JP7331992B2 - Fluorine-containing silane compound - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a fluorine-containing silane compound by a cross-metathesis reaction, and the fluorine-containing silane compound.

Substrates having fluorine atom-containing organic groups on the surface layer are industrially useful in applications such as displays, glasses, and touch panels that require water repellency, oil repellency, and antifouling properties. Here, an organic group containing a fluorine atom exhibits high lubricity, water and oil repellency, and the like, and is therefore suitably used as a surface treatment agent for substrates. By imparting water and oil repellency to the surface of the base material with the surface treatment agent, dirt on the surface of the base material can be easily wiped off, improving the removability of the dirt.

As a method for introducing a fluorine-containing compound to the surface of a substrate, a method using a surface treatment agent containing a fluorine-containing silane compound is known.
For example, Patent Document 1 discloses a surface treatment agent using a compound having two or more silicon atoms in the molecule as a fluorine-containing silane compound.

On the other hand, the olefin metathesis reaction (hereinafter sometimes simply referred to as "olefin metathesis" or "metathesis"), which is a double bond recombination reaction with a metal catalyst, is widely used as a method for producing olefins with various substituents. ing.
For example, Non-Patent Document 1 investigates the reactivity of olefins having various substituents, and Non-Patent Document 2 describes olefin metathesis of a ruthenium complex and vinylidene fluoride (i.e., 1,1-difluoroethylene). being considered.

WO2014/069592

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

However, conventional surface treatment agents containing fluorine-containing silane compounds are concerned about deterioration in performance due to long-term use, and there is room for improvement, for example, insufficient friction durability.

In addition, electron-deficient olefins having electron-withdrawing substituents have low reactivity, and thus are not easily utilized for olefin metathesis. In fact, Non-Patent Document 1 describes that electron-deficient olefins have low reactivity.
Furthermore, since olefins having halogen atoms such as fluorine atoms and chlorine atoms are also electron-deficient olefins, there are almost no reports of their use in olefin metathesis. It is said that it was not obtained.

Therefore, if a fluorine-containing silane compound having a reactive carbon-carbon double bond can be produced simply and efficiently under mild conditions using a fluorine-containing compound that is easily available industrially, it will be possible to obtain crosslinkability on the substrate surface. It is possible to introduce a fluorine-containing alkyl group having a site, and it is possible to produce a highly durable base material compared to existing methods.

The present invention has been made in view of the above-mentioned conventional circumstances, and is capable of simply and efficiently producing a fluorine-containing silane compound having a reactive carbon-carbon double bond under mild conditions by olefin metathesis. An object of the present invention is to provide a method and a novel fluorine-containing silane compound.

As a result of intensive studies, the present inventors have found that the above problems can be solved by cross-metathesis reaction between specific compounds, and have completed the present invention.
That is, the present invention relates to the following <1> to <11>.
<1> A method for producing a compound represented by the following formula (3′), comprising subjecting a compound represented by the following formula (1′) to a cross-metathesis reaction with a compound represented by the following formula (2).

(wherein b is 0 or 1, c is 0, 1 or 2, the sum of c and d is 3, X represents a chlorine atom or an alkoxy group having 1 to 6 carbon atoms, and Z ¹ ~Z ⁴ each independently represents a hydrogen atom or a monovalent organic group, Q is an h-valent organic group containing a fluorine atom and optionally having a hetero atom, and R ⁴ has 4 to 4 carbon atoms. represents an aryl group having 20 or an alkyl group having 1 to 6 carbon atoms, h represents a natural number of 2 or more, multiple Z ¹ and Z ² may be the same or different, and R ⁴ and X are the same If there are more than one in the molecule, they may be the same or different.)

<2> A method for producing a compound represented by the following formula (3), wherein a compound represented by the following formula (1) and a compound represented by the following formula (2) are subjected to a cross-metathesis reaction.

(Wherein, a is 0 or 1, b is 0 or 1, c is 0, 1 or 2, the sum of c and d is 3, X is a chlorine atom or a represents an alkoxy group, Y represents a single bond, an etheric oxygen atom or —CH ₂ O—, Z ¹ to Z ⁴ each independently represent a hydrogen atom or a monovalent organic group, R ¹ represents a fluorine atom or represents a monovalent fluorine-containing organic group, R ² represents a hydrogen atom, a fluorine atom or a monovalent fluorine-containing organic group, R ³ represents a fluorine atom or a monovalent fluorine-containing organic group, and R ¹ and R ² , and any two selected from the group consisting of R ³ may combine with each other to form a ring, R ⁴ represents an aryl group having 4 to 20 carbon atoms or an alkyl group having 1 to 6 carbon atoms, When multiple R ⁴ and X are present in the same molecule, they may be the same or different.)

<3> a is 0 or 1, b is 0, c is 0, X represents a chlorine atom, a methoxy group or an ethoxy group, Y is a single bond, an etheric oxygen atom or —CH ₂ O -, R ¹ is a (per)fluoroalkyl group having 1 to 12 carbon atoms, a (per)fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom, or a 2 to 400 carbon atoms containing an etheric oxygen atom represents a (per)fluoroalkoxy group, and R ² is a fluorine atom, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, or a (per)fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom and R ³ represents a fluorine atom, a trifluoromethyl group, or a (per)fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom.
<4> Z ¹ to Z ⁴ are each independently a hydrogen atom, a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a propoxy group, a phenyl group, a phenyloxy group, a trifluoromethyl group, a pentafluoroethyl group, represents a heptafluoropropyl group, a trifluoromethoxy group, a pentafluoroethoxy group, a heptafluoropropoxy group, a perfluoro(methoxymethoxy) group, a perfluoro(propoxypropoxy) group, a pentafluorophenyl group or a pentafluorophenyloxy group, <2 > or the production method according to <3>.
<5> A compound represented by the following formula (3′).

(Wherein, b is 0 or 1, c is 0, 1 or 2, the sum of c and d is 3, X represents a chlorine atom or an alkoxy group having 1 to 6 carbon atoms, and Q is an h-valent organic group containing a fluorine atom and optionally having a heteroatom, R ⁴ represents an aryl group having 4 to 20 carbon atoms or an alkyl group having 1 to 6 carbon atoms, and h is 2 or more; represents a natural number, and when there are a plurality of R ⁴ and X, they may be the same or different.)

<6> A compound represented by the following formula (4).

(wherein c is 0, 1 or 2, the sum of c and d is 3, Y represents a single bond, an etheric oxygen atom or —CH ₂ O—, and R ¹¹ is a monovalent fluorine-containing represents an organic group, R ² represents a hydrogen atom, a fluorine atom or a monovalent fluorine-containing organic group, R ³ represents a fluorine atom or a monovalent fluorine-containing organic group, and from R ¹¹ , R ² and R ³ Any two selected from the group may be bonded to each other to form a ring, R ⁴ represents an aryl group having 4 to 20 carbon atoms or an alkyl group having 1 to 6 carbon atoms, and a plurality of R ⁴ are present If so, they may be the same or different.)

<7> c is 0, Y represents a single bond, an etheric oxygen atom or —CH ₂ O—, R ¹¹ is a (per)fluoroalkyl group having 1 to 12 carbon atoms, a carbon containing an etheric oxygen atom represents a (per)fluoroalkyl group of 2 to 400 or a (per)fluoroalkoxy group of 2 to 400 carbon atoms containing an etheric oxygen atom, and R ² is a fluorine atom, a trifluoromethyl group, a pentafluoroethyl group, a hepta represents a fluoropropyl group or a (per)fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom, and R ³ represents a fluorine atom, a trifluoromethyl group or a (per)fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom; The compound according to <6> above, which represents a per)fluoroalkyl group.
<8> A compound represented by the following formula (5).

(Wherein, b is 0 or 1, c is 0, 1 or 2, the sum of c and d is 3, Y represents a single bond, an etheric oxygen atom or —CH ₂ O—, R ¹ represents a fluorine atom or a monovalent fluorine-containing organic group, R ² represents a hydrogen atom, a fluorine atom or a monovalent fluorine-containing organic group, R ³ represents a fluorine atom or a monovalent fluorine-containing organic group , R ¹ , R ² and R ³ may be combined to form a ring, and R ⁴ is an aryl group having 4 to 20 carbon atoms or an aryl group having 1 to 6 carbon atoms. represents an alkyl group of and when there are multiple R ^4s , they may be the same or different.)

<9> b is 0, c is 0, Y represents a single bond, an etheric oxygen atom or —CH ₂ O—, R ¹ is a (per)fluoroalkyl group having 1 to 12 carbon atoms, ether represents a (per)fluoroalkyl group having 2 to 400 carbon atoms containing an oxygen atom or a (per)fluoroalkoxy group having 2 to 400 carbon atoms containing an etheric oxygen atom, and R ² is a fluorine atom, a trifluoromethyl group, represents a pentafluoroethyl group, a heptafluoropropyl group, or a (per)fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom, and R ³ is a fluorine atom, a trifluoromethyl group, or a carbon containing an etheric oxygen atom; The compound according to <8> above, which represents a (per)fluoroalkyl group of numbers 2 to 400.
<10> A compound represented by the following formula (6).

(wherein c is 0, 1 or 2, the sum of c and d is 3, Y represents a single bond, an etheric oxygen atom or —CH ₂ O—, R ¹ is a fluorine atom or a monovalent R ² represents a hydrogen atom, a fluorine atom or a monovalent fluorine-containing organic group, R ³ represents a fluorine atom or a monovalent fluorine-containing organic group, R ¹ , R ² , and Any two selected from the group consisting of R ³ may combine with each other to form a ring, R ⁴ represents an aryl group having 4 to 20 carbon atoms or an alkyl group having 1 to 6 carbon atoms, and R ⁵ represents an alkyl group having 1 to 6 carbon atoms, and when there are a plurality of each of R ⁴ and R ⁵ , they may be the same or different.)

<11> c is 0, Y represents a single bond, an etheric oxygen atom or —CH ₂ O—, R ¹ is a (per)fluoroalkyl group having 1 to 12 carbon atoms, a carbon containing an etheric oxygen atom represents a (per)fluoroalkyl group of 2 to 400 or a (per)fluoroalkoxy group of 2 to 400 carbon atoms containing an etheric oxygen atom, and R ² is a fluorine atom, a trifluoromethyl group, a pentafluoroethyl group, a hepta represents a fluoropropyl group or a (per)fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom, and R ³ represents a fluorine atom, a trifluoromethyl group or a (per)fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom; The compound according to <10> above, which represents a per)fluoroalkyl group.

According to the present invention, a novel and useful fluorine-containing silane compound having a reactive carbon-carbon double bond can be produced simply and efficiently under mild conditions.

Although the present invention will be described in detail below, the present invention is not limited to the following embodiments, and can be arbitrarily modified without departing from the gist of the present invention. Further, the present invention relates to olefin metathesis using a metal catalyst, and descriptions of general features common to the prior art may be omitted.
In this specification, the "compound represented by formula (n)" may be simply referred to as "compound (n)".

In the present specification, the number of carbon atoms means the total number of carbon atoms contained in a group as a whole, and when the group does not have a substituent, it represents the number of carbon atoms forming the skeleton of the group. , represents the total sum of the number of carbon atoms forming the skeleton of the group plus the number of carbon atoms in the substituent when the group has a substituent.

An etheric oxygen atom is an oxygen atom that forms an ether bond (--O--) between carbon-carbon atoms.
The aryl group means a monovalent group corresponding to a residue obtained by removing one hydrogen atom bonded to any one of the carbon atoms forming an aromatic ring in an aromatic compound, and a carbocyclic compound A homoaryl group derived from and a heteroaryl group derived from a heterocyclic compound are collectively used.
A (per)fluoroalkyl group is used as a generic term combining a fluoroalkyl group and a perfluoroalkyl group. That is, the group is an alkyl group containing one or more fluorine atoms. The same applies to (per)fluoroalkoxy groups, (per)fluoroaryl groups, and (per)fluoroaryloxy groups.

[Cross metathesis reaction]
In one aspect of the present invention, a compound represented by the following formula (1) (compound (1)) and a compound represented by the following formula (2) (compound (2)) are subjected to a cross-metathesis reaction, The present invention relates to a method for producing a compound (compound (3)) represented by the following formula (3).

In the formula, a is 0 or 1, b is 0 or 1, c is 0, 1 or 2, the sum of c and d is 3, X is a chlorine atom or a C 1-6 represents an alkoxy group, Y represents a single bond, an etheric oxygen atom or —CH ₂ O—, Z ¹ to Z ⁴ each independently represent a hydrogen atom or a monovalent organic group, R ¹ represents a fluorine atom or 1 represents a valent fluorine-containing organic group, R ² represents a hydrogen atom, a fluorine atom or a monovalent fluorine-containing organic group, R ³ represents a fluorine atom or a monovalent fluorine-containing organic group, R ¹ , R ² , Any two selected from the group consisting of and R ³ may combine with each other to form a ring, R ⁴ represents an aryl group having 4 to 20 carbon atoms or an alkyl group having 1 to 6 carbon atoms, and R When ⁴ and X exist in the same molecule, they may be the same or different.
In the cross-metathesis reaction, the left carbene portion of the double bond in formula (1) (the portion obtained by removing CZ ¹ Z ² from compound (1)) and the left carbene portion of the double bond in formula (3) are the same, The carbene portion on the right side of the double bond in formula (2) (the portion of compound (2) excluding CZ ³ Z ⁴ ) is the same as the carbene portion on the right side of the double bond in formula (3).

In another aspect of the present invention, a compound represented by the following formula (1′) (compound (1′)) and a compound represented by the following formula (2) (compound (2)) are cross metathesized. The present invention relates to a method for producing a compound (compound (3')) represented by the following formula (3') by reacting.

In the formula, b is 0 or 1, c is 0, 1 or 2, the sum of c and d is 3, X represents a chlorine atom or an alkoxy group having 1 to 6 carbon atoms, and Z ¹ to Z ⁴ each independently represents a hydrogen atom or a monovalent organic group, Q is an h-valent organic group containing a fluorine atom and optionally having a hetero atom, and R ⁴ has 4 to 20 carbon atoms. represents an aryl group or an alkyl group having 1 to 6 carbon atoms, h represents a natural number of 2 or more, multiple Z ¹ and Z ² may be the same or different, and R ⁴ and X are each the same molecule When there are more than one within, they may be the same or different.
In the cross metathesis reaction, the left carbene portion of the double bond in formula (1′) (the portion obtained by removing CZ ¹ Z ² from compound (1′)) and the left carbene portion of the double bond in formula (3′) are The carbene portion on the right side of the double bond in formula (2) (the portion of compound (2) excluding CZ ³ Z ⁴ ) and the carbene portion on the right side of the double bond in formula (3′) are the same.

(raw material compound)
In the present invention, compound (1) and compound (2) are subjected to a cross-metathesis reaction.

In compound (1) and compound (2), a is 0 or 1, preferably 1.
b is 0 or 1, preferably 0;
c is 0, 1 or 2, preferably 0;
The sum of c and d is three. That is, d is 1, 2 or 3, preferably 3.

X represents a chlorine atom or an alkoxy group having 1 to 6 carbon atoms, and when d is 2 or 3, multiple Xs present in the same molecule may be the same or different.
Examples of alkoxy groups having 1 to 6 carbon atoms include methoxy, ethoxy, and propoxy groups.
Among these, chlorine atom, methoxy group and ethoxy group are preferred.

Y represents a single bond, an etheric oxygen atom or —CH ₂ O—, preferably a single bond or an etheric oxygen atom.

Z ¹ to Z ⁴ each independently represent a hydrogen atom or a monovalent organic group.
Examples of monovalent organic groups include alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, aryl groups having 5 to 20 carbon atoms, aryloxy groups having 5 to 20 carbon atoms, and 1 carbon atom. -12 (per)halogenated alkyl groups, (per)halogenated alkoxy groups of 1 to 12 carbon atoms, (per)halogenated aryl groups of 5 to 20 carbon atoms and (per)halogenated groups of 5 to 20 carbon atoms A group selected from the group consisting of aryloxy groups, the alkyl group, alkoxy group, aryl group, aryloxy group, (per)halogenated alkyl group, (per)halogenated alkoxy group, (per)halogenated aryl Groups selected from the group consisting of groups and (per)halogenated aryloxy groups may contain one or more atoms selected from the group consisting of oxygen, nitrogen, sulfur, phosphorus and silicon atoms.

Among these, preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a propoxy group, a phenyl group, a phenyloxy group, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, They are a trifluoromethoxy group, a pentafluoroethoxy group, a heptafluoropropoxy group, a perfluoro(methoxymethoxy) group, a perfluoro(propoxypropoxy) group, a pentafluorophenyl group and a pentafluorophenyloxy group.

R ¹ represents a fluorine atom or a monovalent fluorine-containing organic group.
Examples of fluorine-containing organic groups include (per)fluoroalkyl groups having 1 to 12 carbon atoms, (per)fluoroalkoxy groups having 1 to 12 carbon atoms, and (per) having 2 to 400 carbon atoms containing an etheric oxygen atom. Examples include fluoroalkyl groups and (per)fluoroalkoxy groups having 2 to 400 carbon atoms containing an etheric oxygen atom.
Among these, preferably, a (per)fluoroalkyl group having 1 to 12 carbon atoms, a (per)fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom, and a (per)fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom. 400 is a (per)fluoroalkoxy group.

^R2 represents a hydrogen atom, a fluorine atom or a monovalent fluorine-containing organic group.
Examples of fluorine-containing organic groups include (per)fluoroalkyl groups having 1 to 12 carbon atoms, (per)fluoroalkoxy groups having 1 to 12 carbon atoms, and (per) having 2 to 400 carbon atoms containing an etheric oxygen atom. Examples include fluoroalkyl groups and (per)fluoroalkoxy groups having 2 to 400 carbon atoms containing an etheric oxygen atom.
Among these, preferred are a fluorine atom, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, and a (per)fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom.

R ³ represents a fluorine atom or a monovalent fluorine-containing organic group, preferably a fluorine atom, a (per)fluoroalkyl group having 1 to 12 carbon atoms, or a (per) having 2 to 400 carbon atoms containing an etheric oxygen atom It is a fluoroalkyl group, more preferably a C2-400 (per)fluoroalkyl group containing a fluorine atom, a trifluoromethyl group or an etheric oxygen atom.

R ⁴ represents an aryl group having 4 to 20 carbon atoms or an alkyl group having 1 to 6 carbon atoms, and when c is 2, two R ⁴ may be the same or different.
Examples of the aryl group having 4 to 20 carbon atoms include phenyl group, naphthyl group and biphenyl group.
Examples of alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group.
Among these, phenyl group, methyl group and ethyl group are preferred.

In another aspect of the present invention, compound (1') and compound (2) undergo cross-metathesis reaction.

h in the compound (1') represents a natural number of 2 or more, and Q is an h-valent organic group containing a fluorine atom and optionally having a heteroatom.
h is preferably a natural number of 2 to 5, more preferably 2 or 3.
Q is preferably a fluorine-containing organic group having 2 to 400 carbon atoms containing an oxygen atom, a fluorine-containing organic group having 2 to 400 carbon atoms containing an oxygen atom and a silicon atom, or the like.
Z ¹ and Z ² in compound (1′) are respectively the same as Z 1 and Z ² of compound ( ¹ ) in the cross-metathesis reaction between compound (1) and compound (2) described above, and are preferred embodiments. The same is true for In addition, multiple Z ¹ and Z ² may be the same or different.

b to d, X, Z ³ , Z ⁴ and R ⁴ in compound (2) are b to d, X and Z of compound (2) in the cross-metathesis reaction between compound (1) and compound (2) described above. ³ , Z ⁴ and R ⁴ , respectively, and preferred embodiments are also the same.

Specific examples of compound (1) include the compounds shown below. In the chemical formula, when multiple types of oxyperfluoroalkylene groups are arranged (for example, [-O-CF ₂ -] _c5 -[-O-CF ₂ -CF ₂ -] _c6 ), the multiple types of oxy The perfluoroalkylene group may be block chain or random chain.

Among these, the following compounds are preferred.

Specific examples of compound (1') include the compounds shown below.

Specific examples of compound (2) include the compounds shown below.

Among these, the following compounds are preferred.

(Generated compound)
Compound (3) is produced by the cross-metathesis of the present invention.
In compound (3), a, b, c, the sum of c and d, X, Y, R ¹ , R ² , R ³ and R ⁴ are the same as defined above. Any two selected from the group consisting of R ¹ , R ² and R ³ may combine with each other to form a ring.
As the compound (3), a is 0 or 1, b is 0, c is 0, d is 3, X is a chlorine atom, a methoxy group or an ethoxy group, Y is a single bond, an etheric oxygen atom or —CH ₂ O. -, R ¹ is a (per)fluoroalkyl group having 1 to 12 carbon atoms, a (per)fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom, or a (per)fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom or ( per)fluoroalkoxy group, R ² is a fluorine atom, trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, or a (per)fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom, R ³ is A compound that is a fluorine atom, a trifluoromethyl group, or a (per)fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom is preferred.

Specific examples of compound (3) include the compounds shown below.

Among these, the following compounds are preferred.

Compound (3') is produced by the cross metathesis of the present invention.
b, c, the sum of c and d, X, Q, ^R4 and h in compound (3') are the same as defined above.
Specific examples of the compound (3') include the compounds shown below.

(Production method)
The present invention relates to a method for producing a fluorine-containing silane compound by cross metathesis, in which "compound (1) and compound (2)" or "compound (1') and compound (2)" are brought into contact with a catalyst. Thus, cross metathesis is performed to obtain an olefin (compound (3) or compound (3')) different from the starting material.

The geometric isomerism on the double bond of compound (1), compound (1′) and compound (2) is not particularly limited.
Compound (1), compound (1') and compound (2) are preferably degassed and dehydrated in order to improve the yield of the desired product. There are no particular restrictions on the degassing operation, but freeze degassing or the like may be performed. There are no particular restrictions on the dehydration operation, but it is usually brought into contact with a molecular sieve or the like. For compound (1), compound (1′) and compound (2), the degassing and dehydration operations are usually carried out before contact with the catalyst.

Compound (1), compound (1′) and compound (2) may contain trace amounts of impurities (eg, hydrogen fluoride, peroxide), and may be purified in order to improve the yield of the desired product. . There are no particular restrictions 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).

Compound (1) or compound (1') and compound (2) may be mixed in advance and charged into the reaction vessel, or may be charged separately. A second olefin may be contacted with the mixture obtained by contacting the first olefin with the catalyst.

The molar ratio of compound (1) or compound (1′) and compound (2) is not particularly limited, but usually 0.01 to 100 mol of the other olefin is preferably used with respect to 1 mol of the standard olefin. is used in an amount of 0.1 to 10 mol.

The catalyst may be introduced as a reagent or generated in-situ.
When used as a reagent, a commercially available catalyst may be used as it is, or a non-commercially available catalyst synthesized from a commercially available reagent by a known method may be used.
In the case of in-system generation, a catalyst prepared from a precursor metal complex by a known method can be used in the present invention.

Examples of catalysts include metal-carbene complex compounds.

Among metal-carbene complex compounds, compounds in which the metal is ruthenium are generally called ruthenium-carbene complexes. C. et al. Chem. Rev. , 2010, 110, 1746-1787. Ruthenium-carbene complexes described in .
Alternatively, a ruthenium-carbene complex commercially available from Aldrich or Umicore can be used.

Specific examples of ruthenium-carbene complexes include bis(triphenylphosphine)benzylideneruthenium dichloride, bis(tricyclohexylphosphine)benzylideneruthenium dichloride, and bis(tricyclohexylphosphine)-3-methyl-2-butenylideneruthenium dichloride. , (1,3-diisopropylimidazol-2-ylidene)(tricyclohexylphosphine)benzylideneruthenium dichloride, (1,3-dicyclohexylimidazol-2-ylidene)(tricyclohexylphosphine)benzylideneruthenium dichloride, (1,3-dimethy thilimidazol-2-ylidene)(tricyclohexylphosphine)benzylideneruthenium dichloride, (1,3-dimesityl-4,5-dihydroimidazol-2-ylidene)(tricyclohexylphosphine)benzylideneruthenium dichloride, [1,3-bis( 2,6-diisopropylphenyl)-4,5-dihydroimidazol-2-ylidene](tricyclohexylphosphine)benzylidene ruthenium dichloride, [1,3-bis(2-methylphenyl)-4,5-dihydroimidazole-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-ylidene) (tricyclohexylphosphine) ethoxymethylidene ruthenium dichloride, (1,3-dimesityl-4,5-dihydroimidazol-2-ylidene) [bis ( 3-bromopyridine)]benzylideneruthenium 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 M71SIMes, Umicore M71SIPr, Umicore M73SIMes, Umicore M73SIPr.

Among these, (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 M71SIMes, Umicore M71SIPr, Umicore M73SIMes, Umicore M73SIPr are particularly preferred.

Among the above complexes, names starting with "Umicore" are trade names of products of Umicore. The ruthenium-carbene complexes may be used alone, or two or more of them may be used in combination. Furthermore, if necessary, it may be used by supporting it on a carrier such as silica gel, alumina, or polymer.

Among metal-carbene complex compounds, compounds in which the metal is molybdenum or tungsten are generally called molybdenum-carbene complexes or tungsten-carbene complexes. (Ed) Olefin Metathesis: Theory and Practice, Wiley, 2014. Molybdenum-carbene complexes or tungsten-carbene complexes described in .
Alternatively, molybdenum-carbene complexes or tungsten-carbene complexes commercially available from, for example, Aldrich and Strem can be used.

The molybdenum-carbene complex or tungsten-carbene complex may be used alone, or two or more of them may be used in combination. Furthermore, if necessary, it may be used by supporting it on a carrier such as silica gel, alumina, or polymer.

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

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

The amount of the catalyst is not particularly limited, but usually 0.0001 to 1 mol, preferably 0.0001 to 1 mol, is used per 1 mol of the standard olefin among the compound (1) or the compound (1') and the compound (2). is used in an amount of 0.001 to 0.2 mol.

The catalyst is usually charged into the reaction vessel as a solid, but it may be dissolved or suspended in a solvent before being charged.

The solvent used at this time is not particularly limited as long as it does not adversely affect the reaction, and organic solvents, fluorine-containing organic solvents, ionic liquids, water and the like can be used singly or in combination. Some or all of the hydrogen atoms in these solvent molecules may be replaced with deuterium atoms.

Examples of organic solvents include aromatic hydrocarbon solvents such as benzene, toluene, o-, m-, p-xylene and mesitylene; aliphatic hydrocarbon solvents such as hexane and cyclohexane; Halogen-based solvents such as dichloroethane, chlorobenzene and o-dichlorobenzene; ether-based solvents such as tetrahydrofuran, dioxane, diethyl ether, glyme and diglyme can be used.

Examples of fluorine-containing organic solvents include hexafluorobenzene, m-bis(trifluoromethyl)benzene, p-bis(trifluoromethyl)benzene, α,α,α-trifluoromethylbenzene, and dichloropentafluoropropane. can do.

As the ionic liquid, for example, various pyridinium salts and various imidazolium salts can be used.

Among the above solvents, benzene, toluene, o-, m-, p-xylene, mesitylene, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, diethyl ether, dioxane, THF (tetrahydrofuran) , hexafluorobenzene, m-bis(trifluoromethyl)benzene, p-bis(trifluoromethyl)benzene, α,α,α-trifluoromethylbenzene, and mixtures thereof are preferred.

From the point of view of improving the yield of the target product, it is preferable to use the degassed and dehydrated solvent. There are no particular restrictions on the degassing operation, but freeze degassing or the like may be performed. The dehydration operation is not particularly limited, but it is usually brought into contact with a molecular sieve or the like. The degassing and dehydration operations are usually performed before contact with the catalyst.

The atmosphere in which the compound (1) or the compound (1') and the compound (2) are brought into contact with the catalyst is not particularly limited. Alternatively, an argon atmosphere is preferred.
However, when an olefin that becomes gaseous under the reaction conditions is used as a raw material, the reaction can be carried out under these gaseous atmospheres.

The phase in which compound (1) or compound (1') and compound (2) are brought into contact with the catalyst is not particularly limited, but a liquid phase is usually used in terms of reaction rate. If at least one of compound (1) or compound (1') and compound (2) is a gas under the reaction conditions, it is difficult to carry out the reaction in liquid phase, so gas-liquid two-phase may be carried out. In addition, a solvent can be used when it implements in a liquid phase.

As the solvent used at this time, the same solvent as used for dissolving or suspending the catalyst can be used. When at least one of compound (1) or compound (1') and compound (2) is liquid under the reaction conditions, the reaction may be carried out without a solvent.

The container for contacting compound (1) or compound (1′) and compound (2) with the catalyst 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. can. In the cross metathesis according to the present invention, gaseous olefins may be handled under the reaction conditions, so a pressure vessel capable of being highly airtight is preferable.

The temperature at which compound (1) or compound (1′) and compound (2) are brought into contact with the catalyst is not particularly limited, but it can usually be carried out in the range of −100 to 200° C. In terms of reaction rate, and preferably 0 to 150°C. In addition, since the reaction does not start at a low temperature and the complex may be rapidly decomposed at a high temperature, it is necessary to appropriately set the lower and upper limits of the temperature. Usually, it is carried out at a temperature below the boiling point of the solvent used.

The contact time of compound (1) or compound (1′) and compound (2) with the catalyst is not particularly limited, but is usually carried out in the range of 1 minute to 48 hours.
The pressure at which compound (1) or compound (1′) and compound (2) are brought into contact with the catalyst is not particularly limited, and may be under increased pressure, normal pressure, or reduced pressure. It is usually about 0.001 to 10 MPa, preferably about 0.01 to 1 MPa.

When the compound (1) or the compound (1') and the compound (2) are brought into contact with the catalyst, an inorganic salt, an organic compound, or a metal complex may coexist as long as the reaction is not adversely affected.

In addition, the mixture of compound (1) or compound (1') and compound (2) and the catalyst may be stirred as long as the reaction is not adversely affected. At this time, as a stirring method, a mechanical stirrer or a magnetic stirrer can be used.

After contacting compound (1) or compound (1') and compound (2) with a catalyst, the desired product is usually obtained as a mixture of multiple olefins and may be isolated by a known method.
Isolation methods include, for example, distillation, column chromatography, and recycle preparative HPLC, and these can be used singly or in combination as necessary.

The compound (3) or compound (3') obtained by this reaction can be identified by a known method similar to that for ordinary organic compounds. Examples thereof include ¹ H-, ¹⁹ F-, ¹³ C-NMR and GC-MS, and these can be used singly or in combination as necessary.

[Compound (4)]
The present invention also relates to a compound (compound (4)) represented by the following formula (4).
Compound (4) is an example of compound (3), and the following compound (4-1) as compound (1) and the following compound (4-2) as compound (2) were catalyzed by the method described above. can be obtained by performing a cross-metathesis reaction by contacting with

In the formula, R ¹¹ represents a monovalent fluorine-containing organic group.
Examples of fluorine-containing organic groups include (per)fluoroalkyl groups having 1 to 12 carbon atoms, (per)fluoroalkoxy groups having 1 to 12 carbon atoms, and (per) having 2 to 400 carbon atoms containing an etheric oxygen atom. Examples include fluoroalkyl groups and (per)fluoroalkoxy groups having 2 to 400 carbon atoms containing an etheric oxygen atom.
Among these, preferably, a (per)fluoroalkyl group having 1 to 12 carbon atoms, a (per)fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom, and a (per)fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom. 400 is a (per)fluoroalkoxy group.

Z ¹ to Z ⁴ , c, the sum of c and d, Y, R ² , R ³ and R ⁴ are the same as defined in compounds (1) to (3) above.
Any two selected from the group consisting of R ¹¹ , R ² and R ³ may combine with each other to form a ring.
As the compound (4), c is 0, d is 3, Y is a single bond, etheric oxygen atom or —CH ₂ O—, R ¹¹ is a (per)fluoroalkyl group having 1 to 12 carbon atoms, etheric oxygen A (per)fluoroalkyl group having 2 to 400 carbon atoms containing an atom or a (per)fluoroalkoxy group having 2 to 400 carbon atoms containing an etheric oxygen atom, R ² being a fluorine atom, a trifluoromethyl group, or a pentafluoroethyl group , a heptafluoropropyl group, or a (per ⁾ fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom; Compounds which are per)fluoroalkyl groups are preferred.

Specific examples of compound (4) include the compounds shown below.

Among these, the following compounds are preferred.

[Compound (5)]
The present invention also relates to a compound (compound (5)) represented by the following formula (5).
Compound (5) is an example of compound (3), and the following compound (5-1) as compound (1) and the following compound (5-2) as compound (2) were catalyzed by the method described above. A cross-metathesis reaction can be carried out by contacting with

Z ¹ to Z ⁴ , b, c, the sum of c and d, Y, R ¹ , R ² , R ³ and R ⁴ are the same as defined in the compounds (1) to (3) above. Any two selected from the group consisting of R ¹ , R ² and R ³ may combine with each other to form a ring.
As the compound (5), b is 0, c is 0, d is 3, Y is a single bond, an etheric oxygen atom or —CH ₂ O—, and R ¹ is a (per)fluoroalkyl group having 1 to 12 carbon atoms. , a (per)fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom or a (per)fluoroalkoxy group having 2 to 400 carbon atoms containing an etheric oxygen atom, R ² being a fluorine atom, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, or a (per)fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom, and R ³ having 2 carbon atoms containing a fluorine atom, a trifluoromethyl group, or an etheric oxygen atom; Compounds with ∼400 (per)fluoroalkyl groups are preferred.

Specific examples of compound (5) include the compounds shown below.

Among these, the following compounds are preferred.

[Compound (6)]
The present invention also relates to a compound (compound (6)) represented by the following formula (6).
Compound (6) is an example of compound (3), and the following compound (6-1) as compound (1) and the following compound (6-2) as compound (2) were catalyzed by the method described above. A cross-metathesis reaction can be carried out by contacting with

In the formula, R ⁵ represents an alkyl group having 1 to 6 carbon atoms, and when multiple R ⁵ are present in the same molecule, they may be the same or different.
Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group and propyl group. Among these, a methyl group and an ethyl group are preferred.
Z ¹ to Z ⁴ , c, the sum of c and d, Y, R ¹ , R ² , R ³ and R ⁴ are the same as defined in the above compounds (1) to (3). Any two selected from the group consisting of R ¹ , R ² and R ³ may combine with each other to form a ring.
As the compound (6), c is 0, d is 3, Y is a single bond, etheric oxygen atom or —CH ₂ O—, R ¹ is a (per)fluoroalkyl group having 1 to 12 carbon atoms, etheric oxygen A (per)fluoroalkyl group having 2 to 400 carbon atoms containing an atom or a (per)fluoroalkoxy group having 2 to 400 carbon atoms containing an etheric oxygen atom, R ² being a fluorine atom, a trifluoromethyl group, or a pentafluoroethyl group , a heptafluoropropyl group, or a (per ⁾ fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom; Compounds which are per)fluoroalkyl groups are preferred.

Specific examples of compound (6) include the compounds shown below.

Among these, the following compounds are preferred.

EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these.

<Commercial reagent>
In the present examples, unless otherwise specified, a commercially available catalyst was directly used for the reaction.
As the solvent (chloroform-d), "chloroform-d" manufactured by Sigma-Aldrich was previously freeze-degassed and then dried with molecular sieve 4A before being used in the reaction.

<Evaluation method>
In this example, the structures of the synthesized compounds were identified by performing ¹ H-NMR and ¹⁹ F-NMR measurements with a nuclear magnetic resonance apparatus "JNM-AL300" manufactured by JEOL Ltd.

<Example 1> Cross metathesis of _{C8F17 - CH2} -CH= _CH2 and trichlorovinylsilane by Umicore M73SIPr catalyst Under nitrogen atmosphere, Umicore M73SIPr catalyst (10 mol%, 0.217 mmol), trichlorovinylsilane (10.9 mmol, 1.0 mmol). 76 g, 5 molar equivalents), C ₈ F ₁₇ —CH ₂ —CH═CH ₂ (2.17 mmol, 1.00 g, 1 molar equivalents) and chloroform-d (3.5 mL) were weighed into a 10 mL flask. Ta.

The flask was heated at 60° C. and reacted for 2 hours. After completion of the reaction, NMR was measured to confirm the formation of Compound A represented by Formula A below. Yield was 74%. Compound A was also isolated by distillation under reduced pressure.
These series of reactions are shown below.

The evaluation results of the obtained compound A are shown below.

(Compound A)
¹ H-NMR (CDCl ₃ , 300 MHz, tetramethylsilane reference): δ (ppm) 3.07 (2H, dt, J=6,17 Hz), 6.14 (1H, d, J=18 Hz), 6. 61 (1H, dt, J=6,18Hz).
¹⁹ F-NMR (CDCl ₃ , 283 MHz, relative to trichlorofluoromethane): δ (ppm) −81.2 (3 F, t, J=11 Hz), −112.8 (2 F, t, J=17 Hz), −122 .2--122.4(6F,m),-123.2--123.4(4F,m),-126.6(2F).

<Example 2> Cross metathesis of perfluoropolyether group-containing olefin (1) and trichlorovinylsilane by Umicore M73SIPr catalyst Under nitrogen atmosphere, Umicore M73SIPr catalyst (10 mol%, 0.006 mmol), trichlorovinylsilane (0.30 mmol, 48 mg, 5 molar equivalents) ), perfluoropolyether group-containing olefin (1) (0.06 mmol, average value of l: 20, average molecular weight: 4000, 0.24 g, 1 molar equivalent) and chloroform-d (0.56 mL) in an NMR measurement tube. Weigh inside. The NMR tube is heated at 60° C. and reacted for 2 hours. After completion of the reaction, NMR is measured to confirm the production of compound B.
These series of reactions are shown below.

<Example 3> Cross metathesis of perfluoropolyether group-containing olefin (3) and trichlorovinylsilane by Umicore M73SIPr catalyst Under nitrogen atmosphere, Umicore M73SIPr catalyst (10 mol%, 0.003 mmol), trichlorovinylsilane (0.15 mmol, 25 mg, 5 molar equivalents) ), perfluoropolyether group-containing olefin (3) (0.03 mmol, average value of m: 21, average value of n: 24, average molecular weight: 4800, 0.15 g) and 1,4-bis(trifluoromethyl) Benzene (0.44 mL) and chloroform-d (0.11 mL) were weighed into an NMR measuring tube. The NMR tube was heated at 60° C. and reacted for 3 hours. After completion of the reaction, NMR was measured to confirm the production of Compound D. Yield was 56%.
These series of reactions are shown below.

<Example 4> Cross-metathesis of fluorine-containing olefin (4) and trichlorovinylsilane by Umicore M73SIPr catalyst Under nitrogen atmosphere, Umicore M73SIPr catalyst (10 mol%, 0.006 mmol), trichlorovinylsilane (0.30 mmol, 48 mg, 5 molar equivalents) were mixed. Fluoroolefin (4) (0.06 mmol, 11 mg) and chloroform-d (0.56 mL) are weighed into an NMR measurement tube. The NMR tube is heated at 60° C. and reacted for 2 hours. After completion of the reaction, NMR is measured to confirm the production of Compound E.
These series of reactions are shown below.

<Example 5> Cross metathesis of fluorine-containing olefin (5) and trichlorovinylsilane by Umicore M73SIPr catalyst Under nitrogen atmosphere, Umicore M73SIPr catalyst (10 mol%, 0.006 mmol), trichlorovinylsilane (0.30 mmol, 48 mg, 5 molar equivalents) were mixed. Fluoroolefin (5) (0.06 mmol, 15 mg) and chloroform-d (0.56 mL) are weighed into an NMR measurement tube. The NMR tube is heated at 60° C. and reacted for 2 hours. After completion of the reaction, NMR is measured to confirm the production of compound F.
These series of reactions are shown below.

<Example 6> Cross metathesis of fluorine-containing olefin (6) and trichlorovinylsilane by Umicore M73SIPr catalyst Under nitrogen atmosphere, Umicore M73SIPr catalyst (10 mol%, 0.006 mmol), trichlorovinylsilane (0.30 mmol, 48 mg, 5 molar equivalents) were mixed. Fluoroolefin (6) (0.06 mmol, 19 mg) and chloroform-d (0.56 mL) are weighed into an NMR measurement tube. The NMR tube is heated at 60° C. and reacted for 2 hours. After completion of the reaction, NMR is measured to confirm the production of compound G.
These series of reactions are shown below.

<Example 7> Cross metathesis of fluorine-containing olefin (7) and trichlorovinylsilane by Umicore M73SIPr catalyst Under nitrogen atmosphere, Umicore M73SIPr catalyst (10 mol%, 0.006 mmol), trichlorovinylsilane (0.30 mmol, 48 mg, 5 molar equivalents) were mixed. Fluoroolefin (7) (0.06 mmol, 12 mg) and chloroform-d (0.56 mL) are weighed into an NMR measurement tube. The NMR tube is heated at 60° C. and reacted for 2 hours. After completion of the reaction, NMR is measured to confirm the production of Compound H.
These series of reactions are shown below.

<Example 8> Cross metathesis of fluorine-containing olefin (8) and trichlorovinylsilane by Umicore M73SIPr catalyst Under nitrogen atmosphere, Umicore M73SIPr catalyst (10 mol%, 0.006 mmol), trichlorovinylsilane (0.30 mmol, 48 mg, 5 molar equivalents) were mixed. Fluoroolefin (8) (0.06 mmol, 22 mg) and chloroform-d (0.56 mL) are weighed into an NMR measurement tube. The NMR tube is heated at 60° C. and reacted for 2 hours. After completion of the reaction, NMR is measured to confirm the production of Compound I.
These series of reactions are shown below.

<Example 9> Cross metathesis of fluorine-containing olefin (9) and trichlorovinylsilane by Umicore M73SIPr catalyst Under nitrogen atmosphere, Umicore M73SIPr catalyst (10 mol%, 0.006 mmol), trichlorovinylsilane (0.30 mmol, 48 mg, 5 molar equivalents) were mixed. Fluoroolefin (9) (0.06 mmol, 17 mg) and chloroform-d (0.56 mL) are weighed into an NMR measurement tube. The NMR tube is heated at 60° C. and reacted for 2 hours. After completion of the reaction, NMR is measured to confirm the production of compound J.
These series of reactions are shown below.

<Example 10> Cross metathesis of fluorine-containing olefin (10) and trichlorovinylsilane by Umicore M73SIPr catalyst Under nitrogen atmosphere, Umicore M73SIPr catalyst (10 mol%, 0.006 mmol), trichlorovinylsilane (0.30 mmol, 48 mg, 5 molar equivalents) were mixed. Fluoroolefin (10) (0.06mmol, 13mg) and chloroform-d (0.56m
L) is weighed into an NMR measuring tube. The NMR tube is heated at 60° C. and reacted for 2 hours. After completion of the reaction, NMR is measured to confirm the production of Compound K.
These series of reactions are shown below.

<Example 11> Cross metathesis of fluorine-containing olefin (11) and trichlorovinylsilane by Umicore M73SIPr catalyst Under nitrogen atmosphere, Umicore M73SIPr catalyst (10 mol%, 0.006 mmol), trichlorovinylsilane (0.30 mmol, 48 mg, 5 molar equivalents) were mixed. Fluoroolefin (11) (0.06 mmol, 18 mg) and chloroform-d (0.56 mL) are weighed into an NMR measurement tube. The NMR tube is heated at 60° C. and reacted for 2 hours. After completion of the reaction, NMR is measured to confirm the production of Compound L.
These series of reactions are shown below.

<Example 12> Cross metathesis of _{C8F17 - CH2} -CH= _CH2 and vinyltrimethoxysilane by Umicore M73SIPr catalyst Under nitrogen atmosphere, Umicore M73SIPr catalyst (10 mol%, 0.006 mmol), vinyltrimethoxysilane (0.006 mmol) 30 mmol, 44 mg, 5 molar equivalents), C ₈ F ₁₇ —CH ₂ —CH═CH ₂ (0.06 mmol, 28 mg, 1 molar equivalents) and chloroform-d (0.54 mL) are weighed into an NMR tube. . The NMR tube is heated at 60° C. and reacted for 2 hours. After completion of the reaction, NMR is measured to confirm the production of compound M.
These series of reactions are shown below.

<Example 13> Cross metathesis of _{C8F17 - CH2} -CH= _CH2 and trichloroallylsilane by Umicore M73SIPr catalyst Under nitrogen atmosphere, Umicore M73SIPr catalyst (10 mol%, 0.006 mmol
l), trichloroallylsilane ( _0.30 mmol, 52 mg, 5 molar equivalents), _C8F17 -CH2- _CH = _CH2 (0.06 mmol, 28 mg, 1 molar equivalents) and chloroform-d (0.54 mL). Weigh into an NMR measuring tube. The NMR tube is heated at 60° C. and reacted for 2 hours. After completion of the reaction, NMR is measured to confirm the production of compound N.
These series of reactions are shown below.

<Example 14> Cross metathesis of C ₈ F ₁₇ -CH ₂ -CH=CH ₂ and trichlorovinylsilane by Umicore M73SIPr catalyst Except that the amount of Umicore M73SIPr catalyst used in Example 1 was changed to 0.1 mol% (0.00217 mmol) The production of compound A is confirmed by the same method as in Example 1.

<Example 15> Cross metathesis of C ₈ F ₁₇ -CH ₂ -CH=CH ₂ and trichlorovinylsilane by Umicore M73SIPr catalyst Same as Example 1 except that the solvent in Example 1 was changed to heavy benzene (C ₆ D ₆ ). The formation of compound A is confirmed by a method.

<Example 16> Cross metathesis of _C8F17 -CH2- _CH = _CH2 and trichlorovinylsilane with Grubbs second generation catalyst _The catalyst in Example 1 was changed to Grubbs second generation catalyst (10 mol%, 0.006 mmol). The production of Compound A is confirmed by the same method as in Example 1, except for the above.
These series of reactions are shown below.

<Example 17> Cross metathesis of perfluoropolyether group-containing olefin (12) and trichlorovinylsilane by Umicore M73SIPr catalyst Under nitrogen atmosphere, Umicore M73SIPr catalyst (10 mol%, 0.003 mmol), trichlorovinylsilane (0.15 mmol, 24 mg, 5 molar equivalents) ), perfluoropolyether group-containing olefin (12) (0.03 mmol, 0.11 g) and 1,4-bis(trifluoromethyl)benzene (0.44 mL), chloroform-d (0.11 mL) in an NMR measurement tube. Weigh into the The NMR tube is heated at 60° C. and reacted for 2 hours. After completion of the reaction, NMR is measured to confirm the production of compound O.
These series of reactions are shown below.

<Example 18> Cross metathesis of perfluoropolyether group-containing olefin (13) and trichlorovinylsilane by Umicore M73SIPr catalyst Under nitrogen atmosphere, Umicore M73SIPr catalyst (10 mol%, 0.003 mmol), trichlorovinylsilane (0.15 mmol, 24 mg, 5 molar equivalents) ), perfluoropolyether group-containing olefin (13) (0.03 mmol, 55 mg) and 1,4-bis(trifluoromethyl)benzene (0.44 mL), chloroform-d (0.11 mL) in an NMR measurement tube. Weigh into The NMR tube is heated at 60° C. and reacted for 2 hours. After completion of the reaction, NMR is measured to confirm the production of compound P.
These series of reactions are shown below.

<Example 19> Cross metathesis of perfluoropolyether group-containing olefin (14) and trichlorovinylsilane by Umicore M73SIPr catalyst Under nitrogen atmosphere, Umicore M73SIPr catalyst (0.003 mmol), trichlorovinylsilane (0.15 mmol, 24 mg), perfluoropolyether group-containing Olefin (13) (0.13 g) and 1,4-bis(trifluoromethyl)benzene (0.44 mL), chloroform-d (0.11 mL) are weighed into an NMR measurement tube. The NMR tube is heated at 60° C. and reacted for 2 hours. After completion of the reaction, NMR is measured to confirm the production of compound Q.
These series of reactions are shown below.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent application (Japanese Patent Application No. 2017-039894) filed on March 2, 2017, the contents of which are incorporated herein by reference.

The fluorine-containing silane compound according to the production method of the present invention can be used as an intermediate for pharmaceuticals and agricultural chemicals, a fingerprint remover, an antifouling agent, and a moisture-proof coating agent.

Claims (6)

A compound represented by the following formula (4).
(wherein c is 0, 1 or 2, the sum of c and d is 3, Y represents an etheric oxygen atom or —CH ₂ O—, and R ¹¹ is a monovalent fluorine-containing organic group , R ² represents a hydrogen atom, a fluorine atom or a monovalent fluorine-containing organic group, R ³ represents a fluorine atom or a monovalent fluorine-containing organic group, and the group consisting of R ¹¹ , R ² and R ³ Any two selected from may combine with each other to form a ring, R ⁴ represents an aryl group having 4 to 20 carbon atoms or an alkyl group having 1 to 6 carbon atoms, and when there are a plurality of R ⁴ , they may be the same or different.
) c is 0 , R ¹¹ is a (per)fluoroalkyl group having 1 to 12 carbon atoms, a (per)fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom, or a carbon number 2 containing an etheric oxygen atom represents a (per)fluoroalkoxy group of ~400, and R ² is a fluorine atom, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, or a (per)fluoro with 2 to 400 carbon atoms containing an etheric oxygen atom 2. The compound according to claim 1, wherein R ³ represents an alkyl group and R 3 represents a (per)fluoroalkyl group having 2 to 400 carbon atoms containing a fluorine atom, a trifluoromethyl group or an etheric oxygen atom. A compound represented by the following formula (5).
(wherein b is 1 , c is 0, 1 or 2, the sum of c and d is 3, Y represents an etheric oxygen atom or —CH ₂ O—, R ¹ is fluorine represents an atom or a monovalent fluorine-containing organic group, R ² represents a hydrogen atom, a fluorine atom or a monovalent fluorine-containing organic group, R ³ represents a fluorine atom or a monovalent fluorine-containing organic group, R ¹ , Any two selected from the group consisting of R ² and R ³ may combine with each other to form a ring, and R ⁴ is an aryl group having 4 to 20 carbon atoms or an alkyl group having 1 to 6 carbon atoms. and when there are multiple ^R4s , they may be the same or different.) c is 0 , R ¹ is a (per)fluoroalkyl group having 1 to 12 carbon atoms, a (per)fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom, or a carbon number 2 containing an etheric oxygen atom represents a (per)fluoroalkoxy group of ~400, and R ² is a fluorine atom, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, or a (per)fluoro with 2 to 400 carbon atoms containing an etheric oxygen atom 4. The compound according to claim 3, wherein R ³ represents an alkyl group and R 3 represents a (per)fluoroalkyl group having 2 to 400 carbon atoms containing a fluorine atom, a trifluoromethyl group or an etheric oxygen atom. A compound represented by the following formula (6).
(wherein c is 0, 1 or 2, the sum of c and d is 3, Y represents an etheric oxygen atom or —CH ₂ O—, R ¹ is a fluorine atom or a monovalent represents a fluorine organic group, R ² represents a hydrogen atom, a fluorine atom or a monovalent fluorine-containing organic group, R ³ represents a fluorine atom or a monovalent fluorine-containing organic group, R ¹ , R ² and R ³ Any two selected from the group consisting of may be bonded to each other to form a ring, R ⁴ represents an aryl group having 4 to 20 carbon atoms or an alkyl group having 1 to 6 carbon atoms, and R ⁵ represents a carbon represents an alkyl group of numbers 1 to 6, and when there are a plurality of R ⁴ and R ⁵ each, they may be the same or different.) c is 0 , R ¹ is a (per)fluoroalkyl group having 1 to 12 carbon atoms, a (per)fluoroalkyl group having 2 to 400 carbon atoms containing an etheric oxygen atom, or a carbon number 2 containing an etheric oxygen atom represents a (per)fluoroalkoxy group of ~400, and R ² is a fluorine atom, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, or a (per)fluoro with 2 to 400 carbon atoms containing an etheric oxygen atom 6. The compound according to claim 5, wherein R ³ represents an alkyl group and R 3 represents a (per)fluoroalkyl group having 2 to 400 carbon atoms containing a fluorine atom, a trifluoromethyl group or an etheric oxygen atom.