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Process for Preparing Fluorine-Containing Dicarbonyl

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Process for Preparing Fluorine-Containing Dicarbonyl Europäisches Patentamt *EP000781752B1* (19) European Patent Office Office européen des brevets (11) EP 0 781 752 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.7: C07C 45/63, C07B 39/00 of the grant of the patent: 21.02.2001 Bulletin 2001/08 (21) Application number: 97103636.3 (22) Date of filing: 01.11.1993 (54) Process for preparing fluorine-containing dicarbonyl compound Verfahren zur Herstellung von fluorierten Dicarbonylverbindungen Procédé de préparation de composés dicarbonylés fluorés (84) Designated Contracting States: • Tomizawa, Ginjiro, MEC Kenkyusho CH DE FR GB IT LI Tsukuba-shi, Ibaraki 305 (JP) (30) Priority: 30.10.1992 JP 31580092 (74) Representative: Hansen, Bernd, Dr. Dipl.-Chem. et al (43) Date of publication of application: Hoffmann Eitle, 02.07.1997 Bulletin 1997/27 Patent- und Rechtsanwälte, Arabellastrasse 4 (62) Document number(s) of the earlier application(s) in 81925 München (DE) accordance with Art. 76 EPC: 93923678.2 / 0 667 332 (56) References cited: • JOURNAL OF ORGANIC CHEMISTRY, vol. 52, (73) Proprietor: DAIKIN INDUSTRIES, LIMITED no. 19, 1987, EASTON US, pages 4307-4310, Osaka-shi Osaka 530 (JP) XP002029446 SUZANNE T.PURRINGTON ET AL: "Selective monofluorination of beta-diketones" (72) Inventors: • Umemoto, Teruo, MEC Kenkyusho Tsukuba-shi, Ibaraki 305 (JP) Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 0 781 752 B1 Printed by Jouve, 75001 PARIS (FR) EP 0 781 752 B1 Description [0001] The present invention relates to a process for preparing a fluorine-containing dicarbonyl compound. In par- ticular, the present invention relates to a process for preparing a fluorine-containing dicarbonyl compound from a readily 5 available dicarbonyl compound as a raw material using a cheap fluorine gas in a single step. [0002] A fluorine-containing dicarbonyl compound of the formula: 1 2 3 R COCFR COR (II) 10 wherein R1 is a hydrogen atom, or a substituted or unsubstituted alkyl or aryl group; R2 is a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl or aryl group; and R3 is a hydrogen atom, or a substituted or unsubstituted alkyl, aryl, alkoxy or aryloxy group, provided that at least two of R1, R2 and R3 may together form a part of a cyclic structure with or without a hetero atom is a useful intermediate in the synthesis of agrochemicals, etc. (see EP-A-0 15 468 766, J. Org. Chem., 48, 724-727 (1983), J. Fluorine Chem., 56, 141 (1992), and Bull. Chem. Soc. Jpn., 54, 3221 (1981)). [0003] As preparation processes of the fluorine-containing dicarbonyl compound of the formula (II), that is, a fluorine- containing β-diketone or β-ketoester, the following processes (1) through (5) are known: 20 (1) The β-diketone or β-ketoester is converted to its metal salt and then reacted with FClO3 (Justus Liebigs Ann. Chim., 677, 9 (1964) and J. Org. Chem., 57, 2196 (1992)); with CH3COOF (J. Org. Chem., 48, 724 (1983)); with N-fluoroperfluoropiperidine (J. Fluorine Chem., 52, 389 (1991)); with a N-fluoropyridinium salt (J. Am. Chem. Soc., 112, 8563 (1990) and JP-A-62-207228); with N-fluorosultam (Tetrahedron Lett., 29, 6087 (1988) and Helv. Chim. Acta., 72, 1248 (1989)). 25 (2) The β-diketone or β-ketoester is reacted with a xenon compound (C19XeF6) (Tetrahedron Lett., 21, 277 (1980)); with CH3COOF (J. Org. Chem., 48, 724 (1983)); with xenon difluoride in the presence of an acid catalyst (J. Chem. Soc., Chem. Commun., 1980, 759); with a N-fluoropyridinium salt in the presence or absence of an acid catalyst (J. Am. Chem. Soc., 112, 8563 (1990) and JP-A-62-207228); with N-fluorobis(trifluoromethanesulfonyl)amide (J. Chem. Soc., Chem. Commun., 1991, 179). 30 (3) The β-diketone or β-ketoester is converted to a corresponding trimethylsilylenol ether and then reacted with fluorine at -78°C (J. Org. Chem., 52, 4309 (1987). (4) The β-ketoester is chlorinated and then reacted with potassium fluoride in a crown ether for a long time (J. Am. Chem. Soc., 58, 1803 (1936) and Synthesis, 1977, 189). (5) From a perfluoroolefin, for example, hexafluoropropene as a starting material, the fluorine containingβ-diketone 35 or β-ketoester is prepared through many steps (Chem. Lett., 1107 (1980) or Izv. Akad. Nauk, SSSR, Ser. Khim., 1980, 2827 (CA95-6431z). [0004] In addition, J. Org. Chem., 57, 2196 (1992) describes that the fluorine-containing β-ketoester is prepared by the fluorination (10 % F2/N2) of the β-ketoester (Process (6)). 40 [0005] But, the processes (1) and (2) have drawbacks that an expensive fluorination reagent should be used, the synthesis of the fluorination reagent is complicated, some reagents should be prepared under a very low reaction temperature condition, and they should be used immediately after their synthesis at the low temperature, since they are decomposed at room temperature. [0006] The processes (3), (4) and (5) require multi-step reactions. Further, the process (3) has drawbacks that the 45 fluorination should be carried out at a very low temperature, and a yield is low, the process (4) has drawbacks that an expensive crown ether should be used, a reaction time is long, and a yield is low, and the process (5) has drawbacks that the starting materials are expensive, and it is not a general process because of the small number of the available starting materials. [0007] The above described fluorination process (6) of the β-ketoester wastes a large amount of the starting material 50 because of an insufficient yield, and produces a variety of by-products. Since a fluorine atom has a small atomic weight (F = 19) and a small polarity, in general, it is difficult to separate fluorine-containing compounds. Therefore, a preparation process which produces a variety of by-products is not an industrially advantageous process, since a complicated separation process is required after the reaction. [0008] Accordingly, none of the above processes (1) through (6) is satisfactory, when they are carried out industrially. 55 [0009] An object of the present invention is to provide a process for preparing a fluorine-containing dicarbonyl com- pound of the formula (II), which can solve the above described drawbacks. [0010] Another object of the present invention is to provide an industrially advantageous process which can prepare 2 EP 0 781 752 B1 a fluorine-containing dicarbonyl compound of the formula (II) in a good yield. [0011] The present invention provides a process for preparing a fluorine-containing dicarbonyl compound of the formula: 5 1 2 3 R COCFR COR (II) wherein R1 is a hydrogen atom, or a substituted or unsubstituted alkyl or aryl group; R2 is a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl or aryl group; and R3 is a hydrogen atom, or a substituted or unsubstituted 10 alkyl, aryl, alkoxy or aryloxy group, provided that at least two of R1, R2 and R3 may together form a part of a cyclic structure with or without a hetero atom, comprising reacting a dicarbonyl compound of the formula: 1 2 3 15 R COCHR COR (I) 1 2 3 wherein R , R and R are the same as defined above with fluorine (F2) in a solvent in the presence of a salt, or an acid having pKa of 6 or less. [0012] In the present invention, the alkyl group means an alkyl group having 1 to 20 carbon atom, preferably 1 to 10 20 carbon atoms. Optionally, the alkyl group may be substituted with a substituent such as a halogen atom, a hydroxyl group, a cyano group, an aryl group, an acyl group, an alkoxy group, an aryloxy group, an acyloxy group, an alkoxy- carbonyl group, an aryloxycarbonyl group, an alkanesulfonyl group, an arylsulfonyl group or an acylamino group. [0013] The aryl group means an aromatic group having 6 to 14 carbon atoms, preferably 6 to 10 carbon atoms. The aryl group may be substituted with a substituent such as an alkyl group, a halogen atom, a cyano group, a nitro group, 25 an acyl group, an acyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkanesulfonyl group or an arylsulfonyl group. [0014] The alkoxy group means an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. The alkoxy group may be substituted by the same substituent as those exemplified in connection with the alkyl group. [0015] The aryloxy group means an arylkoxy group having 6 to 14 carbon atoms, preferably 6 to 10 carbon atoms. 30 The aryloxy group may be substituted by the same substituent as those exemplified in connection with the aryl group. [0016] Examples of the cyclic structure formed by the combination of R1, R2 and R3 are a monocyclic group, a dicyclic group or a polycyclic group, having 3 to 20 members. [0017] The halogen atom may be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. [0018] The dicarbonyl compound of the formula (I) which is used as the raw material in the process may be com- 35 mercially available or synthesized easily by a conventional synthesis method. Examples of the dicarbonyl compound of the formula (I) are as follows: HCOCH2COH, CH3COCH2COH, CH3COCH2COCH3, CH3COCH2CO-C2H5, CH3COCH2COC5H11, CH3COCH2COC8H17, CH3COCH2COC10H21, CH3COCH(CH3)COCH3, CH3COCH(C8H17)COCH3, CH3COCHFCOCH3, CH3CO-CHClCOCH3, CH3COCHBrCOCH3, CH3COCHlCOCH3, PhCOCH2COCH3, 40 CH3COCHPhCOCH3, PhCOCH2COPh, PhCOCHFCOPh, CH3COCH2COCH2Ph, CH3COCH(CH2Ph)COCH3,
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