JP2016160230A - Method for producing fluorine-containing olefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for simply and efficiently producing a fluorine-containing olefin having a comparatively high boiling point and useful for high temperature heat pump heat source or the like from an industrially easily available raw-material under a mild condition.SOLUTION: Provided is a method for producing fluorine-containing olefin compound in which, under the presence of a metal-carbene complex catalyst, such as the following Ru compound or the like, having an olefin metathesis reaction activity, a halogenated olefin, such as the following perfluoro-1-butene or the like, and an ether-containing olefin, such as the following 1,1,3,3,4,4,5,5,5-nona-fluoro-2-methoxy-1-pentene or the like, are reacted.SELECTED DRAWING: None

Description

  The present invention relates to a novel method for producing a fluorinated olefin by olefin metathesis.

  Industrially useful compounds are known as compounds in which some of the hydrogen atoms in the olefin are substituted with fluorine atoms, that is, fluorine-containing olefins. Among them, an olefin having a halogen atom directly bonded to a carbon-carbon double bond and having an alkoxy group is useful as a heat source for a high-temperature heat pump and has a low global warming potential (GWP). Expected to be a GWP working medium.

  However, a method for easily and efficiently producing these compounds has not been established. For example, Patent Document 1 discloses a method of reacting an olefin with fluorine gas in the presence of anhydrous hydrogen fluoride. However, since the heat generated by the reaction is extremely large, it is necessary to perform the reaction at an extremely low temperature such as -70 ° C. is there. There are also many by-products.

  On the other hand, the olefin metathesis reaction (hereinafter sometimes simply referred to as “olefin metathesis” or “cross metathesis”), which is a double bond recombination reaction using a metal catalyst, is widely used as a method for producing olefins having various substituents. ing. However, since an electron-deficient olefin having an electron-withdrawing substituent has low reactivity, it is not easy to use it for olefin metathesis. For example, Non-Patent Document 1 examines the reactivity of olefins having various substituents, and describes that the reactivity of electron-deficient olefins is low. In fact, since olefins having halogen atoms such as fluorine atoms and chlorine atoms are also electron-deficient olefins, there are few reports used for olefin metathesis. For example, in Non-Patent Document 2, olefin metathesis of a ruthenium complex and vinylidene fluoride (ie, 1,1-difluoroethylene) was studied, but the expected products, ie, ethylene and tetrafluoroethylene, were not obtained at all. It has been.

International Publication No. 2012/007310

Chatterjee, A.M. K. et al. , J .; Am. Chem. Soc. 2003, 125, 11360-11370. Trnka, T .; et al. , Angew. Chem. Int. Ed. 2001, 40, 3441-3444.

  Thus, it is not practical to use an olefin having a halogen atom for olefin metathesis. Among them, olefins in which a halogen atom is directly bonded to a carbon atom forming a carbon-carbon double bond are industrially easily available and useful from the viewpoint of commercialization, but are only olefins that are extremely electron-deficient. No report has been used for olefin metathesis because of its difficulty in handling.

  Therefore, in the present invention, an olefin having a halogen atom directly bonded to a carbon atom forming a carbon-carbon double bond, which is easily available industrially, and an olefin containing an etheric oxygen atom, have a relatively high boiling point and are used for a high temperature heat pump. It is an object of the present invention to provide a method for easily and efficiently producing a fluorine-containing olefin useful for a heat source or the like under mild conditions.

  As a result of diligent research, the inventors of the present invention have developed an etheric olefin and an olefin in which a halogen atom is directly bonded to a carbon atom forming a carbon-carbon double bond in the presence of a metal catalyst having a metal-carbon double bond. It has been found that a fluorine-containing olefin can be produced under mild conditions by cross-metathesis with an olefin containing an oxygen atom, and the present invention has been completed.

That is, the present invention relates to the following <1> or <2>.
<1> In the presence of a metal-carbene complex compound (10) having olefin metathesis reaction activity, a compound represented by the following formula (21) and a compound represented by the following formula (31) or represented by the following formula (32) by reacting a compound of the formula _{(C k H m O n F} p Cl q) a method for producing a compound represented by.

However, the symbol in a formula represents the following meaning.
A ²¹ , A ²² , A ^{31 to} A ³⁴ are each independently a functional group selected from the group consisting of the following functional group (i), functional group (ii), functional group (iii), and functional group (iv). It is. A ²¹ and A ²² may be bonded to each other to form a ring. A ³¹ and A ³² may be bonded to each other to form a ring. A ³³ and A ³⁴ may be bonded to each other to form a ring.
X ²¹ , X ³³ , and X ³⁴ are each independently a functional group (viii).
X ²² , X ³¹ and X ³⁵ are each independently a functional group selected from the group consisting of the following functional group (i), functional group (ii), functional group (v) and functional group (vi).
X ³² and X ³⁶ are each independently a functional group selected from the group consisting of the following functional group (vi) and functional group (vii).
k is an integer of 5 to 10, m is an integer of 2 to 10, n is 1 or 2, (p + q) is an integer of 1 or more represented by (2k−m), and p> q, and q is an integer of 0 to 3.
Functional group (i): hydrogen atom.
Functional group (ii): a halogen atom.
Functional group (iii): a monovalent hydrocarbon group having 1 to 20 carbon atoms.
Functional group (iv): C1-C20 monovalent hydrocarbon group containing 1 or more atoms selected from the group consisting of a halogen atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, and silicon atom.
Functional group (v): C1-C6 alkyl group, C1-C6 alkoxy group, C1-C6 (per) halogenated alkyl group, and C1-C6 (per) halogenation A functional group selected from the group consisting of alkoxy groups.
Functional group (vi): a functional group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms containing 1 etheric oxygen atom and a (per) halogenated alkyl group having 1 to 6 carbon atoms containing 1 etheric oxygen atom Group.
Functional group (vii): a functional group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms and a (per) halogenated alkyl group having 1 to 6 carbon atoms.
Functional group (viii): a functional group selected from the group consisting of a hydrogen atom, a fluorine atom, a chlorine atom, an alkyl group having 1 to 2 carbon atoms, and a (per) halogenated alkyl group having 1 to 2 carbon atoms.

<2> a Formula compound represented by a compound represented by _{(C k H m O n F} p Cl q) is represented by the following formula (51) or a compound represented by the following formula (52), wherein <1 process for preparing a compound of the formula _{(C k H m O n F} p Cl q) as described in>.

  However, the symbols in the formula have the same meaning.

  According to the method for producing a fluorine-containing olefin according to the present invention, it is simple and efficient from an olefin having a halogen atom directly bonded to a carbon atom forming a carbon-carbon double bond by olefin metathesis and an olefin containing an etheric oxygen atom. In particular, it is possible to produce a fluorine-containing olefin containing an etheric oxygen atom, which has a relatively high boiling point and is useful as a heat source for a high-temperature heat pump.

Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following embodiments, and can be arbitrarily modified without departing from the gist of the present invention. In addition, the present invention relates to olefin metathesis by a metal catalyst, and description of general features common to the prior art may be omitted.
In the present specification, the “compound represented by the formula (X)” may be simply referred to as “compound (X)”.
The perhalogenated alkyl group means a group in which all hydrogen atoms of the alkyl group are substituted with halogen atoms. The perhalogenated alkoxy group means a group in which all hydrogen atoms of the alkoxy group are substituted with halogen atoms. The same applies to perhalogenated alkoxy groups.
The term “(per) halogenated alkyl group” is used as a general term that includes a halogenated alkyl group and a perhalogenated alkyl group. That is, the group is an alkyl group having one or more halogen atoms. The same applies to the (per) halogenated alkoxy group.
The number of carbon atoms of the hydrocarbon group means the total number of carbon atoms contained in the whole hydrocarbon group, and when the group has no substituent, the number of carbon atoms forming the hydrocarbon group skeleton is When the group has a substituent, the total number is obtained by adding the number of carbon atoms in the substituent to the number of carbon atoms forming the hydrocarbon group skeleton.

<Reaction mechanism>
The present invention relates to a method for producing a fluorine-containing olefin by olefin metathesis. For example, octafluoro-1-butene represented by the following formula (210) and 1,1,3,3 represented by the following formula (310): , 4,4,5,5,5-nonafluoro-2-methoxy-1-pentene in the presence of a metal-carbene complex, the reaction mechanism represented by the following formula (510 1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-4-methoxy-3-heptene is obtained.
In addition, compound (11) and compound (12), which are intermediates shown in the following scheme (a), are described as representative examples of metal-carbene complex compound (10) having olefin metathesis reaction activity. Examples of the specific metal-carbene complex compound (10) include a ruthenium-carbene complex, a molybdenum-carbene complex, or a tungsten-carbene complex (hereinafter also collectively referred to as “metal-carbene complex”).

In the scheme (a), [L] is a ligand, and M is ruthenium, molybdenum, or tungsten.
Olefin metathesis is reversible. That is, in Scheme (a), there is a reverse reaction (reaction represented by an arrow in the reverse direction). However, the details of this point will not be described. In addition, geometric isomers may exist for the olefin to be produced. However, the details of this point are strongly dependent on the individual reactions, and the explanation is omitted.

<Metal-carbene complex compound (10)>
As the metal-carbene complex compound (10), in the above scheme (a), the compound (11) and the compound (12) are shown as examples, but two functionalities bonded to a carbon atom forming a double bond with the metal. Each group is independently a hydrogen atom, a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or an atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom. As long as it is a monovalent hydrocarbon group having 1 to 20 carbon atoms and 1 or more thereof, these may be bonded to each other to form a ring.
Although the compound (10) plays a role as a catalyst in the production method according to the present invention, it means both a substance to be charged as a reagent and a substance generated during the reaction (catalytically active species). Here, the compound (10) is known to show catalytic activity when some of the ligands dissociate under the reaction conditions, and to show catalytic activity without dissociation of the ligands. However, any of them is not limited in the present invention. In general, since olefin metathesis proceeds while repeating coordination and dissociation of olefin to the catalyst, it is not always clear how many ligands other than olefin are coordinated on the catalyst during the reaction. Therefore, in this specification, [L] does not specify the number or type of ligands.

  Among the above catalysts, the compound whose metal is ruthenium is generally referred to as “ruthenium-carbene complex”, for example, Vougioukalakis, G. et al. C. et al. Chem. Rev. 2010, 110, 1746-1787. The ruthenium-carbene complex described in 1) can be used. Further, for example, a ruthenium-carbene complex commercially available from Aldrich or Umicore can be used.

Specific examples of the ruthenium-carbene complex include bis (triphenylphosphine) benzylidene ruthenium dichloride, bis (tricyclohexylphosphine) benzylidene ruthenium dichloride, bis (tricyclohexylphosphine) -3-methyl-2-butenylidene ruthenium dichloride, ( 1,3-diisopropylimidazol-2-ylidene) (tricyclohexylphosphine) benzylideneruthenium dichloride, (1,3-dicyclohexylimidazole-2-ylidene) (tricyclohexylphosphine) benzylideneruthenium dichloride, (1,3-dimesitylimidazole) -2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride, (1,3-dimesityl-4,5-dihydroimidazole) 2-Ilidene) (tricyclohexylphosphine) benzylideneruthenium dichloride, [1,3-bis (2,6-diisopropylphenyl) -4,5-dihydroimidazol-2-ylidene] (tricyclohexylphosphine) benzylideneruthenium dichloride, [1 , 3-bis (2-methylphenyl) -4,5-dihydroimidazol-2-ylidene] (tricyclohexylphosphine) benzylideneruthenium dichloride, [1,3-dicyclohexyl-4,5-dihydroimidazol-2-ylidene] ( Tricyclohexylphosphine) benzylideneruthenium dichloride, bis (tricyclohexylphosphine) ethoxymethylideneruthenium dichloride, (1,3-dimesityl-4,5-dihydroimidazol-2-ylide) ) (Tricyclohexylphosphine) ethoxymethylidene ruthenium dichloride, (1,3-dimesityl-4,5-dihydroimidazol-2-ylidene) [bis (3-bromopyridine)] benzylidene ruthenium dichloride, (1,3-dimesityl- 4,5-dihydroimidazol-2-ylidene) (2-isopropoxyphenylmethylidene) ruthenium dichloride, (1,3-dimesityl-4,5-dihydroimidazol-2-ylidene) [(tricyclohexylphosphoranyl) methylidene ] Dichlororuthenium tetrafluoroborate, Umicore M2, Umicore M51, Umicore M52, Umicore M71 SIMes, Umicore M71 SIPr, Umicore M73 SIMes, Umicore M73 SIPr and the like, (1,3-dimesityl-4,5-dihydroimidazol-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride, (1,3-dimesityl-4,5-dihydroimidazol-2-ylidene) ) (2-isopropoxyphenylmethylidene) ruthenium dichloride, (1,3-dimesityl-4,5-dihydroimidazol-2-ylidene) [(tricyclohexylphosphoranyl) methylidene] dichlororuthenium tetrafluoroborate, Umicore M2, Umicore M51, Umicore M52, Umicore M71 SIMes, Umicore M71 SIPr, Umicore M73 SIMes, and Umicore M73 SIPr are particularly preferable. Of the above complexes, the names beginning with “Umicore” are trade names of Umicore products.
In addition, the said ruthenium carbene complex may be used independently and may be used together 2 or more types. Further, if necessary, it may be supported on a carrier such as silica gel, alumina or polymer.

Among the above catalysts, compounds in which the metal is molybdenum or tungsten are generally referred to as “molybdenum-carbene complex” and “tungsten-carbene complex”. (Ed) Olefin Metathesis: Theory and Practice, Wiley, 2014. The molybdenum-carbene complex or tungsten-carbene complex described in 1) can be used. For example, a molybdenum-carbene complex or a tungsten-carbene complex commercially available from Aldrich or Strem can be used.
The molybdenum-carbene complex or the tungsten-carbene complex may be used alone or in combination of two or more. Further, if necessary, it may be supported on a carrier such as silica gel, alumina or polymer.

  Specific examples of the molybdenum-carbene complex are shown below. Me represents a methyl group, i-Pr represents an isopropyl group, t-Bu represents a tertiary butyl group, and Ph represents a phenyl group.

  Specific examples of the tungsten-carbene complex include the following compounds.

<Raw compound>
In the production of the fluorinated olefin according to the present invention, the raw material compound (21), compound (31), and compound (32) are shown below. The symbols in the formula are the same as defined above.

That is, A ²¹ and A ²² in the compound (21) are each independently a hydrogen atom; a halogen atom; a monovalent hydrocarbon group having 1 to 20 carbon atoms; and a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, or a phosphorus atom. And a functional group selected from the group consisting of a monovalent hydrocarbon group having 1 to 20 carbon atoms containing one or more atoms selected from the group consisting of silicon atoms. A ²¹ and A ²² may be bonded to each other to form a ring.
X ²¹ is a functional group selected from the group consisting of a hydrogen atom, a fluorine atom, a chlorine atom, an alkyl group having 1 to 2 carbon atoms, and a (per) halogenated alkyl group having 1 to 2 carbon atoms.
X ²² represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a (per) halogenated alkyl group having 1 to 6 carbon atoms, or (per) carbon atoms. A functional group selected from the group consisting of a halogenated alkoxy group, an alkyl group having 1 to 6 carbon atoms containing 1 etheric oxygen atom, and a (per) halogenated alkyl group having 1 to 6 carbon atoms containing 1 etheric oxygen atom It is.
X ²¹ and X ²² preferably have a total carbon number of 1 or more.

In view of availability, A ²¹ and A ²² in the compound (21) are each independently a hydrogen atom or a fluorine atom. X ²¹ is more preferably a fluorine atom from the viewpoint of availability. X ²² is preferably an alkyl group having 1 to 5 carbon atoms or a (per) halogenated alkyl group having 1 to 5 carbon atoms from the viewpoint of easy availability, and is a perfluoroalkyl group having 1 to 5 carbon atoms. It is more preferable that it is a linear perfluoroalkyl group having 1 to 5 carbon atoms.

A ³¹ and A ³² in the compound (31) are each independently a hydrogen atom; a halogen atom; a monovalent hydrocarbon group having 1 to 20 carbon atoms; and a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, And a functional group selected from the group consisting of a monovalent hydrocarbon group having 1 to 20 carbon atoms containing one or more atoms selected from the group consisting of silicon atoms. A ³¹ and A ³² may be bonded to each other to form a ring.
X ³¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a (per) halogenated alkyl group having 1 to 6 carbon atoms, ) A function selected from the group consisting of a halogenated alkoxy group, an alkyl group having 1 to 6 carbon atoms containing 1 etheric oxygen atom, and a (per) halogenated alkyl group having 1 to 6 carbon atoms containing 1 etheric oxygen atom. It is a group.
X ³² is an alkyl group having 1 to 6 carbon atoms, a (per) halogenated alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms containing 1 etheric oxygen atom, and a carbon containing 1 etheric oxygen atom. It is a functional group selected from the group consisting of (per) halogenated alkyl groups of formulas 1-6.
That is, the compound (31) is an olefin compound having a partial structure in which at least one etheric oxygen atom (that is, ((per) halogenated) alkoxy group) is directly bonded to a carbon atom constituting a double bond.

In view of availability, A ³¹ and A ³² in the compound (31) are each independently a hydrogen atom or a fluorine atom.
X ³¹ is preferably a halogen atom, an alkyl group having 1 to 5 carbon atoms, or a (per) halogenated alkyl group having 1 to 5 carbon atoms, and a fluorine atom, a chlorine atom, or a perfluoroalkyl group having 1 to 5 carbon atoms. More preferred is a fluorine atom, a chlorine atom, or a linear perfluoroalkyl group having 1 to 5 carbon atoms.
X ³² is preferably an alkyl group having 1 to 3 carbon atoms, or a (per) halogenated alkyl group having 1 to 3 carbon atoms, a linear alkyl group having 1 to 3 carbon atoms, or ( A per) fluoroalkyl group is more preferred.

A ³³ and A ³⁴ in the compound (32) are each independently a hydrogen atom; a halogen atom; a monovalent hydrocarbon group having 1 to 20 carbon atoms; and a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, And a functional group selected from the group consisting of a monovalent hydrocarbon group having 1 to 20 carbon atoms containing one or more atoms selected from the group consisting of silicon atoms. A ³³ and A ³⁴ may be bonded to each other to form a ring.
X ³³ and X ³⁴ are each independently a functional group selected from the group consisting of a hydrogen atom, a fluorine atom, a chlorine atom, an alkyl group having 1 to 2 carbon atoms, and a (per) halogenated alkyl group having 1 to 2 carbon atoms. It is a group.
X ³⁵ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a (per) halogenated alkyl group having 1 to 6 carbon atoms, or (per) carbon atoms. A functional group selected from the group consisting of a halogenated alkoxy group, an alkyl group having 1 to 6 carbon atoms containing 1 etheric oxygen atom, and a (per) halogenated alkyl group having 1 to 8 carbon atoms containing 1 etheric oxygen atom It is.
X ³⁶ represents an alkyl group having 1 to 6 carbon atoms, a (per) halogenated alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms containing 1 etheric oxygen atom, and a carbon containing 1 etheric oxygen atom. It is a functional group selected from the group consisting of (per) halogenated alkyl groups of formulas 1-6.
That is, the compound (32) is an olefin having a partial structure in which at least one etheric oxygen atom (that is, ((per) halogenated) alkoxy group) is directly bonded to the carbon atom adjacent to the carbon atom constituting the double bond. A compound.

In view of availability, A ³³ and A ³⁴ in the compound (32) are each independently a hydrogen atom or a fluorine atom.
X ³³ and X ³⁴ are both preferably fluorine atoms from the viewpoint of availability.
X ³⁵ is preferably a halogen atom, an alkyl group having 1 to 5 carbon atoms, or a (per) halogenated alkyl group having 1 to 5 carbon atoms, more preferably a fluorine atom, a chlorine atom, or a perfluoroalkyl group having 1 to 5 carbon atoms. A fluorine atom, a chlorine atom, or a linear perfluoroalkyl group having 1 to 5 carbon atoms is more preferable.
X ³⁶ is preferably an alkyl group having 1 to 3 carbon atoms, or a (per) halogenated alkyl group having 1 to 3 carbon atoms, and a linear alkyl group having 1 to 3 carbon atoms, or 1 to 3 carbon atoms (per ) A fluoroalkyl group is more preferred.

The total number of carbon atoms of X ²¹ , X ²² , X ³¹ , and X ³² and the total number of carbon atoms of X ²¹ , X ²² , X ³³ , X ³⁴ , X ^35, and X ³⁶ are all integers of 3-8. It is. This is because k in the compound to be produced (51) or compound (52) of the formula _{(C k H m O n F} p Cl q) is 5-10.

  The preferable specific example of a compound (21) is shown below. In addition, "n-" described in the formula of this specification means that it is linear.

  Below, the preferable specific example of a compound (31) and a compound (32) is shown.

<Production compound>
The olefin metathesis of the present invention, a compound represented by the composition formula _{(C k H m O n F} p Cl q) is produced. k is an integer of 5 to 10, m is an integer of 2 to 10, n is 1 or 2, (p + q) is an integer of 1 or more represented by (2k−m), and p> q, and q is an integer of 0 to 3. From the viewpoint of high flame retardancy and stability, p> m is preferable, and q is preferably 0.
When compound (21) and compound (31) are reacted as a raw material compound, a compound represented by the following formula (51) is produced, and when compound (21) and compound (32) are reacted, the following formula (52) Is produced. The symbols in the formula are the same as defined above.
That is, in the compound (51), a fluorine atom, a chlorine atom, or a (per) halogenated alkyl group is directly bonded to one carbon atom forming a carbon-carbon double bond, and the other carbon atom is bonded. Has an etheric oxygen atom bonded directly. In compound (52), a fluorine atom, a chlorine atom, or a (per) halogenated alkyl group is directly bonded to one of the carbon atoms forming the carbon-carbon double bond, and the other carbon atom is adjacent to the other carbon atom. A fluorine atom, a chlorine atom, and an etheric oxygen atom are bonded to the carbon atom.

  Below, a compound (51a) is shown as a preferable example of a compound (51), and a compound (52b) is shown as a preferable specific example of a compound (52).

In the above formula, Xa ²¹ , Xb ²¹ , Xb ³³ and Xb ³⁴ are each independently a hydrogen atom or a fluorine atom. Xa ²² and Xb ³¹ are each independently a functional group selected from the group consisting of an alkyl group having 1 to 5 carbon atoms and a (per) halogenated alkyl group having 1 to 5 carbon atoms. Xa ³² and Xb ³⁶ are each independently a functional group selected from the group consisting of an alkyl group having 1 to 3 carbon atoms and a (per) halogenated alkyl group having 1 to 3 carbon atoms. Xb ²² and Xb ³⁵ are each independently a functional group selected from the group consisting of an alkyl group having 1 to 4 carbon atoms and a (per) halogenated alkyl group having 1 to 4 carbon atoms.

  More preferred specific examples of the compound (51) and the compound (52) are shown below.

<Manufacturing method>
TECHNICAL FIELD The present invention relates to a method for producing a fluorine-containing olefin by olefin metathesis, and typically performs olefin metathesis by contacting two different olefins with a metal-carbene complex to obtain an olefin different from the raw material. It is.

As the raw material olefin, compound (21), compound (31), and compound (32), both terminal and internal olefins can be used. The geometric isomerism on the double bond is not particularly limited.
From the viewpoint of improving the yield of the target product, it is preferable to use deaerated and dehydrated olefin as a raw material. There is no particular limitation on the deaeration operation, but freeze deaeration and the like may be performed. Although there is no restriction | limiting in particular about dehydration operation, Usually, it is made to contact with a molecular sieve etc. For the olefin as a raw material, the degassing and dehydration operations are usually performed before contacting with the metal-carbene complex.
Moreover, since the olefin used as a raw material may contain a trace amount impurity (for example, hydrogen fluoride, a peroxide, etc.), you may refine | purify from the point of the target-product yield improvement. There is no particular limitation on the purification method. For example, it can be carried out according to the method described in the literature (Armarego, WLF et al., Purification of Laboratory Chemicals (Sixth Edition), 2009, Elsevier).

The two types of olefins used as raw materials may be added after mixing in the reaction vessel in advance or may be added separately. In some cases, the second olefin is contacted with a mixture obtained by contacting the first olefin with the metal-carbene complex.
Although there is no particular limitation on the molar ratio of both olefins used as raw materials, the other olefin is used in an amount of about 0.01 to 100 mol, preferably about 0.1 to 10 mol, relative to 1 mol of the normal olefin. .

The metal-carbene complex may be added as a reagent or generated in the system.
When charging as a reagent, a commercially available metal-carbene complex may be used as it is, or a non-commercially available metal-carbene complex synthesized by a known method from a commercially available reagent may be used.
When it is generated in the system, a metal-carbene complex prepared from a metal complex as a precursor by a known method can be used in the present invention.

  Although there is no restriction | limiting in particular as the quantity of the metal-carbene complex to be used, About 0.0001-1 mol is normally used with respect to 1 mol of reference | standard olefins among two types of olefins used as a raw material, Preferably it is 0.8. About 001 to 0.2 mol is used.

  The metal-carbene complex to be used is usually charged into the reaction vessel as a solid, but may be charged after being dissolved or suspended in a solvent. There is no restriction | limiting in particular as a solvent used at this time in the range which does not exert a bad influence on reaction, An organic solvent, a fluorine-containing organic solvent, an ionic liquid, water etc. can be used individually or in mixture. In these solvent molecules, some or all of the hydrogen atoms may be substituted with deuterium atoms.

Examples of the organic solvent include aromatic hydrocarbon solvents such as benzene, toluene, o-, m-, p-xylene and mesitylene; aliphatic hydrocarbon solvents such as hexane and cyclohexane; dichloromethane, chloroform, 1, 2 -Halogen solvents such as dichloroethane, chlorobenzene, o-dichlorobenzene; ether solvents such as tetrahydrofuran, dioxane, diethyl ether, glyme, diglyme, and the like can be used. Examples of the fluorine-containing organic solvent include hexafluorobenzene, m-bis (trifluoromethyl) benzene, p-bis (trifluoromethyl) benzene, α, α, α-trifluoromethylbenzene, dichloropentafluoropropane, and the like. Can be used. As the ionic liquid, for example, various pyridinium salts, various imidazolium salts and the like can be used. Among the above solvents, benzene, toluene, o-, m-, p-xylene, mesitylene, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, diethyl ether, dioxane, THF in terms of solubility of the metal-carbene complex. (Tetrahydrofuran), hexafluorobenzene, m-bis (trifluoromethyl) benzene, p-bis (trifluoromethyl) benzene, α, α, α-trifluoromethylbenzene, and mixtures thereof are preferred.
In addition, it is preferable to use a degassed and dehydrated solvent for improving the yield of the target product. There is no particular limitation on the deaeration operation, but freeze deaeration and the like may be performed. Although there is no restriction | limiting in particular about dehydration operation, Usually, it is made to contact with a molecular sieve etc. The degassing and dehydration operations are usually performed before contacting with the metal-carbene complex.

The atmosphere in which the two olefins and the metal-carbene complex are brought into contact with each other is not particularly limited, but an inert gas atmosphere is preferable from the viewpoint of extending the life of the catalyst, and a nitrogen or argon atmosphere is particularly preferable. However, when using the olefin which becomes gas in reaction conditions as a raw material, it can carry out in these gas atmosphere.
The phase in which the two olefins and the metal-carbene complex are brought into contact with each other is not particularly limited, but a liquid phase is usually used in terms of reaction rate. When at least one of the two kinds of olefins used as a raw material is a gas under the reaction conditions, it is difficult to carry out in the liquid phase, and therefore, it can be carried out in the gas-liquid two phase. In the case of carrying out in the liquid phase, a solvent can be used. As the solvent used at this time, the same solvents as those used for dissolving or suspending the metal-carbene complex can be used. In addition, when at least one is a liquid under reaction conditions among two types of olefin used as a raw material, it can implement without a solvent.

  The container for bringing the two olefins into contact with the metal-carbene complex is not particularly limited as long as it does not adversely affect the reaction. For example, a metal container or a glass container can be used. In addition, since the olefin metathesis concerning this invention may handle the olefin in a gaseous state on reaction conditions, the pressure-resistant container in which high airtightness is possible is preferable.

Although there is no restriction | limiting in particular as temperature which makes 2 types of olefins and metal-carbene complexes contact, It can implement normally in the range of -100-200 degreeC, and 0-150 degreeC is preferable at the point of reaction rate. Note that the reaction does not start at low temperatures, and the complex may be rapidly decomposed at high temperatures. Therefore, it is necessary to appropriately set the lower limit and the upper limit of the temperature. Usually, it is carried out at a temperature below the boiling point of the solvent used.
Although there is no restriction | limiting in particular as time to contact two types of olefins and a metal carbene complex, Usually, it implements in the range of 1 minute-48 hours.
The pressure for bringing the two olefins into contact with the metal-carbene complex is not particularly limited, but may be under pressure, under normal pressure, or under reduced pressure. Usually, it is about 0.001-10 MPa, preferably about 0.01-1 MPa.

  When contacting the two kinds of olefins with the metal-carbene complex, an inorganic salt, an organic compound, a metal complex, or the like may coexist within a range that does not adversely affect the reaction. Moreover, you may stir the mixture of two types of olefins and a metal carbene complex in the range which does not have a bad influence on reaction. At this time, a mechanical stirrer, a magnetic stirrer, or the like can be used as a stirring method.

  After contacting two kinds of olefins with the metal-carbene complex, the target product is usually obtained as a mixture of a plurality of olefins, and therefore may be isolated by a known method. Examples of the isolation method include distillation, column chromatography, recycle preparative HPLC and the like, and these can be used alone or in combination as necessary.

The target product obtained in this reaction can be identified by a known method similar to that for ordinary organic compounds. For example, ¹ H-, ¹⁹ F-, ¹³ C-NMR, GC-MS and the like can be mentioned, and these can be used alone or in combination.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these.
<Commercially available reagents>
In this example, unless otherwise specified, a commercially available catalyst was used as it was for the reaction. As the solvent, a commercially available product was freeze-degassed in advance and dried with molecular sieve 4A before use in the reaction.
<Evaluation method>
In this example, the structure of the synthesized compound was identified by performing ¹ H-NMR and ¹⁹ F-NMR measurements using a nuclear magnetic resonance apparatus (JNM-AL300) manufactured by JEOL Ltd. Moreover, molecular weight was calculated | required by the electron ionization method (EI) using the Shimadzu Corporation gas chromatograph mass spectrometer (GCMS-QP2010Ultra).

<Example 1>
Synthesis of 2-chloro-1,1,3,3,4,4,5,5,5-nonafluoro-1-pentene In a nitrogen atmosphere, 50 mL of THF (tetrahydrofuran) and 1,1-dichloro-2,2 were placed in a flask. -Difluoroethene (5.0 g, 37.6 mmol) was weighed and stirred at -78 ° C, and 15% n-BuLi hexane solution (16.1 g, corresponding to 37.7 mmol as n-BuLi) was added at an internal temperature of -55. Add dropwise to keep below ℃. Next, a mixed solution of 1,1,1,2,2,3,3-heptafluoro-3-iodopropane (11.1 g, 37.6 mmol) and THF 10 mL was added to the reaction solution at an internal temperature of −55 ° C. or lower. The mixture is added dropwise so as to maintain the temperature and reacted at the same temperature for 1 hour to synthesize 2-chloro-1,1,3,3,4,4,5,5,5-nonafluoro-1-pentene. The reaction is shown below.

<Example 2>
Synthesis of 1,1,3,3,4,4,5,5,5-nonafluoro-2-methoxy-1-pentene A 5 mol / L solution of sodium methoxide in a flask (4.1 mL, 20 as sodium methoxide). 5 mmol) and 2-chloro-1,1,3,3,4,4,5,5,5-nonafluoro-1-pentene (5 g, 18.8 mmol) were measured and heated to 1,1,3 , 3,4,4,5,5,5-nonafluoro-2-methoxy-1-pentene. The reaction is shown below.

<Example 3>
Cross metathesis reaction of 1,1,3,3,4,4,5,5,5-nonafluoro-2-methoxy-1-pentene and perfluoro-1-butene with Umicore M73 SIPr catalyst Umicore M73 SIPr catalyst (10 mol%, 0.01 mmol), 1,1,3,3,4,4,5,5,5-nonafluoro-2-methoxy-1-pentene (0.12 mmol, 31.4 mg) and o-dichlorobenzene-d ₄ ( 0.6 mL) is weighed into an NMR measuring tube. After substituting the gas phase part of the NMR tube with perfluoro-1-butene (0.12 mmol, 2.7 mL as a gas), it is heated to 1,1,1,2,2,3,5,5,6, Synthesize 6,7,7,7-tridecafluoro-4-methoxy-3-heptene. The reaction is shown below.

  According to the present invention, a fluorine-containing olefin is conveniently and efficiently produced by a cross-metathesis reaction using an olefin having a halogen atom directly bonded to a carbon atom forming a carbon-carbon double bond and an olefin containing an etheric oxygen atom. Can be manufactured. The fluorine-containing olefin has a relatively high boiling point and is expected to be used as a heat source for high-temperature heat pumps.

Claims (2)

In the presence of a metal-carbene complex compound (10) having olefin metathesis reaction activity, a compound represented by the following formula (21) and a compound represented by the following formula (31) or a compound represented by the following formula (32) by reacting the door, methods of preparing the compounds of the formula _{(C k H m O n F} p Cl q).

However, the symbol in a formula represents the following meaning.
A ²¹ , A ²² , A ^{31 to} A ³⁴ are each independently a functional group selected from the group consisting of the following functional group (i), functional group (ii), functional group (iii), and functional group (iv). It is. A ²¹ and A ²² may be bonded to each other to form a ring. A ³¹ and A ³² may be bonded to each other to form a ring. A ³³ and A ³⁴ may be bonded to each other to form a ring.
X ²¹ , X ³³ , and X ³⁴ are each independently a functional group (viii).
X ²² , X ³¹ and X ³⁵ are each independently a functional group selected from the group consisting of the following functional group (i), functional group (ii), functional group (v) and functional group (vi).
X ³² and X ³⁶ are each independently a functional group selected from the group consisting of the following functional group (vi) and functional group (vii).
k is an integer of 5 to 10, m is an integer of 2 to 10, n is 1 or 2, (p + q) is an integer of 1 or more represented by (2k−m), and p> q, and q is an integer of 0 to 3.
Functional group (i): hydrogen atom.
Functional group (ii): a halogen atom.
Functional group (iii): a monovalent hydrocarbon group having 1 to 20 carbon atoms.
Functional group (iv): C1-C20 monovalent hydrocarbon group containing 1 or more atoms selected from the group consisting of a halogen atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, and silicon atom.
Functional group (v): C1-C6 alkyl group, C1-C6 alkoxy group, C1-C6 (per) halogenated alkyl group, and C1-C6 (per) halogenation A functional group selected from the group consisting of alkoxy groups.
Functional group (vi): a functional group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms containing 1 etheric oxygen atom and a (per) halogenated alkyl group having 1 to 6 carbon atoms containing 1 etheric oxygen atom Group.
Functional group (vii): a functional group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms and a (per) halogenated alkyl group having 1 to 6 carbon atoms.
Functional group (viii): a functional group selected from the group consisting of a hydrogen atom, a fluorine atom, a chlorine atom, an alkyl group having 1 to 2 carbon atoms, and a (per) halogenated alkyl group having 1 to 2 carbon atoms. The compound represented by the formula _{(C k H m O n F} p Cl q) is a compound represented by a compound or formula represented by the following formula (51) (52) of claim 1 formula _{(C k H m O n F} p Cl q) a method for producing a compound represented by.

However, the symbols in the formula have the same meaning.