JP7373809B2 - fluoride compounds - Google Patents

Description

The present disclosure relates to fluorinated compounds (particularly cyclic hypervalent iodine compounds containing vinyl fluoride groups).

Conventionally, various fluorinated compounds, their production methods, and their uses have been known.
For example, Non-Patent Documents 1 and 2 disclose iodotoluene difluoride and steric and regioselective addition of fluorine using this.

Hara et al., Chem. Commun, 1998, pp.965-966 Hara et al., Synthesis, 2004, p2821-2824

The present disclosure aims to provide a fluorinated compound (particularly a cyclic hypervalent iodine compound containing a vinyl fluoride group) and a method for producing the same.

［式中、
波線はシス配置又はトランス配置を表し；
環Ａは、１個以上の置換基を有していてもよい芳香環を表し；及び
Ｒ^１、及びＲ^２は、同一又は異なって、水素、又は有機基を表す。］
で表されるフッ化ビニル基含有環状超原子価ヨウ素化合物。
項２．
Ｒ^１及びＲ^２が、同一又は異なって、
水素、
１個以上の置換基を有していてもよいアルキル基、
１個以上の置換基を有していてもよい芳香族基、又は
１個以上の置換基を有していてもよい複素環基である、
項１記載のフッ化ビニル基含有環状超原子価ヨウ素化合物。
項３．
Ｒ^１が１個以上の置換基を有していてもよいアルキル基である、項２に記載のフッ化ビニル基含有環状超原子価ヨウ素化合物。
項４．
Ｒ^１が１個以上のシクロアルキル基で置換されていてもよいアルキル基である、項２に記載のフッ化ビニル基含有環状超原子価ヨウ素化合物。
項５．
Ｒ^２が水素、又は１個以上の置換基を有していてもよいアルキル基である、項１～４のいずれか一項に記載のフッ化ビニル基含有環状超原子価ヨウ素化合物。
項６．
Ｒ^２が水素である、項１～４のいずれか一項に記載のフッ化ビニル基含有環状超原子価ヨウ素化合物。
項７．
環Ａが１個以上の置換基を有していてもよい芳香族炭素環である、項１～６のいずれか一項に記載のフッ化ビニル基含有環状超原子価ヨウ素化合物。
項８．
式（２）：

［式中、
波線はシス配置又はトランス配置を表し、
環Ａは、１個以上の置換基を有していてもよい芳香環を表し；及び
Ｒ^１、及びＲ^２は、同一又は異なって、水素、又は有機基を表す。］
で表されるフッ化ビニル基含有環状超原子価ヨウ素化合物の製造方法であって、
式（１）：

［式中、Ｒ^１、及びＲ^２は、同一又は異なって、水素、又は有機基を表す。］
で表される化合物を、
式（３）：

［式中の記号は前記と同意義を表す。］
で表される化合物、及び
酸化剤
の存在下で、
フッ素源と反応させる工程Ａを含む、製造方法。
項９．
Ｒ^１及びＲ^２が、同一又は異なって、
水素、
１個以上の置換基を有していてもよいアルキル基、
１個以上の置換基を有していてもよい芳香族基、又は
１個以上の置換基を有していてもよい複素環基である、
項８に記載の製造方法。
項１０．
Ｒ^１及びＲ^２が、同一又は異なって、水素、1個以上の置換基を有してもよいＣ１－Ｃ２０アルキル基である、
項８又は９に記載の製造方法。
項１１．
Ｒ^２が、水素である、
項８～１０のいずれか一項に記載の製造方法。
項１２．
環Ａが、１個以上の置換基を有していてもよい芳香族炭素環である、
項８～１１のいずれか一項に記載の製造方法。The present disclosure includes the following aspects.
Item 1.
Formula (2):

[In the formula,
Wavy lines represent cis or trans configuration;
Ring A represents an aromatic ring which may have one or more substituents; and R ¹ and R ² are the same or different and represent hydrogen or an organic group. ]
A cyclic hypervalent iodine compound containing a vinyl fluoride group represented by:
Item 2.
R ¹ and R ² are the same or different,
hydrogen,
an alkyl group that may have one or more substituents,
An aromatic group which may have one or more substituents, or a heterocyclic group which may have one or more substituents,
Item 1. The vinyl fluoride group-containing cyclic hypervalent iodine compound according to item 1.
Item 3.
Item 3. The vinyl fluoride group-containing cyclic hypervalent iodine compound according to Item 2, wherein R ¹ is an alkyl group that may have one or more substituents.
Item 4.
Item 3. The vinyl fluoride group-containing cyclic hypervalent iodine compound according to Item 2, wherein R ¹ is an alkyl group optionally substituted with one or more cycloalkyl groups.
Item 5.
5. The vinyl fluoride group-containing cyclic hypervalent iodine compound according to any one of Items 1 to 4, wherein R ² is hydrogen or an alkyl group that may have one or more substituents.
Item 6.
5. The vinyl fluoride group-containing cyclic hypervalent iodine compound according to any one of Items 1 to 4, wherein R ² is hydrogen.
Section 7.
7. The vinyl fluoride group-containing cyclic hypervalent iodine compound according to any one of Items 1 to 6, wherein ring A is an aromatic carbocyclic ring that may have one or more substituents.
Section 8.
Formula (2):

[In the formula,
Wavy lines represent cis or trans configuration;
Ring A represents an aromatic ring which may have one or more substituents; and R ¹ and R ² are the same or different and represent hydrogen or an organic group. ]
A method for producing a cyclic hypervalent iodine compound containing a vinyl fluoride group represented by
Formula (1):

[In the formula, R ¹ and R ² are the same or different and represent hydrogen or an organic group. ]
The compound represented by
Formula (3):

[The symbols in the formula have the same meanings as above. ]
In the presence of a compound represented by and an oxidizing agent,
A manufacturing method comprising step A of reacting with a fluorine source.
Item 9.
R ¹ and R ² are the same or different,
hydrogen,
an alkyl group that may have one or more substituents,
An aromatic group which may have one or more substituents, or a heterocyclic group which may have one or more substituents,
The manufacturing method according to item 8.
Item 10.
R ¹ and R ² are the same or different and are hydrogen or a C1-C20 alkyl group which may have one or more substituents,
The manufacturing method according to item 8 or 9.
Item 11.
R ² is hydrogen,
The manufacturing method according to any one of items 8 to 10.
Item 12.
Ring A is an aromatic carbon ring which may have one or more substituents,
The manufacturing method according to any one of items 8 to 11.

［式中、
波線はシス配置又はトランス配置を表し；
Ｒ^１、及びＲ^２は、水素、又は有機基を表し；及び
Ｒは、有機基を表す。］
で表される化合物の製造方法であって、
式（２）：

［式中、
波線は、シス配置又はトランス配置を表し；
環Ａは、１個以上の置換基を有していてもよい芳香環を表し；及び
Ｒ^１、及びＲ^２は、同一又は異なって、水素、又は有機基を表す。］
で表されるフッ化ビニル基含有環状超原子価ヨウ素化合物
を
式（３）：

［式中、Ｒは、前記と同意義を表す。］
で表されるアルキン化合物と反応させる工程Ｂを含む、製造方法。
項Ｂ２．
工程Ｂの反応が、金属触媒の存在下で行われる、項Ｂ１に記載の方法。The present disclosure further includes the following aspects.
Term B1.
Formula (1'):

[In the formula,
Wavy lines represent cis or trans configuration;
R ¹ and R ² represent hydrogen or an organic group; and R represents an organic group. ]
A method for producing a compound represented by
Formula (2):

[In the formula,
Wavy lines represent cis or trans configuration;
Ring A represents an aromatic ring which may have one or more substituents; and R ¹ and R ² are the same or different and represent hydrogen or an organic group. ]
A cyclic hypervalent iodine compound containing a vinyl fluoride group represented by the formula (3):

[Wherein, R represents the same meaning as above.] ]
A manufacturing method comprising step B of reacting with an alkyne compound represented by:
Term B2.
The method according to item B1, wherein the reaction in step B is carried out in the presence of a metal catalyst.

According to the present disclosure, a fluorinated compound (particularly a cyclic hypervalent iodine compound containing a vinyl fluoride group) or a method for producing the same is provided.

The above summary of the present disclosure is not intended to describe each disclosed embodiment or every implementation of the present disclosure.
The following description of the disclosure more particularly exemplifies example embodiments.
In several places in this disclosure, guidance is provided through examples, and the examples can be used in various combinations.
In each case, the exemplary group can function as a non-exclusive and representative group.
All publications, patents and patent applications cited herein are incorporated by reference in their entirety.

1. Terminology As commonly understood by those skilled in the art, the compound represented by formula (1) may be referred to herein as "compound (1)" or "compound of formula (1)". . The same can be said of compounds represented by other formulas.
Unless otherwise specified, symbols and abbreviations in this specification can be understood in accordance with the context of this specification and with reference to common general knowledge.
As used herein, the phrase "comprising" is intended to include the phrase "consisting essentially of" and the phrase "consisting of."
Unless otherwise limited, the steps, treatments, or operations described herein may be performed at room temperature.
As used herein, room temperature can mean a temperature within the range of 10-40°C.
In this specification, the notation "Cn-Cm" (where n and m are each a number) means that the number of carbon atoms is n or more and m or less, as commonly understood by those skilled in the art. represents.

As used herein, "organic compound" is understood in its usual meaning and can be a compound having one or more carbon atoms and one or more hydrogen atoms.

In this specification, a fluorinated organic compound means a compound that can be produced by fluorinating an organic compound, and does not need to contain a hydrogen atom.

In this specification, unless otherwise specified, examples of "halo (group)" can include fluoro (group), chloro (group), bromo (group), and iodo (group).
In this specification, unless otherwise specified, examples of "halogen (atom)" can include fluorine (atom), chlorine (atom), bromine (atom), and iodine (atom).

In this specification, examples of the "aromatic ring" can include aromatic carbocycles and aromatic heterocycles.

In the present specification, unless otherwise specified, examples of "aromatic carbocycle" can include aromatic hydrocarbon rings having 6 to 14 carbon atoms, and specific examples thereof include benzene, naphthalene, anthracene, phenanthrene, and biphenyl.

In the present specification, unless otherwise specified, examples of "aromatic heterocycles" can include 5- or 6-membered aromatic heterocycles, and specific examples thereof include furan rings, thiophene rings, pyrrole rings, and oxazole rings. , isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, 1,2,3-oxadiazole ring, 1,2,4-oxadiazole ring, 1,3,4-oxadiazole ring , furazane ring, 1,2,3-thiadiazole ring, 1,2,4-thiadiazole ring, 1,3,4-thiadiazole ring, 1,2,3-triazole ring, 1,2,4-triazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, and triazine ring.

In the present specification, unless otherwise specified, a further example of the "aromatic heterocycle" is a fused ring of one or more of the 5- or 6-membered aromatic heterocycles and one or more aromatic carbocycles. can be included.

In this specification, "organic group" means
It means a group containing one or more carbon atoms or a group formed by removing one hydrogen atom from an organic compound.
The organic group may contain one or more atoms other than carbon and hydrogen atoms (eg, nitrogen, oxygen, sulfur, phosphorous, silicon, halo).
Examples of organic groups can include (per)fluoroorganic groups and (per)fluoroorganic groups.

As commonly understood by those skilled in the art, the suffix "perhalogeno" means that all hydrogen atoms are replaced with halo groups.
As commonly understood by those skilled in the art, the suffix "perfluoro" means that all hydrogen atoms are replaced with fluoro groups.

Examples of the "organic group" are:
Alkyl group which may have one or more substituents {e.g. (per)halogenoalkyl group [e.g. (per)fluoroalkyl group]},
Alkenyl group optionally having one or more substituents,
an alkynyl group which may have 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,
an aryl group which may have one or more substituents,
an aralkyl group which may have one or more substituents,
a non-aromatic heterocyclic group which may have one or more substituents,
a heteroaryl group optionally having one or more substituents,
cyano group,
aldehyde group,
R ^r O-,
R ^r CO-,
R ^r SO ₂ −,
R ^r OCO-, and R ^r OSO ₂ -
(In these formulas, R ^r is independently,
an alkyl group that may have one or more substituents,
Alkenyl group optionally having one or more substituents,
an alkynyl group which may have 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,
an aryl group which may have one or more substituents,
an aralkyl group which may have one or more substituents,
A non-aromatic heterocyclic group which may have one or more substituents, or a heteroaryl group which may have one or more substituents)
can be included.

In the present specification, an "organic group" is, for example, a hydrocarbon group that may have one or more substituents [the hydrocarbon group includes -NR ^o -, =N-, -N=, -O-, -S-, -C(=O)O-, -OC(=O)-, -C(=O)-, -S(=O)-, -S(=O) ₂ -, -S(=O) ₂ -NR ^o -, -NR ^o -S(=O) ₂ -, -S(=O)-NR ^o -, -NR ^o -S(=O)-, -Si(R ^o ) One or more moieties selected from the group consisting of ₃ - (in these formulas, R ^o is independently a hydrogen atom or an organic group) may be inserted. ] can be.

As commonly understood based on common knowledge in the chemical field, examples of hydrocarbon groups into which heteroatoms are inserted can include non-aromatic heterocyclic groups and heteroaryl groups.

In this specification, the carbon number of the "hydrocarbon group" in the "hydrocarbon group that may have one or more substituents" is, for example, 1 to 100, 1 to 80, 1 to 60, 1 to 40, 1-30, 1-20, or 1-10 (eg, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10).

In this specification,
"Hydrocarbon group optionally having one or more substituents",
"Alkyl group optionally having one or more substituents",
"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 that may have one or more substituents" and "aralkyl group that may have one or more substituents"
Examples of the "substituent" in can include a halo group, 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 substituents can range from 1 to the maximum number that can be substituted (eg, 1, 2, 3, 4, 5, 6).

In this specification, examples of "hydrocarbon group" include alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups, cycloalkadienyl groups, aryl groups, aralkyl groups, and groups that are combinations thereof. can be included.

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

As used herein, a "fluoroalkyl group" is an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
In the present specification, the number of fluorine atoms that the "fluoroalkyl group" has is 1 or more (e.g., 1 to 3, 1 to 6, 1 to 12, the maximum number that can be substituted from 1). be able to.

"Fluoroalkyl group" can include perfluoroalkyl groups.

A "perfluoroalkyl group" is an alkyl group in which all hydrogen atoms are replaced with fluorine atoms. Specific examples of the perfluoroalkyl group can include a trifluoromethyl group (CF ₃ -) and a pentafluoroethyl group (C ₂ F ₅ -).

In the present specification, "fluoroalkyl group" includes, for example, 1 to 20 carbon atoms, 1 to 12 carbon atoms, 1 to 6 carbon atoms, 1 to 4 carbon atoms, 1 to 3 carbon atoms, 6 carbon atoms, and 6 carbon atoms. 5, a fluoroalkyl group having 4 carbon atoms, 3 carbon atoms, 2 carbon atoms, or 1 carbon number.

In this specification, the "fluoroalkyl group" can be a linear or branched fluoroalkyl group.
In this specification, "fluoroalkyl group" specifically includes, for example, fluoromethyl group, difluoromethyl group, trifluoromethyl group (CF ₃ -), 2,2,2-trifluoroethyl group, pentafluoromethyl group, Ethyl group (C ₂ F ₅ -), tetrafluoropropyl group (e.g. HCF ₂ CF ₂ CH ₂ -), hexafluoropropyl group (e.g. (CF ₃ ) ₂ CH -), nonafluorobutyl group, octafluoropentyl group groups (e.g. HCF ₂ CF ₂ CF ₂ CF ₂ CH ₂ -), tridecafluorohexyl groups, and 3,3,4,4,5,5,6,6,7,7,8,8,8- Examples include tridecafluorooctyl group (CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ -).

In this specification, unless otherwise specified, examples of "alkenyl group" include vinyl, 1-propen-1-yl, 2-propen-1-yl, isopropenyl, 2-buten-1-yl, 4- Straight chain or branched C2-C10 alkenyl groups can be included, such as penten-1-yl, and 5-hexen-1-yl.

In this specification, unless otherwise specified, examples of "alkynyl group" include ethynyl, 1-propyn-1-yl, 2-propyn-1-yl, 4-pentyn-1-yl, 5-hexyn- Can include straight or branched C2-C10 alkynyl groups, 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, and cycloheptyl.

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

In this specification, unless otherwise specified, examples of "cycloalkadienyl group" include cyclobutadienyl, cyclopentadienyl, cyclohexadienyl, cycloheptadienyl, cyclooctadienyl, cyclononadienyl. and C4-C10 cycloalkadienyl groups such as cyclodecadienyl.
In this specification, unless otherwise specified, the "aromatic group" can include an "aryl group" and a "heteroaryl group."

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

In this specification, unless otherwise specified, examples of the "aralkyl group" include benzyl, phenethyl, diphenylmethyl, 1-naphthylmethyl, 2-naphthylmethyl, 2,2-diphenylethyl, 3-phenylpropyl, 4- Can include phenylbutyl, 5-phenylpentyl, 2-biphenylylmethyl, 3-biphenylylmethyl, and 4-biphenylylmethyl.

In this specification, unless otherwise specified, the "non-aromatic heterocyclic group" can be monocyclic, bicyclic, tricyclic, or tetracyclic.
In the present specification, unless otherwise specified, a "non-aromatic heterocyclic group" includes, for example, 1 to 4 ring-constituting atoms selected from oxygen atoms, sulfur atoms, and nitrogen atoms in addition to carbon atoms. It can be a non-aromatic heterocyclic group containing heteroatoms.
In this specification, unless otherwise specified, the "non-aromatic heterocyclic group" can be saturated or unsaturated.
In this specification, unless otherwise specified, examples of "non-aromatic heterocyclic group" include tetrahydrofuryl, oxazolidinyl, imidazolinyl (e.g. 1-imidazolinyl, 2-imidazolinyl, 4-imidazolinyl), aziridinyl (e.g. 1 -aziridinyl, 2-aziridinyl), azetidinyl (e.g. 1-azetidinyl, 2-azetidinyl), pyrrolidinyl (e.g. 1-pyrrolidinyl, 2-pyrrolidinyl, 3-pyrrolidinyl), piperidinyl (e.g. 1-piperidinyl, 2-piperidinyl, 3-piperidinyl), azepanyl (e.g. 1-azepanyl, 2-azepanyl, 3-azepanyl, 4-azepanyl), azocanyl (e.g. 1-azocanyl, 2-azocanyl, 3-azocanyl, 4-azocanyl), piperazinyl (e.g. : 1,4-piperazin-1-yl, 1,4-piperazin-2-yl), diazepinyl (e.g. 1,4-diazepin-1-yl, 1,4-diazepin-2-yl, 1,4- diazepin-5-yl, 1,4-diazepin-6-yl), diazocanyl (e.g. 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 (e.g. tetrahydropyran) -4-yl), morpholinyl (eg, 4-morpholinyl), thiomorpholinyl (eg, 4-thiomorpholinyl), 2-oxazolidinyl, dihydrofuryl, dihydropyranyl, dihydroquinolyl, and the like.

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

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

In the present specification, unless otherwise specified, examples of "5- to 18-membered aromatic fused heterocyclic group" include isoindolyl (e.g., 1-isoindolyl, 2-isoindolyl, 3-isoindolyl, 4-isoindolyl, 5-isoindolyl). isoindolyl, 6-isoindolyl, 7-isoindolyl), indolyl (e.g. 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 (e.g. 1-benzo[c]furanyl, 4-benzo[c]furanyl, 5-benzo[c]furanyl), benzo[b]thienyl, (e.g. 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 (e.g. 1-benzo[c]thienyl, 4-benzo[c]thienyl, 5-benzo[c]thienyl), indazolyl (e.g. 1-indazolyl, 2-indazolyl, 3-indazolyl, 4-indazolyl, 5-indazolyl, 6) -indazolyl, 7-indazolyl), benzimidazolyl (e.g. 1-benzimidazolyl, 2-benzimidazolyl, 4-benzimidazolyl, 5-benzimidazolyl), 1,2-benzisoxazolyl (e.g. 1,2-benzisoxazole-3) -yl, 1,2-benzisoxazol-4-yl, 1,2-benzisoxazol-5-yl, 1,2-benzisoxazol-6-yl, 1,2-benzisoxazol-7-yl ), benzoxazolyl (e.g. 2-benzoxazolyl, 4-benzoxazolyl, 5-benzoxazolyl, 6-benzoxazolyl, 7-benzoxazolyl), 1,2-benzo Isothiazolyl (e.g. 1,2-benzisothiazol-3-yl, 1,2-benzisothiazol-4-yl, 1,2-benzisothiazol-5-yl, 1,2-benzisothiazol-yl) 6-yl, 1,2-benzoisothiazol-7-yl), benzothiazolyl (e.g. 2-benzothiazolyl, 4-benzothiazolyl, 5-benzothiazolyl, 6-benzothiazolyl, 7-benzothiazolyl), isoquinolyl (e.g. 1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl), quinolyl (e.g. 2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 8-quinolyl), cinnolinyl (e.g. 3-cinnolinyl, 4-cinnolinyl), 5-cinnolinyl, 6-cinnolinyl, 7-cinnolinyl, 8-cinnolinyl), phthalazinyl (e.g. 1-phthalazinyl, 4-phthalazinyl, 5-phthalazinyl, 6-phthalazinyl, 7-phthalazinyl, 8-phthalazinyl), quinazolinyl (e.g. 2-quinazolinyl, 4-quinazolinyl, 5-quinazolinyl, 6-quinazolinyl, 7-quinazolinyl, 8-quinazolinyl), quinoxalinyl (e.g. 2-quinoxalinyl, 3-quinoxalinyl, 5-quinoxalinyl, 6-quinoxalinyl, 7-quinoxalinyl, 8 -quinoxalinyl), pyrazolo[1,5-a]pyridyl (e.g. 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 (e.g. 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), etc. can.

In this specification, unless otherwise specified,
"Non-aromatic heterocyclic group which may have one or more substituents",
"Benzene ring which may have one or more substituents",
"Heteroaryl group which may have one or more substituents" and "pyridine ring which may have one or more substituents"
Examples of each "substituent" in are a hydrocarbon group that may have one or more substituents, a halo group, a nitro group, a cyano group, an oxo group, a thioxo group, a sulfo group, a sulfamoyl group, a sulfinamoyl group. , and sulfenamoyl groups.
The number of substituents can range from 1 to the maximum number that can be substituted (eg, 1, 2, 3, 4, 5, 6).

［式中、
環Ａは、１個以上の置換基を有していてもよい芳香環を表し；及び
Ｒ^１、及びＲ^２は、同一又は異なって、水素、又は有機基を表す。］
で表されるフッ化ビニル基含有環状超原子価ヨウ素化合物
である。 2. Vinyl fluoride group-containing cyclic hypervalent iodine compound A compound that is an embodiment of the present disclosure is:
Formula (2):

[In the formula,
Ring A represents an aromatic ring which may have one or more substituents; and R ¹ and R ² are the same or different and represent hydrogen or an organic group. ]
It is a cyclic hypervalent iodine compound containing a vinyl fluoride group represented by

R ¹ and R ² are preferably
same or different,
hydrogen,
Alkyl group that may have one or more substituents (e.g., C1-C20 alkyl group that may have one or more substituents, C1-C6 alkyl group),
Aromatic groups that may have one or more substituents (e.g., C6-C20 aryl groups that may have one or more substituents, C6-C10 aryl group), or a heterocyclic group that may have one or more substituents (e.g., a 5- to 20-membered heterocyclic group that may have one or more substituents, 1 5- to 10-membered heterocyclic group which may have more than one substituent)
can be,
More preferably, the same or different hydrogen or alkyl groups optionally having one or more substituents,
More preferably, it can be an alkyl group which may have one or more substituents, which are the same or different,
Even more preferably, they can be the same or different alkyl groups.

R ¹ is more preferably,
Alkyl groups that may have one or more substituents (e.g. C1-C10 alkyl groups that may have one or more substituents, and alkyl groups that may have one or more substituents) good C1-C6 alkyl group)
can be.
The number of carbon atoms in the alkyl group of "the alkyl group which may have one or more substituents" for ^R1 is:
1 to 20 is preferred;
1 to 15 is more preferable;
1 to 10 is more preferable;
1 to 6 are even more preferred, and 1 to 4 are particularly preferred.

R ¹ is also more preferably,
Alkyl group optionally substituted with one or more cycloalkyl groups (e.g. C1-C6 alkyl group optionally substituted with one or more C3-C6 cycloalkyl groups)
can be.

^R2 is
Preferably, it is hydrogen or an alkyl group that may have one or more substituents (e.g., a C1-C20 alkyl group that may have one or more substituents),
More preferably it can be hydrogen or an alkyl group, and most preferably hydrogen.
The number of carbon atoms in the alkyl group in R ² "number of carbon atoms in the alkyl group that may have one or more substituents" is:
1 to 20 is preferred;
1 to 15 is more preferable;
1 to 10 is more preferable;
1 to 5 are even more preferred;
1 to 2 are particularly preferred.
R ¹ and R ² may be connected and together with the carbon atoms to which they are bonded, form a ring which may have one or more substituents. The structure of the "ring that may have one or more substituents" can be understood from the structures of R ¹ and R ² .

Ring A is preferably
Aromatic carbocycle which may have one or more substituents (e.g. aromatic carbocycle having 6 to 14 carbon atoms which may have one or more substituents)
can be.

Ring A is preferably
Aromatic heterocycle which may have one or more substituents (e.g. 5- to 10-membered aromatic heterocycle which may have one or more substituents)
can be.

Ring A is preferably
Aromatic monocycles that may have one or more substituents (e.g., benzene rings that may have one or more substituents; (5- to 6-membered aromatic heterocycle that may have one or more substituents, such as a pyridine ring and a thiophene ring that may have one or more substituents)
can be.

［式中の記号は前記と同意義を表す。］
で表されるフッ化ビニル基含有環状超原子価ヨウ素化合物の製造方法であって、
式（１）：

［式中、Ｒ^１、及びＲ^２は、同一又は異なって、水素、又は有機基を表す。］
で表される化合物を、
置換基を有してもいてもよい２－ヨード安息香酸、及び
酸化剤
の存在下で、
フッ素源と反応させる工程Ａを含む、製造方法
である。 3. Method for producing a cyclic hypervalent iodine compound containing a vinyl fluoride group The method for producing a cyclic hypervalent iodine compound that is an embodiment of the present disclosure is based on the formula (2):

[The symbols in the formula have the same meanings as above. ]
A method for producing a cyclic hypervalent iodine compound containing a vinyl fluoride group represented by
Formula (1):

[In the formula, R ¹ and R ² are the same or different and represent hydrogen or an organic group. ]
The compound represented by
In the presence of 2-iodobenzoic acid which may have a substituent and an oxidizing agent,
This is a manufacturing method including step A of reacting with a fluorine source.

The manufacturing method can be a method for manufacturing the compound that is one aspect of the present disclosure. Therefore, for understanding the production method, reference may also be made to the above description of preferred embodiments of the compound.

［式中、Ｒ^１、及びＲ^２は、同一又は異なって、水素、又は有機基を表す。］
で表される化合物
であることができる。 3.1. Substrate The substrate for the above production method is
Formula (1):

[In the formula, R ¹ and R ² are the same or different and represent hydrogen or an organic group. ]
It can be a compound represented by

R ¹ and R ² are preferably the same or different,
hydrogen,
an alkyl group that may have one or more substituents,
It can be an aromatic group which may have one or more substituents, or a heterocyclic group which may have one or more substituents.
R ² can suitably be hydrogen.
Ring A can be an aromatic carbocycle which may suitably have one or more substituents.

［式中の記号は前記と同意義である。］
で表されるフッ化ビニル基含有環状超原子価ヨウ素化合物
であることができる。 3.2. Target The target of the above manufacturing method is:
Formula (2):

[The symbols in the formula have the same meanings as above. ]
It can be a cyclic hypervalent iodine compound containing a vinyl fluoride group represented by:

R ¹ and R ² and ring A in the target product may be the same or different from those in the target product, but are usually the same.

R ¹ and R ² are preferably the same or different,
hydrogen,
an alkyl group that may have one or more substituents,
It can be an aromatic group which may have one or more substituents, or a heterocyclic group which may have one or more substituents.

R ¹ and R ² are preferably
It can be hydrogen or a C1-C20 alkyl group.

3.3. Process A
In process A,
The compound represented by the above formula (1),
In the presence of 2-iodobenzoic acid, which may optionally have one or more substituents, and an oxidizing agent,
React with fluorine source.

Ring A can preferably be a benzene ring which may have one or more substituents, or a pyridine ring which may have one or more substituents, and more preferably a benzene ring. .

3.3.1 2-iodobenzoic acid which may have one or more substituents Preferred examples of the above-mentioned "2-iodobenzoic acid which may have one or more substituents" are: 2-iodobenzoic acid can be included.

The amount of the “2-iodobenzoic acid which may optionally have a substituent” is:
For the substrate compound (1),
Usually within the range of 0.2 to 10 equivalents, preferably within the range of 0.5 to 5 equivalents,
More preferably, it is within the range of 0.8 to 3 equivalents, and even more preferably within the range of 1 to 2 equivalents.

3.3.2 Oxidizing agent The "oxidizing agent" used in step A is preferably, for example,
(i) Formula: R ^X COOOM
(In the formula,
R ^X is a hydrocarbon group which may have one or more substituents, and M is a hydrogen atom or a metal atom. ),
A compound represented by;
(ii) Formula: R ^X OOM
(In the formula,
R ^X is a hydrogen atom or a hydrocarbon group which may have one or more substituents, and M is a hydrogen atom or a metal atom. )
and (iii) metal oxides.
Examples of the oxidizing agent are:
Metachloroperbenzoic acid, hydrogen peroxide, peracetic acid, perbenzoic acid, tert-butyl hydroperoxide, cumene hydroperoxide, potassium persulfate, potassium hydrogen persulfate-potassium hydrogen sulfate-potassium sulfate mixture, permanganic acid, dichromic acid , tungsten oxide, ruthenium oxide, antimony oxide, osmium oxide, and sulfur trioxide.
A suitable example of the oxidizing agent is
Metachloroperbenzoic acid, hydrogen peroxide, peracetic acid, perbenzoic acid, tert-butyl hydroperoxide, cumene hydroperoxide, potassium persulfate, and potassium hydrogen persulfate-potassium hydrogen sulfate-potassium sulfate mixtures can be included.
A more preferred example of the oxidizing agent may include m-chloroperbenzoic acid.
These may be used alone or in combination of two or more.

The amount of the oxidizing agent may be, for example,
For the substrate compound (1),
Usually within the range of 0.1 to 40 equivalents, preferably within the range of 0.5 to 30 equivalents,
More preferably, it is within the range of 0.8 to 10 equivalents, and even more preferably within the range of 1 to 5 equivalents.

3.3.3 Fluorine Source The "fluorine source" used in step A can preferably be a hydrogen fluoride source. Examples of the “fluorine source” are:
Formula: MF _n (in the formula, M is H, a metal of group 1 of the periodic table, or a metal of group 2 of the periodic table; and n is 1 or 2). Can be included.

M is
Preferably, it can be H, Li, Na, K, Ca, or Cs,
More preferably, it can be H, Na, K, or Ca, and even more preferably, it can be H.

Examples of the “fluorine source” are also:
anhydrous hydrofluoric acid,
Hydrofluoric acid aqueous solution (e.g. hydrofluoric acid aqueous solution with a concentration of 10 to 70% by weight),
mixtures or complexes of hydrofluoric acid and organic bases;
Mixtures or complexes of hydrofluoric acid and inorganic bases can be included.

The mixture or complex of hydrofluoric acid and an organic base is, for example,
Hydrogen fluoride-triethylamine salt [Et ₃ N·nHF (n=1 to 10, or 1 to 5)],
Hydrogen fluoride-pyridine salt [Py・nHF (n=1-10)], and hydrogen fluoride-tetraethylammonium fluoride salt [Et ₄ NF・nHF (n=1-10)]
It can be a salt such as or derived from these.

In the mixture, the mixture or complex of hydrofluoric acid and an organic base is, for example,
HF-KF ( _KHF2 )
etc., or derived from this.

The fluorine sources can be used singly or in combination of two or more.

The amount of the fluorine source is, for example,
As hydrogen fluoride for the substrate compound (1),
Usually within the range of 1 to 70 mol,
Preferably within the range of 3 to 50 mol,
More preferably, it is within the range of 5 to 40 mol, and even more preferably within the range of 10 to 30 mol.
Within the range of 0.1 to 1000 mol, preferably within the range of 0.2 to 500 mol, more preferably within the range of 0.3 to 100 mol, even more preferably within the range of 0.4 to 50 mol, and even more Preferably, it can be within the range of 0.5 to 30 mol.

3.3.4 Acid The reaction in step A can suitably be carried out in the presence of an acid.
The lower limit of the amount of the acid to be used can be, for example, 0.5, 0.6, 0.8, 1, 3, or 5 with respect to Compound (1) as the substrate.
The upper limit of the amount of the acid used can be, for example, 50, 30, 20, or 15 with respect to compound (1) as the substrate.
The amount of the acid used is
for example,
For the substrate compound (1),
Usually within the range of 0.5 to 50 equivalents, preferably within the range of 0.5 to 30 equivalents,
More preferably, it is within the range of 0.6 to 20 equivalents, and even more preferably within the range of 0.8 to 15 equivalents.

Examples of the above “acid” include:
Hydrogen halide or hydrohalic acid, hypohalous acid, halous acid, halogen acid, or perhalogen acid [e.g. sulfuric acid, nitric acid, phosphoric acid, polyphosphoric acid, hydrogen fluoride, hydrofluoric acid, hydrochloric acid, hydrogen bromide] , hydrogen iodide, hypochlorous acid, chlorous acid, chloric acid, perchloric acid, perbromic acid, and periodic acid],
Sulfonic acid, or polymer-supported sulfonic acid such as polystyrene sulfonic acid or fluorinated sulfonic acid resin [Nafion-H (trade name)] [e.g. fluorosulfonic acid, chlorosulfonic acid, methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfone] acid, difluoromethanesulfonic acid, trichloromethanesulfonic acid, perfluorobutanesulfonic acid, perfluorooctanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, nitrobenzenesulfonic acid],
mono- or polycarboxylic acids [e.g. formic acid, acetic acid, propionic acid, chloroacetic acid, bromoacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, glycolic acid, lactic acid, benzoic acid, oxalic acid, succinic acid];
Lewis acid or its ether complex [e.g. SO3 _{, BF3} , _BCl3 , B( _OCH3 ) ₃ , AlCl3, _AlBr3 , _SbF3 , _{SbCl3 , SbF5} , _PF3 , _PF5 , AsF3 _{, AsCl3} , _AsF5 , _TiCl4 , _NbF5 , _TaF5 ];
Examples include acids consisting of Lewis acids and hydrogen halides [e.g. HBF ₄ , HPF ₆ , HAsF ₆ , HSbF ₆ , and HSbCl ₆ ], complexes of these with ethers, etc., or mixtures of two or more of these. .

3.3.5. Conditions for Step A The reaction in Step A can be carried out in the presence or absence of a solvent.
The solvent may be a non-polar solvent or a polar solvent,
A specific example is
The solvent may be either a nonpolar solvent or a polar solvent.
The solvent may be an ester, a ketone, an aromatic compound, an alcohol, an ether, an amine, a nitrogen-containing polar organic compound, a nitrile, a halogenated hydrocarbon, an aliphatic hydrocarbon, a fluorinated solvent, a carbonate, or any other solvent. Can be a combination.

Examples of esters as the solvent can include ethyl acetate, butyl acetate, amyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and a preferred example thereof can include ethyl acetate.

Examples of ketones as the solvent may include acetone, methyl ethyl ketone, diethyl ketone, hexanone, methyl isobutyl ketone, heptanone, diisobutyl ketone, acetonylacetone, methylhexanone, and acetophenone, cyclohexanone, diacetone alcohol, and suitable Examples can include acetone.

Examples of aromatic compounds as the solvent can include anisole, benzene, toluene, xylene, and ethylbenzene, and preferred examples thereof can include benzene and toluene.

Examples of alcohols as the solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, pentanol, hexanol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol. , tripropylene glycol, polypropylene glycol, trimethylene glycol, and hexanetriol, and suitable examples thereof can include methanol and ethanol.

Examples of ethers as the solvent are diethyl ether, dibutyl ether, tetrahydrofuran, tetrahydropyran, dioxane, dimethoxyethane, diethylene glycol diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene. can include glycol monomethyl ether (PGME; also known as 1-methoxy-2-propanol), propylene glycol monoethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, and tetraethylene glycol diethyl ether; Suitable examples may include diethyl ether and tetrahydrofuran.

Examples of amines as the solvent can include monoethanolamine, diethanolamine, and triethanolamine.

Examples of the nitrogen-containing polar organic compound as the solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 2-pyrrolidone, and 1,3-dimethyl-2-imidazolidone. and suitable examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone.

Examples of nitriles as the solvent can include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, and adiponitrile, and a suitable example thereof can include acetonitrile.

Examples of halogenated hydrocarbons as the solvent can include dichloromethane, dichloroethane, chloroform, carbon tetrachloride, tetrachloroethane, trichloroethane, chlorobenzene, dichlorobenzene, and chlorotoluene, and preferred examples thereof include dichloromethane, and chloroform. Can be included.

Examples of aliphatic hydrocarbons as the solvent can include hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, and mineral spirits, and preferred examples thereof can include cyclohexane, heptane.

Examples of the fluorinated solvent may include perfluorobenzene, trifluorotoluene, ditrifluorobenzene, and trifluoroethanol, and preferred examples thereof may include perfluorobenzene and trifluoroethanol.

Examples of carbonates as the solvent can include tetralin dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, ethylene carbonate, and propylene carbonate, and preferred examples thereof can include ethylene carbonate and propylene carbonate.

Examples of such other solvents can include acetic acid, pyridine, dimethyl sulfoxide, sulfolane, and water.
These solvents can be used alone or in combination of two or more.

The amount of solvent used is, for example,
For 1 part by mass of the organic compound (1) as a substrate,
It is usually within the range of 0 to 200 parts by weight, preferably within the range of 0 to 100 parts by weight, and more preferably within the range of 0 to 50 parts by weight.

The temperature of step A is
Usually within the range of -78 to 200°C, preferably within the range of -10 to 100°C,
More preferably, it can be within the range of -65 to 100°C, and even more preferably within the range of 0 to 100°C.

The time for process A is
The time is usually within the range of 0.1 to 72 hours, preferably within the range of 0.1 to 48 hours, and more preferably within the range of 0.1 to 36 hours.

The obtained compound (2) can be isolated or purified, if desired, by conventional methods such as extraction, dissolution, concentration, precipitation, dehydration, adsorption, or chromatography, or a combination thereof.

According to the manufacturing method of the present disclosure, the raw material conversion rate is preferably 10% or more, more preferably 30% or more, even more preferably 50% or more, even more preferably 70% or more, particularly preferably 80% or more. be able to.
According to the production method of the present disclosure, the selectivity of the target compound is preferably 10% or more, more preferably 30% or more, even more preferably 50% or more, even more preferably 70% or more, particularly preferably 80% or more. can be.
According to the production method of the present disclosure, the yield of the target compound is preferably 10% or more, more preferably 30% or more, even more preferably 50% or more, even more preferably 70% or more, particularly preferably 80% or more. can be.

［式中、
波線はシス配置又はトランス配置を表し；
Ｒ^１、及びＲ^２は、水素、又は有機基を表し；及び
Ｒは、有機基を表す。］
で表される化合物の製造方法であって、
式（２）：

［式中、
波線は、シス配置又はトランス配置を表し；
環Ａは、１個以上の置換基を有していてもよい芳香環を表し；及び
Ｒ^１、及びＲ^２は、同一又は異なって、水素、又は有機基を表す。］
で表されるフッ化ビニル基含有環状超原子価ヨウ素化合物［本明細書中、フッ化ビニル基含有環状超原子価ヨウ素化合物（２）と称する場合がある。］を、
式（３）：

［式中、Ｒは、前記と同意義を表す。］
で表されるアルキン化合物と反応させる工程Ｂ
を含む、製造方法
である。
工程Ｂの反応は、所望により、金属触媒及び／又は塩基の存在下で行われる。 4. Method for producing a cyclic hypervalent iodine compound containing a vinyl fluoride group Another embodiment of the present disclosure is a method for producing a cyclic hypervalent iodine compound containing a vinyl fluoride group .
Formula (1'):

[In the formula,
Wavy lines represent cis or trans configuration;
R ¹ and R ² represent hydrogen or an organic group; and R represents an organic group. ]
A method for producing a compound represented by
Formula (2):

[In the formula,
Wavy lines represent cis or trans configuration;
Ring A represents an aromatic ring which may have one or more substituents; and R ¹ and R ² are the same or different and represent hydrogen or an organic group. ]
A vinyl fluoride group-containing cyclic hypervalent iodine compound represented by [this specification may be referred to as a vinyl fluoride group-containing cyclic hypervalent iodine compound (2)]. ]of,
Formula (3):

[Wherein, R represents the same meaning as above.] ]
Step B of reacting with an alkyne compound represented by
It is a manufacturing method including.
The reaction in step B is optionally carried out in the presence of a metal catalyst and/or a base.

The metal in the metal catalyst is
Preferably, it can be a transition metal, and more preferably one or more metals selected from the group consisting of Cu, Pd, Fe, Zr, Co, Ni, Ru, and Rh.

The metal catalyst may have a ligand. Examples of metal catalysts with ligands are:
Palladium catalysts (e.g. palladium acetate, [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride, tris(dibenzylideneacetone)dipalladium, tetrakis(triphenylphosphine)palladium, and bis(triphenylphosphine)palladium dichloride)
can be included.
The metal catalysts may be used alone or in combination of two or more.

The metal catalysts can be used preferably in combination with copper compounds.
Examples of such copper compounds are:
Copper chloride, copper bromide, and copper iodide can be included.
The copper compounds may be used alone or in combination of two or more.

The lower limit of the amount of the metal catalyst to be used with respect to the vinyl fluoride group-containing cyclic hypervalent iodine compound (2) can be, for example, 0.001 equivalent.
The upper limit of the amount can be, for example, 1 equivalent.

Examples of the bases are:
Organic bases (e.g. triethylamine, tributylamine, isopropylamine, diethylamine, diisopropylamine, diisopropylethylamine); and inorganic bases (e.g. sodium carbonate, potassium carbonate, and cesium carbonate)
can be included.

The bases may be used alone or in combination of two or more.

The upper limit of the amount of the base to be used with respect to the vinyl fluoride group-containing cyclic hypervalent iodine compound (2) can be, for example, 1 equivalent.
The lower limit of that amount can be, for example, 50 equivalents.

A liquid organic base can also be used as a solvent in the step B reaction.

The reaction in step B may be carried out in the presence of a solvent. Examples of the solvent can include those exemplified for step A above.

The amount of solvent used is, for example,
For 1 part by mass of the organic compound (1) as a substrate,
It is usually within the range of 0 to 200 parts by weight, preferably within the range of 0 to 100 parts by weight, and more preferably within the range of 0 to 50 parts by weight.

The temperature of step B is
The temperature is usually within the range of -78 to 200°C, preferably within the range of -10 to 100°C, and more preferably within the range of 0 to 100°C.

The time for process B is
The time is usually within the range of 0.1 to 72 hours, preferably within the range of 0.1 to 48 hours, and more preferably within the range of 0.1 to 36 hours.

The obtained compound (2) can be isolated or purified, if desired, by conventional methods such as extraction, dissolution, concentration, precipitation, dehydration, adsorption, or chromatography, or a combination thereof.

According to the manufacturing method of the present disclosure, the raw material conversion rate is preferably 10% or more, more preferably 30% or more, even more preferably 50% or more, even more preferably 70% or more, particularly preferably 80% or more. be able to.
According to the production method of the present disclosure, the selectivity of the target compound is preferably 10% or more, more preferably 30% or more, even more preferably 50% or more, even more preferably 70% or more, particularly preferably 80% or more. can be.
According to the production method of the present disclosure, the yield of the target compound is preferably 10% or more, more preferably 30% or more, even more preferably 50% or more, even more preferably 70% or more, particularly preferably 80% or more. can be.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

The meanings of symbols and abbreviations in the examples are shown below.
Pr: Pyridine mCPBA: Metachloroperbenzoic acid

Example 1
2-Iodine benzoic acid (1.5 eq.), mCPBA (1.5 eq.), dichloromethane, Py·HF (20 eq.), and 1-Octyne 1a (0.5 mmol) were added. Then, BF ₃ ·OEt ₂ (10 eq.) was added at -65°C, and the mixture was further stirred at room temperature. Thereafter, quenching, separation, solvent distillation, and purification were performed to obtain the target product 2a in a yield of 84% (Table 1, Entry 1).

Examples 2 to 9
The same operation was performed except that 1-Octyne was changed to the following alkynes 1b to 1f to obtain the corresponding target products 2b to 2f. The results are shown in Table 1 (Entry 2-7).

Claims (10)

Formula (2):

[In the formula,
Wavy lines represent cis or trans configuration;
Ring A represents an aromatic carbon ring having 6 to 14 carbon atoms which may have from 1 to the maximum number of substituents ;
R ¹ and R ² are the same or different,
hydrogen,
an alkyl group which may have from 1 to the maximum number of substituents ,
Alkenyl group optionally having from 1 to the maximum number of substituents,
an alkynyl group which may have from 1 to the maximum number of substituents;
Cycloalkyl group optionally having from 1 to the maximum number of substituents,
Cycloalkenyl group optionally having from 1 to the maximum number of substituents,
Cycloalkadienyl group optionally having from 1 to the maximum number of substituents,
an aryl group which may have from 1 to the maximum number of substituents, or
Aralkyl group optionally having from 1 to the maximum number of substituents
represents; and
The substituents are the same or different and represent at least one selected from the group consisting of a halo group, a nitro group, a cyano group, an oxo group, a thioxo group, a sulfo group, a sulfamoyl group, and a sulfenamoyl group. ]
A cyclic hypervalent iodine compound containing a vinyl fluoride group represented by: R ¹ and R ² are the same or different,
hydrogen,
an alkyl group which may have from 1 to the maximum number of substituents, or
An aryl group that may have one to the maximum number of substituents that can be substituted ,
The vinyl fluoride group-containing cyclic hypervalent iodine compound according to claim 1. The vinyl fluoride group-containing cyclic hypervalent iodine compound according to claim 1 or 2, wherein R ¹ is an alkyl group which may have from 1 to the maximum number of substituents. The vinyl fluoride group-containing cyclic hypervalent iodine compound according to claim 1 or 2, wherein R ¹ is an alkyl group optionally substituted with one to the maximum number of substitutable cycloalkyl groups. The vinyl fluoride group-containing cyclic superatom according to any one of claims 1 to 4, wherein R ² is hydrogen or an alkyl group optionally having one to the maximum number of substituents. Valent iodine compounds. The vinyl fluoride group-containing cyclic hypervalent iodine compound according to any one of claims 1 to 4, wherein R ² is hydrogen. Formula (2):

[In the formula,
Wavy lines represent cis or trans configuration;
Ring A represents an aromatic carbon ring having 6 to 14 carbon atoms which may have from 1 to the maximum number of substituents; and R ¹ and R ² are the same or different;
hydrogen,
an alkyl group which may have from 1 to the maximum number of substituents ,
Alkenyl group optionally having from 1 to the maximum number of substituents,
an alkynyl group which may have from 1 to the maximum number of substituents;
Cycloalkyl group optionally having from 1 to the maximum number of substituents,
Cycloalkenyl group optionally having from 1 to the maximum number of substituents,
Cycloalkadienyl group optionally having from 1 to the maximum number of substituents,
an aryl group which may have from 1 to the maximum number of substituents, or
Aralkyl group optionally having from 1 to the maximum number of substituents
represents; and
The substituents are the same or different and represent at least one selected from the group consisting of a halo group, a nitro group, a cyano group, an oxo group, a thioxo group, a sulfo group, a sulfamoyl group, and a sulfenamoyl group. ]
A method for producing a cyclic hypervalent iodine compound containing a vinyl fluoride group represented by
Formula (1):

[ The symbols in the formula have the same meanings as above. ]
The compound represented by
Formula (3):

[The symbols in the formula have the same meanings as above. ]
In the presence of a compound represented by and an oxidizing agent,
A manufacturing method comprising step A of reacting with a fluorine source. R ¹ and R ² are the same or different,
hydrogen,
an alkyl group which may have from 1 to the maximum number of substituents, or
An aryl group that may have one to the maximum number of substituents that can be substituted ,
The manufacturing method according to claim 7. R ¹ and R ² are the same or different,
hydrogen, or
A C1-C20 alkyl group that may have from 1 to the maximum number of substituents that can be substituted ,
The manufacturing method according to claim 7 or 8. R ² is hydrogen,
The manufacturing method according to any one of claims 7 to 9.