KR101894765B1 - Transition metal complex having amide group for olefin metathesis and Application thereof - Google Patents

Abstract

The present invention relates to a transition metal complex containing N-heterocyclic carbene, which is more versatile and can be used for olefin metathesis reaction through introduction of functional groups capable of controlling various reactivity, and a novel transition metal complex, It is about the metathesis reaction.

Description

Transition metal complexes for olefin metathesis reactions containing amide groups and their applications {Transition metal complex having amide group for olefin metathesis and application thereof}

TECHNICAL FIELD The present invention relates to transition metal complexes for olefin metathesis reactions containing an amide group and their applications, and more specifically to a transition metal complex containing N-heterocyclic carbene and an amide group, which is more versatile and has various reactivity The present invention relates to a novel transition metal complex which can be used for olefin metathesis reaction through the introduction of an adjustable functional group and a metathesis reaction of an olefin using the same.

Olefin metathesis is a valuable synthesis method for the formation of carbon-carbon double bonds, especially for organic synthesis and polymer synthesis applications.

As a study on the catalyst for olefin metathesis reaction, a homogeneous catalyst using a transition metal complex can be used. Up to now, there has been proposed a method for preparing a transition metal carbene compound from such transition metal complexes and using the same as a catalyst for olefin metathesis reaction Is being studied continuously.

As a related art, U.S. Patent Application Publication No. 2007/0043180 (Feb. 22, 2007) discloses an olefin metathesis reaction using a transition metal complex in which an ether functional group is coordinated to a ruthenium central metal and includes a carbene ligand, In Patent Document 10-2014-0131553 (Nov. 13, 2014), an olefin metathesis reaction using a complex containing a quaternary onium group in an inert ligand is described.

However, in the case of transition metal complexes containing existing carbene ligands, it is necessary to design a carbene ligand in order to obtain a Jacobene ligand through a complicated multistage reaction, and it is also disadvantageous that a chemically equivalent amount of Wittig reagent, which is always difficult to handle, is required. In addition, the introduction of various substituents in the ligand has many limitations in that it is not easy to appropriately substitute or change the carbene side ligand.

Therefore, there is a continuing need for research into the development of novel transition metal complex catalysts capable of appropriately controlling the catalyst efficiency and reactivity to the extent desired by the user by the introduction of appropriate ligands in the transition metal complexes.

U.S. Published Patent Application No. 2007/0043180 (Feb. Patent Document 10-2014-0131553 (Nov. 13, 2014)

In order to solve the above problems, the present invention provides a novel transition metal complex containing a phosphine ligand or N-heterocyclic carbene as a ligand and further including an amide group, and a process for producing the same.

In addition, the present invention provides a method for performing an olefin metathesis reaction using the transition metal complex as a catalyst.

The present invention provides a transition metal complex represented by the following formula (A).

(A)

(L1) M (A) (L2) n (L3) m

In the above formula (A)

M is ruthenium,

L1 is a phosphine ligand containing a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a carbene derivative having a nitrogen-containing heterocycle, which is a N-heterocyclic carbene ligand &Quot;

L2 and L3 are the same or different and independently of each other are a monovalent ligand selected from the group consisting of halogen, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryloxy, ego,

delete

n and m are each 1,

Wherein A is a ligand represented by the following structural formula A.

[Structural Formula A]

In the structural formula A, the substituents R11 to R13 are the same or different and are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, A substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms having at least any one selected from O, N, S and Si, a substituted or unsubstituted C1 to C30 alkyl group having 1 to 30 carbon atoms, A substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryloxy group, a substituted or unsubstituted C1 to C30 alkylamine group, a substituted or unsubstituted C6 to C30 arylamine group, A substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, a cyano group, and a halogen group,
The substituents R11 and R12 are not connected to each other to form a ring,

'은 카벤의 전자쌍을 의미한다. remind '

'Means Carben's electron pair.

The 'substituted' in the 'substituted or unsubstituted' refers to a group selected from the group consisting of deuterium, a cyano group, a halogen group, a hydroxy group, a nitro group, an alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, An aryl group having 7 to 24 carbon atoms, an alkoxy group having 1 to 24 carbon atoms, an alkylsilyl group having 1 to 24 carbon atoms, an arylsilyl group having 6 to 24 carbon atoms, and an aryloxy group having 6 to 24 carbon atoms. Quot; means substituted with at least one substituent.

The present invention also provides a method for performing a metathesis reaction of an olefin using the transition metal complex described above as a catalyst.

The homogeneous catalysts used in the double bond metathesis reactions reported so far require the synthesis of ligands at various stages for the synthesis of carban ligands and also have limited methods for the introduction of various substituents in the ligand, However, in the case of the novel compounds represented by the above formula (A) in the present invention, it is possible to easily introduce various substituents into the amide, thereby varying the properties such as the activity or reactivity of the catalyst for the metathesis reaction There is an advantage that it can be adjusted.

Further, according to the present invention, in the introduction of a carban ligand for the preparation of a transition metal complex catalyst, synthesis of a ligand having various structural and electrical characteristics due to the structural diversity of the amide itself can be carried out in only two steps And is advantageous in the production and supply economics of the ligand, and the reaction used for the production of the amide double bond is more accessible than the Wittig reagent for preparing the double bond ligand in the prior art and generates phosphine oxide as a by-product Vinyl acetate can be used, which is more environmentally friendly in the synthesis and introduction of the carban ligand.

The transition metal complexes of the present invention are excellent in activity as catalysts for olefin metathesis reaction and have an advantage of controlling activity through proper control of substituents in the ligand.

Figure 1 shows the activity of a catalyst obtained according to an embodiment of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings, which illustrate preferred embodiments in which the present invention can be readily practiced by those skilled in the art. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the following description, well-known functions or constructions are not described in detail to avoid obscuring the subject matter of the present invention.

The present invention relates to a transition metal complex comprising an N-heterocyclic carbene ligand and also comprising an amide as a ligand.

More specifically, the transition metal complex according to the present invention is represented by the following formula (A).

(A)

(L1) M (A) (L2) n (L3) m

In the above formula (A)

M is a transition metal,

L 1 means a phosphine ligand containing a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or N-heterocyclic carbene ligand,

L2 and L3 are the same or different and are each independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C50 aryl, A substituted or unsubstituted arylalkyl group having 7 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, Or a substituted or unsubstituted C 1 -C 30 alkoxy group, a substituted or unsubstituted C 6 -C 30 aryloxy group, a substituted or unsubstituted hetero atom, O, N Or a heteroaryl group having 2 to 50 carbon atoms and S; Lt; / RTI &

Or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms or a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, carbon monoxide, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms or a substituted or unsubstituted carbon number A substituted or unsubstituted alkyl group having 6 to 50 aryl groups, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms or a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted hetero atom, O, N, Or an aromatic heterocyclic compound having 2 to 50 carbon atoms and S,

n and m are the same or different and independently selected from 0 to 2, and when n or m is 2, a plurality of L2 or L3 are the same or different,

Wherein A is a ligand represented by the following structural formula A.

[Structural Formula A]

In the structural formula A, the substituents R11 to R13 are the same or different and are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, A substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms having at least any one selected from O, N, S and Si, a substituted or unsubstituted C1 to C30 alkyl group having 1 to 30 carbon atoms, A substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryloxy group, a substituted or unsubstituted C1 to C30 alkylamine group, a substituted or unsubstituted C6 to C30 arylamine group, A substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, a cyano group, and a halogen group,

'은 카벤의 전자쌍을 의미한다. remind '

'Means Carben's electron pair.

In the present invention, 'substituted' in the 'substituted or unsubstituted' refers to a group selected from the group consisting of deuterium, a cyano group, a halogen group, a hydroxy group, a nitro group, an alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, An alkenyl group having 2 to 24 carbon atoms, a heteroalkyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, an arylalkyl group having 7 to 24 carbon atoms, a heteroaryl group having 2 to 24 carbon atoms, An alkoxy group having 1 to 24 carbon atoms, an alkylamino group having 1 to 24 carbon atoms, an arylamino group having 6 to 24 carbon atoms, a heteroarylamino group having 1 to 24 carbon atoms, an alkylsilyl group having 1 to 24 carbon atoms, an arylamino group having 6 to 24 carbon atoms An arylsilyl group having 1 to 24 carbon atoms, or an aryloxy group having 6 to 24 carbon atoms.

In consideration of the range of the alkyl or aryl group in the "substituted or unsubstituted C1-C30 alkyl group" or "substituted or unsubstituted C6-C50 aryl group" in the present invention, The carbon number of the alkyl group having 1 to 30 carbon atoms and the aryl group having 6 to 50 carbon atoms means the total number of carbon atoms constituting the alkyl moiety or the aryl moiety when it is considered that the substituent is not substituted without considering the substituted moiety will be. For example, a phenyl group substituted with a butyl group at the para position should be considered to correspond to an aryl group having 6 carbon atoms substituted with a butyl group having a carbon number of 4.

The aryl group, which is a substituent used in the compound of the present invention, is an organic radical derived from an aromatic hydrocarbon by elimination of one hydrogen, includes a single or fused ring system, and when the aryl group has a substituent, fused to form additional rings

Specific examples of the aryl group include a phenyl group, o-biphenyl group, m-biphenyl group, p-biphenyl group, o-terphenyl group, m- terphenyl group, p- terphenyl group, naphthyl group, anthryl group, An aromatic group such as a phenyl group, an indenyl group, a fluorenyl group, a tetrahydronaphthyl group, a perylenyle group, a crycenyl group, a naphthacenyl group and a fluoranthenyl group, and at least one hydrogen atom of the aryl group may be substituted with a deuterium atom, a halogen atom a N (R ') (R''),R' and R "are independently from each other C 1 -C 10 -, a hydroxy group, a nitro group, a cyano group, a silyl group, an amino group _{(-NH 2, -NH (R)} , A hydrazine group, a hydrazone group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, an alkyl group having 1 to 24 carbon atoms An alkenyl group having 1 to 24 carbon atoms, a heteroalkyl group having 1 to 24 carbon atoms, It may be substituted with a heteroaryl group of a small number of 6 to 24 aryl group, C 6 -C 24 arylalkyl group, having 2 to 24 carbon atoms or heteroaryl group having 2 to 24.

The heteroaryl group which is a substituent used in the compound of the present invention is a heteroaryl group having 2 to 24 carbon atoms in which the heteroaryl group includes 1,2 or 3 hetero atoms selected from N, O, P, Si, S, Ge, Refers to a ring aromatic system, which rings may be fused to form a ring. And at least one hydrogen atom of the heteroaryl group may be substituted with the same substituent as the aryl group.

In the present invention, the aromatic heterocyclic ring means that at least one of aromatic carbons in the aromatic hydrocarbon ring is substituted with at least one hetero atom selected from N, O, P, Si, S, Ge, Se and Te.

Specific examples of the alkyl group as the substituent used in the present invention include methyl, ethyl, propyl, isopropyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl and hexyl. The hydrogen atom may be substituted with the same substituent as in the case of the aryl group.

Specific examples of the alkoxy group used as the substituent in the compound of the present invention include methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, isoamyloxy, hexyloxy, At least one hydrogen atom in the alkoxy group may be substituted with the same substituent as in the case of the aryl group.

At least one of R 11 to R 13 may contain a fluorine atom, and the fluorine atom may be substituted with an alkyl group, an aryl group, a cycloalkyl group, a heteroaryl group, an alkoxy group, an aryloxy group, an alkylamine group, May be replaced with some or all of them in place of hydrogen.

In the present invention, when the amide is coordinated to a transition metal with a ligand, the amide represented by the structural formula A can be bonded to a transition metal such as ruthenium, such as oxygen atom in the amide group and carbene of carbene, have.

[Structural formula 1]

Herein, the ligand of the 5-membered ring which is bonded to the ruthenium atom in the structural formula 1 and contains two nitrogen atoms is an exemplary structure of the N-heterocyclic carbene ligand. L1 and L2 are each a monovalent ligand, the substituents R11 to R13 in the amide correspond to the same substituents as defined above, and the substituents R and R 'in the N-heterocyclic carbene ligand are the same as the substituents R11 to R13 in the amide .

The complexes in the present invention can control the reaction mode of the olefin metathesis reaction by appropriately selecting the substituents R11 to R13 which are substituents in the amide.

More specifically, when the substituent is an electron donating group, the activity of the catalyst may be slowed, and when the substituent is an electron withdrawing group, the activity of the catalyst is accelerated Can make the characteristic appear.

For example, at least one of the substituents R11 to R13 may introduce a substituent containing a fluorine atom to introduce the substituent into the property of an electron-attracting agent, thereby exhibiting rapid activity in an olefin metathesis reaction.

In the present invention, the N-heterocyclic carbene ligand may be represented by the following formula (B).

[Chemical Formula B]

In the above formula (B)

X1 is any one selected from O, S, N-R2, C-R3 and C-R4R5,

The bond between X1 and Y1, Y1 and Y2, Y2 and Y3 may have a single bond or a double bond,

Y1 to Y3 may be the same or different and are each selected from N, N-R6, C-R7, and C-R8R9,

m is an integer selected from 0 to 3, and when m is 2 or more, a plurality of Y 2 s may be the same or different from each other. In this case, each Y 2 bond may be a single bond or a double bond,

R 1 to R 9 are the same or different from each other and each independently represent hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, A substituted or unsubstituted aryloxy group having 7 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, A heteroaryl group having 2 to 50 carbon atoms and unsubstituted and having a hetero atom O, N or S,

R1 and R2 are not hydrogen or deuterium,

'은 카벤의 전자쌍을 의미한다. remind '

'Means Carben's electron pair.

In the present invention, the N-heterocyclic carbene may be obtained by deprotonating a N-heterocyclic carbene precursor salt with a base. In this case, the N-heterocyclic carbene precursor salt can be used without being limited to the kind of N-heterocyclic carbene if it can produce N-heterocyclic carbene, which is a carbene derivative having a nitrogen-containing heterocycle through deprotonation reaction. May be a compound represented by the following formula (C).

≪ RTI ID = 0.0 &

In the above formula (C)

X1 is any one selected from O, S, N-R2, C-R3 and C-R4R5,

The bond between X1 and Y1, Y1 and Y2, Y2 and Y3 may have a single bond or a double bond,

Y1 to Y3 may be the same or different and are each selected from N, N-R6, C-R7, and C-R8R9,

m is an integer selected from 0 to 3, and when m is 2 or more, a plurality of Y 2 s may be the same or different from each other. In this case, each Y 2 bond may be a single bond or a double bond,

Wherein R 1 to R 9 are independently selected from the group consisting of hydrogen, deuterium, halogen, an alkyl group having 1 to 30 carbon atoms, an aryl group having 5 to 50 carbon atoms, an arylalkyl group having 5 to 50 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, A cycloalkyl group having 3 to 30 carbon atoms, a cycloalkenyl group having 5 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, a hetero atom having 2 to 20 carbon atoms, To 50 heteroaryl groups, R < 1 > and R < 2 > are not hydrogen or deuterium,

X ^- is a monovalent anion that matches the cation and charge balance of the N-heterocyclic carbene precursor.

Illustratively, X ^- is selected from the group consisting of a halogen anion, a sulfonic acid anion (RSO3-, R is alkyl, aryl, cycloalkyl, etc.), tetrafluoroborate anion (BF4-), hexafluorophosphate anion (PF6-) And a plate anion (-OTf).

In the formula (B) of the present invention, when X1 is a carbon atom including a substituent R3, preferably R3 may be a substituent other than hydrogen or deuterium, and at least one of R4 and R5 is other than hydrogen and deuterium It is preferably a substituent.

At this time, the N-heterocyclic carbene precursor represented by the above formula (C) may undergo a deprotonation reaction with a base to form N-heterocycarbox.

In this case, the deprotonation reaction of the N-heterocyclic carbene precursor with a base can be represented by the following reaction formula (2).

[Reaction Scheme 2]

Wherein R 1, X 1, Y 1 to Y 3, m and X are the same as defined above, and B: in the above reaction formula 2, deprotonation of a proton bonded to a carbon between X 1 and a nitrogen atom as a base yields N -Hetero ring carbene.

In the present invention, the base for dehydrogenating the N-heterocyclic carbene precursor to produce N-heterocyclic carbene may deprotonate a proton bonded to the carbon between X1 and the nitrogen atom in the N-heterocyclic carbene precursor And can be used without limitation, and preferably an alkali metal hydride; A hydroxide of an alkali metal; Alkoxy salts of alkali metals; An alkali metal salt of a primary amine or a secondary amine deprotonated with hydrogen bonded to a nitrogen atom; An alkyl anion having 1 to 30 carbon atoms in which hydrogen bonded to a carbon atom is deprotonated, or an alkali metal salt of a cycloalkyl anion having 3 to 40 carbon atoms or an aryl anion having 6 to 30 carbon atoms.

Illustratively, the base may be NaH, KH, LiH or the like as an alkali metal hydride, KOH, NaOH or the like as a hydroxide of an alkali metal, KOtBu may be used as an alkoxy salt of an alkali metal, , Alkali metal salts of ammonia, primary amines or secondary amines combined with hydrogen to form a deprotonated group, NaNH2, LDA (Lithium diisopropylamide) or the like can be used, and hydrogen bonded to a carbon atom is deprotonated and an alkyl anion having 1 to 30 carbon atoms , Or a cycloalkyl anion having 3 to 40 carbon atoms or an aryl anion having 6 to 30 carbon atoms, MeLi, n-BuLi, t-BuLi, PhLi and the like can be used.

The base used for deprotonating the N-heterocyclic carbene precursor may be used in a molar ratio of 1 to 10 equivalents (equiv.), Preferably 1 to 5 equivalents, relative to the content of the N-heterocyclic carbene precursor Can be used.

More specifically, the N-heterocyclic carbene ligand in the complex represented by the formula (A) of the present invention may be represented by any one of the following formulas (B-1) to (B-13).

[Formula B-1] [Formula B-2] [Formula B-3]

[Formula B-4] [Formula B-5] [Formula B-6]

[Formula B-7] [Formula B-8] [Formula B-9]

[Formula B-10] [Formula B-11] [Formula B-12]

[Formula B-13]

Wherein R1 and R2 are the same as defined above,

R 'is selected from the group consisting of hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 50 carbon atoms, A substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted hetero atom, O, N or S, And a heteroaryl group having 2 to 50 carbon atoms,

n is an integer of 1 to 8,

When a plurality of the substituents R 'exist in one molecule, each R' may be the same or different.

Illustratively, the N-heterocyclic carbene may be any one selected from the following formulas (B-20) to (B-37).

[Formula B-20] [Formula B-21] [Formula B-22]

[Formula B-23] [Formula B-24] [Formula B-25]

[Formula B-26] [Formula B-27] [Formula B-28]

[Formula B-29] [Formula B-30] [Formula B-31]

[Formula B-32] [Formula B-33] [Formula B-34]

[Formula B-35] [Formula B-36] [Formula B-37]

The transition metal that can be used in the transition metal complex according to the present invention may be any one selected from ruthenium, iron, cobalt, rhodium, iridium, osmium, molybdenum and tungsten, but is not limited thereto. The transition metal may be ruthenium, osmium, rhodium, iridium, and more preferably ruthenium may be used.

As the transition metal complex which can be used in the present invention, any compound which can be represented by the above-mentioned formula (A) can be used without limitation, and preferably a halide of a transition metal complex can be used.

In the present invention, L2 and L3 corresponding to the ligands which may be additionally contained in addition to the phosphine ligand or N-heterocyclic carbene (NHC) ligand and the amide ligand in the transition metal complex represented by the above formula (A) include monovalent ligands or neutral ligands Can be used. In this case, the types and the numbers of L2 and L3 may be composed of only a monovalent ligand or a neutral ligand depending on the type of metal or oxidized water, or they may be mixed to be coordinated to the center metal as a ligand, Can also be appropriately determined.

In one embodiment, in the complex catalyst represented by the above formula (A), L2 and L3 are the same or different and independently of each other are a halogen selected from F, Cl, Br and I, and n and m may be 1 .

In a more preferred embodiment of the present invention, the ligand L2 and L3 may each be Cl when the transition metal is ruthenium and n and m are 1, respectively.

The present invention also relates to a process for the preparation of N-heterocyclic carbene ligands; Or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms and an additional carbene ligand, wherein a transition metal containing no amide as a ligand A method for preparing a transition metal complex represented by the above formula (A) by contacting an amide compound containing a double bond with a complex, wherein the amide including the double bond substitutes an additional carbene ligand in the transition metal complex .

In this case, the amide compound may be a compound in which a vinyl group is bonded to a nitrogen atom as a double bond.

In the present invention, a method for preparing the transition metal complex represented by the above formula (A) can be illustrated by the following reaction formula (1).

[Reaction Scheme 1]

(L1) M (Cb) (Y) k (L2) n (L3) m  + A '-> (L1) M (A) (L2) n (L3) m

Wherein M, L1, L2, L3, m, n and A are as defined above,

A 'is an amide to which a substituent containing a vinyl group is bonded to a nitrogen atom,

Cb is a carban ligand represented by the following structural formula M,

[Structural formula M]

R21 and R22 in the structural formula M are the same or different and are independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C6-50 aryl, A substituted or unsubstituted arylalkyl group having 7 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms An alkyl group, a substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, O, N or S, and is a heteroaryl group having 2 to 50 carbon atoms,

Y is selected from the group consisting of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C50 aryl, substituted or unsubstituted C7 to C50 arylalkyl, Or a substituted or unsubstituted C 2 -C 30 alkenyl group, a substituted or unsubstituted C 2 -C 20 alkynyl group, a substituted or unsubstituted C 3 -C 30 cycloalkyl group, a substituted or unsubstituted C 5 -C 30 cycloalkene A substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted hetero atom, a heteroaryl group having 2 to 50 carbon atoms having O, N or S, A monovalent ligand selected from the group consisting of: Lt; / RTI &

Or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms or a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, carbon monoxide, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms or a substituted or unsubstituted carbon number A substituted or unsubstituted alkyl group having 6 to 50 aryl groups, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms or a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted hetero atom, O, N, Or an aromatic heterocyclic compound having 2 to 50 carbon atoms and S,

K is an integer of 1 or 2, and when k is 2, each Y is the same or different from each other.

That is, in the present invention, the transition metal complex, such as the structure of the above formula (A), may be an N-heterocyclic carbene ligand; Or a phosphine ligand; and an amide ligand; for this purpose, the N-heterocyclic carbene ligand; Or a phosphine ligand, and substituting an amide containing a double bond in the present invention to a transition metal complex containing no amide, a complex represented by the above formula (A) can be prepared.

The reaction conditions for the reaction include a solvent and a reaction temperature which can be used in the conventional ligand substitution reaction in the transition metal complex. For promoting the reaction, a halogen salt of a transition metal may be used. Preferably, Can be used.

Illustratively, copper (I) chloride can be used for the ligand displacement reaction.

Further, the solvent which can be used for the above-mentioned ligand substitution reaction can be suitably used by a person skilled in the art by using any one or a mixture selected from commonly available hydrocarbons, halogenated hydrocarbons, alcohols, ethers, cyclized ethers, ketones and amides The reaction temperature may vary depending on the solvent and the reactants used, and may be in the range of 0 to 200 ° C, preferably in the range of room temperature (25 ° C) to 100 ° C.

The present invention also provides a method for performing a metathesis reaction of an olefin using a transition metal complex containing the amide as a ligand as a catalyst.

Illustratively, the metathesis reaction of the olefin may be a cyclization (ring closure) metathesis reaction of an olefin.

For this purpose, the content of the catalyst used in the present invention may be in the range of 0.1 to 30 mol%, preferably 1 to 20 mol%, based on the content of the transition metal complex.

In order to perform the olefin metathesis reaction using the complex catalyst, a solvent may be used, and any one selected from hydrocarbons, halogenated hydrocarbons, alcohols, ethers, cyclized ethers, ketones, Can be appropriately used by a person skilled in the art.

The reaction temperature may vary depending on the solvents and reactants used, and may be in the range of 0 to 200 ° C, preferably in the range of room temperature (25 ° C) to 100 ° C.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. It will be apparent, however, to those skilled in the art that these embodiments are for further explanation of the present invention and that the scope of the present invention is not limited thereby.

<Examples>

Hereinafter, a method for producing a transition metal complex according to an embodiment of the present invention will be described in detail.

NMR spectra, X-ray crystallography, and elemental analysis were used for analyzing compounds such as ligands and complexes obtained by the production method of the present invention. Yield (yield (%)) of the compound of the present invention was measured by NMR.

¹ H NMR analysis was also performed using a Bruker DPX300, AMX400, Agilent 400-MR, JEOL ECA400, or JEOL ECA400SL instrument to obtain NMR spectra. At this time, an appropriate amount of the transition metal complex obtained in the present invention was transferred to an NMR tube in a glove box, and CD ₂ Cl ₂ or benzene-d ₆ was used as a solvent.

Preparation of transition metal complexes

Production Example 1

Synthesis of (1,3-bis (2,4,6-trimethylphenyl) -2-imidazolidinylidene) dichloro ((nitrogen-phenylacetamido) methylene) ruthenium>

(2,4,6-trimethylphenyl) -2-imidazolidinylidene) dichloro (phenyl) amide in a 25 ml Schlenk glass tube in a nitrogen and oxygen free glove box, (32.24 mg, 0.2 mmol), copper (I) chloride (19.80 mg, 0.2 mmol) and dichloro (tricyclohexylphosphine) ruthenium (84.90 mg, 0.1 mmol) 4 ml of methane is added.

Seal the lid of the Schlenk glass tube with a rubber septa and take it out of the glove box. After further sealing with parafilm, it is stirred at 40 ° C for 12 hours. After completion of the reaction, the product was separated by silica chromatography using dichloromethane-methanol mixture as mobile phase under argon to obtain the desired product (1,3-bis (2,4,6-trimethylphenyl) -2- ((Nitrogen-phenylacetamido) methylene) ruthenium can be obtained.

(M, 2H), 6.71 (s, 4H), 6.70-6.65 (m, IH), 6.71 (s, , 6.45 (m, 2H), 3.43 (s, 4H), 2.64 (brs,

Production Example 2

Synthesis of (1,3-bis (2,4,6-trimethylphenyl) -2-imidazolidinylidene) dichloro ((nitrogen- (4-methoxyphenyl) acetamido) methylene) ruthenium>

Dichloro (phenylmethylene) (tricyclohexylphosphine) ruthenium (84.90 mg, 0.1 mmol), a nitrogen- (38.25 mg, 0.2 mmol), copper (I) chloride (19.80 mg, 0.2 mmol) and dichloromethane (4 ml) under the same conditions as in Preparation Example 1 Reacted to give (1,3-bis (2,4,6-trimethylphenyl) -2-imidazolidinylidene) dichloro ((nitrogen- (4- methoxyphenyl) acetamido) methylene) .

(M, 6H), 6.81 (d, J = 9.16, 2H), 4.29 (br s, 1H) (S, 3H), 2.50 (s, 3H), 2.44 (brs, 6H), 2.27 (s, 3H) , &Lt; / RTI &gt; 3H), 1.89 (s, 3H) ppm

Production Example 3

Synthesis of (1,3-bis (2,4,6-trimethylphenyl) -2-imidazolidinylidene) dichloro ((nitrogen-phenylbenzamido) methylene) ruthenium>

Dichloro (phenylmethylene) (tricyclohexylphosphine) ruthenium (84.90 mg, 0.1 mmol), a nitrogen- The reaction was carried out under the same conditions as in Preparation Example 1 using 4-phenyl-nitrogen-vinylbenzamide (44.66 mg, 0.2 mmol), copper (I) chloride (19.80 mg, 0.2 mmol) and dichloromethane 3-bis (2,4,6-trimethylphenyl) -2-imidazolidinylidene) dichloro ((nitrogen-phenylbenzamido) methylene) ruthenium.

(D, J = 6.85, 2H), 6.80-6.65 (m, 8H), 6.55 (m, 1H) 2H), 6.43 (d, J = 8.80,2H), 3.51 (s, 4H), 2.57 (brs,

Production Example 4

((Nitrogen- (4-methoxyphenyl) -4-nitrobenzoimido) methylene < / RTI > ) Synthesis of ruthenium>

Dichloro (phenylmethylene) (tricyclohexylphosphine) ruthenium (84.90 mg, 0.1 mmol), a nitrogen- (59.66 mg, 0.2 mmol), copper (I) chloride (19.80 mg, 0.2 mmol) and 4 ml of dichloromethane were added to a solution of 1 to give (1,3-bis (2,4,6-trimethylphenyl) -2-imidazolidinylidene) dichloro ((Nitro- (4-methoxyphenyl) -4- Nitrobenzenamido) methylene) ruthenium could be obtained.

(S, 2H), 6.91 (s, 2H), 6.91-6.58 (brs, 4H), 6.36 (s, (s, 2H), 6.28 (s, 2H), 3.42 (s, 4H), 3.10 (s, 3H), 2.91-2.31 (brd,

Production Example 5

(4-nitro-nitrogen- (4-nitrophenyl) benzamido) methylene < / RTI > ) Synthesis of ruthenium>

Dichloro (phenylmethylene) (tricyclohexylphosphine) ruthenium (84.90 mg, 0.1 mmol), 4- (4-methoxyphenyl) (62.65 mg, 0.2 mmol), copper (I) chloride (19.80 mg, 0.2 mmol) and dichloromethane (4 ml) in the same manner as in Production Example 1 to give (1,3-bis (2,4,6-trimethylphenyl) -2- imidazolidinylidene) dichloro ((4-nitro- Phenyl) benzamido) methylene) ruthenium.

(S, 1 H), 7.25 (d, J = 9.03 (s, 1H), 7.52 (D, J = 9.03, 2H), 6.97 (s, 1H), 6.93-6.80 (brs, 2H) (brs, 3H), 1.83 (brs, 3H) ppm

Production Example 6

Synthesis of (1,3-bis (2,4,6-trimethylphenyl) -2-imidazolidinylidene) dichloro (4-nitro-nitrogen-phenylbenzamido) methylene) ruthenium>

Dichloro (phenylmethylene) (tricyclohexylphosphine) ruthenium (84.90 mg, 0.1 mmol), 4- (4-methoxyphenyl) (53.65 mg, 0.2 mmol) and copper (I) chloride (19.80 mg, 0.2 mmol) and dichloromethane (4 ml) under the same conditions as in Production Example 1 Dichloro (4-nitro-nitrogen-phenylbenzamido) methylene) ruthenium was obtained in the same manner as in Example 1, except that (1, 3-bis (2,4,6-trimethylphenyl) -2-imidazolidinylidene) .

(D, J = 8.37, 2H), 7.59 (d, J = 8.70, 2H), 7.46-7.28 (s, 1H), 7.28 (s, IH), 7.18 (s, IH), 7.12 (s, IH), 6.81 (s, IH), 6.69 (d, J = 8.03 Hz, 2H), 4.40 ~ 4.23 3H), 2.52 (s, 3H), 2.44 (s, 3H), 2.53 (s, 2.32 (s, 3 H), 1.67 (s, 3 H) ppm

Production Example 7

((2,2-difluoro-nitrogen-phenylacetamido) methylene) ruthenium of the formula < (1,3-bis (2,4,6-trimethylphenyl) Synthesis>

(Tricyclohexylphosphine) ruthenium (84.90 mg, 0.1 mmol), 2, 3-bis (2,4,6-trimethylphenyl) -2- imidazolidinylidene) (39.44 mg, 0.2 mmol), copper (I) chloride (19.80 mg, 0.2 mmol) and 4 ml of dichloromethane were used in the same manner as in Production Example 1, except that 2-difluoro-nitrogen-phenyl- Dichloro ((2,2-difluoro-nitrogen-phenylacetamido) -2,3-dihydro- &lt; / RTI &gt; Methylene) ruthenium.

(M, 3H), 7.00 (d, J = 7.83 Hz, 2H), 6.95-6.80 (m, (brs, 4H), 6.09 ( t, J HF = 52.33, 1H), 4.10 (s, 4H), 2.41 (brs, 12H), 2.12 (brs, 6H) ppm

Production Example 8

Dichloro ((2,2-difluoro-nitrogen- (4-methoxyphenyl) acetamidine (4-methoxyphenyl) &Lt; / RTI > methylene) ruthenium &

 (Tricyclohexylphosphine) ruthenium (84.90 mg, 0.1 mmol), 2, 3-bis (2,4,6-trimethylphenyl) -2- imidazolidinylidene) (45.44 mg, 0.2 mmol), copper (I) chloride (19.80 mg, 0.2 mmol) and 4 ml of dichloromethane were used in the same manner as in Reference Example 1, using 2-difluoro- Nitro- (4- methoxyphenyl) And reacted under the same conditions as in Preparation Example 1 to give (1,3-bis (2,4,6-trimethylphenyl) -2-imidazolidinylidene) dichloro ((2,2-difluoro- - (4-methoxyphenyl) acetamido) methylene) ruthenium.

(M, 4H), 6.95-6.80 (br s, 1H), 6.85-6.53 (brs, 4H) , 4H), 5.31 (t, J HF = 52.33, 1H), 3.34 (s, 4H), 3.10 (s, 3H), 2.52 (brs, 12H), 1.87 (brs, 6H) ppm

Production Example 9

Dichloro ((2,2,2-trifluoro-nitrogen-phenylacetamido) methylene) - < / RTI > Synthesis of ruthenium>

(Tricyclohexylphosphine) ruthenium (84.90 mg, 0.1 mmol), 2, 3-bis (2,4,6-trimethylphenyl) -2- imidazolidinylidene) (43 mg, 0.2 mmol), copper (I) chloride (19.80 mg, 0.2 mmol) and 4 ml of dichloromethane were added to a solution of the compound of Preparation Example 1 Was reacted under the same conditions as (1,3-bis (2,4,6-trimethylphenyl) -2-imidazolidinylidene) dichloro ((2,2,2-trifluoro- Acetamido) methylene) ruthenium could be obtained.

(M, 2H), 6.41 (m, 2H), 6.80 (m, 2H), 6.80 (m, (d, J = 7.94 Hz, 2H), 3.36 (s, 4H), 2.52 (brs,

&Lt; Evaluation test of catalyst performance of the present invention (ring closure (closed ring) metathesis reaction) >

Using the catalysts thus prepared, diethyldialyl malonate was subjected to ring closure (ring closure) metathesis reaction to try to evaluate the activity of the complexes prepared by the present invention.

As a representative example, 0.001 mM of a stock solution of benzene substituted with deuterium containing 0.002 mmol of the above prepared ruthenium catalyst in a 2 ml volumetric flask, in a glove box free of oxygen and moisture, It makes it. Add 0.5 ml of stock solution to a sealable NMR tube using a Hamilton syringe.

After the NMR tube was sealed and then taken out of the glove box and sealed with an additional parafilm, diethyldiallyl malonate (12.02 mg, 0.05 mmol) was added to the NMR tube and then subjected to NMR The conversion rate is shown in Table 1, and the conversion rate according to time in Table 1 is shown in FIG.

[Table 1]

As shown in Table 1 and FIG. 1, the transition metal complex according to the present invention shows a conversion rate of olefin metathesis reaction of 99% or more.

Claims (13)

A transition metal complex represented by the following formula (A).
(A)
(L1) M (A) (L2) n (L3) m
In the above formula (A)
M is ruthenium,
L1 is a phosphine ligand containing a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a carbene derivative having a nitrogen-containing heterocycle, which is a N-heterocyclic carbene ligand &Quot;
L2 and L3 are the same or different and independently of each other are a monovalent ligand selected from the group consisting of halogen, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryloxy, ego,
n and m are each 1,
Wherein A is a ligand represented by the following structural formula A.
[Structural Formula A]

In the structural formula A, the substituents R11 to R13 are the same or different and are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, A substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms having at least any one selected from O, N, S and Si, a substituted or unsubstituted C1 to C30 alkyl group having 1 to 30 carbon atoms, A substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryloxy group, a substituted or unsubstituted C1 to C30 alkylamine group, a substituted or unsubstituted C6 to C30 arylamine group, A substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, a cyano group, and a halogen group,
The substituents R11 and R12 are not connected to each other to form a ring,
remind '

'Means Carben's electron pair.
The 'substituted' in the 'substituted or unsubstituted' refers to a group selected from the group consisting of deuterium, a cyano group, a halogen group, a hydroxy group, a nitro group, an alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, An aryl group having 7 to 24 carbon atoms, an alkoxy group having 1 to 24 carbon atoms, an alkylsilyl group having 1 to 24 carbon atoms, an arylsilyl group having 6 to 24 carbon atoms, and an aryloxy group having 6 to 24 carbon atoms. Quot; means substituted with at least one substituent. delete The method according to claim 1,
L2 and L3 in the formula (A) are the same or different and independently of each other are a halogen selected from F, Cl, Br and I. The method according to claim 1,
Wherein the N-heterocyclic carbene ligand is a compound represented by the following formula (B).
[Chemical Formula B]

In the above formula (B)
X1 is any one selected from O, S, N-R2, C-R3 and C-R4R5,
The bond between X1 and Y1, Y1 and Y2, Y2 and Y3 may have a single bond or a double bond,
Y1 to Y3 may be the same or different and are each selected from N, N-R6, C-R7, and C-R8R9,
m is an integer selected from 0 to 3, and when m is 2 or more, a plurality of Y 2 s may be the same or different from each other. In this case, each Y 2 bond may be a single bond or a double bond,
R 1 to R 9 are the same or different from each other and each independently represent hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, A substituted or unsubstituted aryloxy group having 7 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, A heteroaryl group having 2 to 50 carbon atoms and unsubstituted and having a hetero atom O, N or S,
R1 and R2 are not hydrogen or deuterium,
remind '

'Means Carben's electron pair. 5. The method of claim 4,
Wherein said N-heterocyclic carbene ligand is any one selected from the following Formulas B-1 to B-9.
[Formula B-1] [Formula B-2] [Formula B-3]

[Formula B-4] [Formula B-5] [Formula B-6]

[Formula B-7] [Formula B-8] [Formula B-9]

Wherein R1 and R2 are as defined in claim 4,
R 'is selected from the group consisting of hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 50 carbon atoms, A substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted hetero atom, O, N or S, And a heteroaryl group having 2 to 50 carbon atoms,
n is an integer of 1 to 6,
When a plurality of the substituents R 'exist in one molecule, each R' may be the same or different. 6. The method of claim 5,
Wherein said N-heterocyclic carbene is any one selected from the following Formulas B-20 to B-28, and Formulas B-30 to B-37.
[Formula B-20] [Formula B-21] [Formula B-22]

[Formula B-23] [Formula B-24] [Formula B-25]

[Formula B-26] [Formula B-27] [Formula B-28]

[Formula B-30] [Formula B-31]

[Formula B-32] [Formula B-33] [Formula B-34]

[Formula B-35] [Formula B-36] [Formula B-37]

delete The method according to claim 1,
Wherein the oxygen atom in the amide group in the structural formula A and the carbon atom of carbene are bonded to the transition metal. The method according to claim 1,
Wherein at least one of the substituents R11 to R13 is a substituent group containing a fluorine atom. delete A metathesis reaction of an olefin is carried out using the transition metal complex according to any one of claims 1, 3 to 6, and 8 to 9 as a catalyst. 12. The method of claim 11,
Wherein the metathesis reaction is a cyclization (ring-closing) metathesis reaction. The method according to claim 1,
Wherein said N-heterocyclic carbene ligand is any one selected from the following Formulas B-10 to B-13.
[Formula B-10] [Formula B-11] [Formula B-12]

[Formula B-13]

R1 and R2 are the same or different from each other and each independently represent a halogen, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C1- A substituted or unsubstituted aryloxy group, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, A heteroaryl group having 2 to 50 carbon atoms having O, N or S,
R 'is selected from the group consisting of hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 50 carbon atoms, A substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted hetero atom, O, N or S, And a heteroaryl group having 2 to 50 carbon atoms,
n is an integer of 1 to 8,
When a plurality of the substituents R 'exist in one molecule, each R' may be the same or different.

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