WO2002066452A1 - Procedes permettant la preparation d'ethers cycliques fluores et leur utilisation - Google Patents

Procedes permettant la preparation d'ethers cycliques fluores et leur utilisation Download PDF

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WO2002066452A1
WO2002066452A1 PCT/JP2002/001564 JP0201564W WO02066452A1 WO 2002066452 A1 WO2002066452 A1 WO 2002066452A1 JP 0201564 W JP0201564 W JP 0201564W WO 02066452 A1 WO02066452 A1 WO 02066452A1
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compound
compound represented
following formula
formula
group
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PCT/JP2002/001564
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English (en)
Japanese (ja)
Inventor
Hidekazu Okamoto
Takashi Okazoe
Kunio Watanabe
Masahiro Ito
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Asahi Glass Company, Limited
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Priority to JP2002565968A priority Critical patent/JPWO2002066452A1/ja
Publication of WO2002066452A1 publication Critical patent/WO2002066452A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms

Definitions

  • the present invention relates to a method for producing industrially useful fluorinated cyclic unsaturated ethers and fluorinated saturated cyclic ethers (hereinafter collectively referred to as fluorinated cyclic ethers), their uses, and the fluorination.
  • the present invention relates to a novel compound useful as an intermediate for producing a cyclic ether. '
  • the following method is known as a method for synthesizing a fluorinated cyclic ether.
  • An object of the present invention is to provide a method for producing a fluorinated cyclic ether with high yield, which is a method suitable for industrial practice and economically advantageous. Disclosure of the invention)
  • the present invention provides a method for producing a fluorinated cyclic ether useful as a functional agent or the like, using a compound that can be obtained at low cost. Further, the present invention provides an industrially useful continuous process by recycling the fluoride compound obtained in the ester decomposition reaction step in the production method. Further, the present invention provides a novel compound useful as an intermediate for the production of a fluorinated cyclic ether.
  • the fluorinated cyclic ethers produced according to the present invention have excellent properties as an alternative to black fluorocarbons (CFCs), have zero ozone depletion potential (ODP), and have a global warming potential (GWP) was also found to be a very small compound, and provided useful applications using this fluorinated cyclic ether.
  • the present invention provides each invention having the following configurations.
  • the compound represented by the following formula (5) is thermally decomposed to at least one kind of fluorination selected from the compound represented by the following formula (6a) and the compound represented by the following formula (6b)
  • AF represents a perfluorotetrahydrofuranyl group.
  • X represents a fluorine atom or 10-M + (however, M + represents a counter ion).
  • the compound represented by the following formula (5f) wherein X is a fluorine atom is represented by the compound represented by the following formula (1) and the compound represented by the following formula (2).
  • the compound represented by the following formula (3) is reacted to obtain a compound represented by the following formula (3), and the compound represented by the formula (3) is fluorinated to give a compound represented by the following formula (4).
  • the production method according to the above 1 or 2 which is a compound obtained by subjecting the ester bond of the compound represented by the formula to a decomposition reaction.
  • AF has the same meaning as described above.
  • Re represents a monovalent organic group.
  • R eF the same monovalent organic group and R c, or a monovalent organic group R c is fluorinated.
  • X 1 represents a halogen atom.
  • A is a group represented by the following formula (1a), the following formula (1b), the following formula (1c), and the following formula (Id), or a hydrogen atom in the selected formula: A group represented by the formula in which at least one is substituted with a fluorine atom.
  • the compound represented by the formula (1) is a compound represented by the following formula (1); the compound represented by the formula (3) is a compound represented by the following formula (3); 4) 4.
  • a 1 is a group represented by the following formula (la-l), the following formula (lb-1), the following formula (lc_l), and the following formula (ld-l): A group represented by the formula in which at least one hydrogen atom in the formula is substituted with a fluorine atom.
  • the compound represented by the formula (3) is converted into a compound represented by the formula (5) and a compound represented by the following formula (2a) from a reaction product obtained by decomposing an ester bond of the compound represented by the formula (4). 5.
  • the compound represented by the following formula (5) is thermally decomposed to give one or more compounds selected from the compounds represented by the following formula (6a) and the compounds represented by the following formula (6b): Get, next A compound represented by the following formula (7a) and a compound represented by the following formula (6b) obtained by reducing the compound represented by the formula (6a)
  • a method for producing a fluorinated saturated cyclic ether characterized in that at least one kind of a fluorinated saturated cyclic ether selected from the compounds represented by the formula (7b) is obtained.
  • R C 1 and R eF 1 are a perfluoroalkyl group, a perfluoro (partial alkyl) alkyl group, a perfluoro (ether alkyl containing an oxygen atom) group, and a perfluoro (partially alkyl (containing an etheric oxygen atom) Alkyl)) group, or Indicates a fluorotetrahydrofuranyl group.
  • the functional agent according to the above 10 or 11 which is a draining dry solvent, a dry etching agent, or a cleaning agent.
  • a compound represented by the formula (5) is referred to as a compound (5).
  • the following compound (5) is thermally decomposed to obtain one or more fluorinated unsaturated cyclic ethers selected from the following compounds (6a) and (6b).
  • AF in the formula (5) represents a perfluorotetrahydrofuranyl group.
  • One COX group in (5) may be bonded to the 2- or 3-position of the perfluorotetrahydrofuranyl group (A F ), and is preferably bonded to the 2-position . That is, AF is preferably a 2 ⁇ -fluorotetrahydrofuranyl group, and compound (5) is preferably the following compound (5a).
  • X represents a fluorine atom or one O—M +.
  • M + is selected from cations capable of forming a salt with a carboxylic acid, preferably an alkali metal cation, and more preferably K + and Na + .
  • a method for producing a compound in which X in compound (5) is 10-M + one COF group in compound (5f) in which X in compound (5) is a fluorine atom is converted into one COOH.
  • a method of forming a salt, or after reacting the compound (5f) with 2 times or more moles of MOH (M is a compound wherein the cation is M + and an alkali metal atom is preferred). It is preferable to employ a method of heating and drying under reduced pressure.
  • X is a fluorine atom
  • Compound (5f) is obtained by reacting compound (1) with compound (2) to give compound (3), fluorinating compound (3) to give compound (4), and converting the ester bond of compound (4) to It is preferably a compound obtained by a decomposition reaction.
  • AF has the same meaning as described above.
  • RG represents a monovalent organic group.
  • R eF the same monovalent organic group and R G, or a monovalent organic group R G is fluorinated.
  • X 1 represents a halogen atom.
  • A is a group represented by the following formula (la), the following formula (lb), the following formula (lc), and the following formula (Id), or one or more hydrogen atoms in the selected formula:
  • the line extending from the ring is a bond (the position of the carbon atom of the five-membered ring to which the bond is bonded is not limited).
  • A is a group having a bond to _CH 2 OH at the 2-position, that is, the following formulas (la-1), the following formulas (la-2), the following formulas (la-3), and the following formulas (1a- A group represented by the formula selected from 4) or a group (A 1 ) represented by a formula in which at least one hydrogen atom in the selected formula is substituted with a fluorine atom is preferable.
  • A is preferably a group having no fluorine atom, that is, a group represented by a formula selected from formulas (la), (lb), (1c) and (1d).
  • a group represented by a) or a group represented by the formula (lb) is preferable, and a group represented by the formula (la-1) or a group represented by the formula (la-2) is particularly preferable.
  • R G is: Shows a valent organic group.
  • R c is preferably a group having 1 to 20 carbon atoms, particularly preferably a group having 1 to 10 carbon atoms, from the viewpoint of solubility in a liquid phase used during the fluorination reaction. Further, R c is preferably a group containing a fluorine atom (that is, a fluoromonovalent organic group), such as a fluoroalkyl group, a fluoro (partial cycloalkyl) group, or a fluoroalkyl group.
  • a fluoro (etheric oxygen atom-containing alkyl) group, a fluoro (partial port (etheric oxygen atom-containing alkyl)) group, or AF described later are preferred.
  • R e is preferably a perfluorinated monovalent organic group, such as a perfluorinated alkyl group, a perfluoro (partially alkyl) group, a perfluorinated (alkyl containing an etheric oxygen atom) group, and a perfluorinated (partially substituted alkyl) group.
  • (Etheric oxygen atom-containing alkyl)) group or AF described below is particularly preferred.
  • a partially-cropped group refers to a group that has been substituted with chlorine to the extent that a hydrogen atom remains.
  • AF represents a perfluorotetrahydrofuran group, and a perfluoro (2-tetrahydrofuranyl) group is preferable.
  • the compound (2) a commercially available product may be used, but the compound (2a) (R CF COF (2C) is a compound that can be produced together with the compound (5) in a decomposition reaction of an ester bond of the compound (4) described later. a)) may be used.
  • the method using the compound (2a) as the compound (2) is particularly preferable because it can be a continuous production method. That is, R G in compound (2) is preferably the same group as, and particularly preferably R c is a perfluoromonovalent organic group. Preferred embodiments of the perfluoro monovalent organic group are as described above.
  • RG in compound (2) is AF
  • compound (5) when compound (5) is used as compound (2), a product resulting from a decomposition reaction of an ester bond of compound (4) is produced.
  • the esterification reaction of compound (1) with compound (2) may be carried out in the presence of a solvent, but is preferably carried out in the absence of a solvent, from the viewpoint of volumetric efficiency.
  • alkali metal fluoride preferably NaF, KF, etc.
  • trialkylamine or the like is used as a HF scavenger.
  • a HF scavenger it may be present in the reaction system, and it is preferable that a HF scavenger is present. When no HF scavenger is used, it is preferable to discharge HF out of the reaction system by accompanying HF with a nitrogen gas stream. When using an alkali metal fluoride, the amount
  • the reaction temperature of the compound (1) with the compound (2) is preferably from 50 ° C to + 100 ° C.
  • the reaction time of the reaction can be appropriately changed depending on the supply rate of the raw materials and the amount of the compound used in the reaction.
  • the reaction pressure (gauge pressure, hereinafter the same) is preferably 0 to 2 MPa.
  • the molar ratio of the compound (1) to the compound (2) is preferably such that the amount of the compound (2) was 0.5 to 5 times, more preferably 1 to 2 times, the mole of the compound (1).
  • the crude product containing the compound (3) formed by the reaction of the compound (1) with the compound (2) may be purified according to the purpose or used as it is for the next reaction. From the viewpoint of stably performing the fluorination reaction in the step of, the compound in the crude product
  • a method for purifying the crude product a method for distilling the crude product as it is, a method for treating the crude product with dilute alkaline water or the like to separate the crude product, and a method for extracting the crude product with an appropriate organic solvent and then distilling the crude product Method, silica gel column chromatography, and the like.
  • Specific examples of the compound (3) include the following compounds. However, A 1 and AF have the same meaning as described above.
  • the compound (3) is fluorinated.
  • the method of the fluorination reaction include a method using C O F 3 , an ECF method, and a method using fluorine gas.
  • the liquid phase fluorination method performed by introducing fluorine gas into the liquid phase is used. Is preferred.
  • one or more fluorine atoms are bonded in the molecule of compound (3).
  • the fluorine gas in the liquid phase fluorination reaction may be used as it is, or may be a fluorine gas diluted with an inert gas such as nitrogen gas.
  • an inert gas such as nitrogen gas.
  • the fluorine gas concentration is preferably at least 10 Vo 1%, particularly preferably at least 20 Vo 1%.
  • the liquid phase is preferably formed from a solvent capable of dissolving fluorine (F 2 ).
  • a solvent having high solubility of compound (3) is preferably used, and particularly a solvent that can dissolve compound (3) by 1% by mass or more, particularly a solvent that can dissolve compound (3) by 5% by mass or more is used.
  • the amount of the solvent is preferably at least 5 times the mass of the compound (3), particularly preferably 10 to 100 times the mass.
  • examples thereof include alkylamines and inert fluids.
  • the fluorine content (the fluorine content is the ratio of the mass of fluorine atoms to the molecular weight) of the compound (3) is preferably at least 10% by mass, and particularly preferably from 10 to 86% by mass. If the fluorine content is too low, the solubility in the liquid phase will be extremely low And the reaction system of the fluorination reaction becomes non-uniform.
  • the upper limit of the fluorine content is not limited, but if it is too high, it is difficult to obtain the compound (3), the price is high, and it is not economical.
  • the molecular weight of the compound (3) is preferably 200 to 1000, since the undesirable fluorination reaction in the gas phase can be prevented and the liquid phase fluorination reaction can be carried out smoothly. If the molecular weight is too small, the compound (3) is likely to evaporate, so that a decomposition reaction may occur in the gas phase during the fluorination reaction in the liquid phase. On the other hand, if the molecular weight is too large, purification of compound (3) may be difficult.
  • the reaction format of the fluorination reaction may be a notch system or a continuous system.
  • the continuous method is preferable from the viewpoint of the reaction yield and the selectivity.
  • the fluorine gas may be diluted with an inert gas such as nitrogen gas, regardless of whether the method is carried out by the notch method or the continuous method.
  • fluorine gas in the fluorination reaction, it is preferable to supply fluorine gas so that the amount of fluorine is always an excess equivalent to the hydrogen atom in the compound (3), particularly 1.5 times equivalent or more (that is, 1.5 times or more). It is preferable from the viewpoint of selectivity that fluorine gas be used so that the molar ratio becomes twice or more. It is preferable that the fluorine gas always keeps an excess equivalent from the start point to the end point of the reaction. For this purpose, it is preferable to introduce the compound (3) into a liquid phase in which fluorine is dissolved.
  • the reaction temperature of the liquid-phase fluorination reaction is usually preferably not lower than 160 ° C and not higher than the boiling point of the compound (3). From the viewpoint of reaction yield, selectivity, and low industrial practice, the reaction temperature was 150 ° C. -10 ° C is particularly preferred, and -20 ° C to + 50 ° C is particularly preferred.
  • the reaction pressure of the fluorination reaction is particularly preferably 0 to 2 MPa from the viewpoints of reaction yield, selectivity, and ease of industrial implementation.
  • the CH bond-containing compound aromatic hydrocarbons are preferable, and benzene, toluene and the like are particularly preferable.
  • the addition amount of the C one H bond-containing compound is preferably from 0.1 to 10 mole 0/0 to hydrogen atoms in the compound (3), and even in particular from 0.1 to 5 Mo ⁇ preferable.
  • the C—H bond-containing compound is preferably added in a state where fluorine gas is present in the reaction system. Further, when a C—H bond-containing compound is added, it is preferable to pressurize the reaction system.
  • the pressure at the time of pressurization is preferably 0.01 to 5 MPa.
  • HF is produced as a by-product, so a HF scavenger must coexist in the reaction system for the purpose of removing the by-product HF, or the HF scavenger and the outlet gas come into contact at the reactor gas outlet.
  • a HF scavenger In the fluorination reaction, HF is produced as a by-product, so a HF scavenger must coexist in the reaction system for the purpose of removing the by-product HF, or the HF scavenger and the outlet gas come into contact at the reactor gas outlet. Is preferred.
  • the HF scavenger include the same examples as described above, and NaF is preferable.
  • the amount is preferably 1 to 20 times, and more preferably 1 to 5 times, the molar amount of the total hydrogen atoms present in the compound (3).
  • the crude product containing the compound (4) obtained by the fluorination reaction may be used as it is in the next step, or may be purified to high purity.
  • Examples of the purification method include a method of distilling the crude product as it is under normal pressure or reduced pressure.
  • Compound (4) is a compound obtained by fluorinating compound (3), and is preferably a compound obtained by perfluorinating compound (3).
  • the R CF the preferred same groups as R c, Perufuruoro monovalent organic groups are particularly preferred, Perufuruo port alkyl group, Perufuruoro (partial black port alkyl) group, Perufuruoro (ether oxygen atom-containing alkyl) group, A perfluoro (partial chroma (alkyl containing an etheric oxygen atom)) group or a perfluorotetrahydrofuranyl group is particularly preferred.
  • Specific examples of the compound (4) include the following compounds. However, AF has the same meaning as described above.
  • Compound (4) is converted into a compound (5) in which X is a fluorine atom by a decomposition reaction of an ester bond.
  • the decomposition reaction of the ester bond can be carried out by heating, or by reacting with an electrophile or in the presence of a nucleophile.
  • the type of reaction can be selected depending on the boiling point and stability of compound (4).
  • the reaction temperature of the gas phase method is preferably from 50 to 350 ° C, particularly preferably from 50 to 300, particularly preferably from 150 to 250 ° C.
  • an inert gas that is not directly involved may coexist in the reaction system. Examples of the inert gas include nitrogen gas and carbon dioxide gas.
  • the amount of the inert gas is preferably about 0.01 to 50% based on the compound (4). Large amounts of inert gas may reduce product recovery.
  • the ester bond decomposition reaction is carried out by a gas phase method, it is preferable to use a tubular reactor.
  • the residence time is 0.1 seconds to 10 minutes based on the empty tower. It is preferable to set the temperature.
  • a gas phase reaction using a tubular reactor it is preferable to fill the reaction tube with a glass, an alkali metal salt, or an alkaline earth metal salt in order to promote the reaction.
  • the reaction pressure is not particularly limited, but when the compound (4) is a high-boiling compound, the reaction is preferably performed under reduced pressure. On the other hand, when the compound (4) is a low-boiling compound, it is preferable to carry out the reaction under pressure because the decomposition of the product is suppressed and the reaction rate increases.
  • reaction temperature in the liquid phase method is preferably from 50 to 300 ° C, particularly preferably from 100 to 250 ° C.
  • a solvent may or may not be present, and the absence of a solvent is preferred from the viewpoint of volumetric efficiency and suppression of by-products.
  • a solvent may or may not be used in the reaction, and no solvent may be used. Is preferred from the viewpoint of volumetric efficiency and suppression of by-products.
  • F— fluorine anion
  • alkali metal fluoride NaF, KF and CsF are preferred, and NaF is particularly preferred from the viewpoint of economy.
  • the nucleophile may be used in a catalytic amount or in excess.
  • the amount of the nucleophile is preferably from 1 to 500 mol%, more preferably from 10 to 100 mol%, particularly preferably from 5 to 50 mol%, based on compound (4).
  • the lower limit of the reaction temperature is preferably 130 ° C., and the upper limit is preferably the boiling point of the solvent or the boiling point of the compound (4).
  • the normal reaction temperature is preferably 120 ° C. (: up to 250 ° C.) In this method, the reaction is carried out while continuously taking out the compound (5) formed. Is preferred.
  • the reaction product of the ester decomposition reaction contains the compound (2a) together with the compound (5).
  • compound (2a) can be separated from compound (5) and used for another purpose.
  • Compound (2a) is a useful intermediate that can be converted into another useful compound.
  • compound (3) when the esterification reaction is carried out using the compound (2a) as the compound (2) to be subjected to an esterification reaction with the compound (1), the compound (3) can be produced.
  • Compound (.5) can be produced by the method.
  • compound (2a) is a compound in which R c in compound (2) is R CF and X is a fluorine atom.
  • the compound (5) can be produced by reusing the compound (2a) as the compound (2).
  • the compound (5) is thermally decomposed.
  • the reaction conditions for the thermal decomposition are not particularly limited.
  • the pyrolysis reaction is preferably performed by a pyrolysis reaction in the gas phase.
  • the reaction temperature of the gas phase thermal decomposition reaction is preferably from 250 to 400 ° C, more preferably from 280 to 350 ° C.
  • the reaction temperature in the gas phase thermal decomposition reaction is preferably from 150 to 300 ° C, more preferably from 200 to 280 ° C. If the reaction temperature in the gas phase pyrolysis reaction is too low, the conversion tends to be low. On the other hand, if the reaction temperature in the gas-phase pyrolysis reaction is too high, the amount of generated compounds other than the target compound tends to increase.
  • a deCOFX reaction occurs and a double bond is formed in the furan ring to produce compound (6a) or compound (6b). Further, in these compounds, a transfer reaction of a double bond further occurs, and a compound (6b) can be produced from the compound (6b) to produce a compound (6a) from the compound (6b).
  • a transfer reaction of a double bond further occurs, and a compound (6b) can be produced from the compound (6b) to produce a compound (6a) from the compound (6b).
  • compound (6 a) is generated, and the compound (6b) is generated in the thermal decomposition reaction of the compound (5) in which _COF is bonded to the 3-position.
  • the product when a double bond transfer reaction occurs in a part of the product, the product can be a compound (6a) and a compound (6b).
  • two kinds of compounds are usually formed in the pyrolysis reaction.
  • the composition of the product of the thermal decomposition reaction can vary depending on the reaction conditions and the like.
  • the composition is not particularly limited.
  • the compound (6a) and the compound (6b) may be used as they are for the intended purpose, but are usually used after being converted to other compounds.
  • the compound (6a) and the compound (6b) may be separated and purified and then converted to another compound. Since the compound (6b) has a close boiling point and requires time-consuming separation, it is preferable to convert these to other compounds without separating them.
  • One or more selected fluorinated saturated cyclic ethers can be obtained.
  • a hydrogen atom is added to the carbon-carbon unsaturated double bond of compound (6a) or compound (6b).
  • This reduction reaction is preferably carried out using hydrogen, and the catalyst It is particularly preferred to use hydrogen in the presence of As the catalyst, a metal-supported catalyst is preferable.
  • the metal-supported catalyst is preferably a catalyst in which a metal is supported by 0.5 to 5% by weight / 0 , preferably:! To 3% by weight based on the carrier.
  • the metal-supported catalyst is preferably a catalyst in which a metal is supported on activated carbon, an activated carbon catalyst in which palladium is supported, an activated carbon catalyst in which palladium as a main component and a Group 8 element other than palladium are supported, or Au Particularly preferred is an activated carbon catalyst carrying
  • the Group 8 element other than palladium one or more elements selected from Fe, Co, Ni, Ru, Rh, Ir, and Pt are preferable.
  • the amount of the Group 8 element other than palladium is preferably 0.01 to 50% by mass with respect to palladium.
  • the carrier is activated carbon
  • activated carbon derived from plant material is preferred over activated carbon derived from mineral substances, and coconut shell activated carbon is particularly preferred.
  • the shape of the carrier can be shaped coal of about 2 to 5 mm in length, crushed coal of about 4 to 50 mesh, granular coal, etc., and crushed coal of about 4 to 20 mesh or length Coking coal of the order of about 2 to 5 mm is preferred.
  • the catalyst in which a metal is supported on activated carbon is preferably prepared by a method in which a metal component is supported on a carrier, dried, and then reduced and activated with hydrogen.
  • the catalyst prepared by this method has the advantage of high durability and does not require activation even when used for a long time.
  • the amount of hydrogen is preferably at least 2 times the stoichiometric amount based on the total amount of the substrate for the reduction reaction, and more preferably 3 to 8 times the molar amount of the target compound in high yield. This is preferred.
  • the temperature of the reduction reaction is preferably from 130 to 250 ° C at normal pressure, more preferably from 150 to 200 ° C.
  • the reaction pressure is not particularly limited.
  • the reaction time of the reduction reaction is preferably 4 to 60 seconds, particularly preferably 8 to 40 seconds, as a contact time with the catalyst.
  • the reduction reaction uses water with an inert gas such as nitrogen to control excessive temperature rise. It may be performed while diluting the element.
  • compound (7a) is reduced when compound (6a) is reduced, and compound (7b) is reduced when compound (6b) is reduced.
  • the product of the thermal decomposition reaction is a compound
  • Compound (6a), compound (6b), compound (7a), and compound (7b) obtained by the production method of the present invention have excellent properties as an alternative compound to a fluorofluorocarbon. It has a low ozone depletion potential and a very low global warming potential. These compounds or a mixture of one or more of these compounds is a compound useful as a functional agent.
  • the functional agent examples include a refrigerant, a cleaning agent, a draining dry solvent, a solvent, a polymerization solvent, a dry etching agent, a resin foaming agent, and the like.
  • the functional agent containing one or two fluorinated unsaturated cyclic ethers selected from the compound (6a) and the compound (6b) is used as a draining dry solvent, a dry etching agent, or a cleaning agent. It is preferably used as an agent.
  • Compound (7a) and compound (7b) are functional agents containing one or two selected fluorinated saturated cyclic ethers, especially those containing compound (7a) are dry etching agents. It is preferable to use them.
  • an oxygen atom is present in the structure of the fluorinated cyclic ether of the present invention, When it is used as a dry etching agent, there is an advantage that the operation of adding oxygen during dry etching can be omitted.
  • the following compound useful as an intermediate of the functional agent can be provided.
  • R C 1 and R CF 1 represent a perfluoroalkyl group, a perfluoro (partial alkyl) alkyl group, a perfluoro (alkyl containing an etheric oxygen atom) group, and a perfluoro (partially An oxygen atom-containing alkyl)) group, or a perfluorotetrahydrofuranyl group.
  • R C1 and R CF1 are preferably a group having 1 to 20 carbon atoms, and particularly preferably a group having 1 to 10 carbon atoms. Further, as R C 1 and R CF 1 , a perphnoleo alkyl group,
  • gas chromatography is referred to as GC
  • gas chromatography mass spectrometry is referred to as GC-MS.
  • the purity determined from the peak area ratio of GC is referred to as GC purity, and the yield is referred to as GC yield.
  • the yield determined from the peak area ratio of the NMR spectrum is referred to as the NMR yield.
  • tetramethylsilane is described as TMS
  • CC 1 and FCC IF 2 are described as R—113.
  • the NMR spectrum data is shown as an apparent chemical shift range.
  • the pressure was adjusted to normal pressure, the above-mentioned benzene solution (6 mL) was injected while maintaining the temperature in the reactor at 40 ° C, the benzene injection port of the auto tare was closed, and the outlet valve of the autoclave was closed.
  • the pressure became 0.2 OMPa, the fluorine gas inlet pulp of the autoclave was closed, and stirring was continued for 0.4 hour.
  • the same operation was repeated three times.
  • the total injection volume of benzene was 0.33 g and the total injection volume of R-113 was 33 mL. Furthermore, nitrogen gas was blown for 1.0 hour.
  • the desired product was quantified by 19 F-NMR, formation of the compound (4b_l) was confirmed, and the yield was 64%.
  • Example 2 The compound (4b-l) (2.1 g) obtained in Example 2 was charged into a flask together with NaF powder (0.02 g), and the mixture was vigorously stirred at 140 ° C for 10 hours in an oil bath. For a while. A reflux condenser adjusted to a temperature of 20 ° C. was installed at the top of the flask. After cooling, a liquid sample (2.0 g) was recovered. The collected liquid sample was reacted in an aqueous KOH solution containing 2.5 times the molar amount of K ⁇ H of compound (4b-1), and water was removed to obtain compound (5a-l) .
  • Catalyst shown in Table 1 (l O OmL) Reaction tube made of Inconel 600 (1/2 inch diameter Lm), heat it from outside and keep it at 120 ° C, introduce compound (6b) at a flow rate of 0.2mo 1Zh, and simultaneously introduce hydrogen at a flow rate of 1.Omo lZh.
  • the reaction was performed by introduction.
  • compound (7b) was obtained with the results shown in Table 1 below.
  • the catalyst used was such that 100 parts by mass of crushed coconut shell and 2 parts by mass of a metal component were supported.
  • the fluorination step was carried out in the same manner as in Example 2, except that the compound (3b-1) in Example 2 was changed to 5.5 g of the compound (3a-1) obtained in Example 6.
  • Example 4 Compounds in Example 4 (5 a- 1), instead of the compound obtained in Example 8 (5 a- 2), the same procedure was followed as in Example 4 except changing the K 2 C_ ⁇ 3 to Na 2 C0 3 Compound (6a) was obtained as the main component.
  • the yield of compound (6a) was 61.0%.
  • the formation of ⁇ compound (6b) was also observed in the product.
  • Example 11-11 A 150 mm diameter silicon wafer having a silicon oxide film formed on its surface was set in a parallel plate type plasma etching apparatus, the system was evacuated, and then distilled from the product of Example 4. The compound (6b) obtained in this manner was gasified and introduced at 50 m for 17 minutes (at a gas temperature of 20). The pressure in the system 39. 9Pa (absolute pressure) in the Set, the plasma in the plasma density 10 9 cm- 3 was irradiated for 60 seconds was etched experiment. The etching rate is determined by adjusting the film pressure at any three points on the wafer before and after etching. The measurement was performed, and the average of the etching rates at three points was determined to be 2000 minutes or more for Z minutes or more, and to be less than that for X. The result was ⁇ .
  • Example 11-12 The same measurement as in Example 11-11 was performed, except that the compound (6a) was changed to the compound (6a) obtained in Example 9. The result was ⁇ .
  • Example 1 except that compound (6a) is changed to octafluorocyclopentene
  • Example 12 Example of evaluation as a draining dry solvent
  • the state of the mixed solvent was determined to be A by the following A to D.
  • the state of water floating on the liquid surface was determined as A by the following A to D, and the result was A.
  • the object to be washed was immersed and washed in isododecane (60 ° C) for 30 seconds, and then the compound (7a) obtained in Example 10 was used while containing the compound (7b).
  • the compound (7a) was immersed and rinsed at 30 for 30 seconds, and finally steam-washed in the vapor zone of the compound (7a) for 30 seconds.
  • the residual ratio of the cutting oil was calculated from the mass measurement results of the object to be cleaned before and after the application of the cutting oil and after the cleaning and drying, and the dried state of the object to be cleaned immediately after the steam cleaning was observed.
  • the result of evaluation based on the standard was A.
  • Oil residual ratio A less than 0.1% by weight, B 0.1% to less than 0.5% by weight, C: 0.5% to less than 2% by weight, D 2% by weight or more.
  • the dry state was evaluated according to the following criteria, and the result was A. A Immediately dried, B: Slowly dried, C: Partially dried, D: Unable to dry. Industrial applicability>
  • the present invention provides a method suitable for industrial practice and for producing a fluorinated cyclic ether with high yield in an economically advantageous manner.
  • the fluorinated cyclic ether of the present invention is a compound useful as a functional agent such as a draining dry solvent, a dry etching agent, or a cleaning agent. Further, according to the present invention, there is provided a novel compound useful as an intermediate of a fluorinated cyclic ether.

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

Abstract

La présente invention concerne: des procédés permettant la préparation d'un éther cyclique fluoré insaturé utile et d'un éther cyclique fluoré saturé utile, à partir de substances peu onéreuses; une utilisation peu onéreuse de l'éther cyclique fluoré insaturé et de l'éther cyclique fluoré saturé; un nouveau composé pouvant être utilisé en tant qu'intermédiaire pour ces esters. Selon l'invention, un composé (5) représenté ci-dessous est décomposé thermiquement pour produire au moins un éther cyclique fluoré insaturé correspondant au composé (6a) ou au composé (6b) représentés ci-dessous. La réduction de l'éther cyclique fluoré insaturé donne au moins un éther cyclique fluoré saturé correspondant au composé (7a) ou au composé (7b) représentés ci-dessous. Dans la formule (5), AF représente perfluoro tétrahydrofuranyle et X représente fluor ou O?-M+ (où M+¿ est un ion antagoniste).
PCT/JP2002/001564 2001-02-21 2002-02-21 Procedes permettant la preparation d'ethers cycliques fluores et leur utilisation WO2002066452A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004018443A1 (fr) * 2002-08-21 2004-03-04 Asahi Glass Company, Limited Fluoropolymeres permeables aux ultraviolets et pellicules les utilisant
WO2004050649A1 (fr) * 2002-12-04 2004-06-17 Asahi Glass Company, Limited Compose comprenant un cycle perfluoro a cinq chainons
EP1498941A2 (fr) * 2003-07-15 2005-01-19 Air Products And Chemicals, Inc. Fluorocarbures oxygénés non saturés pour applications de gravure sélective anisotrope
WO2005117082A1 (fr) * 2004-05-31 2005-12-08 National Institute Of Advanced Industrial Science And Technology Gaz de gravure sèche et procédé de gravure sèche

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0985752A (ja) * 1995-09-25 1997-03-31 Toshiba Corp 金型用洗浄剤

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0985752A (ja) * 1995-09-25 1997-03-31 Toshiba Corp 金型用洗浄剤

Non-Patent Citations (1)

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Title
BUDDRUS JOACHIM, HERZOG HELMUT: "Oxidation of cyclic ethers by iodine tris(trifluoroacetate). Synthesis and NMR analysis of some diastereomeric 3-deoxypentofluranose derivatives", CHEM. BER., vol. 112, no. 4, 1979, pages 1260 - 1266, XP002951513 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004018443A1 (fr) * 2002-08-21 2004-03-04 Asahi Glass Company, Limited Fluoropolymeres permeables aux ultraviolets et pellicules les utilisant
US7442815B2 (en) 2002-08-21 2008-10-28 Asahi Glass Company, Limited Ultraviolet transmitting fluoropolymer and pellicle comprising said polymer
WO2004050649A1 (fr) * 2002-12-04 2004-06-17 Asahi Glass Company, Limited Compose comprenant un cycle perfluoro a cinq chainons
EP1498941A2 (fr) * 2003-07-15 2005-01-19 Air Products And Chemicals, Inc. Fluorocarbures oxygénés non saturés pour applications de gravure sélective anisotrope
EP1498941A3 (fr) * 2003-07-15 2005-05-04 Air Products And Chemicals, Inc. Fluorocarbures oxygénés non saturés pour applications de gravure sélective anisotrope
WO2005117082A1 (fr) * 2004-05-31 2005-12-08 National Institute Of Advanced Industrial Science And Technology Gaz de gravure sèche et procédé de gravure sèche
JPWO2005117082A1 (ja) * 2004-05-31 2008-04-03 独立行政法人産業技術総合研究所 ドライエッチングガスおよびドライエッチング方法

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