United States Patent 19 11) Patent Number: 4,600,787 Marhold Et Al
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United States Patent 19 11) Patent Number: 4,600,787 Marhold et al. 45) Date of Patent: Jul. 15, 1986 (54 PROCESS FOR THE PREPARATION OF 4,157,344 6/1979 Feiring ................................ 568/588 AROMATC COMPOUNDS WHICH 4,377,711 3/1983 Rico et al. ........................... 568/649 CONTAIN PERFLUORINATED 4,438,275 3/1984 Lantzsch et al. ................... 549/434 SDE-CHAINS BONDED WIAA 4,496,750 1/1985 Anderson et al. .................. 549/455 HETEROATOM FOREIGN PATENT DOCUMENTS 75) Inventors: Albrecht Marhold, Leverkusen; Erich 2329625 5/1977 France . Klauke, Odenthal, both of Fed. Rep. of Germany OTHER PUBLICATIONS 73) Assignee: Bayer Aktiengesellschaft, Sheppard, Journ. Amer. Chem. Soc. 83, pp. 4860-4861, Leverkusen, Fed. Rep. of Germany (1961). 21 Appl. No.: 602,849 The Journal of Organic Chemistry, Band 44, Nr. 16, Aug. 3, 1979, Seiten 2907-2910; H. O. House et al.: 22 Filed: Apr. 23, 1984 "Enones With Strained Double Bonds. 2. the bicyclo 30) Foreign Application Priority Data 4.3.1) decane System'. Apr. 27, 1983 (DE) Fed. Rep. of Germany ....... 331547 Primary Examiner-Ethel G. Love Attorney, Agent, or Firm-Sprung, Horn, Kramer & 51 Int. Cl. .................... C07D 319/14: CO7C 51/00; Woods CO7C 43/20 52 U.S. Cl. ................................ 549/362; 260/543 F; 57 ABSTRACT 260/543 R; 549/434; 568/649; 568/655 58) Field of Search ....................... 549/380, 434, 362; Aromatic compounds which contain perfluorinated 568/649, 655; 260/543 F, 543 R side-chains bonded via a heteroatom are prepared by treating aromatic compounds, which contain side 56) References Cited chains which are perhalogenated, but only partially U.S. PATENT DOCUMENTS fluorinated, and bonded via heteroatom, with a catalyst 2,776,992 1/1957 Gregory .......................... 260/543 F capable of transferring halogen atoms. 3,219,690 11/1965 Sheppard ........................ 260/543 F 4,110,345 8/1978 Berkelhammer et al. .......... 549/434 16 Claims, No Drawings 4,600,787 1. 2 Examples of suitable heteroatoms, via which side PROCESS FOR THE PREPARATION OF chains which are perhalogenated but only partially AROMATIC COMPOUNDS WHICH CONTAIN fluorinated are bonded to the aromatic nucleus, are PERFLUORNATED SDE-CHAINS BONDED VA oxygen, sulphur and/or nitrogen atoms. A HETEROATOM 5 A preferred group of compounds which can be em ployed in the process according to the invention are The present invention relates to a process for the those of the formula preparation of aromatic compounds, which contain perfluorinated side-chains bonded via a heteroatom, from aromatic compounds, which contain side-chains 10 R1 (I) which are perhalogenated, but only partially fluori nated, and bonded via a heteroatom, by treatment with X-CFHall3 a catalyst. Aromatic compounds which contain perfluorinated side-chains bonded via a heteroatom are important in 15 R3 termediate products for the preparation of herbicides (see DE-OS (German Published Specification) No. in which, independently of one another, 2,848,531) and insecticides (see DE-OS (German Pub R1 represents hydrogen, C1C4-alkyl, C6-C8-aryl, lished Specification) No. 2,837,524 and DE-OS (Ger COF, COCl, NO2, SOCl, CN, 0-C1-C4-alkyl, man Published Specification) No. 3,023,328). 20 0-C6-C8-aryl, F, Cl or Br, It is known that aromatic compounds which contain R2 represents hydrogen, NO2, SO2Cl, F, Clor Br, perfluorinated side-chains bonded via a heteroatom can R3 represents hydrogen, COF, COC, F, Clor Br, or be prepared by reacting the corresponding perchlori R1 and R3 together represent a carbocyclic ring hav nated compounds with hydrogen fluoride. The disad ing 3 or 4 C atoms, vantage of this process is that, in general, an excess of 25 X represents 0, S or N-C1-C4-alkyl, hydrogen fluoride has to be employed, and this can be n represents 1 or 2 and recovered only with difficulty, or has to be destroyed. Hal represents Cl and/or Br. A further disadvantage is that any other groups present Another preferred group of compounds which can be which can be fluorinated, for example acid chloride employed in the process according to the invention are groups, are also fluorinated; in general, this is undesir 30 those of the formula able and implies an additional consumption of hydrogen fluoride. Thus, for example, DE-OS (German Published R (II) Specification) No. 2,117,650 discloses that, depending on the way in which the reaction is carried out, the fluorination of 4-trichloromethoxybenzoyl chloride 35 with hydrogen fluoride gives 4-trifluoromethoxybenz oyl fluoride and/or 4-difluorochloromethoxybenzoyl fluoride, but not 4-trifluoromethoxybenozyl chloride. A process for the preparation of aromatic compounds 40 in which which contain perfluorinated side-chains bonded via a R1, R2, R3 and X have the meaning given in formula heteroatom has now been found, which is characterised (I) and in that aromatic compounds, which contain side-chains A represents CFHal, C2FHals, C2F2Hal2 or C2F3Hal, which are perhalogenated, but only partially fluori wherein Hal represents Cl and/or Br. nated, and bonded via a heteroatom, are treated with a 45 Compounds which are particularly preferably em catalyst capable of transferring halogen atoms. ployed in the process according to the invention are In the process according to the invention, it is possi 2-fluoro-2-chloro-benzodioxole, 3-difluorochlorome ble to employ the most diverse aromatic compounds thoxybenzoyl fluoride, 2-difluoromethoxy-trichlorome which contain side-chains which are perhalogenated, thoxybenzene, 6-nitro-2-chloro-2,3,3-trifluoro-benzo but only partially fluorinated, and bonded via a hetero 50 1,4-dioxene, 4-difluorochloromethoxy-nitrobenzene, atom. These aromatic compounds can contain further 3-difluorochloromethoxy-nitrobenzene, 4-difluoro substituents, for example alkyl, aryl, fluoroformyl, chlo chloromethoxy-3-methylnitrobenzene, 4-difluoro roformyl, nitro, chlorosulphonyl, cyano, O-alkyl, 0-aryl chloromethoxy-chloroformylbenzene, 3-difluoro and/or halogen groups. It is possible for one such sub chloromethoxy-2,4-dichlorotoluene, 3-difluoro stituent to be present or, independently of one another, 55 chloromethoxy-4,6-dichlorotoluene, 3-difluoro for several, for example 2 to 4, identical or different chloromethoxy-2,4,6-trichlorotoluene and 2-chloro substituents of this type to be present. The aromatic 2,3,3-trifluoro-benzo-1,4-dioxene. compounds can also be substituted by a carbocyclic The aromatic compounds which are to be used in the 9. process according to the invention and which contain fe aromatic compounds can contain, per molecule, 60 side-chains which are perhalogenated, but only partially one or more of the side-chains which are perhalogen fluorinated, and bonded via a heteroatom can be ob ated but only partially fluorinated. These side-chains tained, for example, in a simple manner, by fluorination can also be present as a cyclic structure. This is then of the corresponding compounds which are perhalo preferably bonded to the aromatic nucleus via two het genated but fluorine-free. The fluorination can be car eroatoms. The side-chains which are perhalogenated 65 ried out, for example, using hydrogen fluoride or alkali but only partially fluorinated preferably contain 1 or 2 metal fluorides. Since hydrogen fluoride is in general atoms and, as halogens, and in addition to fluorine, capable of replacing all halogen atoms present by fluo preferably chlorine and/or bromine. rine atoms, special measures have to be taken in the 4,600,787 3 4. fluorination with hydrogen fluoride in order to obtain -continued compounds having a side-chain which is only partially O F fluorinated. Alkali metal fluorides are in general only N / C capable of replacing some of the halogen atoms present / N by fluorine atoms. For this reason, the fluorination of 5 O F aromatic compounds which contain side-chains which are perhalogenated but fluorine-free and bonded via a COF COC (2) heteroatom is preferably carried out using alkali metal fluorides. 10 catalyst G Examples of catalysts which are capable of transfer OCFC OCF ring halogen atoms and are suitable for the process according to the invention are Lewic acids, in particu After the process according to the invention has been lar the halides of the elements boron, aluminium, tin, carried out, in general a mixture is obtained which con arsenic, antimony, titanium, molybdenum and iron. The 15 tains, as component A, the resulting aromatic com fluorides, chlorides and bromides of these elements are pound containing perfluorinated side-chains bonded via preferred. Aluminium trichloride, aluminium tribro heteroatoms, and, as component(s) B, the correspond mide, boron trichloride, boron trifluoride, arsenic pen ing aromatic compound containing perhalogenated, tachloride, antimony pentachloride, molybdenum pen fluoride-free side-chains bonded via heteroatoms and tachloride, titanium tetrachloride and iron trichloride 20 /or aromatic compound(s) which have a lower fluorine are particularly preferred. If aluminium chloride is used content than the starting compound, and where rele as the catalyst, this is preferably used as a mixture with vant, as component(s) C, solvents, unreacted starting sodium chloride. compound and/or by-products. The catalysts can be employed, for example, in 25 The process involves halogen interchange transfer in amounts of 0.001 to 0.1 mol per mol of aromatic com one or more fluoro-halo substituents bound to the aro pound. It is preferable to use 0.005 to 0.05 mol of cata matic nucleus via a hetero atom. lyst, based on the aromatic compound. These mixtures can be worked up, for example, by The treatment with the catalyst can be carried out, distillation. Component A has in general the lowest for example, at temperatures in the range from 0 to 30 boiling point, so this can be separated off first, while the 150° C. Temperatures in the range from 20' to 140 C. process according to the invention is being carried out are preferred.