JP7116294B2 - Cyclic carbonate compound and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a cyclic carbonate compound (especially a fluorine-containing cyclic carbonate compound) and the like.

Cyclic carbonate compounds (particularly fluorine-containing cyclic carbonate compounds) are extremely important compounds as functional materials, various chemical products such as pharmaceutical and agricultural compounds, and intermediates thereof.
Therefore, it is always desired to provide a new method for producing a cyclic carbonate compound.

Non-Patent Document 1 describes a method for producing a fluorine-containing cyclic carbonate compound.

Kerouredan et al., Synthesis, 2008, 24, pp3903-3918

An object of the present invention is to provide a novel method for producing a cyclic carbonate compound.

［式中、
Ｒ^Xは、水素原子、有機基を表し、
Ｘは、ハロゲン原子を表し、
Ｙは、水素原子、又はハロゲン原子を表し、及び
ｎは、１、又は２の数を表す。］
で表される化合物［本明細書中、化合物（１Ｂ）と称する場合がある。］の製造方法であって、
式（２）：

［式中、
Ｒ^Xは、水素原子、有機基を表し、
Ｘは、ハロゲン原子を表し、
Ｙは、水素原子、又はハロゲン原子を表し、及び
ｎは、１、又は２の数を表す。］
で表される化合物［本明細書中、化合物（２）と称する場合がある。］を、
ホスゲンと反応させる工程１を含む、
製造方法、
により前記課題が解決できることを見出し、本発明を完成するに至った。 As a result of intensive studies, the present inventors have found formula (1B):

[In the formula,
R ^X represents a hydrogen atom or an organic group;
X represents a halogen atom,
Y represents a hydrogen atom or a halogen atom, and n represents the number of 1 or 2; ]
A compound represented by [herein sometimes referred to as compound (1B). ] A method for producing
Formula (2):

[In the formula,
R ^X represents a hydrogen atom or an organic group;
X represents a halogen atom,
Y represents a hydrogen atom or a halogen atom, and n represents the number of 1 or 2; ]
A compound represented by [this specification may be referred to as compound (2). ]of,
comprising step 1 of reacting with phosgene;
Production method,
The present inventors have found that the above problems can be solved by the method, and completed the present invention.

The present invention includes the following aspects.

［式中、
Ｒ^Xは、水素原子、有機基を表し、
Ｘは、ハロゲン原子を表し、
Ｙは、水素原子、又はハロゲン原子を表し、及び
ｎは、１、又は２の数を表す。］
で表される化合物の製造方法であって、
式（２）：

［式中、
Ｒ^Xは、水素原子、有機基を表し、
Ｘは、ハロゲン原子を表し、
Ｙは、水素原子、又はハロゲン原子を表し、及び
ｎは、１、又は２の数を表す。］
で表される化合物を、
ホスゲンと反応させる工程１を含む、
製造方法。
項２．
Ｒ^Ｘは、水素原子、又は１個以上の置換基を有していてもよい炭化水素基［当該炭化水素基には、－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）－、－Ｓ（＝Ｏ）－ＮＲ^ｏ－、及び－ＮＲ^ｏ－Ｓ（＝Ｏ）－（これらの式中、Ｒ^ｏは、独立して、水素原子、又は有機基である。）からなる群より選択される１個以上の部分が挿入されていてもよい。］である項１に記載の製造方法。
項３．
Ｒ^Xは、水素原子、アルキル基、又はフルオロアルキル基である項２に記載の化合物。
項４．
Ｘは、フッ素原子である項１～３のいずれか一項に記載の製造方法。
項５．
Ｙは、ハロゲン原子である項１～４のいずれか一項に記載の製造方法。
項６．
ホスゲンは、モノホスゲン、トリホスゲン、又はフルオロホスゲンである、項１～５のいずれか一項に記載の製造方法。
項７．
（１）項１中に記載されている前記式（１Ｂ）で表される化合物、及び
（２）式（１Ｄ）：

［式中、
Ｒ^１Ｄは、アルキル基を表し、及び
ｎは、１、又は２の数を表す。］
で表される化合物
を含有する組成物。
項８．
項７に記載の組成物の製造方法であって、
（Ａ）２，２－ジアルキル－１，３－ジオキソラン－４－カルボアルデヒド及びその３量体の混合物にフッ素化剤を作用させてフッ素化する工程、及び
（Ｂ）工程（Ａ）の生成物を、式：Ｒ^１Ｄ－ＯＨ（式中の記号は、前記と同意義を表す。）で表されるアルコールの存在下で、脱アセトニド化する工程を含む、
製造方法。
項９．
前記フッ素化剤が、脱酸素的フッ素化剤である項８に記載の製造方法。
項１０．
Ｒ^１Ｄが直鎖状又は分枝鎖状のＣ１－Ｃ４アルキルである項８又は９の製造方法。
項１１．
４－（ジメトキシメチル）－１，３－ジオキソラン。 Section 1.
Formula (1B):

[In the formula,
R ^X represents a hydrogen atom or an organic group;
X represents a halogen atom,
Y represents a hydrogen atom or a halogen atom, and n represents the number of 1 or 2; ]
A method for producing a compound represented by
Formula (2):

[In the formula,
R ^X represents a hydrogen atom or an organic group;
X represents a halogen atom,
Y represents a hydrogen atom or a halogen atom, and n represents the number of 1 or 2; ]
A compound represented by
comprising step 1 of reacting with phosgene;
Production method.
Section 2.
R ^X is a hydrogen atom or a hydrocarbon group optionally having 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)-, -S(=O)-NR ^o -, and -NR ^o -S(=O)-( In these ^formulas , each R 2 is independently a hydrogen atom or an organic group.) may be inserted with one or more moieties selected from the group consisting of. ] The manufacturing method according to item 1.
Item 3.
Item 3. The compound according to Item 2, wherein R ^X is a hydrogen atom, an alkyl group, or a fluoroalkyl group.
Section 4.
Item 4. The production method according to any one of Items 1 to 3, wherein X is a fluorine atom.
Item 5.
Item 5. The production method according to any one of Items 1 to 4, wherein Y is a halogen atom.
Item 6.
Item 6. The production method according to any one of Items 1 to 5, wherein phosgene is monophosgene, triphosgene, or fluorophosgene.
Item 7.
(1) the compound represented by formula (1B) described in item 1, and (2) formula (1D):

[In the formula,
R ^1D represents an alkyl group and n represents the number 1 or 2; ]
A composition containing a compound represented by
Item 8.
A method for producing the composition according to Item 7,
(A) a step of fluorinating a mixture of 2,2-dialkyl-1,3-dioxolane-4-carbaldehyde and a trimer thereof with a fluorinating agent, and (B) the product of step (A) is deacetonidated in the presence of an alcohol represented by the formula: R ^1D -OH (the symbols in the formula have the same meanings as above),
Production method.
Item 9.
Item 9. The production method according to Item 8, wherein the fluorinating agent is a deoxidizing fluorinating agent.
Item 10.
10. A process according to item 8 or 9, wherein R ^1D is linear or branched C1-C4 alkyl.
Item 11.
4-(dimethoxymethyl)-1,3-dioxolane.

INDUSTRIAL APPLICABILITY According to the present invention, a novel cyclic carbonate compound (especially a fluorine-containing cyclic carbonate compound) is provided, and a method for producing the same is provided.

Terms The symbols and abbreviations used in the present specification can be understood as meanings commonly used in the technical field to which the present invention belongs, in accordance with the context of the present specification, unless otherwise specified.
As used herein, the phrase "comprising" is intended to encompass the phrase "consisting essentially of" and the phrase "consisting of".
Unless otherwise limited, any step, treatment, or operation described herein may be performed at room temperature.
As used herein, room temperature means a temperature within the range of 10-40°C.
In the present specification, the notation "Cn-Cm" (where n and m are numbers) represents that the number of carbon atoms is n or more and m or less, as is commonly understood by those skilled in the art. .

In this specification, unless otherwise specified, examples of "halogen atom" can include fluorine, chlorine, bromine, and iodine.

As used herein, "organic group" means a group containing one or more carbon atoms (or a group formed by removing one hydrogen atom from an organic compound).

Examples of such "organic groups" are
an alkyl group optionally having one or more substituents,
an alkenyl group optionally having one or more substituents,
an alkynyl group optionally having one or more substituents,
a cycloalkyl group optionally having one or more substituents,
a cycloalkenyl group optionally having one or more substituents,
a cycloalkadienyl group optionally having one or more substituents,
an aryl group optionally having one or more substituents,
an aralkyl group optionally having one or more substituents,
a non-aromatic heterocyclic group optionally having one or more substituents,
a heteroaryl group optionally having one or more substituents,
cyano group,
aldehyde group,
R ^r O-,
R ^r CO—,
^RrSO2- _,
R ^r OCO-, and R ^r OSO ₂ -
(wherein R ^r is independently
an alkyl group optionally having one or more substituents,
an alkenyl group optionally having one or more substituents,
an alkynyl group optionally having one or more substituents,
a cycloalkyl group optionally having one or more substituents,
a cycloalkenyl group optionally having one or more substituents,
a cycloalkadienyl group optionally having one or more substituents,
an aryl group optionally having one or more substituents,
an aralkyl group optionally having one or more substituents,
non-aromatic heterocyclic group optionally having one or more substituents, or heteroaryl group optionally having one or more substituents)
can include

As used herein, an "organic group" is, for example, a hydrocarbon group optionally having 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)-, -S(=O)-NR ^o -, and -NR ^o -S( =O)- (in these formulas, R 2 ^o is independently a hydrogen atom or an organic group). One or more moieties selected from the group may be inserted. ].
Examples of such heteroatom-inserted hydrocarbon groups can include non-aromatic heterocyclic groups and heteroaryl groups, as is commonly understood based on common knowledge in the chemical arts.

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

In this specification,
"a hydrocarbon group optionally having one or more substituents",
"an alkyl group optionally having one or more substituents",
"an alkenyl group optionally having one or more substituents",
"an alkynyl group optionally having one or more substituents",
"a cycloalkyl group optionally having one or more substituents",
"a cycloalkenyl group optionally having one or more substituents",
"a cycloalkadienyl group optionally having one or more substituents",
"Aryl group optionally having one or more substituents" and "Aralkyl group optionally having one or more substituents"
Examples of "substituents" in can respectively include halogen atoms, nitro groups, cyano groups, oxo groups, thioxo groups, sulfo groups, sulfamoyl groups, sulfinamoyl groups, and sulfenamoyl groups.
The number of substituents may be in the range of 1 to the maximum substitutable number (eg, 1, 2, 3, 4, 5, 6).

As used herein, examples of "hydrocarbon groups" include alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups, cycloalkadienyl groups, aryl groups, aralkyl groups, and groups that are combinations thereof. can include

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.

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 possessed by the "fluoroalkyl group" is 1 or more (eg, 1 to 3, 1 to 6, 1 to 12, the maximum number that can be substituted from 1). be able to.
A "fluoroalkyl group" includes a perfluoroalkyl group.
A "perfluoroalkyl group" is an alkyl group in which all hydrogen atoms are substituted with fluorine atoms. Specific examples of such perfluoroalkyl groups include trifluoromethyl groups (CF ₃ —) and pentafluoroethyl groups (C ₂ F ₅ —).
In the present specification, the "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, It can be a fluoroalkyl group having 5, 4 carbons, 3 carbons, 2 carbons, or 1 carbons.
As used herein, a "fluoroalkyl group" can be a linear or branched fluoroalkyl group.
As used herein, "fluoroalkyl group" specifically includes, for example, fluoromethyl group, difluoromethyl group, trifluoromethyl group (CF ₃ -), 2,2,2-trifluoroethyl group, pentafluoro Ethyl group _{( C2F5-} ), tetrafluoropropyl group (e.g. _HCF2CF2CH2- ), hexafluoropropyl group ₍ e.g. _{( CF3} ) _2CH- ), nonafluorobutyl group, octafluoropentyl groups (eg, HCF ₂ CF ₂ CF ₂ CF ₂ CH ₂ —), tridecafluorohexyl groups, and the like.

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

In the present specification, unless otherwise specified, examples of "alkynyl group" include ethynyl, 1-propyn-1-yl, 2-propyn-1-yl, 4-pentyn-1-yl, 5-hexyne- It can include C2-C10 alkynyl groups, straight or branched, such as 1-yl.

Unless otherwise specified herein, examples of "cycloalkyl group" include C3-C7 cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and the like.

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

In the present specification, unless otherwise specified, examples of "cycloalkadienyl group" include cyclobutadienyl, cyclopentadienyl, cyclohexadienyl, cycloheptadienyl, cyclooctadienyl, cyclononadienyl , cyclodecadienyl, and the like.

As used herein, unless otherwise specified, an "aryl group" can be monocyclic, bicyclic, tricyclic, or tetracyclic.
Unless otherwise specified herein, the "aryl group" can be a C6-C18 aryl group.
As used herein, unless otherwise specified, examples of "aryl groups" include phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, and 2-anthryl.

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

Unless otherwise specified herein, the "non-aromatic heterocyclic group" can be monocyclic, bicyclic, tricyclic, or tetracyclic.
In the present specification, unless otherwise specified, the "non-aromatic heterocyclic group" includes, for example, 1 to 4 ring-constituting atoms selected from carbon atoms, oxygen atoms, sulfur atoms, and nitrogen atoms. It can be a non-aromatic heterocyclic group containing heteroatoms.
In the present specification, unless otherwise specified, the "non-aromatic heterocyclic group" can be saturated or unsaturated.
In the present 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 the "heteroaryl group" include monocyclic aromatic heterocyclic groups (eg, 5- or 6-membered monocyclic aromatic heterocyclic groups), and aromatic condensed Heterocyclic groups (eg, 5- to 18-membered aromatic condensed heterocyclic groups) can be included.

In the present specification, unless otherwise specified, examples of "5- or 6-membered monocyclic aromatic heterocyclic group" include pyrrolyl (eg, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl), furyl (eg : 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 the "5- to 18-membered aromatic condensed heterocyclic group" include isoindolyl (e.g., 1-isoindolyl, 2-isoindolyl, 3-isoindolyl, 4-isoindolyl, 5- 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- 6-yl, 1,2-benzisothiazol-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]pyridine-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]pyridin-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 be included.

In this specification, unless otherwise specified,
"Non-aromatic heterocyclic group optionally having one or more substituents", and "heteroaryl group optionally having one or more substituents"
Examples of each "substituent" in are hydrocarbon groups optionally having one or more substituents, halogen atoms, nitro groups, cyano groups, oxo groups, thioxo groups, sulfo groups, sulfamoyl groups, sulfinamoyl groups , and sulfenamoyl groups.
The number of substituents may be in the range of 1 to the maximum substitutable number (eg, 1, 2, 3, 4, 5, 6).

［式中、
Ｒ^Xは、水素原子、有機基を表し、
Ｘは、ハロゲン原子を表し、
Ｙは、水素原子、又はハロゲン原子を表し、及び
ｎは、１、又は２の数を表す。］
で表される化合物（２）を、
ホスゲンと反応させる工程１を含む。 Method for producing compound (1B) The method for producing compound (1B) of the present invention comprises:
Formula (2):

[In the formula,
R ^X represents a hydrogen atom or an organic group;
X represents a halogen atom,
Y represents a hydrogen atom or a halogen atom, and n represents the number of 1 or 2; ]
The compound (2) represented by
Includes step 1 of reacting with phosgene.

In the production method, the symbols in the formula (2) can correspond to the symbols in the formula (1B).

X is preferably a fluorine atom.

R ^X is preferably a hydrogen atom or a hydrocarbon group optionally having 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)-, -S(=O)-NR ^o -, and -NR ^o -S(=O )—(wherein R 2 ^o is independently a hydrogen atom or an organic group), one or more moieties may be inserted therein. ].

Suitable examples of the "hydrocarbon group optionally having one or more substituents" are
It includes unsubstituted hydrocarbon groups.

R ^X is more preferably a hydrogen atom, an alkyl group, or a fluoroalkyl group.
Preferable examples of the “fluoroalkyl group” for R 1 ^X include straight-chain or branched-chain fluoroalkyl groups having 1 to 3 carbon atoms [preferred specific examples: —CF ₃ , —CF ₂ H, — _CFH2 , _-CH2CF3 , _-CH2CF2H , _{-CH2CFH2 , -CF2CF3 , -CF2CF2H , -CF2CFH2 , -CFHCF3 , -CFHCF2H , -CFHCFH2 , -CH ( CF3 ) 2 , -CH2C2F5} , _-CH2CF2CF3 , _{-CH2CF2CF2H ,} and _{-CF2CF2CF3 ] ;} And more preferred examples include -CH ₂ CF ₃ and -CF ₂ CF ₃ .

R ^X is more preferably a hydrogen atom, a methyl group, or a trifluoromethyl group (--CF ₃ ).

R ^X is particularly preferably a hydrogen atom.

X is particularly preferably a fluorine atom.

Y is preferably a halogen atom.
Y is particularly preferably a fluorine atom.

n is particularly preferably 1.

Preferably,
R ^X is a hydrogen atom or a methyl group,
Y is a halogen atom,
X is a halogen atom and n is the number 1 or 2.

Preferably,
R ^X is a hydrogen atom or a methyl group,
Y is a fluorine atom,
X is a fluorine atom and n is 1.

Examples of phosgene used in step 1 include monophosgene, diphosgene, triphosgene, and fluorophosgene. Among them, monophosgene, triphosgene and fluorophosgene are preferred, and triphosgene is more preferred.

Examples of phosgene used in step 1 include precursors of monophosgene (eg diphosgene, triphosgene).

The amount of phosgene used in step 1 is preferably in the range of 0.1 to 5 mol, more preferably in the range of 0.3 to 4 mol, in terms of phosgene, per 1 mol of the compound of formula (2). within, and more preferably between 0.5 and 2 moles.
In the phosgene conversion, 1 mol of triphosgene is converted into 3 mol of phosgene, and 1 mol of diphosgene is converted into 2 mol of phosgene.

The reaction of step 1 can be suitably carried out in the presence of a nucleophile.
As the nucleophilic agent, for example, a base can be used.
The base can be an inorganic base or an organic base, preferably an organic base.
Examples of such inorganic bases include lithium hydroxide, potassium hydroxide, sodium hydroxide, calcium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate.
Suitable examples of such organic bases include amines.
Examples of such catalysts include triethylamine, diisopropylethylamine, and pyridine.
The said catalyst can be used individually by 1 type or in combination of 2 or more types.
The amount of the catalyst used is preferably in the range of 0.01 to 100 mol, more preferably in the range of 0.1 to 80 mol, and still more preferably It can be in the range of 0.5 to 60 mol, more preferably in the range of 1 to 40 mol.

The upper limit of the reaction temperature in step 1 can be preferably -10°C, more preferably -20°C, even more preferably -30°C, and even more preferably -40°C.
The lower limit of the reaction temperature in step 1 can be preferably -200°C, more preferably -150°C, even more preferably -100°C, and even more preferably -80°C.
The reaction temperature in step 1 is preferably in the range of -200 to -10°C, more preferably in the range of -150 to -20°C, more preferably in the range of -100°C to -30°C, still more preferably in the range of -100°C to -30°C. , and particularly preferably in the range of -80 to -40°C.

The upper limit of the reaction time for step 1 can preferably be 30 minutes, more preferably 25 minutes, and even more preferably 20 minutes.
The lower limit of the reaction time for step 1 can preferably be 5 minutes, more preferably 10 minutes, and even more preferably 15 minutes.
The reaction time for step 1 can preferably be in the range of 5-30 minutes, more preferably in the range of 10-25 minutes, and even more preferably in the range of 15-20 minutes.

According to the production method of the present invention, the compound represented by the formula (1B) is preferably 1 to 30%, more preferably 2 to 25%, still more preferably 3 to 20%, still more preferably 4 to Yields of 10% and particularly preferably in the range from 5% to 6% are obtained.

, Step A is preferably carried out in the absence of a base or under conditions in which the amount of base is low.
Specifically, the following conditions are preferable.
The upper limit of the amount of the base can be, for example, preferably 5 mol, more preferably 4 mol, and still more preferably 3 mol, per 1 mol of the compound represented by formula (2).
The lower limit of the amount of the base is preferably 0.01 mol, more preferably 0.1 mol, and still more preferably 0.5 mol, per 1 mol of the compound represented by the formula (2). be able to.
The amount of the base is preferably within the range of 0.01 to 5, more preferably 0.1 to 4, and still more preferably 0.5, per 1 mol of the compound represented by the formula (2). can be in the range of ~3.

The reaction of step 1 can be carried out in the presence or absence of an inert gas (eg nitrogen gas).

The reaction of step 1 can be suitably carried out in a solvent.
Examples of such solvents are
(1) hydrocarbon solvents such as hexane, heptane, cyclohexane, petroleum ether, benzene, toluene, and xylene;
(2) chlorinated solvents such as dichloromethane, dichloroethane, tetrachloroethane, and carbon tetrachloride; and (3) ethereal solvents such as diethyl ether, diisopropyl ether, THF, DME, and dioxane.
The said solvent can be used individually by 1 type or in combination of 2 or more types.

If desired, the reaction in step 1 can be terminated by means such as washing the reaction product solution with water.

Each of the compounds represented by the formula (1B) obtained in step 1 is optionally subjected to a conventional method such as extraction, dissolution, concentration, precipitation, adsorption, or chromatography, or a combination thereof. It can be isolated or purified.
If desired, unreacted raw materials can be recovered and reused.

Composition The present invention also provides a composition containing the compound represented by the above formula (1B) and the compound represented by the above formula (1D).

In the combination of the compound represented by the formula (1B) and the compound represented by the formula (1D) in the composition, the common symbol in the formula (1B) and the formula (1D) The substituents, etc. can each be the same or different, but are preferably the same.

The composition can also be produced by simultaneously producing the compound represented by the formula (1B) and the compound represented by the formula (1D) by the production method, or the compound represented by the formula (1B) and the compound represented by the formula (1D).

The symbol R ^1D in formula (1D) above is preferably straight or branched C1-C4 alkyl, and more preferably methyl.

The molar ratio of the compound represented by the formula (1B) and the compound represented by the formula (1D) is
preferably within the range of 0.1:99.9 to 99.9:0.1,
more preferably within the range of 1:99 to 99:1,
More preferably within the range of 10:90 to 90:10,
Even more preferably within the range of 20:80 to 80:20, and particularly preferably within the range of 40:60 to 60:40.

Method for producing the composition The composition of the present invention [that is, the composition containing the compound represented by the formula (1B) and the compound represented by the formula (1D)] is prepared by, for example,
(A) 2,2-dialkyl-1,3-dioxolane-4-carbaldehyde [hereinafter sometimes referred to as a carbaldehyde compound. ] and a mixture of ^trimers thereof are reacted with a fluorinating agent to fluorinate, and (B) the product of step (A) is represented by the formula: Including the step of deacetonidation in the presence of an alcohol represented by
It can be manufactured by a manufacturing method.

Process (A)
Suitable examples of the carbaldehyde compound used in step (A) are
2,2-di(C1-C4 alkyl)-1,3-dioxolane-4-carbaldehyde, and more preferred examples thereof include
It includes 2,2-dimethyl-1,3-dioxolane-4-carbaldehyde.

The molar ratio of the carbaldehyde compound and its trimer in the mixture is
preferably within the range of 0.1:99.9 to 99.9:0.1,
more preferably within the range of 1:99 to 99:1,
More preferably within the range of 10:90 to 90:10,
Even more preferably within the range of 20:80 to 80:20, and particularly preferably within the range of 40:60 to 60:40.

The fluorinating agent used in step (A) is preferably an oxygen-scavenging fluorinating agent.
The fluorinating agent specifically consists of sulfur tetrafluoride (SF ₄ ), dimethylaminosulfur trifluoride, diethylaminosulfur trifluoride, morpholinosulfur trifluoride, and bis(2-methoxyethyl)aminosulfur trifluoride. It can be one or more selected from the group.

The amount of the fluorinating agent used is based on 1 mol of the total amount of the carbaldehyde compound and its trimer (converted to monomer),
preferably within the range of 1 to 10 mol,
More preferably it can be in the range of 1 to 7 mol, and even more preferably in the range of 1 to 5 mol.

Step (B)
The amount of alcohol represented by the formula: R ^1D —OH is
With respect to 1 mol of the total amount of the carbaldehyde compound and its trimer (converted to monomer),
preferably 2 mol or more, and more preferably 5 mol or more,
More preferably 10 mol or more,
can be
It can also be used as a reaction solvent by using a solvent amount.

An alcohol represented by the formula: R ^1D —OH can be used in large excess relative to the carbaldehyde compound and its trimer, and can also function as a reaction solvent.

R ^1D is preferably linear or branched C1-C4 alkyl, and more preferably methyl, corresponding to formula (1D) above.

The resulting composition can be isolated or purified, if desired, by conventional methods such as extraction, dissolution, concentration, precipitation, adsorption, or chromatography, or combinations thereof.
If desired, unreacted raw materials can be recovered and reused.

4-(Dimethoxymethyl)-1,3-dioxolan-2- one Among the compounds that can be produced by the production method of the present invention, 4-(dimethoxymethyl)-1,3-dioxolan- 2-one is a novel compound. .
Thus, the present invention also provides such compounds.

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.
In the examples, the following abbreviations may be used.

Example 1
4-(Difluoromethyl)-1,3-dioxolan-2-one To 14.5 g of 3,3-difluoropropane-1,2-diol, 300 g of dichloromethane, 40 g of pyridine and 15.0 g of triphosgene were added at -78°C. 4 g was added and stirred for an additional 15 minutes.
After completion of the reaction, the reaction product liquid was washed with water and purified by column chromatography.
1.08 g of 4-(difluoromethyl)-1,3-dioxolan-2-one were obtained as an oil.
Analysis was performed by ¹ H NMR and ¹⁹ F NMR.

Example 2
Preparation of 4-(difluoromethyl)-1,3-dioxolan-2-one and 4-(dimethoxymethyl)-1,3-dioxolan-2-one 2,2-dimethyl-1,3-dioxolan-4-carbohydrate 200 mL of dichloromethane was added to 10 g of a mixture of aldehyde and its trimer (10:1), and after cooling, 22 mL of DAST was added.
After stirring, the mixture was treated with a saturated aqueous sodium hydrogencarbonate solution, and extracted and concentrated with dichloromethane.
The obtained mixture was re-dissolved in 30 mL of methanol, and 2.4 g of p-toluenesulfonic acid monohydrate was added under cooling and stirred.
It was treated with a small amount of triethylamine, filtered and concentrated. 250 ml of dichloromethane was added to the resulting mixture to redissolve it, and 0.1 ml of DMF and 40 mL of pyridine were mixed and stirred. After purging with nitrogen, a solution of 15.4 g of triphosgene in 50 ml of dichloromethane was added dropwise at -78°C.
After the solution was warmed to room temperature and stirred, ice water was added. After liquid separation, the organic phase was washed three times with a 10 wt % aqueous citric acid solution, and then the organic layer was dried and concentrated.
The mixture was purified by column chromatography to give the desired product 4-(difluoromethyl)-1,3-dioxolan-2-one 2.4 g and 4-(dimethoxymethyl)-1,3-dioxolan-2- On 0.6 g was obtained.
Analysis was performed by ¹ H NMR and ¹⁹ F NMR.

Example 3
(1) Preparation of 3,3-dimethoxypropane-1,2-diol 60 ml of water was added to 5.1 g of 3,3-dimethoxy-1-propene, and after purging with nitrogen, 0.3 M permanganic acid was added at 0°C. 150 ml of potassium aqueous solution was added dropwise.
The solution was returned to room temperature and stirred for 2 hours.
After that, the mixture was heated and stirred at the reflux temperature for 1 hour.
It was returned to room temperature, filtered, and 120 g of K ₂ CO ₃ was added to the filtrate. After that, extraction was performed with 50 ml of ethyl acetate, and this operation was performed 5 times. The organic layer was dried and concentrated to obtain 2.0 g of the desired product.
Analysis was performed by ¹ H NMR and ¹⁹ F NMR.

(2) Preparation of 4-(dimethoxymethyl)-1,3-dioxolan-2-one To 2.0 g of 3,3-dimethoxypropane-1,2-diol, 30 ml of dichloromethane, 0.01 ml of DMF, and 3.49 g of pyridine were mixed and stirred. After purging with nitrogen, a solution of 1.74 g of triphosgene and 10 ml of dichloromethane was added dropwise at -78°C. The solution was brought to room temperature and ice water was added.
After liquid separation, the organic phase was washed three times with a 10 wt % aqueous citric acid solution, and then the organic layer was dried and concentrated to obtain 1.72 g of the desired product.
Analysis was performed by ¹ H NMR and ¹⁹ F NMR.

Claims (7)

Formula (1B):

[In the formula,
R ^X represents a hydrogen atom or an organic group;
X represents a halogen atom,
Y represents a hydrogen atom or a halogen atom, and n represents the number of 1 or 2; ]
A method for producing a compound represented by
Formula (2):

[In the formula,
R ^X represents a hydrogen atom or an organic group;
X represents a halogen atom,
Y represents a hydrogen atom or a halogen atom, and n represents the number of 1 or 2; ]
A compound represented by
comprising a step 1 of reacting with phosgene ;
The reaction temperature in step 1 is -10°C or lower.
Production method. R ^X is a hydrogen atom or a hydrocarbon group optionally having 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)-, -S(=O)-NR ^o -, and -NR ^o -S(=O)-( In these ^formulas , each R 2 is independently a hydrogen atom or an organic group.) may be inserted with one or more moieties selected from the group consisting of. ] The manufacturing method according to claim 1 . 3. The production method according to claim 2, wherein R ^X is a hydrogen atom, an alkyl group, or a fluoroalkyl group. The production method according to any one of claims 1 to 3, wherein X is a fluorine atom. The production method according to any one of claims 1 to 4, wherein Y is a halogen atom. The production method according to any one of claims 1 to 5, wherein phosgene is monophosgene, triphosgene, or fluorophosgene. The production method according to any one of claims 1 to 6, wherein step 1 is performed in the presence of a nucleophilic agent containing an organic base.