WO2023090086A1

WO2023090086A1 - Secondary monohydrofluoroalkane selective adduct and method for producing same

Info

Publication number: WO2023090086A1
Application number: PCT/JP2022/039834
Authority: WO
Inventors: 積森本; 裕亮東; 実生也鈴木; 萌細川; 洋介岸川
Original assignee: 国立大学法人奈良先端科学技術大学院大学; ダイキン工業株式会社
Priority date: 2021-11-19
Filing date: 2022-10-26
Publication date: 2023-05-25

Abstract

Provided are a secondary monohydrofluoroalkane selective adduct and a method for producing the same. A compound represented by formula (3) is produced by means of a method including a step for reacting a compound represented by formula (1) with a compound represented by formula (2) in the presence of a base. (In the formulae, R1, R2 and R3 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a hydrocarbon group which may have at least one substituent, -ORA, -CORA, -COOQ1, -CONRBRC, -NRBRC, -NH-CORA or -NH-COORA; RA represents a hydrocarbon group which may have at least one substituent; RB and RC each independently represent a hydrogen atom or a hydrocarbon group which may have at least one substituent, or RB and RC may be bound to each other to form a ring in conjunction with a nitrogen atom adjacent thereto; EWG represents an electron withdrawing group; two arbitrary radicals among R1, R2, R3 and EWG may be bound to each other to form a ring; and R4 and R5 each independently represent a fluoroalkyl group which may have at least one substituent and may contain an oxygen atom between carbon atoms therein, or a fluoroalkoxy group which may have at least one substituent and may contain an oxygen atom between carbon atoms therein, and R4 and R5 may be bound to each other to form a ring.)

Description

Selective adduct of secondary monohydrofluoroalkanes and method for producing the same

The present disclosure relates to selective adducts of secondary monohydrofluoroalkanes and methods for producing the same.

Since fluorine functional groups have mimic effects, blocking effects, and hydrophobic effects, fluorine functional groups are often introduced in the development of pharmaceuticals and agrochemicals. A heptafluoroisopropyl group ((CF ₃ ) ₂ CF group) and the like have higher functions, and are known to exhibit higher activity than the CF ₃ group when used in the insecticide flubendiamide, for example.

As a method for introducing a (CF ₃ ) ₂ CF group or the like into an ethylenically unsaturated compound (double bond), a method utilizing a radical addition reaction is known. For example, (CF ₃ ) ₂ CF groups are introduced into ethylenically unsaturated compounds by preparing (CF ₃ ) ₂ CFAg from AgF and hexafluoropropene (HFP) (Non-Patent Document 1).

The method of Non-Patent Document 1 has problems that AgF is expensive and usable reactants and substrates are limited. Methods for the addition, particularly regioselective addition, of secondary monohydrofluoroalkanes, rather than (CF ₃ ) ₂ CFAg, to ethylenically unsaturated compounds have not been investigated so far.

The main object of the present disclosure is to provide a selective adduct of secondary monohydrofluoroalkanes and a method for producing the same.

The present disclosure includes the following aspects.
Section 1.
Formula (3) below:

(In the formula,
R ¹ , R ² , and R ³ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a hydrocarbon group optionally having one or more substituents, —OR ^A , —COR ^A , -COOR ^A , -CONR ^B R ^C , -NR ^B R ^C , -NH-COR ^A , or -NH-COOR ^A ;
^RA is a hydrocarbon group optionally having one or more substituents,
R ^B and R ^C are each independently a hydrogen atom or a hydrocarbon group optionally having one or more substituents, or R ^B and R ^C are adjacent nitrogen atoms bound to each other may form a ring with
EWG is an electron withdrawing group,
Any two of R ¹ , R ² , R ³ , and EWG may combine with each other to form a ring,
R ⁴ and R ⁵ each independently optionally have one or more substituents, a fluoroalkyl group optionally containing an oxygen atom between carbon atoms, or one or more substituents and a fluoroalkoxy group which may contain an oxygen atom between carbon atoms,
R ⁴ and R ⁵ may combine with each other to form a ring. )
A method for producing a compound represented by
Formula (1) below:

(Wherein, R ¹ , R ² , R ³ , and EWG are the same as above.)
and a compound represented by the following formula (2):

(In the formula, R ⁴ and R ⁵ are the same as above.)
A production method comprising the step of reacting a compound represented by in the presence of a base.
Section 2.
Item 2. The production method according to Item 1, wherein the pKa of the base is in the range of 10-20.
Item 3.
The base is a quaternary ammonium salt, MHF _p (where M is Na, K, or Cs and p is a number corresponding to the valence), and MF (where M is Na, K , or Cs).
Section 4.
Item 4. The production method according to any one of Items 1 to 3, wherein the base comprises a quaternary ammonium salt.
Item 5.
Item 3 or 4, wherein the quaternary ammonium salt is at least one selected from the group consisting of tetrabutylammonium fluoride, tetrabutylammonium hydroxide, tetramethylammonium fluoride, and tetramethylammonium hydroxide. manufacturing method.
Item 6.
In the above formulas (1) and (3),
EWG is —COOR ⁶ , —COR ⁶ , —SO _n R ⁶ , —CONR ⁷ R ⁸ , —PO(OR ⁹ )(OR ¹⁰ ), or a cyano group;
R ⁶ is a C _1-12 hydrocarbon group optionally having one or more substituents,
R ⁷ and R ⁸ are each independently a hydrogen atom or a C _1-12 hydrocarbon group optionally having one or more substituents,
R ⁹ and R ¹⁰ are each independently a hydrogen atom or a C _1-12 hydrocarbon group optionally having one or more substituents,
n is 1 or 2;
Item 6. The production method according to any one of Items 1 to 5.
Item 7.
In the above formulas (1) and (3),
Any one of items 1 to 6, wherein R ¹ , R ² and R ³ are each independently a hydrogen atom or a C _1-12 hydrocarbon group optionally having one or more substituents The manufacturing method described in .
Item 8.
In the above formulas (2) and (3),
R ⁴ and R ⁵ are each independently a fluoroC _1-10 alkyl group or a fluoroC _1-10 alkoxy group;
Item 8. The production method according to any one of Items 1 to 7.
Item 9.
Item 9. The production method according to any one of items 1 to 8, wherein the compound represented by formula (2) is 1,1,1,2,3,3,3-heptafluoropropane.
Item 10.
Item 10. The production method according to any one of Items 1 to 9, wherein the reaction is carried out in a solvent.
Item 11.
Item 11. The production method according to Item 10, wherein the solvent is at least one selected from the group consisting of hydrocarbon solvents, ether solvents, amide solvents, sulfoxide solvents, and nitrile solvents.
Item 12.
Formula (3A) below:

[In the formula,
R ³¹ is a hydrogen atom or a C _1-12 hydrocarbon group optionally having one or more substituents,
R ⁶¹ is a C _1-12 alkyl group optionally having one or more substituents, a cycloalkyl group optionally having one or more substituents, or having one or more substituents is an aryl group that may be (However, _when ^R61 is a C4 alkyl group optionally having one or more substituents, the _C4 alkyl group is a branched _C4 alkyl group.)]
A compound represented by
Item 13.
The following formula (3B):

[In the formula,
R ³² is a hydrogen atom or a C _1-12 hydrocarbon group optionally having one or more substituents,
R ⁷¹ and R ⁸¹ are each independently a C _1-12 alkyl group optionally having one or more substituents, or an aryl group optionally having one or more substituents . (However, R ⁷¹ and R ⁸¹ are not _C2 alkyl groups optionally having one or more substituents at the same time.)]
A compound represented by
Item 14.
Formula (4) below:

(In the formula,
R ¹¹ , R ¹² and R ¹³ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a hydrocarbon group optionally having one or more substituents, —OR ^A , —COR ^A , -COOR ^A , -CONR ^B R ^C , -NR ^B R ^C , -NH-COR ^A , or -NH-COOR ^A ;
^RA is a hydrocarbon group optionally having one or more substituents,
R ^B and R ^C are each independently a hydrogen atom or a hydrocarbon group optionally having one or more substituents, or R ^B and R ^C are adjacent nitrogen atoms bound to each other may form a ring with
R ¹⁶ is an electron withdrawing group,
Any two of R ¹¹ , R ¹² , R ¹³ and R ¹⁶ may be bonded to each other to form a ring,
R ¹⁴ and R ¹⁵ each independently optionally have one or more substituents, a fluoroalkyl group optionally containing an oxygen atom between carbon atoms, or one or more substituents is a fluoroalkoxy group which may contain an oxygen atom between the carbon atoms, and R ¹⁴ and R ¹⁵ may be bonded to each other to form a ring,
m is 2 or 3; )
A compound represented by
Item 15.
Formula (3) below:

(In the formula,
R ¹ , R ² , and R ³ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a hydrocarbon group optionally having one or more substituents, —OR ^A , —COR ^A , -COOR ^A , -CONR ^B R ^C , -NR ^B R ^C , -NH-COR ^A , or -NH-COOR ^A ;
^RA is a hydrocarbon group optionally having one or more substituents,
R ^B and R ^C are each independently a hydrogen atom or a hydrocarbon group optionally having one or more substituents,
EWG is an electron withdrawing group,
Any two of R ¹ , R ² , R ³ , and EWG may combine with each other to form a ring,
R ⁴ and R ⁵ each independently optionally have one or more substituents, a fluoroalkyl group optionally containing an oxygen atom between carbon atoms, or one or more substituents and a fluoroalkoxy group optionally containing an oxygen atom between carbon atoms,
R ⁴ and R ⁵ may combine with each other to form a ring. )
A compound represented by
Formula (4) below:

(In the formula,
R ¹¹ , R ¹² and R ¹³ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a hydrocarbon group optionally having one or more substituents, —OR ^A , —COR ^A , -COOR ^A , -CONR ^B R ^C , -NR ^B R ^C , -NH-COR ^A , or -NH-COOR ^A ;
^RA is a hydrocarbon group optionally having one or more substituents,
R ^B and R ^C are each independently a hydrogen atom or a hydrocarbon group optionally having one or more substituents, or R ^B and R ^C are adjacent nitrogen atoms bound to each other may form a ring with
R ¹⁶ is an electron withdrawing group,
Any two of R ¹¹ , R ¹² , R ¹³ and R ¹⁶ may be bonded to each other to form a ring,
R ¹⁴ and R ¹⁵ each independently optionally have one or more substituents, a fluoroalkyl group optionally containing an oxygen atom between carbon atoms, or one or more substituents is a fluoroalkoxy group which may contain an oxygen atom between the carbon atoms, and R ¹⁴ and R ¹⁵ may be bonded to each other to form a ring,
m is 2 or 3; )
A composition containing a compound represented by
Item 16.
Item 16. The composition according to Item 15, containing 0.0001 to 150 parts by mass of the compound represented by Formula (4) per 100 parts by mass of the compound represented by Formula (3).
Item 17.
17. The composition according to Item 15 or 16, containing 0.0001 to 100 parts by mass of the compound represented by Formula (4) per 100 parts by mass of the compound represented by Formula (3).
Item 18.
Item 18. The composition according to any one of items 15 to 17, containing 0.0001 to 50 parts by mass of the compound represented by the formula (4) with respect to 100 parts by mass of the compound represented by the formula (3). thing.
Item 19.
Formula (5) below:

(In the formula,
R ²¹ , R ²² and R ²³ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a hydrocarbon group optionally having one or more substituents, —OR ^A , —COR ^A , -COOR ^A , -CONR ^B R ^C , -NR ^B R ^C , -NH-COR ^A , or -NH-COOR ^A ;
^RA is a hydrocarbon group optionally having one or more substituents,
R ^B and R ^C are each independently a hydrogen atom or a hydrocarbon group optionally having one or more substituents, or R ^B and R ^C are adjacent nitrogen atoms bound to each other may form a ring with
Any two of R ²¹ , R ²² , and R ²³ may combine with each other to form a ring,
R ²⁴ and R ²⁵ each independently optionally have one or more substituents, a fluoroalkyl group optionally containing an oxygen atom between carbon atoms, or one or more substituents is a fluoroalkoxy group which may contain an oxygen atom between the carbon atoms, and R ²⁴ and R ²⁵ may be bonded to each other to form a ring,
R ²⁶ is —OR ²⁷ or —NR ²⁸ R ²⁹ ;
R ²⁷ is a hydrocarbon group optionally having one or more substituents,
R ²⁸ and R ²⁹ are each independently a hydrogen atom or a hydrocarbon group optionally having one or more substituents. )
Item 15 that does not contain the compound represented by or contains more than 0 parts by mass and 50 parts by mass or less of the compound represented by the formula (5) with respect to 100 parts by mass of the compound represented by the formula (3) 19. The composition of any one of claims 1-18.

The present disclosure provides selective adducts of secondary monohydrofluoroalkanes and methods for producing the same.

All publications, patents and patent applications cited herein are hereby incorporated by reference as is.

<Term>
Unless otherwise specified, the symbols and abbreviations in this specification can be understood in accordance with the context of this specification and have meanings commonly used in the technical field to which this disclosure belongs.

In this specification, the phrase "contains" is intended to include the phrase "consisting essentially of" and the phrase "consisting of".

Any step, treatment, or operation described herein may be performed at room temperature unless otherwise specified.

In this specification, room temperature can mean a temperature within the range of 10-40°C.

In the present specification, the notation “C _nm ” (where n and m are each positive integers and n<m) means that the number of carbon atoms is n, as is commonly understood by those skilled in the art. It is equal to or greater than m and equal to or less than m.

As used herein, the term "hydrocarbon group" is a concept that includes both saturated hydrocarbon groups and unsaturated hydrocarbon groups. Examples of "hydrocarbon groups" include alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups, cycloalkadienyl groups, aryl groups, and aralkyl groups.

As used herein, the "alkyl group" includes, for example, methyl group, ethyl group, propyl group (n-propyl group, isopropyl group), butyl group (n-butyl group, isobutyl group, sec-butyl group, tert- butyl group), pentyl group, and hexyl group, straight or branched C _1-20 alkyl groups, and the like.

As used herein, the "alkenyl group" includes, for example, vinyl group, 1-propen-1-yl group, 2-propen-1-yl group, isopropenyl group, 2-buten-1-yl group, 4- Linear or branched C _2-20 alkenyl groups such as penten-1-yl group and 5-hexen-1-yl group are included.

As used herein, the "alkynyl group" includes, for example, ethynyl group, 1-propyn-1-yl group, 2-propyn-1-yl group, 4-pentyn-1-yl group, and 5-hexyne-1 and straight or branched chain C _2-20 alkynyl groups such as -yl groups.

As used herein, the “cycloalkyl group” includes, for example, C _3-10 cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and adamantyl groups.

As used herein, the “cycloalkenyl group” includes, for example, C _3-10 cycloalkenyl groups such as cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, and cycloheptenyl group.

As used herein, the "cycloalkadienyl group" includes, for example, a cyclobutadienyl group, a cyclopentadienyl group, a cyclohexadienyl group, a cycloheptadienyl group, a cyclooctadienyl group, and a cyclononadienyl group. and C _4-10 cycloalkadienyl groups such as cyclodecadienyl groups.

As used herein, an "aryl group" can be, for example, monocyclic, bicyclic, tricyclic, or tetracyclic. The “aryl group” includes, for example, C _6-18 aryl groups such as phenyl group, 1-naphthyl group, 2-naphthyl group, 2-biphenyl group, 3-biphenyl group, 4-biphenyl group and 2-anthryl group. and the like.

As used herein, the "aralkyl group" includes, for example, a benzyl group, a phenethyl group, a diphenylmethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 2,2-diphenylethyl group, a 3-phenylpropyl group, and C _7-19 aryl groups such as 4-phenylbutyl, 5-phenylpentyl, 2-biphenylmethyl, 3-biphenylmethyl, and 4-biphenylmethyl groups.

In the present specification, the substituents of the "hydrocarbon group optionally having one or more substituents" include, for example, halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, a hydroxyl group, mercapto group, amino group, nitro group, cyano group and the like. The number of substituents is, for example, one or more and the maximum substitutable number or less (eg, 2, 3, 4, or 5). Examples of the "hydrocarbon group optionally having one or more substituents" include haloalkyl groups, hydroxyalkyl groups and the like. The "haloalkyl group" may be, for example, the above "alkyl group" substituted with one or more halogen atoms. The "hydroxyalkyl group" may be, for example, the above "alkyl group" substituted with one or more hydroxyl groups.

As used herein, the term "fluoroalkyl group" is a concept that includes both non-perfluoroalkyl groups and perfluoroalkyl groups. The "fluoroalkyl group" may be, for example, the above "alkyl group" substituted with one or more fluorine atoms. As the "fluoroalkyl group optionally containing an oxygen atom between carbon atoms", for example,
_CF3- ,
CH ₃ —CF ₂ —,
CHF ₂ -CH ₂ -,
CF ₃ —CH ₂ —,
CF ₃ -CF ₂ -,
CF ₃ —CF ₂ —CH ₂ —,
CF ₃ -CF ₂ -CF ₂ -,
(CF ₃ ) ₂ CF-,
CF ₃ —O—CF ₂ —,
CF ₃ —O—CF(CF ₃ )—,
CF ₃ -CF ₂ -CF ₂ -CF ₂ -,
CF ₃ -CF ₂ -CF(CF ₃ )-CF ₂ -,
CF ₃ —O—CH ₂ —CH ₂ —,
CF ₃ —O—CH(CF ₃ )—CH ₂ —,
CF ₃ -O-CF ₂ -CF ₂ -,
(CF ₃ CF ₂ )(CF ₂ )CF-,
(CF ₃ ) ₃ C-,
CF ₃ -CF ₂ -O-CF ₂ -,
CF ₃ -CF ₂ -CF ₂ -CF ₂ -CF ₂ -,
CF ₃ -CF ₂ -O-CF ₂ -CF ₂ -,
CF ₃ —O—CF ₂ —O—CF ₂ —,
CF ₃ -CF ₂ -CF ₂ -CF ₂ -CF ₂ -CF ₂ -,
CF ₃ -CF ₂ -CF ₂ -O-CH ₂ -CF ₂ -,
CF ₃ -CF ₂ -CF ₂ -O-CF ₂ -CF ₂ -,
CF ₃ -CF ₂ -CF ₂ -CF ₂ -CF ₂ -CF ₂ -CF ₂ -,
CF ₃ -CF ₂ -CF ₂ -CF ₂ -CF ₂ -CF ₂ -CF ₂ -CF ₂ -,
_CHF2 - _CF2 - _CF2 - _CF2 - _CF2 - _CF2 - _CF2 - _CH2- ,
CF ₃ -CF(CF ₃ )-CF ₂ -,
CF ₃ -CF ₂ -CF(CF ₃ )-,
CF ₃ -CF ₂ -CF ₂ -O-CF(CF ₃ )-CF ₂ -,
CF ₃ -CF ₂ -CF ₂ -O-CF(CF ₃ )-CF ₂ -O-CF(CF ₃ )-CF ₂ - and CF ₃ -CF ₂ -CF ₂ -O-[CF(CF ₃ ) -CF ₂ -O-] ₂ -CF(CF ₃ )-CF ₂ -
Linear or branched fluoroC _1-10 alkyl groups, fluoroC _1-4 _{alkoxyfluoroC 1-4 alkyl groups, fluoroC 1-4} _{alkoxyfluoroC} _1-4 alkoxyfluoroC _{1- 4-} alkyl group and the like. "A fluoroalkyl group which may have one or more substituents and which may contain an oxygen atom between carbon atoms" means the above "fluoroalkyl group which may contain an oxygen atom between carbon atoms" ” has one or more substituents (e.g., hydroxyl group, mercapto group, amino group, nitro and at least one selected from a cyano group, etc.).

As used herein, the term "fluoroalkoxy group" is a concept that includes both non-perfluoroalkoxy groups and perfluoroalkoxy groups. As the "fluoroalkoxy group optionally containing an oxygen atom between carbon atoms", for example,
CF ₃ —O—,
CF ₃ —CH ₂ —O—,
CF ₃ -CF ₂ -O-,
CF ₃ -CF ₂ -CF ₂ -O-,
CF ₃ -CF ₂ -CF ₂ -CF ₂ -O-,
CF ₃ —O—CF ₂ —O—,
CF ₃ -O-CF ₂ -CF ₂ -CF ₂ -O-,
CF ₃ —O—CH ₂ —CF ₂ —CF ₂ —O—
CF ₃ -CF ₂ -O-CF ₂ -CF ₂ -O-,
_CF3 - _CF2 - _CF2 -O- _CH2 - _CF2 - _CF2 -O-,
CF ₃ -CF ₂ -CF ₂ -O-CF ₂ -CF ₂ -CF ₂ -O-,
CF ₃ -CF(CF ₃ )-O-,
CF ₃ -CF ₂ -CF(CF ₃ )-O-,
CF ₃ -CF(CF ₃ )-CF(CF ₃ )-O-,
CF ₃ -CF ₂ -CF ₂ -O-CF(CF ₃ )-CF ₂ -O-,
CF ₃ -CF ₂ -CF ₂ -O-[CF(CF ₃ )-CF ₂ -O-] ₂ -O- and CF ₃ -CF ₂ -CF ₂ -O-[CF(CF ₃ )-CF ₂ -O-] ₃ -O-
Linear or branched fluoro-C _1-10 alkoxy groups, fluoro-C _1-4 alkoxyfluoro-C _1-4 alkoxy groups, such as. "A fluoroalkoxy group which may have one or more substituents and which may contain an oxygen atom between carbon atoms" refers to the above "a fluoroalkoxy group which may contain an oxygen atom between carbon atoms" ” has one or more substituents (e.g., hydroxyl group, mercapto group, amino group, nitro and at least one selected from a cyano group, etc.).

As used herein, the term “electron-withdrawing group” refers to a functional group having a positive Hammett's substituent constant σp value. The definition of the σp value and the σp value of each functional group can be referred to, for example, Hansch, C et al., Chem. Rev., 91, pp. 165-195 (1991). As the "electron-withdrawing group", for example,
-COR,
-COOR,
-COSR,
_-CONH2 ,
-CONHR,
-CON(R) ₂ ,
-CSR,
—CSOR,
_-CSNH2 ,
—CSNHR,
-CSN(R) ₂ ,
-CN (cyano group),
-SOR,
—SO ₂ R, and —PO(OR) ₂
etc.
Here, R is a hydrocarbon group which may independently have one or more substituents. The substituent that can optionally be substituted on the hydrocarbon group is preferably an electron-withdrawing group. , -COR, -COOH, -COOR and the like. The number of substituents is, for example, one or more and the maximum substitutable number or less (eg, 2, 3, 4, or 5).

<Method for Producing Compound Represented by Formula (3)>
A method for producing a compound represented by formula (3) includes a step of reacting a compound represented by formula (1) with a compound represented by formula (2) in the presence of a base (hereinafter referred to as "step A”).

Compounds R ¹ , R ² and R ³ represented by formula (1) each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, or a hydrocarbon group optionally having one or more substituents. , -OR ^A , -COR ^A , -COOR ^A , -CONR ^B R ^C , -NR ^B R ^C , -NH-COR ^A , or -NH-COOR ^A .
In one embodiment, R ¹ , R ² , and R ³ are each independently preferably a hydrogen atom or a hydrocarbon group optionally having one or more substituents. It is more preferably a C _1-12 hydrocarbon group optionally having one or more substituents.
In another embodiment, R ¹ , R ² , and R ³ are each independently
hydrogen atom, alkyl group optionally having one or more substituents, cycloalkyl group optionally having one or more substituents, aryl optionally having one or more substituents or an aralkyl group optionally having one or more substituents,
A hydrogen atom, an alkyl group optionally having one or more substituents, an aryl group optionally having one or more substituents, or an aralkyl optionally having one or more substituents more preferably a group,
It is more preferably a hydrogen atom, an alkyl group optionally having one or more substituents, or an aryl group optionally having one or more substituents,
A hydrogen atom, a C _1-12 alkyl group optionally having one or more substituents, or a C _6-12 aryl group optionally having one or more substituents is particularly preferred.

Suitable combinations of R ¹ , R ² and R ³ include, for example,
(a) a combination in which R ¹ and R ² are hydrogen atoms and R ³ is a hydrocarbon group optionally having one or more substituents;
(b) R ¹ and R ² are hydrogen atoms, and R ³ is an alkyl group optionally having one or more substituents, an aryl group optionally having one or more substituents, or a combination that is an aralkyl group optionally having one or more substituents,
(c) R ¹ and R ² are hydrogen atoms, and R ³ is an alkyl group optionally having one or more substituents or an aryl group optionally having one or more substituents combination,
(d) one of R ¹ and R ² is a hydrogen atom and the other is a hydrocarbon group optionally having a hydroxyl group, -OR ^A , -COOR ^A , -NR ^B R ^C , -NH-COR ^A , or a combination of —NH—COOR ^A and R ³ is a hydrogen atom,
(e) one of R ¹ and R ² is a hydrogen atom and the other is an alkyl group optionally having one or more substituents, an aryl group optionally having one or more substituents, aralkyl group optionally having one or more substituents, hydroxyalkyl group optionally having one or more substituents, -OR ^A , -COOR ^A , -NR ^B R ^C , -NH- COR ^A , or a combination of —NH—COOR ^A and R ³ is a hydrogen atom;
(f) one of R ¹ and R ² is a hydrogen atom and the other is an alkyl group optionally having one or more substituents, an aryl group optionally having one or more substituents, a hydroxyalkyl group optionally having one or more substituents, -OR ^A , -COOR ^A , -NR ^B R ^C , -NH-COR ^A , or -NH-COOR ^A , and R ³ is hydrogen combinations that are atoms,
(g) Combinations in which R ¹ , R ² and R ³ are hydrogen atoms, and the like.

R ^A is a hydrocarbon group optionally having one or more substituents (eg, C _1-12 hydrocarbon group), preferably alkyl optionally having one or more substituents group (eg, C _1-12 alkyl group), aryl group optionally having one or more substituents (eg, C _6-12 aryl group), or having one or more substituents aralkyl group (eg, C _7-12 aralkyl group).

R ^B and R ^C are each independently a hydrogen atom or a hydrocarbon group optionally having one or more substituents (eg, a C _1-12 hydrocarbon group), preferably a hydrogen atom, Alkyl groups optionally having one or more substituents (eg C _1-12 alkyl groups), aryl groups optionally having one or more substituents (eg C _6-12 aryl groups ), or an aralkyl group optionally having one or more substituents (eg, a C _7-12 aralkyl group). R ^B and R ^C may combine with each other to form a ring together with the adjacent nitrogen atoms. Examples of the ring include pyrrole, piperidine, 1,3-dioxoisoindoline and the like.

EWG is an electron withdrawing group. EWG is preferably —COOR ⁶ , —COR ⁶ , —SO _n R ⁶ , —CONR ⁷ R ⁸ , —PO(OR ⁹ )(OR ¹⁰ ), or a cyano group, and —COOR ⁶ , —CONR ⁷ R ⁸ , —SO _n R ⁶ , —PO(OR ⁹ )(OR ¹⁰ ), or a cyano group is more preferred, and —COOR ⁶ , —CONR ⁷ R ⁸ , or a cyano group is even more preferred. The 1,4-addition reaction of the compound represented by the formula (2) can be selectively allowed to proceed with respect to the compound represented by the formula (1) having such an EWG, and the 1,2-addition The reaction can be partially or completely inhibited.

In one embodiment, R ⁶ is preferably a C _1-12 hydrocarbon group optionally having one or more substituents.
In another embodiment, R ⁶ is an alkyl group optionally having one or more substituents, a cycloalkyl group optionally having one or more substituents, It is preferably an aryl group which may have one or more substituents, or an aralkyl group which may have one or more substituents.
In yet another embodiment, R ⁶ is an alkyl group optionally having one or more substituents, an aryl group optionally having one or more substituents, or one or more substituents It is more preferably an aralkyl group optionally having one or more substituents, a C _1-12 alkyl group optionally having one or more substituents, a C ₆ optionally having one or more substituents _-12 aryl group or C _7-12 aralkyl group optionally having one or more substituents is more preferable.

In one embodiment, R ⁷ and R ⁸ are each independently preferably a hydrogen atom or a C _1-12 hydrocarbon group optionally having one or more substituents.
In another embodiment, R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group optionally having one or more substituents, optionally having one or more substituents A cycloalkyl group, an aryl group optionally having one or more substituents, or an aralkyl group optionally having one or more substituents is preferable, and a hydrogen atom, one or more substituents more preferably an alkyl group optionally having a group, an aryl group optionally having one or more substituents, or an aralkyl group optionally having one or more substituents, hydrogen atom, C _1-12 alkyl group optionally having one or more substituents, C _6-12 aryl group optionally having one or more substituents, or one or more substituents It is more preferably a C _7-12 aralkyl group optionally having

In one embodiment, R ⁹ and R ¹⁰ are each independently preferably a hydrogen atom or a C _1-12 hydrocarbon group optionally having one or more substituents.
In another embodiment, R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group optionally having one or more substituents, optionally having one or more substituents A cycloalkyl group, an aryl group optionally having one or more substituents, or an aralkyl group optionally having one or more substituents is preferable, and a hydrogen atom, one or more substituents more preferably an alkyl group optionally having a group, an aryl group optionally having one or more substituents, or an aralkyl group optionally having one or more substituents, hydrogen atom, C _1-12 alkyl group optionally having one or more substituents, C _6-12 aryl group optionally having one or more substituents, or one or more substituents It is more preferably a C _7-12 aralkyl group optionally having

Any two of R ¹ , R ² , R ³ , and EWG, for example, R ¹ (or R ² ) and EWG, may combine with each other to form a ring. For example, the compound represented by formula (1) has R ¹ (or R ² ) and EWG bound together to form a ring, represented by any of the following formulas (1-1) to (1-5). It may be a compound that is

The compound represented by formula (1) is preferably a compound represented by any one of the following formulas (1-6) to (1-15).

(In the formula,
R ³³ , R ³⁴ , R ³⁵ , R ³⁶ and R ³⁷ are a hydrogen atom, a halogen atom, an alkyl group, or a fluoroalkyl group (preferably a trifluoromethyl group),
R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ , R ⁶⁸ , RD ^, ^RE , ^RF , ^RG and ^RH are alkyl, cycloalkyl, aryl or aralkyl a group, and R ⁷² and R ⁸² are each independently a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group;
^R91 and ^R101 are each independently a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. )

Compounds R ⁴ and R ⁵ represented by formula (2) each independently may have one or more substituents, and a fluoroalkyl group optionally containing an oxygen atom between carbon atoms , or a fluoroalkoxy group which may have one or more substituents and which may contain an oxygen atom between carbon atoms. R ⁴ and R ⁵ are each independently a fluoroalkyl group optionally having one or more substituents, a fluoroalkoxy group optionally having one or more substituents, one or more It is preferably a fluoroalkoxyfluoroalkyl group which may have a substituent or a fluoroalkoxyfluoroalkoxy group which may have one or more substituents, and has one or more substituents. more preferably a fluoroalkyl group optionally having one or more substituents or a fluoroalkoxy group optionally having one or more substituents, and a fluoroC _1-10 alkyl group optionally having one or more substituents or a fluoro-C _1-10 alkoxy group optionally having one or more substituents, and an aspect in which these groups have no substituents is also preferred.

A preferred combination of R ⁴ and R ⁵ is a combination in which R ⁴ and R ⁵ are fluoroalkyl groups optionally having one or more substituents, and R ⁴ and R ⁵ are one or more A combination of optionally substituted fluoro-C _1-10 alkyl groups is more preferred.

R ⁴ and R ⁵ may combine with each other to form a ring. The ring can be, for example, a 4-membered ring, a 5-membered ring, or a 6-membered ring. The compound represented by formula (2) having the ring is preferably a compound represented by any one of the following formulas (2-1) to (2-7).

Suitable examples of the compound represented by formula (2) include 1,1,1,2,3,3,3-heptafluoropropane and the like.

The selectivity of the 1,2-addition reaction and the 1,4-addition reaction in addition reactions such as the compound represented by formula (1) and the compound represented by formula (2) is represented by formula (2). It is believed that the more sterically bulky R ⁴ and R ⁵ of the compound, the better the selectivity of the 1,4-addition reaction. From the viewpoint of selective 1,4-addition reaction, R ⁴ and R ⁵ may be short chain substituents such as trifluoromethyl group (CF ₃ —) or CF ₃ CF ₂ CF ₂ CF ₂ It may also be a long-chain substituent that is bulkier than CF ₃ —, such as O—.

The amount of the compound represented by formula (2) is not particularly limited, but for example, 1 mol or more, 1.5 mol or more, or 2 mol or more per 1 mol of the compound represented by formula (1) is preferably 20 mol or less, 15 mol or less, or 10 mol or less. The amount of the compound represented by formula (2) to be used can be within a range in which the above lower limit and the above upper limit are arbitrarily combined.

Base The base is not particularly limited, and any base can be used. Examples of bases include linear tertiary amines such as N,N-diisopropylethylamine (DIPEA); 1,4-diazabicyclo[2.2.2]octane (DABCO) and 1,8-bis(dimethylaminonaphthalene). cyclic amines such as diazabicycloundecene (DBU), diazabicyclononene (DBN) and other cyclic amidine bases, as well as quaternary ammonium salts, MH(Z) _p (where M is a metal, Z is a halogen and p is a number corresponding to the valence), M(Z) _k (where M is a metal, Z is a halogen, and k is a number corresponding to the valence of the metal ) and the like. The presence of a bulky group in the cationic site of the base allows the reaction to proceed efficiently.

Examples of the quaternary ammonium salt include the following formula (6):

(In the formula, Q ¹ to Q ⁴ are each independently a hydrocarbon group optionally having one or more substituents, and any two of Q ¹ to Q ⁴ are bonded to each other. may form a ring, and X is halogen, OH, HSO ₄ , SO ₄ ^2- , BH ₄ , BF ₄ , ClO ₄ , NO ₃ or PF ₆ .)
or a hydrate thereof, tris(dimethylamino)sulfonium difluorotrimethylsilicate (TASF), and the like.

Q ¹ to Q ⁴ are each independently an alkyl group optionally having one or more substituents, a cycloalkyl group optionally having one or more substituents, one or more substituents It is preferably an aryl group which may have a group or an aralkyl group which may have one or more substituents, an alkyl group which may have one or more substituents or 1 It is more preferably an aryl group optionally having one or more substituents, more preferably an alkyl group optionally having one or more substituents, and a C _1-4 alkyl group. It is particularly preferred to have In addition, although a halogen atom, a hydroxyl group, a mercapto group, etc. are mentioned as said substituent, it is not limited to these.

Examples of the ring formed by combining any two of Q ¹ to Q ⁴ include, but are not limited to, 5- or 6-membered rings of pyrrolidine, piperidine, morpholine, and the like.

The halogen represented by X is fluorine, chlorine, bromine or iodine, preferably fluorine.

X is preferably halogen or OH, more preferably fluorine or OH.

Suitable examples of the compound represented by formula (6) include tetrabutylammonium fluoride, tetrabutylammonium hydroxide, tetramethylammonium fluoride, tetramethylammonium hydroxide and the like.

In MH(Z) _p and M(Z) _k , M is preferably an alkali metal or an alkaline earth metal, more preferably an alkali metal, and further preferably Na, K, or Cs. preferable. Z is preferably fluorine. The MH(Z) _p is preferably MHF _p (where M is Na, K, or Cs, and p is a number corresponding to the valence), and the M(Z) _k is MF (where M is Na, K, or Cs).

A base can be used individually by 1 type or in combination of 2 or more types. In one embodiment, the base is a quaternary ammonium salt, MHF _p (where M is Na, K, or Cs and p is a number corresponding to the valence), and MF (where M is Na, K, or Cs.) preferably contains at least one selected from the group consisting of, more preferably a quaternary ammonium salt. In this embodiment, the quaternary ammonium salt is preferably at least one selected from the group consisting of tetrabutylammonium fluoride, tetrabutylammonium hydroxide, tetramethylammonium fluoride, and tetramethylammonium hydroxide. .

The lower limit of the pKa of the base is, for example, 10, preferably 11, more preferably 12. The upper limit of the pKa of the base is, for example, 20, preferably 16, more preferably 15. The pKa of the base is, for example, within the range of 10-20, preferably within the range of 10-15. For pKa values of bases, reference can be made to, for example, Kagaku Binran (Fundamentals) Revised 6th Edition, The Chemical Society of Japan (Maruzen Publishing), and the like.

The amount of the base to be used is not particularly limited. It is preferably 5 mol or less, 4 mol or less, 3 mol or less, or 2 mol or less. The amount of the base to be used can be within a range in which the above lower limit and the above upper limit are arbitrarily combined.

The reaction of solvent step A may be carried out in a solvent. The solvent may be, for example, a nonpolar solvent, an aprotic polar solvent, or a protic polar solvent. Examples of the solvent include, but are not limited to, the following solvents.
・Hydrocarbon solvents [Examples: chain hydrocarbons such as n-hexane, aromatic hydrocarbons such as benzene, toluene, and p-xylene]
・Halogen-based solvents [Examples: Haloalkanes such as dichloromethane, dichloroethane, and perfluorohexane; Haloarenes such as chlorobenzene; Haloalkylarenes such as trifluorotoluene and hexafluorometaxylene]
・Nitrile-based solvents [e.g. chain nitriles such as acetonitrile, propionitrile and acrylonitrile; cyclic nitriles such as benzonitrile]
- Amide solvents [e.g. carboxylic acid amides (e.g. chain amides such as formamide, N-methylformamide, N,N-dimethylformamide, cyclic amides such as N-methylpyrrolidone), phosphoric acid amides (e.g. hexamethyl phosphate amide)]
Ether-based solvents [Examples: chain ethers such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether; cyclic ethers such as tetrahydrofuran (THF) and dioxane]
・Urea-based solvent [Example: N,N-dimethylpropylene urea]
・Ester-based solvent [Example: Acetate ester]
・ Sulfoxide solvent [Example: dimethyl sulfoxide (DMSO)]
・Nitro-based solvents [e.g. nitromethane, nitrobenzene]
・Ketone solvent [Example: acetone, methyl ethyl ketone]
・Mixed solvent of two or more of these

The solvent is preferably at least one selected from the group consisting of hydrocarbon solvents, ether solvents, amide solvents, sulfoxide solvents, and nitrile solvents.

The amount of the solvent used is not particularly limited, but for example, it is preferably 0.1 mL or more, 0.5 mL or more, or 1 mL or more, 100 mL or less, or 50 mL with respect to 1 mmol of the compound represented by formula (1). or less, or preferably 30 mL or less. The amount of the solvent used can be within a range in which the above lower limit and the above upper limit are arbitrarily combined.

The drying agent step A reaction can be carried out in the presence or absence of water. When implemented in the presence of water, the amount of water may be, for example, 5 parts by mass or less with respect to 100 parts by mass of the reaction liquid. To reduce the water content, the reaction of step A may be carried out in the presence of a drying agent. Examples of desiccants include zeolite and the like. Examples of zeolites include molecular sieves 3A, 4A, and 5A (Union Showa), Zeolum 3A and 4A (Tosoh), and the like.

The reaction of metal oxide step A can be carried out in the presence or absence of a metal oxide. Examples of metal oxides include zeolite, silica, and alumina, which are mentioned as examples of the desiccant. The amount of the metal oxide used is, for example, 100 parts by mass or more, 200 parts by mass or more, or preferably 300 parts by mass or more with respect to 100 parts by mass of the compound represented by formula (1), and 35000 parts by mass. Below, it is preferably 30,000 parts by mass or less, or 25,000 parts by mass or less. The amount of the metal oxide used can be within a range in which the lower limit and the upper limit are arbitrarily combined.

Reaction temperature The reaction temperature in step A is not particularly limited as long as the reaction proceeds. The lower limit of the reaction temperature is, for example, −20° C. or higher, preferably 0° C. or higher, and more preferably 10° C. or higher. The upper limit of the reaction temperature is, for example, 150° C. or lower, preferably 120° C. or lower, and more preferably 100° C. or lower. The reaction temperature can be in any combination of the lower limit and the upper limit.

Reaction time The reaction time of step A is not particularly limited as long as the reaction proceeds. The lower limit of the reaction time is, for example, 0.1 hour or longer, preferably 0.5 hour or longer, and more preferably 1 hour or longer. The upper limit of the reaction time is, for example, 72 hours or less, preferably 50 hours or less. The reaction time can be within a range in which the above lower limit and the above upper limit are arbitrarily combined.

Compounds R ¹ , R ² , R ³ , R ⁴ , R ⁵ and EWG represented by formula (3) are “compounds represented by formula (1)” and “compounds represented by formula (2)”. It is as described in

Suitable combinations of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and EWG include, for example, combinations shown in Table 1 below.

In addition to step A, the method for producing the compound represented by formula (3) can include optional steps, for example, purification steps such as filtration, extraction, distillation, column chromatography, and washing.

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ in the compound formula (4) represented by the formula (4) are respectively R ¹ and R 2 in the formulas (1) to ( ³ ) , R ³ , R ⁴ , R ⁵ , and EWG. Compounds of formula (4) can represent by-products of the step A reaction.

In formula (4), for example,
R ¹¹ , R ¹² and R ¹³ are each independently a hydrogen atom or a hydrocarbon group optionally having one or more substituents (eg, a C _1-12 hydrocarbon group),
R ¹⁶ is —COOR ¹⁷ , —CONR ¹⁸ R ¹⁹ _, or a cyano group;
R ¹⁷ is a C _1-12 hydrocarbon group optionally having one or more substituents,
R ¹⁸ and R ¹⁹ are each independently a hydrogen atom or a C _1-12 hydrocarbon group optionally having one or more substituents,
Any two of R ¹¹ , R ¹² , R ¹³ and R ¹⁶ may be bonded to each other to form a ring,
R ¹⁴ and R ¹⁵ each independently optionally have one or more substituents, a fluoroalkyl group optionally containing an oxygen atom between carbon atoms, or one or more substituents is a fluoroalkoxy group which may have an oxygen atom between the carbon atoms, and R ¹⁴ and R ¹⁵ may combine with each other to form a ring.

It is preferable that m is 2 or 3.

Composition The composition contains the compound represented by Formula (3) and the compound represented by Formula (4).

The upper limit of the content of the compound represented by formula (4) is, for example, 300 parts by mass, preferably 250 parts by mass, more preferably 200 parts by mass with respect to 100 parts by mass of the compound represented by formula (3). be. The lower limit of the content of the compound represented by formula (4) is, for example, 0.0001 parts by mass, 0.0005 parts by mass, or 0.001 parts by mass with respect to 100 parts by mass of the compound represented by formula (3). , 0.005 parts by weight, or 0.01 parts by weight.

The upper limit of the content of the compound represented by formula (4) may be, for example, 9 mol, 8 mol, 7 mol, or 6 mol with respect to 1 mol of the compound represented by formula (3), It may be preferably 5 mol, 4 mol, 3 mol or 2 mol, more preferably 1 mol. The lower limit of the content of the compound represented by formula (4) is, for example, 0.0001 mol, 0.0005 mol, 0.001 mol, 0.005, per 1 mol of the compound represented by formula (3). mol, or 0.01 mol. The content of the compound represented by the formula (4) can be within a range in which the lower limit and the upper limit are arbitrarily combined.

Methods for quantifying the content of the compound represented by formula (4) include NMR, HPLC, IR, GC, GC/MS, and LC/MS methods. Among these, the GC/MS method is more suitable for quantifying trace components.

The composition has the following formula (5):

(In the formula,
R ²¹ , R ²² and R ²³ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a hydrocarbon group optionally having one or more substituents, —OR ^A , —COR ^A , -COOR ^A , -CONR ^B R ^C , -NR ^B R ^C , -NH-COR ^A , or -NH-COOR ^A ;
^RA is a hydrocarbon group optionally having one or more substituents,
R ^B and R ^C are each independently a hydrogen atom or a hydrocarbon group optionally having one or more substituents,
Any two of R ²¹ , R ²² , and R ²³ may combine with each other to form a ring,
R ²⁴ and R ²⁵ each independently optionally have one or more substituents, a fluoroalkyl group optionally containing an oxygen atom between carbon atoms, or one or more substituents is a fluoroalkoxy group which may contain an oxygen atom between the carbon atoms, and R ²⁴ and R ²⁵ may be bonded to each other to form a ring,
R ²⁶ is —OR ²⁷ or —NR ²⁸ R ²⁹ ;
R ²⁷ is a hydrocarbon group optionally having one or more substituents,
R ²⁸ and R ²⁹ are each independently a hydrogen atom or a hydrocarbon group optionally having one or more substituents. )
It may contain a compound represented by.

R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ in formula (5) correspond to R ¹ , R ² , R ³ , R ⁴ and R ⁵ in formulas (1) to (3) respectively You may —OR ²⁷ or —NR ²⁸ R ²⁹ may correspond to —OR ⁶ and —NR ⁷ R ⁸ in formulas (1)-(3), respectively. The compound represented by the formula (5) is a compound represented by the formula (2) with respect to the compound represented by the formula (1) in which EWG is —COOR ⁶ or —CONR ⁷ R ⁸ . - may correspond to an adduct compound.

The content of the compound represented by formula (5) is, for example, 50 parts by mass or less, preferably 45 parts by mass or less, more preferably 40 parts by mass or less with respect to 100 parts by mass of the compound represented by formula (3). , more preferably 35 parts by mass or less, particularly preferably 30 parts by mass or less. The content of the compound represented by formula (5) is, for 100 parts by mass of the compound represented by formula (3), for example, more than 0 parts by mass, 0.0001 parts by mass or more, 0.001 parts by mass or more, Or it can be 0.01 parts by mass or more. The content of the compound represented by the formula (5) can be within a range in which the lower limit and the upper limit are arbitrarily combined.

The content of the compound represented by formula (5) can be quantified, for example, by the same method as the method for quantifying the content of the compound represented by formula (4).

The method for producing the compound represented by formula (3) of the present disclosure is represented by formula (2) for the compound represented by formula (1) in which EWG is —COOR ⁶ or —CONR ⁷ R ⁸ The 1,4-addition of the compound can be selectively allowed to proceed, and the 1,2-addition can be partially or completely suppressed. Accordingly, the present disclosure can also provide compositions that do not contain a compound of formula (5) (or that contain a compound of formula (5) below the detection limit).

Hereinafter, one embodiment of the present disclosure will be described in more detail by way of examples, but the present disclosure is not limited thereto.
In each example, mass spectrometry analysis was performed by the GC/MS measurement method.

[Example 1]
A 20 mL autoclave was charged with benzyl acrylate (41 mg, 0.25 mmol), N,N-dimethylformamide (2 mL), and a 1.0 M solution of tetrabutylammonium fluoride in THF (0.25 mL, 0.25 mmol) at room temperature. 1.6 mmol of 2H-heptafluoropropane was added. The reaction was allowed to proceed at room temperature for 5 hours. After 5 hours, the pressure was released and the autoclave was opened for analysis. The yield of benzyl 4,5,5,5-tetrafluoro-4-(trifluoromethyl)pentanoate was 41%, and 2-(2,3,3,3-tetrafluoro-2-(trifluoromethyl The yield of dibenzyl)propyl)glutarate was 3% (the yield (%) is a unit based on mol of the raw material (benzyl acrylate)).

[Example 2]
In a 20 mL autoclave, benzyl acrylate (41 mg, 0.25 mmol), N,N-dimethylformamide (2 mL), tetramethylammonium fluoride tetrahydrate (41 mg, 0.25 mmol), molecular sieves 3A (300 mg) was added at room temperature. 1.6 mmol of 2H-heptafluoropropane was added. The reaction was allowed to proceed at room temperature for 5 hours. After 5 hours, the pressure was released and the autoclave was opened for analysis. The yield of benzyl 4,5,5,5-tetrafluoro-4-(trifluoromethyl)pentanoate was 50%. The yield of dibenzyl 2-(2,3,3,3-tetrafluoro-2-(trifluoromethyl)propyl)glutarate was 40%.
[Example 2A]
By the same procedure as in Example 2 except that molecular sieves 3A were not used, the yield of benzyl 4,5,5,5-tetrafluoro-4-(trifluoromethyl)pentanoate was 54%. The yield of dibenzyl 2-(2,3,3,3-tetrafluoro-2-(trifluoromethyl)propyl)glutarate was 34%.
[Example 2B]
(i) molecular sieves 4A (300 mg), (ii) molecular sieves 5A (300 mg), (iii) inactivated molecular sieves 4A (300 mg), (iv) _Al2O3 instead of molecular sieves _3A (300 mg). (300 mg) was operated in the same manner as in Example 2, the yields of benzyl 4,5,5,5-tetrafluoro-4-(trifluoromethyl)pentanoate were, respectively, ( i) 58%, (ii) 49%, (iii) 52%, (iv) 13%, 2-(2,3,3,3-tetrafluoro-2-(trifluoromethyl)propyl)glutaric acid The yields of dibenzyl were (i) 50%, (ii) 40%, (iii) 45% and (iv) 5%, respectively.

[Example 3]
A 20 mL autoclave was charged with benzyl acrylate (41 mg, 0.25 mmol), DMSO (2 mL), tetrabutylammonium fluoride in 1.0 M THF (0.25 mL, 0.25 mmol) at room temperature. 1.6 mmol of 2H-heptafluoropropane was added. The reaction was allowed to proceed at room temperature for 5 hours. After 5 hours, the pressure was released and the autoclave was opened for analysis. The yield of benzyl 4,5,5,5-tetrafluoro-4-(trifluoromethyl)pentanoate was 20%. The yield of dibenzyl 2-(2,3,3,3-tetrafluoro-2-(trifluoromethyl)propyl)glutarate was 5%.

[Example 4]
A 20 mL autoclave was charged with benzyl acrylate (41 mg, 0.25 mmol), 1,4-dioxane (2 mL), tetrabutylammonium fluoride in 1.0 M THF (0.25 mL, 0.25 mmol) at room temperature. 1.6 mmol of 2H-heptafluoropropane was added. The reaction was allowed to proceed at room temperature for 5 hours. After 5 hours, the pressure was released and the autoclave was opened for analysis. The yield of benzyl 4,5,5,5-tetrafluoro-4-(trifluoromethyl)pentanoate was 17%. The yield of dibenzyl 2-(2,3,3,3-tetrafluoro-2-(trifluoromethyl)propyl)glutarate was 1%.

[Example 5]
N-benzyl-N-methylacrylamide (44 mg, 0.25 mmol), N,N-dimethylformamide (1 mL), and 1.0 M THF solution of tetrabutylammonium fluoride (0.25 mL, 0.25 mmol) were added to a 20 mL autoclave at room temperature. I put it in. 1.6 mmol of 2H-heptafluoropropane was added. The reaction was allowed to proceed at room temperature for 15 hours. After 15 hours, the pressure was released, the autoclave was opened, and ¹⁹ FNMR measurement and mass spectrometry were performed to confirm the presence of N-benzyl-4,5,5,5-tetrafluoro-N-methyl-4-(trifluoromethyl)pentanamide. bottom.

[Example 6]
Benzyl methacrylate (44 mg, 0.25 mmol), N,N-dimethylformamide (2 mL), tetramethylammonium fluoride tetrahydrate (41 mg, 0.25 mmol), molecular sieves 4A (300 mg) were added to a 20 mL autoclave. Put in at room temperature. 1.6 mmol of 2H-heptafluoropropane was added. The reaction was allowed to proceed at room temperature for 15 hours. After 15 hours, the pressure was released and the autoclave was opened for analysis. The yield of benzyl 4,5,5,5-tetrafluoro-2-methyl-4-(trifluoromethyl)pentanoate was 19%.
[Example 6A]
As in Example 6, except that tetrabutylammonium fluoride in 1.0 M THF (0.25 mL, 0.25 mmol) was used instead of tetramethylammonium fluoride tetrahydrate (41 mg, 0.25 mmol). The work-up gave a 9% yield of benzyl 4,5,5,5-tetrafluoro-2-methyl-4-(trifluoromethyl)pentanoate.

[Example 7]
Acrylonitrile (13 mg, 0.25 mmol), N,N-dimethylformamide (2 mL), tetramethylammonium fluoride tetrahydrate (41 mg, 0.25 mmol), molecular sieves 3A (300 mg) were added to a 20 mL autoclave at room temperature. I put it in. 1.6 mmol of 2H-heptafluoropropane was added. The reaction was allowed to proceed at room temperature for 5 hours. After 5 hours, the pressure was released and the autoclave was opened for analysis. The yield of 4,5,5,5-tetrafluoro-4-(trifluoromethyl)pentanenitrile was 56%.

[Example 8]
In a 20 mL autoclave, cinnamate nitrile (32 mg, 0.25 mmol), N,N-dimethylformamide (2 mL), tetramethylammonium fluoride tetrahydrate (41 mg, 0.25 mmol), molecular sieves 3A (300 mg ) was added at room temperature. 1.6 mmol of 2H-heptafluoropropane was added. The reaction was allowed to proceed at room temperature for 5 hours. After 5 hours, the pressure was released and the autoclave was opened for analysis. The yield of 4,5,5,5-tetrafluoro-3-phenyl-4-(trifluoromethyl)pentanenitrile was 8%.

[Example 9]
Phenylvinylsulfone (42 mg, 0.25 mmol), N,N-dimethylformamide (2 mL), tetramethylammonium fluoride tetrahydrate (41 mg, 0.25 mmol), molecular sieves 3A (300 mg) were added to a 20 mL autoclave. was added at room temperature. 1.6 mmol of 2H-heptafluoropropane was added. The reaction was allowed to proceed at room temperature for 5 hours. After 5 hours, the pressure was released and the autoclave was opened for analysis. The yield of ((3,4,4,4-tetrafluoro-3-(trifluoromethyl)butyl)sulfonyl)benzene was 48%.
[Example 9A]
((3,4,4,4-tetrafluoro-3-(trifluoromethyl) The yield of butyl)sulfonyl)benzene was 89%.

[Example 10]
In a 20 mL autoclave, phenyl vinyl sulfoxide (38 mg, 0.25 mmol), N,N-dimethylformamide (2 mL), tetramethylammonium fluoride tetrahydrate (41 mg, 0.25 mmol), molecular sieves 3A (300 mg). was added at room temperature. 1.6 mmol of 2H-heptafluoropropane was added. The reaction was allowed to proceed at room temperature for 20 hours. After 20 hours, the pressure was released and the autoclave was opened for analysis. The yield of ((3,4,4,4-tetrafluoro-3-(trifluoromethyl)butyl)sulfinyl)benzene was 23%.

[Example 11]
In a 20 mL autoclave, diethyl benzylidenemalonate (62 mg, 0.25 mmol), N,N-dimethylformamide (2 mL), tetramethylammonium fluoride tetrahydrate (41 mg, 0.25 mmol), molecular sieves 3A (300 mg ) was added at room temperature. 1.6 mmol of 2H-heptafluoropropane was added. The reaction was allowed to proceed at room temperature for 5 hours. After 5 hours, the pressure was released and the autoclave was opened for analysis. The yield of diethyl 2-(2,3,3,3-tetrafluoro-1-phenyl-2-(trifluoromethyl)propyl)malonate was 33%.

[Example 12]
In a 20 mL autoclave, diethyl vinylphosphonate (41 mg, 0.25 mmol), N,N-dimethylformamide (2 mL), tetramethylammonium fluoride tetrahydrate (41 mg, 0.25 mmol), molecular sieves 3A (300 mg ) was added at room temperature. 1.6 mmol of 2H-heptafluoropropane was added. The reaction was allowed to proceed at room temperature for 5 hours. After 5 hours, the pressure was released and the autoclave was opened for analysis. The yield of diethyl (3,4,4,4-tetrafluoro-3-(trifluoromethyl)butyl)phosphonate was 20%.

[Example 13]
A 20 mL autoclave was charged with benzyl acrylate (41 mg, 0.25 mmol), N,N-dimethylacetamide (2 mL), and tetramethylammonium fluoride tetrahydrate (41 mg, 0.25 mmol) at room temperature. 1.6 mmol of 2H-heptafluoropropane was added. The reaction was allowed to proceed at room temperature for 5 hours. After 5 hours, the pressure was released and the autoclave was opened for analysis. The yield of benzyl 4,5,5,5-tetrafluoro-4-(trifluoromethyl)pentanoate was 47%. The yield of dibenzyl 2-(2,3,3,3-tetrafluoro-2-(trifluoromethyl)propyl)glutarate was 39%.

[Example 14]
In a 20 mL autoclave, 2-phenylpropan-2-yl acrylate (47.5 mg, 0.25 mmol), N,N-dimethylformamide (2 mL), tetramethylammonium fluoride tetrahydrate (41 mg, 0.25 mmol) was added at room temperature. 1.6 mmol of 2H-heptafluoropropane was added. The reaction was allowed to proceed at room temperature for 5 hours. After 5 hours, the pressure was released and the autoclave was opened for analysis. The yield of 2-phenylpropan-2-yl 4,5,5,5-tetrafluoro-4-(trifluoromethyl)pentanoate was 60%.
[Example 14A]
The same procedure as in Example 14 was performed except that the amount of N,N-dimethylformamide was changed to 0.5 mL, 1 mL, and 5 mL. The yields were 23%, 48%, and 43%, respectively. rice field.
[Example 14B]
The yield was 50% by the same procedure as in Example 14, except that the reaction time was changed to 10 hours.

[Example 15]
In a 20 mL autoclave, 1-phenylethyl acrylate (44 mg, 0.25 mmol), N,N-dimethylformamide (2 mL), tetramethylammonium fluoride tetrahydrate (41 mg, 0.25 mmol), molecular sieves 4A. (300 mg) was added at room temperature. 1.6 mmol of 2H-heptafluoropropane was added. The reaction was allowed to proceed at room temperature for 5 hours. After 5 hours, the pressure was released and the autoclave was opened for analysis. The yield of 1-phenylethyl 4,5,5,5-tetrafluoro-4-(trifluoromethyl)pentanoate was 43%. The yield of di(1-phenylethyl) 2-(2,3,3,3-tetrafluoro-2-(trifluoromethyl)propyl)glutarate was 40%.
[Example 15A]
By the same procedure as in Example 15 except that molecular sieves 4A were not used, the yield of 1-phenylethyl 4,5,5,5-tetrafluoro-4-(trifluoromethyl)pentanoate was 45%. and the yield of di(1-phenylethyl) 2-(2,3,3,3-tetrafluoro-2-(trifluoromethyl)propyl)glutarate was 26%.

[Example 16]
In a 20 mL autoclave, 2-phenylpropan-2-yl acrylate (47.5 mg, 0.25 mmol), N,N-dimethylformamide (2 mL), tetramethylammonium fluoride tetrahydrate (41 mg, 0.25 mmol) , molecular sieves 4A (300 mg) were added at room temperature. 1.6 mmol of 2H-heptafluoropropane was added. The reaction was allowed to proceed at room temperature for 5 hours. After 5 hours, the pressure was released and the autoclave was opened for analysis. The yield of 2-phenylpropan-2-yl 4,5,5,5-tetrafluoro-4-(trifluoromethyl)pentanoate was 78%.

[Example 17]
In a 20 mL autoclave, (3s,5s,7s)-adamantan-1-yl acrylate (51.5 mg, 0.25 mmol), N,N-dimethylformamide (2 mL), tetramethylammonium fluoride tetrahydrate (41 mg, 0.25 mmol) and molecular sieves 4A (300 mg) were added at room temperature. 1.6 mmol of 2H-heptafluoropropane was added. The reaction was allowed to proceed at room temperature for 5 hours. After 5 hours, the pressure was released and the autoclave was opened for analysis. The yield of (3s,5s,7s)-adamantan-1-yl 4,5,5,5-tetrafluoro-4-(trifluoromethyl)pentanoate was 64%. The yield of di((3s,5s,7s)-adamantan-1-yl) 2-(2,3,3,3-tetrafluoro-2-(trifluoromethyl)propyl)glutarate was 18%. .
[Example 17A]
By the same procedure as in Example 17 except that molecular sieves 4A was not used, 4,5,5,5-tetrafluoro-4-(trifluoromethyl)pentanoic acid (3s,5s,7s)-adamantane- The yield of 1-yl was 26%, and 2-(2,3,3,3-tetrafluoro-2-(trifluoromethyl)propyl)glutarate di((3s,5s,7s)-adamantane-1 -yl) was 6%.

[Example 18]
In a 20 mL autoclave, 2,4,4-trimethylpentan-2-yl acrylate (46 mg, 0.25 mmol), N,N-dimethylformamide (2 mL), tetramethylammonium fluoride tetrahydrate (41 mg , 0.25 mmol) and molecular sieves 4A (300 mg) were added at room temperature. 1.6 mmol of 2H-heptafluoropropane was added. The reaction was allowed to proceed at room temperature for 5 hours. After 5 hours, the pressure was released and the autoclave was opened for analysis. The yield of 2,4,4-trimethylpentan-2-yl 4,5,5,5-tetrafluoro-4-(trifluoromethyl)pentanoate was 64%.

[Example 19]
In a 20 mL autoclave, 2-phenylpropan-2-yl acrylate (47.5 mg, 0.25 mmol), N,N-dimethylformamide (2 mL), tetramethylammonium fluoride tetrahydrate (41 mg, 0.25 mmol) , N,N-diisopropylethylamine (32.3 mg, 0.25 mmol), molecular sieves 4A (300 mg) were charged at room temperature. 1.6 mmol of 2H-heptafluoropropane was added. The reaction was allowed to proceed at room temperature for 5 hours. After 5 hours, the pressure was released and the autoclave was opened for analysis. The yield of 1-phenylethyl 4,5,5,5-tetrafluoro-4-(trifluoromethyl)pentanoate was 80%.
[Example 19A]
By the same procedure as in Example 19 except that molecular sieves 4A were not used, the yield of 1-phenylethyl 4,5,5,5-tetrafluoro-4-(trifluoromethyl)pentanoate was 37%. Met.
[Example 19B]
By the same procedure as in Example 19 except that N,N-diisopropylethylamine (32.3 mg, 0.25 mmol) was changed to diazabicycloundecene (38.1 mg, 0.25 mmol), 4,5,5,5 The yield of 1-phenylethyl-tetrafluoro-4-(trifluoromethyl)pentanoate was 44%.
[Example 19C]
By the same procedure as in Example 19, except that N,N-diisopropylethylamine (32.3 mg, 0.25 mmol) was changed to 1,8-bis(dimethylamino)naphthalene (53.6 mg, 0.25 mmol), 4, The yield of 1-phenylethyl 5,5,5-tetrafluoro-4-(trifluoromethyl)pentanoate was 86%.
[Example 19D]
Same as Example 19 except N,N-diisopropylethylamine (32.3 mg, 0.25 mmol) was replaced with 1,8-bis(dimethylamino)naphthalene (53.6 mg, 0.25 mmol) and no molecular sieves 4A was used. The yield of 1-phenylethyl 4,5,5,5-tetrafluoro-4-(trifluoromethyl)pentanoate was 56%.
[Example 19E]
In the same manner as in Example 19, except that N,N-diisopropylethylamine (32.3 mg, 0.25 mmol) was changed to 1,4-diazabicyclo[2.2.2]octane (28.0 mg, 0.25 mmol), 4, The yield of 1-phenylethyl 5,5,5-tetrafluoro-4-(trifluoromethyl)pentanoate was 83%.

[Example 20]
In a 20 mL autoclave, methyl 2-(1,3-dioxoisoindolin-2-yl)acrylate (58 mg, 0.25 mmol), N,N-dimethylformamide (2 mL), tetramethylammonium fluoride/4 water. Hydrate (41 mg, 0.25 mmol) and molecular sieves 4A (300 mg) were added at room temperature. 1.6 mmol of 2H-heptafluoropropane was added. The reaction was allowed to proceed at room temperature for 5 hours. After 5 hours, the pressure was released and the autoclave was opened for analysis. The yield of methyl 2-(1,3-dioxoisoindolin-2-yl)-4,5,5,5-tetrafluoro-4-(trifluoromethyl)pentanoate was 63%.

[Example 21A]
By the same procedure as in Example 20 except that molecular sieves 4A was not used, 2-(1,3-dioxoisoindolin-2-yl)-4,5,5,5-tetrafluoro-4- The yield of methyl (trifluoromethyl)pentanoate was 75%.

Claims

Formula (3) below:

(In the formula,
R 1 , R 2 , and R 3 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a hydrocarbon group optionally having one or more substituents, —OR A , —COR A , -COOR A , -CONR B R C , -NR B R C , -NH-COR A , or -NH-COOR A ;
RA is a hydrocarbon group optionally having one or more substituents,
R B and R C are each independently a hydrogen atom or a hydrocarbon group optionally having one or more substituents, or R B and R C are adjacent nitrogen atoms bound to each other may form a ring with
EWG is an electron withdrawing group,
Any two of R 1 , R 2 , R 3 , and EWG may combine with each other to form a ring,
R 4 and R 5 each independently optionally have one or more substituents, a fluoroalkyl group optionally containing an oxygen atom between carbon atoms, or one or more substituents and a fluoroalkoxy group which may contain an oxygen atom between carbon atoms,
R 4 and R 5 may combine with each other to form a ring. )
A method for producing a compound represented by
Formula (1) below:

(Wherein, R 1 , R 2 , R 3 , and EWG are the same as above.)
and a compound represented by the following formula (2):

(In the formula, R 4 and R 5 are the same as above.)
A production method comprising the step of reacting a compound represented by in the presence of a base.
The production method according to claim 1, wherein the pKa of said base is in the range of 10-20.
The base is a quaternary ammonium salt, MHF p (where M is Na, K, or Cs and p is a number corresponding to the valence), and MF (where M is Na, K , or Cs).
The production method according to any one of claims 1 to 3, wherein the base comprises a quaternary ammonium salt.
5. The method according to claim 3 or 4, wherein the quaternary ammonium salt is at least one selected from the group consisting of tetrabutylammonium fluoride, tetrabutylammonium hydroxide, tetramethylammonium fluoride, and tetramethylammonium hydroxide. Method of manufacture as described.
In the above formulas (1) and (3),
EWG is —COOR 6 , —COR 6 , —SO n R 6 , —CONR 7 R 8 , —PO(OR 9 )(OR 10 ), or a cyano group;
R 6 is a C 1-12 hydrocarbon group optionally having one or more substituents,
R 7 and R 8 are each independently a hydrogen atom or a C 1-12 hydrocarbon group optionally having one or more substituents,
R 9 and R 10 are each independently a hydrogen atom or a C 1-12 hydrocarbon group optionally having one or more substituents,
n is 1 or 2;
The production method according to any one of claims 1 to 5.
In the above formulas (1) and (3),
any one of claims 1 to 6, wherein R 1 , R 2 and R 3 are each independently a hydrogen atom or a C 1-12 hydrocarbon group optionally having one or more substituents; The manufacturing method described in the paragraph.
In the above formulas (2) and (3),
R 4 and R 5 are each independently a fluoroC 1-10 alkyl group or a fluoroC 1-10 alkoxy group;
The production method according to any one of claims 1 to 7.
The production method according to any one of claims 1 to 8, wherein the compound represented by formula (2) is 1,1,1,2,3,3,3-heptafluoropropane.
The production method according to any one of claims 1 to 9, wherein the reaction is carried out in a solvent.
The production method according to claim 10, wherein the solvent is at least one selected from the group consisting of hydrocarbon solvents, ether solvents, amide solvents, sulfoxide solvents, and nitrile solvents.
Formula (3A) below:

[In the formula,
R 31 is a hydrogen atom or a C 1-12 hydrocarbon group optionally having one or more substituents,
R 61 is a C 1-12 alkyl group optionally having one or more substituents, a cycloalkyl group optionally having one or more substituents, or having one or more substituents is an aryl group that may be (However, when R61 is a C4 alkyl group optionally having one or more substituents, the C4 alkyl group is a branched C4 alkyl group.)]
A compound represented by
The following formula (3B):

[In the formula,
R 32 is a hydrogen atom or a C 1-12 hydrocarbon group optionally having one or more substituents,
R 71 and R 81 are each independently a C 1-12 alkyl group optionally having one or more substituents, or an aryl group optionally having one or more substituents . (However, R 71 and R 81 are not C2 alkyl groups optionally having one or more substituents at the same time.)]
A compound represented by
Formula (4) below:

(In the formula,
R 11 , R 12 and R 13 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a hydrocarbon group optionally having one or more substituents, —OR A , —COR A , -COOR A , -CONR B R C , -NR B R C , -NH-COR A , or -NH-COOR A ;
RA is a hydrocarbon group optionally having one or more substituents,
R B and R C are each independently a hydrogen atom or a hydrocarbon group optionally having one or more substituents, or R B and R C are adjacent nitrogen atoms bound to each other may form a ring with
R 16 is an electron withdrawing group,
Any two of R 11 , R 12 , R 13 and R 16 may be bonded to each other to form a ring,
R 14 and R 15 each independently optionally have one or more substituents, a fluoroalkyl group optionally containing an oxygen atom between carbon atoms, or one or more substituents is a fluoroalkoxy group which may contain an oxygen atom between the carbon atoms, and R 14 and R 15 may be bonded to each other to form a ring,
m is 2 or 3; )
A compound represented by
Formula (3) below:

(In the formula,
R 1 , R 2 , and R 3 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a hydrocarbon group optionally having one or more substituents, —OR A , —COR A , -COOR A , -CONR B R C , -NR B R C , -NH-COR A , or -NH-COOR A ;
RA is a hydrocarbon group optionally having one or more substituents,
R B and R C are each independently a hydrogen atom or a hydrocarbon group optionally having one or more substituents,
EWG is an electron withdrawing group,
Any two of R 1 , R 2 , R 3 , and EWG may combine with each other to form a ring,
R 4 and R 5 each independently optionally have one or more substituents, a fluoroalkyl group optionally containing an oxygen atom between carbon atoms, or one or more substituents and a fluoroalkoxy group which may contain an oxygen atom between carbon atoms,
R 4 and R 5 may combine with each other to form a ring. )
A compound represented by
Formula (4) below:

(In the formula,
R 11 , R 12 and R 13 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a hydrocarbon group optionally having one or more substituents, —OR A , —COR A , -COOR A , -CONR B R C , -NR B R C , -NH-COR A , or -NH-COOR A ;
RA is a hydrocarbon group optionally having one or more substituents,
R B and R C are each independently a hydrogen atom or a hydrocarbon group optionally having one or more substituents, or R B and R C are adjacent nitrogen atoms bound to each other may form a ring with
R 16 is an electron withdrawing group,
Any two of R 11 , R 12 , R 13 and R 16 may be bonded to each other to form a ring,
R 14 and R 15 each independently optionally have one or more substituents, a fluoroalkyl group optionally containing an oxygen atom between carbon atoms, or one or more substituents is a fluoroalkoxy group which may contain an oxygen atom between the carbon atoms, and R 14 and R 15 may be bonded to each other to form a ring,
m is 2 or 3; )
A composition containing a compound represented by
16. The composition according to claim 15, containing 0.0001 to 150 parts by mass of the compound represented by formula (4) with respect to 100 parts by mass of the compound represented by formula (3).
The composition according to claim 15 or 16, containing 0.0001 to 100 parts by mass of the compound represented by formula (4) per 100 parts by mass of the compound represented by formula (3).
0.0001 to 50 parts by mass of the compound represented by the formula (4) with respect to 100 parts by mass of the compound represented by the formula (3), according to any one of claims 15 to 17 Composition.
Formula (5) below:

(In the formula,
R 21 , R 22 and R 23 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a hydrocarbon group optionally having one or more substituents, —OR A , —COR A , -COOR A , -CONR B R C , -NR B R C , -NH-COR A , or -NH-COOR A ;
RA is a hydrocarbon group optionally having one or more substituents,
R B and R C are each independently a hydrogen atom or a hydrocarbon group optionally having one or more substituents, or R B and R C are adjacent nitrogen atoms bound to each other may form a ring with
Any two of R 21 , R 22 , and R 23 may combine with each other to form a ring,
R 24 and R 25 each independently optionally have one or more substituents, a fluoroalkyl group optionally containing an oxygen atom between carbon atoms, or one or more substituents is a fluoroalkoxy group which may contain an oxygen atom between the carbon atoms, and R 24 and R 25 may be bonded to each other to form a ring,
R 26 is —OR 27 or —NR 28 R 29 ;
R 27 is a hydrocarbon group optionally having one or more substituents,
R 28 and R 29 are each independently a hydrogen atom or a hydrocarbon group optionally having one or more substituents. )
Does not contain the compound represented by, or contains more than 0 parts by mass and 50 parts by mass or less of the compound represented by the formula (5) with respect to 100 parts by mass of the compound represented by the formula (3) 19. The composition according to any one of 15-18.