: ^-NMR 5(CDC13); 2.45 (s, 3H) , 7.38(d, 1H), 7.4 6(m, 2H). l-chloro-4-heptafluoroisopropyl-2-methoxybenzene Physical property: ^-NMR 5(CDC13); 3.95 (s, 3H) , 7.12(s, 1H), 7.14 (d, 1H), 7.50(d, 1H) . l-bromo-4-heptafluoroisopropyl-2-methylbenzene Physical property: ^-NMR 8(CDC13); 2.48 (s, 3H) , /, 7.27(d, 1H) , 7.45(s, 1H) , 7.66(d, 1H);. l-bromo-4-heptafluoroisopropy1-3-methylbenzene Physical property: 'H-NMR 5 (CDC13) ; 2.50(d, 3H) , 7.34(d, 1H) , 7.42(d, 1H) , 7.46(s, 1H) . l-bromo-2,6-dimethyl-4-heptafluoroisopropylbenzene Physical property: ^-NMR 5 (CDC13) ; 2.48 (s, 6H) , 7.29(s, 2H). l-bromo-4-heptafluoroisopropyl-2-methoxybenzene Physical property: XH-NMR 8 (CDC13) ; 3.944(s, 3H) , 7.08 (brs, 2H), 7.67(d, 1H) . l-bromo-3-fluoro-4-heptafluoroisopropylbenzene Physical property: ^-NMR 8(CDC13); 7.39-7.52(m, 3H) . 19F-NMR 5(CDC13) ; -75.77(6F), -106.64(1F), -178.61(IF). l-bromo-4-heptafluoroisopropyl-2-methylthiobenzene Physical property: ^-NMR 8(CDC13); 2.51 (s, 3H) , 7.21(m, 1H), 7.285(s, 1H) , 7.645(d, 1H). l-bromo-2,6-dichloro-4-heptafluoroisopropylbenzene Physical property: ^-NMR S(CDC13); 7.604 (s, 2H) . 19F-NMR 8(CDC13) ; -75.98 (6F), -182.61 (IF). l-iodo-4-heptafluoroisopropyl-3-methylbenzene Physical property: 'H-NMR S(CDC13); 2.47(d, 3H) , 7.18(d, 1H), 7.62(d, 1H) , 7.68(s, 1H) . nD 1.4142 (24.2°C) l-iodo-4-heptafluoroisopropyl-2-methylbenzene Physical property: :H-NMR 5{CDC13); 2.504 (s, 3H) , 7.10(d, 1H), 7.44(s, 1H) , 7.94(d, 1H). l-iodo-2,6-dimethy1-4-heptafluoroisopropylbenzene Physical property: XH-NMR 5;CDC13); 2.54(3, 6H) , 7.26(s, 2H) . 19F-NMR 8(CDC13) ; -76.15(d, 7F) , -183.28(m, IF) . 1-iodo-4-heptaf luoroisopropyl-2-ir.ethylbenzene Physical property: lH-NMR .8 (CDC1,) ; 2,511s, Physical property: H-NMR 5(CDC13); 2.50 7.06 (d, 1H) , 7.235(s, 1H) , 7.91(d, 1H) . l-iodo-4-heptafluoroisopropyl-2-methoxybenzene Physical property: ^-NMR 5(CDC13); 3.93(3, '-H>, 6.94(d, 1H) , 6.98(s, 1H), 7.90(d, 1H). 2. Preparation of alkylbenzenes Example 5 Preparation of l-methyl-2-heptafluoro- isopropylbenzene In an ice bath, concentrated hydrochlori' acid (90 ml) was diluted with water (30 ml), and a solution of 4-heptafluoroisopropyl-3-methylaniline ' 30 g, 109 mmols) in glacial acetic acid (30 ml) was a'-aec* thereto. Then, an aqueous sodium nitrite (8 g, 11'-mmols) solution-(15 ml) was slowly added so that t: ^ reaction temperature might not be higher than 5°C. After completion of the addition, the reaction mix" -re was further stirred for 1 hour, hypophosphrous aciv (50 ml) was added, the temperature of the mixture was slowly increased, and the mixture was stirred at room temperature for 15 hours. Then hexane was added to the mixture to separate an organic layer, the organic layer was washed twice with water, once with an aqueous saturated sodium hydrogen carbonate solution and once with an aqueous saturated sodium chloride solution, dried with anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a crude product (19 g) of the intended compound. According to similar reactions, the following compounds were prepared. 1-methyl-3~heptafluoroisopropylbenzene Physical property: XH-NMR 5(CDC13); 2.42(s, 3H) , 7.35-7.41(m-4H). 1,2-dimethyl-3~heptafluoroisopropylbenzene Physical property: 'H-NMR 5(CDC13); 2.35 (s, 3H) , 2.40(d, 3H), 7.13-7.19(m, 1H), 7.29-7.63(m, 2H). 1-ethyl-3-heptafluoroisopropylbenzene Physical property: 'H-NMR 5 (CDC13) ; 1.27(t, 3H) , 2.73(dd, 2H), 7.37-7.48(m, 4H). 19F-NMR 8(CDC13) ; -76.23(d, 7F) , -183.G8(m, IF) . 1-chloromethyl-2-heptafluoroisopropylbenzene Physical property: LH-NMR 8 (CDC13) ; 4.79(d, 2H) , 7.44(m, 1H), 7.52-7.63(m, 3H). l-methyl-2-heptafluoroisopropyl-5-methylthiobenzene Physical property: XH-NMR 5 (CDC13) ; 2.49(d, 3H) , 2.495(s, 3H) , 7.09(s, 1H) , 7.11(d, 1H) , 7.37(d, 1H) . 2-heptafluoroisopropylbenzyl alcohol Physical property: ^-NMR 5(CDC13); 'l.925(d, 2H) , 7.41 (d, 1H) , 7.51-7.59(111, 2H) , 7.81(d/ 1H/ • l-methyl-2-heptafluoroisopropyl-5-methoxyl"-nzene Physical property: ^-NMR 8(CDC13); ;'-49(d, 3H) , 3.824(3, 3H), 6.78(s, 1H), 6.79(d, 1H) , 7.^0(d, 1H) . nD 1.4114 (24.2°C) 2!-heptafluoroisopropylbenzyl acetate Physical property: lH-NMR 5(CDC13); >'.125(s, 3H) , 5.32(d/ 2H) , 7.44(m, 1H), 7.51-7.59(m, 3H/« l-bromomethyl-2-heptafluoroisopropylbenze--" Physical property: ^-NMR 5(CDC13); A.68(d, 2H) , 7.4 0-7.4 5(111, 1H) , 7.50-7.58 (m, 3H) . 3. Preparation of benzoic acids Example 7 Preparation of methyl 4-heptaf i0ro" isopropyl-3-methylbenzoate In an^autoclave, l-iodo-4-hep~a: - uoro-isopropyl-3-methylbenzene (1.0 g, 2.6 mr.c - -■) > palladium chloride (10 ml, 2 mol%) , triphenylphosph: '-e 8 mol%) and triethylamine (0.52 g, 5.2 mmcl;.. were suspended in methanol (10 ml). Then, the -nner atmosphere of the- autoclave was replaced by --'fbon monoxide, and the pressure in the vessel was wrought to about 14 atm. The suspension in the vessel v-,:i heated to about 120° and stirred for 8 hours- Then ' he reaction mixture was cooled to room temperat ,' '-' the insolubles were filtered off, and the filtrav was concentrated and then purified by silica gel ' 'luinn chromatography (hexane: ethyl acetate = 9:1) ' '> obtain the intended product (0.77 g, yield 94%). Example 8 Preparation of ethyl 2-f luoro-4-h^ '•' a- fluoroisopropylbenzoate In an autoclave, l-bromo-2-fluoro-4 -heptafluoroisopropylbenzene (10.0 g, 29 mmols > dichlorobis (triphenylphosphine) palladium (1. C '•:'/ 5 mol%) and triethylamine (3.5 g, 35 mmols) wer=; suspended in ethanol (60 ml). Then, the inne' atmosphere of the autoclave was repalced by c^'-oon monoxide, and the pressure in the vessel was .- ' ^ught to about 14 atm. The suspension in the vessel w^ - heated to about 120°C and stirred for about 8 hours. :hen the reaction mixture was cooled to room temperatur - / the insolubles were filtered off, and the filtrate was concentrated and then purified by silica gel column chromatography (hexane : ethyl acetate = 9 : 1) to obtain the intended product (7.4 g, yield 75%). Example 9 Preparation of methyl 4-heptafluoro-isopropylbenzoate In an autoclave, l-bromo-4-heptafluoroisopropylbenzene (11.8 g, 31.7 mmols), dichlorobis(triphenylphosphine)palladium (1.1 g, 5 mol%) and potassium carbonate (3.2 g, 31.7 mmols) were suspended in methanol (50 ml). Then the inner atmosphere of the autoclave was replaced by carbon monoxide and the pressure in the vessel was brought to about 14 atm. The suspension in the vessel was heated to about 110°C and stirred for 6 hours. Then the reaction mixture was cooled to room temperature, then the insolubles were filtered off, and the filtrate was concentrated and then purified by silica gel column chromatography (hexane : ethyl acetate = 9 : 1) to obtain the intended product (7.4 g, yield 75%). In the same manner as described abovew, the following compounds were prepared. methyl 2,6-dimethyl-4-heptafluoroisopropylbenzoate Physical property: ^-NMR 5 (CDCl,/ ; 2.37(s, 6H) , 3.94 (s, 3H), 7.27 (s, 2H) . methyl 4-heptaf luoro isopropy 1-2-me thoxyi>enzont e Physical property: ^-NMR 5(CDCl./; 3.92(s, 3H) , 3.95(s, 3H) , 7.19(S/ 1H) , 7.21(d, 1H) , 7.87(d, 1H) . methyl 4-heptafluoroisopropyl-2-methyl.o'-nzoat e Physical property: m.p. 39 - 40°^' ethyl 2,6-dimethyl-4-heptafluoroisopropylbenzoate Physical property: :H-NMR 5(CDCl; ; 1-4L(t, 3H) , 2.38(s, 6H) , 4.43(dd, 2H) , 7.33(s, 2H, . methyl 3-fluoro-4-heptafluoro isopropyl.v-nzoat.e Physical property: LH-NMR 5(CDCl, ; 3.965(s, 3H) , 7.72(t, 1H), 7.86(m, 1H), 7.96(m, 1H). methyl 4-heptaf luoro isopropyl- 3-me thy l.o--nzoate Physical property: ^-NMR 8(CDCl-: ; 2.59(d, 3H), 3.94(s, 3H), 7.56(d, 1H), 7.914(d, 1H. , 7.955(s, 1H). methyl 4-heptafluoroisopropyl-2-methyls ,lfonylbenzoate Physical property: ^-NMR 8(CDCi-: ■ 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 processes relati'-':' to benzoic acids U.S.P'. No. 3,462,482 descried'- that some benzoic anilides having a heptaf luorci I'-P^Py1 acaricide. It also discloses a process for producing 4-heptafluoroisopropylbenzoic acid used as a starting material therefor. In this process, 4-heptafluorobenzoic acid is prepared via 1-methyl-4-heptafluoroisopropylbenzene from l-methyl-4- (1-trifluoromethyl-1-hydroxy-2, 2, 2-trifluoroethyl)benzene as the starting material. This process, however, uses highly toxic compounds such as SF4 and chromic acid in the production and hence is not satisfactory for practical use. According to the process of this invention, 4-heptafluoroisopropylbenzoic acid can be produced via 1-cyano-4-heptafluoroisopropylbenzene or 1-halo-4-heptafluoroisopropylbenzene (wherein "halo" denotes a chlorine atom, bromine atom or iodine atom) by using 4-heptafluoroisopropylaniline as the starting material; thus, the process is more suited to practical use. Example 10 Preparation of 4-heptafluoroisopropylbenzoic acid NaOH H+ i-C3F7 (( )> COOCH3 ► ► 1-C3F7 {[ )) COOH McOH, H20 In an ice bath, a solution of sodium hydroxide (0,1 g, 2.5 mmols) dissolved in water (4 ml) was added dropwise to a solution of methyl 4- heptafluoroisopropylbenzoate (0.5 g, 1.5 mmols) in ethanol (4 ml). The resulting mixture was stirred for about 2 hours, then hexane and water were added thereto, and an aqueous'layer was separated. The aqueous layer was made to acidify by addition of 3N hydrochloric acid, and ethyl acetate was added thereto to separate an organic layer. The organic layer was dried with anhydrous sodium sulfate, and then concentrated under reduced pressure to obtain the intended product (9.0 g, yield 93%). Example 11 Preparation of 4-heptafluoroisopropyl-3-methylbenzoic acid In an ice bath, a solution of sodium hydroxide (0.1 g, 2.5 mmols) dissolved in water (4 ml) was added dropwise to a solution of methyl 4-heptafluoroisopropyl-3-methylbenzoate (0.4 g, 1.3 mmols) dissolved in methanol (4 ml). . The resulting mixture was stirred for about 2 hours, and then hexane and water were added thereto to separate an aqueous layer. The aqueous layer was made to acidify by addition of 3N hydrochloric acid, and then ethyl acetate was added thereto to separate an organic layer. , L The organic layer was dried with anhydrous sodium sulfate and then concentrated under reduced pressure to obtain the intended product (0.32 g, yield 84%). Example 12 Preparation of 2-fluoro~4~heptafluoro-isopropylbenzoic acid In an ice bath, a solution of sodium hydroxide (0.1 g, 2.5 mmols) dissolved in water (4 ml) was added dropwise to a solution of ethyl 2-fluoro-4-heptafluoroisopropylbenzoate (0.5 g, 1.5 mmols) dissolved in ethanol (4 ml). The resulting mixture was stirred for about 2 hours, and then hexane and water were added thereto to separate an aqueous layer. The aqueous layer was made to acidify by addition of 3N hydrochloric acid, and then ethyl acetate was added thereto to -separate an organic layer. The organic layer was dried with anhydrous sodium sulfate, and then concentrated under reduced pressure to obtain the intended product (0.38 g, yield 83%). In a similar manner, the following compounds ) were prepared. 2-fluoro-4-heptafluoroisopropylbenzoic acid Physical property: ^-NMR 5 (CDC1,) ; 7.484(d, 1H) , 7.52(d, 1H), 8.18(t, 1H) , 10.55(brs, 1H). 4-heptafluoroisopropyl-2-methoxybenzoic acid Physical property: ^-NMR 5 (CDC13) ; 4.124(s, 3H) > 7.28(3, 1H) , 7.37(1(1, 1H) , 8.27 (d, 1H) . m.p. 96 - 97°C 4-heptafluoroisopropyl-2-methylbenzoic acid Physical property: ^-NMR 5 (CDC13) ;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 property: ^-NMR 5 (CDC13) ; 2.505(s, '6H) , 7.34 (s, 2H) . m.p. 80 - 81°C 3-fluoro-4-heptafluoroisopropylbenzoic acid Physical property: ^-NMR 5 (CDC13) ; 7.784(t, 1H) , 7.94(d, 1H) , 8.05(111, 1H) , 11.40(brs, 1H) . 19F-NMR 5(CDC13) ; -75.49(6F), -107.54(1F), -178.29(1F) . m.p. 54 - 58°C 4-heptafluoroisopropy1-3-methylbenzoic acid Physical property: 'H-NMR .5 (CDC13) ; 2.62 (d, 3H) , 7.62(d, 1H) , 8.00(d, 1H) , 8.03(s, 1H>'. m.p. 129 - 130°C 4-heptafluoroisopropy1-2-methylsulfonylbenzoic acid Physical property: 'H-NMR 5 (CDC13) ; 3.45(s, 3H) , 7.99(m, 2H), 8.41(s, 1H), 9.42(brs, 1H). 4. Preparation of benzoic acid halides Example 13 Preparation of 4-heptafluoroisopropyl-3- methylbenzoyl chloride 4-Heptafluoroisopropyl-3-methylbenzoic acid (0.32 g, 1.0 initio 1) was dissolved in thionyl chloride (3 ml)r one drop of dimethylformamide (DMF) was added thereto, and the mixture was heated under reflux for 3 hours. After completion of reaction, the reaction mixture was cooled to room temperature, and thionyl chloride was distilled off under reduced pressure to obtain a crude product of the intended compound. In a similar manner, the following compounds were prepared. 3-heptafluoroisopropylbenzoyl chloride Physical property: 'H-NMR 5(CDC13) ; 7 . 71(t, 1H), 7.94(d, 1H), 8.33(d, 1H), 8.37(s, 1H) . 19F-NMR 5(CDC13); -76.04 (6F)/ -182.83 (IF). 4-heptafluoroisopropyl-2-methylbenzoyl chloride Physical property: LH-NMR 5(CDC13); 2.65 (s, 3H) , 7.555 (s, 1H), 7.615(d, 1H), 8.31(d, 1H) . 4-heptafluoroisopropyl-2-methoxybenzoyl chloride Physical property: 'H-NMR 5(CDC13) ; 3.984(s, 3H) , 7.22(s, 1H), 7.30(d, 1H) , 8.15(01, 1H) . 4-heptafluoroisopropyl-2-methylthiobenzoyl chloride Physical property: ^-NMR 5(CDC13); 3.34(3, 3H) , 8.04 (s-, 1H) , 8.40 (s, 1H) . 47heptafluoroisopropyl-2-methylsulfonylbenzoyl chloride Physical property: ^-NMR 5(CDC13); 3.34 (s, 3H) , 8.04 (s, 2H), 8.40 (s, 1H) . 4-heptafluoroisopropyl-3-methylbenzoyl chloride Physical property: LH-NMR 5(CDC13); 2.64(d, 3H) , 7.66(d, 1H), 8.00-8.05(m, 2H). 5. ' Preparation of benzamide Example 14 Preparation of 4-heptafluoroisopropyl-3- methylbenzamide In an ice bath, an aqueous ammonia solution (5 ml) was added to the crude product (0.4 g) of 4-heptafluoroisopropyl-3-methylbenzoyl' chloride, and the resulting mixture was stirred for about 30 minutes. Ethyl acetate was added thereto to separate an organic layer, the organic layer was dried with anhydrous sodium sulfate and then concentrated under reduced pressure to obtain the intended product (0.3 g, yield (crude) 98%). In a similar manner, the following compounds were prepared. 4-heptafluoroisopropyl-2-methylbenzamide Physical property: ^-NMR 5 (CDC13) ; 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 property: 'H-NMR 5 (CDCl,) ; 6.47(brs, 2H) , 7.66-7.71(m, 3H). 19F-NMR 5(CDC13) ; -75.64(6F), -107.53(1F), -178.44(IF). m.p. 85 - 86°C 4-heptafluoroisopropyl-3-methylbenzamide Physical property: ^-NMR 5 (CDC13) ; 2.53 (d, 3H) , 7.59(d, 1H) , 7.86(d, 1H), 7.90(s, 1H) . m.p. 66 - 68°C 6. Preparation of cyanobenzenes Example 15 Preparation of l-cyano-4-heptafluoro- isopropyl-3-methylbenzene 4-Heptafluoroisopropyl-3-methylbenzamide (0.3 g, 1 mmol) was dissolved in :thionyl chloride (4 ml) and heated under reflux for 1 hour. The reaction mixture was cooled to room temperature, then thionyl chloride was distilled off under reduced pressure, and the residue was purified by silica -gel column chromatography (hexane : ethyl acetate =9 : 1) to obtain the intended product (0.22 g, yield 78%). In a similar manner, the following compounds were prepared. l-cyano-4-heptafluoroisopropyl-2-methylbenzene Physical property: 'H-NMR 5(CDCl3); 2.41 (s, 3H) , 7.33-7.41(m, 3H). l-cyano-4-heptafluoroisopropyl-2-methoxybenzene Physical property: ^-NMP. 5 (CDC13) ; 2.41(s, 3H) , 7.33-7.41(m, 3H). l-cyano-3-fluoro-4-heptafluoroisopropylbenzene Physical property: ^-NM?. 5 (CDC13) ; 7.55(d, 1H) , 7.63(d, 1H), 7.79(t, 1H). l-cyano-4-heptafluoroisopropyl-2-methylbenzene Physical property: LH-NH?. 5 (CDCl3) ; 2.59 (d, 3H) , 7.60 (brs, 3H) . 7. Preparation of phenols Example 16 Preparation of 4-hep-afluoroisopropyl-3- methylphenol in an ice bath, 4-heptafluoroisopropyl-3- IA mmols) was dissolved in glacial methylaniline (5 g, 18 mmox/ ■A ,os ml) and concentrated sulfuric acid acetic acid (25 ml), duu Tbpn a solution of sodium (3.6 g) was added thereto. Then a soi 1 c^ dissolved in water (3 ml) was nitrite (1.4 g, 20 mmols) dissolve ^ 4. fhe reaction temperature might be slowly added so that the reacuu u. u <_ nor nftpr completion of the addition not higher than c. w1--1> - - birred further for 30 the reaction mixture was otirrea ml) was added thereto, the minutes, then water U ^> e h-fed to about 80°C and stirred resulting mixture was heatea rlDHnn of reaction, the for 5 hours. After completion oi rrr^d to room temperature, hexane reaction mixture was c^---1 . ,.rsrate an organic layer, the was added thereto to separate • n c ua^^ ™ice with water, once with a organic layer was wasr.e. -« j- - vvdroaen carbonate solution saturated aqueous sodiu... -7^ * , _^ aaueous sodium chloride and once with a satura-^- aqueu , . , -4.V, -->vdrous sodium sulfate, solution, dried with e--7aiuu ~--s^ pressure and purified by concentrated under rea-^- Pre ^^---ocjraphy (hexane : ethyl silica gel column chrc...a-^- ^ ,, _ v._-^ t-he intended product (4.0 g, acetate = 3 : 1) to ofc-* — -a yield 81%) . were prepared. 4-heptafluoroisopropy- - _2-r.erhylphenol <_. physical property.> _, - -- 7 30 (d, 1H) , 7.33 (s, 1H) . 5.80(brs, 1H), 6.84(d, --.. , • ^a' _^-r.erhcxyphenol 4-heptaf luoroisopropy-^ _--~»r the following compounds In a similar - -—i--L 6.74(d, 1H), 6.94(s, 1H) , 6.96(d, 1H). 4-heptafluoroisopropyl-3-methylphenol Physical property: ^-NMR 6 (CDC13) ; 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 property: ^-NMR 5 (CDC13) ; 3.89 (s, 3H) , 3.94(s, 6H), 5.82(s, 1H), 6.785(s, 2H). 2,6-dimethyl-4-heptafluoroisopropylphenol Physical property: ^-NMR 5 (CDC13) ; 2.26(s, 6H) , 5.3(brs, 1H) , 7.19(s, 2H) . 8. Preparation of benzenesulfonyl halides Example 17 Preparation of 4-heptafluoroisopropyl-3- methylbenzenesulfonyl chloride In an ice bath, 4-heptafluoroisopropyl-3-methylaniline (5 g, 18.2 mmols) was dissolved in glacial acetic acid (5 ml) and further, concentrated hydrochloric acid (15 ml) was added thereto. Then, a solution of sodium nitrite (1.4 g, 20 mmols) dissolved in water (3 ml) was slowly added so that the reaction temperature might be not higher than 0°C. After completion of the addition, the reaction mixture was stirred further for 20 minutes. The resulting diazonium salt solution was slowly"added to a separately prepared mixture of sodium hydrogen sulfite (5.3 g, 51 mmols), copper chloride (0.35 g, 3.5 mmols), glacial acetic acid (34 ml) and concentrated hydrochloric acid (7 ml) at room temperature. The resulting mixture was stirred at room temperature for 2.5 hours, then hexane was added thereto to separate an organic layer, the organic layer was dried with anhydrous sodium sulfate and then concentrated under reduced pressure to obtain the intended product (4.4 g, yield 67%). In a similar manner, the following compounds were prepared. 4-heptafluoroisopropyl-2-methylbenzenesulfonyl chloride Physical property: "H-NMR 8(CDCl3); 2.88 (s, 3H), 7.69(brs, 2H), 8.21(d, 1H). 4-heptafluoroisopropyl-2-methoxybenzenesulfonyl chloride Physical property: 'H-NMR 5(CDC13); 4.125 (s, 3H), 7.34(s, 1H), 7.35(d, 1H), 8.10(d, 1HJ . 3-fluoro-4-heptafluoroisopropylbenzenesulfonyl chloride Physical property: NMR 5(CDC13); 7.89-8.03 (m, 3H) . 19F-NMR 5(CDC13) ; -75.23(6F), -177.9(1F) 4-heptafluoroisopropyl-3-methylbenzenesulfonyl chloride Physical property: XH-NMR 5(CDC13); 2.69(d, 3H), 7.77(d/ 1H), 7.95(d, 1H) , 7.97(s, 1H) . 2, 6-dimethyl-4-heptafluoroisopropylbenzenesulfonyl chloride Physical property: ^-NMR 5(CDC13); 2.09 (s, 6H) , 7.32 (d, 2H) . Into 20 ml of tetrahydrofuran (THF) containing 1.0 g of aqueous 28% ammonia solution was added dropwise, with ice cooling, 2 ml of a THF solution of 0.6 g (1.65 mmols) of 3-fluoro-4-heptafluoroisopropylbenzenesulfonyl chloride. The resulting solution was stirred at room temperature for 2 hours, then poured into water, and the intended product was extracted with ethyl acetate. The liquid extract was washed with a saturated aqueous sodium chloride solution, then dried, the solvent was distilled off under reduced pressure, and the residue obtained was purified by silica gel column chromatography to obtain 0.5 g of the intended product. Physical property: ^-NMR 8(CDCla); 7.76 (brs, 2H) , 7.91-7.95(m, 2H) , 8.06(t, 1H). In a similar manner/ the following compound was obtained. 4-heptafluoroisopropyl-3-methylbenzenesulfonamide Physical property: lH-NMR 5(CDC13); 2.62(d, 3H)', 4.87(brs, 2H) , 7.65 (d, 1H) , 7,83 (d, 1H) , 7.86(d, 1H) . 10. Preparation of phenylhydrazines Example■18 Preparation of 2, 6-dimethyl-4-heptafluoro- isopropylphenylhydrazine hydrochloride 2, 6-Dimethyl-4-heptafluoroisopropylaniline (10 g, 34.7 mmols) was added into hydrochloric acid (30 ml), and an aqueous solution (24 ml) of sodium nitrite (2.6 g, 2 mmols) was driopwise added thereto-at a temperature not higher than 5°C. After 15 minutes of further stirring, the resulting diazonium salt solution was added dropwise at room temperature to an aqueous hydrochloric acid solution (85 ml) containing anhydrous tin chloride (20.4 g, 108 mmols). The precipitated cake-like solid was collected by filtration and washed successively with water and hexane to obtain the intended product (8.5 g, yield 72%). Physical property: ^-NMR S(CDC13); 2.474 (s, 6H) , 7.37 (S/ 2H), 9.99(brs, 2H) . 19F-NMR 5(CDC13) ; -70.81(d, 7F) , -177.36(01, IF) . In a similar manner, the following compounds were obtained. 4-heptafluoroisopropyl-2-methylphenylhydrazine Physical property: ^-NMR 8(CDC13); 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 property: XH-NMR 5(CDC13); 4.06 (brs, 2H) , 5.83(brs,1H), 7.47 (s, 2H) . 19F-NMR 5(CDC13) ; -76.23(6F), -182.45(1F) 11. Preparation of isocyanates Example 19 Preparation of 4-heptafluoroisopropylphenyl isocyanate A toluene solution (5 ml) containing 4-heptafluoroisopropylaniline (3 g, 10.9 mmols) was dropwise added to a toluene solution (70 ml) containing triphosgene (1.1 g, 3.6 mmols) while the reaction-mixture was being warmed. After completion of the addition, the reaction liquid was heated under reflux for 4 hours, then the solvent was distilled off under reduced pressure, hexane was added to the resulting residue to form a suspension, which was then fittered, and the filtrate obtained was concentrated to obtain the intended product (3 g). In a similar manner, the following compound was obtained. 4-heptafluoroisopropyl-2-methoxyisocyanate Physical property: XH-NMR 5(CDC13); 3.895 (s, 3H), 7.07 (s, 1H) , 7.10-7.16(m, 2H) . m.p. 38 - 39°C. 12. Preparation of benzaldehydes 2-heptafluoroisopropylbenzaldehyde Physical property: ^-NMR 8(CDC13); 7.68 (m,. 3H) , 8.04(m, 1H), 10.48(d, 1H). 13. Preparation of isothiocyanates Example 20 Preparation of 4-heptafluoroisopropyl-2-methoxyphenyl isothiocyanate Thiophosgene (1.3 g, 11.5 mmols) was added dropwise at room temperature to a solution of 4-heptafluoroisopropyl-2-methoxyaniline (1.3 g, 11.5 mmols) dissolved in toluene (100 ml), the resulting mixture was heated under reflux for 2 hours, then brought back to room temperature, and the solvent was distilled off under reduced pressure to obtain the intended product (3.3 g, 10.9 mmols) . Physical property: XH-NMR 5(CDC13); 3.96(s, 3H) , 7.10(s, 1H), 7,11-7.22(m, 2H). 14. Preparation of acetophenones Example 21 Preparation of 4-heptafluoroisopropyl- acetophenone To n-butanol (50 ml) were added l-bromo-4-heptafluoroisopropylbenzene (8.0 g, 24.6 mmols), n-butylvinyl ether (11.1 mmols), sodium carbonate (11.7 g, 111 mmols), dppp (1,3-bis(diphenylphosphino)propane, 0.87 g, 1.8 mmols) and palladium acetatet(0.28 g, 17.4 mmols), and the resulting mixture was heated under reflux for 11 hours. The reaction liquid was brought back to room temperature, filtered, the filtrate obtained was concentrated, an aqueous JN nyarocnioric acid (40 ml) was added to tbe residue, the resulting mixture was stirred vigorously for 30 minutes, then extracted with hexane/ the organic layer was washed with a saturated aqueous sodium chloride solution, the solvent was distilled off under reduced pressure, and the residue obtained was purified by silica gel column chromatography to obtain the intended product (5.6 g, yield 79%) Physical property: ^-NMR 5(CDC13); 2.65 (s, 3H) , 7.74(d, 2H), 8.08(d, 2H). nD 1.4341 (21.5°C) In a similar manner, the following compounds were obtained. 2,6-dimethyl-4-heptafluoroisopropylacetophenone Physical property: LH-NMR 5(CDC13); 2.31 (s, 6H) , 2.50 (s, 3H) , 7.25(s, 2H) . 19F-NMR 5(CDC13) ; -76.06(6F), -183.33(1F). 3-fluoro-4-heptafluoroisopropylacetophenone Physical property: ^-NMR 5(CDCl3); 2.64 (s, 3H) , 7.73-7.79(m, 2H) , 7.86(m, 1H) . •4-heptafluoroisopropyl-3-methylacetophenone Physical property: 'H-NMR 5(CDCl3); 2.61(d, 3H) , 2.624(s, 3H), 7.60(d, 1H) , 7.83(d, 1H) , 7.85(s, 1H) . 4-heptafluoroisopropyl-2-methylacetophenone Physical property: 'H-NMR 5 (CDC13) ; 2.565(s, 3H) , 2.60(s, 3H) , 7.49(s, 1H) , 7.504(d, 1H) , 7.76(d, 1H) . 15. Preparation of diazonium salt 4-heptafluoroisopropyl-3-methylphenyldiazonium tetrafluoroborate Physical property: ^-NMR 5(CDC13) ; 2.67S(d, 'Ml) , 8.25(d, 1H) , 8.7 4(d, 1H) , 8.81 (s, 1H) . 19F-NMR 5(CDC13) ; -69.40(6F), -143 . 99 (4F) , -174.51(IF). The prefluoroisopropylbenzene derivative of this invention can be used, for example, for producing the following compound, which exhibits pesticidal activity. Reference Example 1 Preparation of 1,l-dimethyl-3-(4-heptafluoroisopropylphenyl)urea A tetrahydrofuran solution (2 ml) containing 4-heptafluoroisopropylphenyl isocyanate (1 g, 3.5 ramols) was added into tetrahydrofuran (15 ml) containing dimethylaruine (50% aq., 0.38 g, 4.2 mmol-s) at room temperature. The resulting reaction mixture was stirred further for 2 hours, then poured into water, extracted with ethyl acetate, the organic layer was washed with a saturated aqueous sodium chloride solution, then the solvent was distilled off under reduced pressure, and the residue obtained was purified by column chromatography to obtain the intended product (0.84 g, yield 75%) . Physical property: m.p. 151.4 - 154.2°C Reference Example 2: Test for herbicidal effect on paddy field weeds pre-emergence Soil was filled into 1/10000 are pots and brought into a state of paddy field, in which seeds of barnyard grass (Echinochloa crus-galli Beauv.) and bulrush (Scirpus juncoides Ro^cb. ) were made to be before germination. The soil in the pots were treated with a solution containing a predetermined dosage of a chemical agent comprising a compound obtained in Reference Example 1 as the active ingredient. Twenty one days after the treatment, the herbicidal effect was investigated, the result was compared with that in untreated plot to calculate the weedkilling rate, and the herbicidal effect was judged according to the following criterion. Criterion for herbicidal effect: 5 Weedkilling rate is 100%. 4 Weedkilling rate is 90-99%. 3 Weedkilling rate is 70-89%. 2 Weedkilling rate is 40-69%. 1 Weedkilling rate is 1-39%. 0 --- Weedkilling rate" is 0%. At the same time, phytotoxicity on paddy rice was investigated, and judged according to the following criterion. Criterion for phytotoxicity on paddy rice: 5 Weedkilling rate is 100%. 4 Weedkilling rate is 90-99%. Weedkilling rate Weedkilling rate Weedkilling rate Weedkilling rate is 70-89%. is 40-69%. is 21-39%. is 0-20 (No phytotoxicity). 3 2 1 0 As a result, herbicidal effects on barnyard jrass (Echinochloa crus-galli Beauv.) and bulrush (Scirpus juncoideg Roxb.) were rated "4" and "2" at the iosage of 5 kg/ha, and there was no phytotoxicity (rated "0") on the paddy rice treated. Reference Example 3: Herbicidal effect on upland weeds pre-emergence Polyethylene-made vats having a size of 10 cm (length) x 20 cm (width) x 5 cm (height) were filled with soil, sown with seeds of Arabidopsjg thialiana, bent grass (Agrestic spp.) and raonochoria (Mofiochoria veginalis), and with seeds of wheat and soybean plant as upland crop plants, and then covered with soil. Then, a liquid preparation of an agent comprising a prescribed concentration of a compound obtained in Reference Example 1 as active ingredient was sprayed. Fourteen days after the treatment, the herbicidal effect was investigated, from which weed-killing rate was calculated in the same manner as in Reference Example 2, and the herbicidal effect was judged. At tlie same time, phytotoxicity on soybean plant and wheal: was investigated and judged according to the criterion mentioned in Reference Example 1. As a result, herbicidal effects' on Arahidopsis ihuLllana and monochoria (Honochoria veainalis) wer" rated "5", and that of bent grass fAarostis spp.) was rated "4" respectively, at the dosage of 5 kg/ha. Further, there was no phytotoxicity (rated "0") on the wheat and soybean plant treated. Reference Example 4: Herbicidal effect on upland weeds after emergenc Poly-thylene-made vats having a size of 10 cm (length) x 20 ':m (width) x 5 cm (height) were filled with soil, sow:, with the seeds of the upland weeds mentioned below and with seeds of soybean plant and wheat as uplaiW crop plants, and then covered with soil. The plants were made to grow up until they reached the 1 ».o 2 leaved stage, after which an agent comprising a prescribed concentration of a compound obtained in Reference Example 1 as active ingredient was sprayed. Four'.een days after the treatment, the herbicidal effect was investigated, from which weed-killing rate w-,s calculated in the same manner as in Reference Example 2 and the results were judged. At the same time, phytotoxicity on soybean plant and wheat was inv—^-^^ and iudc?ed in the same manner as in WE CLAIM: 1. A perfluoroisopropylbenzene derivative represented by the formula (I) or salts thereof: wherein Xx is a hydrogen atom, halogen atom, 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 alkylcarbonyloxy (C1-C6)) alkyl group; X2 is a hydrogen atom, halogen atom, formyl group, hydroxy group, (C1-C6)alkyl group, halof(C1-C6) alkyl group, (C1-C6) (C1-C6) (C1-C6) alkoxy group, (Cx-C6) alkylthio group, ((C1-C6)) alkylsulf inyl group, (C1-C6) alkylsulf onyl group, hydroxy ((C1-C6)) alkyl group or -C(=0)-R1 (wherein RX is a hydrogen atom, halogen atom, hydroxy group, (C1-C6) alkyl group, ((C1-C6) alkoxy group or NR2R3 (wherein R2 and R3 may be the same or different and are each a hydrogen atom, (C1-C6)alkyl group or (C1-C6)alkoxy group)); X3 is a hydrogen atom, halogen atom, hydroxy group, cyano group, isocyanate group, isothiocyanate group, hydrazino group, diazo group, mercapto group, (C1-C6)alkoxy group, (C1-C6) alkylthio group, -C(=0)-R1 (wherein R, is the same as defined above) or -S07-R4 (wherein R4 is a halogen atom, hydroxy group, (C1-C6) alkyl group or NR5R6 (wherein R5 and R6 may be the same or different and are each a hydrogen atom or (C1-C6) C6)alkyl group)); and X4 is a hydrogen atom, halogen atom, (C1-C6)alkyl group or (C1-C6) alkoxy group; provided that (1) when X17 X2 and X4 are each a hydrogen atom, then X3 is not a hydroxycarbonyl group or methoxycarboxyl group, (2) when X1 and X4 are each a hydrogen atom and X2 is a formyl group, then X3 is not a methoxy group, (3) when any one of Xx, X2 and X3 is a methoxy group, then X4 and the remaining two of Xx, X2 and X3 are not each a hydrogen atom, (4) when any one of X2 and X3 is a hydroxyl group, then Xx, X4 and the remaining one of X2 and X3 are not each a hydrogen atom, (5) when any one of X1; X2, X3 and X4 is a fluorine atom, then the remaining three of Xlf X2, X3 and X4 are not each a hydrogen atom, (6) when Xx, X2 and X4 are each a hydrogen atom, then X3 is not a chlorine atom, bromine atom or iodine atom, (7) when any one of Xlf X2, X3 and X4 is a methyl group, then the remaining three of Xlf X2, X3 and X4 are not each a hydrogen atom, (8) when X17 X2 and X4 are each a hydrogen atom, then X3 is not an isopropyl group or chloromethyl group, (9) when Xx, X3 and X4 are each a hydrogen atom, then X2 is not a trifluoromethyl group, (10) when Xx and X4 are each a methyl group and X2 is a hydrogen atom, then X3 is not a hydrogen atom or heptafluoroisopropyl group, (11) when Xa and X3 are each a hydrogen atom and any one of X2 and X4 is a hydrogen atom, then the remaining one of X2 and X4 is not a heptafluoroisopropyl group, (12) when Xx is a hydrogen atom, X3 is a hydroxycarbonyl group, and any one of X2 and X4 is a hydrogen atom, then the remaining one of X2 and X4 is not a heptafluoroisopropyl group, (13) when Xu X2 and X4 are each a hydrogen atom, then X3 is not a chlorocarbonyl group, (14) when any three of Xl X2, X3 and X4 are each a hydrogen atom, then the remaining one of Xl X2, X3 and X4 is not a hydrogen atom or nitro group, (15) when X3 is a hydrogen atom, any two of Xx, X2 and X4 are each a hydrogen atom, then the remaining one of Xw X2 and X4 is not a methoxycarbonyl group, (16) when Xl X2 and X4 are each a hydrogen atom, then X3 is not a heptafluoroisopropyl group, (17) when X3 and X4 are each a hydrogen atom, any one of Xl and X2 is a hydrogen atom, then the remaining one of X1 and X2 is not an iodine atom, (18) each of Xl X2, X3 and X4 does not simultaneously represent a fluorine atom, (19) when Xx is a hydrogen atom, any two of X2/ X3 and X4 are each a hydrogen atom, then the remaining one of X2, X3 and X4 is not a 2,2,2-trifluoro-l-trifluoromethylethyl group, and (20) when Xx and X3 are each a hydrogen atom, any one of X2 and X4 is a hydrogen atom, then the remaining one of X2 and X4 is not a bromine atom or hydroxycarbonyl group. 2. The perfluoroisopropylbenzene derivative or the salts thereof according to claim 1, wherein Xx is a formyl group, (C1-C6) alkyl group, halo (C1-C6) alkyl group, hydroxy (C1-C6) alkyl group or (C1-C6) alkylcarbonyloxy (C1-C6) C6) alkyl group; and X2, X3 and X4 are each a hydrogen atom, 3. The perfluoroisopropylbenzene derivative or the salts thereof according to claim 1, wherein Xx, X3 and X4 are each a hydrogen atom; and X2 is a alkyl group, halo (C1-C6) alkyl group, hydroxy (C1-C6) 4. alkyl group, (C1-C6) alkyl carbonyl group or -C (=0)-Ra (wherein Rx is a hydrogen atom, halogen atom, (Cx-C6) alkyl group, (C2-C6) alkoxy group, or NR2R3 (wherein R2 and R3 may be the same or different and are each a hydrogen atom, (C1-C6)alkyl group or (C1-C6) alkoxy group)), provided that X2 is not a heptafluoroisopropyl group, or 2,2,2-trifluoro-l-trifluoromethylethyl group. 4. The perfluoroisopropylbenzene derivative or the salts thereof according to claim 1, wherein Xx, X2 and X4 are each a hydrogen atom; and X3 is an isocyanate group, isothiocyanate group or (C1-C6)alkylcarbonyl group. 5. The perfluoroisopropylbenzene derivative or the salts thereof according to claim 1, wherein X2 and X4 are each a hydrogen atom; X2 is a hydroxy group, (Cx-C6) alkyl group or (C^-Cg) alkoxy group; and X3 is a halogen atom, hydroxy group, cyano group, isocyanate group, isothiocyanate group, hydrazino group, -C(=0)-Rx (wherein Rx is a hydrogen atom, hydroxy group, halogen atom, (C1-C6)alkyl group, (C1-C6) alkoxy group or NR2R3 (wherein R2 and R3 may be the same or different and are each a hydrogen atom, (C1-C6) alkyl group or (C1-C6) alkoxy group) ) or -S02-R4 (wherein R4 is a halogen atom, hydroxy group or NR5R6 (wherein R5 and R6 may be the same or different and are each a hydrogen atom or (C1-C6) alkyl group)). 6. The perfluoroisopropylbenzene derivative or the salts thereof according to claim 1, wherein Xx and X4 are each a hydrogen atom; X2 is a halogen atom; and X3 is a halogen atom or -C(=0)-R1 (wherein RX is a halogen atom, hydroxy group, (C1-C6) alkyl group, (C1-C6)alkoxy group or NR2R3 (wherein R2 and R3 may be the same or different and are each a hydrogen atom or (C1-C6) alkyl group)). 7. The perfluoroisopropylbenzene derivative or the salts thereof according to claim 1, wherein Xx is a halogen atom or (C1-C6)alkyl group; X2 and X4 are each a hydrogen atom; and X3 is a halogen atom, hydroxy group, cyano group, diazo group, -C(=0)-R1 (wherein RX is a halogen atom, hydroxy group, (C1-C6)alkyl group, [Cx-C6) alkoxy group or NR2R3 (wherein R2 and R3 may be the same or different and are each a hydrogen atom or (Cx-C6)alkyl group)) or S02-R4 (wherein R4 is a halogen atom, hydroxy group or NR5R6 (wherein R5 and R6 may be the same or different and are each a hydrogen atom or (C1-C6) alkyl group) ) . 8. The perfluoroisopropylbenzene derivative or the salts thereof according to claim 1, wherein X2 and X4 are each a hydrogen atom; Xx is a (C1-C6)alkylthio group; and X3 is a halogen atom or -C(=0)-R1 (wherein Rx is a halogen atom, hydroxy group or (Cx-C6)alkoxy group). 9. The perfluoroisopropylbenzene derivative or the salts thereof according to claim 1, wherein Xx is a hydrogen atom; X2 and X4 are each a (Cx-C6) alkyl group; and X3 is a halogen atom, hydrazine group, -C(=0)-R1 (wherein Rt is a halogen atom, hydroxy group, (C^- C6) alkyl group, (C1-C6) alkoxy group or NR2R3 (wherein R2 and R3 may be the same or different and are each a hydrogen atom or (C1-C6) alkyl group)) or -S02-R4 (wherein R4 is a halogen atom, hydroxy group or NR5R6 (wherein R5 and R6 are the same as defined above)). 10. The perfluoroisopropylbenzene derivative and the salts thereof according to claim 1, wherein Xx is a hydrogen atom; X2 and X4 are each a methoxy group; and X is a hydroxy group. 11. The perfluoroisopropylbenzene derivative and the salts thereof according to claim 1, wherein X2, X3 and X4 are each a hydrogen atom; and Xx is a formyl group, hydroxymethyl group, chloromethyl group, bromomethyl group or acetoxymethyl group. 12. The perfluoroisopropylbenzene derivative and the salts thereof according to claim 1, wherein Xx, X3 and X4 are each a hydrogen atom; and X2 is a formyl group, ethyl group, chloromethyl group, hydroxymethyl group, acetyl group or N-methoxy-N-methylaminocarboxyl group. 13. The perfluoroisopropylbenzen derivative or the salts thereof according to claim 1, wherein Xx, X2 and X4 are each a hydrogen atom; and X3 is an isocyanate group or acetyl group. 14. The perfluoroisopropylbenzene derivative or the salts thereof according to claim 1, wherein Xx and X4 are each a hydrogen atom; X2 is a methyl group; and X3 is a chlorine atom, bromine atom, iodine atom, hydroxy group, cyano group, isothiocyanate group, hydrazino group, (C1-C6) (wherein Rx is a hydrogen atom, chlorine atom, hydroxy group, methoxy group or amino group) or -S02-R4 (wherein R4 is a chlorine atom or amino group). 15. The perfluoroisopropylbenzene derivative or the salts thereof according to claim 1, wherein Xx and X4 are each a hydrogen atom; X2 is a methoxy group; and X3 is a chlorine atom, bromine atom, iodine atom, cyano group, hedroxy group, mercapto group, isocyanate group, isothiocyanate group, "C(=0)-R1 (wherein RX is a hydrogen atom, chlorine atom, methoxy group, hydroxy group or amino group) or -S02-R4 (wherein R4 is a chlorine atom or amino group). 16. The perfluoroisopropylbenzene derivative or the salts thereof according to claim 1, wherein Xx and X4 are each a hydrogen atom; X2 is a fluorine atom; and X3 is a bromine atom or -C(=0)-R1 (wherein RX is a chlorine atom, hydroxy group, methoxy group or ethoxy group). 17. The perfluoroisopropylbenzene derivative or the salts thereof according to claim 1, wherein X2 and X4 are each a hydrogen atom; Xx is a methyl group; and X3 is a bromine atom, hydroxy group, cyano group, diazo group, -C(=0)-Rx (wherein Rx is a chlorine atom, hydroxy group, methyl group, methoxy group or amino group) or -S02-R4 (wherein R4 is a chlorine atom or amino group) . 18. The perfluoroisopropylbenzene derivative or the salts thereof according to claim 1, wherein X2 and X4 are each a hydrogen atom; Xx is a fluorine atom; and X3 is a chlorine atom, bromine atom, cyano group, -C(-0)-R1 (wherein Ra is a chlorine atom, hydroxy group, methyl group, methoxy group or amino group) or -S02-R4 (wherein R4 is a chlorine atom or amino group) . 19. The perfluoroisopropylbenzene derivative or the salts thereof according to claim 1, wherein X2 and X4 are each a hydrogen atom; X, is a methylthio group; and X3 is a bromine atom, iodine atom or -C(=0)-R! (wherein Rx is a chlorine atom, hydroxy group or methoxy group) . 20. The perfluoroisopropylbenzene derivative or the salts thereof according to claim 1, wherein Xa is a hydrogen atom; X2 and X4 are each a methyl group; and X3 is a chlorine atom, bromine atom, iodine atom, carboxyl group, methoxycarbonyl group, acetyl group, hydrazino group or -S02-R4 (wherein R4 is a chlorine atom or amino group). 21. The perfluoroisopropylbenzene derivative or the salts thereof according to claim 1, wherein Xx is a hydrogen atom, X2 and X4 are each a methoxy group and X3 is a hydroxy group.

Full Text

DESCRIPTION PERFLUOROISOPROPYLBENZEN DERIVATIVE
TECHNICAL FIELD
This invention relates to a novel perfluoro-isopropylbenzene derivative or salts thereof.
BACKGROUND ART
Since perfluoroisopropylbenzenes have a perfluoroalkyl group, which exhibits mainly physicochemically distinctive features, they are useful as intermediates or raw materials for synthesizing agricultural chemicals, medicines, dye stuffs surface active agents, wetting agents, dispersing agents, rubber materials, releasing agents, water and oil repelling agents, optical materials, gas separation membrane materials, resist materials, antifouling paints, weather-proofing paints,- paper-converting agents, textile-treating agents, functional resins having such characteristics as heat resistance and weather resistance, antistatic agents, photographic toners, liquid crystal materials and solvents (refer, for example, to "Advanced Technology of Halogen Chemicals" published by CMC).
Heretofore,' not many reports have been made on examples of production of perfluosoisopropyl-benzenes.
Previously known methods in the literature

for introducing a perfluoroisopropyl group into a benzene ring are, for example:
(a) a method of replacing a halogen in a
halogenated benzenes by using 2-iodoheptafluoropropane
in the presence of metallic copper, for example,
methods described in (1) Tetrahedron, £5, 5921 (1969),
(2) German Patent publication No. 2606982, (3) Journal Chem. Soc. Jpn., 1876 (1972), (4) J. Chem. Soc. Perkin Trans. 1, 661 (1980), and (5) Bull. Chem. Soc. Jpn., 65, 2141 (1992). These methods, however, are industrially disadvantageous in that prior introduction of a halogen atom to the appropriate position of benzenes is necessary, excess of copper is required and the reaction temperature is high. Moreover, depending on the kind of substituents of benzenes, the yield is low and good results are not obtained.
(b) a method of reacting hexafluoropropene on
fluoronitrobenzenes in the presence of a fluorine
anion, for example, the methods described in (1) J.
Chem. Soc. C, 2221 (1968), (2) J. Soc' Org. Synth.
Chem., Jpn., 21, 993 (1969), (3) J. Chem. Soc. Jpn.,
198 (1976) and (4) Tetrahedron, 51, 13167 (1995). In
these methods, however, the substrateis which can be
used are restricted to those which have been strongly
activated by electron withdrawing groups, e.g.,
perfluoronitrobenzenes and dinitrofluorobenzenes, so that the methods are limited as to the substituent, structure, etc. of obtainable compounds.

(c) a method of reacting an unsubstituted or
substituted phenyl Grignard reagent with
hexafluoroacetone and then reacting 1-hydroxy-l-trifluoromethyl-2,2,2-trifluoroethylbenzenes thus obtained with an appropriate fluorinating agent, for example, the method described in Canadian Pat. No, 1,022,573. This method, however, is not always economically advantageous because it uses in the reaction industrially difficult-to-handle reagents, such as hydrofluoric acid and SF4.
(d) a method of reacting (heptafluoroisopropyl)
phenyliodonium trifluoromethanesulfonate with phenols
to obtain perfluoroisopropylphenols, described in Bull.
Chem. Soc. Jpn., .57., 3361 (1984). This method,
however, is not promising for industrial practice owing
to the use of expensive reagent and low selectivity as
to the perfluoroisopropylated position of the compound
obtained.
(e) a method of reacting iodobenzenes, in the
presence of palladium catalyst, with a
perfluoroisopropylzinc compound prepared from 2-iodoheptafluoropropane and zinc in the system, to obtain perfluoroisopropylbenzenes, described in Chemistry Letters, 137 (1982). This method, however, is not industrially advantageous owing to its reaction conditions wherein zinc is to be used and the reaction needs to be conducted under ultrasonic waves.
In the prior processes for producing

perfluoroisopropylbenzenes, the intended compounds are produced by introducing a perfluoroisopropyl group into intended benzenes by the above-mentioned methods or by subjecting the perfluoroisopropylbenzenes produced'by the above-mentioned methods to structural transformation. Both processes are not satisfactory in
practice.
Since previous processes are thus not suited to practical use, few examples are known of the production of perfluoroisopropylbenzenes. However, since the perfluoroisopropyl group is a substituent having distinctive features both physically and biochemically, the literature in several fields describes the. usefulness of benzenes having a perfluoroisopropyl group introduced thereinto.
As to benzoic acids having a perf luoroisopropyl group as a subs-ituent/ for example, JP-A-9-319147 discloses that phthalic acids having a perfluoroisopropyl group on the benzene ring is useful as a positively chargeable charge-controlling agent and as a toner for electrostatic image developing, and JP-A-59-69755 discloses that some of -he benzoic amides having a perfluoroisopropyl group are useful as a
photographic cyan coupler.
As to 'perfluoroisopropylber.zenesulfomc
acids, for exmaple, U.S.P. No. 35C1322 describes that some of the sulfonic acids and their salts are useful as a wetting agent and dispersing agent and discloses a

method of producing 4-heptafluorobenzoic acid from 1-methyl-4-(l-trifluoromethyl-l-hydroxy-2,2,2-trifluoroethyl)benzene as the starting material via 1-methyl-4-heptafluoroisopropylbenzene. This method, however, is industrially disadvantageous because it uses highly toxic reagent as SF4 and chromic acid and hence results in high cost of production facilities and waste proposal.
In the previous known methods, in general, it is necessary to introduce a halogen atom beforehand to the position into which a perfluoroisopropyl group is to be introduced, or the benzenes to which a perfluoroisopropyl group can be introduced are limited to those having a certain substituent, such as phenols and nitrobenzenes. Consequently, the kinds of substituents of perfluoroisopropylbenzenes produced in the past are small in number. Furthermore, all of the methods described aboye are not suited to mass production. Therefore, in spite of the perfluoroisopropyl group being a substituent which has physically distinctive features and is promising for its usefulness in various fields, not much perfluoroisopropylbenzenes have hitherto been produced.
DISCLOSURE OF THE INVENTION
The objects of this invention are to provide a novel and useful perfluoroisopropylbenzene derivative or the salts thereof, and to provide a process for

producing, in the manner described in JP-11-229304, various perfluoroisopropylbenzene derivatives in a simple manner and with good yield by using easily producible perfluoroisopropylanilines, and various novel perfluoroisopropylbenzene derivatives.
According to this invention, there are provided a perfluoroisopropylbenzene derivative represented by the formula (I) or salts thereof:

i-CtF, ( ) X, 0)
-3r7

wherein Xx is a hydrogen atom, halogen atom, formyl group, (C^-Cg) alkyl group, halo (C^-Cg) alkyl group, (Ct-C6)alkoxy group, (C^-Cg) alkylthio group, hydroxy (C:-C6) alkyl group or (Cx-C6) alkylcarbonyloxy (Cx-Ce) alkyl group; X2 is a hydrogen atom, halogen atom, formyl group, hydroxy group, (C^-Cg) alkyl group, halolC^-C6) alkyl group, (C^-Cg) alkoxy group, "(C^Cg) alkylthio group, (Cj^-Cg) alkylsulfinyl group, (C^-Cg) alkylsulfonyl group, hydroxy (C1-C6) alkyl group or -C(=0)-R1 (wherein RX is a hydrogen atom, halogen atom, hydroxy group, (Cx-C6) alkyl group, (C^Cg) alkoxy group or NR2R3 (wherein R2 and R3 may be the same or different and are each a

hydrogen atom, (C1-C6)alkyl group or (d-CJ alkoxy group)); X3 is a hydrogen atom, halogen atom, hydroxy group, cyano group, isocyanate group, isothiocyanate group, hydrazino group, diazo group, mercapto group, (C^-Cs) alkoxy group, (Ci-CJ alkylthio group, -c (=0) -R1 (wherein Rx is the same as defined above) or -S02-R4 (wherein R4 is a halogen atom, hydroxy group, (C^-CJalkyl group or NR5R6 (wherein R5 and R6 may be the same or different and are each a hydrogen atom or (Cx~ C6)alkyl group)); and X4 is a hydrogen atom, halogen atom, (Ci-C^alkyl group or (C^Cg) alkoxy group; provided that
(1) when Xx, X2 and X4 are each a hydrogen atom, then X3 is not a hydroxycarbonyl group or methoxycarboxyl group,
(2) when Xx and X4 are each a hydrogen atom and X2 is a formyl group, then X3 is not a inethoxy group,

(3) when any one of Xl7 X2 and X3 is a methoxy group, then X4 and the remaining two of Xx/ X2 and X3 are not each a hydrogen atom,
(4) when any one of X2 and X3 is a hydroxyl group, then Xx, X4 and the remaining one of X2 and X3 are not each a hydrogen atom,

(5) when any one of X17 X2, X3 and X4 is a fluorine atom, then the remaining three of Xx, X2, X3 and X4 are not each a hydrogen atom,
(6) when Xx, X2 and X4 are each a hydrogen atom, then X3 is not a chlorine atom, bromine atom or iodine

atom,
(7) when any one of X:, X2, X, and X4 is a methyl
group, then the remaining three of X^ X2, X3 and X4 are
not each a hydrogen atom,
(8) when xlf X2 and X4 are each a hydrogen atom, then X3 is not an isopropyl group or chloromethyl group,
(9) when Xx, X3 and X4 are each a hydrogen atom, then X2 is not a trifluoromethyl group, and
(10) when X1 and X4 are each a methyl group and X, is a hydrogen atom, then X3 is not a hydrogen atom or heptafluoroisopropyl group.
MODE FOR CARRYING OUT THE INVENTICM .
As to the definition of the formula (I), which represents the perfluoroisopropylbenzene derivative of this invention, in the definition of its respective substituents, "i" means iso, "sec-" means secondary and "t" means tertiary, an "alkyl group" or "alkyl", which indicates an alkyl moiety, may be both of a straight chain or a branched chain, and a " (C\-C6)alkyl group" refers to an alkyl group having 1-6 carbon atoms, which may be, for example, a methyl group, ethyl group, propyl group, i-propyl group, butyl group, sec-butyl group, t-butyl group, neopentyl group., 1,2-dimethylpropyl group, hexyl group and heptyl group.
A "halogen atom" indicates a chlorine atom, bromine atom, iodine atom or fluorine atom; a "halo [C^ C6) alkyl group, which may be the s^r.e or different,

indicates a straight or branched chain alkyl group having 1-6 carbon atoms wherein at least one of the hydrogen atoms has been substituted with a halogen atom, and may be, for example, a 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 and 6-bromohexyl group.
An "alkoxy group" or "alkoxy" moiety means a straight or branched chain alkoxy group, and a "{Cx-C6)alkoxy group" refers, for example, to a methoxy group, ethoxy group, i-propoxy group, sec-butoxy group, t-butoxy group, 1,2-dimethylpropoxy group and hexyloxy group.
A "halo (C^-Cg) alkoxy group", which may be the same or -different, indicates a straight or branched chain alkoxy group having 1-6 carbon atoms wherein at least one of the hydrogen atoms has been substituted with a halogen atom, and may be, for example, a difluoromethoxy group, trifluoromethoxy group, 2-chloroethoxy group, 2-bromoethoxy group, 2,2,2-trifluoroethoxy-group, pentafluoroethoxy group, .1,1, 2, 2-tetraf luoroethoxy group, 3-chlorobutoxy group, 3-bromobutoxy group, 1-chloropentyloxy group, 1-chlorohexyloxy group and 6-bromohexyloxy group.
A " (Ct-C6) alkylthio group" refers to a

straight or branched chain alkylthio gioup having 1-6 carbon atoms and may be, for example, • • methylthio group, ethylthio group, i-propylthio gioup, sec-butyl thio group, t-butylthio group and hexylthio group.
A "halo(Ci-CJ alkylthio group", which may be the same or different, refers to a str-ilght or branched chain alkylthio group having 1-6 carbon atoms wherein at least one of the hydrogen atoms has been substituted with a halogen atom, and may be, for example, a difluoromethylthio group, trifluoromethylthio group, 2,2,2-trifluoroethylthio group, 1,1,2,X-tetrafluoroethylthio group, 2-chloroeth'/lthio group and
3-bromoethylthio group.
A "hydroxy (Ci-CJalkyl group", which may be the same or different, refers to a straight or branched chain alkyl group having 1-6 carbon at/>.'ns wherein at least one of the hydrogen atoms has be';-'- substituted with a hydroxy group, and may be, for example, a hydroxymethyl group, 1-hydroxyethyl gro -P anci hydroxyethyl group.
Some examples of the represer.native processes for producing the perfluoroisopropylber.zene derivative represented by the formula (I) of this invention are described below,- but the invention is r.ot limited thereby-

p. 2497.
The compounds wherein W is a sulfur atom may be produced, for example, according to the methods described in J. Chem. Soc. (1942) p. 374, J. Am. Chem. Soc. (1946) 68, p. 2506, Liebigs Ann. Chem. (1962) 657, 98 and Bull. Chem. Soc. Jpn. (1975) 48, p. 2981.
The anilines represented by the formula (II), a starting material, may be produced according to the method described in JP-11-338707.

wherein Yx, Y2 and Y3 are the same as defined above, and Y4 is a hydrogen atom, halogen* atom, hydroxy .group, sulfonyl halide group or hydrazino g^oup or the salt
thereof.
/
By reacting a diazonium salt of an aniline, obtained by reacting an aniline represented by the formula (II) with sodium nitrite, etc. by using an acidic solvent, and a metal halide with each other in

the presence or absence of a metal catalyst, such as copper, the perfluoroisopropylbenzene derivative represented by the formula (I-b) can be produced.
In the present process, among the perfluoroisopropylbenzene derivatives represented by the formula (I-b), the compounds wherein Y4 is a hydrogen atom may be produced, for example, according to the methods described in J. Chem. Soc, p. 2095 (1949): Org. React., 2, p.262 (1944), Org. Synth., (1955) III, 295 and J. Am. Chem., £2, p.1251 (1961), those wherein Y4 is a fluorine atom according to the method described in Org. React., 5, p.193 (1949) and J. Org. Chem., JI6, p. 63 (1971), those wherein Y4 is a chlorine atom according to the method described in Org. Synth., I. p.170 (1941) and J. Chem. Soc, p.819 (1945), those wherein Y4 is a bromine atom according to the method described in Org. Synth. Ill, p.185 (1955) and J. Org. Chem., 23, p.1139 (1958) and those wherein Y4 is an iodine atom according to the method described in J. Org. Chem. 3, p.55 (1938), J. Am. Chem. Soc. 7_Q, p.157 (1948), J. Am. Chem. Soc. 92, p.2175 (1970) and J. Am. Chem. Soc. .93, p.4845 (1971).
The compounds wherein Y4 is a hydroxy group may be produced-, for example, according to the methods described in Org. Synth., I, p.404 (1941), Org. Synth., Ill, p.130 (1955), Can. J. Chem, 11, p.1653 (1963) and J. Org. Chem., 32, p.3844 (1967), those wherein Y4 is a sulfonyl halide group according to the methods

described in J. Prakt. Chem. [2]152, p.251 (1939) and Reel. Trav. Chiiru Pays-Bas., £1/ p.22 (1965), and those wherein Y4 is a hydrazine) group or its salt according to the method described in Org. Synth., I, p.442 (1941)'.
In the perfluoroisopropylbenzene derivatives, the compounds wherein Y4 is an aldehyde group may be produced by oxidizing the compounds wherein Y4 is a hydroxy group obtained by the above-mentioned methods, according to a conventional method.

wherein Ylf Y2 and Y3 are the same as defined above, Y5 is a chlorine atom, iodine atom or bromine atom, and R is a hydrogen atom or (C^-C^)alkyl grdup.
By reacting the halogenated benzenes represented by the formula (III) with carbon monoxide in the presence of a base, organic phosphorus compound, such as triphenylphosphine and bisdiphenyl-phosphinobutane, transition metal, such as palladium,

nickel and cobalt, or its complex, and an inert solvent, the perfluoroisopropylbenzene derivatives represented by the formula (I-c) can be produced.
This process can be conducted, for example, according to the methods described in Bull. Chem. Soc. Jpn., I£, p.2075 (1975) and J. Am, Chem. Soc. Ill, p.8742 (1989).
By starting from the perfluoro-isopropylbenzene derivatives represented by the formula (I-c) and through the method described below, ^erfluoroisopropylbenzene derivatives represented by :he formulas (I-d), (I-e), (I-f) and (I-g) can be produced.

wherein Y17 Y2, Y, and R are the same as defined above, and Hal is a halogen atom.
shown above may be conducted by conventional metr-^ds .
EXAMPLES
Some representative examples of this invention are described below with reference to Examples, but the invention is not limited thereto. 1. Preparation of halobenzenes Example 1 Preparation of l-chloro-4-heptafluoro-
isopropylbenzene

Concentrated hydrochloric acid (30 ml) was diluted with water (10 ml), and 4-heptafluoro-isopropylaniline (10 g, 38.3 mmols) was added thereto to form a suspension. Th'en, aqueous sodium nitrite (2.9 g, 42 mmols) solution (10 ml) was slowly added thereto so that the reaction temperature might be not higher than 10°C. After completion of the addition, the reaction mixture was stirred for further 20 minutes. The resulting diazonium salt solution was slowly added at room temperature to a solution of copper chloride (I) (5.7 g, 57 mmols) in hydrochloric acid (25 ml) prepared separately. Then the reaction mixture was stirred at room-temperature for 30 minutes, heated for 1 hour, then cooled to room temperature, hexane was added to the reaction mixture to separate an organic layer, the organic layer was washed once with water, twice with an aqueous sodium thiosulfate solution and once with a saturated aqueous sodium chloride solution, dried with anhydrous sodium sulfate, and then concentrated under reduced pressure to obtain a crude product (8.6 g, yield (crude) 80%) of the intended compound.
Physical property: ^-NMR 5(CDC13): 7.49(d, 2H) , 8.07(d, 2H).
Example 2 Preparation of l-bromo-2-fluoro-4-heptafluoroisopropylbenzene

An aqueous 47% hydrogen bromide solution (50 ml) was diluted with water (15 ml), and 2-flnoro-4-heptafluoroisopropylaniline (15,7 g, 56 mmol."t a time at 65°C to a separately prepared solution of copper bromide (I) (4.0 g, 26 mmols) in an aqueous 47% hydrogen bromide solution (40 ml) , the resul1 i-n(3 reaction mixture was stirred at 60-80°C for '/ hours, then cooled to room temperature, hexane was odded thereto to separate an organic layer, the organic layer was washed once.with water, twice with an aq~;eous sodium thiosulfate solution and once with a saturated aqueous sodium chloride solution. Then the organic layer was dried with anhydrous sodium sulfate and concentrated under reduced pressure to obtai'- a crude product (15 g, yield (crude) 78%) of the intended compound.

Physical property: ^-NMR 5(CDC1,): 7.294(d, 1H) , 7.39(d, 1H), 7.72 (t, 1H) . nD 1.4318 (21.3°C)
Example 3 Preparation of l-bromo-3-heptafluoro-isopropylbenzene

An aqueous hydrochloric acid solution (60 ml) was diluted with water (20 ml), and 2-bromo-4-heptafiuoroisopropylaniline (20 g, 59 mmols) was added thereto to form a suspension. Then an aqueous sodium nitrite (4.3 g, 62 mmols) solution (15 ml) was slowly added to the suspension so that the reaction temperature might be 5°C. After completion of the addition, the reaction mixture was stirred for further 30 minutes. To the resulting diazonium salt solution was added dropwise at 5-10°C hypophosphorous acid (35 ml) in several portions over 1 hour. After completion of the addition, the reaction mixture was further stirred at room temperature for 3 hours, then hexane was added thereto to separate an organic layer, the organic layer was washed once with water and once with an aqueous saturated sodium chloride solution, dried with anhydrous sodium sulfate, then concentrated under

reduced pressure, and the resulting residue was purified by column chromatography to obtain the intended product (17.2 g, yield (crude) 90%).
Physical property: XH-NMR 5(CDC13): 7.39 (t, 1H) , 7.554(d, 1H) , 7.69 (m, 1H) , 7.76(s, 1H) .
Example 4 Preparation of 4-heptafluoroisopropyl-iodobenzene

In an ice bath, concentrated sulfuric acid (7.5 g, 76.6 mmols) was diluted with water (30 ml), and 4-heptafluoroisopropylaniline (10 g, 38.3 mmols) was added thereto. Then an aqueous sodium nitrite (2.9 g, 42 mmols) solution (20 ml) was slowly added so that the reaction temperature might be not higher than 0°C, the reaction mixture was further stirred for 20 minutes, and then concentrated sulfuric acid (3.8 g) was added. The resulting diazonium salt solution was slowly added at room temperature to a separately prepared aqueous potassium iodide (9.5 g, 57.5 mmols) ■ solution (20 ml). Then the resulting mixture was heated under reflux for 1 hour, then cooled to room- temperature, hexane was added thereto to separate an organic layer, the organic layer was washed once with water, twice with an aqueous sodium thiosulfate solution and once with an aqueous

saturated sodium chloride solution, dried with anhydrous sodium sulfate, and then concentrated under reduced pressure to obtain a crude product (13 g, yield (crude) 87%) of the intended compound.
In the same manner as above, the following perfluoroisopropylbenzene derivatives were obtained. l-chloro-3-fluoro-4-heptafluoroisopropylbenzene
Physical property: XH-NMR 5(CDC13); 7.23-7.33(m, 2H), 7.56(t, 1H),
19F-NMR 5(CDC13) ; -75.82(6F), -106.73 (IF), -178.6(1F). l-chloro-2,6-dimethyl-4-heptafluoroisopropylbenzene
Physical property: ^I-NMR 5(CDC13); 2.44 (s, 6H) , 7.305(s, 2H). l-chloro-4-heptafluoroisopropyl-2-methylbenzene
Physical property: ^-NMR 5(CDC13); 2.45 (s, 3H) , 7.38(d, 1H), 7.4 6(m, 2H). l-chloro-4-heptafluoroisopropyl-2-methoxybenzene
Physical property: ^-NMR 5(CDC13); 3.95 (s, 3H) , 7.12(s, 1H), 7.14 (d, 1H), 7.50(d, 1H) . l-bromo-4-heptafluoroisopropyl-2-methylbenzene
Physical property: ^-NMR 8(CDC13); 2.48 (s, 3H) ,
/,
7.27(d, 1H) , 7.45(s, 1H) , 7.66(d, 1H);. l-bromo-4-heptafluoroisopropy1-3-methylbenzene
Physical property: 'H-NMR 5 (CDC13) ; 2.50(d, 3H) , 7.34(d, 1H) , 7.42(d, 1H) , 7.46(s, 1H) . l-bromo-2,6-dimethyl-4-heptafluoroisopropylbenzene
Physical property: ^-NMR 5 (CDC13) ; 2.48 (s, 6H) ,

7.29(s, 2H). l-bromo-4-heptafluoroisopropyl-2-methoxybenzene
Physical property: XH-NMR 8 (CDC13) ; 3.944(s, 3H) , 7.08 (brs, 2H), 7.67(d, 1H) . l-bromo-3-fluoro-4-heptafluoroisopropylbenzene
Physical property: ^-NMR 8(CDC13); 7.39-7.52(m, 3H) .
19F-NMR 5(CDC13) ; -75.77(6F), -106.64(1F), -178.61(IF). l-bromo-4-heptafluoroisopropyl-2-methylthiobenzene
Physical property: ^-NMR 8(CDC13); 2.51 (s, 3H) , 7.21(m, 1H), 7.285(s, 1H) , 7.645(d, 1H). l-bromo-2,6-dichloro-4-heptafluoroisopropylbenzene
Physical property: ^-NMR S(CDC13); 7.604 (s, 2H) . 19F-NMR 8(CDC13) ; -75.98 (6F), -182.61 (IF). l-iodo-4-heptafluoroisopropyl-3-methylbenzene
Physical property: 'H-NMR S(CDC13); 2.47(d, 3H) , 7.18(d, 1H), 7.62(d, 1H) , 7.68(s, 1H) .
nD 1.4142 (24.2°C) l-iodo-4-heptafluoroisopropyl-2-methylbenzene
Physical property: :H-NMR 5{CDC13); 2.504 (s, 3H) , 7.10(d, 1H), 7.44(s, 1H) , 7.94(d, 1H). l-iodo-2,6-dimethy1-4-heptafluoroisopropylbenzene
Physical property: XH-NMR 5;CDC13); 2.54(3, 6H) , 7.26(s, 2H) .
19F-NMR 8(CDC13) ; -76.15(d, 7F) , -183.28(m, IF) . 1-iodo-4-heptaf luoroisopropyl-2-ir.ethylbenzene

Physical property: lH-NMR .8 (CDC1,) ; 2,511s, Physical property:
H-NMR 5(CDC13); 2.50
7.06 (d, 1H) , 7.235(s, 1H) , 7.91(d, 1H) . l-iodo-4-heptafluoroisopropyl-2-methoxybenzene
Physical property: ^-NMR 5(CDC13); 3.93(3, '-H>, 6.94(d, 1H) , 6.98(s, 1H), 7.90(d, 1H).
2. Preparation of alkylbenzenes
Example 5 Preparation of l-methyl-2-heptafluoro-
isopropylbenzene

In an ice bath, concentrated hydrochlori' acid (90 ml) was diluted with water (30 ml), and a solution of 4-heptafluoroisopropyl-3-methylaniline ' 30 g, 109 mmols) in glacial acetic acid (30 ml) was a'-aec* thereto. Then, an aqueous sodium nitrite (8 g, 11'-mmols) solution-(15 ml) was slowly added so that t: ^ reaction temperature might not be higher than 5°C. After completion of the addition, the reaction mix" -re was further stirred for 1 hour, hypophosphrous aciv (50 ml) was added, the temperature of the mixture was

slowly increased, and the mixture was stirred at room temperature for 15 hours. Then hexane was added to the mixture to separate an organic layer, the organic layer was washed twice with water, once with an aqueous saturated sodium hydrogen carbonate solution and once with an aqueous saturated sodium chloride solution, dried with anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a crude product (19 g) of the intended compound.
According to similar reactions, the following compounds were prepared. 1-methyl-3~heptafluoroisopropylbenzene
Physical property: XH-NMR 5(CDC13); 2.42(s, 3H) , 7.35-7.41(m-4H). 1,2-dimethyl-3~heptafluoroisopropylbenzene
Physical property: 'H-NMR 5(CDC13); 2.35 (s, 3H) , 2.40(d, 3H), 7.13-7.19(m, 1H), 7.29-7.63(m, 2H). 1-ethyl-3-heptafluoroisopropylbenzene
Physical property: 'H-NMR 5 (CDC13) ; 1.27(t, 3H) , 2.73(dd, 2H), 7.37-7.48(m, 4H).
19F-NMR 8(CDC13) ; -76.23(d, 7F) , -183.G8(m, IF) . 1-chloromethyl-2-heptafluoroisopropylbenzene
Physical property: LH-NMR 8 (CDC13) ; 4.79(d, 2H) , 7.44(m, 1H), 7.52-7.63(m, 3H). l-methyl-2-heptafluoroisopropyl-5-methylthiobenzene
Physical property: XH-NMR 5 (CDC13) ; 2.49(d, 3H) , 2.495(s, 3H) , 7.09(s, 1H) , 7.11(d, 1H) , 7.37(d, 1H) .

2-heptafluoroisopropylbenzyl alcohol
Physical property: ^-NMR 5(CDC13); 'l.925(d, 2H) , 7.41 (d, 1H) , 7.51-7.59(111, 2H) , 7.81(d/ 1H/ • l-methyl-2-heptafluoroisopropyl-5-methoxyl"-nzene
Physical property: ^-NMR 8(CDC13); ;'-49(d, 3H) , 3.824(3, 3H), 6.78(s, 1H), 6.79(d, 1H) , 7.^0(d, 1H) .
nD 1.4114 (24.2°C) 2!-heptafluoroisopropylbenzyl acetate
Physical property: lH-NMR 5(CDC13); >'.125(s, 3H) , 5.32(d/ 2H) , 7.44(m, 1H), 7.51-7.59(m, 3H/« l-bromomethyl-2-heptafluoroisopropylbenze--"
Physical property: ^-NMR 5(CDC13); A.68(d, 2H) , 7.4 0-7.4 5(111, 1H) , 7.50-7.58 (m, 3H) .
3. Preparation of benzoic acids
Example 7 Preparation of methyl 4-heptaf i0ro"
isopropyl-3-methylbenzoate

In an^autoclave, l-iodo-4-hep~a: - uoro-isopropyl-3-methylbenzene (1.0 g, 2.6 mr.c - -■) > palladium chloride (10 ml, 2 mol%) , triphenylphosph: '-e 8 mol%) and triethylamine (0.52 g, 5.2 mmcl;.. were suspended in methanol (10 ml). Then, the -nner

atmosphere of the- autoclave was replaced by --'fbon monoxide, and the pressure in the vessel was wrought to about 14 atm. The suspension in the vessel v-,:i heated to about 120° and stirred for 8 hours- Then ' he reaction mixture was cooled to room temperat ,' '-' the insolubles were filtered off, and the filtrav was concentrated and then purified by silica gel ' 'luinn chromatography (hexane: ethyl acetate = 9:1) ' '> obtain the intended product (0.77 g, yield 94%).
Example 8 Preparation of ethyl 2-f luoro-4-h^ '•' a-
fluoroisopropylbenzoate

In an autoclave, l-bromo-2-fluoro-4 -heptafluoroisopropylbenzene (10.0 g, 29 mmols > dichlorobis (triphenylphosphine) palladium (1. C '•:'/ 5 mol%) and triethylamine (3.5 g, 35 mmols) wer=; suspended in ethanol (60 ml). Then, the inne' atmosphere of the autoclave was repalced by c^'-oon monoxide, and the pressure in the vessel was .- ' ^ught to about 14 atm. The suspension in the vessel w^ - heated to about 120°C and stirred for about 8 hours. :hen the reaction mixture was cooled to room temperatur - / the

insolubles were filtered off, and the filtrate was concentrated and then purified by silica gel column chromatography (hexane : ethyl acetate = 9 : 1) to obtain the intended product (7.4 g, yield 75%).
Example 9 Preparation of methyl 4-heptafluoro-isopropylbenzoate

In an autoclave, l-bromo-4-heptafluoroisopropylbenzene (11.8 g, 31.7 mmols), dichlorobis(triphenylphosphine)palladium (1.1 g, 5 mol%) and potassium carbonate (3.2 g, 31.7 mmols) were suspended in methanol (50 ml). Then the inner atmosphere of the autoclave was replaced by carbon monoxide and the pressure in the vessel was brought to about 14 atm. The suspension in the vessel was heated to about 110°C and stirred for 6 hours. Then the reaction mixture was cooled to room temperature, then the insolubles were filtered off, and the filtrate was concentrated and then purified by silica gel column chromatography (hexane : ethyl acetate = 9 : 1) to obtain the intended product (7.4 g, yield 75%).
In the same manner as described abovew, the following compounds were prepared.

methyl 2,6-dimethyl-4-heptafluoroisopropylbenzoate
Physical property: ^-NMR 5 (CDCl,/ ; 2.37(s, 6H) ,
3.94 (s, 3H), 7.27 (s, 2H) .
methyl 4-heptaf luoro isopropy 1-2-me thoxyi>enzont e
Physical property: ^-NMR 5(CDCl./; 3.92(s, 3H) , 3.95(s, 3H) , 7.19(S/ 1H) , 7.21(d, 1H) , 7.87(d, 1H) . methyl 4-heptafluoroisopropyl-2-methyl.o'-nzoat e
Physical property: m.p. 39 - 40°^' ethyl 2,6-dimethyl-4-heptafluoroisopropylbenzoate
Physical property: :H-NMR 5(CDCl; ; 1-4L(t, 3H) , 2.38(s, 6H) , 4.43(dd, 2H) , 7.33(s, 2H, . methyl 3-fluoro-4-heptafluoro isopropyl.v-nzoat.e
Physical property: LH-NMR 5(CDCl, ; 3.965(s, 3H) , 7.72(t, 1H), 7.86(m, 1H), 7.96(m, 1H). methyl 4-heptaf luoro isopropyl- 3-me thy l.o--nzoate
Physical property: ^-NMR 8(CDCl-: ; 2.59(d, 3H), 3.94(s, 3H), 7.56(d, 1H), 7.914(d, 1H. , 7.955(s, 1H). methyl 4-heptafluoroisopropyl-2-methyls ,lfonylbenzoate
Physical property: ^-NMR 8(CDCi-: ■ 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 processes relati'-':' to benzoic acids
U.S.P'. No. 3,462,482 descried'- that some benzoic anilides having a heptaf luorci I'-P^Py1
acaricide. It also discloses a process for producing 4-heptafluoroisopropylbenzoic acid used as a starting material therefor. In this process, 4-heptafluorobenzoic acid is prepared via 1-methyl-4-heptafluoroisopropylbenzene from l-methyl-4- (1-trifluoromethyl-1-hydroxy-2, 2, 2-trifluoroethyl)benzene as the starting material. This process, however, uses highly toxic compounds such as SF4 and chromic acid in the production and hence is not satisfactory for practical use.
According to the process of this invention, 4-heptafluoroisopropylbenzoic acid can be produced via 1-cyano-4-heptafluoroisopropylbenzene or 1-halo-4-heptafluoroisopropylbenzene (wherein "halo" denotes a chlorine atom, bromine atom or iodine atom) by using 4-heptafluoroisopropylaniline as the starting material; thus, the process is more suited to practical use.
Example 10 Preparation of 4-heptafluoroisopropylbenzoic acid

NaOH H+
i-C3F7 (( )> COOCH3 ► ► 1-C3F7 {[ )) COOH
McOH, H20

In an ice bath, a solution of sodium hydroxide (0,1 g, 2.5 mmols) dissolved in water (4 ml) was added dropwise to a solution of methyl 4-

heptafluoroisopropylbenzoate (0.5 g, 1.5 mmols) in ethanol (4 ml). The resulting mixture was stirred for about 2 hours, then hexane and water were added thereto, and an aqueous'layer was separated. The aqueous layer was made to acidify by addition of 3N hydrochloric acid, and ethyl acetate was added thereto to separate an organic layer. The organic layer was dried with anhydrous sodium sulfate, and then concentrated under reduced pressure to obtain the intended product (9.0 g, yield 93%).
Example 11 Preparation of 4-heptafluoroisopropyl-3-methylbenzoic acid

In an ice bath, a solution of sodium hydroxide (0.1 g, 2.5 mmols) dissolved in water (4 ml) was added dropwise to a solution of methyl 4-heptafluoroisopropyl-3-methylbenzoate (0.4 g, 1.3 mmols) dissolved in methanol (4 ml). . The resulting mixture was stirred for about 2 hours, and then hexane and water were added thereto to separate an aqueous layer. The aqueous layer was made to acidify by addition of 3N hydrochloric acid, and then ethyl acetate was added thereto to separate an organic layer.
, L

The organic layer was dried with anhydrous sodium sulfate and then concentrated under reduced pressure to obtain the intended product (0.32 g, yield 84%).
Example 12 Preparation of 2-fluoro~4~heptafluoro-isopropylbenzoic acid

In an ice bath, a solution of sodium hydroxide (0.1 g, 2.5 mmols) dissolved in water (4 ml) was added dropwise to a solution of ethyl 2-fluoro-4-heptafluoroisopropylbenzoate (0.5 g, 1.5 mmols) dissolved in ethanol (4 ml). The resulting mixture was stirred for about 2 hours, and then hexane and water were added thereto to separate an aqueous layer. The aqueous layer was made to acidify by addition of 3N hydrochloric acid, and then ethyl acetate was added thereto to -separate an organic layer. The organic layer was dried with anhydrous sodium sulfate, and then concentrated under reduced pressure to obtain the intended product (0.38 g, yield 83%).
In a similar manner, the following compounds ) were prepared.
2-fluoro-4-heptafluoroisopropylbenzoic acid

Physical property: ^-NMR 5 (CDC1,) ; 7.484(d, 1H) , 7.52(d, 1H), 8.18(t, 1H) , 10.55(brs, 1H). 4-heptafluoroisopropyl-2-methoxybenzoic acid
Physical property: ^-NMR 5 (CDC13) ; 4.124(s, 3H) > 7.28(3, 1H) , 7.37(1(1, 1H) , 8.27 (d, 1H) .
m.p. 96 - 97°C 4-heptafluoroisopropyl-2-methylbenzoic acid
Physical property: ^-NMR 5 (CDC13) ;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 property: ^-NMR 5 (CDC13) ; 2.505(s, '6H) , 7.34 (s, 2H) .
m.p. 80 - 81°C 3-fluoro-4-heptafluoroisopropylbenzoic acid
Physical property: ^-NMR 5 (CDC13) ; 7.784(t, 1H) , 7.94(d, 1H) , 8.05(111, 1H) , 11.40(brs, 1H) .
19F-NMR 5(CDC13) ; -75.49(6F), -107.54(1F), -178.29(1F) .
m.p. 54 - 58°C 4-heptafluoroisopropy1-3-methylbenzoic acid
Physical property: 'H-NMR .5 (CDC13) ; 2.62 (d, 3H) , 7.62(d, 1H) , 8.00(d, 1H) , 8.03(s, 1H>'.
m.p. 129 - 130°C 4-heptafluoroisopropy1-2-methylsulfonylbenzoic acid
Physical property: 'H-NMR 5 (CDC13) ; 3.45(s, 3H) , 7.99(m, 2H), 8.41(s, 1H), 9.42(brs, 1H).

4. Preparation of benzoic acid halides
Example 13 Preparation of 4-heptafluoroisopropyl-3-
methylbenzoyl chloride

4-Heptafluoroisopropyl-3-methylbenzoic acid (0.32 g, 1.0 initio 1) was dissolved in thionyl chloride (3 ml)r one drop of dimethylformamide (DMF) was added thereto, and the mixture was heated under reflux for 3 hours. After completion of reaction, the reaction mixture was cooled to room temperature, and thionyl chloride was distilled off under reduced pressure to obtain a crude product of the intended compound.
In a similar manner, the following compounds were prepared. 3-heptafluoroisopropylbenzoyl chloride
Physical property: 'H-NMR 5(CDC13) ; 7 . 71(t, 1H), 7.94(d, 1H), 8.33(d, 1H), 8.37(s, 1H) .
19F-NMR 5(CDC13); -76.04 (6F)/ -182.83 (IF). 4-heptafluoroisopropyl-2-methylbenzoyl chloride
Physical property: LH-NMR 5(CDC13); 2.65 (s, 3H) , 7.555 (s, 1H), 7.615(d, 1H), 8.31(d, 1H) . 4-heptafluoroisopropyl-2-methoxybenzoyl chloride
Physical property: 'H-NMR 5(CDC13) ; 3.984(s, 3H) ,

7.22(s, 1H), 7.30(d, 1H) , 8.15(01, 1H) .
4-heptafluoroisopropyl-2-methylthiobenzoyl chloride
Physical property: ^-NMR 5(CDC13); 3.34(3, 3H) , 8.04 (s-, 1H) , 8.40 (s, 1H) . 47heptafluoroisopropyl-2-methylsulfonylbenzoyl chloride
Physical property: ^-NMR 5(CDC13); 3.34 (s, 3H) , 8.04 (s, 2H), 8.40 (s, 1H) . 4-heptafluoroisopropyl-3-methylbenzoyl chloride
Physical property: LH-NMR 5(CDC13); 2.64(d, 3H) , 7.66(d, 1H), 8.00-8.05(m, 2H).
5. ' Preparation of benzamide
Example 14 Preparation of 4-heptafluoroisopropyl-3-
methylbenzamide

In an ice bath, an aqueous ammonia solution (5 ml) was added to the crude product (0.4 g) of 4-heptafluoroisopropyl-3-methylbenzoyl' chloride, and the resulting mixture was stirred for about 30 minutes. Ethyl acetate was added thereto to separate an organic layer, the organic layer was dried with anhydrous sodium sulfate and then concentrated under reduced pressure to obtain the intended product (0.3 g, yield

(crude) 98%).
In a similar manner, the following compounds
were prepared.
4-heptafluoroisopropyl-2-methylbenzamide
Physical property: ^-NMR 5 (CDC13) ; 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 property: 'H-NMR 5 (CDCl,) ; 6.47(brs, 2H) , 7.66-7.71(m, 3H).
19F-NMR 5(CDC13) ; -75.64(6F), -107.53(1F), -178.44(IF).
m.p. 85 - 86°C 4-heptafluoroisopropyl-3-methylbenzamide
Physical property: ^-NMR 5 (CDC13) ; 2.53 (d, 3H) , 7.59(d, 1H) , 7.86(d, 1H), 7.90(s, 1H) .
m.p. 66 - 68°C
6. Preparation of cyanobenzenes
Example 15 Preparation of l-cyano-4-heptafluoro-
isopropyl-3-methylbenzene

4-Heptafluoroisopropyl-3-methylbenzamide (0.3 g, 1 mmol) was dissolved in :thionyl chloride (4 ml) and

heated under reflux for 1 hour. The reaction mixture was cooled to room temperature, then thionyl chloride was distilled off under reduced pressure, and the residue was purified by silica -gel column chromatography (hexane : ethyl acetate =9 : 1) to obtain the intended product (0.22 g, yield 78%).
In a similar manner, the following compounds
were prepared. l-cyano-4-heptafluoroisopropyl-2-methylbenzene
Physical property: 'H-NMR 5(CDCl3); 2.41 (s, 3H) ,
7.33-7.41(m, 3H). l-cyano-4-heptafluoroisopropyl-2-methoxybenzene
Physical property: ^-NMP. 5 (CDC13) ; 2.41(s, 3H) ,
7.33-7.41(m, 3H). l-cyano-3-fluoro-4-heptafluoroisopropylbenzene
Physical property: ^-NM?. 5 (CDC13) ; 7.55(d, 1H) ,
7.63(d, 1H), 7.79(t, 1H). l-cyano-4-heptafluoroisopropyl-2-methylbenzene
Physical property: LH-NH?. 5 (CDCl3) ; 2.59 (d, 3H) ,
7.60 (brs, 3H) .
7. Preparation of phenols
Example 16 Preparation of 4-hep-afluoroisopropyl-3-
methylphenol

in an ice bath, 4-heptafluoroisopropyl-3-
IA mmols) was dissolved in glacial methylaniline (5 g, 18 mmox*/
■A ,os ml) and concentrated sulfuric acid acetic acid (25 ml), duu
Tbpn a solution of sodium (3.6 g) was added thereto. Then a soi
1 c^ dissolved in water (3 ml) was nitrite (1.4 g, 20 mmols) dissolve
^ 4. fhe reaction temperature might be slowly added so that the reacuu
u. u <_ nor nftpr completion of the addition not higher than c. w1--1> - - birred further for 30 the reaction mixture was otirrea
ml) was added thereto, the minutes, then water U ^>
e h-fed to about 80°C and stirred resulting mixture was heatea
rlDHnn of reaction, the for 5 hours. After completion oi
rrr^d to room temperature, hexane reaction mixture was c^---1
*. ,.rsrate an organic layer, the was added thereto to separate
• n c ua^^ ™ice with water, once with a organic layer was wasr.e. -«
j- - vvdroaen carbonate solution saturated aqueous sodiu... -7^ *
, _^ aaueous sodium chloride and once with a satura-^- aqueu
, . , -4.V, -->vdrous sodium sulfate, solution, dried with e--7aiuu
~--s^ pressure and purified by concentrated under rea-^- Pre
^^---ocjraphy (hexane : ethyl silica gel column chrc...a-^- ^
,, _ v._-^ t-he intended product (4.0 g, acetate = 3 : 1) to ofc-* — -a
yield 81%) .
were prepared. 4-heptafluoroisopropy-
- _2-r.erhylphenol
<_. physical property.> _, - -- 7 30 (d, 1H) , 7.33 (s, 1H) . 5.80(brs, 1H), 6.84(d, --.. , • ^a'
_^-r.erhcxyphenol
4-heptaf luoroisopropy-^
_--~»r the following compounds In a similar - -—i--L

6.74(d, 1H), 6.94(s, 1H) , 6.96(d, 1H). 4-heptafluoroisopropyl-3-methylphenol
Physical property: ^-NMR 6 (CDC13) ; 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 property: ^-NMR 5 (CDC13) ; 3.89 (s, 3H) , 3.94(s, 6H), 5.82(s, 1H), 6.785(s, 2H). 2,6-dimethyl-4-heptafluoroisopropylphenol
Physical property: ^-NMR 5 (CDC13) ; 2.26(s, 6H) , 5.3(brs, 1H) , 7.19(s, 2H) .
8. Preparation of benzenesulfonyl halides
Example 17 Preparation of 4-heptafluoroisopropyl-3-
methylbenzenesulfonyl chloride

In an ice bath, 4-heptafluoroisopropyl-3-methylaniline (5 g, 18.2 mmols) was dissolved in glacial acetic acid (5 ml) and further, concentrated hydrochloric acid (15 ml) was added thereto. Then, a solution of sodium nitrite (1.4 g, 20 mmols) dissolved in water (3 ml) was slowly added so that the reaction

temperature might be not higher than 0°C. After completion of the addition, the reaction mixture was stirred further for 20 minutes. The resulting diazonium salt solution was slowly"added to a separately prepared mixture of sodium hydrogen sulfite (5.3 g, 51 mmols), copper chloride (0.35 g, 3.5 mmols), glacial acetic acid (34 ml) and concentrated hydrochloric acid (7 ml) at room temperature. The resulting mixture was stirred at room temperature for 2.5 hours, then hexane was added thereto to separate an organic layer, the organic layer was dried with anhydrous sodium sulfate and then concentrated under reduced pressure to obtain the intended product (4.4 g, yield 67%).
In a similar manner, the following compounds were prepared. 4-heptafluoroisopropyl-2-methylbenzenesulfonyl chloride
Physical property: "H-NMR 8(CDCl3); 2.88 (s, 3H), 7.69(brs, 2H), 8.21(d, 1H).
4-heptafluoroisopropyl-2-methoxybenzenesulfonyl chloride
Physical property: 'H-NMR 5(CDC13); 4.125 (s, 3H), 7.34(s, 1H), 7.35(d, 1H), 8.10(d, 1HJ . 3-fluoro-4-heptafluoroisopropylbenzenesulfonyl chloride
Physical property: NMR 5(CDC13); 7.89-8.03 (m, 3H) .
19F-NMR 5(CDC13) ; -75.23(6F), -177.9(1F) 4-heptafluoroisopropyl-3-methylbenzenesulfonyl chloride

Physical property: XH-NMR 5(CDC13); 2.69(d, 3H), 7.77(d/ 1H), 7.95(d, 1H) , 7.97(s, 1H) . 2, 6-dimethyl-4-heptafluoroisopropylbenzenesulfonyl chloride
Physical property: ^-NMR 5(CDC13); 2.09 (s, 6H) , 7.32 (d, 2H) .

Into 20 ml of tetrahydrofuran (THF) containing 1.0 g of aqueous 28% ammonia solution was added dropwise, with ice cooling, 2 ml of a THF solution of 0.6 g (1.65 mmols) of 3-fluoro-4-heptafluoroisopropylbenzenesulfonyl chloride. The resulting solution was stirred at room temperature for 2 hours, then poured into water, and the intended product was extracted with ethyl acetate. The liquid extract was washed with a saturated aqueous sodium chloride solution, then dried, the solvent was distilled off under reduced pressure, and the residue obtained was purified by silica gel column chromatography to obtain 0.5 g of the intended product.

Physical property: ^-NMR 8(CDCla); 7.76 (brs, 2H) , 7.91-7.95(m, 2H) , 8.06(t, 1H).
In a similar manner/ the following compound was obtained. 4-heptafluoroisopropyl-3-methylbenzenesulfonamide
Physical property: lH-NMR 5(CDC13); 2.62(d, 3H)', 4.87(brs, 2H) , 7.65 (d, 1H) , 7,83 (d, 1H) , 7.86(d, 1H) .
10. Preparation of phenylhydrazines
Example■18 Preparation of 2, 6-dimethyl-4-heptafluoro-
isopropylphenylhydrazine hydrochloride

2, 6-Dimethyl-4-heptafluoroisopropylaniline (10 g, 34.7 mmols) was added into hydrochloric acid (30 ml), and an aqueous solution (24 ml) of sodium nitrite (2.6 g, 2 mmols) was driopwise added thereto-at a temperature not higher than 5°C. After 15 minutes of further stirring, the resulting diazonium salt solution was added dropwise at room temperature to an aqueous hydrochloric acid solution (85 ml) containing anhydrous tin chloride (20.4 g, 108 mmols). The precipitated cake-like solid was collected by filtration and washed

successively with water and hexane to obtain the intended product (8.5 g, yield 72%).
Physical property: ^-NMR S(CDC13); 2.474 (s, 6H) , 7.37 (S/ 2H), 9.99(brs, 2H) .
19F-NMR 5(CDC13) ; -70.81(d, 7F) , -177.36(01, IF) .
In a similar manner, the following compounds were obtained. 4-heptafluoroisopropyl-2-methylphenylhydrazine
Physical property: ^-NMR 8(CDC13); 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 property: XH-NMR 5(CDC13); 4.06 (brs, 2H) , 5.83(brs,1H), 7.47 (s, 2H) .
19F-NMR 5(CDC13) ; -76.23(6F), -182.45(1F)
11. Preparation of isocyanates
Example 19 Preparation of 4-heptafluoroisopropylphenyl
isocyanate

A toluene solution (5 ml) containing 4-heptafluoroisopropylaniline (3 g, 10.9 mmols) was dropwise added to a toluene solution (70 ml) containing

triphosgene (1.1 g, 3.6 mmols) while the reaction-mixture was being warmed. After completion of the addition, the reaction liquid was heated under reflux for 4 hours, then the solvent was distilled off under reduced pressure, hexane was added to the resulting residue to form a suspension, which was then fittered, and the filtrate obtained was concentrated to obtain the intended product (3 g).
In a similar manner, the following compound was obtained. 4-heptafluoroisopropyl-2-methoxyisocyanate
Physical property: XH-NMR 5(CDC13); 3.895 (s, 3H), 7.07 (s, 1H) , 7.10-7.16(m, 2H) . m.p. 38 - 39°C.
12. Preparation of benzaldehydes
2-heptafluoroisopropylbenzaldehyde
Physical property: ^-NMR 8(CDC13); 7.68 (m,. 3H) , 8.04(m, 1H), 10.48(d, 1H).
13. Preparation of isothiocyanates
Example 20 Preparation of 4-heptafluoroisopropyl-2-methoxyphenyl isothiocyanate

Thiophosgene (1.3 g, 11.5 mmols) was added dropwise at room temperature to a solution of 4-heptafluoroisopropyl-2-methoxyaniline (1.3 g, 11.5 mmols) dissolved in toluene (100 ml), the resulting mixture was heated under reflux for 2 hours, then brought back to room temperature, and the solvent was distilled off under reduced pressure to obtain the intended product (3.3 g, 10.9 mmols) .
Physical property: XH-NMR 5(CDC13); 3.96(s, 3H) , 7.10(s, 1H), 7,11-7.22(m, 2H).
14. Preparation of acetophenones
Example 21 Preparation of 4-heptafluoroisopropyl-
acetophenone

To n-butanol (50 ml) were added l-bromo-4-heptafluoroisopropylbenzene (8.0 g, 24.6 mmols), n-butylvinyl ether (11.1 mmols), sodium carbonate (11.7 g, 111 mmols), dppp (1,3-bis(diphenylphosphino)propane, 0.87 g, 1.8 mmols) and palladium acetatet(0.28 g, 17.4 mmols), and the resulting mixture was heated under reflux for 11 hours. The reaction liquid was brought back to room temperature, filtered, the filtrate

obtained was concentrated, an aqueous JN nyarocnioric acid (40 ml) was added to tbe residue, the resulting mixture was stirred vigorously for 30 minutes, then extracted with hexane/ the organic layer was washed with a saturated aqueous sodium chloride solution, the solvent was distilled off under reduced pressure, and the residue obtained was purified by silica gel column chromatography to obtain the intended product (5.6 g, yield 79%)
Physical property: ^-NMR 5(CDC13); 2.65 (s, 3H) , 7.74(d, 2H), 8.08(d, 2H).
nD 1.4341 (21.5°C)
In a similar manner, the following compounds were obtained. 2,6-dimethyl-4-heptafluoroisopropylacetophenone
Physical property: LH-NMR 5(CDC13); 2.31 (s, 6H) , 2.50 (s, 3H) , 7.25(s, 2H) .
19F-NMR 5(CDC13) ; -76.06(6F), -183.33(1F). 3-fluoro-4-heptafluoroisopropylacetophenone
Physical property: ^-NMR 5(CDCl3); 2.64 (s, 3H) , 7.73-7.79(m, 2H) , 7.86(m, 1H) . •4-heptafluoroisopropyl-3-methylacetophenone
Physical property: 'H-NMR 5(CDCl3); 2.61(d, 3H) , 2.624(s, 3H), 7.60(d, 1H) , 7.83(d, 1H) , 7.85(s, 1H) . 4-heptafluoroisopropyl-2-methylacetophenone
Physical property: 'H-NMR 5 (CDC13) ; 2.565(s, 3H) , 2.60(s, 3H) , 7.49(s, 1H) , 7.504(d, 1H) , 7.76(d, 1H) .

15. Preparation of diazonium salt 4-heptafluoroisopropyl-3-methylphenyldiazonium tetrafluoroborate
Physical property: ^-NMR 5(CDC13) ; 2.67S(d, 'Ml) , 8.25(d, 1H) , 8.7 4(d, 1H) , 8.81 (s, 1H) .
19F-NMR 5(CDC13) ; -69.40(6F), -143 . 99 (4F) , -174.51(IF).
The prefluoroisopropylbenzene derivative of this invention can be used, for example, for producing the following compound, which exhibits pesticidal activity.
Reference Example 1 Preparation of 1,l-dimethyl-3-(4-heptafluoroisopropylphenyl)urea
A tetrahydrofuran solution (2 ml) containing 4-heptafluoroisopropylphenyl isocyanate (1 g, 3.5 ramols) was added into tetrahydrofuran (15 ml) containing dimethylaruine (50% aq., 0.38 g, 4.2 mmol-s) at room temperature. The resulting reaction mixture was stirred further for 2 hours, then poured into water, extracted with ethyl acetate, the organic layer was washed with a saturated aqueous sodium chloride solution, then the solvent was distilled off under reduced pressure, and the residue obtained was purified by column chromatography to obtain the intended product (0.84 g, yield 75%) .
Physical property: m.p. 151.4 - 154.2°C

Reference Example 2: Test for herbicidal effect on paddy field weeds pre-emergence
Soil was filled into 1/10000 are pots and brought into a state of paddy field, in which seeds of barnyard grass (Echinochloa crus-galli Beauv.) and bulrush (Scirpus juncoides Ro^cb. ) were made to be before germination. The soil in the pots were treated with a solution containing a predetermined dosage of a chemical agent comprising a compound obtained in Reference Example 1 as the active ingredient.
Twenty one days after the treatment, the herbicidal effect was investigated, the result was compared with that in untreated plot to calculate the weedkilling rate, and the herbicidal effect was judged according to the following criterion. Criterion for herbicidal effect:
5 Weedkilling rate is 100%.
4 Weedkilling rate is 90-99%.
3 Weedkilling rate is 70-89%.
2 Weedkilling rate is 40-69%.
1 Weedkilling rate is 1-39%.
0 --- Weedkilling rate" is 0%.
At the same time, phytotoxicity on paddy rice was investigated, and judged according to the following criterion.
Criterion for phytotoxicity on paddy rice:
5 Weedkilling rate is 100%.
4 Weedkilling rate is 90-99%.

Weedkilling rate
Weedkilling rate
Weedkilling rate
Weedkilling rate
is 70-89%. is 40-69%. is 21-39%. is 0-20
(No phytotoxicity).
3 2 1 0
As a result, herbicidal effects on barnyard jrass (Echinochloa crus-galli Beauv.) and bulrush (Scirpus juncoideg Roxb.) were rated "4" and "2" at the iosage of 5 kg/ha, and there was no phytotoxicity (rated "0") on the paddy rice treated.
Reference Example 3: Herbicidal effect on upland weeds pre-emergence
Polyethylene-made vats having a size of 10 cm (length) x 20 cm (width) x 5 cm (height) were filled with soil, sown with seeds of Arabidopsjg thialiana, bent grass (Agrestic spp.) and raonochoria (Mofiochoria veginalis), and with seeds of wheat and soybean plant as upland crop plants, and then covered with soil. Then, a liquid preparation of an agent comprising a prescribed concentration of a compound obtained in Reference Example 1 as active ingredient was sprayed.
Fourteen days after the treatment, the herbicidal effect was investigated, from which weed-killing rate was calculated in the same manner as in Reference Example 2, and the herbicidal effect was judged.

At tlie same time, phytotoxicity on soybean plant and wheal: was investigated and judged according to the criterion mentioned in Reference Example 1.
As a result, herbicidal effects' on Arahidopsis ihuLllana and monochoria (Honochoria veainalis) wer" rated "5", and that of bent grass fAarostis spp.) was rated "4" respectively, at the dosage of 5 kg/ha. Further, there was no phytotoxicity (rated "0") on the wheat and soybean plant treated.
Reference Example 4: Herbicidal effect on upland weeds
after emergenc
Poly-thylene-made vats having a size of 10 cm
(length) x 20 ':m (width) x 5 cm (height) were filled with soil, sow:, with the seeds of the upland weeds mentioned below and with seeds of soybean plant and wheat as uplaiW crop plants, and then covered with soil. The plants were made to grow up until they reached the 1 ».o 2 leaved stage, after which an agent comprising a prescribed concentration of a compound obtained in Reference Example 1 as active ingredient
was sprayed.
Four'.een days after the treatment, the
herbicidal effect was investigated, from which weed-killing rate w-,s calculated in the same manner as in Reference Example 2 and the results were judged. At the same time, phytotoxicity on soybean plant and wheat was inv—^-^^ and iudc?ed in the same manner as in

WE CLAIM:
1. A perfluoroisopropylbenzene derivative represented by the formula (I) or salts thereof:

wherein Xx is a hydrogen atom, halogen atom, 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 alkylcarbonyloxy (C1-C6)) alkyl group; X2 is a hydrogen atom, halogen atom, formyl group, hydroxy group, (C1-C6)alkyl group, halof(C1-C6) alkyl group, (C1-C6) (C1-C6) (C1-C6) alkoxy group, (Cx-C6) alkylthio group, ((C1-C6)) alkylsulf inyl group, (C1-C6) alkylsulf onyl group, hydroxy ((C1-C6)) alkyl group or -C(=0)-R1 (wherein RX is a hydrogen atom, halogen atom, hydroxy group, (C1-C6) alkyl group, ((C1-C6) alkoxy group or NR2R3 (wherein R2 and R3 may be the same or different and are each a hydrogen atom, (C1-C6)alkyl group or (C1-C6)alkoxy group)); X3 is a hydrogen atom, halogen atom, hydroxy group, cyano group, isocyanate group, isothiocyanate group, hydrazino group, diazo group, mercapto group, (C1-C6)alkoxy group, (C1-C6) alkylthio group, -C(=0)-R1

(wherein R, is the same as defined above) or -S07-R4
(wherein R4 is a halogen atom, hydroxy group,
(C1-C6) alkyl group or NR5R6 (wherein R5 and R6 may be the
same or different and are each a hydrogen atom or (C1-C6)
C6)alkyl group)); and X4 is a hydrogen atom, halogen
atom, (C1-C6)alkyl group or (C1-C6) alkoxy group; provided
that
(1) when X17 X2 and X4 are each a hydrogen atom, then X3 is not a hydroxycarbonyl group or methoxycarboxyl group,
(2) when X1 and X4 are each a hydrogen atom and X2 is a formyl group, then X3 is not a methoxy group,
(3) when any one of Xx, X2 and X3 is a methoxy group, then X4 and the remaining two of Xx, X2 and X3 are not each a hydrogen atom,
(4) when any one of X2 and X3 is a hydroxyl group, then Xx, X4 and the remaining one of X2 and X3 are not each a hydrogen atom,

(5) when any one of X1; X2, X3 and X4 is a fluorine atom, then the remaining three of Xlf X2, X3 and X4 are not each a hydrogen atom,
(6) when Xx, X2 and X4 are each a hydrogen atom, then X3 is not a chlorine atom, bromine atom or iodine atom,
(7) when any one of Xlf X2, X3 and X4 is a methyl group, then the remaining three of Xlf X2, X3 and X4 are not each a hydrogen atom,
(8) when X17 X2 and X4 are each a hydrogen atom,

then X3 is not an isopropyl group or chloromethyl group,
(9) when Xx, X3 and X4 are each a hydrogen atom, then X2 is not a trifluoromethyl group,
(10) when Xx and X4 are each a methyl group and X2 is a hydrogen atom, then X3 is not a hydrogen atom or heptafluoroisopropyl group,
(11) when Xa and X3 are each a hydrogen atom and any one of X2 and X4 is a hydrogen atom, then the remaining one of X2 and X4 is not a heptafluoroisopropyl group,
(12) when Xx is a hydrogen atom, X3 is a hydroxycarbonyl group, and any one of X2 and X4 is a hydrogen atom, then the remaining one of X2 and X4 is not a heptafluoroisopropyl group,
(13) when Xu X2 and X4 are each a hydrogen atom, then X3 is not a chlorocarbonyl group,
(14) when any three of Xl X2, X3 and X4 are each a hydrogen atom, then the remaining one of Xl X2, X3 and X4 is not a hydrogen atom or nitro group,

(15) when X3 is a hydrogen atom, any two of Xx, X2 and X4 are each a hydrogen atom, then the remaining one of Xw X2 and X4 is not a methoxycarbonyl group,
(16) when Xl X2 and X4 are each a hydrogen atom, then X3 is not a heptafluoroisopropyl group,
(17) when X3 and X4 are each a hydrogen atom, any one of Xl and X2 is a hydrogen atom, then the remaining one of X1 and X2 is not an iodine atom,
(18) each of Xl X2, X3 and X4 does not

simultaneously represent a fluorine atom,
(19) when Xx is a hydrogen atom, any two of X2/ X3 and X4 are each a hydrogen atom, then the remaining one of X2, X3 and X4 is not a 2,2,2-trifluoro-l-trifluoromethylethyl group, and
(20) when Xx and X3 are each a hydrogen atom, any one of X2 and X4 is a hydrogen atom, then the remaining one of X2 and X4 is not a bromine atom or hydroxycarbonyl group.
2. The perfluoroisopropylbenzene derivative or
the salts thereof according to claim 1, wherein Xx is a
formyl group, (C1-C6) alkyl group, halo (C1-C6) alkyl group,
hydroxy (C1-C6) alkyl group or (C1-C6) alkylcarbonyloxy (C1-C6)
C6) alkyl group; and X2, X3 and X4 are each a hydrogen
atom,
3. The perfluoroisopropylbenzene
derivative or the salts thereof according to claim 1,
wherein Xx, X3 and X4 are each a hydrogen atom; and X2 is
a alkyl group, halo (C1-C6) alkyl group, hydroxy (C1-C6)
4. alkyl group, (C1-C6) alkyl carbonyl group or -C (=0)-Ra
(wherein Rx is a hydrogen atom, halogen atom, (Cx-C6) alkyl group, (C2-C6) alkoxy group, or NR2R3 (wherein R2 and R3 may be the same or different and are each a hydrogen atom, (C1-C6)alkyl group or (C1-C6) alkoxy group)), provided that X2 is not a heptafluoroisopropyl group, or 2,2,2-trifluoro-l-trifluoromethylethyl group.
4. The perfluoroisopropylbenzene derivative or
the salts thereof according to claim 1, wherein Xx, X2

and X4 are each a hydrogen atom; and X3 is an isocyanate group, isothiocyanate group or (C1-C6)alkylcarbonyl group.
5. The perfluoroisopropylbenzene derivative or the salts thereof according to claim 1, wherein X2 and X4 are each a hydrogen atom; X2 is a hydroxy group, (Cx-C6) alkyl group or (C^-Cg) alkoxy group; and X3 is a halogen atom, hydroxy group, cyano group, isocyanate group, isothiocyanate group, hydrazino group, -C(=0)-Rx (wherein Rx is a hydrogen atom, hydroxy group, halogen atom, (C1-C6)alkyl group, (C1-C6) alkoxy group or NR2R3 (wherein R2 and R3 may be the same or different and are each a hydrogen atom, (C1-C6) alkyl group or (C1-C6) alkoxy group) ) or -S02-R4 (wherein R4 is a halogen atom, hydroxy group or NR5R6 (wherein R5 and R6 may be the same or different and are each a hydrogen atom or (C1-C6) alkyl group)).
6. The perfluoroisopropylbenzene derivative or the salts thereof according to claim 1, wherein Xx and X4 are each a hydrogen atom; X2 is a halogen atom; and X3 is a halogen atom or -C(=0)-R1 (wherein RX is a halogen atom, hydroxy group, (C1-C6) alkyl group, (C1-C6)alkoxy group or NR2R3 (wherein R2 and R3 may be the same or different and are each a hydrogen atom or (C1-C6) alkyl group)).
7. The perfluoroisopropylbenzene derivative or the salts thereof according to claim 1, wherein Xx is a halogen atom or (C1-C6)alkyl group; X2 and X4 are each a

hydrogen atom; and X3 is a halogen atom, hydroxy group, cyano group, diazo group, -C(=0)-R1 (wherein RX is a halogen atom, hydroxy group, (C1-C6)alkyl group, [Cx-C6) alkoxy group or NR2R3 (wherein R2 and R3 may be the same or different and are each a hydrogen atom or (Cx-C6)alkyl group)) or S02-R4 (wherein R4 is a halogen atom, hydroxy group or NR5R6 (wherein R5 and R6 may be the same or different and are each a hydrogen atom or (C1-C6) alkyl group) ) .
8. The perfluoroisopropylbenzene derivative or the salts thereof according to claim 1, wherein X2 and X4 are each a hydrogen atom; Xx is a (C1-C6)alkylthio group; and X3 is a halogen atom or -C(=0)-R1 (wherein Rx is a halogen atom, hydroxy group or (Cx-C6)alkoxy group).
9. The perfluoroisopropylbenzene derivative or the salts thereof according to claim 1, wherein Xx is a hydrogen atom; X2 and X4 are each a (Cx-C6) alkyl group; and X3 is a halogen atom, hydrazine group, -C(=0)-R1 (wherein Rt is a halogen atom, hydroxy group, (C^-
C6) alkyl group, (C1-C6) alkoxy group or NR2R3 (wherein R2 and R3 may be the same or different and are each a hydrogen atom or (C1-C6) alkyl group)) or -S02-R4 (wherein R4 is a halogen atom, hydroxy group or NR5R6 (wherein R5 and R6 are the same as defined above)).
10. The perfluoroisopropylbenzene derivative and
the salts thereof according to claim 1, wherein Xx is a
hydrogen atom; X2 and X4 are each a methoxy group; and X

is a hydroxy group.
11. The perfluoroisopropylbenzene
derivative and the salts thereof according to claim 1,
wherein X2, X3 and X4 are each a hydrogen atom; and Xx is
a formyl group, hydroxymethyl group, chloromethyl
group, bromomethyl group or acetoxymethyl group.
12. The perfluoroisopropylbenzene derivative and the salts thereof according to claim 1, wherein Xx, X3 and X4 are each a hydrogen atom; and X2 is a formyl group, ethyl group, chloromethyl group, hydroxymethyl group, acetyl group or N-methoxy-N-methylaminocarboxyl group.
13. The perfluoroisopropylbenzen derivative or the salts thereof according to claim 1, wherein Xx, X2 and X4 are each a hydrogen atom; and X3 is an isocyanate group or acetyl group.
14. The perfluoroisopropylbenzene derivative or the salts thereof according to claim 1, wherein Xx and X4 are each a hydrogen atom; X2 is a methyl group; and X3 is a chlorine atom, bromine atom, iodine atom, hydroxy group, cyano group, isothiocyanate group, hydrazino group, (C1-C6) (wherein Rx is a hydrogen atom, chlorine atom, hydroxy group, methoxy group or amino group) or -S02-R4 (wherein R4 is a chlorine atom or amino group).
15. The perfluoroisopropylbenzene derivative or
the salts thereof according to claim 1, wherein Xx and
X4 are each a hydrogen atom; X2 is a methoxy group; and

X3 is a chlorine atom, bromine atom, iodine atom, cyano group, hedroxy group, mercapto group, isocyanate group, isothiocyanate group, "C(=0)-R1 (wherein RX is a hydrogen atom, chlorine atom, methoxy group, hydroxy group or amino group) or -S02-R4 (wherein R4 is a chlorine atom or amino group).
16. The perfluoroisopropylbenzene derivative or the salts thereof according to claim 1, wherein Xx and X4 are each a hydrogen atom; X2 is a fluorine atom; and X3 is a bromine atom or -C(=0)-R1 (wherein RX is a chlorine atom, hydroxy group, methoxy group or ethoxy group).
17. The perfluoroisopropylbenzene derivative or the salts thereof according to claim 1, wherein X2 and X4 are each a hydrogen atom; Xx is a methyl group; and X3 is a bromine atom, hydroxy group, cyano group, diazo group, -C(=0)-Rx (wherein Rx is a chlorine atom, hydroxy group, methyl group, methoxy group or amino group) or -S02-R4 (wherein R4 is a chlorine atom or amino group) .
18. The perfluoroisopropylbenzene derivative or
the salts thereof according to claim 1, wherein X2 and
X4 are each a hydrogen atom; Xx is a fluorine atom; and
X3 is a chlorine atom, bromine atom, cyano group,
-C(-0)-R1 (wherein Ra is a chlorine atom, hydroxy group,
methyl group, methoxy group or amino group) or -S02-R4
(wherein R4 is a chlorine atom or amino group) .
19. The perfluoroisopropylbenzene derivative or
the salts thereof according to claim 1, wherein X2 and

X4 are each a hydrogen atom; X, is a methylthio group; and X3 is a bromine atom, iodine atom or -C(=0)-R! (wherein Rx is a chlorine atom, hydroxy group or methoxy group) .
20. The perfluoroisopropylbenzene derivative or
the salts thereof according to claim 1, wherein Xa is a
hydrogen atom; X2 and X4 are each a methyl group; and X3
is a chlorine atom, bromine atom, iodine atom, carboxyl
group, methoxycarbonyl group, acetyl group, hydrazino
group or -S02-R4 (wherein R4 is a chlorine atom or amino
group).
21. The perfluoroisopropylbenzene derivative or
the salts thereof according to claim 1, wherein Xx is a
hydrogen atom, X2 and X4 are each a methoxy group and X3
is a hydroxy group.

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in-pct-2002-1181-che-correspondance others.pdf

in-pct-2002-1181-che-correspondance po.pdf

in-pct-2002-1181-che-description complete duplicate.pdf

in-pct-2002-1181-che-description complete original.pdf

in-pct-2002-1181-che-form 1.pdf

in-pct-2002-1181-che-form 19.pdf

in-pct-2002-1181-che-form 26.pdf

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Patent Number

242541

Indian Patent Application Number

IN/PCT/2002/1181/CHE

PG Journal Number

36/2010

Publication Date

03-Sep-2010

Grant Date

31-Aug-2010

Date of Filing

01-Aug-2002

Name of Patentee

NIHON NOHYAKU CO., LTD

Applicant Address

1-2-5, NIHONBASHI, CHOU-KU, TOKYO, JP

Inventors:

#	Inventor's Name	Inventor's Address
1	MASANOBU ONISHI	1-1-6-311 , TSUZUYAMADRI, TONDABAYASHI-SHI, OSAKA ,JP
2	KENICHI IKEDA	18-6 ,KAMYODAI 1-CHOME ,IZUMI-SHI ,OSAKA, JP
3	TAKASHI SHIMAOKA,	90-18 ,KITAHANADACHO 4-CHO, SAKAI-SHI, OSAKA ,JP
4	MASSANORI YOSHIDA	2-5-3 ,KOYODAI, HASHIMOTO-SHI, WAKAYAMA, JP

PCT International Classification Number

C07C 22/08

PCT International Application Number

PCT/JP01/00722

PCT International Filing date

2001-02-01

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	2000-27982	2000-02-04	Japan