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 particular, 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 compound 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

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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 alkoxycarbonyl 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, ClCH2COCH2COCH3, BrCH2COCH2COCH3, CF3CO-CH2COCH3, CF3COCH2COCF3, CF3COCHFCOCF3, C6H5COCH2COC6H5, C6F5COCH2COC6F5, C6F5COCHFCOC6F5,

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HCOCH2COOCH3, HCOCH2COOC2H5, CH3COCH2COOC2H5, CH3COCH2COO-C3H7, CH3COCH2COOC4H9, CH3COCH2COOC8H17, CH3COCH(CH3)COOCH3, PhCH2COCH2COOCH3, CH3COCH2COOPh, CH3COCH2COOCH2Ph, CH3CO-CHPhCOOC3H7, CH3COCH(CH2Ph)COOC2H5, CH3COCHFCOOC2H5, CH3CO- 55 CHCICOOC2H5, CH3COCHBrCOOC2H5, CH3COCHICOOC2H5, FCH2COCH2-COOC2H5, CICH2COCH2COOCH3,

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[0019] The process is characterized in that the dicarbonyl compound of the formula (I) is reacted with ﬂuorine in a solvent in the presence of a salt, or an acid having a pKa of 6 or less. 55 [0020] The salt herein used means a compound prepared by a reaction of an acid and a base. [0021] As an acid herein used, any acid to be used in conventional reactions may be used. Speciﬁc examples of the acid are:

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sulfuric acid, nitric acid, phosphoric acid, polyphosphoric acid, hydrogen halides, hydrohalogenic acids, hypohalogenic acids, halogenous acids, halogenic acids, or perhalogenic acids (e.g. hydrogen fluoride, hydrofluoric acid, hydrogen chloride, hydrochloric acid, hydrogen bromide, hydrogen iodide, hypochlorous acid, chlorous acid, chloric acid, perchloric acid, perbromic acid, periodic acid); 5 sulfonic acids (e.g. fluorosulfonic acid, chlorosulfonic acid, methanesulfonic acid, ethanesulfonic acid, butanesul- fonic acid, octanesulfonic acid, trifluoromethanesulfonic acid, difluoromethanesulfonic acid, trichloromethanesul- fonic acid, perfluorobutanesulfonic acid, perfluorooctanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, nitrobenzenesulfonic acid), and polymeric sulfonic acids (e.g. polystyrenesulfonic acid); carboxylic acids (e.g. formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, trimethyl- 10 acetic acid, caproic acid, heptanoic acid, caprylic acid, nonaic acid, chloroacetic acid, bromoacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, glycolic acid, lactic acid, benzoic acid, oxalic acid, succinic acid), and polymeric carboxylic acids (e.g. polyacrylic acid);

[0022] Lewis acids (e.g. BF3, BCl3, B(OCH2)3, B(OCOCH3)3, AlCl3, SbF3, SbCl3, SbF6, PF3, PF5, AsP3, AsCl3, AsF5, 15 TiCl4) and their complexes with ethers acids comprising a Lewis acid and a hydrogen halide (e.g. HBF5, HSbF3, HPF5, HAsF6, HSbCl3) and their complexes with ehter; or carbonic acid. [0023] As the base constituting the salt, any base to be used in conventional reactions may be used. Speciﬁc examples of the base are:

20 metal hydroxides (e.g. sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide); metal alkoxides (e.g. sodium methoxide, sodium ethoxide, sodium butoxide, potassium methoxide, potassium ethoxide, potassium butoxide, lithium methoxide, lithium ethoxide); metal hydrides (e.g. sodium hydride, potassium hydride, lithium hydride, calcium hydride); 25 alkali metals (e.g. sodium, potassium, lithium); metal oxides (e.g. magnesium oxide, calcium oxide); ammonia and amines (e.g. methylamine, ethylamine, diethylamine, triethylamine, trimethylamine, propylamine, butylamine, tributylamine, aniline, dimethylaniline, pyridine, methylpyridine, dimethylpyridine, trimethylpyridine, ha- lopyridine, ethylenediamine, N,N,N',N'-tetramethylenediamine, 1,5-diazabicyclo[4.3.0]-nonan-5-ene, 1,4-diazabi- 30 cyclo[2.2.2]octane, quinoline); polymeric amines (e.g. polyallylamine, polyvinylpyridine); ammonium hydroxide, salts of ammonium hydroxide (e.g. tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, octyltriethylammonium hydroxide, benzyltrimethylammonium hydroxide), or polymeric ammonium hydroxide salts (e.g. Amberlite resin).

35 [0024] The salt is a compound synthesized by a reaction of the above acid and the above base. Speciﬁc examples of the salt are:

metal or amine salts of sulfuric acid or sulfonic acids (e.g. sodium sulfate, sodium hydrogensulfate, potassium sulfate, potassium hydrogensulfate, lithium sulfate, cesium sulfate, calcium sulfate, magnesium sulfate, ammonium 40 sulfate, triethylammonium sulfate, pyridinium sulfate, trimethylpyridinium sulfate, polyallylammonium sulfate, polyvinylpyridinium sulfate, sodium methanesulfonate, ammonium methanesulfonate, tetramethylammonium methanesulfonate, potassium ethanesulfonate, lithium butanesulfonate, sodium benzenesulfonate, sodium toluenesul- fonate, sodium trifluoromethanesulfonate, sodium polystyrenesulfonate); metal or amine salts of carboxylic acids (e.g. sodium formate, ammonium formate, sodium acetate, potassium 45 acetate, lithium acetate, magnesium acetate, calcium acetate, ammonium acetate, methylammonium acetate, di- ethylammonium acetate, triethylammonium acetate, tetraethylammonium acetate, pyridinium acetate, sodium propionate, potassium propionate, sodium butyrate, polyallylammonium acetate, polyvinylpyridinium acetate, sodium isobutyrate, sodium valerate, sodium nonanate, sodium chloroacetate, sodium bromoacetate, sodium trichloroa- cetate, sodium trifluoroacetate, sodium glycolate, sodium lactate, sodium benzoate, sodium oxalate, sodium suc- 50 cinate, polysodium acrylate); metal or amine salts of hydrogen halides, hydrohalogenic acids, hypohalogenic acids, halogenous acids, halogenic acids, or perhalogenic acids (e.g. sodium fluoride, potassium fluoride, cesium fluoride, ammonium fluoride, tetraethylammonium fluoride, tetrabutylammonium fluoride, polyallylammonium fluoride, sodium chloride, ammonium chloride, sodium hypochlorite, sodium chlorite, sodium chlorate, sodium perchlorate, sodium perbromate, sodium 55 periodate); metal or amine salts of phosphoric acid (e.g. sodium phosphate, potassium phosphate, sodium hydrogenphos- phate, sodium dihydrogenphosphate, ammonium phosphate, pyridinium phosphate); metal or amine salts of nitric acid (e.g. sodium nitrate, potassium nitrate, ammonium nitrate, pyridinium nitrate);

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metal or amine salts of carbonic acid (e.g. sodium carbonate, lithium carbonate, potassium carbonate, sodium hydrogencarbonate, ammonium carbonate); metal or amine salts of acids comprising a Lewis acid and a hydrogen halide (e.g. NaBF4, KBF4, LlBF4, NaSbF6, NaAsF6, NaPF5, NH4BF4, NH4SbF5, NH4PF6); 5 phosphonium salts (e.g. tetramethylphosphonium ﬂuoride, tetrametylphosphonium acetate, tetraphenylphospho- nium ﬂuoride);

and mixtures thereof. [0025] An amount of the salt is selected from a range from a catalytic amount to a large excess amount. Preferably, 10 an amount of the salt is from 0.1 to 20 moles, more preferably from 0.5 to 10 moles per one mole of the dicarbonyl compound of the formula (II). [0026] The acid is an acid having pKa of 6 or less, preferably a stronger acid than acetic acid (pKa 4.56). Preferably, it has a pKa of less than 4.5. Examples of such acid are:

15 sulfuric acid, nitric acid, phosphoric acid, polyphosphoric acid, hydrogen halides, hydrohalogenic acids, hypohalogenic acids, halogenous acids, halogenic acids, or perhalogenic acids such as hydrogen fluoride, hydrofluoric acid, hydrogen chloride, hydrochloric acid, hydrogen bromide, hydrogen iodide, hypochlorous acid, chlorous acid, chloric acid, perchloric acid, perbromic acid, periodic acid); sulfonic acids (e.g. fluorosulfonic acid, chlorosulfonic acid, methanesulfonic acid, ethanesulfonic acid, butanesul- 20 fonic acid, octanesulfonic acid, trifluoromethanesulfonic acid, difluoromethanesulfonic acid, trichloromethanesul- fonic acid, perfluorobutanesulfonic acid, perfluorooctanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, nitrobenzenesulfonic acid), and polymeric sulfonic acids (e.g. polystyrenesulfonic acid); carboxylic acids (e.g. formic acid, chloroacetic acid, bromoacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, glycolic acid, lactic acid, benzoic acid, oxalic acid, succinic acid); 25 Lewis acids (e.g. BF3, BCl3, B(OCH2)3, B(OCOCH3)3, AlCl3, SbF3, SbCl3, SbF6, PF3, PF5, AsP3, AsCl3, AsF5, TiCl4) and their complexes with ethers; acids comprising a Lewis acid and a hydrogen halide (e.g. HBF5, HSbF3, HPF5, HAsF6, HSbCl3) and their complexes with ehter; and their mixtures.

[0027] When a weak acid such as acetic acid is used as a solvent, an acid different from the weak acid is used. 30 [0028] An amount of the acid used is from a catalytic amount to a large excess amount based on the amount of the dicarbonyl compound of the formula (II). This acid may be used as the solvent. [0029] The kind of the solvent is not limited in the process of the present invention. In addition to halogenated hydrocarbons having 1 to 5 carbon atoms (e.g. chloroform, dichloromethane, chloromethane, carbon tetrachloride, chlo- roethane, dichloroethane, trichloroethane, tetrachloroethane, trichlorotrifluoroethane, tetrafluoroethane, chlorotrifluor- 35 oethane, perfluoropentane, wherein chloroform is preferred), and nitrile compounds (e.g. acetonitrile, propionitrile, wherein acetonitrile is preferred) there can be used other halogenated hydrocarbons (e.g. perfluorohexane, perfluorooctane), water, the above described acids, acetic acid, propionic acid, butyric acid, isobutyric acid, alcohols (e.g. methanol, ethanol, trifluoroethanol, propanol, isopropanol, hexafluor- oisopropanol, butanol, sec.-butanol, tert.-butanol), carboxylic anhydrides (e.g. acetic anhydride, propionic anhydride, 40 formic anhydride), ethers (e.g. diethyl ether, dipropyl ether, dibutyl ether, tetraydrofuran), ketones (e.g. acetone, methyl ethyl ketone, diethyl ketone), alkanes (e.g. hexane, octane, cyclohexane), esters (e.g. ethyl acetate, ethyl formate, propyl formate, methyl propionate, ethyl propionate), and their mixtures. [0030] Among them, the aliphatic acids, halogenated hydrocarbons, alcohols, nitrile compounds and their mixtures are preferred, and the aliphatic acids and nitrile compounds, in particular, their mixture are more preferred. Examples 45 of the aliphatic acid to be used as the solvent are formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, and trifluoroacetic acid. Among them, acetic acid is preferred. [0031] Preferred examples of the nitrile compound are acetonitrile and propionitrile. Among them, acetonitrile is more preferred. [0032] Fluorine (F2) to be used in the present invention is preferably used in a diluted form with an inert gas so that 50 a volume percentage of the inert gas is from 99.9 % to 50 %, to suppress the violent reactivity of the fluorine. Examples of the diluent inert gas are nitrogen, helium argon or carbon dioxide. [0033] An amount of the fluorine may not be uniformly determined, since it varies with an introduction manner, a reaction temperature, a kind of the reaction solvent, a reaction apparatus. A person skilled in the art can easily determine the amount of the fluorine to be used by carrying out some simple preliminary experiments with aiming an amount 55 necessary for substantially disappearing the dicarbonyl compound of the formula (I) which is the starting material. [0034] A reaction temperature is selected from a range between -120°C and +80°C. To carry out the reaction effec- tively in a high yield, the reaction temperature is preferably from -100°C to +50°C, in particular, from -80°C to +30°C. [0035] When the aliphatic acid is used as the solvent, and the base such as the metal, metal hydroxide, metal hydride,

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metal alkoxide, metal oxide or amine is used, apparently, a metal salt or amine salt of the aliphatic acid is formed through the reaction between the solvent and the base. Similarly, when the above acidic solvent such as hydrogen fluoride or phosphoric acid is used, the solvent reacts with the base to form a corresponding salt. [0036] In the case of the dicarbonyl compound of the formula (I) in which R2 is a hydrogen, a product which is 5 produced after twice repeating the reaction of the present invention according to the following reaction formula, that is, a fluorine-containing carbonyl compound of the formula (II) in which R2 is a fluorine atom is obtained:

Alternatively, when R2 in the formula (I) is a fluorine atom, the difluorinated dicarbonyl compound can be obtained by a single step. 15 [0037] According to the present invention, the fluorine-containing carbonyl compound of the formula (II) is prepared in a good yield in a single step from the dicarbonyl compound of the formula (I), which is commercially available or easily synthesized, as the starting material using cheap fluorine gas. This fluorine-containing dicarbonyl compound can be used as a highly active intermediate of agrochemicals.

20 EXAMPLES

[0038] The present invention will be illustrated by Examples, which do not limit the scope of the invention in any way.

Example 1 25 [0039]

[0040] A mixed gas of 5 % F2/95 % N2 was flowed at a rate of 15 ml/min. in a mixture of ethyl cyclohexanone- 2-carboxylate (340 mg, 2 mmol), sodium acetate (165 mg, 2 mmol) and acetic acid (2 ml), while stirring and cooling on a water bath at 12°C. An amount of supplied F2 was 86 ml (3.8 mmol). [0041] After the reaction, the reaction mixture was quantitatively analyzed by 19F-NMR to find that ethyl 2-fluorocy- 40 clohexnanone-2-carboxylate was formed in a yield of 88 %. The structure of the product was confirmed by comparing the product, which was isolated by post treatment, with the structure of the standard sample according to the conventional method.

Examples 220 45 [0042] Under the conditions shown in Table 1, ethyl cyclohexanone-2-carboxylate was ﬂuorinated in the same manner as in Example 1. The results are shown in Table 1 together with those of Example 1.

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Examples 21 to 25

55 [0043] Under the conditions shown in Table 2, various dicarbonyl compounds were ﬂuorinated in the same manner as in Example 1. The results are shown in Table 2. The structures of the products were identiﬁed by comparing the spectra of the products with those of the standard samples.

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Comparative Examples 1 to 6

[0044] Under the conditions shown in Table 3, various dicarbonyl compounds were ﬂuorinated in the same manner as in Example 1. The results are shown in Table 3. The structures of the products were identiﬁed by comparing the 5 spectra of the products with those of the standard samples.

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Claims

1. 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 10 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, 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.

20 2. The process according to claim 1. wherein said solvent is at least one solvent selected from the group consisting of nitrile compounds and aliphatic acids.

3. The process according to claim 1, wherein said solvent is a mixture of a nitrile compound and an aliphatic acid.

25 4. The process according to claim 1, wherein an acid having pKa of less than 4.5 is used.

Patentansprüche

30 1. Verfahren zur Herstellung einer ﬂuorhaltigen Dicarbonylverbindung der Formel:

1 2 3 R COCFR COR (II)

35 wobei R1 ein Wasserstoffatom oder eine substituierte oder unsubstituierte Alkyl- oder Arylgruppe ist; R2 ein Was- serstoffatom, ein Halogenatom oder eine substituierte oder unsubstituierte Alkyl- oder Arylgruppe ist; und R3 ein Wasserstoffatom oder eine substituierte oder unsubstituierte Alkyl-, Aryl-, Alkoxy- oder Aryloxygruppe ist, voraus- gesetzt, dass mindestens zwei aus R1, R2 und R3 zusammen einen Teil einer cyclischen Struktur mit oder ohne Heteroatom bilden können, umfassend die Reaktion einer Dicarbonylverbindung der Formel: 40

1 2 3 R COCHR COR (I)

1 2 3 45 wobei R , R und R die selben sind wie oben deﬁniert, mit Fluor (F2) in einem Lösungsmittel in Anwesenheit eines Salzes oder einer Säure mit einem pKa von 6 oder weniger.

2. Verfahren gemäss Anspruch 1, wobei das Lösungsmittel mindestens ein Lösungsmittel, ausgewählt aus der Grup- pe bestehend aus Nitrilverbindungen und aliphatischen Säuren, ist.

50 3. Verfahren gemäss Anspruch 1, wobei das Lösungsmittel eine Mischung einer Nitrilverbindung und einer aliphatischen Säure ist.

4. Verfahren gemäss Anspruch 1, wobei eine Säure mit einem pKa von weniger als 4,5 verwendet wird.

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Revendications

1. Procédé pour préparer un composé dicarbonylé ﬂuoré de formule :

5 1 2 3 R COCFR COR (II)

où R1 est un atome d'hydrogène ou un groupe alkyle ou aryle substitué ou non substitué, R2 est un atome d'hy- drogène, un atome d'halogène ou un groupe alkyle ou aryle substitué ou non substitué, et R3 est un atome d'hy- 10 drogène ou un groupe alkyle, aryle, alcoxy ou aryloxy substitué ou non substitué, à condition qu'au moins deux groupes parmi R1, R2, R3 puissent former ensemble une partie d'une structure cyclique avec ou sans hétéroatome, comprenant la réaction d'un composé dicarbonylé de formule :

1 2 3 15 R COCHR COR (I)

1 2 3 où R , R et R sont tels que déﬁnis ci-dessus avec du ﬂuor (F2) dans un solvant en présence d'un sel ou d'un acide ayant un pKa de 6 ou moins.

20 2. Procédé selon la revendication 1, dans lequel ledit solvant est au moins un solvant choisi dans le groupe consistant en les composés nitrile et les acides aliphatiques.

3. Procédé selon la revendication 1, dans lequel ledit solvant est un mélange d'un composé nitrile et d'un acide aliphatique. 25 4. Procédé selon la revendication 1, dans lequel un acide ayant un pKa inférieur à 4,5 est utilisé.