JP2002322156A - Fluorine-containing organic compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new fluorine-containing organic compound, which may be used as a safe fluorination agent having a low vapor pressure. SOLUTION: The fluorine-containing organic compound is represented by formulas (A-1) or (A-2) [wherein, R<1> to R<12> are each independently H, F, Cl, Br, I, or a 1-6C alkyl group which may have fluorine substituents; RA, RB, RC are each independently a 1-18C alkyl which may have fluorine substituents].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel fluorine-containing organic compound which can be used, for example, as a fluorinating agent.

[0002]

2. Description of the Related Art As a fluorination technique, particularly a fluorination technique using a fluorinating agent, 2,2-difluoro-1,3-dimethylimidazolidine described in JP-A-2000-38370 is used. A method of using as an agent is known. However, the fluorinating agent has a relatively high vapor pressure, and the danger of poisoning due to vapor inhalation or the like cannot be completely denied.

[0003]

An object of the present invention is to provide a novel fluorine-containing organic compound which has a low vapor pressure and can be used as a safer fluorinating agent.

[0004]

Means for Solving the Problems As a result of diligent studies, the present inventors have found that, unlike the method of simply increasing the molecular weight using only carbon and hydrogen atoms, if an ether bond is introduced into the N-substituent, The inventors have found that the boiling point is relatively high and the vapor pressure is relatively low, and the present invention has been completed.

That is, the fluorine-containing organic compound of the present invention is a compound represented by the general formula (A-1).

[0006]

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(Wherein, R ^{1 to} R ¹² each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an alkyl group having 1 to 6 carbon atoms which may be substituted by fluorine. Table R ^a, R ^B are each independently, represent a fluorine-substituted having 1 to 18 carbon atoms which may have alkyl group.) Furthermore, different fluorinated organic compound of the invention, the general formula (a-2) Compound.

[0008]

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Wherein R ¹ , R ² , R ⁵ , R ⁶ , R ⁹ ,
R ¹⁰ , R ¹¹ and R ¹² each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or an alkyl group having 1 to 6 carbon atoms which may be substituted by fluorine.
R ^A and R ^C each have 1 to 18 carbon atoms which may be substituted by fluorine;
Represents an alkyl group. As the fluorine-containing organic compound represented by the general formula (A-1), a compound represented by the general formula (A-3) can be given.

[0010]

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(Wherein, R ^A and R ^B have the same meanings as described above.) Further, as the fluorine-containing organic compound of the general formula (A-2),
The compound represented by General Formula (A-4) is mentioned.

[0012]

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(Wherein, R ^A and R ^C are as defined above)

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

As described above, the fluorine-containing organic compound according to the present invention is a compound represented by the general formulas (A-1) and (A-2).

In the general formula (A-1) or (A-2), R ^{1 to} R ¹² may be each independently hydrogen, fluorine, chlorine, bromine, iodine or fluorine-substituted. Represents an alkyl group having 1 to 6 carbon atoms.

C 1 to C 6 which may be substituted by fluorine
May be linear or branched, and particularly preferably has 1 to 3 carbon atoms.

Examples of the fluorine-substituted or unsubstituted alkyl group having 1 to 3 carbon atoms include a methyl group, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, an ethyl group,
2-fluoroethyl group, 2,2-difluoroethyl group,
2,2,2-trifluoroethyl group, 1-fluoroethyl group, 1,1-difluoroethyl group, 1,2-difluoroethyl group, 1,1,2-trifluoroethyl group,
2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, 1,2,2,2-tetrafluoroethyl group, perfluoroethyl group, propyl group, 3-fluoropropyl group, 3 , 3-difluoropropyl group,
3,3,3-trifluoropropyl group, 2-fluoropropyl group, 2,2-difluoropropyl group, 2,3-difluoropropyl group, 2,2,3-trifluoropropyl group, 2,3,3- Trifluoropropyl group, 2,2
3,3-tetrafluoropropyl group, 2,3,3,3-
Tetrafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 1-fluoropropyl group, 1,
3-difluoropropyl group, 1,3,3-trifluoropropyl group, 1,3,3,3-tetrafluoropropyl group, 1,2-difluoropropyl group, 1,2,2-trifluoropropyl group, 1 , 2,3-trifluoropropyl group, 1,2,2,3-tetrafluoropropyl group,
1,2,3,3-tetrafluoropropyl group, 1,2,2
2,3,3-pentafluoropropyl group, 1,2,3
3,3-pentafluoropropyl group, 1,2,2,3
3,3-hexafluoropropyl group, 1,1-difluoropropyl group, 1,1,3-trifluoropropyl group,
1,1,3,3-tetrafluoropropyl group, 1,1,
3,3,3-pentafluoropropyl group, 1,1,2-
Trifluoropropyl group, 1,1,2,2-tetrafluoropropyl group, 1,1,2,3-tetrafluoropropyl group, 1,1,2,2,3-pentafluoropropyl group, 1,1, 2,3,3-pentafluoropropyl group,
1,1,2,2,3,3-hexafluoropropyl group,
1,1,2,3,3,3-hexafluoropropyl group,
Perfluoropropyl group, 2-propyl group, 1-fluoro-2-propyl group, 1,1-difluoro-2-propyl group, 1,1,1-trifluoro-2-propyl group,
1,3-difluoro-2-propyl group, 1,1,3-trifluoro-2-propyl group, 1,1,1,3-tetrafluoro-2-propyl group, 1,1,3,3-tetra Fluoro-2-propyl group, 1,1,1,3,3-pentafluoro-2-propyl group, 1,1,1,3,3,3-
Hexafluoro-2-propyl group, 2-fluoro-2-
Propyl group, 1,2-difluoro-2-propyl group,
1,1,2-trifluoro-2-propyl group, 1,1,
1,2-tetrafluoro-2-propyl group, 1,2,3
-Trifluoro-2-propyl group, 1,1,2,3-tetrafluoro-2-propyl group, 1,1,1,2,3-
Pentafluoro-2-propyl group, 1,1,2,3,3
-Pentafluoro-2-propyl group, 1,1,1,2,2
Examples thereof include a 3,3-hexafluoro-2-propyl group and a perfluoro-2-propyl group.

R ^{1 to} R ¹² are preferably a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, an ethyl group, a 2,2,2-trifluoroethyl group, a 2,2 or
2-trifluoroethyl group, perfluoroethyl group, propyl group, 3,3,3-trifluoropropyl group, 2,
2,3,3,3-pentafluoropropyl group, perfluoropropyl group, 2-propyl group, 1,1,1-trifluoro-2-propyl group, 1,1,1,3,3,3-hexa Examples thereof include a fluoro-2-propyl group and a perfluoro-2-propyl group.

More preferably, hydrogen atom, methyl group, trifluoromethyl group, ethyl group, 2,2,2-trifluoroethyl group, perfluoroethyl group, propyl group, perfluoropropyl group, 2-propyl group, 1,1,1,
3,3,3-hexafluoro-2-propyl group, perfluoro-2-propyl group, and particularly preferably,
Examples include a hydrogen atom, a methyl group, a trifluoromethyl group, an ethyl group, a 2,2,2-trifluoroethyl group, and a perfluoroethyl group.

In the formulas (A-1) and (A-2), R ^A , R ^B and R ^C each independently represent an alkyl group having 1 to 18 carbon atoms which may be substituted by fluorine. May be linear or branched. It preferably has 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms.

Specific examples of the fluorine-substituted or unsubstituted alkyl group having 1 to 3 carbon atoms include methyl, fluoromethyl, difluoromethyl, trifluoromethyl, ethyl, 2-fluoroethyl, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 1
-Fluoroethyl group, 1,1-difluoroethyl group,
1,2-difluoroethyl group, 1,1,2-trifluoroethyl group, 1,2,2-trifluoroethyl group, 1,
1,2,2-tetrafluoroethyl group, 1,2,2,2
-Tetrafluoroethyl group, perfluoroethyl group, propyl group, 3-fluoropropyl group, 3,3-difluoropropyl group, 3,3,3-trifluoropropyl group,
2-fluoropropyl group, 2,2-difluoropropyl group, 2,3-difluoropropyl group, 2,2,3-trifluoropropyl group, 2,3,3-trifluoropropyl group, 2,2,3 3-tetrafluoropropyl group,
2,3,3,3-tetrafluoropropyl group, 2,2
3,3,3-pentafluoropropyl group, 1-fluoropropyl group, 1,3-difluoropropyl group, 1,3
3-trifluoropropyl group, 1,3,3,3-tetrafluoropropyl group, 1,2-difluoropropyl group,
1,2,2-trifluoropropyl group, 1,2,3-trifluoropropyl group, 1,2,2,3-tetrafluoropropyl group, 1,2,3,3-tetrafluoropropyl group, 1, 2,2,3,3-pentafluoropropyl group, 1,2,3,3,3-pentafluoropropyl group,
1,2,2,3,3,3-hexafluoropropyl group,
1,1-difluoropropyl group, 1,1,3-trifluoropropyl group, 1,1,3,3-tetrafluoropropyl group, 1,1,3,3,3-pentafluoropropyl group, 1,1 , 2-trifluoropropyl group, 1,1,
2,2-tetrafluoropropyl group, 1,1,2,3-
Tetrafluoropropyl group, 1,1,2,2,3-pentafluoropropyl group, 1,1,2,3,3-pentafluoropropyl group, 1,1,2,2,3,3-hexafluoropropyl Group, 1,1,2,3,3,3-hexafluoropropyl group, perfluoropropyl group, 2-propyl group, 1-fluoro-2-propyl group, 1,1-difluoro-2-propyl group, 1 , 1,1-trifluoro-
2-propyl group, 1,3-difluoro-2-propyl group, 1,1,3-trifluoro-2-propyl group, 1,
1,1,3-tetrafluoro-2-propyl group, 1,
1,3,3-tetrafluoro-2-propyl group, 1,
1,1,3,3-pentafluoro-2-propyl group,
1,1,1,3,3,3-hexafluoro-2-propyl group, 2-fluoro-2-propyl group, 1,2-difluoro-2-propyl group, 1,1,2-trifluoro-2
-Propyl group, 1,1,1,2-tetrafluoro-2-
Propyl group, 1,2,3-trifluoro-2-propyl group, 1,1,2,3-tetrafluoro-2-propyl group, 1,1,1,2,3-pentafluoro-2-propyl group 1,1,2,3,3-pentafluoro-2-propyl group, 1,1,1,2,3,3-hexafluoro-2
-Propyl group and perfluoro-2-propyl group.

Of these, a methyl group, a trifluoromethyl group, an ethyl group, a 2,2,2-trifluoroethyl group, a perfluoroethyl group, a propyl group,
3,3,3-trifluoropropyl group, 2,2,3
3,3-pentafluoropropyl group, perfluoropropyl group, 2-propyl group, 1,1,1-trifluoro-
Examples thereof include a 2-propyl group, a 1,1,1,3,3,3-hexafluoro-2-propyl group, a perfluoro-2-propyl group, and the like.

More preferably, methyl, trifluoromethyl, ethyl, 2,2,2-trifluoroethyl, perfluoroethyl, propyl, perfluoropropyl, 2-propyl, 1,1 , 1,3,3,3
-Hexafluoro-2-propyl group, perfluoro-2
-Propyl group and the like, and particularly preferably a methyl group, a trifluoromethyl group, an ethyl group, a 2,2,2-trifluoroethyl group and a perfluoroethyl group.

Specific examples of the compound represented by the general formula (A-1) include 2,2-difluoro-1,3-bis (2-methoxyethyl) imidazolidine, 2,2-difluoro-1, 3-bis (2-ethoxyethyl) imidazolidine, 2,2-difluoro-1,3-bis (2-propoxyethyl) imidazolidine, 2,2-difluoro-
1,3-bis (2- (2-propoxy) ethyl) imidazolidin, 2,2-difluoro-1- (2-methoxyethyl) -3- (2-ethoxyethyl) imidazolidin,
2,2-difluoro-1- (2-methoxyethyl) -3
-(2-propoxyethyl) imidazolidine, 2,2-
Difluoro-1- (2-methoxyethyl) -3- (2-
(2-propoxy) ethyl) imidazolidine, 2,2-
Difluoro-1- (2-ethoxyethyl) -3- (2-
Propoxyethyl) imidazolidine, 2,2-difluoro-1- (2-ethoxyethyl) -3- (2- (2-propoxy) ethyl) imidazolidine, 2,2-difluoro-1- (2-propoxyethyl) -3- (2- (2-
Propoxy) ethyl) imidazolidine,

2,2-difluoro-1,3-bis (fluoromethoxyethyl) imidazolidin, 2,2-difluoro-1,3-bis (difluoromethoxyethyl) imidazolidin, 2,2-difluoro-1,3 -Bis (trifluoromethoxyethyl) imidazolidine, 2,2-difluoro-1,3-bis (2,2,2-trifluoroethoxyethyl) imidazolidine, 2,2-difluoro-
1,3-bis (perfluoroethoxyethyl) imidazolidine, 2,2-difluoro-1,3-bis (2,2,
2,3,3,3-hexafluoropropoxyethyl) imidazolidine, 2,2-difluoro-1,3-bis (perfluoropropoxyethyl) imidazolidine, 2,2
-Difluoro-1,3-bis (1,1,1,3,3,3
-Hexafluoro-2-propoxyethyl) imidazolidine, 2,2-difluoro-1,3-bis (perfluoro-2-propoxyethyl) imidazolidine,

2,2-difluoro-1- (2-methoxypropyl) -3- (2-methoxyethyl) imidazolidine 2,2-difluoro-1- (1-methoxy-2-propyl) -3- (2 -Methoxyethyl) imidazolidine,
2,2-difluoro-1- (2-methyl-2-methoxypropyl) -3- (2-methoxyethyl) imidazolidine, 2,2-difluoro-1- (2-methyl-1-methoxy-2-propyl) ) -3- (2-Methoxyethyl) imidazolidine, 2,2-difluoro-1- (3-methoxy-2-butyl) -3- (2-methoxyethyl) imidazolidine, 2,2-difluoro-1- (3-methyl-3
-Methoxy-2-butyl) -3- (2-methoxyethyl) imidazolidine, 2,2-difluoro-1- (2-
Methyl-3-methoxy-2-butyl) -3- (2-methoxyethyl) imidazolidine, 2,2-difluoro-1
-(2,3-dimethyl-3-methoxy-2-butyl)-
3- (2-methoxyethyl) imidazolidine, 2,2-
Difluoro-1- (2-methoxybutyl) -3- (2-
Methoxyethyl) imidazolidine, 2,2-difluoro-1- (3-methyl-2-methoxybutyl) -3- (2
-Methoxyethyl) imidazolidine, 2,2-difluoro-1- (1-methoxy-2-butyl) -3- (2-methoxyethyl) imidazolidine, 2,2-difluoro-
1- (3-methyl-1-methoxy-2-butyl) -3-
(2-methoxyethyl) imidazolidine, 2,2-difluoro-1- (3-methoxy-2-pentyl) -3-
(2-methoxyethyl) imidazolidine, 2,2-difluoro-1- (4-methyl-3-methoxy-2-pentyl) -3- (2-methoxyethyl) imidazolidine,
2,2-difluoro-1- (2-methoxy-3-pentyl) -3- (2-methoxyethyl) imidazolidine,
2,2-difluoro-1- (4-methyl-2-methoxy-3-pentyl) -3- (2-methoxyethyl) imidazolidine, 2,2-difluoro-1- (4-methoxy-
3-hexyl) -3- (2-methoxyethyl) imidazolidine, 2,2-difluoro-1- (2-methyl-4-
Methoxy-3-hexyl) -3- (2-methoxyethyl) imidazolidine, 2,2-difluoro-1- (5-
Methyl-4-methoxy-3-hexyl) -3- (2-methoxyethyl) imidazolidine, 2,2-difluoro-
1- (2,5-dimethyl-4-methoxy-3-hexyl) -3- (2-methoxyethyl) imidazolidine,

2,2-difluoro-1,3-bis (2-
Methoxyethyl) -4-methylimidazolidine, 2,2
-Difluoro-1,3-bis (2-methoxyethyl)-
4,4-dimethylimidazolidine, 2,2-difluoro-1,3-bis (2-methoxyethyl) -4,5-dimethylimidazolidine, 2,2-difluoro-1,3-bis (2-methoxyethyl ) -4,4,5-Trimethylimidazolidine, 2,2-difluoro-1,3-bis (2
-Methoxyethyl) -4,4,5,5-tetramethylimidazolidine;

2,2-difluoro-1,3-bis (2-
Methoxyethyl) -4-ethylimidazolidin, 2,2
-Difluoro-1,3-bis (2-methoxyethyl)-
4,4-diethylimidazolidine, 2,2-difluoro-1,3-bis (2-methoxyethyl) -4,5-diethylimidazolidine, 2,2-difluoro-1,3-bis (2-methoxyethyl ) -4,4,5-triethylimidazolidine, 2,2-difluoro-1,3-bis (2
-Methoxyethyl) -4,4,5,5-tetraethylimidazolidine,

2,2-difluoro-1,3-bis (2-
Methoxyethyl) -4-propylimidazolidine, 2,
2-difluoro-1,3-bis (2-methoxyethyl)
-4,4-dipropylimidazolidine, 2,2-difluoro-1,3-bis (2-methoxyethyl) -4,5-
Dipropyl imidazolidine, 2,2-difluoro-1,
3-bis (2-methoxyethyl) -4,4,5-tripropylimidazolidine, 2,2-difluoro-1,3-
Bis (2-methoxyethyl) -4,4,5,5-tetrapropylimidazolidine;

2,2-difluoro-1,3-bis (2-
Methoxyethyl) -4- (2-propyl) imidazolidine, 2,2-difluoro-1,3-bis (2-methoxyethyl) -4,4-bis (2-propyl) imidazolidine, 2,2-difluoro -1,3-bis (2-methoxyethyl) -4,5-bis (2-propyl) imidazolidin, 2,2-difluoro-1,3-bis (2-methoxyethyl) -4,4,5- Tris (2-propyl) imidazolidine, 2,2-difluoro-1,3-bis (2-methoxyethyl) -4,4,5,5-tetrakis (2-propyl) imidazolidine,

2,2-difluoro-1,3-bis (2-
Methoxyethyl) -4-methyl-5-propylimidazolidine, 2,2-difluoro-1,3-bis (2-methoxyethyl) -4-methyl-4-ethylimidazolidine, 2,2-difluoro-1, 3-bis (2-methoxyethyl) -4,5-diethyl-4- (2-propyl) imidazolidine, 2,2-difluoro-1,3-bis (2
-Methoxyethyl) -4,4,5-trimethyl-5-ethylimidazolidine, 2,2-difluoro-1,3-bis (2-methoxyethyl) -4,5-dimethyl-4,5
-Diethyl imidazolidine,

2,2-difluoro-1,3-bis (2-
Methoxyethyl) -4-fluoroimidazolidine, 2,
2-difluoro-1,3-bis (2-methoxyethyl)
-4,4-difluoroimidazolidine, 2,2-difluoro-1,3-bis (2-methoxyethyl) -4,5-
Difluoroimidazolidine, 2,2-difluoro-1,
3-bis (2-methoxyethyl) -4,4,5-trifluoroimidazolidine, 2,2-difluoro-1,3-
Bis (2-methoxyethyl) -4,4,5,5-tetrafluoroimidazolidine;

2,2-difluoro-1,3-bis (2-
Methoxyethyl) -4-chloroimidazolidine, 2,2
-Difluoro-1,3-bis (2-methoxyethyl)-
4,4-dichloroimidazolidine, 2,2-difluoro-1,3-bis (2-methoxyethyl) -4,5-dichloroimidazolidine, 2,2-difluoro-1,3-bis (2-methoxyethyl ) -4,4,5-Trichloroimidazolidine, 2,2-difluoro-1,3-bis (2
-Methoxyethyl) -4,4,5,5-tetrachloroimidazolidine,

2,2-difluoro-1,3-bis (2-
Methoxyethyl) -4-bromoimidazolidin, 2,2
-Difluoro-1,3-bis (2-methoxyethyl)-
4,4-dibromoimidazolidine, 2,2-difluoro-1,3-bis (2-methoxyethyl) -4,5-dibromoimidazolidine, 2,2-difluoro-1,3-bis (2-methoxyethyl ) -4,4,5-Tribromoimidazolidine, 2,2-difluoro-1,3-bis (2
-Methoxyethyl) -4,4,5,5-tetrabromoimidazolidine;

2,2-difluoro-1,3-bis (2-
Methoxyethyl) -4-iodoimidazolidine, 2,2
-Difluoro-1,3-bis (2-methoxyethyl)-
4,4-diiodoimidazolidine, 2,2-difluoro-1,3-bis (2-methoxyethyl) -4,5-diiodoimidazolidine, 2,2-difluoro-1,3-bis (2- (Methoxyethyl) -4,4,5-triiodoimidazolidine, 2,2-difluoro-1,3-bis (2
-Methoxyethyl) -4,4,5,5-tetraiodoimidazolidine;

2,2-difluoro-1,3-bis (2-
Methoxyethyl) -4-fluoro-5-iodoimidazolidine, 2,2-difluoro-1,3-bis (2-methoxyethyl) -4,4-difluoro-5-chloroimidazolidine, 2,2-difluoro- 1,3-bis (2-methoxyethyl) -4-chloro-4-bromoimidazolidin, 2,2-difluoro-1,3-bis (2-methoxyethyl) -4,4,5-trichloro-5- Bromoimidazolidine, 2,2-difluoro-1,3-bis (2-methoxyethyl) -4,5-difluoro-4,5-dichloroimidazolidine,

2,2-difluoro-1,3-bis (2-
Methoxyethyl) -4-methyl-5-iodoimidazolidine, 2,2-difluoro-1,3-bis (2-methoxyethyl) -4,4-dimethyl-5-chloroimidazolidine, 2,2-difluoro- 1,3-bis (2-methoxyethyl) -4-chloro-4-bromo-5-ethylimidazolidine, 2,2-difluoro-1,3-bis (2-
Methoxyethyl) -4,5-dimethyl-5-bromoimidazolidine, 2,2-difluoro-1,3-bis (2-
Methoxyethyl) -4-fluoro-4,5-dimethylimidazolidine;

2,2-difluoro-1- (2-trifluoromethoxypropyl) -3- (2-methoxyethyl)
Imidazolidine 2,2-difluoro-1- (1-methoxy-2-propyl) -3- (2-methoxyethyl) -4-fluoroimidazolidin, 2,2-difluoro-1- (2-methyl-
2-methoxypropyl) -3- (2-methoxyethyl)
-4-trifluoromethylimidazolidine, 2,2-difluoro-1- (2-fluoromethyl-1-methoxy-
2-propyl) -3- (2-methoxyethyl) -4-methylimidazolidine, 2,2-difluoro-1- (1,
1,1-trifluoro-3-trifluoromethoxy-2
-Butyl) -3- (2-methoxyethyl) imidazolidine, 2,2-difluoro-1- (3-methyl-3-trifluoromethoxy-2-butyl) -3- (2-methoxyethyl) -4- Chloroimidazolidine, 2,2-difluoro-1- (2-trifluoromethyl-3-methoxy-
2-butyl) -3- (2-methoxyethyl) -4-iodoimidazolidine, 2,2-difluoro-1- (2,3
-Dimethyl-3-methoxy-2-butyl) -3- (2-
Methoxyethyl) -4-bromoimidazolidin, 2,2
-Difluoro-1- (2-methoxy-2-ethylbutyl) -3- (2-methoxyethyl) -4-trifluoromethylimidazolidine, 2,2-difluoro-1-
(2,3-dimethyl-2-methoxybutyl) -3- (2
-Methoxyethyl) -4- (2,2,2-trifluoroethyl) imidazolidin, 2,2-difluoro-1-
(1-methoxy-4,4,4-trifluoro-2-butyl) -3- (2-methoxyethyl) imidazolidine,
2,2-difluoro-1- (3-methyl-1-methoxy-4-fluoro-2-butyl) -3- (2-methoxyethyl) imidazolidine, 2,2-difluoro-1- (3
-Methoxy-3-ethyl-2-pentyl) -3- (2-
Methoxyethyl) -4-bromoimidazolidin, 2,2
-Difluoro-1- (2,4-dimethyl-3-methoxy-2-pentyl) -3- (2-methoxyethyl) imidazolidine, 2,2-difluoro-1- (2-methoxy-
3-pentyl) -3- (2-trifluoromethoxyethyl) -4-trifluoromethylimidazolidine, 2,2
-Difluoro-1- (4-methyl-2-methoxy-3-
Pentyl) -3- (4-methoxy-3-hexyl)-
4,4-difluoroimidazolidine, 2,2-difluoro-1- (4-methoxy-3-hexyl) -3- (2-
Ethoxyethyl) -4,4,5,5-tetrafluoroimidazolidine, 2,2-difluoro-1- (2-methyl-4-methoxy-3-ethyl-3-hexyl) -3-
(2-methoxyethyl) imidazolidine, 2,2-difluoro-1- (3,5-dimethyl-4-methoxy-3-
Hexyl) -3- (2-methoxyethyl) imidazolidine, 2,2-difluoro-1- (2,3,4,5-tetramethyl-4-methoxy-3-hexyl) -3- (2-
Methoxyethyl) imidazolidine,

2,2-difluoro-1,3-bis (2-
Trifluoromethoxyethyl) -4-methylimidazolidine, 2,2-difluoro-1,3-bis (2-methoxybutyl) -4,4-bis (trifluoromethyl) imidazolidine, 2,2-difluoro-1 , 3-bis (2-
Methoxypropyl) -4,5-dimethylimidazolidine, 2,2-difluoro-1,3-bis (2-methoxy-3-pentyl) -4,4,5-trimethylimidazolidine, 2,2-difluoro-1 , 3-bis (4-methoxy-3-hexyl) -4,4,5,5-tetramethylimidazolidine;

2,2-difluoro-1,3-bis (2-
Methoxy-3-hexyl) -4-ethylimidazolidine, 2,2-difluoro-1,3-bis (2-trifluoromethoxyethyl) -4,4-diethylimidazolidine, 2,2-difluoro-1,3 -Bis (2-methoxybutyl) -4,5-diethylimidazolidine, 2,2-
Difluoro-1,3-bis (2-methoxypropyl)-
4,4,5-tris (perfluoroethyl) imidazolidine, 2,2-difluoro-1,3-bis (2-methoxy-3-pentyl) -4,4,5,5-tetraethylimidazolidine,

2,2-difluoro-1,3-bis (2-
Methoxy-1-fluoroethyl) -4-propylimidazolidine, 2,2-difluoro-1,3-bis (2-methoxy-1-chloroethyl) -4,4-dipropylimidazolidine, 2,2-difluoro- 1,3-bis (2-
(Methoxy-1-fluoroethyl) -4,5-dipropylimidazolidine, 2,2-difluoro-1,3-bis (2-methoxy-1-fluoroethyl) -4,4,5-
Tripropyl imidazolidine, 2,2-difluoro-
1,3-bis (2-methoxy-1-fluoroethyl)-
4,4,5,5-tetrapropylimidazolidine,

2,2-difluoro-1,3-bis (2-
Methoxy-1-fluoroethyl) -4- (2-propyl) imidazolidine, 2,2-difluoro-1,3-bis (2-methoxy-1-fluoroethyl) -4,4-bis (2-propyl) Imidazolidine, 2,2-difluoro-1,3-bis (2-methoxy-1-fluoroethyl) -4,5-bis (2-propyl) imidazolidine,
2,2-difluoro-1,3-bis (2-methoxy-1
-Fluoroethyl) -4,4,5-tris (1,1,1
-Trifluoro-2-propyl) imidazolidine, 2,
2-difluoro-1,3-bis (2-methoxy-1-fluoroethyl) -4,4,5,5-tetrakis (2-propyl) imidazolidine;

2,2-difluoro-1,3-bis (2-
Methoxyethyl) -4-trifluoromethyl-5-propylimidazolidine, 2,2-difluoro-1,3-bis (2-methoxy-1-fluoroethyl) -4-methyl-4-ethylimidazolidine, 2, 2-difluoro-
1,3-bis (2-methoxybutyl) -4,5-diethyl-4- (1,1,1,3,3,3-hexafluoro-
2-propyl) imidazolidine, 2,2-difluoro-
1,3-bis (2-trifluoromethoxyethyl)-
4,4,5-trimethyl-5-ethylimidazolidine,
2,2-difluoro-1,3-bis (2-methoxypropyl) -4,5-dimethyl-4,5-diethylimidazolidine,

2,2-difluoro-1,3-bis (2-
(Fluoromethoxyethyl) -4-fluoroimidazolidine, 2,2-difluoro-1,3-bis (2-methoxy-1-fluoroethyl) -4,4-difluoroimidazolidine, 2,2-difluoro-1,3 -Bis (2-methoxybutyl) -4,5-difluoroimidazolidine,
2,2-difluoro-1,3-bis (2-methoxy-3
-Pentyl) -4,4,5-trifluoroimidazolidine, 2,2-difluoro-1,3-bis (2-trifluoromethoxy-3-pentyl) -4,4,5,5-tetrafluoroimidazolidine ,

2,2-difluoro-1,3-bis (2-
Methoxy-1-fluoroethyl) -4-chloroimidazolidine, 2,2-difluoro-1,3-bis (2-methoxybutyl) -4,4-dichloroimidazolidine, 2,
2-difluoro-1,3-bis (2-methoxy-3-pentyl) -4,5-dichloroimidazolidine, 2,2-
Difluoro-1,3-bis (2-trifluoromethoxy-3-pentyl) -4,4,5-trichloroimidazolidine, 2,2-difluoro-1,3-bis (2-fluoromethoxyethyl) -4, 4,5,5-tetrachloroimidazolidine,

2,2-difluoro-1,3-bis (3-
Methyl-2-methoxybutyl) -4-bromoimidazolidine, 2,2-difluoro-1,3-bis (1-methoxy-4,4,4-trifluoro-2-butyl) -4,4
-Dibromoimidazolidine, 2,2-difluoro-1,
3-bis (2-methoxy-1-chloroethyl) -4,5
-Dibromoimidazolidine, 2,2-difluoro-1,
3-bis (2-methoxy-1-bromoethyl) -4,
4,5-tribromoimidazolidine, 2,2-difluoro-1,3-bis (4-methoxy-3-hexyl)-
4,4,5,5-tetrabromoimidazolidine,

2,2-difluoro-1,3-bis (1-
Methoxy-4,4,4-trifluoro-2-butyl)-
4-iodoimidazolidine, 2,2-difluoro-1,
3-bis (3-methyl-2-methoxybutyl) -4,4
-Diiodoimidazolidine, 2,2-difluoro-1,
3-bis (2-methoxy-1-bromoethyl) -4,5
-Diiodoimidazolidine, 2,2-difluoro-1,
3-bis (4-methoxy-3-hexyl) -4,4,5
-Triiodoimidazolidine, 2,2-difluoro-
1,3-bis (2-methoxy-1-chloroethyl)-
4,4,5,5-tetraiodoimidazolidine,

2,2-difluoro-1,3-bis (2-
Methoxy-1,1-difluoroethyl) -4-fluoro-5-iodoimidazolidine, 2,2-difluoro-
1,3-bis (2-methoxy-1,1,2,2-tetrafluoroethyl) -4,4-difluoro-5-chloroimidazolidine, 2,2-difluoro-1,3-bis (2
-Methoxybutyl) -4-chloro-4-bromoimidazolidine, 2,2-difluoro-1,3-bis (2-methoxypropyl) -4,4,5-trichloro-5-bromoimidazolidine, 2,2 -Difluoro-1,3-bis (2-methoxy-1-fluorobutyl) -4,5-difluoro-4,5-dichloroimidazolidine,

2,2-difluoro-1,3-bis (2-
Methoxyethyl) -4-methyl-5-iodoimidazolidine, 2,2-difluoro-1,3-bis (2-methoxyethyl) -4,4-dimethyl-5-chloroimidazolidine, 2,2-difluoro- 1,3-bis (2-methoxyethyl) -4-chloro-4-bromo-5-ethylimidazolidine, 2,2-difluoro-1,3-bis (2-
Methoxyethyl) -4,5-dimethyl-5-bromoimidazolidine, 2,2-difluoro-1,3-bis (2-
Methoxyethyl) -4-fluoro-4,5-dimethylimidazolidine;

2,2-difluoro-1,3-bis (2-
Trifluoromethoxy-1,1,2,2-tetrafluoroethyl) -4,4,5,5-tetrafluoroimidazolidine, 2,2-difluoro-1,3-bis (2-trifluoromethoxy-1, 1,2,2-tetrafluoroethyl) -4,4,5,5-tetra (trifluoromethyl) imidazolidine, 2,2-difluoro-1,3-bis (2-trifluoromethoxy-1,1,1 Examples thereof include (2,2-tetrafluoroethyl) -4,5-difluoro-4,5-bis (trifluoromethyl) imidazolidine and the like, but are not limited to these exemplified compounds.

Of these, preferred are 2,2-difluoro-1,3-bis (2-methoxyethyl) imidazolidin and 2,2-difluoro-1,3-bis (2-ethoxyethyl) imidazolidin. Yes, and more preferably,
2,2-difluoro-1,3-bis (2-methoxyethyl) imidazolidine.

Specific examples of the compound represented by the general formula (A-2) include 2,2-difluoro-1- (2
-Methoxyethyl) -3-methylimidazolidine, 2,
2-difluoro-1- (2-methoxyethyl) -3-ethylimidazolidine, 2,2-difluoro-1- (2-
Methoxyethyl) -3-propylimidazolidine, 2,
2-difluoro-1- (2-methoxyethyl) -3-
(2-propyl) imidazolidine, 2,2-difluoro-1- (2-ethoxyethyl) -3-methylimidazolidine, 2,2-difluoro-1- (2-methyl-2-methoxypropyl) -3- Ethyl imidazolidine, 2,2
-Difluoro-1- (2-methoxyethyl) -3- (2
-Propyl) -4-methyl-5-iodoimidazolidine, 2,2-difluoro-1- (2-fluoromethyl-
1-methoxy-2-propyl) -3-ethyl-4-methylimidazolidine, 2,2-difluoro-1- (2-methoxypropyl) -3-methyl-4,5-dimethylimidazolidine, 2,2- Difluoro-1- (2-methoxy-1-fluoroethyl) -3-ethyl-4,5-dipropylimidazolidine, 2,2-difluoro-1- (2-
Methoxy-1-fluoroethyl) -3,4-dimethyl-
4-ethylimidazolidin, 2,2-difluoro-1-
(2-methoxybutyl) -3-trifluoromethyl-
4,5-difluoroimidazolidine, 2,2-difluoro-1- (2-methoxy-1-fluoroethyl) -3-
(2-propyl) -4-chloroimidazolidine, 2,2
-Difluoro-1- (4-methoxy-3-hexyl)-
3-propyl-4,4,5-triiodoimidazolidine, 2,2-difluoro-1- (2-methoxy-1,1
-Difluoroethyl) -3-ethyl-4-fluoro-5
-Iodoimidazolidine, 2,2-difluoro-1-
(2-methoxyethyl) -3,4-dimethyl-5-iodoimidazolidine, 2,2-difluoro-1- (2-trifluoromethoxy-1,1,2,2-tetrafluoroethyl) -3-tri Fluoromethyl imidazolidine,
2,2-Difluoro-1- (2-trifluoromethoxy-1,1,2,2-tetrafluoroethyl) -3-trifluoromethyl-4,4,5,5-tetrafluoroimidazolidine and the like. However, the present invention is not limited to these exemplified compounds.

Of these, 2,2-difluoro-1- (2-methoxyethyl) -3-methylimidazolidin and 2,2-difluoro-1- (2-methoxyethyl) -3-ethylimidazolidin are preferred. , 2,2-difluoro-1- (2-methoxyethyl) -3-propylimidazolidine and 2,2-difluoro-1- (2-methoxyethyl) -3- (2-propyl) imidazolidine; Preferably, 2,2-difluoro-1- (2
-Methoxyethyl) -3-methylimidazolidine.

The fluorine-containing organic compounds represented by the general formula (A-1) or (A-2) are each represented by the general formula (B-1)

[0056]

Embedded image

Or (B-2)

[0058]

Embedded image

Using the nitrogen-containing compound represented by the formula as a raw material, it can be obtained safely and easily.

First, the nitrogen-containing compounds represented by the general formulas (B-1) and (B-2), which are the starting materials, are prepared by utilizing a general reaction as described in the book of Synthetic Organic Chemistry. Can be synthesized. For example, N, N′-dialkylalkylenediamines are obtained by a dialkylamination reaction of 1,2-alkylenedihalides, and then a ring closing reaction is performed with urea to give 1,3-dialkyl-2-imidazolidinone. And the like.

As a specific example, for example, when synthesizing N, N'-bis (2-methoxyethyl) -2-imidazolidinone, an excess of about 90% is added to 2-methoxyethylamine.
At 1, ° C, 1,2-dichloroethane is gradually added and reacted,
Unreacted 2-methoxyethylamine is distilled off and N, N '
After obtaining bis- (2-methoxyethyl) ethylenediamine as an intermediate, urea is dissolved in the intermediate at 120 ° C., the temperature is raised to about 200 ° C., and a ring-closing reaction is performed to obtain a target product. There is.

When the desired substituents at the 1- and 3-positions of the fluorine-containing compounds represented by the general formulas (A-1) and (A-2) are different, for example, in the case of a dialkylamination reaction, First, a monoalkylamination reaction corresponding to the 1-position substituent of the imidazolidinone ring of the target substance is performed, and then an alkylamination agent corresponding to the 3-position substituent is reduced. And then closing the ring to obtain the nitrogen-containing compounds represented by the general formulas (B-1) and (B-2).

The compound represented by the general formula (A-1) or (A
The fluorine-containing organic compound represented by the formula (B-2)
The halogen-containing reaction is carried out by reacting the nitrogen-containing compound represented by 1) or (B-2) with a halogenating agent, followed by the action of a metal salt of fluorine in a non-reactive solvent to carry out the halogen exchange reaction. By doing so, it can be obtained safely and easily.

In the halogenation reaction, phosgene or oxalyl chloride, thionyl chloride, thionyl bromide, phosphorus pentachloride, phosphorus tribromide and the like can be used as a halogenating agent.

The temperature of the halogenation reaction varies depending on the type of the halogenating agent. For example, when oxalyl chloride is used as the halogenating agent, the temperature is usually 0 ° C.
To 100 ° C, preferably 20 ° C to 50 ° C.

In the halogenation reaction, an organic solvent may or may not be used. As such an organic solvent, any organic solvent that is inert to the reaction can be used.For example, hexane, octane, aliphatic hydrocarbon solvents such as decane, for example, benzene, toluene, xylene and the like Aromatic hydrocarbon solvents such as chlorobenzene, o-chlorotoluene, m-chlorotoluene, p-
Halogenated aromatic hydrocarbon solvents such as chlorotoluene, for example, chloroform, halogenated hydrocarbon solvents such as ethylene dichloride, for example, tetrahydrofuran, dioxane, dibutyl ether, anisole, ether solvents such as diphenyl ether, such as acetonitrile Aprotic polar solvents and the like, but are not limited thereto. still,
These organic solvents may be used alone or in combination.

When the halogenating agent is allowed to act, considering the reaction efficiency, it is desirable that the nitrogen-containing compound and the halogenating agent used in the halogenation reaction and the organic solvent do not contain water. In some cases, it is preferable to perform a dehydration treatment prior to the reaction.

In the halogen exchange reaction, silver fluoride, cesium fluoride, rubidium fluoride, potassium fluoride, sodium fluoride and the like can be used as the metal salt of fluorine, and silver fluoride is preferred. .

The temperature of the halogen exchange reaction is usually
The temperature is 0 ° C to 200 ° C, preferably 20 ° C to 100 ° C, more preferably 40 ° C to 80 ° C.

In the halogen exchange reaction, the amount of the metal salt of fluorine used is equivalent to the halogen atom contained in the halogenated organic compound (B-1) or (B-2). And it is preferably 1 to 3 equivalents.

In the halogen exchange reaction, an organic solvent may or may not be used. As such an organic solvent, any organic solvent that is inert to the reaction can be used.For example, hexane, octane, aliphatic hydrocarbon solvents such as decane, for example, benzene, toluene, xylene and the like Aromatic hydrocarbon solvents such as chlorobenzene, o-chlorotoluene, m-chlorotoluene, p-
Halogenated aromatic hydrocarbon solvents such as chlorotoluene, for example, chloroform, halogenated hydrocarbon solvents such as ethylene dichloride, for example, tetrahydrofuran, dioxane, dibutyl ether, anisole, ether solvents such as diphenyl ether, such as acetonitrile Aprotic polar solvents and the like, but are not limited thereto. still,
These organic solvents may be used alone or in combination.

In the halogen exchange reaction, in consideration of the reaction efficiency, it is desirable that the fluorine metal salt and the organic solvent do not contain water. If desired, dehydration treatment may be carried out prior to the reaction. Application may be preferred.

The halogen exchange reaction can be carried out in the presence of a catalyst such as a quaternary alkyl ammonium salt or a quaternary alkyl phosphonium salt.

The obtained general formula (A-1) or (A-
The fluorinated organic compound represented by 2) can be used as a fluorinating agent for the next fluorination reaction as it is in the reaction solution, or it can be used for the next fluorination reaction after removing the inorganic salt by filtration. it can. Or after isolation by distillation or the like,
It can be used for the next fluorination reaction.

The compound represented by formula (A-1) or (A-
The fluorination reaction using the fluorine-containing organic compound represented by 2) is extremely easy, and can be performed using a usual reaction apparatus.

The fluorination reaction using the fluorinated organic compound represented by the general formula (A-1) or (A-2) includes an alcoholic hydroxyl group as described in JP-A-2000-38370. To a fluorine group, conversion of a phenolic hydroxyl group to a fluorine group, fluorination of carbonyl (C = O) such as formyl group and ketone (C
F ₂ ), fluoride of carboxylic acid (—COOH) (−
COF) and the like.

For example, when it is used as a fluorinating agent in a fluorination reaction of alcohols, for example, when the alcohols are directly charged into the reaction mass after halogen exchange and reacted for several hours, the corresponding fluorides can be obtained in high yield. Kind can be obtained. After the fluorination reaction, the compound represented by the general formula (A-1)
Alternatively, the fluorine-containing organic compound represented by (A-2) can be recovered as a nitrogen-containing organic compound represented by formula (B-1) or (B-2).

[0078]

The present invention will be described in more detail with reference to the following examples, which, of course, are not intended to limit the scope of the present invention.

Reference Example 1 Synthesis of 1,3-bis (2-methoxyethyl) -2-imidazolidinone: equipped with a cooling tube, a stirrer, and a thermometer. 500 g of DMF and 43 g of ethylene urea were put into the 2 L flask thus set. While maintaining the inside of the flask at 60 ° C. and stirring, 50 g of a 60% NaH-mineral oil suspension was added thereto over 2 hours.
A time reaction was performed. Further, 179.4 g of 2-chloroethyl methyl ether was added dropwise over 3 hours.
For 3 hours. After cooling to room temperature, the solvent was distilled off,
The solid was removed by filtration to obtain 119 g of crude 1,3-bis (2-methoxyethyl) -2-imidazolidinone. This is purified by a silica gel column and then distilled, and as a fraction distilled at a tower head temperature of about 120 ° C. and a tower pressure of about 40 Pa, purified 1,3-bis (2-methoxyethyl) -2-imidazolide 30 g of nonone was obtained.

Example 1 2,2-difluoro-1,
Synthesis of 3-bis (2-methoxyethyl) imidazolidine: equipped with a condenser, a stirrer, and a thermometer, and after replacing the inside with nitrogen, put 1,3- into a 200 mL glass flask pressurized slightly with nitrogen. 101 g of bis (2-methoxyethyl) -2-imidazolidinone was added and kept at 40 ° C. with stirring. To this, 128.2 g of oxalyl chloride was gradually added dropwise, and the mixture was reacted for 50 hours with stirring as it was.
A reaction solution was obtained. Here, 50 mL of acetonitrile dehydrated using Molecular Sieves 3A was added, and the internal temperature was maintained at 40 ° C. while stirring. Further, under a nitrogen atmosphere, 50.5 g of silver (I) fluoride ground in a mortar was gradually added. At that time, due to heat generation, the temperature was gradually added so that the temperature did not exceed 50 ° C. The mixture was stirred at a reaction temperature of 50 ° C. for 10 hours to obtain a reaction solution containing 2,2-difluoro-1,3-bis (2-methoxyethyl) imidazolidine. Solids were removed from this reaction solution by filtration, and acetonitrile as a solvent was distilled off with an evaporator to obtain a reaction concentrate. The reaction concentrate is distilled to obtain a fraction having a temperature of about 95 ° C. at the top of the distillation column and a pressure of about 150 Pa, and 2,2-difluoro-1,3
-Bis (2-methoxyethyl) imidazolidine was obtained.
¹ H-NMR and ¹³ C-NMR obtained as this fraction
1 and 2 show the measurement results.

<Use Example 1> Synthesis of n-octyl fluoride (conversion of alcoholic hydroxyl group to fluorine group): equipped with a cooling pipe and a stirrer, the inside was replaced with nitrogen, and then the state was slightly pressurized with nitrogen. In a 50 mL two-neck glass flask, add 1
0.1 g of -octanol was added, 0.3 g of 2,2-difluoro-1,3-bis (2-methoxyethyl) imidazolidine obtained in Example 1 was added, and the mixture was kept at 40 ° C for 2 hours with stirring. Was. After completion of the reaction, the reaction solution was diluted with acetonitrile, and the production of n-octyl fluoride was confirmed by GC-MS measurement of the reaction diluent. The reaction yield was 81%.

Comparative Example 1 2,2-difluoro-1,
Boiling point of 3-dimethylimidazolidine: The boiling point of 2,2-difluoro-1,3-dimethylimidazolidine was measured and found to be 47 ° C./4.9 kPa (37 mmHg).

[0083]

According to the present invention, it is possible to provide a novel fluorine-containing organic compound which has a low vapor pressure and can be used as a more safe fluorinating agent.

[Brief description of the drawings]

FIG. 1 is a ¹ H-NMR spectrum of a compound synthesized in Example 1.

FIG. 2 is a ¹³ C-NMR spectrum of the compound synthesized in Example 1.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Ryoichi Seki 580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals, Inc. (72) Inventor Naoki Asashige 580-32, Nagaura Sodegaura-shi, Chiba Mitsui Chemicals, Inc.

Claims (4)

[Claims] 1. A fluorine-containing organic compound represented by the general formula (A-1). Embedded image (Wherein, R ^{1 to} R ¹² each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an alkyl group having 1 to 6 carbon atoms which may be substituted by fluorine.
^A, the R ^B are each independently, represent a fluorine optionally substituted alkyl group having 1 to 18 carbon atoms. ) 2. A fluorine-containing organic compound represented by the general formula (A-2). Embedded image (Wherein, R ¹ , R ² , R ⁵ , R ⁶ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹²
Is independently a hydrogen atom, a fluorine atom, a chlorine atom,
It represents a bromine atom, an iodine atom, or an alkyl group having 1 to 6 carbon atoms which may be substituted by fluorine. ^RA and ^RC represent an alkyl group having 1 to 18 carbon atoms which may be substituted by fluorine. ) 3. The fluorine-containing organic compound according to claim 1, represented by the general formula (A-3). Embedded image (In the formula, R ^A and R ^B are as defined above.) 4. The fluorine-containing organic compound according to claim 2, represented by the general formula (A-4). Embedded image (In the formula, R ^A and R ^C are as defined above.)