Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C331/00—Derivatives of thiocyanic acid or of isothiocyanic acid
  • C07C331/16—Isothiocyanates
  • C07C331/28—Isothiocyanates having isothiocyanate groups bound to carbon atoms of six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C17/00—Preparation of halogenated hydrocarbons
  • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C17/00—Preparation of halogenated hydrocarbons
  • C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C22/00—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom
  • C07C22/02—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings
  • C07C22/04—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings containing six-membered aromatic rings
  • C07C22/08—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings containing six-membered aromatic rings containing fluorine
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C233/00—Carboxylic acid amides
  • C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
  • C07C233/65—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C243/00—Compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
  • C07C243/10—Hydrazines
  • C07C243/22—Hydrazines having nitrogen atoms of hydrazine groups bound to carbon atoms of six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
  • C07C25/02—Monocyclic aromatic halogenated hydrocarbons
  • C07C25/13—Monocyclic aromatic halogenated hydrocarbons containing fluorine
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C255/00—Carboxylic acid nitriles
  • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
  • C07C255/50—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton to carbon atoms of non-condensed six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C265/00—Derivatives of isocyanic acid
  • C07C265/12—Derivatives of isocyanic acid having isocyanate groups bound to carbon atoms of six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
  • C07C309/78—Halides of sulfonic acids
  • C07C309/86—Halides of sulfonic acids having halosulfonyl groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
  • C07C309/78—Halides of sulfonic acids
  • C07C309/86—Halides of sulfonic acids having halosulfonyl groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
  • C07C309/87—Halides of sulfonic acids having halosulfonyl groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing singly-bound oxygen atoms bound to the carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
  • C07C311/15—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings
  • C07C311/16—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the sulfonamide groups bound to hydrogen atoms or to an acyclic carbon atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C317/00—Sulfones; Sulfoxides
  • C07C317/44—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
  • C07C39/24—Halogenated derivatives
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C43/00—Ethers; Compounds having groups, groups or groups
  • C07C43/02—Ethers
  • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
  • C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C43/00—Ethers; Compounds having groups, groups or groups
  • C07C43/02—Ethers
  • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
  • C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
  • C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
  • C07C45/515—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being an acetalised, ketalised hemi-acetalised, or hemi-ketalised hydroxyl group
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C47/00—Compounds having —CHO groups
  • C07C47/52—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings
  • C07C47/55—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing halogen
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
  • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
  • C07C49/80—Ketones containing a keto group bound to a six-membered aromatic ring containing halogen
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/58—Preparation of carboxylic acid halides
  • C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring

Definitions

• This invention relates to a novel perfluoroisopropylbenzene derivative or salts thereof.
• 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).
• the substrates 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.
• 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.
• 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
• JP-A-59-69755 discloses that some of the benzoic amides having a perfluoroisopropyl group are useful as a photographic cyan coupler.
• 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.
• X 1 is a hydrogen atom, halogen atom, formyl group, (C 1 -C 6 )alkyl group, halo(C 1 -C 6 )alkyl group, (C 1 -C 6 )alkoxy group, (C 1 -C 6 )alkylthio group, hydroxy(C 1 -C 6 )alkyl group or (C 1 -C 6 )alkylcarbonyloxy(C 1 -C 6 )alkyl group;
• X 2 is a hydrogen atom, halogen atom, formyl group, hydroxy group, (C 1 -C 6 )alkyl group, halo(C 1 -C 6 )alkyl group, (C 1 -C 6 )alkoxy group, (C 1 -C 6 )alkylthio group, (C 1 -C 6 )alkylsulfinyl group, (C 1 -C 6 )alkylsulf
• a “halogen atom” indicates a chlorine atom, bromine atom, iodine atom or fluorine atom; a “halo(C 1 -C 6 )alkyl group, which may be the same 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.
• alkoxy group or “alkoxy” moiety means a straight or branched chain alkoxy group
• a “(C 1 -C 6 )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 1 -C 6 )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-tetrafluoroethoxy group, 3-chlorobutoxy group, 3-bromobutoxy group, 1-chloropentyloxy group, 1-chlorohexyloxy group and 6-bromohexyloxy group.
• a “(C 1 -C 6 ) alkylthio group” refers to a straight or branched chain alkylthio group having 1-6 carbon atoms and may be, for example, a methylthio group, ethylthio group, i-propylthio group, sec-butylthio group, t-butylthio group and hexylthio group.
• Y 1 , Y 2 and Y 3 may be the same or different and are each a hydrogen atom, hydroxy group, chlorine atom, bromine atom, fluorine atom, (C 1 -C 6 )alkyl group, (C 1 -C 6 )alkoxy group or hydroxy(C 1 -C 6 )alkyl group, and W is an oxygen atom or sulfur atom.
• the compounds wherein W is an oxygen atom may be produced, for example, according to the methods described in J. Am. Chem. Soc., (1937) 79, p. 1236, Org. Synth. II, (1943) p. 453, J. Org. Chem., (1966) 31, p. 596, Angew. Chem. Int. Ed. Engl (1987), 26(9), p. 894, and Angew. Chem. Int. Ed. Engl (1995), 34(22), 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.
• anilines represented by the formula (II), a starting material may be produced according to the method described in JP-11-338707.
• Y 1 , Y 2 and Y 3 are the same as defined above, and Y 4 is a hydrogen atom, halogen atom, hydroxy group, sulfonyl halide group or hydrazino group or the salt thereof.
• the compounds wherein Y 4 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., 83, p.1251 (1961), those wherein Y 4 is a fluorine atom according to the method described in Org. React., 5, p.193 (1949) and J. Org.
• Y 4 is a hydroxy group
• the compounds wherein Y 4 is a hydroxy group may be produced, for example, according to the methods described in Org. Synth., I, p.404 (1941), Org. Synth., III, p.130 (1955), Can. J. Chem, 41, p.1653 (1963) and J. Org. Chem., 32, p.3844 (1967), those wherein Y 4 is a sulfonyl halide group according to the methods described in J. Prakt. Chem. [2]152, p.251 (1939) and Recl. Trav. Chim. Pays-Bas., 84, p.22 (1965), and those wherein Y 4 is a hydrazino group or its salt according to the method described in Org. Synth., I, p.442 (1941).
• the compounds wherein Y 4 is an aldehyde group may be produced by oxidizing the compounds wherein Y 4 is a hydroxy group obtained by the above-mentioned methods, according to a conventional method.
• Y 1 , Y 2 and Y 3 are the same as defined above, Y 5 is a chlorine atom, iodine atom or bromine atom, and R is a hydrogen atom or (C 1 -C 12 )alkyl group.
• This process can be conducted, for example, according to the methods described in Bull. Chem. Soc. Jpn., 48, p.2075 (1975) and J. Am. Chem. Soc. 111, p.8742 (1989).
• perfluoroisopropylbenzene derivatives represented by the formula (I-c) By starting from the perfluoroisopropylbenzene derivatives represented by the formula (I-c) and through the method described below, perfluoroisopropylbenzene derivatives represented by the formulas (I-d), (I-e), (I-f) and (I-g) can be produced.
• 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.
• aqueous hydrochloric acid solution 60 ml was diluted with water (20 ml), and 2-bromo-4-heptafluoroisopropylaniline (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.
• hypophosphorous acid 35 ml
• 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%).
• U.S. Pat. No. 3,462,482 describes that some benzoic anilides having a heptafluoroisopropyl group, for example, 4-(heptafluoroisopropyl)benz-4-chloroanilide, are useful as a herbicide, pesticide and 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 1-methyl-4-(1-trifluoromethyl-1-hydroxy-2,2,2-trifluoroethyl)benzene as the starting material. This process, however, uses highly toxic compounds such as SF 4 and chromic acid in the production and hence is not satisfactory for practical use.
• benzoic anilides having a heptafluoroisopropyl group for example, 4-(heptafluoroisopropyl)
• 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.
• 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%).
• 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).
• reaction liquid was brought back to room temperature, filtered, the filtrate obtained was concentrated, an aqueous 3N hydrochloric acid (40 ml) was added to the 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%)
• the prefluoroisopropylbenzene derivative of this invention can be used, for example, for producing the following compound, which exhibits pesticidal activity.
• 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 Roxb.) 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.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Applications Claiming Priority (2)

Related Child Applications (1)

Publications (1)

Family

ID=18553470

Family Applications (2)

Family Applications After (1)

Country Status (8)

Cited By (5)

Families Citing this family (7)

Citations (5)

Family Cites Families (6)

• 2001
  • 2001-02-01 HU HU0204389A patent/HUP0204389A3/hu unknown
  • 2001-02-01 WO PCT/JP2001/000722 patent/WO2001056962A1/ja not_active Ceased
  • 2001-02-01 EP EP01902731A patent/EP1253128A4/en not_active Withdrawn
  • 2001-02-01 AU AU2001230565A patent/AU2001230565A1/en not_active Abandoned
  • 2001-02-01 CN CNB018045227A patent/CN1221504C/zh not_active Expired - Fee Related
  • 2001-02-01 KR KR1020027009953A patent/KR20020077414A/ko not_active Ceased
  • 2001-02-01 US US10/182,549 patent/US20030187233A1/en not_active Abandoned
  • 2001-02-02 TW TW090102173A patent/TWI291945B/zh active
• 2004
  • 2004-10-22 US US10/969,974 patent/US7169955B2/en not_active Expired - Fee Related

Patent Citations (5)

Also Published As

Similar Documents

Legal Events