WO1998043933A1 - Procede de production d'hydrocarbures fluores, non satures et aliphatiques - Google Patents

Procede de production d'hydrocarbures fluores, non satures et aliphatiques Download PDF

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Publication number
WO1998043933A1
WO1998043933A1 PCT/JP1998/001463 JP9801463W WO9843933A1 WO 1998043933 A1 WO1998043933 A1 WO 1998043933A1 JP 9801463 W JP9801463 W JP 9801463W WO 9843933 A1 WO9843933 A1 WO 9843933A1
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WIPO (PCT)
Prior art keywords
carbon
double bond
fluorine
chlorine atom
less
Prior art date
Application number
PCT/JP1998/001463
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English (en)
Japanese (ja)
Inventor
Toshirou Yamada
Mitsuru Sugawara
Hiromi Goto
Original Assignee
Nippon Zeon Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Zeon Co., Ltd. filed Critical Nippon Zeon Co., Ltd.
Publication of WO1998043933A1 publication Critical patent/WO1998043933A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
    • C07C17/208—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being MX

Definitions

  • unsaturated compounds having a fluorine atom on a carbon atom constituting a carbon-carbon double bond have been known as a raw material monomer of a fluorinated polymer. It has also been noted as an alternative fluorocarbon and its intermediates, as a raw material for the synthesis of pharmaceuticals, agricultural chemicals, liquid crystals, and the like.
  • a method of producing the compound by a reaction in which a chlorine atom bonded to a carbon atom is replaced by a fluorine atom is known.
  • a halo of a hydrocarbon having a carbon-carbon double bond and having at least one fluorine-substitutable chlorine atom on the carbon constituting the double bond is exemplified.
  • an alkali metal fluoride such as potassium fluoride in a non-protonic polar solvent to obtain a fluorine compound.
  • the invention of the present application solves the above-mentioned problems of the prior art, and uses an industrial grade alkali metal fluoride to be less expensive and more expensive.
  • aliphatic unsaturated fluorine is useful as a substitute for fluorocarbon and its intermediates, pharmaceuticals, agricultural chemicals, liquid crystals, and as a raw material for synthesizing various polymers. It is an object of the present invention to provide a new method for producing a hydrogenated hydrocarbon compound.
  • This application provides the following inventions in order to solve such a problem.
  • An aliphatic unsaturated hydrocarbon compound having a carbon-carbon double bond and having at least one fluorine-substituted chlorine atom on the carbon constituting the double bond.
  • mechanically pulverized Alkali metal fluoride having a particle diameter of 100 m or less with respect to chlorine atoms in the aliphatic unsaturated hydrocarbon compound.
  • Luo Lidoca ⁇ React at a rate of 0.5 equivalent or more
  • aliphatically unsaturated hydrocarbon compound having a fluorine atom which can be substituted by fluorine has a fluorine atom other than a chlorine atom
  • any of the foregoing 10 or 13 wherein the aliphatic unsaturated hydrocarbon compound having a fluorine atom which can be substituted by fluorine is an alicyclic compound having 3 to 8 carbon atoms. Manufacturing method.
  • any of the above 10 or 18 wherein the amount of the solvent used is 1 to 10 times the amount of the above-mentioned aliphatically unsaturated hydrocarbon compound having a fluorine atom which can be substituted with fluorine. Manufacturing method.
  • At least one fluorine-substituted chlorine atom having a carbon-carbon double bond and having carbon on the double bond As a raw material in the present invention, at least one fluorine-substituted chlorine atom having a carbon-carbon double bond and having carbon on the double bond.
  • the type of the aliphatic unsaturated hydrocarbon compound having the general formula (1) is not particularly limited. In addition, it may have a suitable substituent as long as it does not inhibit a substitution reaction from a chlorine atom to a fluorine atom.
  • Such a raw material hydrocarbon compound is, for example, a compound represented by the general formula
  • R, and R 2 each independently represent an alkyl group, a chlorine atom, a fluorine atom, an alkyl chloride group, an alkyl fluoride group, an alkyl chloride fluoride group.
  • R, and R 2 (Shown as an alkylene group, an alkylene chloride group, an alkylene fluoride group, or an alkylene chloride group) which are bonded to each other to form a ring.
  • Chlorinated hydrocarbon compounds or fluorinated fluorinated hydrocarbon compounds When these compounds are used as a raw material, for example, the following products may be used.
  • R 3 and R 4 are each independently an alkyl group, a fluorine atom, an alkyl fluoride group, or R 3 and R are bonded to each other to form a ring Which represents an alkylene group or a fluorinated alkylene group which forms an alkylene group), thereby obtaining an aliphatically unsaturated fluorinated hydrocarbon compound represented by the formula:
  • R,, R 2 is chloride A alkyl group, in the case that having a chlorine atom such as chloride A Ruki les down group, the amount of Al Ca Li metal carrier Luo Li de, control of the other reaction conditions
  • R 3 and R * an alkyl chloride group, an alkyl chloride fluoride group, or R and R 4 are bonded to each other to form a ring. It can be an alkylene chloride group or a fluorinated alkylene group.
  • Alkyl chloride group fluorinated alkyl group, fluorinated alkyl group corresponding to R 1, R 2 , R a, and R in the above formula, or a ring bonded to each other; , Alkylene chloride, fluorinated alkylene, and fluorinated alkylene
  • the carbon number of the len group is not particularly limited, but is usually 11 to 15, preferably 2 to 10, and more preferably 2 to 6.
  • chain hydrocarbon compound represented by the above formula as a raw material compound for a linear hydrocarbon compound, 1,2-dichloro-1- , 3, 3, 3 — Trifluoropropene, 1, 2, 3 — Trichlore 1, 3, 3 — Trifluoropropene, 1, 1,, 2 — Trichloro3,3,3,3—Trifluoropropene, 2,3—Dicyclo mouth 1,1,1,1,4,4,4,4-hexafluoro 2 — Bun, 1, 2, 3, 3 — Trichlore 1, 1, 4, 4, 4 1 Pen Fluoro 2 — Bun, 1, 1, 1, 2, 3 — ⁇ Trachloro 1,4,4,4 ⁇ Trafluoro2 — bun, 1,1,1,1,2,3—Pentacro mouth_4,4,4— Trifluoro 2 — bun, 1, 1, 1, 2, 3, 4 — hexacyclo 1 , 4 — difluoro 2 — butene, 1, 1, 1, 1, 2, 3, 4, 4 — heptachloro 1-4
  • the metal fluoride used is not particularly limited, but for example, lithium fluoride, sodium fluoride, fluoride fluoride, and the like. Cesium fluoride, rubidium fluoride, etc. are exposed. Of these, sodium fluoride and potassium fluoride are preferred from the viewpoint of reactivity, and potassium fluoride is particularly preferred.
  • two or more kinds of the above-mentioned alkali metal fluorides may be used as a mixture.
  • the particle size of the alkali metal fluoride may be 100 m or less, but is preferably 50 m or less, particularly preferably 30; um or less from the viewpoint of reaction efficiency. It is.
  • the particle diameter in this case is the longest diameter (major diameter) of the particles measured on the SEM photograph.
  • the lower limit of the particle size is not particularly limited.However, from the viewpoint of mechanical pulverization and cost and handling, the lower limit of the particle size is not limited. In general, a standard of about 5 to 10 m can be set.
  • the mechanical pulverization method provides an alkali metal fluoride at a low cost, and in the reaction of the present invention, the one having the above particle size exhibits excellent reaction activity. Become. When the particle diameter is 100 m or less, the surface activation is remarkable due to the pulverization, and an efficient fluorination reaction is possible even with a small amount of use. In addition, particles having a particle diameter exceeding 100 ⁇ m may be mixed with particles having a particle diameter of less than 1 ⁇ 0 m.However, considering economics, etc. It is most preferred to use an alkali metal fluoride of 0 jum or less.
  • the method of mechanically pulverizing Alkali metal fluoride is not particularly limited.
  • Solvents such as colloid mills, jet mills, dispersers, hammer mills, homogenizers, filter mills, ball mills, and mixers
  • a wet pulverization method in which a slurry is formed. Of these, wet pulverization is preferred in order to prevent moisture absorption before pulverization and before charging into the reactor.o
  • the content of the alkali metal fluoride having a particle diameter of 100 m or less is at least 0.5 equivalent to the chlorine atom of the substrate.
  • J is usually 0.5-5 equivalents, preferably 13 equivalents, more preferably 1-2 equivalents.
  • Alkali metal fluorides may include those having a particle size of more than 100 m, and in that case, the total amount of alkali metal fluorides Is at least 1.0 equivalent, usually 1 to 5 equivalents, preferably 1 to 3 equivalents, more preferably 112 equivalents, based on the chlorine atom of the substrate. .
  • the solvent for the fluorination reaction of the present invention is not particularly limited as long as it is an aromatic polar solvent, and dimethylformamide, dimethylacetate Chain amides such as amides, N—Methylpyrrolidon, N—Cyclic amides such as methylbiperidone—, N, N—Dimethylimidida Urethanes such as zolidinone, dimethylsulfoxide, dimethylsulfoxide, dimethylsulfoxide, dimethyls
  • Examples include sulfur-containing solvents such as rufone and sulfolane.
  • sulfur-containing solvents such as rufone and sulfolane.
  • dimethylformamide, N—methylpyrrolidon, N, N—dimethylimidazolidinone, dimethylsulfoxynide, etc. are used. You. In the reaction, two or more of the above polar solvents may be used in combination.
  • the amount of the solvent used is 110 to 110 times, preferably 1.2 to 6 times, and more preferably 1.5 to the weight of the alkali metal fluoride used.
  • the range is three times as large. If the amount of the solvent is too small, stirring may be poor, and if the amount is too large, a side reaction product may be generated, and any of these may reduce the yield of the target compound. It's better.
  • the reaction temperature employed in the method of the present invention is 50-25 ° C, preferably 8 °-180 ° C, more preferably 100-16 It is in the range of 0 ° C. If the reaction temperature is too low, the reaction does not proceed sufficiently.On the other hand, if the reaction temperature is too high, the intermediate product is released out of the reaction system quickly, and side reactions occur. However, neither of these methods is preferable because it decreases the yield of the target substance.
  • the reaction time is appropriately selected depending on the reaction conditions, but is usually 0.5 to 25 hours, preferably "! To 9 hours.
  • the reaction pressure is not particularly limited, and may be pressurized or depressurized depending on the case.
  • the method of the present invention is performed in an open system.
  • a closed system as described in U.S. Pat. No. 3,024,290, relatively large amounts of solvent and alkaline metal fluoride are used.
  • solvent and alkaline metal fluoride are used.
  • the reaction By carrying out the reaction in an open system as in the present invention, the produced aliphatic unsaturated hydrofluorinated hydrocarbon compound is taken out of the system without staying in the reaction system.
  • the desired product can be obtained in high yield.
  • reaction vessel equipped with a rectification column and to carry out the reaction in a solvent in which alkali metal fluoride is dispersed. No. At this time, only the target product is concentrated and isolated with good purity from the top of the rectification column, and at the same time, the raw materials and the reaction intermediates are refluxed without escaping out of the system. It is desirable to carry out the reaction while returning it to the reaction vessel.
  • a rectification column should be installed directly in the reaction vessel.
  • the target product is withdrawn sequentially from the top of the rectification column simultaneously with the sequential dropwise supply of the raw materials, and the raw materials and reaction intermediates are always returned to the reaction vessel.
  • the amount of solvent and the amount of metal fluoride can be significantly reduced while improving the yield while improving the yield. Is possible.
  • the reaction product can be obtained by controlling the temperature at the top of the rectification column.
  • the temperature at the top of the column can be set near the boiling point of the product (specifically determined by the pressure) by setting a reflux ratio commensurate with the capacity of the rectification column.
  • the collection of the object can be carried out in accordance with ordinary law.
  • the particle size of the alkali metal fluoride is appropriately adjusted, including the ease of access.
  • an aliphatically unsaturated fluorinated hydrocarbon compound can be produced in a cost-effectively and selectively in a higher yield than in the conventional method.
  • the granular calcium fluoride was ground using an Oster Mini Blender for 15 minutes so that the particle major diameter became 10 ⁇ m or less.
  • the average particle diameter after pulverization was 30 m.
  • a refrigerant at 120 ° C. was passed through the Jim-Roat cooler, and the fraction trap was cooled to 170 ° C.
  • the fraction trap was cooled to 170 ° C by flowing a refrigerant at 120 ° C through a Jimroth cooler provided at the top of the rectification tower. .
  • 2-dicyclo mouth 1, 3, 3, 4, 4, 5, 5 — Hexafluorocyclopentene 30.3 milliliter (4 9.977 g, 0.204 mol) were charged.
  • the temperature inside the flask was raised to 135 ° C for 0.3 hours. After the start of temperature rise, the raw materials were sequentially dropped within a period of 3 to 3.0 hours. After 1.9 hours (3.6 hours from the start of the reaction) after the temperature at the top of the column has stabilized at the boiling point of the product (27 ° C), the distillate is removed. did. Withdrawal was carried out until the temperature at the top of the column started to rise and reached the boiling point of dimethylformamide (6.7 hours from the start of the reaction). 3,3,4,4,5,5—age Kutafluorocyclopentane was obtained in a yield of 51%.
  • the reaction was carried out for 7.5 hours in the same manner as in Example 1 except that the method of sequentially dropping the raw materials was changed to a method in which all the raw materials were charged from the beginning. , 4,5,5—octafluorocyclopentene was obtained in a yield of 70%.
  • the selection of the particle size of the aluminum metal fluoride allows the conversion of the aliphatic unsaturated hydrocarbon compound having a chlorine atom to the aliphatic unsaturated hydrocarbon compound. Fluorohydrocarbon compounds can be obtained inexpensively and in good yield.
  • the reaction is carried out in an open system while feeding the aliphatic unsaturated hydrocarbon compound having a chlorine atom as the raw material and extracting the intended reaction product from the top of the rectification column.
  • the target substance can be obtained with high efficiency and high purity.
  • Fluorinated hydrocarbons such as fluoroalkene obtained by the method of the present invention can be more easily hydrolyzed by a conventional method. It is possible to manufacture ruro alkanes.
  • the fluoroalkene obtained by the process of the present invention and the fluoroalkane obtained by hydrogenating it are used as an alternative fluorone and an intermediate thereof, and It is also useful as a raw material for the synthesis of pharmaceuticals, agricultural chemicals, liquid crystals, polymers and the like.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Cette invention se rapporte à un procédé de production à haut rendement d'un hydrocarbure fluoré, non saturé, aliphatique et doté d'une grande pureté, et ce à faible coût. Ce procédé consiste à faire réagir un hydrocarbure non saturé, aliphatique, comportant une double liaison carbone-carbone et au moins un atome de chlore remplaçable par un atome de fluor et relié à l'atome de carbone engagé dans la double liaison, avec au moins 0,5 équivalent, par équivalent d'atome de chlore de l'hydrocarbure non saturé, aliphatique, considéré comme base, d'un fluorure de métal alcalin, pulvérisé mécaniquement et doté d'un diamètre de particule inférieur à 100 νm.
PCT/JP1998/001463 1997-03-31 1998-03-31 Procede de production d'hydrocarbures fluores, non satures et aliphatiques WO1998043933A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP9/81046 1997-03-31
JP8104697 1997-03-31

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WO1998043933A1 true WO1998043933A1 (fr) 1998-10-08

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7145046B2 (en) 2001-02-02 2006-12-05 Solvay Fluor Und Derivate Gmbh Production of fluorine compounds
JP2008031028A (ja) * 2006-04-27 2008-02-14 Sumitomo Chemical Co Ltd フッ化カリウム分散液およびそれを用いる含フッ素有機化合物の製造方法
JP2013117034A (ja) * 2005-11-01 2013-06-13 E I Du Pont De Nemours & Co フルオロオレフィンを含む組成物およびそれらの使用
US8911640B2 (en) 2005-11-01 2014-12-16 E I Du Pont De Nemours And Company Compositions comprising fluoroolefins and uses thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62212331A (ja) * 1986-03-13 1987-09-18 バイエル・アクチエンゲゼルシヤフト ３―フルオロ―２―（フルオロメチル）―プロペンの製造方法
JPH0995458A (ja) * 1995-09-29 1997-04-08 Nippon Zeon Co Ltd フッ化炭化水素化合物の製造法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62212331A (ja) * 1986-03-13 1987-09-18 バイエル・アクチエンゲゼルシヤフト ３―フルオロ―２―（フルオロメチル）―プロペンの製造方法
JPH0995458A (ja) * 1995-09-29 1997-04-08 Nippon Zeon Co Ltd フッ化炭化水素化合物の製造法

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7145046B2 (en) 2001-02-02 2006-12-05 Solvay Fluor Und Derivate Gmbh Production of fluorine compounds
JP2013117034A (ja) * 2005-11-01 2013-06-13 E I Du Pont De Nemours & Co フルオロオレフィンを含む組成物およびそれらの使用
JP2014169455A (ja) * 2005-11-01 2014-09-18 E.I.Du Pont De Nemours And Company フルオロオレフィンを含む組成物およびそれらの使用
US8911640B2 (en) 2005-11-01 2014-12-16 E I Du Pont De Nemours And Company Compositions comprising fluoroolefins and uses thereof
JP2008031028A (ja) * 2006-04-27 2008-02-14 Sumitomo Chemical Co Ltd フッ化カリウム分散液およびそれを用いる含フッ素有機化合物の製造方法

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