TW593301B - Processes for producing fluorinated cyclic ethers and use thereof - Google Patents

Abstract

This invention provides processes for producing a useful, fluorinated, unsaturated, cyclic ether and a useful fluorinated, saturated, cyclic ether from inexpensive materials; an effective use of the fluorinated, unsaturated, cyclic ether and the fluorinated, saturated, cyclic ether; and a novel compound which is useful as an intermediate for these ethers. A compound (5) shown below is thermally decomposed to obtain at least one fluorinated, unsaturated, cyclic ether selected between the compound (6a) and compound (6b) shown below. Reducing the fluorinated, unsaturated, cyclic ether gives at least one fluorinated, saturated, cyclic ether selected between the compound (7a) and compound (7b) shown below. In the formula (5), AF represents perfluorotetrahydrofuranyl and X represents fluorine or -O<->M<+> (in which M<+> represents a counter ion).

Description

593301 A7 __ B7_ V. Description of the invention () The present invention relates to the industrially useful methods for the production of fluorinated cyclic unsaturated ethers and fluorinated saturated cyclic ethers (hereinafter referred to as fluorinated cyclic ethers) and uses thereof. And novel compounds useful as intermediates for the production of the fluorinated cyclic ether. In the prior art, a method for synthesizing a fluorinated cyclic ether is known as follows. (1) A method for reacting tetrahydrofuran with coF 3 (Journal of chemical Soc. C. 1969, (13), 1739). However, more than 30 compounds are produced in this method, and there is a problem that the selectivity of the target is extremely low. (2) A method for thermally decomposing a potassium salt of perfluoro (tetrahydrofuranyl 2-carboxylic acid) in the presence of K 2 C03 (Zh.〇i * g. Khim., 1 977, 13 (12 ), 2573). However, the potassium salt of perfluoro (tetrahydrofuran-2-carboxylic acid) is not easy to obtain, therefore, this method is not easy to be used as an industrially applicable one. That is, the prior fluorinated cyclic ether production method has extremely low yield and is extremely difficult. There must be problems such as the use of expensive raw materials, and there is no industrially feasible production method. The present invention provides a method suitable for industrial implementation and a method which is economically advantageous and a method for producing a fluorinated cyclic ether with good yield. &lt; Invention of the invention &gt; The present invention provides a method for producing a useful fluorinated cyclic ether, such as a functional agent, using a compound which can be obtained at a low cost. It also provides a fluorate compound obtained by recycling the ester decomposition reaction step of the manufacturing method. This paper is sized to a suitable financial standard (CNS) A4 specification (210X297 mm) '' &gt; 4- (Please read first Note on the back, please fill out this page again) Order printed by the Ministry of Economic Affairs Intellectual Property Bureau employee consumer cooperative printed by the Ministry of Economic Affairs Intellectual Property Bureau employee consumer cooperative printed by 5330301 A7 __ B7 V. Description of the invention ("After the process of industrially useful continuous process The present invention further provides novel compounds useful as intermediates for the production of fluorinated cyclic ethers. The fluorinated cyclic ethers produced by the present invention have good properties as chlorofluorocarbons (CFCs) instead of chemical compounds Those whose ozone destruction coefficient (◦ D p) is zero and those whose global warming coefficient (GWP) is also extremely small, use this fluorinated cyclic ether to provide effective applications. That is, the present invention provides Each inventor consists of the following components: 1 · After thermally decomposing a compound represented by the following formula (5), fluorine of the compound represented by the following formula (6 a) and the compound represented by the following formula (6 b) is obtained. A method for producing a fluorinated unsaturated cyclic ether characterized by converting an unsaturated cyclic ether. However, AF represents a perfluorotetrahydrofuranyl group: κ represents a fluorine atom or -0-M + (However, M + is an ion.) By AF COX (5)

2. The method for producing a compound represented by the formula (5) is the compound represented by the following formula (5a). This paper size applies Chinese National Standard (CMS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page)

-5- 593301 A7 B7 V. Description of the invention ()

3. In the compound represented by formula (5), X is a compound represented by formula (5 f) below a fluorine atom, and the compound represented by formula (1) below is reacted with the compound represented by formula (2) below. For the compound represented by formula (3), the compound represented by formula (3) is used as the compound represented by formula (4) after fluorination. The compound is produced by the method described in 1 or 2. However, A F has the same meaning as above. r c represents a monovalent organic group. r c F is the same as Re e-monovalent organic group, or R C represents a fluorinated monovalent organic group.乂 1 is a halogen atom. A is selected from the group represented by the following formula (la), (lb), (lc), and (Id), or one or more hydrogen atoms in the selected formula are substituted by fluorine atoms The one shown in the formula. A C H 9 〇 H (1;) R c C 〇 X 1 (2) A c H 9 〇 C〇 R c (3) A F C F 0 0 C 0 R c F (4) A F C 〇 F (5 f

QC (la) (lb) (ic) ㈤) 4. The compound represented by formula (1) is a compound represented by the following formula (i), and the compound represented by formula (3) is a compound represented by the following formula (3) This paper size applies the Chinese National Standard (CNS) A4 specification (21〇297mm) ----------- Zhuang Yi-{Please read the precautions on the back before filling this page}-Order economy Printed by the Consumer Cooperatives of the Ministry of Intellectual Property Bureau-6-593301 A7 ____B7 ___ V. Inventor (4), the compound represented by formula (4) where a F is 2-perfluorotetrahydrofuranyl, formula (5 ί) The production method described in the above 3, wherein the representative compound is a compound represented by the following formula (5a). However, 'R e has the same meaning as the above. A 1 is selected from the group represented by the following formula (1 a-1), the following formula (lb-1), the following formula (lc-1), and the following formula (1 d-1), or the selected one In the formula, one or more hydrogen atoms are replaced by a fluorine atom. A 1 C Η 2 Ο Η (1) A 1 C Η 2 0 C 0 R c (3) (Please read the notes on the back before filling this page)

(lc-1 1>

, 1T

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Compounds not represented by formula (3) are obtained by reacting the reaction product of the compound represented by formula (4) with a decomposition reaction to obtain the compound represented by formula (5) and The method described in 3 or 4 for obtaining the compound after reacting the compound represented by the following formula (2a). However, R e F has the same meaning as the above. R c F C 〇 F (2a) δ. The production method described in 3, 4 or 5 which is performed after reacting fluorination with fluorine in the liquid phase. 7 · The compound represented by the following formula (5) is thermally decomposed to obtain more than one species. The paper size is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) 593301 A7 B7 5. Description of the invention (&amp; selected from the following formula ( After the compound represented by 6 a) and the compound represented by the following formula (6 b) is subjected to a reduction reaction of the one or more compounds, one or more compounds selected from the formula (· 6 a) are obtained. A method for producing a fluorinated saturated cyclic ether characterized by a compound represented by the following formula (7 a) and a compound represented by the formula (6 b) which is reduced by a fluorinated saturated cyclic ether of the compound represented by the formula (7 b). However, AF and X have the same meanings as above. AFC〇X (5)

(6a) F H (7a)

(6b)

(Tb) 8 A method for producing a compound represented by the formula (5) in which 7 is represented by the following formula. Compounds shown (Please read the notes on the back before filling out this page)

-、 1T Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs

(5a) COFA compound of any one of the formula ΓΛ, 〇 / 'CH2OCORcl Nv〇 / ^ ch2ocorC1 (3a-2> (3b-2)

CFl This paper size is applicable to Chinese National Standard (CNS) A4 specification (210 × 297 mm) -8- 5933301 A7 B7 V. Description of the invention ($ ', but R ° 1 and R u F 1 represent perfluoroalkyl, perfluoro (part Part of chloroalkyl) group, perfluoro (alkyl group containing etheric oxygen atom) group, perfluoro (part of chlorine (group containing etheric oxygen atom t)) group, or the complete tetrahydrofuranyl group. 10. A fluorinated unsaturated cyclic ether containing one or more compounds selected from the compound represented by the following formula (6 a) and the compound represented by the following formula (6 b), or one or more members selected from the group consisting of the following formula (7 a) A functional agent of a fluorinated saturated cyclic ether of the compound shown and the compound represented by the following formula (7b).

1 1. A functional agent containing a compound represented by the following formula (7a). (Read the notes on the back and then fill out this page) |

, 1T

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1 2 · The 10 or 11 functional agent in dehydration solvent, dry etchant, or detergent. &lt; Best mode for carrying out the invention &gt; In the following detailed description of the book, the compound represented by the formula (5) is referred to as a compound (5). The compounds represented by other formulas are also recorded by the same method. This: In the invention, 'The following compound (5) is thermally decomposed to obtain 1 -9-593301 A7 B7 5. Description of the invention (, more than one selected from the following compounds fluorinated unsaturated cyclic ethers. And the following compound (6 b ) Of (5)

AFC〇X

㈣ F

F 〇 (6b) (Please read the precautions on the back before filling out this page)-Equipment-Order A in Formula (5) represents perfluorotetrahydrosulfanyl. One of the compounds (5) may be bonded to the COX group at the 2-position or the 3-position of the perfluorotetrahydrofuranyl (A F) group, and it is preferable to bind to the 2-position. That is, it is preferable to use 2-perfluorotetrahydrofuranyl as the A F, and it is preferable to use the compound (5 a) below as the compound (5).

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. X stands for fluorine atom or a ◦ Μ +. M + is selected from those which can form carboxylic acid and salt cations, and alkali metal cations are preferred, and K + and Na + are particularly desirable. Among the compounds (5), a method for producing a compound in which X is 10-M + is that a COF group of the compound (5) in which X is a fluorine atom is converted into a COF group. The method of salt, or the reaction of mol more than 2 moles in the compound (5 f) (M type cation is the M +, preferably alkali metal atom.), Then the paper size is added under reduced pressure. Applicable to China National Standard (CNS) A4 specification (210X297 mm) -10- 593301 A7 _____B7__ V. Description of the invention (please make the method of heat drying. (Please read the precautions on the back before filling this page) In the matrix compound (5), X is a fluorine atom, and the compound (5f) is the compound (1) and the compound (2) as the reacted compound (3), and the compound (3) is used as the fluorinated compound. (4), the ester of the compound (4) is preferably obtained after the decomposition reaction of the compound. However, AF has the same meaning as above. Re represents a monovalent organic group. Re F and Re are the same. A monovalent organic group, or R e represents a fluorinated monovalent organic group. X1 is a halogen atom A is selected from the group represented by the following formula (1a), (1b), (1c) 'and (1d), or a hydrogen atom in the selected formula The base represented by the above formula substituted by a fluorine atom: AC Η 2 Ο Η (1) R c C 〇X 1 (2) ACH 2 0 C 0 R c (3) AFCF 2 0 C 0 R c F (4 ) AFC 〇F (5 f) Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs Θ (la) (lb) (lc) (Id) In addition, the compound (5) where X is -0_M + (5) The method for producing the method. The esterification reaction of the compound (1) and the compound (2), the fluorination reaction of the compound (3), and the ester-combining decomposition reaction of the compound (4) can be combined with WO of the inventor. 〇 / 5 6 6 9 4 The paper size of each respondent is applicable. National National Standard (CNS) A4 Specification (210 X 297 mm) -11-593301 A7 _______B7 --- V. Description of Invention ($ Method It is performed under the same means and conditions. This method can produce industrial compound (5) from cheap compound) and compound (2) with excellent efficiency. In the formula (1 a) to (1 d), the ring extended For hand binding, (the position of the 5-membered ring carbon atom to which the binding hand is bound is not limited), and these groups are monovalent. That is, the compound (1) represents binding to a C Η 2 The 〇Η group is a compound at the 2 or 3 position of the group represented by the formula (1 a) to the formula (1 c) or any combination thereof-C Η 2 〇 Η group is the 2 position of the group shown by the formula (1 d) Compounds up to 5th place. A is at the base of two persons having a combination with-C Η 2〇Η, that is, selected from the following formula (la-1), (la-2), (la-3), And the base represented by the formula (la-4) below, or one or more hydrogen atoms in the selected formula is preferably the base (A 1) of the formula substituted by a fluorine atom. (Please read the notes on the back before filling this page}

Ό ^ Ο u (la-1) (lb -1) (Id) printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs on behalf of those who do not have a fluorine atom, that is, selected from formula (1 a), formula (1 b), the formula (1c), and the formula (1d) are shown in the formula, especially the formula (1a) or the formula (1b) is better for stomach, more preferably The base represented by the formula (1 a-1) or the base represented by the formula (1 a-2) is most preferable. Specific examples of the compound (1) are as follows.

The standard of this paper is applicable. National Standard (CNS) A4 (210X297 mm) -12- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 5933301 A7 B7 V. Description of the invention (10) Compounds that react with compound (1) In (2), R e represents a monovalent organic group. As an example of R e, from the viewpoint of the solubility in the liquid phase when used in a fluorination reaction, it is preferable that the carbon number is 1 to 20, and the carbon number 1 to 10 is more preferred. Best. In addition, it is preferable for Re to use a group containing a fluorine atom (that is, a fluorine monovalent organic group), a fluoroalkyl group, a fluorine (partial chloroalkyl) group, and a fluorine (an alkyl group containing an etheric oxygen atom). A radical is preferred, a fluorine (partially chlorinated (alkyl group containing etheric oxygen atom)) radical, or AF as described below. Re is more preferably a perfluoro monovalent organic radical, especially a perfluoroalkyl radical, Perfluoro (partially chloroalkyl) groups, perfluoro (partially chlorinated alkyl groups containing etheric oxygen atoms) groups, perfluoro (partially chlorinated (alkyl ether groups containing etheric oxygen atoms) groups, perfluoro (partially chlorinated alkyl groups) An alkyl group having an etheric oxygen atom, or AF described later is particularly desirable. However, a partially chlorinated group refers to a group substituted with chlorine for a residual hydrogen atom. As a compound (2) Specific examples are as follows for compound examples. However, AF represents perfluorotetrahydrofuryl and perfluoro (2-tetrahydrofuryl). CF3CF2COF ^ CF3CF2CF2CF (CF3) COF ^ CF3CF> CF2CF (CF3) CF2. CF (CF3) COF ''

The AfC〇F compound (2) can also be used as a commercial product, or the compound (2a) (R c F c〇F ( 2 a)). The method of using the compound (2 a) as the compound (2) is to make the paper continuously. The paper size applies the Chinese National Standard (CNS) A4 specification (21〇 &gt; &lt; 297 公 ^ &quot; 'β-- ·- ,-, 玎, ---- Φ ---, (Please read the notes on the back before filling this page) 593301 A7 ______B7 V. Description of the invention ((Please read the notes on the back before filling this page) The method is particularly desirable. That is, it is preferable that the RC in the compound (2) is the same as that of R e F, and it is particularly preferable that RC is a perfluorinated monovalent organic group. The ideal form of the organic group is as described above. When compound R2 is a F in compound (2), that is, when compound (5) is used as compound (2), the ester-binding decomposition reaction of compound (4) is performed. If the product is a compound (5), it is desirable to have the advantage of not requiring a product separation step. The esterification reaction between the compound (1) and the compound (2) can be performed in the presence of a solvent, but from the volume efficiency side Obviously, it is better to carry out in the absence of a solvent. Also, in the reaction of the compound (1) and the compound (2) HF is generated, so in the reaction system, alkali metal fluorides (NaF, KF, etc.), ternary amines, etc., which are η F collectors, can also be present, and the presence of HF collectors is better. If When η F collector is not used, it is better to let HF out of the reaction system with nitrogen flow. The weight when using alkali metal fluoride is 1 to 10 times mole of compound (2). It is suitable for the user. The reaction temperature of compound (1) and compound (2) printed by employee consumer cooperatives is preferably between 50 ° C and +100 ° C. In addition, the reaction time can be based on the supply rate of the raw materials and the compounds used in the reaction The amount is appropriately changed. The reaction pressure (the gauge pressure is the same below) is preferably 0 to 2 MP a. The amount ratio of the compound (1) to the compound (2) is 0. 5 for the compound (2). It is preferred to be 5 times mole, especially 1 to 2 times mole. The crude product of compound (3) produced by the reaction of compound (1) and compound (2) can also be refined according to its purpose. , Or this paper size can be directly applied to Chinese National Standard (CNS) A4 specification (210X 297 mm) -14- 593301 A7 _B7___ 5. Explanation of the invention (12) Used in the next reaction, etc. From the viewpoint of stabilizing the fluorination reaction in the following steps, the compound (3) in the crude product is separated and purified. (Please read the precautions on the back before filling in this page) As the method for refining the crude product, such as the method of directly distilling the crude product, the crude product is treated with dilute alkali water and then liquid separation Methods: The method of extracting the crude product with an appropriate organic solvent and then performing distillation, such as silica gel column chromatography. Specific examples of the compound (3) are as follows. However, "Bao1 and Renren" has the same meaning as in the above. In the present invention, the compound (3) is fluorinated. As a method for winning the reaction, for example, a method using COF 3, a method using ECF method, or a method of fluorine gas, fluorine gas is introduced into the liquid phase. It is preferable to perform liquid phase fluorination method later. During the fluorination reaction, a fluorine atom of more than 1 atom is bonded to the molecule of the compound (3). Hereinafter, the form in which the fluorination reaction is carried out by liquid phase fluorination The fluorine gas in the liquid phase fluorination reaction can be used directly, or it can be diluted with inert gas such as nitrogen. When using the diluted fluorine gas, the fluorine gas concentration is 10 V ο 1% or more, especially 20 V ο is more than 1%. The liquid phase is preferably formed by a solvent obtained by dissolving fluorine (F 2). The solvent is preferably a solvent with a high solubility of the compound (3). 1% by mass or more of the solvent of the compound (3), especially soluble Applicable to China National Standard (CNS) A4 specification (210X297 mm) '--15- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5933301 Μ__Β7_ V. Description of the invention () 3 Solvent users who have more than 5 mass% The amount of solvent is preferably 5 times or more the mass of compound (3), especially 10 to 100 times the mass is more preferred. Examples of solvents that can be used for liquid phase fluorination are: perfluoroalkanes , Perfluoroethers, perfluoropolyethers, chlorofluorocarbons, chlorofluoropolyethers, perfluoroalkylamines, inactive fluids, etc., and it is easy to react and then deal with the advantages of the following points. The compound (4), the compound (5), or the compound (2a) is more preferable. The fluorine content of the compound (3) (the fluorine content refers to the mass ratio of fluorine atom to the molecular weight) is preferably 10% by mass or more, particularly 10 to 86% by mass is the best. When the content of fluorine is too small, the solubility in the liquid phase is extremely low, and the reaction system of the fluorination reaction becomes uneven, and the compound (3) cannot be made when the continuous reaction proceeds. The problem of effective feeding in the middle of the reaction exists. Moreover, the fluorine content is not The upper limit is set, but if it is too high, it is difficult to obtain the compound (3), the price is too high, and the problem of uneconomical appears. In addition, if the molecular weight of the compound (3) is 200 ~ 1000, it can prevent the Ideal fluorination reaction, can successfully carry out liquid phase fluorination reaction. When the molecular weight is too small, the compound (3) is easily gasified, and liquid phase fluorination reaction may cause decomposition reaction in the gas phase. On the contrary, if the molecular weight is too large, It may cause difficulty in refining the compound (3). The reaction form of the fluorination reaction may be batch or continuous. From the viewpoint of reaction yield and selectivity, continuous type is particularly preferred. In addition, when the fluorine gas is carried out in a batch type or in a continuous type, it is possible to use one diluted with an inert gas such as nitrogen. This paper size applies to China National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)

-16- 593301 A7 __ B7____ V. Description of the invention (4) In the fluorination reaction, the amount of fluorine in the hydrogen atom in the compound (3) often requires excessive fluorine equivalents to be placed in the fluorine gas, especially 1.5 times. A fluorine gas having an equivalent weight (that is, 1.5 times or more moles) has a better selection rate. It is advisable to maintain an excess of fluorine gas from the beginning to the end of the reaction. Therefore, 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 generally higher than -60 t, and the boiling point of the compound ('3) is preferably lower than the boiling point of the compound (' 3). 0 t ~ + 100 ° C is preferred, and especially 20 ° C ~ + 50 ° C is most preferred. The reaction yield of fluorination is 0 to 2 MP a. The reaction yield, selectivity, and industrial ease of implementation are the most desirable. In addition, in the liquid phase fluorination reaction, in order to efficiently perform fluorination, it is preferable to add a C-fluorene-containing binding compound to the reaction system, or to perform ultraviolet irradiation. As the C-fluorene-containing compound, an aromatic hydrocarbon group is preferred, and benzene, toluene, etc. are particularly preferred. The C-fluorene-containing binding compound is preferably added in an amount of 0.1 to 10 mole% of the hydrogen atom in the compound (3), and more preferably 0.1 to 5 mole%. The C- 者 -containing binding compound is preferably added in the reaction system in the presence of fluorine gas. Furthermore, when adding a C-fluorene-binding compound, it is preferable to pressurize the reaction system. The pressure during pressurization is preferably from 0 · 0 1 to 5 MPa. In the fluorination reaction, as a by-product of H F appears, it is preferable to co-exist the collector of H F in the reaction system for the purpose of removing the H F of the by-product, or to contact the collector with the outlet gas at the gas outlet of the reactor. As the H F collector is the same example as above, and Na F is the ideal one. The paper size is suitable for financial and family care standards (CNS) A4 (210X 297 mm)--17- (Please read the precautions on the back before filling this page)

1.1T printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5933301 Α7 Β7 V. Description of the invention (5) The amount of coexisting HF collector in the reaction system is 1 ~ 20 times the total hydrogen atom amount in compound (3) For ears, 1 to 5 times moles is better (please read the precautions on the back before filling this page). Crude organisms containing compound (4) obtained from the fluorination reaction can also be used directly in the following steps, or they can be purified to high purity. As a purification method, for example, a method in which the crude product is directly distilled at normal pressure or under reduced pressure. The compound (4) is a compound whose compound (3) is fluorinated, and the compound (3) is Perfluorinated compounds are preferred. Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The fluorination reaction is a reaction in which C-变换 is converted to C-F, and the responder adds fluorine to the unsaturated bond. In the generated compound (4), AF is the group corresponding to A, and R e F is the group corresponding to Re. In these groups, the arrangement of carbon atoms is not changed before and after the fluorination reaction, and the corresponding compound (3) is obtained. Compounds. However, when a carbon-carbon unsaturated bond occurs in the compound (3), the unsaturated state may be changed by adding one or more fluorine atoms to the unsaturated state. It is preferred that R e F is the same as that of R ϋ. Particularly, a perfluoro monovalent organic group is preferred, and a perfluoroalkyl group, a perfluoro (partial chloroalkyl) group, and a perfluoro ( Ether-containing oxygen atom alkyl) groups, perfluoro (partial chlorine (ether-containing oxygen atom alkyl)) groups, or perfluorotetrahydrofuranyl are the best. Specific examples of the compound (4) are as follows. However, A F has the same meaning as above. CF3CF2CF2OCF (CF3) COOCF2Af, CF3CF2CF2OCF (CF3) CF2OCF (CF3) COOCF2Af, AfCOOCF2Af 〇 This paper is applicable. National standard (CNS) A4 specification (210 × 297 mm) -18- 593301 A7 B7 5. Description of the invention () (Please read the precautions on the back before filling in this page) Compound (4) is a compound (5) where X is converted to a fluorine atom after a decomposition reaction by ester bonding. The ester-binding decomposition reaction can be performed by heating method or in the presence of a nucleating agent or after reacting with an electron-seeking agent. When the ester-binding decomposition reaction is carried out by heating, the reaction form can be selected by the boiling point and stability of the compound (: 4). When the compound (4) is a compound that is easily vaporized, it is preferable to perform a gas phase method in which the outlet gas containing the obtained compound (5) is condensed and recovered after continuous decomposition in the gas phase. The reaction temperature of the gas phase method is 50 ~ 35 ° C, and 50 '~ 300 ° C is more preferable, and 150 ~ 250 ° C is most preferable. In the gas phase method, an inactivated gas having no direct relationship can also coexist in the reaction system. Examples of non-activated gas include nitrogen and carbon dioxide gas. The amount of inactivated gas is preferably 0. 0 1 to 50% of the compound (4). When the amount of inactive gas is too large, the recovery amount of the product will decrease. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. For the ester-binding decomposition reaction using the gas phase method, it is advisable to use a tubular reactor. When using a tubular reactor, the residence time is preferably 0.1 seconds to 10 minutes based on the empty tower. In the gas-phase reaction using a tubular reactor, for the purpose of promoting the reaction, it is preferable to fill the reaction tube with glass, an alkali metal salt, or an alkaline earth metal salt. The reaction pressure is not particularly limited. In general, when the compound C 4) is a high-boiling compound, it is preferable to perform the reaction under reduced pressure. In addition, when the compound (4) is a low boiling point compound, decomposition of the product is suppressed and the reaction rate becomes high. Therefore, it is preferable to perform the reaction under pressure. This paper scale applies Chinese National Standard (CNS) A4 (2K) X297g t) -19- 593301 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention () 7 Also, the compound (4) is not easy In the case of gasified compounds, a liquid phase method using liquid heating directly in the reactor is preferred. The reaction pressure of this method is not limited. The product containing the fluorinated cyclic ether (5) can also be taken out of the reactor after heating, but the fluorinated cyclic ether (5) has a lower boiling point than the compound (4). After the conversion, it is advisable to take it out continuously. The reaction temperature of the liquid phase method is preferably 50 to 300 ° C, and more preferably 100 to 250 ° C. In addition, the liquid phase method can be used with or without a solvent, and it is better to control the side products by volumetric efficiency and the presence of a solvent. When the ester-binding decomposition reaction is performed in a method of reacting with a nucleating agent or an electron-seeking agent in the liquid phase, the presence or absence of a solvent in the reaction can be considered from the viewpoint of volume efficiency and suppression of by-products. The absence of a solvent is preferred. As the nucleating agent, a fluoride anion (F_) is preferable, and a fluorine anion derived from an alkali metal oxide is particularly preferable. Examples of alkali metal compounds:

Na F, KF, C s F are preferred, and Na F is more economical. It is not necessary to use a catalyst amount 'or an excess amount for the nucleating agent. It is particularly desirable that the nuclear dose is 1 to 500 mole% of the compound (4). 10 to 100 mole% is particularly desirable, and 5 to 50 mole% is the best. The lower limit of the reaction temperature is preferably -30 ° C, and the upper limit is preferably the boiling point of the solvent or the boiling point of the compound (4). The general reaction temperature is-2 0 ° C ~ 2 50 ° C is particularly desirable. In this method, it is preferable to perform the reaction while taking out the produced compound (5) continuously. The reaction product of the ester decomposition reaction contains the compound (5) and also the compound (2a). Compound (2 a) and compound (5) are different. The paper size is applicable to Chinese National Standard (CNS) A4 (210X 297 mm) (Please read the precautions on the back before filling this page)

-20- 593301 A 7 _B7__ V. Description of the invention () 8 When the compound is the same, compound (2 a) can be used for other purposes after being separated from compound (5), and compound (2 a) can be used as a useful intermediate for other useful compounds. Body. In addition, when the compound (2a) is used for the compound (2) which is subjected to an esterification reaction with the compound (1), when the esterification reaction is performed, the compound (3) can be produced, and the compound (3) can be produced by the aforementioned method. (5), for example: Compound (2a) in Compound (2), in which R e is Re e F, and X is a compound of fluorine atom. The compound (2a) can be reused as the compound (2) to produce the compound (5). In the present invention, the compound (5) is thermally decomposed. The reaction conditions for thermal decomposition are not particularly limited. Generally, the thermal decomposition reaction is performed after the thermal decomposition reaction in the gas phase. When X of the compound (5) is a fluorine atom, the reaction temperature of the gas-phase thermal decomposition reaction is preferably 250 to 400 ° C, and more preferably 280 to 350 ° C. In addition, when X is 10-M +, the reaction temperature in the gas-phase thermal decomposition reaction is preferably 150-300 T: preferably, 20-280 ° C. When the reaction temperature is too low in the gas-phase thermal decomposition reaction, the conversion rate decreases. Conversely, if the reaction temperature is too high in the gas-phase thermal decomposition reaction, the amount of compounds other than the production target compound is increased. In the thermal decomposition reaction of the compound (5), a de-C ◦ reaction occurs, and a double bond is formed in the furan ring, resulting in the compound (6a) or the compound (6b). Furthermore, among the compounds, the compound (6a) from the compound undergoing a double bond transfer reaction (6b) and the compound (6b) can produce the compound C6a). For example: 2-position compound with a COF (this paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) (please read the precautions on the back before filling in this page))

、 1T Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -21 &gt; 593301 A7 B7 V. Invention Description () 9 (Please read the precautions on the back before filling this page) 5) Compounds generated in the thermal decomposition reaction (6 a ) The compound (5) bound to a COF at position 3 again produces a compound (6b). Furthermore, after a double bond transfer reaction occurs in some products, the products are two types: &amp; compound (6 a) and compound (6 b). In the thermal decomposition reaction, two kinds of compounds are generally formed. In particular, the compound (5) in which X is from 10 K + is the compound (6 b), and the compound (5) in which X is from 10 — N a + is the compound (6 a) is preferentially formed. The product composition of the thermal decomposition reaction can be changed by reaction conditions and the like. When the product is both the compound (6a) and the compound (6b), the composition is not particularly limited. Compounds (6a) and (6b) can be directly used for the purpose, and they are usually used after being changed to other compounds. When two kinds of compounds are produced, the compound (6 a) and the compound (6 b) may be separated and purified and then converted into other compounds. The compounds (6 a) and the compound (6 b) have similar boiling points, and the two are separated. The method is extremely cumbersome, so it is advisable not to perform such separation and convert to other compounds. Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Furthermore, in the present invention, after one or more compounds selected from the compound (6a) and the compound (6b) are subjected to a reduction reaction, one or more selected from The compound (6 a) is reduced below the compound (7 a), and the compound (6 b) is reduced to the fluorinated saturated cyclic ether of the compound (7 b).

The standard of this paper is applicable. National National Standard (CNS) A4 specification (210X297 mm) -22- 5933301 A7 ____ B7 V. Description of the invention (in the reduction reaction of $ 0, the compound (6a), compound (6b) A hydrogen atom is added to the carbon-carbon unsaturated double bond. This reduction reaction is particularly desirable for those using hydrogen as the catalyst in the presence of the catalyst. Those who support the catalyst with a metal should be the catalyst. The metal-supported catalyst is preferably 0.5 to 5% by weight of the supported metal, and more preferably 1 to 3% by weight of the supported metal. Furthermore, as a metal-supported catalyst in activated carbon Metal-bearing catalysts should especially use activated carbon catalysts that support palladium, active carbon catalysts that contain palladium as the main component and 8-element elements other than Kimba, or activated carbon catalysts that support au Among them, 8 elements other than pins are preferably one or more selected from fe, Co, Ni, Ru, Rh, Ir, and Pt. The amount of 8 elements other than palladium is IE 0 · 〇1 ~ 50% by mass is preferred. When the carrier is activated carbon, the ratio of activated carbon using plant matter as the raw material is based on minerals. The activated carbon is better, especially coconut shell activated carbon. The shape of the carrier can be shaped carbon with a length of about 2 ~ 5 mm, and the shape of crushed carbon, granular carbon, etc. with a mesh screen of about 4 ~ 50 mm. The crushed carbon of 4 ~ 20 mesh sieve or the shaped carbon with a length of about 2 ~ 5 mm is more preferred. After the catalyst of the active carbon-carrying metal is supported by the carrier metal component, it is dried. After hydrogen reduction, it should be prepared by the activation method. The catalyst prepared by this method has the advantages of high durability and long-term use without the need for activation. At the time of activation, it is particularly effective at 1000 ~ 300 ° C. 2000 ~ 300 ° C) is preferred for hydrogen reduction method. The amount of hydrogen is based on the chemistry of the total amount of the reduction reaction substrate. When measuring the quantity, it is better to use more than 2 times moles, and more preferably 3 to 8 times moles to obtain a high yield. This paper scale applies Chinese national standards. icNS) A4 Regulation $ (210X: 297 mm 1 · 1 —-23- (Please read the precautions on the back before filling this page)

1.1T printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5933301 A7 B7 V. Description of the invention (for those who want to be the target compounds. (Please read the precautions on the back before filling this page) The temperature of the reduction reaction is usually under normal pressure 1 3 0 ~ 2 50 ° C is preferred, especially 150 ~ 2 0 ° C is preferred. The reaction pressure is not particularly limited. The reaction time of the reduction reaction is 4 ~ 60 seconds for the contact time of the catalyst. It is particularly preferable that it is 8 to 40 seconds. Furthermore, the reduction reaction is to control the excessive temperature rise, and it can also be performed while diluting hydrogen with an inert gas such as nitrogen. This reduction reaction produces a reducing compound (6a) When the compound (7a) and the reduced compound (6b) are present, the product formed by the compounds (7a) and (7b) is present. The composition of the product of the reduction reaction is changed by the matrix composition of the reduction reaction. Ministry of Economic Affairs When the product of the reduction reaction printed by the Intellectual Property Bureau's consumer cooperative is made of compound (7a) and compound (7b), these can also be used directly for the purpose, or can be separated. Since the compound ( 7 a) and The boiling point of the compound (7b) is different. Therefore, it is suitable to perform the separation by distillation during the separation. When the product of the thermal decomposition reaction is the compound (6a) and the compound (6b), the compound obtained by the reduction reaction is In the case of the compound (7a), it is preferable to obtain the compound (7a) by distillation and separation after the reduction reaction. The compound (6a), the compound (6b), the compound (7a), and the compound obtained by the production method of the present invention (7 b) Those who have good characteristics as chlorofluorocarbon replacement compounds, those with zero ozone destruction coefficient, and extremely low global warming coefficient. These compounds or mixtures of these compounds For functional compounds that are useful, the paper size is applicable. National National Standard (CNS) A4 specification (210X297 mm) -24-593301 A7 -_______ B7__ V. Description of the invention (Examples of functional agents: refrigerant, detergent, Examples of solvents, solvents, polymerization solvents, dry etchants, resin foaming agents, etc., containing one or two fluorinated unsaturated cyclic ethers selected from compound (6a) and compound (6b) Of It is suitable for users to use water as a drying solvent, a dry etchant, or a detergent. In addition, it contains one or two fluorinated saturated cyclic ethers selected from compound (7a) and compound (7b). The functional agent, especially the functional agent containing the compound (_ 7 a) is preferably used as a dry etchant. The fluorinated cyclic ether structure of the present invention has oxygen atoms, so when it is used as a dry etchant The advantages of the operation of adding oxygen in dry etching can be omitted. The present invention further provides a compound described below which is useful as the functional agent intermediate.

(3b-2) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (Please read the precautions on the back before filling this page)

Cl

CFl (4b-2) 〇ch2ocorC1 (3a-2) However, Re 1 and Re F 1 represent perfluoroalkyl, perfluoro (partially chloroalkyl), and perfluoro (ether ether-containing alkane) Group), perfluoro (partially chlorinated (alkyl group containing etheric oxygen atom)), or perfluorotetrahydrofuranyl. Examples of Re 1 and Re F 1 are: a group having 1 to 20 carbon atoms, particularly A radical having a carbon number of 1 to ◦ is more preferred. In addition, as for Re 1 and Re F 1, a perfluoroalkyl group or a perfluoro (ether oxygen atom alkyl group) is more preferred. [Example] ch2〇cor This paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) -25-

For T M S, C C

593301 A7 B7 ____ V. Description of the Invention (Hereinafter, the present invention will be specifically described according to the examples, but the present invention is not limited thereto. In the following, the gas chromatography method is referred to as GC and the gas chromatography mass analysis is referred to as GC- MS. The purity obtained from the G C. vertex area ratio is described as GC purity, and the yield is described as GC yield. The yield obtained from the NMR spectrum vertex area ratio is described as NMR yield. Also, tetramethyl Silane is recorded as FCC1F2 as R-113. The NMR spectrum data is represented by the range of appearance chemical shift. [Example 1] Production example of compound (3 b-1) through esterification step ch2oh + fcocf (cf3) ocf2cf2cf3 ( Please read the notes on the back before filling out this page}

ch2oc〇cf (cf3) ocf2cf2cf3 (3b-l) g Printed and placed 2-tetrahydrofurfuryl alcohol (20 g) and triethylamine (2 1.8 in the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs into the flask, then placed in an ice bath Stirring was carried out. At an internal temperature of 10 ° C or lower, FC Ri (CF 3 (CF 3) CF 2 CF 2 c P (7 1 · 5 g)) was dripped into Wei Ri Temple for 1 hour. After dripping, stir at room temperature for 2 hours, and add water (50 ml) at an internal temperature below 5 ° C. The obtained crude liquid was separated, and then washed with water (50 ml) into the lower layer of 2, and then dried with magnesium sulfate, and then filtered to obtain a crude liquid. Obtained under reduced pressure to make 8 8 ~ 8 9 ° C / 2.7 KP a (absolute _ fraction of the target ester compound (66, 3 g). The GC purity is 98%. The compound was determined after NMR analysis ( 3 b — 1). -26-593301 A7 B7 V. Description of the invention (&gt; 4 'H NMR (300.4 MHz, CDCl35TMS) 5 (ppm): 1 · 6 〇 ~ 1 · 7 3 (m, 1 Η ), 1.86 to 2.10 (m, 3H), 3. 76 to 3.91 (m, 2H), 4. 1 4 to 4 · 2 2 (m, 1 Η), 4.28 to 4.47 (m, 2H) 〇19F-NMR (282.7MHz, CDCl3, CFCl3) 5 (ppm): -79.9 (1F), -81.3 (3F), -8 2 · 1 (3F), -8 6 · 4 (1 F), (Please read the notes on the back before filling out this page) 12 9 2 F), 1 1

F [Example 2] Production Example (3b-1) of Compound (4b-1) by the fluorination step

(4b-l)

\ 'CP2OCOCF (CF3) OCF2CF2CF3 F Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy 5 0 0 m 1 Add R — 1 1 3 (3 1 3 g

) After stirring, keep at 25 ° C. A cooler maintained at a temperature of 20 t, a filling layer of Na F particles, and a cooler maintained at 10 ° C were arranged in line at the gas outlet of the autoclave. In addition, the liquid condensed by the cooler maintained at -10 ° C was set as a liquid return line for returning the autoclave. After nitrogen was blown in for 1 hour, a fluorine gas diluted with nitrogen to 20% was blown in at a flow rate of 8.08 L / h for 1 hour. While blowing in fluorine gas at the same flow rate, the compound (3 b — 1) (5.01 g) obtained in Example 1 was dissolved in R — 1 1 3 (100). ) A4 size (210X297mm) -27-593301 A7 ___ _B7_ V. The solution of invention description (knowledge g) is injected in 4 · 7 hours. (Please read the precautions on the back before filling this page) and then use the same flow rate While blowing in the fluorine gas, the R-1 1 3 solution (9 m 1) with a benzene concentration of 0.01 g / m 1 was heated from 2 5 t to 40 ° C, and the benzene was closed after the autoclave was injected. Note the inlet and close the outlet valve of the autoclave and continue to stir for 0.4 hours. Then make the pressure normal pressure and keep the internal temperature of the reactor at 40 ° C. At the same time, inject the benzene solution (6 ml) and close the autoclave inlet. Close the outlet valve of the pressure cooker again. After the pressure is 0 · 20 MPa, close the fluorine gas inlet valve of the pressure cooker and continue stirring for 0.4 hours. Repeat the same operation 3 times. The total amount of benzene injected is 0_ 3 3 g, the total injection of R-1 1 3 is 3 3 m 1. Nitrogen is blown in for 1 hour. The target is 19 F -After quantification by NMR, it was confirmed that the compound (4 b-1) was produced, and the yield was 64%. 19F-NMR (3 76.0 MHz, CDCh, CFCl3) 6 (ppm): -8 0.3. (1 F),-8 1 · 9 (3 F), printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-82.1 C3F),-83.5 to-84.8 (2F), -85.5 to-88.0 (3F), 126.5 (1 F),-127.4 (1F),-128.1 (1F), -1 3 0.2 (2 F), 130.4 (1F), -1 3 2.2 (1 F),-1 3 5. 8 (1 F). [Example 3] Production example of compound (5 a-1) through the ester decomposition step The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm)-28- 593301 A7 B7 V. Description of the invention (deduction (4b -l)

COF

F F

COOK Put the compound (4 b-1) (2 · 1 g) and Na F powder (0 · 0 2 g) obtained in Example 2 into a flask and stir vigorously while in an oil bath 1 4 0 Heating was performed at ° C for 10 hours. The top of the flask was equipped with a reflux device to adjust the temperature to 20 ° C. Recover the cooled liquid sample (2.0 g). The recovered liquid sample was reacted in an aqueous KOH solution containing compound (4b-1) 2 · 5 times the molar amount of KOH, and the compound (5a-1) was obtained after removing water. [Example 4] Production Example of Compound (6 b) The compound (5 a — 1) obtained in Example 3 was the same as that in the literature (zh. Org. Khim ·, 1977 13 (12), 2573) in 2 2 and K2C 03 was heated at the same time to obtain the compound (6 b) as the main product. The yield of the compound (6b) was 71.2%. The presence of compound (6a) was also confirmed in the product. (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (5a -1)

F [Example 5] The compound obtained by the compound (7 b) in the fast-prototyping step is obtained by repeating the reaction of Examples 1 to 4 (6 b This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ) -29- 593301 B7 △ □ 5. Description of the invention (After that, reduction reaction is carried out. The catalyst (100m 1) shown in Table 1 is poured into a nickel-chromium-iron refractory gold 600 reaction tube (1/2 in diameter) i nch, 1 cm in length), this is heated from the outside and maintained at 120 ° C 'to introduce compound (6 b) at a flow rate of 0 · 2 m ◦ 1 / h, while at the same time 1 · 0 m ο 1 / After introducing hydrogen at a flow rate of h, the reaction was performed. After analyzing the gas at the outlet of the reactor by GC, the compound (7b) of the result was obtained in the results in Table 1 below. In addition, the catalyst used coconut for 100 parts by mass Shell crushed carbon is for those who carry 2 parts by mass of metal components. (Please read the precautions on the back before filling out this page} [Table 1] Reduction Example Catalyst (Mole ratio) Reaction of Compound (7b) Compound (6b) Rate 'selection rate 1 Pd 1 0 0% 9 5% 2 Pd-Pt (10: 1) 1 0 0% 96% 3 Pd-Au (10: 1) 100% 9 8%- Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Example 6] Production Example of Compound (3 a-1) by Esterification Step CH2OH Ten FCOCF (CF3) OCF2CF2CF3

CH2〇COCF (CF3) OCF2CF2CF3 (3a_l) Change the 2-tetrahydrofurfuryl ether (2 0 g) in Example 2 to 2-furfuryl alcohol. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -30 -593301 A7 B7 V. Explanation of the invention (except for (2 1 g)), the esterification step was performed in the same manner as in Example 1 to determine the formation of compound (3 a-1). 19F-NMR (2 82.7 MHz, CDCh? CFCl3 ) 5 (ppm): -7 9 · 9 (1 F),-8 1 · 3 (3 F),-8 2. 1 (3 F),-8 6 · 4 (1 F),-129.5 (2F ), -131.5 (1F). [Example 7] Production Example of Compound (4 b-1) by fluorination step

F F, cf2〇cocf (cf 3) OCF2CF2CF3 (3a-l) ----- ^ Bu

F (4b-1) The compound (3 b-1) in Example 2 was changed to 5.5 g of Example 6 except that the compound (3 a-1) was obtained, and the fluorination step was performed in the same manner as in Example 2. F-NMR was used to quantify the fluoride after the reaction, and it was confirmed that the compound (4 b-1) was formed, and the yield was 64%. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page)! 9F-NMR (37 6.0MHz, CDCl3, CFCl3) 6 (ppm): -8 0. 3 (1 F) ,-81.9 (3F), -82. 1 (3 F),-83.5 to-84.8 C2F), -85.5--88.〇 (3F),-126.5 (1 F),-1 2 7 · 4 (1 F), — 1 2 8 · 1 (1 F), -1 3 0.2 (2 F), 130.4 (1F), -1 3 2 · 2 (1 F),-1 3 5. 8 (1 F). This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -31-593301 A7 B7 V. Description of the invention ([Example 8] Production example of compound (5 a-2) through ester decomposition step (4b -1)

COF

F F

CO〇Isj * ^ (5a-2) In Example 3, except that K〇Η was changed to NaoΗ, the reaction was carried out in the same manner as in the ester decomposition step of Example 3 to obtain the compound (5a-2). --------- P Pack II (Please read the precautions on the back before filling out this page) [Example 9] Production example of the compound

F Order Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs to change the compound (5 a-1) of M 4 to the compound (5 a-2) obtained in Example 8, and change K 2 C03 to Na 2 C. Except 3, the same method as in Example 4 was followed to obtain the main compound (6a). The yield of the compound (6 a) is 61. 0%. It was also confirmed that a compound (6 b) was formed in the product. [Example 1 0] Production Example of Compound (7a) by Reduction Step Compound (6a) obtained by repeating the reaction of Examples 6 to 9 The compound (6a) containing the compound (6b) directly after use is shown in Table 2. In the presence of a catalyst, a reduction step was performed in the same manner as in Example 5 to obtain a compound (7a). Applicable to China Paper Standard (CNS) A4 (210X297 mm) at this paper scale -32- 593301 A7 B7 V. Description of the Invention (The results of GC analysis of the reaction gas at the extrusion port are shown in Table 2. Compounds were also identified in the outlet gas. (7 b). 丄 Table 2] Reduction Example Catalyst (Mole ratio) Compound (6a) Compound (7a) Reaction Rate Selectivity ^ 1 Pd 100% 94% — 2 Pd-Pt (10: l ) 100% 95% 3 Pd-Au (10: 1) 1 0 0% 98% (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs [Example 1 1] as Evaluation Example of Dry Etching Agent (Example 1-1) A silicon wafer with a diameter of 150 mm and a silicon oxide film formed on the long surface was fixed in a parallel flat-plate plasma etching device. After the inside was made into a vacuum, Example 4 was generated. After the compound (6 b) obtained by chemical distillation is gasified, it is introduced into 50 m 1 / min (gas temperature 20. (:). The internal pressure is set to 3 9 · 9 P a (absolute pressure) to make the plasma density Etch 3 etch it ο) check the etch point of the compacted film etch 3 to enter the second for any second ο circle 6 day Once into the 3 1 INTRODUCTION Hai erosion speed at the Department of

Degree of C m X Instant engraving

A 〇 is the minute of the reporter 〇 is the result of the combination 〇

IX Things 1 combined and will,} Foreign 2

For example, the method of change and change measurement \ 1 | / jIRi cd IX is the result. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -33- 593301 A7 B7 V. Description of the invention (h ( Example 1 1 to 3) Comparative Example The compound (6 a) was changed to octafluorocyclopentene except that it was measured by the method of Example 1 1-1 R. If the result was X, the contact etching reaction did not proceed at all, Shi Xi A yellow-brown polymer deposit on the wafer. [Example 1 2] As an evaluation example of dehydration and drying solvent, the stainless steel mesh sieve (5 cm X 5 cm) was washed in advance, and the person immersed in water was washed. Clean article. The compound (7 a) synthesized in Example 10 was directly used as the compound (7 b). After adding ethanol to the compound (7 b), the ethanol concentration was adjusted to a mixed solvent of 5% by mass. Then it was washed. The net was immersed in a mixed solvent at 30 ° C, and the water was removed by ultrasound for 1 minute. Then, the compound was cleaned by steam for 30 seconds in the steam field of compound (7 a). Observe the dryness of the steam wash, The state of the mixed solvent after immersion and removal of water, and the water floating on the liquid level of the mixed solvent when immersion is removed The state of A is determined by the following A to D. A: A; no spots are completely dry. B; dry but slightly spotted. C; residual moisture. D; extremely residual moisture. In addition, the state of the mixed solvent According to the following A ~ D, the judgment result is A. A; no turbidity. B; slightly white turbidity. C; white turbidity. D; strong white turbidity. In addition, the state of the water floating on the liquid surface is A ~ The result of D's judgment is A. A; floats quickly. B; floats slowly. C; floats slowly. D; water floats very slowly. This paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ( (Please read the notes on the back before filling out this page) .i% 4 ·

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, 1T-34- 593301 A7 _B7_ V. Description of the invention ($ 2 [Example 1 3] As an example of the evaluation of detergents and wetting agents (Please read the precautions on the back before Fill in this page) Apply cutting oil (trade name: Daphnicut AS-40HO Idemitsu Kosan Co., Ltd.) to a stainless steel mesh sieve (5 cm X 5 cm) that has been cleaned in advance, and heat it at 100 ° C for 1 hour The object to be washed is immersed and washed in the isododecane (60 ° C) for 30 seconds. The compound (7 a) obtained in Example 10 below directly contains the compound (7 b ). Use compound (7 a) for 30 seconds at 30 t: dipping and wetting, and finally, steam clean in the steam area of compound (7 a) for 30 seconds. Coating with cutting oil The residual rate of cutting oil was calculated after measuring the mass of the cleaned material before and after coating and drying, and the dry state of the cleaned material after steam cleaning was observed. The result of evaluation based on the following criteria was A. The residual ratio of the oil is A; less than 0.1% by weight, and B; 0.1% by weight to 0.5% by weight 0.5% to 2% by weight, D; 2% by weight or more. In addition, the dry state is evaluated according to the following criteria and the result is A. A; immediately dried, B; slowly dried, C; partially dried , D; not dried. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs &lt; Industrial availability &gt; A method for a fluorinated cyclic ether with good efficiency. The fluorinated cyclic ether of the present invention is a compound useful as a functional agent such as a desiccant, a dry etchant, or a detergent, and the present invention can provide— As a novel compound useful as a fluorinated cyclic ether intermediate. This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) -35-

Claims (1)

593301 A8 B8 C8 D8 Australian version 丨 ii Ό Β I ¥, Patent Application No. 9110303 Patent Application No. 9 Chinese Application for Patent Scope Amendment January 30, 1993 Amendment 1 · Manufacture of a fluorinated unsaturated cyclic ether The method is characterized in that, after thermally decomposing a compound represented by the following formula (5), one or more compounds selected from the compounds represented by the following formula (6 a) and the compounds represented by the following formula (6 b) are fluorinated and unsaturated. For cyclic ethers, however, AF represents perfluorotetrahydrofuranyl, X represents a fluorine atom, or 10′M + (where M + is a counter ion). AF COX (5) (Please read the precautions on the back before completing this page) (6 a) F (6b) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 2. The manufacturing method as described in item 1 of the scope of patent application, wherein the compound represented by the formula is a compound represented by the following formula (5 a) 3. The manufacturing method according to item 1 of the scope of patent application, wherein in the compound shown in the formula (where X is a fluorine atom, X is a compound represented by the formula (5)), and the compound represented by the following formula (1) and the following formula ( 2) Compounds shown on this paper are in accordance with Chinese National Standard (CNS) A4 specifications (21 × 297 mm) 593301 8 88 8 ABCD 6. The scope of patent application is reacted as the compound shown by formula (3) below. (3) The compound represented by the following formula (4) is fluorinated as a compound represented by the following formula (4), and the compound obtained by the ester bond of the compound represented by the formula (4) is obtained by a decomposition reaction, where AF has the same meaning as the above, rc Represents a monovalent organic group, R c F and R c are the same monovalent organic group, or RC represents a fluorinated monovalent organic group, X1 represents a halogen atom, and A is selected from the following formula (la), the following formula ( lb), the group represented by the following formula (lc) and the following formula (id), or the group represented by the formula in which one or more hydrogen atoms are replaced by fluorine atoms: ACH2〇H (1) RcC. X] (2) ACH2 OCORc (3) AF CF2 OCORCF (4) AF C〇F (5 f) --------- βί ^-(Please read the notes on the back first Then fill out this page), 1Τ (la) (lb) (lc) (id) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. o As in the manufacturing method for the third item of the patent application, where the compound in formula (1) is the following formula (1) The compound represented by) and the compound represented by formula (3) are compounds represented by the following formula (3). Among the compounds represented by formula (4), AF is 2-perfluorotetrahydrofuranyl, and the compound represented by formula (5f) The compound is a compound represented by the following formula (5a), wherein Rc has the same meaning as the above, and A1 is selected from the following formula (1 a to 1), the following formula (lb — 1), and the following formula (lc — 1) The following paper standards apply to the Chinese National Standard (CNS) A4 specifications (210X297 mm)-2-5330301 Λ8 B8 C8 ______ DS VI. The base represented by the hydrogen atom (1 d — 1) on the scope of patent application 'or In this selection formula, L is a group shown to be substituted by a fluorine atom, A3 CH2 OH ⑴ A3 CH2 〇C〇Rc (3) (la_l) (lb-1) (1c -1) (Id -1) 5. If the compound represented by formula (3) in the manufacture of item 3 or 4 of the scope of application for a patent is obtained from the reaction product of the chemical bond and decomposition reaction obtained by formula (4), the formula (5) is obtained. After the compound represented by the following formula (2a), the compound obtained by the reaction of the compound represented by the formula (1) represented by the formula (2a), wherein .R e F is the same as R c F 〇CF (2a). 6. A method for producing a fluorinated unsaturated cyclic ether, wherein the compound represented by the formula (1) and the compound represented by the following formula (2) are compounds represented by the following formula (3), and the formula (3) The reaction with fluorine in the compound is fluorinated to form a compound represented by the following formula (4), and the compound represented by) is ester-bonded to undergo a decomposition reaction to become a compound represented by the following formula. This paper is selected from the compound shown by the following formula (62) and the following formula (6b). The paper size is applicable to the Chinese national standard. (CNS) standard 4 inverse (2 丨 OX 297). The ester compound of the compound and The compound reacts with the Ministry of Intellectual Property, employees, and cooperatives, and the product is decomposed in the liquid phase by the formula (4 (5f)), and the chemical composition shown is W301 Λ8 B8 C8 ^ __ T. One or more fluorinated unsaturated cyclic ethers, but 'AF has the same meaning as above, R c represents a monovalent organic group, R e F and Re are the same monovalent organic group, or R c represents one fluorinated one. Valent organic group, X1 represents a halogen atom, and A is selected from the following formula (la), the following formula (lb), and the following formula (Lc) and the base represented by the following formula (Id), or the base represented by the formula in which one or more hydrogen atoms are replaced by fluorine atoms: AC 选取 2 Ο Η (1) (3) ( 4) (5 f) Printed by the staff of the Intellectual Property Bureau of the Ministry of Economy (Please read the note on the back and read this page first, then fill in this page) d (3c) (Id) 7 · —A method for producing a fluorinated saturated cyclic ether, which is characterized by the thermal decomposition of the compound represented by the following formula (5) After obtaining more than one compound selected from the compound represented by the following formula (6 a) and the compound represented by the following formula (6 b), the paper size applies the Chinese national standard (〇 奶) 六 ^ 格格 (2) 0 &gt;(297; points) 593301 A8 B8 C8 D8 6. Scope of patent application: After performing the reduction reaction of more than one compound, one or more compounds selected from the formula (6 a) are reduced to the following formula (7 a) A compound represented by the formula and a compound represented by the formula (6 b) which has been reduced is a fluorinated saturated cyclic ether of the compound represented by the formula (7 b), in which, human 1: and) (respectively have the same meaning as the above AF COX (5) (6a) F R F Η (7 a) (6b) ρ (7b) 8. The manufacturing method according to item 7 of the scope of patent application, wherein the compound represented by formula 5) is a compound represented by the following formula (5a) F 'F F — ^ —— F .F (5a) COF 9 · One of the following formulas (3a — 2), (3b-2), (4 Employee Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs printed one time (read the note on the back first) Please fill in this page again for any one of the compounds shown in b) 2), in which Re 1 and Re F 1 respectively show perfluorinated alkyl 'perfluorinated (partially chloroalkyl) and perfluorinated (Alkyl group containing etheric oxygen atom) group 'Perfluorinated (partially chlorinated (alkyl group containing etheric oxygen atom) group or perfluorinated tetrahydrofuranyl group. This paper is based on China National Standards (CNS) A4 specifications (2) 0 &gt; (297 mm) State 301 Α8 Β8 C8 D8, patent application scope CH2〇C〇Rc], 〇 / \ cH2〇C〇RC] CF] (3b-2) (4b-2) 1 〇 ·-a functional agent containing one or more selected from the following formula (6 a) Fluorinated unsaturated cyclic ether of the compound represented by the formula and the compound represented by the following formula (6 b), or one or more selected from the compounds represented by the following formula (7 a) and the compound represented by the following formula (7 b) Fluorinated saturated cyclic ether F \ JP KFF (6a) F (6b) ^ -----—II —J) i — i i---· I I I 1 · (Please read the note on the back before filling this page) (7a) F F (7b) functional agents, characterized by containing a 1T compound represented by the following formula (7a) 7 (7a) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Silk Economy 1 2. If the functional agent in the scope of patent application No. 10 or No. 11 is used, the functional agent is a dehydrating solvent, a dry etchant, or Detergents This paper uses the Chinese national standard (CNS) M specifications (2) (× 297 cm)