WO2001030740A1 - Procede de production de composes a base de fluorodicarbonyle - Google Patents

Procede de production de composes a base de fluorodicarbonyle Download PDF

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Publication number
WO2001030740A1
WO2001030740A1 PCT/JP2000/007393 JP0007393W WO0130740A1 WO 2001030740 A1 WO2001030740 A1 WO 2001030740A1 JP 0007393 W JP0007393 W JP 0007393W WO 0130740 A1 WO0130740 A1 WO 0130740A1
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fluorine
concentration
continuously
flow rate
fluorine gas
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PCT/JP2000/007393
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English (en)
Japanese (ja)
Inventor
Sumi Ishihara
Kenji Adachi
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Daikin Industries Ltd.
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Publication of WO2001030740A1 publication Critical patent/WO2001030740A1/fr

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    • 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
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/307—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms

Definitions

  • the present invention relates to a method for producing a fluorine-containing dicarbonyl compound by fluorinating a dicarbonyl compound with fluorine gas.
  • a method for producing a fluorinated dicarbonyl compound by fluorinating a dicarbonyl compound with fluorine gas is known [Japanese Patent Application No. 6-510893 (WO 94Zl 0120), Japanese Patent Application Laid-Open No. 9-255611, 095/1 4646].
  • an object of the present invention is to efficiently perform a reaction for producing a fluorine-containing dicarbonyl compound by fluorinating the dicarbonyl compound with fluorine gas.
  • the present inventors have conducted intensive studies and found that in order to efficiently perform fluorination of a dicarbonyl compound with fluorine gas, in particular, when the number of moles of the dicarbonyl compound in the raw material was set to 100, The relative number of moles of fluorine introduced per minute is in the range of 0.0001 to 2.0.
  • the fluorination may be performed by controlling the flow rate and / or the concentration of the fluorine gas, and the present invention has been achieved.
  • fluorination proceeds more efficiently by using a mixed solvent of acetonitrile and formic acid as a reaction solvent.
  • the present invention provides a method for producing a fluorine-containing dicarbonyl compound represented by the following general formula (2) by fluorinating a raw material comprising a dicarbonyl compound represented by the following general formula (1) with fluorine:
  • the present invention relates to a method for producing a fluorinated dicarbonyl compound, wherein the fluorination is performed at least in part while changing the relative number of moles of the fluorine gas with respect to the dicarbonyl compound.
  • Ri is a hydrogen atom, a substituted or unsubstituted alkyl group, or an aryl group
  • R2 is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or an aryl group
  • R 3 is a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an alkoxy group, or an aryloxy group, wherein at least two of R 1 , R 2, and R 3 are combined to form a heteroatom
  • a part of the annular structure may be formed with or without interposition of a ring structure.
  • the fluorinated dicarbonyl compound of the present invention when the number of moles of the dicarbonyl compound as the raw material is 100, The flow rate and / or concentration of the fluorine is controlled so that the relative mole number of the fluorine is in the range of 0.0001 to 2.0 (more preferably, 0.001 to 1.5). By doing so, the fluorination reaction can be performed efficiently. If the number of moles introduced is less than 0.0001, the reaction time becomes too long and the effect is poor, and if the number of moles introduced exceeds 2.0, the solvent is scattered from the reaction solution by the introduction of fluorine gas. It is easy and dangerous.
  • the alkyl group in the general formulas (1) and (2) is preferably an alkyl group having 1 to 20 (more preferably 1 to 10) carbon atoms.
  • Alkyl group represents 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, or an alkane sulfonyl group, as the case may be. And it may be substituted by a substituent such as an arylsulfonyl group or an acylamino group.
  • the aryl group is preferably an aromatic group having 6 to 14 carbon atoms (more preferably 6 to 10 carbon atoms), and the aryl group is also an alkyl group, a halogen atom, a cyano group, a nitro group, an acyl group, It may be substituted by a substituent such as an acyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkanesulfonyl group, or an arylsulfonyl group.
  • the alkoxy group preferably means an alkoxy group having 1 to 20 (more preferably 1 to 10) carbon atoms, and the alkoxy group may be substituted by the same substituent as in the case of the above alkyl group.
  • the aryloxy group preferably means an aryloxy group having 6 to 14 carbon atoms (more preferably, 6 to 10 carbon atoms), and the aryloxy group is also substituted by the same substituent as in the above aryl group. May be.
  • the halogen atom can be fluorine, chlorine, bromine or iodine. Examples of the cyclic structure that can be formed by combining R 1 , R 2, and R 3 include a monocyclic, bicyclic, or polycyclic structure having 3 to 20 members.
  • the dicalponyl compound represented by the general formula (1) as a raw material is a compound that can be easily obtained industrially or can be easily synthesized by a general synthesis method.
  • Examples of the dicarbonate compound of the general formula (1) include the following.
  • Fluorine (F 2 ) used in the method for producing a fluorine-containing dicarbonyl compound of the present invention is used to suppress the violent reaction.
  • Fluorine gas diluted with an inert gas such that the volume of the inert gas is in the range of 99.9% to 50% (preferably 9.9% to 70%, more preferably 97% to 80%) Good to use.
  • the inert gas used for dilution include nitrogen, helium, argon, and carbon dioxide.
  • the method of introducing fluorine is very important in order to efficiently fluorinate the dicarbonyl compound.
  • the amount of the raw material dicarbonyl compound in the reaction system gradually decreases, so in order to proceed with the fluorination efficiently, the amount of introduced fluorine must also be reduced. No. Otherwise, not only would excess fluorine be wasted, but it could also cause additional side reactions. This is extremely uneconomical and requires the disposal of excess fluorine, which is highly reactive, and poses both safety and environmental concerns.
  • the amount of fluorine introduced should be reduced at first to suppress side reactions due to the heat generated by fluorination, or to carry out the reaction safely. It is desirable to increase the amount gradually and then decrease it again as the amount of dicarbonyl compound in the reaction system decreases.
  • the amount of fluorine introduced can be represented by the relative number of moles introduced per minute, assuming that the number of moles of the starting dicarbonyl compound before reaction is 100, from 0.0001 to 2
  • the flow rate or the Z and concentration of the diluted fluorine gas may be controlled stepwise or / and continuously so as to fall within the range of 0.0 (preferably within the range of 0.001 to 1.5) ( The following is a summary of aspects of this control.
  • At least a part of the fluorination is performed while changing the flow rate of the fluorine gas stepwise and / or continuously. At this time, the flow rate of the fluorine gas is reduced stepwise or / and continuously, or the flow rate of the fluorine gas is stepwise or / and continuously increased and then reduced.
  • At least a part of the fluorination is performed while changing the concentration of the fluorine gas stepwise or / and continuously. At this time, the concentration of the fluorine gas is reduced stepwise and / or continuously. Alternatively, the concentration of the fluorine gas is increased stepwise or / and continuously, and then decreased.
  • At least part of the fluorination is performed while changing the flow rate and the concentration of the fluorine gas stepwise or / and continuously.
  • the flow rate and the concentration of the fluorine gas are reduced stepwise or / and continuously.
  • the flow rate of the fluorine gas is decreased stepwise and / or continuously, and the concentration of the fluorine gas is increased stepwise and / or continuously and then decreased.
  • the flow rate of the fluorine gas is increased stepwise or / and continuously, and then reduced, and the concentration of the fluorine gas is reduced stepwise or / and continuously.
  • the flow rate and concentration of the fluorine gas may be varied stepwise or / and continuously. Increase continuously and then decrease.
  • the method of changing the flow rate and / or the concentration of the fluorine gas may be various other than the above embodiments.
  • the period of the change may be a part of the whole fluorination reaction, or may be changed throughout. In this case, the change should start at a certain time after the start of the fluorination, but the initial stage of the fluorination is rather low and then raised to a high level, and the reaction proceeds smoothly. After confirming that the flow rate and / or concentration should be reduced. After this change, there may be a period during which the flow rate and / or concentration is increased, and this may be performed, for example, at the final stage of the fluorination reaction.
  • the reaction may be performed in a batch system or a continuous system.
  • the raw material dicarbonyl compound dissolved in a solvent together with an additive such as a salt or an acid, or in the case where an acid also serves as a solvent, together with fluorine gas without adding other solvents It can be introduced into a continuous reactor to perform at least part of the fluorination continuously.
  • the method of introducing the fluorine gas may be performed by appropriately changing the flow rate and / or the concentration as described above in accordance with the amount or concentration or the introduction rate of the dicarbonate compound as the raw material to be added at the same time.
  • examples of the continuous reaction apparatus include a reaction apparatus of a packed tower system and the like.
  • a parallel flow system in which the raw material and the fluorine gas flow in the same direction or a countercurrent system in which the raw material and the fluorine gas flow in the opposite direction can be adopted.
  • the co-current method is used, the relative concentration of the fluorine gas with respect to the raw material gradually decreases, so that the present invention can be implemented more effectively.
  • the conditions of the fluorination reaction (solvents, additives such as salts and acids, reaction temperatures, etc.) except for the method of introducing fluorine already include the fluorine of the dicarbonyl compound.
  • the amount of the solvent to be used may be freely adjusted according to the substrate. Even if the amount is very small, for example, 5% by weight or less based on the substrate, the solvent is used as the solvent.
  • an acid having a pKa of less than 4.5 examples include sulfuric acid, nitric acid, phosphoric acid, polyphosphoric acid, hydrogen fluoride, hydrofluoric acid, hydrogen chloride, hydrochloric acid, hydrogen bromide, hydrogen iodide, hypochlorous acid, and hypochlorous acid.
  • Hydrogen halide or hydrohalic acid such as chloric acid, chloric acid, perchloric acid, perbronic acid, or periodic acid, hypohalous acid, hypohalous acid, halogenic acid, or perhalogenic acid;
  • Fluorosulfonic acid chlorosulfonic acid, methanesulfonic acid, methanesulfonic acid, butanesulfonic acid, butanesulfonic acid, octanesulfonic acid, trifluoromethanesulfonic acid, difluorodomesulfonic acid, trichloromethanesulfonic acid, perfluorobenzosulfonic acid, perflu Sulfonic acid such as olooctanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, nitrobenzenesulfonic acid or polymer-supported sulfonic acid such as polystyrenesulfonic acid;
  • Carboxylic acids such as formic acid, chloroacetic acid, bromoacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, glycolic acid, lactic acid, benzoic acid, oxalic acid, and succinic acid; BF 3, BC 1 3, B (0 CH 3) 3, B (0 COCH 3) 3, A 1 C 1 3, S b F 3, S b C 1 3, S b F 6, PF 3, PF 5 , a s F 3, a s C 1 3, a s F 5, T i CI 4 Lewis acid such or complexes with its ether, HB F 5, HS b F 6, HPF 6, HA s F 4, complex with HS b C l 6 such as an acid or an ether such as consisting of a Lewis acid and a hydrogen halide;
  • these acids may be used in other solvents, halogenated hydrocarbons (e.g., chloroform, dichloromethane, carbon tetrachloride, chloroethane, dichloroethane, trichloroethane, tetrachloroethane, trichloromouth trifluoroethane, tetrafluoroethane).
  • halogenated hydrocarbons e.g., chloroform, dichloromethane, carbon tetrachloride, chloroethane, dichloroethane, trichloroethane, tetrachloroethane, trichloromouth trifluoroethane, tetrafluoroethane.
  • Trifluoroacetane, perfluoropentane, etc. Trifluoroacetane, perfluoropentane, etc.), nitrile compounds (eg, acetonitrile, propionitrile, etc.), water, acetic acid, propionic acid, butyric acid, isobutyric acid, alcohol (eg, methanol) , Ethanol, trifluoroethanol, propanol, isopropanol, hexafluoroisopropanol, HCF 2 C F2 C H2 OH, H (CF 2 CF 2 ) 2 CH 2 0H, H (CF 2 CF 2 ) 3 CH 2 OH, etc.).
  • reaction efficiency is further improved as compared with the case where only formic acid is used as a solvent.
  • the mixing ratio of formic acid and acetonitrile is also important, and the proportion of acetonitrile is preferably 80% or less, more preferably 35% or less.
  • the reaction efficiency is improved even if the flow rate and concentration of the diluted fluorine gas are constant, and the present invention makes it possible to control the amount of fluorine introduced.
  • the reaction efficiency is further improved.
  • the reaction temperature may be appropriately set according to the reactivity of the substrate to be fluorinated and the solvent used, and can be selected from a range of 180 ° C to + 80 ° C. Economically preferred is -50 ° C to + 50 ° C, especially -30 ° C to + 30 ° C.
  • the reaction temperature does not need to be kept constant, and may be freely changed during the reaction.
  • the present invention controls the amount of introduced fluorine gas (particularly, changes the flow rate and / or concentration) when fluorinating a dicarbonyl compound with fluorine gas.
  • the efficiency of the general formula (2) can be improved in a single step with high efficiency. Fluorine-containing dicarbonyl compounds can be produced with good yield.
  • FIG. 1 is a graph showing the relationship between the equivalent number of fluorine, the production rate of a target substance, and the reaction time in Examples 1 and 9.
  • FIG. 2 is a graph showing the relationship between the number of equivalents of fluorine and the flow rate and concentration of the diluted fluorine gas in Example 1.
  • FIG. 3 is a graph showing the relationship between the number of equivalents of fluorine and the relative number of moles of fluorine introduced in Example 1.
  • FIG. 4 is a graph showing the relationship between the number of equivalents of fluorine, the production rate of the target substance, and the reaction time in Examples 2 and 9.
  • FIG. 5 is a graph showing the relationship between the number of equivalents of fluorine and the flow rate and concentration of the diluted fluorine gas in Example 2.
  • FIG. 6 is a graph showing the relationship between the number of equivalents of fluorine and the relative number of moles of fluorine introduced in Example 2.
  • FIG. 7 is a graph showing the relationship between the equivalent number of fluorine, the production rate of the target substance, and the reaction time in Example 3 and Examples 10 and 11.
  • FIG. 8 is a graph showing the relationship between the number of equivalents of fluorine and the flow rate and concentration of the diluted fluorine gas in Example 3.
  • FIG. 9 is a graph showing the relationship between the number of equivalents of fluorine and the relative number of moles of fluorine introduced in Example 3.
  • FIG. 10 is a graph showing the relationship between the equivalent number of fluorine, the production rate of the target substance, and the reaction time in Example 4 and Examples 10 and 11.
  • FIG. 11 is a graph showing the relationship between the number of equivalents of fluorine and the flow rate and concentration of the diluted fluorine gas in Example 4.
  • FIG. 12 is a graph showing the relationship between the number of equivalents of fluorine and the relative number of moles of fluorine introduced in Example 4.
  • FIG. 13 is a graph showing the relationship between the number of equivalents of fluorine, the production rate of the target substance, and the reaction time in Examples 5 and 9.
  • FIG. 14 is a graph showing the relationship between the number of equivalents of fluorine and the flow rate and concentration of the diluted fluorine gas in Example 5.
  • FIG. 15 is a graph showing the relationship between the number of equivalents of fluorine and the relative number of moles of fluorine introduced in Example 5.
  • FIG. 16 is a graph showing the relationship between the equivalent number of fluorine, the production rate of the target substance, and the reaction time in Examples 6 and 12.
  • FIG. 17 is a graph showing the relationship between the number of equivalents of fluorine and the flow rate and concentration of the diluted fluorine gas in Example 6.
  • Figure 18 shows the number of fluorine equivalents and the relative moles of fluorine introduced in Example 6. It is a graph which shows the relationship with a number.
  • FIG. 19 is a graph showing the relationship between the number of equivalents of fluorine, the production rate of the target substance, and the reaction time in Examples 1, 6, and 13.
  • FIG. 20 is a graph showing the relationship between the number of equivalents of fluorine, the production rate of the target substance, and the reaction time in Examples 7 and 1.
  • FIG. 21 is a graph showing the relationship between the number of equivalents of fluorine and the flow rate and concentration of the diluted fluorine gas in Example 7.
  • FIG. 22 is a graph showing the relationship between the number of equivalents of fluorine and the relative number of moles of fluorine introduced in Example 7.
  • FIG. 23 is a graph showing the relationship between the equivalent number of fluorine, the production rate of the target substance, and the reaction time in Examples 8 and 9.
  • FIG. 24 is a graph showing the relationship between the number of equivalents of fluorine and the flow rate and concentration of the diluted fluorine gas in Example 8.
  • FIG. 25 is a graph showing the relationship between the number of equivalents of fluorine and the relative number of moles of fluorine introduced in Example 8.
  • FIG. 26 is a graph showing the relationship between the number of equivalents of fluorine and the flow rate and concentration of the diluted fluorine gas in Example 13.
  • FIG. 27 is a graph showing the relationship between the number of equivalents of fluorine and the relative number of moles of fluorine introduced in Example 13.
  • the “relative mole number of F 2 ” is defined as the relative mole number of fluorine introduced per minute when the mole number of the starting dicarbonyl compound before reaction is 100, and the flow rate of fluorine gas per minute. And concentration.
  • Figures 1 to 27 are graphs of the experimental data in Tables 3 to 15, respectively.
  • Fig. 1 shows the results together with Comparative Example 9 (introduced at a constant dilution fluorine gas flow rate of 190 ml / min). The results were graphed. Fluorine required for the target to raw material ratio to be 99.5: 0.5 was 132 mmo 1 (1.65 eq: equivalent), and the reaction time was 3 O Omin. Was. The raw material 3-keto_n-methyl valerate was set at 100 The relative number of moles of fluorine introduced per space was determined from the flow rate and concentration of fluorine gas, and plotted against the number of equivalents of fluorine to create Figure 3.
  • Fig. 7 shows a comparative example 10 (introduced at a constant fluorine concentration of 10%), and a comparative example. The results were graphed together with 1 1 (introduced at a constant fluorine concentration of 5%). Fluorine required for the ratio of the target substance to the raw material to be 96.8: 3.2 was 100 mmo 1 (2.0 eq), and the reaction time was 402 min. The relative number of moles of fluorine introduced per minute with respect to the starting material, 3-keto-n-methyl valerate, is 100. Calculated from the flow rate and concentration of raw gas, plotted against the number of fluorine equivalents,
  • fluorobenzene 469 ⁇ 1 (5 mmo 1) was added as a reference substance, and 19 F_NMR was measured.
  • the target substance, 2-fluoro-3-keto-1 n methyl monovalerate was 70.8%, It was confirmed that 2.4% of the product, 2,2-difluoro-3-keto-n-methyl valerate, was produced. ⁇ .
  • Example 3 The procedure was carried out in the same manner as in Example 3 except that the concentration of the diluted fluorine gas was in accordance with the method shown in Table 6 and FIG.
  • the amount of fluorine required for the target to raw material ratio to be 97.4: 2.6 was lOOmmol (2.0 eq), and the reaction time was 420 min.
  • the yield by 19 F-NMR was 73.0% for 2-fluoro-3-keto-n-methyl valerate, and 2.6% for 2,2-difluoro-13-keto-n-methyl valerate.
  • the procedure was carried out in the same manner as in Example 1 except that the flow rate and concentration of the diluted fluorine gas were in accordance with the methods shown in Table 7 and FIG.
  • the amount of fluorine required for the target to raw material ratio to become 100: 0 was 136 mmo 1 (1.7 eq), and the reaction time was 34 Omin.
  • the yield by 19 F-NMR was 77.6% for 2-fluoro-3-keto-n-methyl valerate and 2.4% for 2,2-difluoro-3-keto-n-methyl valerate. .
  • the flow rate and concentration of the diluted fluorine gas were set in accordance with the method shown in Table 10 and Figure 24, and the reaction temperature was further increased to 6 ° C and then to 12 ° C for up to 1.2 equivalents of fluorine.
  • the procedure was as in Example 1, except that the temperature was increased from 4 equivalents to 20 ° C and from 15 equivalents to 27 ° C.
  • Fluorine required for the ratio of the target substance to the raw material to be 96.5: 3.5 was 128 mmol (1.6 eq), and the reaction time was 397 min.
  • the yield by i 9 F-NMR was 72.7% for 2-fluoro-3-keto-n-methyl valerate and 3.1% for 2,2-difluoro-3-keto-n-methyl valerate.
  • Example 1 The procedure was the same as in Example 1, except that the flow rate of the diluted fluorine gas was fixed at 19 Oml / min and the concentration was fixed at 10%. Fluorine required for the ratio of the target substance to the raw material to be 97.2: 2.8 was 20 Omol (2.5 eq), and the reaction time was 257 min. The 19 F-NMR yields were 73.5% for 2-fluoro-1,3-keto-n-methylvalerate and 2.6% for 2,2-difluoro-13-keto_n-methyl valerate. Was. Example 1 0
  • the amount of fluorine required to reach 4.1 was 100 mmol (2.0 eq), and the reaction time was 485 min.
  • the 19 F-NMR yield was 2-1.6-keto-n-methylvalerate, 71.6%, 2,2-difluoro-3.
  • Fig. 2, Fig. 5, Fig. 8, Fig. 11, Fig. 11, Fig. 14, Fig. 17, Fig. 21, Fig. 24, and Fig. 26 show the flow rate and concentration of diluted fluorine gas for each example with respect to the number of equivalents of fluorine. .
  • the amount of fluorine introduced per minute relative to the number of equivalents of fluorine ie, the relative number of moles of fluorine introduced per minute when the number of moles before the reaction of the starting dicarbonyl compound is 100
  • Figure 3 Figure 6, Figure 9, Figure 12, Figure 15, Figure 18, Figure 22, Figure 25, and Figure 27.
  • Tables 1 and 2 list the reaction conditions for each case, and Tables 3 to 15 show the experimental data for each case.
  • Example 6 using a mixed solvent of formic acid and acetonitrile, it can be seen that the reaction efficiency was further improved as compared with Example 1 using only formic acid as a solvent. .
  • Example 13 where the mixing ratio is 1: 5, the mixing ratio of 2: 1 is also important.
  • the reaction efficiency is clearly lower than that of Example 6.
  • the yield of 2-fluoro-3-keto-n-methyl valerate, which is the target substance, and 2,2-difluoro-3-keto-n-methyl valerate, which is a by-product was 74 in Example 1. 7%, 2.3% and Example 6 are 79.5% and 2.7%, while Example 13 is 61.1% and 5.6%. The rate decreased and by-products increased.
  • the ratio of acetonitrile is preferably 80% or less, more preferably 35% or less.
  • the reaction efficiency was improved even when the flow rate and concentration of the diluted fluorine gas were constant (comparison between Example 9 and Example 12).
  • the reaction efficiency was further improved (Examples 6 and 12: Figure 16).

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Abstract

La présente invention concerne un procédé de production de composés à base de fluorodicarbonyle, de formule générale (2):R1 COCFR2 COR3, par fluoration de composés à base de dicarbonyle, de formule générale (1):COCHR2 COR3, avec du fluor. Selon ce procédé, au moins une partie de la fluoration susmentionnée est effectuée avec changement du rapport molaire du gaz de fluor sur le composé à base de dicarbonyle. R1 représente hydrogène, alkyle éventuellement substitué ou aryle, R2 représente hydrogène, halogéno, alkyle éventuellement substitué ou aryle et R3 représente hydrogène, alkyle éventuellement substitué, aryle, alkoxy ou arylalkoxy ou, alternativement, au moins deux de R?1, R2 et R3¿ peuvent être unis, afin de former une partie d'une structure cyclique qui peut impliquer un hétéroatome. Selon ce procédé, la fluoration des composés à base de dicarbonyle (1) avec du gaz de fluor, qui permet de donner des composés à base de fluorodicarbonyle, peut être effectuée de manière efficace.
PCT/JP2000/007393 1999-10-26 2000-10-23 Procede de production de composes a base de fluorodicarbonyle WO2001030740A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002051789A1 (fr) * 2000-12-26 2002-07-04 Tosoh F-Tech, Inc. Procede de preparation d'esters d'acide 2-fluoro-3-oxoalkylcarboxylique
JP2017197511A (ja) * 2016-04-28 2017-11-02 三和ペイント工業株式会社Ｓａｍｈｗａ Ｐａｉｎｔｓ Ｉｎｄ．Ｃｏ．，Ｌｔｄ． ジフルオロアルコール化合物の製造方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995014646A1 (fr) * 1993-11-20 1995-06-01 Bnfl Fluorochemicals Ltd Preparation de dicarbonyles
US5569778A (en) * 1992-10-30 1996-10-29 Daikin Industries Ltd. Process for preparing fluorine-containing dicarbonyl compound
EP0891962A1 (fr) * 1996-03-26 1999-01-20 F-Tech Inc. Procede pour preparer des composes dicarbonyle fluores

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5569778A (en) * 1992-10-30 1996-10-29 Daikin Industries Ltd. Process for preparing fluorine-containing dicarbonyl compound
WO1995014646A1 (fr) * 1993-11-20 1995-06-01 Bnfl Fluorochemicals Ltd Preparation de dicarbonyles
EP0891962A1 (fr) * 1996-03-26 1999-01-20 F-Tech Inc. Procede pour preparer des composes dicarbonyle fluores

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002051789A1 (fr) * 2000-12-26 2002-07-04 Tosoh F-Tech, Inc. Procede de preparation d'esters d'acide 2-fluoro-3-oxoalkylcarboxylique
US7019162B2 (en) 2000-12-26 2006-03-28 Tosoh F-Tech, Inc. Process for preparing 2-fluoro-3-oxoalkylcarboxylic acid ester
JP2017197511A (ja) * 2016-04-28 2017-11-02 三和ペイント工業株式会社Ｓａｍｈｗａ Ｐａｉｎｔｓ Ｉｎｄ．Ｃｏ．，Ｌｔｄ． ジフルオロアルコール化合物の製造方法

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