Organic compounds -- part of the class 532-570 series – Organic compounds – Carboxylic acid esters
Patent
1995-04-28
1996-10-29
Reamer, James H.
Organic compounds -- part of the class 532-570 series
Organic compounds
Carboxylic acid esters
560125, 560 51, 560174, 560178, 568316, 568348, 568393, C07C 67287
Patent
active
055697780
DESCRIPTION:
BRIEF SUMMARY
FIELD OF THE INVENTION
This application is a 371 of PCT/JP93/01584, Nov. 1, 1993.
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 available dicarbonyl compound as a raw material using a cheap fluorine gas in a single step.
PRIOR ART
A fluorine-containing dicarbonyl compound of the formula: or aryl group; R.sup.2 is a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl or aryl group; and R.sup.3 is a hydrogen atom, or a substituted or unsubstituted alkyl, aryl, alkoxy or aryloxy group, provided that at least two of R.sup.1, R.sup.2 and R.sup.3 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-0 468 766, J. Org. Chem., 48, 724-727 (1983), J. Fluorine Chem., 56, 141 (1992), and Bull. Chem. Soc. Jpn., 54, 3221 (1981)).
As preparation processes of the fluorine-containing dicarbonyl compound of the formula (11), that is, a fluorine-containing .beta.-diketone or .beta.-ketoester, the following processes (1) through (5) are known: and then reacted with FCIO.sub.3 (Justus Liebigs Ann. Chim., 677, 9 (1964) and J. Org. Chem., 57, 2196 (1992)); with CH.sub.3 COOF (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)). (C.sub.19 XeF.sub.6) (Tetrahedron Lett., 21,277 (1980)); with CH.sub.3 COOF (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). trimethylsilylenol ether and then reacted with fluorine at -78.degree. C. (J. Org. Chem., 52, 4309 (1987). fluoride in a crown ether for a long time (J. Am. Chem. Soc., 58, 1803 (1936) and Synthesis, 1977, 189). material, the fluorine containing .beta.-diketone or .beta.-ketoester is prepared through many steps (Chem. Lett., 1107 (1980) or Izv. Akad. Nauk, SSSR, Ser. Khim., 1980, 2827 (CA95-6431z).
In addition, J. Org. Chem., 57, 2196 (1992) describes that the fluorine-containing .beta.-ketoester is prepared by the fluorination (10 % F.sub.2 /N.sub.2) of the .beta.-ketoester (Process (6)).
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.
The processes (3), (4) and (5) require multi-step reactions. Further, the process (3) has drawbacks that the 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.
The above described fluorination process (6) of the .beta.-ketoester wastes a large amount of the starting material 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.
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REFERENCES:
Lerman, et al., J. Org. Chem. 1983, 48, (1983), 724-727.
Bumgardner, et al., J. Fluorine Chem., 56, (1992), 141-146.
Kagaruki, et al., Bull. Chem. Soc. Jpn., 54, (1981), 3221-3222.
Machleidt, Justus Liebigs Ann. Chim., (1964), 676,66-75.
Takeuchi, et al., J. Org. Chem., 57, (1992), 2196-2199.
Banks, et al., J. Fluorine Chem., 52, (1991), 389-401.
Umemoto, et al., J. Am. Chem. Soc., 112, (1990), 8563-8575.
Differding, et al., Tetrahedron Lett., 29, (1988), 6087-6090.
Differding, et al., Helv. Chim. Acta., 72, (1989), 1248-1252.
Yemul, et al., Tetrahedron Lett., 21, (1980), 277-280.
Zajc, et al., J. Chem. Soc., Chem. Commun., (1980), 759-760.
Xu, et al., J. Chem. Soc., Chem. Commun., (1991), 179-181.
Purrington, et al., J. Org. Chem., 52, (1987), 4307-4310.
Buchman, J. Am. Chem. Soc., 58, (1936), 1803-1805.
Fitjer, Synthesis, (1977), 189-191.
Ishikawa, et al., Chem. Lett., 1107-1110, (1980).
Kurykin, Chem. Abstracts 95:6431z (1981).
Tomizawa Ginjiro
Umemoto Teruo
Daikin Industries Ltd.
Reamer James H.
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