JP2018145183A - Fluorine-substituted nitrogen-containing heterocyclic compound, and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new fluorine-substituted nitrogen-containing heterocyclic compound.SOLUTION: The present invention provides a compound represented by formula (1) or a salt thereof [where A is CR, carbene carbon, or C=R; --- is a double bond if A is CR, while it is a single bond if A is carbene carbon; Ris O, S, or NR; Ris a hydrogen atom or an organic group; each R is the same or different every time it occurs and represents a hydrogen atom or an organic group; Ris a hydrogen atom, a fluorine atom, a chlorine atom, Rf, or ORf; and Rf is a fluoroalkyl group].SELECTED DRAWING: None

Description

  The present invention relates to a fluorine-substituted nitrogen-containing heterocyclic compound and a production method thereof.

Among the fluorine-substituted nitrogen-containing heterocyclic compounds, N-heterocyclic carbene (NHC) is widely used as a ligand or an organic catalyst of a metal complex, such as a nitrogen atom on the imidazolylidene ring and the 4,5-position. By introducing various substituents into the steric environment, the three-dimensional environment and electronic state in the vicinity of the carbene can be precisely controlled.
So far, synthesis examples of NHC in which chlorine is introduced at the 4th and 5th positions of the imidazolylidene ring are known (Non-Patent Document 1), but synthesis of the corresponding fluorine analog has not been achieved.

Y. Zhang et al., Angew. Chem. Int. Ed., 2014, 53, p6482.

  In view of the above prior art, it is desired to provide new fluorine-substituted nitrogen-containing heterocyclic compounds, particularly N-heterocyclic carbene (NHC).

As a result of intensive studies, the present inventors have studied a method for synthesizing an imidazolium salt as a synthesis precursor of a novel NHC having fluorine at positions 4 and 5 from TFE in a short process.
When TFE was pressurized against a THF solution of N, N′-diphenylformamidine deprotonated with a base, an amidine in which a trifluorovinyl group was introduced on one nitrogen was obtained. When this was treated with lithium tetrafluoroborate, CN bond formation and subsequent elimination of fluoride ions proceeded to obtain 4,5-difluoroimidazolium salt.
As a result of further research based on the findings, the present inventors have completed the present invention.

  The present invention includes the following aspects.

Item 1.
Formula (1):
[Where:
A represents CR ^p , a carbene carbon, or C═R ^A ,
--- is a double bond when A is CR ^p , while it is a single bond when A is a carbene carbon;
R ^A represents O, S, or NR;
R ^p represents a hydrogen atom or an organic group,
R is the same or different at each occurrence and represents a hydrogen atom or an organic group;
R ^X represents a hydrogen atom, a fluorine atom, a chlorine atom, Rf or ORf, and R ^Y represents a fluorine atom or Rf, or R ^X and R ^Y are two carbons adjacent to each other. Together with the atoms may form a hydrocarbon ring having one or more fluorine atoms,
Rf represents a fluoroalkyl group or a ring having one or more fluorine atoms. ]
Or a salt thereof.
Item 2.
A is CR ^p, compound or salt thereof according to claim 1.
Item 3.
Item 3. The compound or a salt thereof according to Item 2, wherein R ^p is a hydrogen atom.
Item 4.
Item 2. The compound or a salt thereof according to Item 1, wherein A is a carbene carbon.
Item 5.
Item 2. The compound or a salt thereof according to Item 1, wherein A is C = R ^A.
Item 6.
R 1 is the same or different at each occurrence, and R is an aryl group optionally having one or more substituents or a heteroaryl group optionally having one or more substituents 5. The compound according to any one of 4 or a salt thereof.
Item 7.
The compound or a salt thereof according to any one of Items 1 to 5, wherein R ^X is a fluorine atom.
Item 8.
Item 3. A method for producing the compound according to Item 2,
Formula: R—NH—CH═N—R [wherein the symbols in the formula are as defined above. The compound represented by the above formula (F-) (R ^x- ) C = C (-R ^x ) ( -F) [wherein R ^X is the same or different at each occurrence and represents the same meaning as described above. A step of reacting with a compound represented by formula A2
Manufacturing method.
Item 9.
Item 4. A method for producing the compound according to Item 3,
A production method comprising the step B of reacting the compound according to item 2 with a base to obtain the compound according to item 3.
Item 10.
Item 5. A ligand comprising the compound according to item 4.
Item 11.
Item 5. A catalyst containing the compound according to item 4.
Item 12.
The monomer which consists of a compound of claim | item 2-7.
Item 13.
Item 13. A polymer containing a structural unit derived from the monomer according to Item 12.
Item 14.
Item 6. An additive for an electrolyte solution comprising the compound according to Item 2 or 5.

  According to the present invention, a new fluorine-substituted nitrogen-containing heterocyclic compound, particularly N-heterocyclic carbene (NHC) is provided.

It is the result of the molecular structure analysis by X-ray diffraction measurement.

Terms Symbols and abbreviations in this specification can be understood within the context of this specification unless otherwise specified, and can be understood as meanings commonly used in the technical field to which the present invention belongs.
In this specification, the phrase “containing” is intended to encompass the phrase “consisting essentially of” and the phrase “consisting of”.
Unless specifically limited, the steps, processes, or operations described herein can be performed at room temperature.
In this specification, room temperature means a temperature within the range of 10 to 40 ° C.
In the present specification, the notation “Cn-Cm” (where n and m are numbers) represents that the number of carbon atoms is n or more and m or less, as is generally understood by those skilled in the art. .

  In the present specification, unless otherwise specified, examples of the “halogen atom” may include fluorine, chlorine, bromine, and iodine.

  In the present specification, the “organic group” means a group containing one or more carbon atoms (or a group formed by removing one hydrogen atom from an organic compound).

Examples of such “organic groups”
An alkyl group optionally having one or more substituents,
An alkenyl group optionally having one or more substituents,
An alkynyl group optionally having one or more substituents,
A cycloalkyl group optionally having one or more substituents,
A cycloalkenyl group optionally having one or more substituents,
A cycloalkadienyl group optionally having one or more substituents,
An aryl group optionally having one or more substituents,
An aralkyl group optionally having one or more substituents,
A non-aromatic heterocyclic group optionally having one or more substituents,
A heteroaryl group optionally having one or more substituents,
A cyano group,
An aldehyde group,
RO-,
RCO-,
RSO ₂ -,
ROCO-, and ROSO ₂ -
(In these formulas, R is independently
An alkyl group optionally having one or more substituents,
An alkenyl group optionally having one or more substituents,
An alkynyl group optionally having one or more substituents,
A cycloalkyl group optionally having one or more substituents,
A cycloalkenyl group optionally having one or more substituents,
A cycloalkadienyl group optionally having one or more substituents,
An aryl group optionally having one or more substituents,
An aralkyl group optionally having one or more substituents,
A non-aromatic heterocyclic group optionally having one or more substituents, or a heteroaryl group optionally having one or more substituents)
Can be included.

In the present specification, the “organic group” is, for example, a hydrocarbon group that may have one or more substituents [the hydrocarbon group includes —NR— (wherein R represents a hydrogen atom Or an organic group.), One or more parts selected from the group consisting of = N-, -N =, -O-, and -S- may be inserted. ].
Examples of the “hydrocarbon group having one or more moieties selected from the group consisting of —NR—, ═N—, —N═, —O—, and —S—” are non-aromatic complex Ring groups and heteroaryl groups can be included.

  In the present specification, the “hydrocarbon group” in the “hydrocarbon group optionally having one or more substituents” has, for example, 1 to 20 or 1 to 10 carbon atoms (eg, 1, 2). 3, 4, 5, 6, 7, 8, 9, 10).

In this specification,
"Hydrocarbon group optionally having one or more substituents",
“An alkyl group optionally having one or more substituents”;
“An alkenyl group optionally having one or more substituents”,
"Alkynyl group optionally having one or more substituents",
"Cycloalkyl group optionally having one or more substituents",
“Cycloalkenyl group optionally having one or more substituents”,
“Cycloalkadienyl group optionally having one or more substituents”,
"Aryl group optionally having one or more substituents",
"Aralkyl group optionally having one or more substituents",
"Non-aromatic heterocyclic group optionally having one or more substituents",
"Heteroaryl group optionally having one or more substituents",
“Non-aromatic heterocyclic group optionally having one or more substituents” and “Heteroaryl group optionally having one or more substituents”
Examples of the “substituent” in can include a halogen atom, a nitro group, a cyano group, an oxo group, a thioxo group, a sulfo group, a sulfamoyl group, a sulfinamoyl group, and a sulfenamoyl group, respectively.
The number of the substituents can be within a range from 1 to the maximum number that can be substituted (eg, 1, 2, 3, 4, 5, 6).

  In the present specification, examples of the “hydrocarbon group” are groups that are alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups, cycloalkadienyl groups, aryl groups, aralkyl groups, and combinations thereof. Can be included.

  In the present specification, unless otherwise specified, examples of the “alkyl group” include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl. It can include straight or branched C1-C10 alkyl groups such as, nonyl, and decyl.

  In the present specification, unless otherwise specified, examples of the “alkenyl group” include vinyl, 1-propen-1-yl, 2-propen-1-yl, isopropenyl, 2-buten-1-yl, 4- Linear or branched C2-10 alkenyl groups such as penten-1-yl and 5-hexen-1-yl can be included.

  In the present specification, unless otherwise specified, examples of the “alkynyl group” include ethynyl, 1-propyn-1-yl, 2-propyn-1-yl, 4-pentyn-1-yl, 5-hexyn- It can include a linear or branched C2-C10 alkynyl group, such as 1-yl.

  In the present specification, unless otherwise specified, examples of the “cycloalkyl group” can include C3-C7 cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and the like.

  In the present specification, unless otherwise specified, examples of the “cycloalkenyl group” may include C3-C7 cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl and the like.

  In the present specification, unless otherwise specified, examples of the “cycloalkadienyl group” include cyclobutadienyl, cyclopentadienyl, cyclohexadienyl, cycloheptadienyl, cyclooctadienyl, cyclononadienyl. And C4-C10 cycloalkadienyl groups such as cyclodecadienyl.

In the present specification, unless otherwise specified, the “aryl group” may be monocyclic, bicyclic, tricyclic, or tetracyclic.
In the present specification, unless otherwise specified, the “aryl group” may be a C6-C18 aryl group.
In the present specification, unless otherwise specified, examples of the “aryl group” may include phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, and 2-anthryl.

  In the present specification, unless otherwise specified, examples of the “aralkyl group” include benzyl, phenethyl, diphenylmethyl, 1-naphthylmethyl, 2-naphthylmethyl, 2,2-diphenylethyl, 3-phenylpropyl, 4-phenyl Phenylbutyl, 5-phenylpentyl, 2-biphenylylmethyl, 3-biphenylylmethyl, and 4-biphenylylmethyl can be included.

In the present specification, unless otherwise specified, the “non-aromatic heterocyclic group” may be monocyclic, bicyclic, tricyclic, or tetracyclic.
In the present specification, unless otherwise specified, the “non-aromatic heterocyclic group” is, for example, 1 to 4 ring atoms selected from an oxygen atom, a sulfur atom, and a nitrogen atom in addition to a carbon atom. It can be a non-aromatic heterocyclic group containing a heteroatom.
In the present specification, unless otherwise specified, the “non-aromatic heterocyclic group” may be saturated or unsaturated.
In the present specification, unless otherwise specified, examples of the “non-aromatic heterocyclic group” include tetrahydrofuryl, oxazolidinyl, imidazolinyl (eg, 1-imidazolinyl, 2-imidazolinyl, 4-imidazolinyl), aziridinyl (eg: 1 -Aziridinyl, 2-aziridinyl), azetidinyl (eg 1-azetidinyl, 2-azetidinyl), pyrrolidinyl (eg 1-pyrrolidinyl, 2-pyrrolidinyl, 3-pyrrolidinyl), piperidinyl (eg 1-piperidinyl, 2-piperidinyl, 3-piperidinyl), azepanyl (eg 1-azepanyl, 2-azepanyl, 3-azepanyl, 4-azepanyl), azocanyl (eg 1-azocanyl, 2-azocanyl, 3-azocanyl, 4-azocanyl), piperazinyl (eg : 1,4-piperazin-1-yl, 1,4-pipera N-2-yl), diazepinyl (eg, 1,4-diazepin-1-yl, 1,4-diazepin-2-yl, 1,4-diazepin-5-yl, 1,4-diazepin-6-yl) ), Diazocanyl (eg, 1,4-diazocan-1-yl, 1,4-diazocan-2-yl, 1,4-diazocan-5-yl, 1,4-diazocan-6-yl, 1,5- Diazocan-1-yl, 1,5-diazocan-2-yl, 1,5-diazocan-3-yl), tetrahydropyranyl (eg, tetrahydropyran-4-yl), morpholinyl (eg, 4-morpholinyl), Thiomorpholinyl (eg, 4-thiomorpholinyl), 2-oxazolidinyl, dihydrofuryl, dihydropyranyl, dihydroquinolyl and the like can be included.

  In the present specification, unless otherwise specified, examples of the “heteroaryl group” include a monocyclic aromatic heterocyclic group (eg, a 5- or 6-membered monocyclic aromatic heterocyclic group), and an aromatic condensed group. Heterocyclic groups (eg, 5- to 18-membered aromatic fused heterocyclic groups) can be included.

  In the present specification, unless otherwise specified, examples of the “5- or 6-membered monocyclic aromatic heterocyclic group” include pyrrolyl (eg, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl), furyl (eg, : 2-furyl, 3-furyl), thienyl (example: 2-thienyl, 3-thienyl), pyrazolyl (example: 1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl), imidazolyl (example: 1-imidazolyl, 2- Imidazolyl, 4-imidazolyl), isoxazolyl (eg: 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl), oxazolyl (eg: 2-oxazolyl, 4-oxazolyl, 5-oxazolyl), isothiazolyl (eg: 3-isothiazolyl, 4 -Isothiazolyl, 5-isothiazolyl), thiazolyl (eg 2-thiazolyl, 4-thiazolyl, 5-thiazolyl) Triazolyl (eg: 1,2,3-triazol-4-yl, 1,2,4-triazol-3-yl), oxadiazolyl (eg: 1,2,4-oxadiazol-3-yl, 1,2 , 4-oxadiazol-5-yl), thiadiazolyl (eg, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl), tetrazolyl, pyridyl (eg, 2-pyridyl) , 3-pyridyl, 4-pyridyl), pyridazinyl (eg: 3-pyridazinyl, 4-pyridazinyl), pyrimidinyl (eg: 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl), pyrazinyl and the like.

  In the present specification, unless otherwise specified, examples of the “5- to 18-membered aromatic condensed heterocyclic group” include isoindolyl (eg, 1-isoindolyl, 2-isoindolyl, 3-isoindolyl, 4-isoindolyl, 5- Isoindolyl, 6-isoindolyl, 7-isoindolyl), indolyl (eg, 1-indolyl, 2-indolyl, 3-indolyl, 4-indolyl, 5-indolyl, 6-indolyl, 7-indolyl), benzo [b] furanyl ( Examples: 2-benzo [b] furanyl, 3-benzo [b] furanyl, 4-benzo [b] furanyl, 5-benzo [b] furanyl, 6-benzo [b] furanyl, 7-benzo [b] furanyl) Benzo [c] furanyl (eg 1-benzo [c] furanyl, 4-benzo [c] furanyl, 5-benzo [c] furanyl), benzo [b Thienyl, (eg, 2-benzo [b] thienyl, 3-benzo [b] thienyl, 4-benzo [b] thienyl, 5-benzo [b] thienyl, 6-benzo [b] thienyl, 7-benzo [b ] Thienyl), benzo [c] thienyl (eg 1-benzo [c] thienyl, 4-benzo [c] thienyl, 5-benzo [c] thienyl), indazolyl (eg 1-indazolyl, 2-indazolyl, 3 -Indazolyl, 4-indazolyl, 5-indazolyl, 6-indazolyl, 7-indazolyl), benzimidazolyl (eg 1-benzimidazolyl, 2-benzimidazolyl, 4-benzimidazolyl, 5-benzimidazolyl), 1,2-benzisoxazolyl (Example: 1,2-benzisoxazol-3-yl, 1,2-benzisoxazol-4-y 1,2-benzisoxazol-5-yl, 1,2-benzisoxazol-6-yl, 1,2-benzisoxazol-7-yl), benzoxazolyl (eg 2-benzoxazolyl) , 4-benzoxazolyl, 5-benzoxazolyl, 6-benzoxazolyl, 7-benzoxazolyl), 1,2-benzisothiazolyl (example: 1,2-benzisothiazole- 3-yl, 1,2-benzisothiazol-4-yl, 1,2-benzisothiazol-5-yl, 1,2-benzisothiazol-6-yl, 1,2-benzisothiazol-7- Yl), benzothiazolyl (eg 2-benzothiazolyl, 4-benzothiazolyl, 5-benzothiazolyl, 6-benzothiazolyl, 7-benzothiazolyl), isoquinolyl (eg 1 -Isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl), quinolyl (eg, 2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 8-quinolyl), cinnolinyl (eg, 3-cinnolinyl, 4 -Cinnolinyl, 5-cinnolinyl, 6-cinnolinyl, 7-cinnolinyl, 8-cinnolinyl), phthalazinyl (eg 1-phthalazinyl, 4-phthalazinyl, 5-phthalazinyl, 6-phthalazinyl, 7-phthalazinyl, 8-phthalazinyl), quinazolinyl (Example: 2-quinazolinyl, 4-quinazolinyl, 5-quinazolinyl, 6-quinazolinyl, 7-quinazolinyl, 8-quinazolinyl), quinoxalinyl (eg: 2-quinoxalinyl, 3-quinoxalinyl, 5-quinoxalinyl, 6-quinoxalinyl, 7- Quinoxalinyl, 8- Noxalinyl), pyrazolo [1,5-a] pyridyl (eg, pyrazolo [1,5-a] pyridin-2-yl, pyrazolo [1,5-a] pyridin-3-yl, pyrazolo [1,5-a] ] Pyridin-4-yl, pyrazolo [1,5-a] pyridin-5-yl, pyrazolo [1,5-a] pyridin-6-yl, pyrazolo [1,5-a] pyridin-7-yl) Imidazo [1,2-a] pyridyl (eg, imidazo [1,2-a] pyridin-2-yl, imidazo [1,2-a] pyridin-3-yl, imidazo [1,2-a] pyridine- 5-yl, imidazo [1,2-a] pyridin-6-yl, imidazo [1,2-a] pyridin-7-yl, imidazo [1,2-a] pyridin-8-yl) and the like can be included. .

Compound The present invention may be referred to as the following compound of the following formula (1) [herein referred to as compound (1). ]I will provide a.
Formula (1-0):
[Where:
A represents CR ^p , a carbene carbon, or C═R ^A ,
--- is a double bond when A is CR ^p , while it is a single bond when A is a carbene carbon;
R ^A represents O, S, or NR;
R ^p represents a hydrogen atom or an organic group, R represents the same or different at each occurrence, and represents a hydrogen atom or an organic group;
R ^X represents a hydrogen atom, a fluorine atom, a chlorine atom, Rf or ORf, and R ^Y represents a fluorine atom or Rf, or R ^X and R ^Y are two carbons adjacent to each other. Together with the atoms may form a hydrocarbon ring having one or more fluorine atoms,
Rf represents a fluoroalkyl group or a hydrocarbon ring group having one or more fluorine atoms. ]
Or a salt thereof.
In the present specification, examples of the ring of “hydrocarbon ring having one or more fluorine atoms” are as follows:
Aromatic carbon rings such as benzene ring and naphthalene ring C3-C8 cycloalkane such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane;
C5-C8 cycloalkene such as cyclopentene, cyclohexene, cycloheptene, cyclooctene;
C5-C8 cycloalkadiene such as cyclopentadiene, cyclohexadiene, cycloheptadiene, cyclooctadiene; and bicyclo [2.1.0] pentane, bicyclo [2.2.1] heptane, bicyclo [3.2.1 It can include C5-C8 bridged ring hydrocarbons such as octane, bicyclo [2.2.1] hept-2-ene, tricyclo [2.2.1.0] heptane.
In the present specification, the “hydrocarbon ring group having one or more fluorine atoms” is a group formed by removing one hydrogen atom from the “hydrocarbon ring having one or more fluorine atoms”. Can be.
Formula (1):
[Where:
A represents CR ^p , a carbene carbon, or C═R ^A ,
--- is a double bond when A is CR ^p , while it is a single bond when A is a carbene carbon;
R ^A represents O, S, or NR;
R ^p represents a hydrogen atom or an organic group, R represents the same or different at each occurrence, and represents a hydrogen atom or an organic group;
R ^X represents a hydrogen atom, a fluorine atom, a chlorine atom, Rf, or ORf, and Rf represents a fluoroalkyl group. ]
Or a salt thereof.

Aspect 1A
In a preferred embodiment of the invention, A is CR ^p .
In this embodiment, the compound (1) is a compound represented by the following formula (1A0) [in this specification, sometimes referred to as a compound (1A0). ].
Formula (1A0):
[The symbol in the formula represents the same meaning as the symbol in the formula (1-0). ]
One embodiment of the compound of the formula (1A0) is a compound represented by the following formula (1A) [in this specification, sometimes referred to as a compound (1A). ].
[The symbol in the formula represents the same meaning as the symbol in the formula (1). ]
Or a salt thereof.

R ^p may preferably be a hydrogen atom or an alkyl group (eg, C1-C6 alkyl group).
In one embodiment of the present invention, R ^p is preferably a hydrogen atom.

  R is preferably the same or different at each occurrence and may be an alkyl group optionally having one or more substituents, preferably an aryl group optionally having one or more substituents, or It can be a heteroaryl group optionally having one or more substituents.

The “alkyl group optionally having one or more substituents” is preferably an unsubstituted C1-C6 alkyl group (eg, isopropyl group, t-Bu group, isobutyl group) which may be branched. , Neopentyl group).
The aryl group of the “aryl group optionally having one or more substituents” can preferably be a phenyl group.
The substituent of the “aryl group optionally having one or more substituents” is preferably an alkyl group, and more preferably a C1-C6 alkyl group.
The number of the substituents can be within a range from 1 to the maximum number that can be substituted (eg, 1, 2, 3, 4, 5, 6).

The heteroaryl group of the “heteroaryl group optionally having one or more substituents” is preferably a 5- or 6-membered nitrogen-containing heteroaryl group (eg, pyridyl group, furyl group, thienyl group, quinolyl). Group, morpholino group, imidazolyl group, pyrazolyl group, oxazolyl group, indolyl group, quinolyl group).
The substituent of the “heteroaryl group optionally having one or more substituents” may preferably be an alkyl group, and more preferably a C1-C6 alkyl group.
The number of the substituents can be within a range from 1 to the maximum number that can be substituted (eg, 1, 2, 3, 4, 5, 6).

R ^X can suitably be a fluorine atom or Rf.
R ^X can more preferably be a fluorine atom or Rf.
R ^Y can preferably be a fluorine atom.
R ^X and R ^Y together with two adjacent carbon atoms form a ring to form a hydrocarbon ring (eg, benzene ring) having one or more fluorine atoms. It is also preferable.
Suitable examples of the ring include hexafluorocyclopentene and tetrafluorobenzene.

Compound (1A0), which is a salt salt of the compound of Embodiment 1A, can be a compound represented by the following formula (1Aa0).
Formula (1A):
[Wherein, X ⁻ represents a counter anion, and other symbols have the same meaning as described above. ]
A compound represented by
The compound (1A) which is a salt can be a compound represented by the following formula (1Aa).
Formula (1A):
[Wherein, X ⁻ represents a counter anion, and other symbols have the same meaning as described above. ]
A compound represented by

Examples of counter anions represented by X ⁻ include BF 4 ⁻ , OSO ₂ Rf ⁻ , PF ₆ ⁻ , SbS ₆ ⁻ , N (SO ₂ Ph) ₂ ⁻ , N (SO ₂ Rf) ₂ ⁻ _, and C (SO ₂ Rf) ₃ ^- is included.

Aspect 1B
In a preferred embodiment of the invention, A is a carbene carbon.
In this embodiment, compound (1) is a compound represented by the following formula (1B0) [in this specification, sometimes referred to as compound (1B0). ].
Formula (1B0):
[The symbol in the formula represents the same meaning as the symbol in the formula (1-0). ]
One embodiment of the compound of the formula (1B0) is a compound represented by the following formula (1A) [in this specification, sometimes referred to as a compound (1B). ].
[The symbol in the formula represents the same meaning as the symbol in the formula (1A). ]
The compound salt represented by these.

  R is the same or different at each occurrence, and preferably an alkyl group optionally having one or more substituents, an aryl group optionally having one or more substituents, or one or more It can be a heteroaryl group optionally having a substituent.

The “alkyl group optionally having one or more substituents” is preferably an unsubstituted C1-C6 alkyl group (eg, isopropyl group, t-Bu group, isobutyl group) which may be branched. , Neopentyl group).
The aryl group of the “aryl group optionally having one or more substituents” can preferably be a phenyl group.
The substituent of the “aryl group optionally having one or more substituents” is preferably an alkyl group, and more preferably a C1-C6 alkyl group.
The number of the substituents can be within a range from 1 to the maximum number that can be substituted (eg, 1, 2, 3, 4, 5, 6).

The heteroaryl group of the “heteroaryl group optionally having one or more substituents” is preferably a 5- or 6-membered nitrogen-containing heteroaryl group (eg, pyridyl group, furyl group, thienyl group, quinolyl). Group, morpholino group, imidazolyl group, pyrazolyl group, oxazolyl group, indolyl group, quinolyl group).
The substituent of the “heteroaryl group optionally having one or more substituents” may preferably be an alkyl group, and more preferably a C1-C6 alkyl group.
The number of the substituents can be within a range from 1 to the maximum number that can be substituted (eg, 1, 2, 3, 4, 5, 6).

R ^X can suitably be a fluorine atom or Rf.
R ^X can more preferably be a fluorine atom.

Aspect 1C
In yet another preferred embodiment of the invention, A is C = R ^A.
In this embodiment, compound (1) is a compound represented by the following formula (1C0) [in this specification, sometimes referred to as compound (1C0). ].
Formula (1C0):
[The symbol in the formula represents the same meaning as the symbol in the formula (1-0). ]
One embodiment of the compound of formula (1C0) is a compound represented by the following formula (1C) [in this specification, sometimes referred to as compound (1C)]. ].
[Where:
R ^A represents ═O, ═S, or ═NR, and other symbols have the same meanings as the symbols in Formula (1A). ]

  R is the same or different at each occurrence, and is preferably a hydrogen atom, an alkyl group optionally having one or more substituents, an aryl group optionally having one or more substituents, Or it can be a heteroaryl group which may have one or more substituents.

The “alkyl group optionally having one or more substituents” is preferably an unsubstituted C1-C6 alkyl group (eg, isopropyl group, t-Bu group, isobutyl group) which may be branched. , Neopentyl group).
The substituent of the “aryl group optionally having one or more substituents” is preferably an alkyl group, and more preferably a C1-C6 alkyl group.
The number of the substituents can be within a range from 1 to the maximum number that can be substituted (eg, 1, 2, 3, 4, 5, 6).

The substituent of the “heteroaryl group optionally having one or more substituents” may preferably be an alkyl group, and more preferably a C1-C6 alkyl group.
The number of the substituents can be within a range from 1 to the maximum number that can be substituted (eg, 1, 2, 3, 4, 5, 6).

R ^X can suitably be a fluorine atom or Rf.
R ^X can more preferably be a fluorine atom.

Production Method The production method of the compound of the present invention will be described below.
Compound (1) can be produced by the production method described later or a production method similar thereto.

Of the compound (1A0) and the compound (1A) included therein, a compound in which R ^p is a hydrogen atom [in this specification, sometimes referred to as a compound (1A-H). ] For example
Formula: R—NH—CH═N—R [wherein the symbols in the formula are as defined above. A compound represented by the formula (sometimes referred to herein as an amidine compound) by reacting with a base to deprotonate, and the product of the step A1 represented by the formula: (F- ) (R ^x- ) C = C (-R ^x ) (-F) [wherein R ^X is the same or different at each occurrence and represents the same meaning as described above. Step A2 to obtain a compound (1A-H) by reacting with a compound represented by the formula (sometimes referred to herein as a fluoroalkene compound).
It can manufacture by the manufacturing method containing.

Process A1
In step A1, the amidine compound is reacted with a base to be deprotonated.
Suitable examples of the base include alkali metal hydrides [eg LiH, NaH, KH], and organic lithium [eg lithium diisopropylamide, LDA (Lithium diisopropylamide), LiTMP (Lithium 2,2,6,6-tetramethylpiperidide). ), LHMDS (Lithium hexamethyldisilazide)].

  The said base can be used individually by 1 type or in combination of 2 or more types.

The upper limit of the reaction temperature in this step is preferably 80 ° C, more preferably 50 ° C, and even more preferably 40 ° C.
The lower limit of the reaction temperature in this step is preferably −40 ° C., more preferably −20 ° C., and even more preferably 0 ° C.
The reaction temperature in this step is preferably within the range of −40 to 80 ° C., more preferably within the range of −20 to 40 ° C., and even more preferably within the range of 0 to 30 ° C.
There is a tendency that the lower the upper limit of the temperature during the reaction in this step, the side reaction can be suppressed.
When the lower limit of the temperature during the reaction in the step is higher, the progress of the target reaction tends to be promoted.

The upper limit of the reaction time in this step can be preferably 3 days, more preferably 2 days, and even more preferably 20 hours.
The lower limit of the reaction time in this step is preferably 30 minutes, more preferably 1 hour, and even more preferably 2 hours.
The reaction time of the step can be preferably in the range of 30 minutes to 3 days, more preferably in the range of 1 hour to 2 days, and still more preferably in the range of 2 hours to 1 day. .

The upper limit of the amount of the base can be preferably 3 mol, more preferably 2 mol, and still more preferably 1.5 mol with respect to 1 mol of the raw amidine compound.
The lower limit of the amount of the base is preferably 0.5 mol, more preferably 0.8 mol, and still more preferably 1 mol with respect to 1 mol of the starting amidine compound.
The amount of the base is preferably within a range of 0.5 to 3 mol, more preferably within a range of 0.8 to 2 mol, and even more preferably 1 to 1.5 mol, with respect to 1 mol of the starting amidine compound. It can be in the molar range.
By carrying out the reaction in this amount, the desired product can be obtained efficiently.

The reaction can be carried out in the presence or absence of an inert gas (eg, nitrogen gas).
The reaction can be suitably carried out in the presence of a solvent.
Examples of such solvents are:
(1) Hydrocarbon solvents such as hexane, heptane, cyclohexane, petroleum ether, benzene, toluene, and xylene;
And (2) ether solvents such as diethyl ether, diisopropyl ether, THF, methyl THF, DME, CPME, and dioxane.
Is mentioned.

Process A2
In step A2, the product of step A1 is reacted with the fluoroalkene compound.
Step A2 is preferably
Reacting the product of the step A1 with the fluoroalkene compound and the product of the step A2a with an inorganic lithium salt or a trialkylsilyl group (eg, trimethylsilyl (TMS) group, triethylsilyl (TES) group) , Tert-butyldimethylsilyl, triisopropylsilyl (TIPS) group, and tert-butyldiphenylsilyl (TBDPS) group) to obtain a compound (1A-H).
Here, the compound (1A-H) obtained in Step A2b is a salt containing an anion of the inorganic lithium salt [Example: BF ₄ salt, PF ₆ salt, SbF ₆ salt, OTf salt, N (SO ₂ Ph) ₂ salt, N (SO ₂ Rf) ₂ salt, LiC (SO ₂ Rf) ₃ salt, Cl salt, etc.].
The product of step A1 includes a salt of the amidine compound.

The upper limit of the amount of the fluoroalkene compound is preferably 50 moles, more preferably 20 moles, and even more preferably 5 moles with respect to 1 mole of the salt of the amidine compound as a raw material.
The lower limit of the amount of the fluoroalkene compound is preferably 0.8 mol, more preferably 1.2 mol, and still more preferably 1.5 mol with respect to 1 mol of the salt of the amidine compound as a raw material. Can do.
The amount of the fluoroalkene compound is preferably within the range of 0.8 to 50 mol, more preferably within the range of 1.2 to 20 mol, and even more preferably with respect to 1 mol of the salt of the amidine compound as the raw material. Can be in the range of 1.5 to 5 moles.
By carrying out the reaction in this amount, the desired product can be obtained efficiently.

  When the fluoroalkene compound is a gas, the compound may be introduced into the reaction system by pressurization, for example.

The upper limit of the reaction temperature in the step A2a is preferably 80 ° C, more preferably 40 ° C, and still more preferably 20 ° C.
The lower limit of the reaction temperature in the step A2a is preferably −60 ° C., more preferably −30 ° C., and still more preferably −10 ° C.
The reaction temperature in the step A2a is preferably in the range of −60 to 80 ° C., more preferably in the range of −30 to 40 ° C., and still more preferably in the range of −10 to 20 ° C.
There is a tendency that the lower the upper limit of the temperature during the reaction in the step, the side reactions can be suppressed.
When the lower limit of the temperature during the reaction in the above step is higher, the progress of the target reaction tends to be promoted.

The upper limit of the reaction time in the step A2a is preferably 7 days, more preferably 2 days, and even more preferably 1 day.
The lower limit of the reaction time in the step A2a is preferably 30 minutes, more preferably 1 hour, and still more preferably 3 hours.
The reaction time of the step A2a is preferably in the range of 30 minutes to 7 days, more preferably in the range of 1 hour to 2 days, and still more preferably in the range of 3 hours to 1 day. it can.

  The reaction in the step A2b is preferably carried out in the presence of an inorganic lithium salt or a compound containing a trialkylsilyl group.

Examples of the compound containing an inorganic lithium salt or a trialkylsilyl group include LiBF ₄ , and LiPF ₆ , LiSbF ₆ , LiOTf, LiN (SO ₂ Ph) ₂ , LiN (SO ₂ Rf) ₂ , LiC (SO ₂ Rf) ₃ , TMS-Cl, TMS-OTf are included. Of these, LiBF ₄ is preferable.

  The timing of addition of the reaction system of the compound containing an inorganic lithium salt or trialkylsilyl group may be simultaneous with the introduction of the fluoroalkene compound or after the introduction of the fluoroalkene compound.

The upper limit of the amount of the inorganic lithium salt is preferably 5 moles, more preferably 3 moles, and even more preferably 1.5 moles with respect to 1 mole of A2a as the raw material.
The lower limit of the amount of the inorganic lithium salt is preferably 0.5 mol, more preferably 0.8 mol, and still more preferably 1 mol with respect to 1 mol of the raw material A2a.
The amount of the inorganic lithium salt is preferably in the range of 0.5 to 5 mol, more preferably in the range of 0.8 to 3 mol, and still more preferably 1 to 1 mol of A2a as the raw material. It can be in the range of 1.5 moles.
By carrying out the reaction in this amount, the desired product can be obtained efficiently.

The upper limit of the reaction time in the step A2b is preferably 5 days, more preferably 3 days, and even more preferably 1 day.
The lower limit of the reaction time in the step A2b is preferably 30 minutes, more preferably 1 hour, and still more preferably 5 hours.
The reaction time of the step A2b is preferably in the range of 30 minutes to 5 days, more preferably in the range of 1 hour to 3 days, and still more preferably in the range of 5 hours to 1 day. it can.

  The reaction can be carried out in the presence or absence of an inert gas (eg, nitrogen gas).

The reaction can be suitably carried out in the presence of a solvent.
Examples of such solvents are:
(1) Hydrocarbon solvents such as hexane, heptane, cyclohexane, petroleum ether, benzene, toluene, and xylene;
And (2) ether solvents such as diethyl ether, diisopropyl ether, THF, methyl THF, DME, CPME, and dioxane.
Is mentioned.

Of the compound (1A0) and the compound (1A) included therein, the compound in which R ^p is an organic group is, for example,
The compound (1A-H) is represented by the formula: R ^p C (—OR ^q ) ₃ [wherein R ^q represents an alkyl group. ] It can manufacture by the manufacturing method including the process Ap made to react with the orthoester (it may only be called an orthoester in this specification) represented by this.

The step Ap can be produced by a method similar to a known method (for example, the method described in Synthetic Communications, 2007, 37, 2655-2661).
In the present specification, the expression “known method” includes known conditions, which are only described for the sake of convenience. A person skilled in the art may appropriately modify the known method and adapt it to the production method of the present invention based on common general technical knowledge.

Compound (1B0) and compound (1B) included therein are, for example,
It can manufacture with the manufacturing method including the process B which makes a compound (1A-H) react with a base.

  Suitable examples of the base include alkali metal hydrides [eg LiH, NaH, KH], and organic lithium [eg lithium diisopropylamide, LDA (Lithium diisopropylamide), LiTMP (Lithium 2,2,6,6-tetramethylpiperidide). ), LHMDS (Lithium hexamethyldisilazide)].

The upper limit of the reaction temperature in this step is preferably 80 ° C, more preferably 50 ° C, and even more preferably 30 ° C.
The lower limit of the reaction temperature in this step is preferably −40 ° C., more preferably −20 ° C., and even more preferably 0 ° C.
The reaction temperature in this step is preferably within the range of −40 to 80 ° C., more preferably within the range of −20 to 50 ° C., and even more preferably within the range of 0 to 30 ° C.
There is a tendency that the lower the upper limit of the temperature during the reaction in this step, the side reaction can be suppressed.
When the lower limit of the temperature during the reaction in the step is higher, the progress of the target reaction tends to be promoted.

The upper limit of the reaction time in this step can be preferably 7 days, more preferably 3 days, and even more preferably 1 day.
The lower limit of the reaction time in this step is preferably 30 minutes, more preferably 1 hour, and even more preferably 5 hours.
The reaction time of the step can be preferably in the range of 30 minutes to 7 days, more preferably in the range of 1 hour to 3 days, and still more preferably in the range of 5 hours to 1 day. .

The upper limit of the amount of the base is preferably 5 mol, more preferably 3 mol, and still more preferably 1.5 mol, with respect to 1 mol of the compound (1A-H).
The lower limit of the amount of the base is preferably 0.8 mol, more preferably 0.9 mol, and still more preferably 1 mol with respect to 1 mol of the compound (1A-H).
The amount of the base is preferably in the range of 0.8 to 5 mol, more preferably in the range of 0.9 to 3 mol, and still more preferably 1 to 1 mol with respect to 1 mol of the compound (1A-H). It can be in the range of 1.5 moles.
By carrying out the reaction in this amount, the desired product can be obtained efficiently.

  The reaction can be carried out in the presence or absence of an inert gas (eg, nitrogen gas).

Among compounds (1C0) and (1C), a compound in which R ^A is C═O can be obtained by a known method (for example, Angew. Chem. Int. Ed. 2012, 51, 232-234., Journal of Organometallic Chemistry). 2001, 617-618, 242-253. And Journal of Organometallic Chemistry 2013, 743, 44-48.).

Among compounds (1C0) and (1C), a compound in which R ^A is NH is a method similar to a known method (for example, the method described in Org. Biomol. Chem. 2007, 5, 523). Specifically, it can be produced, for example, by azidation using Me ₃ SiN ₃ and substitution with an organic group as desired (eg, alkylation).

Among compounds (1C0) and (1C), a compound in which R ^A is O is a method similar to a known method (for example, the method described in Journal of Organometallic Chemistry 617-618 (2001) 242-253). Specifically, for example, it can be produced by reacting compound (1b) with NO.

Among the compounds (1C0) and (1C), a compound in which R ^A is S is a method similar to a known method (for example, the method described in Journal of Organometallic Chemistry 743 (2013) 44-48). Specifically, for example, a compound having —Cu-tertbutyl is prepared in place of R ^p in formula (1), and the compound is reacted with S-DMF in the presence of K ⁺ [CF ₃ B (OMe) ₃ ]. It can manufacture by the method of making it react with.

  If desired, the compound produced by the above-described method can be isolated or purified by a conventional method such as extraction, dissolution, concentration, precipitation, dehydration, adsorption, or chromatography, or a combination thereof.

Application
Ligand The compound of the present invention can function as a ligand to form a complex such as a metal catalyst.
Accordingly, the present invention also provides a ligand comprising the compound of the present invention.
The ligand of the present invention can have a strong coordination ability due to its bulk and strong electron donating property.
In particular, the compound (1B) can be suitably used as a ligand.

Catalyst The present invention also provides a catalyst containing a compound of the present invention.
Here, as will be understood from the above description of the ligand, the present invention also provides a catalyst containing the compound of the present invention as a ligand. The catalyst can be produced based on common general technical knowledge depending on its structure.
In particular, a preferred embodiment of the catalyst of the present invention contains compound (1B).
The catalyst of the present invention can be used for, for example, a cross-coupling reaction, a cycloaddition reaction, or CH bond activation.

Monomer The compound of the present invention can be used as a monomer for a polymer.
Accordingly, the present invention also provides a monomer comprising the compound of the present invention.
In particular, the compounds (1A) and (1C) can be preferably used as monomers.

Polymer As described above, one embodiment of the compound of the present invention can be used as a monomer.
Accordingly, the present invention also provides a polymer having one or more structural units derived from the monomer of the present invention.
The monomer of this invention which the said polymer contains can be 1 type, or 2 or more types.
Although the content of the structural unit derived from the monomer of the present invention in the polymer is not particularly limited, for example, it can be 0.01 to 100% by mass in terms of monomer weight.
The polymer of the present invention may contain a structural unit derived from a monomer other than the monomer of the present invention. In this case, the “monomer other than the monomer of the present invention” is not particularly limited as long as it can be combined with the monomer of the present invention. Examples thereof include, for example, ethylene, propylene, vinyl acetate, methyl Including acrylate, methyl methacrylate, tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, chlorotrifluoroethylene and the like.
The said polymer can be manufactured based on technical common sense according to the structure.

Electrolyte Additive The compound of the present invention can be used as an additive (for example, a negative electrode film forming agent and an overcharge inhibitor) of an electrolyte solution of a lithium ion battery.
In particular, the compounds (1A) and (1C) can be suitably used as an additive for the electrolyte solution of such a lithium ion battery.
The amount used can be appropriately set according to the type and purpose of the compound used.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this.

Example A1
Under a nitrogen gas atmosphere, 1 (5.3 g, 27 mmol) in THF (150 mL) was added to a 300 mL two-necked flask containing NaH (744 mg, 31 mmol) and THF (50 mL), and the mixture was stirred for 17 hours. After concentration under reduced pressure, the solid was removed by filtration and THF extraction, and the filtrate was concentrated under reduced pressure to obtain a white solid (6.0 g, crude). Purification by recrystallization (THF / hexane, -36 ° C.) gave 5.8 g (yield 98%) of Compound 2 as a white solid.
(Compound 2 )
sodium N, N'-diphenyl formimidamidinate Na [Ph-NCHN-Ph]
¹ H NMR (400 MHz, THF-d ₈ , rt, δ / ppm): 6.53 (t, J = 7.0 Hz, 2 H, p-Ph), 6.79 (d, J = 8.0 Hz, 4 H, o- Ph), 6.95 (dd, J = 8.0, 7.0 Hz, 4 H, m-Ph), 8.67 (s, 1H, -CH).

Example A2
In a nitrogen gas atmosphere, an autoclave (50 mL) containing Compound 2 (654 mg, 3 mmol) and THF (10 ml) was cooled in an ice bath, and TFE (3.5 atm, 7 mmol) was added under pressure. Stir for hours. After degassing TFE, the solid in the reaction solution was removed by filtration, and the solid was thoroughly washed with 90 ml of THF and combined with the filtrate. As an internal standard, α, α, α-trifluorotoluene (100 μl) was added thereto, and ¹⁹ F-NMR was measured to confirm that Compound 3 was produced at 23%.
(Compound 3 )
N, N'-diphenyl-N- (1,2,2-trifluorovinyl) formimidamide [CF ₂ = CF (Ph) -NCHN-Ph]
¹⁹ F NMR (376 MHz, THF / THF-d ₈ , rt, δ / ppm): -108.9 (dd, J = 43.0, 69.7 Hz, 1F), -120.9 (dd, J = 69.7, 111.8 Hz, 1F) , -145.4 (dd, J = 43.0, 111.8 Hz, 1F).

To the filtrate of the reaction solution containing Compound 3 , 1 equivalent of LiBF ₄ (65 mg, 0.69 mmol) was added and reacted at room temperature for 60 hours, then heated to 60 ° C. and reacted for 5 hours. The reaction solution was concentrated to about 1/5, and the precipitated solid was removed by filtration. The solid obtained by concentrating the filtrate was washed with 10 ml each of hexane and toluene, and recrystallized at −20 ° C. with methanol to obtain 94 mg (yield: 10%) of Compound 4 crystals. .
(Compound 4 )
1,3-diphenyl-4,5-difluoro-imidazolium tetrafluoroborate
¹ H NMR (400 MHz, CD ₂ Cl ₂ , rt, δ / ppm): 7.55-7.85 (m, 10 H, Ph), 8.66 (s, 1H, -CH).
^{19 F NMR (376 MHz, CD} 2 Cl 2, rt, δ / ppm): -154.2 (br, 4F, BF 4 -), -156.7 (s, 2F, = CF-).
¹³ C { ¹ H, ¹⁹ F} NMR (100 MHz, CD ₂ Cl ₂ , rt, δ / ppm): 122.5 (NCHN), 125.4, 129.6 (= CF-), 130.6 (ipso-C), 131.0, 132.4 (p-Ph).

Example A3
Compound 3 (0.007 mmol), TMSCl (1.0 μL), deuterated THF (0.6 ml), and α, α, α-trifluorotoluene as an internal standard were added to a pressure-resistant NMR tube and reacted at 40 ° C. for 11 hours. ^{In 19} F NMR, a peak derived from compound 5 was observed at δ-161.2 ppm ( ¹⁹ F-NMR yield 8%, conversion rate 67%), and a decrease in compound 3 (67% conversion) was confirmed.
In addition, compound 3 (0.018 mmol), TMS-OTf (3.2 μL), deuterated THF (0.6 ml), and α, α, α-trifluorotoluene as an internal standard were added to a pressure-resistant NMR tube and reacted at room temperature for 60 hours. I let you. As a result, the production of Compound 6 was confirmed ( ¹⁹ F-NMR yield 22%, conversion 35%)).

Example B1
In a 100 mL two-necked flask equipped with a distillation apparatus, 2,4,6-trimethylaniline (13.5 g, 100 mmol), CH (OEt) ₃ (7.7 g, 50 mmol), and CH ₃ COOH (160 mg, 2.5 mmol) The reaction was carried out at a temperature in the range of 120 ° C. to 160 ° C. for 4 hours while distilling off ethanol under a nitrogen gas atmosphere. The solid was obtained by cooling to room temperature. This was washed with hexane (150 mL) cooled in a water bath, and the washed solid was dried under reduced pressure to obtain 13.6 g (yield 98%) of Compound 7 as a white solid.

Example B2
In a glove box, NaH (960 mg, 40 mmol) and THF (20 mL) were added to a 100 mL two-necked flask, and compound 7 (7.45 g, 27 mmol) dissolved in THF (80 mL) was added under a nitrogen gas atmosphere. added. After stirring at room temperature for 40 hours, it was confirmed that H ₂ was not generated, and the solvent was distilled off under reduced pressure to precipitate a white solid. Excess NaH was removed by THF extraction and filtration, and the filtrate was concentrated under reduced pressure to obtain Compound 8 as a white solid. The white solid was crushed, hexane was added and azeotroped to quantitatively obtain a powdery white solid of Compound 8 .
(Compound 8 )
sodium N, N'-dimesityl formimidamidinate Na [Ar-NCHN-Ar]: Ar = 2,4,6-Me ₃ -C ₆ H _2-
¹ H NMR (400 MHz, THF-d ₈ , rt, δ / ppm): 2.08 (s, 18 H, -CH ₃ ), 6.59 (s, 4 H, 3,5-CH), 7.46 (s, 1H , -CH).

Example B3
Compound 8 (30 mg, 0.1 mmol) is dissolved in THF-d ₈ (0.4 mL) in the glove box, added to the pressure-resistant NMR tube, and α, α, α-trifluorotoluene (3 μL) is added as an internal standard substance. It was. Thereafter, TFE (2.0 atm, 0.2 mmol) was pressurized. After standing at 0 ° C. for 17 hours, TFE was degassed, and NMR was measured to identify Compound 9 .
(Compound 9 )
N, N'-dimesityl-N- (1,2,2-trifluorovinyl) formimidamide [CF ₂ = CF (Ar) -NCHN-Ar]: Ar = 2,4,6-Me ₃ -C ₆ H _2-
¹ H NMR (400 MHz, THF / THF-d ₈ , rt, δ / ppm): 2.02 (s, 6 H, -CH ₃ ), 2.13 (s, 3 H, -CH ₃ ), 2.22 (s, 3 H, -CH ₃ ), 2.28 (s, 6 H, -CH ₃ ), 6.71 (s, 2 H, 3,5-CH), 6.92 (s, 2 H, 3,5-CH), 7.50 (br s, 1H, -CH).
¹⁹ F NMR (376 MHz, THF / THF-d ₈ , rt, δ / ppm): -111.6 (dd, J = 41.8, 79.0 Hz, 1F), -122 to -124 (br, 1F), -143 ~ -145 (br, 1F).

Example B4
In a glove box, compound 8 (605 mg, 2 mmol) was dissolved in THF (10 mL), added to an autoclave (50 mL), and TFE (2.0 atm, 700 mg, 7 mmol) was pressurized. After stirring at 0 ° C. for 20 hours, TFE was degassed, the solid was removed by filtration, the solid was washed with THF, and the washing was combined with the filtrate. LiBF ₄ (186 mg, 2 mmol) was added thereto, and the mixture was stirred at 60 ° C. for 10 hours. When the solvent was distilled off under reduced pressure, a white solid was precipitated. The solid was washed with THF (10 mL × 2 times), and components soluble in CHCl ₃ were extracted. The solvent was distilled off under reduced pressure to obtain Compound 10 (320 mg, 38% yield) as a white solid.
(Compound 10 )
1,3-dimesityl-4,5-difluoro-imidazolium tetrafluoroborate
¹ H NMR (400 MHz, CDCl ₃ , rt, δ / ppm): 2.22 (s, 12 H, -CH ₃ ), 2.37 (s, 6 H, -CH ₃ ), 7.10 (s, 4 H, 3, 5-CH), 9.12 (t, J = 2.2 Hz, 1H, -CH).
^{19 F NMR (376 MHz, CDCl} 3, rt, δ / ppm): -154.4 (br, 4F, BF 4 -), -157.3 (s, 2F, = CF-).

Example C1
Add 2,6-diisopropylaniline (17.7 g, 100 mmol), CH (OEt) ₃ (7.5 g, 50 mmol), CH ₃ COOH (160 mg, 2.5 mmol) to a 200 mL two-necked flask equipped with a distillation apparatus. The reaction was carried out for 7 hours at a temperature within the range of 120 ° C. to 160 ° C. while distilling off ethanol under a nitrogen gas atmosphere. When the temperature was lowered to room temperature, a white solid was precipitated. This was washed with hexane (150 mL) cooled in an ice bath, and the solid was dried under reduced pressure to obtain Compound 11 (6.6 g, yield 37%) as a white solid.

Example C2
Under a nitrogen gas atmosphere, a THF solution (80 mL) of compound 11 (7.1 g, 20 mmol) was added to a 100 mL two-necked flask containing NaH (600 mg, 25 mmoll) and THF (20 mL) at room temperature. Stir for 34 hours. The solvent was distilled off under reduced pressure, THF was added in the glove box, excess NaH was removed by filtration, and the filtration was concentrated under reduced pressure to obtain a white solid. The solid was crushed and azeotropically added with hexane to obtain Compound 12 (7.5 g, yield 100%) as a powdery solid.
(Compound 12 )
sodium N, N'-di (2,6-diisopropylphenyl) formimidamidinate Na [Ar-NCHN-Ar]: Ar = 2,6- ⁱ Pr ₂ -C ₆ H _3-
¹ H NMR (400 MHz, THF-d ₈ , rt, δ / ppm): 1.07 (d, J = 6.8 Hz, 24 H, -CH ₃ ), 3.58 (obscured by residual protonated THF, 4 H, (CH ₃ ) ₂ CH-), 6.63 (t, J = 7.4 Hz, 2 H, 4-CH), 6.84 (d, J = 7.4 Hz, 4 H, 3-CH), 7.38 (s, 1H, -CH).

Example C3
In a glove box, 12 (37 mg, 0.1 mmol) was dissolved in THF-d ₈ (0.4 mL), added to a pressure resistant NMR tube, and TFE (2.0 atm, 0.2 mmol) was pressurized. After standing at 0 ° C. for 17 hours, TFE was degassed, and NMR was measured to confirm the formation of Compound 13 .
(Compound 13 )
N, N'-di (2,6-diisopropylphenyl) -N- (1,2,2-trifluorovinyl) formimidamide [CF ₂ = CF (Ar) -NCHN-Ar]
Ar = 2,6- ⁱ Pr ₂ -C ₆ H _3-
¹⁹ F NMR (376 MHz, THF / THF-d ₈ , rt, δ / ppm): -111.3 (dd, J = 41.4, 78.3 Hz, 1F), -116 to -124 (br, 1F), -140 ~ -150 (br, 1F).

Example C4
In a glove box, Compound 12 (740 mg, 2 mmol) was dissolved in THF (10 mL), added to the autoclave (50 mL), and TFE (2.0 atm, 600 mg, 6 mmol) was pressurized. After stirring at 0 ° C. for 20 hours, TFE was degassed, the solid was removed by filtration, the solid was washed with THF, and the washing was combined with the filtrate. There _{LiBF 4 (186 mg, 2 mmol} ) and the mixture was stirred at 60 ° C. 10 hours. When the solvent was distilled off under reduced pressure, a white solid was precipitated. The solid was washed with THF (20 mL), and components soluble in CHCl ₃ were extracted. The solvent was distilled off under reduced pressure to obtain Compound 14 (470 mg, yield 46%) as a white solid.
(Compound 14 )
1,3-dimesityl-4,5-difluoro-imidazolium tetrafluoroborate
¹ H NMR (400 MHz, CDCl ₃ , rt, δ / ppm): 1.29 (d, J = 7.2 Hz, 12 H, -CH ₃ ), 1.30 (d, J = 7.2 Hz, 12 H, -CH ₃ ) , 2.43 (qq, J = 7.2, 7.2 Hz, 4 H, (CH ₃ ) ₂ CH-), 7.39 (d, J = 8.0 Hz, 4 H, 3-CH), 7.64 (t, J = 8.0 Hz, 2 H, 4-CH), 9.45 (t, J = 2.0 Hz, 1H, -CH).
^{19 F NMR (376 MHz, CDCl} 3, rt, δ / ppm): -154.8 (br, 4F, BF 4 -), -156.6 (s, 2F, = CF-).

Example C5
Under a nitrogen gas atmosphere, Compound 14 (53 mg, 0.1 mmol), NaHMDS (18 mg, 0.1 mmol), and THF (about 20 mL) were added to a 100 mL eggplant flask and stirred at room temperature for 4 hours. The solvent was distilled off under reduced pressure, followed by extraction with toluene, the solid was removed by filtration, and the filtrate was evaporated to dryness in vacuo for 4 hours to remove HMDS (bp 126 ° C.), whereby compound 15 (27 mg, 27 mg, Yield 64%) was obtained.
The generation of carbene was confirmed by ¹³ C NMR.
(Compound 15 )
1,3-bis (2,6-diisopropylphenyl) -4,5-difluoro-imidazolidene (IPrF)
¹ H NMR (400 MHz, C ₆ D ₆ , rt, δ / ppm): 1.19 (d, J = 6.8 Hz, 12 H, -CH ₃ ), 1.26 (d, J = 6.8 Hz, 12 H, -CH ₃ ), 3.04 (qq, J = 6.8, 6.8 Hz, 4 H, (CH ₃ ) ₂ CH-), 7.14 (d, J = 7.8 Hz, 4 H, 3-CH), 7.26 (t, J = 7.8 Hz, 2 H, 4-CH).
¹⁹ F NMR (376 MHz, C ₆ D ₆₃ , rt, δ / ppm): -163.2 (s, 2F, = CF-).
¹³ C NMR (100 MHz, C ₆ D ₆₃ , rt, δ / ppm): 206.7 (t, 3JCF = 22.8 Hz, NCN), 147.0 (s, oC), 133.4 (s, ipso-C), 130.1 (s , pC), 129.9 (dd, 1JCF = 268.0, 3JCF = 26.6Hz, N = CF), 124.1 (s, mC), 29.2 (s, -CH), 24.5 (s, -CH3), 23.3 (s,- CH3).

Example C6
In a glove box, compound 14 (53 mg, 0.10 mmol) was suspended in THF (10 mL) and added to a 50 mL eggplant flask. A solution of KO ^t Bu (13 mg, 0.12 mmol) in THF (10 mL) was added thereto and stirred at room temperature for 60 hours. The solvent was distilled off under reduced pressure, the solid was removed by toluene extraction and filtration, and the filtrate was concentrated under reduced pressure to obtain a yellow oily substance. Pentane was added thereto and azeotroped to obtain Compound 15 (44 mg, 100% yield) as a yellow solid.

Example D1
Compound 15 (IPrF) (11.3 mg, 0.027 mmol) and 0.6 ml of heavy benzene were placed in a pressure-resistant NMR tube, and Ni (cod) ₂ (24 mg, 0.08 mmol) was added. Subsequently, carbon monoxide (3 atm, 0.3 mmol) was pressurized and reacted at room temperature for 30 minutes. Carbon monoxide was degassed, the solvent was distilled off under reduced pressure, the solid was removed by toluene extraction and filtration, and the filtration was concentrated under reduced pressure to obtain a gray solid (17 mg). When purified by recrystallization (THF / hexane, -36 ° C.), colorless transparent crystals Ni (CO) 3 (IPrF) were precipitated. The obtained colorless and transparent crystals (0.50 × 0.12 × 0.12 mm) were mounted on a single crystal X-ray diffractometer Rigaku R-AXIS RAPID, and diffraction data were measured at −150 ° C. The results are shown in FIG.
Ni (CO) ₃ (IPrF): IPrF = 1,3-bis (2,6-diisopropylphenyl) -4,5-difluoro-imidazolidene
¹ H NMR (400 MHz, C ₆ D ₆ , rt, δ / ppm): 1.08 (d, J = 6.4 Hz, 12 H, -CH ₃ ), 1.20 (d, J = 6.4 Hz, 12 H, -CH ₃ ), 2.84 (qq, J = 6.4, 6.4 Hz, 4 H, (CH ₃ ) ₂ CH-), 7.11 (d, J = 7.8 Hz, 4 H, 3-CH), 7.26 (t, J = 7.8 Hz, 2 H, 4-CH).
¹⁹ F NMR (376 MHz, C ₆ D ₆₃ , rt, δ / ppm): -158.8 (s, 2F, = CF-).

Example E1: Synthesis of IMesF
In a glove box, compound e5 (50 mg, 0.11 mmol) and KO ^t Bu (15 mg, 0.13 mmol) were added to a 50 mL eggplant flask, and toluene (10 mL) was added. After stirring at room temperature for 4 hours, the white suspension gradually turned into a yellow solution, and a colorless transparent solid was deposited on the wall of the eggplant flask. The solid was removed by filtration, the solid was washed with toluene (10 mL), the filtrate and the washing were combined, and this was concentrated under reduced pressure to give yellow solid IMesF (31 mg, 79%).
¹ H NMR (400 MHz, C ₆ D ₆ , rt, δ / ppm): 2.09 (s, 6H, p-CH ₃ ), 2.16 (s, 12H, o-CH ₃ ), 6.73 (s, 4H, m ¹³ C NMR (100 MHz, C ₆ D ₆ , rt, δ / ppm): 17.9 (s, o-CH ₃ ), 21.0 (s, p-CH ₃ ), 129.4 (s, m-CH ), 128-130.7 (dd, ¹ J _CF = 260 Hz, ² J _CF = 26.3 Hz, backbone), 133.7 (s, ipso-C), 136.1 (s, o-CCH ₃ ), 138.7 (s, p- CH), 205.5 (t, ³ J _CF = 22.7 Hz). ¹⁹ F NMR (376 MHz, C ₆ D ₆ , rt, δ / ppm): -163.7 (s, 2F, backbone).

Example F1: Reaction of amidinate with perfluorobenzene
In the glove box, N, N′-bis (2,6-diisopropylphenyl) formamidinate (compound f1) (193.3 mg, 1.0 mmol) was dissolved in THF (8 mL). perfluorobenzene (560.0 mg, 3.0 mmol) was added and reacted at 40 ° C. for 10 hours. The solution was concentrated under reduced pressure to give a brown highly viscous solid. This was washed with a small amount of hexane and dried under reduced pressure to obtain a milky white solid. Toluene (30 mL) was added and filtered, and the filtrate was dried under reduced pressure to obtain Compound f2 (313 mg, 59%) as a milky white solid.
Spectral Data
N, N'-bis (2,6-diisopropylphenyl) -N- (2,3,4,5,6-pentafluorophenyl) formimidamide [C ₆ F ₅ (Ar) -NCHN-Ar] (2): Ar = 2 , 6- ⁱ Pr ₂ -C ₆ H _3-
¹ H NMR (400 MHz, THF-d ₈ , rt, δ / ppm): 1.11 (d, J = 7.2 Hz, 24H, -CH ₃ ), 3.20 (m, 2H, (CH ₃ ) ₂ CH-), 3.29 (m, 2H, (CH ₃ ) ₂ CH-), 6.92 (t, J = 7.4 Hz, 1H, 4-CH), 7.02 (d, J = 7.6 Hz, 2H, 3-CH), 7.25 (d , J = 7.6 Hz, 2H, 3-CH), 7.34 (t, J = 7.6 Hz, 1H, 4-CH). ¹⁹ F NMR (376 MHz, THF-d ₈ , rt, δ / ppm): -143.6 (br, 2F), -163.1 (br, 1F), -167.7 (br, 2F).

Example F2: NHC salt synthesis using BF ₃ -Et ₂ O (JY NMR tube experiment)

In a glove box, compound f2 (26.5 mg, 0.05 mmol), BF ₃ -Et ₂ O (7.1 mg, 0.05 mmol) and C ₆ D ₆ (0.4 mL) were added to an NMR tube equipped with a vacuum valve. The undissolved residue of compound f2 was observed in the tube. The tube was heated to 80 ° C. and the reaction was followed using ¹ H, ¹⁹ F NMR. When reacted at 80 ° C. for 40 hours, a colorless transparent solid of compound f3 precipitated in the tube. The solid obtained by distilling off the solvent under reduced pressure was washed with hexane (1 mL × 2 times) and THF (0.5 mL × 2 times) to obtain a white solid (20.9 mg, 70%) of compound f3. .
Spectral Data
1,3-bis (2,6-diisopropylphenyl) -4,5,6,7-tetrafluorobenzimidazolium tetrafluoroborate (f3):
¹ H NMR (400 MHz, THF-d ₈ , rt, δ / ppm): 1.22 (d, J = 6.8 Hz, 24H, -CH ₃ ), 2.58 (m, 4H, (CH ₃ ) ₂ CH-), 7.51 (d, J = 8.0 Hz, 4H, 3-CH), 7.69 (t, J = 7.8 Hz, 2H, 4-CH), 10.3 (s, 1H, NCHN). ¹⁹ F NMR (376 MHz, THF- d ₈ , rt, δ / ppm): -158.8 (m, 2F), -160.2 (s, 4F, BF ₄ ), -163.7 (m, 2F). ¹¹ B NMR (128 MHz, THF-d ₈ , rt , δ / ppm): -3.38 (s).

Example F3: Synthesis of carbene species
In a glove box, compound f3 (298.0 mg, 0.50 mmol) and toluene (10 mL) were added to a 50 mL eggplant flask. In the flask, the undissolved residue of compound f3 was observed. When LiHMDS (83.7 mg, 0.50 mmol) was added thereto, the color of the solution remained colorless and transparent, but white wrinkles that seemed to be LiBF ₄ were formed. After stirring at room temperature for 1 hour, the solvent was distilled off under reduced pressure, and components soluble in hexane (20 mL × 3 times) were extracted from the resulting solid. When the hexane solution was concentrated under reduced pressure, a white solid (242.5 mg, 95%) was obtained.
Spectral Data
1,3-bis (2,6-diisopropylphenyl) -4,5,6,7-tetrafluorobenzimidazol-2-ylidene (BIPrF, f4):
¹ H NMR (400 MHz, C ₆ D ₆ , rt, δ / ppm): 1.14 (d, J = 6.8 Hz, 12H, -CH ₃ ), 1.23 (d, J = 6.8 Hz, 12H, -CH ₃ ) , 2.80 (m, 2H, (CH ₃ ) ₂ CH-), 7.18 (d, J = 8.0 Hz, 4H, 3-CH), 7.32 (d, J = 7.6 Hz, 2H, 4-CH). ¹⁹ F NMR (376 MHz, C ₆ D ₆ , rt, δ / ppm): -163.1 (m, 2F), -165.5 (m, 2F). ¹³ C { ¹ H} NMR (100 MHz, C ₆ D ₆ , rt , δ / ppm): 23.0, 24.7, 29.3, 122.6 (m), 124.0, 130.1, 133.8 (m), 137.7 (m), 146.3, 237.1 (m, NCN).

Example F4:
Synthesis of nickel carbonyl NHC complex (pressure NMR tube experiment)

In the glove box, BIPrF (510.6 mg, 0.10 mmol), Ni (cod) ₂ (30.5 mg, 0.10 mmol) and C ₆ D ₆ (0.5 mL) were added to a pressure resistant NMR tube. When CO (3.5 atm) was pressurized, the color of the solution changed from dark red to colorless and transparent. After standing at room temperature for 1 hour, the solvent was distilled off under reduced pressure to obtain a white solid (65.4 mg, quant.) Of Ni (CO) ₃ (BIPrF).
Spectral Data
Ni (CO) ₃ (BIPrF): BIPrF = 1,3-bis (2,6-diisopropylphenyl) -4,5,6,7-tetrafluorobenzimidazol-2-ylidene
¹ H NMR (400 MHz, C ₆ D ₆ , rt, δ / ppm): 1.14 (d, J = 6.8 Hz, 12H, -CH ₃ ), 1.23 (d, J = 6.8 Hz, 12H, -CH ₃ ) , 2.80 (m, 2H, (CH ₃ ) ₂ CH-), 7.18 (d, J = 8.0 Hz, 4H, 3-CH), 7.32 (d, J = 7.6 Hz, 2H, 4-CH). ¹⁹ F NMR (376 MHz, C ₆ D ₆ , rt, δ / ppm): -163.1 (m, 2F), -165.5 (m, 2F). ¹³ C { ¹ H} NMR (100 MHz, C ₆ D ₆ , rt , δ / ppm): 23.2, 24.4, 29.2, 122.8 (m), 124.7, 131.2, 133.5 (m), 135.3, 138.2 (m), 146.1, 196.6 (CO), 215.2 (NCN).
IR (in hexane, CO): 2061 cm ^-1 , 1992 cm ^-1 , 1983 cm ^-1

Example G1: Imidazolium salt synthesis using perfluorocyclopentene
(NMR tube experiment with vacuum valve)

In the glove box, N, N′-bis (2,6-diisopropylphenyl) formamidinate g1 (19.3 mg, 0.05 mmol) was dissolved in THF-d ₈ (0.4 mL) and added to the NMR tube with a vacuum valve. Α, α, α-trifluorotoluene (1.0 μL) was added as an internal standard. Perfluorocyclopentene (31.8 mg, 0.15 mmol) was added thereto, and allowed to stand at room temperature, and ¹ H, ¹⁹ F NMR was measured. When perfluorocyclopentene was added, the color of the solution changed from light yellow to dark yellow. In addition, a transparent solid that seems to be NaF was deposited in the tube. ^{From 19} F NMR measurement, it was confirmed that the compound g2 was produced (105%, ¹⁹ F NMR Yield). The reaction solution was filtered, and the filtrate was added to an NMR tube equipped with a vacuum valve. LiBF ₄ (4..6 mg, 0.05 mmol) was added thereto and reacted at 60 ° C. for 10 hours. There was no change in the color of the solution before and after adding LiBF ₄ . After 10 hours of reaction, a white precipitate that appeared to be LiF was formed in the tube. Formation of imidazolium (3) was confirmed by drying the solution under reduced pressure, extracting by adding CDCl ₃ and measuring NMR. Thereafter, the solution in the tube was transferred to an eggplant flask and dried under reduced pressure to obtain Compound g3 (31.2 mg, 100%, crude) as a pale yellow solid.
Spectral Data
N, N'-bis (2,6-diisopropylphenyl) -N- (2,3,3,4,4,5,5-heptafluorocyclopentenyl) formimidamide (g2):
¹ H NMR (400 MHz, THF-d ₈ , rt, δ / ppm): 1.12 (d, J = 6.8 Hz, 12H, -CH ₃ ), 1.21 (d, J = 6.4 Hz, 6H, -CH ₃ ) , 1.30 (d, J = 6.8 Hz, 6H), 2.95 (m, 2H, (CH ₃ ) ₂ CH-), 3.07 (m, 2H, (CH ₃ ) ₂ CH-), 7.00 (t, J = 7.4 Hz, 1H, 4-CH), 7.07 (d, J = 7.4 Hz, 2H, 3-CH), 7.32 (d, J = 7.6 Hz, 2H, 3-CH), 7.45 (t, J = 7.6 Hz, ¹⁹ F NMR (376 MHz, THF-d ₈ , rt, δ / ppm): -108.2 (m, 2F), -116.6 (m, 2F), -131.0 (s, 2F), -148.1 (br, 1F).
fluorocyclopentene-fused 1,3-bis (2,6-diisopropylphenyl) imidazolium tetrafluoroborate (g3):
¹ H NMR (400 MHz, CDCl ₃ , rt, δ / ppm): 1.29 (d, J = 7.2 Hz, 12H, -CH ₃ ), 1.31 (d, J = 7.2 Hz, 12H, -CH ₃ ), 2.22 (m, 2H, (CH ₃ ) ₂ CH-), 7.42 (d, J = 8.0 Hz, 4H, 3-CH), 7.68 (t, J = 7.8 Hz, 2H, 4-CH), 10.44 (s, ¹⁹ F NMR (376 MHz, CDCl ₃ , rt, δ / ppm): -111.3 (s, 4F), -122.8 (s, 2F), -153.6 (s, 4F, BF ₄ ).

Example G2: Synthesis of carbene species (NMR tube experiment with vacuum valve)

In a glove box, compound g3 (31.2 mg, 0.05 mmol) and KO ^t Bu (6.7 mg, 0.06 mmol) were weighed into a 100 mL eggplant flask, toluene (20 mL) was added, and the mixture was stirred at room temperature for 1 hour. After 1 hour, an orange suspension was formed, and a transparent solid which was thought to be KBF ₄ was precipitated. The solid was removed by filtration, and the filtrate was dried under reduced pressure to obtain Compound g4 (25.0 mg, 93%, crude) as a pale yellow solid.
Spectral Data
fluorocyclopentene-fused 1,3-bis (2,6-diisopropylphenyl) imidazol-2-ylidene (IPrF (CP), g4):
¹ H NMR (400 MHz, C ₆ D ₆ , rt, δ / ppm): 1.19 (d, J = 6.8 Hz, 12H, -CH ₃ ), 1.21 (d, J = 7.2 Hz, 12H, -CH ₃ ) , 2.80 (m, 2H, (CH ₃ ) ₂ CH-), 7.10 (d, J = 7.6 Hz, 4H, 3-CH), 7.22 (d, J = 7.8 Hz, 2H, 4-CH). ¹⁹ F NMR (376 MHz, C ₆ D ₆ , rt, δ / ppm): -109.5 (s, 4F), -120.5 (s, 2F). ¹³ C { ¹ H} NMR (100 MHz, C ₆ D ₆ , rt , δ / ppm): 22.3, 25.1, 28.3, 109.7 (m), 117.9 (m), 124.7, 130.7, 133.8, 134.6 (m), 146.0, 240.5 (m, NCN).

Example G3: Synthesis of nickel carbonyl NHC complex (pressure-resistant NMR tube experiment)
In the glove box, IPrF (CP) (10.7 mg, 0.02 mmol) and Ni (cod) ₂ (5.5 mg, 0.02 mmol) were dissolved in C ₆ D ₆ (0.5 mL) and added to a pressure resistant NMR tube. Α, α, α-trifluorotoluene (2.0 μL) was added as an internal standard, and CO (3.0 atm,> 0.2 mmol) was pressurized. After standing at room temperature for 1 hour, ¹ H NMR and ¹⁹ F NMR were measured. After that, the reaction solution was concentrated under reduced pressure to obtain a gray solid (15.6 mg, crude,> 100%). This was purified by recrystallization (hexane, −37 ° C.) to obtain a gray solid (13.0 mg, 96%).
Spectral Data (NMR: 2017/10/14)
Ni (CO) ₃ (IPrF (CP)):
¹ H NMR (400 MHz, C ₆ D ₆ , rt, δ / ppm): 1.11 (d, J = 6.8 Hz, 12H, -CH ₃ ), 1.31 (d, J = 6.4 Hz, 12H, -CH ₃ ) , 2.67 (m, 4H, (CH ₃ ) ₂ CH-), 7.08 (d, J = 7.6 Hz, 4H, 3-CH), 7.22 (d, J = 7.6 Hz, 2H, 4-CH). ¹⁹ F NMR (376 MHz, C ₆ D ₆ , rt, δ / ppm): -109.0 (t, J = 3.6 Hz, 4F), -123.7 (m, 2F). ¹³ C { ¹ H} NMR (100 MHz, C ₆ D ₆ , rt, δ / ppm): 23.9, 24.5, 29.2, 109.9 (m), 116.9 (m), 125.2, 131.7, 133.2, 134.8 (m), 146.1, 196.3 (CO), 218.6 (NCN).
IR (in hexane, CO): 2063 cm ^-1 , 1991 cm ^-1 , 1985 cm ^-1

Claims (14)

Formula (1):
[Where:
A represents CR ^p , a carbene carbon, or C═R ^A ,
--- is a double bond when A is CR ^p , while it is a single bond when A is a carbene carbon;
R ^A represents O, S, or NR;
R ^p represents a hydrogen atom or an organic group,
R is the same or different at each occurrence and represents a hydrogen atom or an organic group;
R ^X represents a hydrogen atom, a fluorine atom, a chlorine atom, Rf, or ORf;
R ^Y represents a fluorine atom, or Rf, or R ^X and R ^Y together with two adjacent carbon atoms form a hydrocarbon ring having one or more fluorine atoms. And Rf represents a fluoroalkyl group or a ring having one or more fluorine atoms. ]
Or a salt thereof. A is CR ^p, compound or salt thereof according to claim 1. ^Rp is a hydrogen atom, The compound of Claim 2, or its salt. The compound or its salt of Claim 1 whose A is carbene carbon. The compound or its salt of Claim 1 whose A is C = ^RA . 2. R is the same or different at each occurrence and is an aryl group which may have one or more substituents or a heteroaryl group which may have one or more substituents. The compound or its salt as described in any one of -5. ^RX is a fluorine atom, The compound or its salt as described in any one of Claims 1-6. It is a manufacturing method of the compound of Claim 2, Comprising:
Formula: R—NH—CH═N—R [wherein the symbols in the formula are as defined above. The compound represented by the above formula (F-) (R ^x- ) C = C (-R ^x ) ( -F) [wherein R ^X is the same or different at each occurrence and represents the same meaning as described above. A step of reacting with a compound represented by formula A2
Manufacturing method. It is a manufacturing method of the compound of Claim 3, Comprising:
A production method comprising the step B of reacting the compound according to claim 2 with a base to obtain the compound according to claim 3. A ligand comprising the compound according to claim 4. The catalyst containing the compound of Claim 4. The monomer which consists of a compound as described in any one of Claims 2-7. The polymer containing the structural unit derived from the monomer of Claim 12. The additive for electrolyte solutions which consists of a compound of Claim 2 or 5.