JPH0789945A - Production of fluoroalkanecarboxamide derivative - Google Patents

Abstract

PURPOSE:To readily obtain the derivative excellent in herbicidal activity by reacting an iminothiazoline compound with a fluoroolefin compound in the presence of a primary or 9 secondary amine compound and then, reacting the reactional product with water. CONSTITUTION:(A) An iminothiazoline compound of formula I (R<1> is halogen, halogen-substntuted alkyl, etc.; R<2> is H or halogen; R<3> is methyl, ethyl, chlorine atom or bromine atom) is made to react with (B) a fluoroolefin compound of formula II (X and Y are H, chlorine atom, fluorine atom or trifluoromethyl, with the proviso that when X is H or a chlorine atom, Y is a fluorine atom or trifluoromethyl) in the presence of (C) a primary or 5 secondary amine compound (preferably ethylene diamine or N-methylethylenediamine) and then, the reactional product is made to react with water to provide the objective fluoroalkanecarboxamide derivative of formula III [e.g. 2-difluoroacetylimino-3-(3- trifluoromethyl-phenyl)-5-methylthiazoline].

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a fluoroalkanecarboxamide derivative.

BACKGROUND OF THE INVENTION Certain difluoroacetamide derivatives have excellent herbicidal activity and a method for producing the same is disclosed in US Pat.
2, 798, etc., the production method requires difluoroacetic acid which is not always easily available on an industrial scale (Org, Prep, Proced. Int., 19, 468 (1987).
Therefore, an advantageous method for producing the difluoroacetamide derivative without using difluoroacetic acid has been desired.

[0002]

Means for Solving the Problems The present inventors have conducted extensive studies to find an advantageous method for producing a fluoroalkanecarboxamide derivative represented by the following general formula 9 containing the difluoroacetamide derivative. formula
Conversion 7

[Chemical 7] [In the formula, R ¹ represents a halogen atom, a halogen-substituted alkyl group or a halogen-substituted alkoxy group, R ² represents a hydrogen atom or a halogen atom, and R ³ represents a methyl group, an ethyl group, a chlorine atom or a bromine atom. ] The iminothiazoline compound shown by these or its salt (for example, inorganic acid salts, such as hydrochloride, hydrobromide, and a sulfate), and general formula
Conversion 8

Embedded image XYC═CF ₂ [wherein, X and Y are the same or different and are a hydrogen atom,
It represents a chlorine atom, a fluorine atom or a trifluoromethyl group. However, when X is a hydrogen atom or a chlorine atom, Y
Represents a fluorine atom or a trifluoromethyl group. ]
With a fluoroolefin compound represented by the formula (1) in the presence of a primary amine compound or a secondary amine compound, and (b) reacting the reaction product with water.

[Chemical 9] [In the formula, R ¹ , R ² , R ³ , X and Y have the same meanings as described above. The present invention was completed by finding that a fluoroalkanecarboxamide derivative represented by the following formula can be easily obtained. That is, the present invention provides (a) an iminothiazoline compound represented by the general formula (7) or a salt thereof and a fluoroolefin compound represented by the general formula (8) in the presence of a primary amine compound or a secondary amine compound. Provided is a method for producing a fluoroalkanecarboxamide derivative represented by the general formula (9), which comprises a step of reacting, and (b) a step of reacting the reaction product with water. According to the production method of the present invention, the fluoroalkanecarboxamide derivative represented by the general formula 9 can be produced in one pot by using the fluoroolefin compound represented by the general formula 8 which is easily available.

The iminothiazoline compound represented by the general formula 7, which is the starting material compound used in the present invention, is
It can be obtained by the method described in European Patent Application EP-A-600489, published specification, US Pat. No. 5,312,798, and the like. In general formula 7,
Examples of the “halogen” include fluorine, chlorine and bromine, and examples of the halogen-substituted alkyl group include a C ₁ -C ₆ alkyl group substituted with one or more halogen atoms such as trifluoromethyl group. As the halogen-substituted alkoxy group, for example, one or more halogen atoms such as difluoromethoxy group, trifluoromethoxy group, 1,1,2,2-tetrafluoroethoxy group, 2,2,2-trifluoroethoxy group, etc. substituted C ₁ -C ₆ alkoxy group. In the general formula 9, the general formula 10

XYCHC = O [In the formula, X and Y have the same meanings as described above. Examples of the fluoroalkanoyl group represented by] include a difluoroacetyl group, a chlorofluoroacetyl group, 2,
2,3,3-tetrafluoropropanoyl group, 2,2-
An example is a bis (trifluoromethyl) acetyl group.

Examples of the iminothiazoline compound represented by the general formula 7 include 2-imino-3- (3-trifluoromethylphenyl).
-5-Methylthiazoline 2-imino-3- (3,5-dichlorophenyl) -5-
Methylthiazoline 2-imino-3- (3-difluoromethoxyphenyl)
-5-methylthiazoline 2-imino-3- (3-chlorophenyl) -5-methylthiazoline 2-imino-3- (3-trifluoromethoxyphenyl) -5-methylthiazoline 2-imino-3- (4-fluoro -3-Trifluoromethylphenyl) -5-methylthiazoline 2-imino-3- (3-trifluoromethylphenyl)
-5-ethylthiazoline 2-imino-3- (3-trifluoromethylphenyl)
-5-chlorothiazoline 2-imino-3- (3-trifluoromethylphenyl)
-5-bromothiazoline and the like.

Examples of the fluoroalkanecarboxamide derivative represented by the general formula 9 are 2-difluoroacetylimino-3- (3-trifluoromethylphenyl) -5-methylthiazoline 2-difluoroacetylimino-3.
-(3,5-Dichlorophenyl) -5-methylthiazoline 2-difluoroacetylimino-3- (3-difluoromethoxyphenyl) -5-methylthiazoline 2-difluoroacetylimino-3- (3-chlorophenyl) -5-methyl Thiazoline 2-difluoroacetylimino-3- (3-trifluoromethoxyphenyl) -5-methylthiazoline 2-difluoroacetylimino-3- (4-fluoro-
3-Trifluoromethylphenyl) -5-methylthiazoline 2-difluoroacetylimino-3- (3-trifluoromethylphenyl) -5-ethylthiazoline 2-difluoroacetylimino-3- (3-trifluoromethylphenyl)- 5-chlorothiazoline 2-difluoroacetylimino-3- (3-trifluoromethylphenyl) -5-bromothiazoline and the like.

2-chlorofluoroacetylimino-3-
(3-Trifluoromethylphenyl) -5-methylthiazoline 2-chlorofluoroacetylimino-3- (3,5-dichlorophenyl) -5-methylthiazoline 2-chlorofluoroacetylimino-3- (3-difluoromethoxyphenyl) -5-Methylthiazoline 2-chlorofluoroacetylimino-3- (3-chlorophenyl) -5-methylthiazoline 2-chlorofluoroacetylimino-3- (3-trifluoromethoxyphenyl) -5-methylthiazoline 2-chlorofluoro Acetylimino-3- (4-fluoro-3-trifluoromethylphenyl) -5-methylthiazoline 2-chlorofluoroacetylimino-3- (3-trifluoromethylphenyl) -5-ethylthiazoline 2-chlorofluoroacetylimino -3- (3- Trifluoromethylphenyl) -5-chlorothiazoline 2-chlorofluoroacetylimino-3- (3-trifluoromethylphenyl) -5-bromothiazoline and the like.

2- (2,3,3,3-tetrafluoropropanoylimino) -3- (3-trifluoromethylphenyl) -5-methylthiazoline 2- (2,3,3,3-tetrafluoropropaline Noylimino) -3- (3,5-dichlorophenyl) -5-methylthiazoline 2- (2,3,3,3-tetrafluoropropanoylimino) -3- (3-difluoromethoxyphenyl) -5
-Methylthiazoline 2- (2,3,3,3-tetrafluoropropanoylimino) -3- (3-chlorophenyl) -5-methylthiazoline 2- (2,3,3,3-tetrafluoropropanoylimino) -3- (3-trifluoromethoxyphenyl)-
5-Methylthiazoline 2- (2,3,3,3-tetrafluoropropanoylimino) -3- (4-fluoro-3-trifluoromethylphenyl) -5-methylthiazoline 2- (2,3,3,3 3-Tetrafluoropropanoylimino) -3- (3-trifluoromethylphenyl) -5
-Ethylthiazoline 2- (2,3,3,3-tetrafluoropropanoylimino) -3- (3-trifluoromethylphenyl) -5
-Chlorothiazoline 2- (2,3,3,3-tetrafluoropropanoylimino) -3- (3-trifluoromethylphenyl) -5
-Bromothiazoline and the like.

2- (2,2-bis (trifluoromethyl) acetylimino) -3- (3-trifluoromethylphenyl) -5-methylthiazoline 2- (2,2-bis (trifluoromethyl) acetylimino ) -3- (3,5-Dichlorophenyl) -5-methylthiazoline 2- (2,2-bis (trifluoromethyl) acetylimino) -3- (3-difluoromethoxyphenyl) -5
-Methylthiazoline 2- (2,2-bis (trifluoromethyl) acetylimino) -3- (3-chlorophenyl) -5-methylthiazoline 2- (2,2-bis (trifluoromethyl) acetylimino) -3 -(3-trifluoromethoxyphenyl)-
5-Methylthiazoline 2- (2,2-bis (trifluoromethyl) acetylimino) -3- (4-fluoro-3-trifluoromethylphenyl) -5-methylthiazoline 2- (2,2-bis (tri Fluoromethyl) acetylimino) -3- (3-trifluoromethylphenyl) -5
-Ethylthiazoline 2- (2,2-bis (trifluoromethyl) acetylimino) -3- (3-trifluoromethylphenyl) -5
-Chlorothiazoline 2- (2,2-bis (trifluoromethyl) acetylimino) -3- (3-trifluoromethylphenyl) -5
-Bromothiazoline and the like.

The primary amine compound or secondary amine compound used in the present invention may be substituted with a group inert to the reaction, and is a compound which can be added to the fluoroolefin compound represented by the general formula (8). There is no particular limitation. Examples of the first amine compound and the second amine compound include a first monoamine compound and a second monoamine compound, respectively. The first monoamine compound has the general formula

Embedded image Q-NH ₂ wherein, Q is C1-C20 alkyl groups, C3-C10
Alkoxyalkyl group, C3-C10 alkylthioalkyl group, C3-C10 cycloalkyl group, C4-
C20 cycloalkylalkyl group, C3-C10 alkenyl group, C3-C10 alkynyl group, C7-C1
0 aralkyl group, C6-C10 heteroaralkyl group, C5-C10 heteroaryl group or C6-C1
2 represents an arylamine group. ], The preferred first monoamine compound is, for example, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine, n. -Hexylamine, 2-ethylhexylamine, n-octylamine, dodecylamine, tetradecylamine, octadecylamine, icosylamine, 2-methoxyethylamine, 2-ethoxyethylamine, 3-methoxypropylamine, 3-ethoxypropylamine, 2- Methylthioethylamine, cyclohexylmethylamine, cyclopentylamine, cyclohexylamine, allylamine, propargylamine, benzylamine, phenethylamine, 3-phenyl-1-pro Triethanolamine, 4-phenyl-1-butylamine, and aniline, and the like, but is not limited thereto.

The second monoamine compound has the general formula

Embedded image Q ¹ —NH—Q ² [wherein, Q ¹ and Q ² are the same or different and represent the same meaning as Q, or Q ¹ and Q ² are bonded at the terminal to form C ¹ -NH ² C3 alkyl optionally tetramethylene group optionally substituted with a group, C1-C3 alkyl optionally pentamethylene group optionally substituted with a group or C1-C3 alkyl group optionally substituted by CH ₂ CH ₂ OCH ₂ CH, ₂
May be represented. The preferred second monoamine compound is, for example, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, dipentylamine, dihexylamine, diallylamine, dicyclohexylamine, N. -Ethylmethylamine, N-methylpropylamine, N-methylisopropylamine, N-methylbutylamine, N-methylhexylamine, N-methylcyclohexylamine, N-ethylpropylamine, N-ethylisopropylamine, N
-Ethylbutylamine, N-ethylhexylamine, N
-Ethylcyclohexylamine, N-methylbenzylamine, N-ethylbenzylamine, dibenzylamine,
Examples thereof include, but are not limited to, N-methylaniline, N-ethylaniline, N-propylaniline, pyrrolidine, piperidine, pipecoline, morpholine and the like.

Further, the first amine compound and the second amine compound may be a first polyamine compound and a second polyamine compound, respectively. The first polyamine compound and the second polyamine compound have the general formula

Embedded image Q ³ Q ⁴ N—Z—NQ ⁵ Q ⁶ [wherein Z is a phenylene group, a (CH ₂ ) ₂ group or a (CH _2
2 ) ₃ groups, Q ³ , Q ⁴ , Q ⁵ and Q ⁶ are the same or different and have the same meaning as Q, or
³ and Q ⁴ , and Q ⁵ and Q ⁶ are bonded to each other at their ends to form (CH
₂ ) ₂ group (the ethylene group may be substituted with a C1-C3 alkyl group) or NH (CH ₂ ) ₂ group (the ethylene group may be substituted with a C1-C3 alkyl group) You may. However, at least one of Q ³ , Q ⁴ , Q ⁵ and Q ⁶ represents a hydrogen atom. ] The preferred first polyamine compound and second polyamine compound are, for example, ethylenediamine,
N-methylethylenediamine, N, N-dimethylethylenediamine, N, N'-dimethylethylenediamine,
N, N, N'-trimethylethylenediamine, N-ethylethylenediamine, N, N-diethylethylenediamine, N, N'-diethylethylenediamine, N, N,
N'-triethylethylenediamine, N, N-dimethyl-N'-ethylethylenediamine, N, N-diethyl-
N'-methylethylenediamine, N-propylethylenediamine, N-methyl-1,3-propanediamine,
N, N-dimethyl-1,3-propanediamine, N,
N'-dimethyl-1,3-propanediamine, N, N-
Diethyl-1,3-propanediamine, N, N'-diethyl-1,3-propanediamine, N, N-dibutyl-
1,3-propanediamine, N, N, N'-trimethyl-1,3-propanediamine, methyliminobispropylamine, piperazine, N-methylpiperazine, 2-methylpiperazine, 1- (2-aminoethyl) piperidine , 4- (2-aminoethyl) morpholine, 1- (2-
Aminoethyl) pyrrolidine, 1- (2-aminoethyl)
Piperazine, 2- (2-aminoethyl) pyridine, 4-
(3-aminopropyl) morpholine, 1- (3-aminopropyl) pipecoline, 1-amino-4-methylpiperazine, 1,3-di- (4-piperidyl) propane, acetaldehyde ammonia, phenylenediamine and the like can be mentioned. However, the present invention is not limited to these.

Examples of the fluoroolefin compound represented by the general formula 8 include, but are not limited to, fluoroethylene, tetrafluoroethylene, hexafluoropropene, octafluoroisobutene and chlorotrifluoroethylene. In the present invention, the base used as necessary is not particularly limited as long as it can capture hydrogen fluoride generated by the reaction, and the above-mentioned primary amine compound or secondary amine compound is used as it is. You can also Besides,
Examples of the base used include inorganic bases such as alkali hydroxide (sodium hydroxide, potassium hydroxide, etc.), alkali carbonate (sodium carbonate, potassium carbonate, etc.), alkali hydrogen carbonate, triethylamine, N, N-dimethylaniline, N, Examples thereof include organic bases such as N-diethylaniline, pyridine and quinoline, but are not limited thereto. The step (a) and the step (b) can be carried out by adding a solvent as necessary. Examples of the solvent used include N, N-dimethylformamide, N, N
-Aprotic polar solvent such as dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide, alkyl nitrile solvent such as acetonitrile and propionitrile,
Tetrahydrofuran, dimethoxyethane, diglyme,
Examples thereof include ether solvents such as triglyme, halogen-containing solvents such as chloroform and dichloroethane, aromatic hydrocarbon solvents such as benzene and toluene, and mixed solvents thereof, but are not limited thereto.

In step (a), the reaction temperature is usually 0.
C. to 200.degree. C., preferably 20.degree. C. to 150.degree. C. or the boiling point of the solvent, the reaction time varies depending on the reaction conditions, but is usually 3 to 60 hours, and the amount of the reaction reagent is The primary amine compound and the secondary amine compound are usually used in a proportion of 1 to 10 moles, and the base used, if necessary, in a proportion of 1 to 10 moles, per 1 mole of the iminothiazoline compound represented by the general formula (7). The fluoroolefin compound represented by the general formula 8 is usually present in a proportion of 1 mol to a large excess. The reaction is carried out at atmospheric pressure, or 1 kg / c
It can be performed at m ^{2 to} 10 kg / cm ² (gauge). Step (a) is usually carried out by adding the fluoroolefin compound represented by the general formula 8 to a solution of the iminothiazoline compound of the general formula 7 and the primary amine compound or the secondary amine compound, or (i) the general formula formula
After reacting the fluoroolefin compound represented by Chemical formula 8 with the primary amine compound or the secondary amine compound, (i
i) It is carried out by reacting the reaction product with the iminothiazoline compound represented by the general formula. The reaction mixture in step (a) can then be reacted with water to obtain the desired product. Since step (b) is usually performed after step (a), step (b) may be performed in the solvent used in step (a), or may be performed in another solvent. Examples of such a solvent include the solvents mentioned in step (a).

In step (b), the reaction temperature is usually 0.
C. to 100.degree. C. or the boiling point of the solvent, the reaction time is usually from momentary to 1 hour, and the amount of the reaction reagent is 1 mol of the iminothiazoline compound represented by the general formula 7 and water is usually 1 mol. Molar to large excess. The reaction solution after the reaction in step (b) can be subjected to usual post-treatments such as extraction with an organic solvent and concentration to isolate the desired compound of the present invention. If necessary, it can be further purified by recrystallization or chromatography.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Example 1 2-Imino-3- (3-trifluoromethylphenyl)
0.75 g (3.0 mmol) of 5-methylthiazoline, 1.06 g (14.5 mmol) of diethylamine and 0.91 g of triethylamine
A solution of (9.0 mmol) of N, N-dimethylformamide in 15 ml was stirred at 50 ° C. for 17 hours while flowing tetrafluoroethylene gas (flow rate of about 0.3 l / hr) in a reaction vessel under vigorous stirring. . After allowing to cool, pour the reaction solution into ice water,
It was extracted with ethyl acetate. The ethyl acetate layer was washed with water and then with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated. The residue was subjected to silica gel column chromatography (elution solvent; n-hexane: ethyl acetate =).
2: 1), 2-difluoroacetylimino-3-
0.83 g (2.4 mmol, yield 81%) of (3-trifluoromethylphenyl) -5-methylthiazoline was obtained. mp. 123.9 ° C. ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 2.39 (s, 3H), 5.89 (t, 1H, J = 5)
4.9 Hz), 6.97 (s, 1H), 7.6 to 7.8 (m, 4H) Example 2 2-imino-3- (3-trifluoromethylphenyl)
0.55 g (2.0 mmol) -5-methylthiazoline, 0.51 g (6.0 mmol) piperidine and 0.61 g (6.
0 mmol) of N, N-dimethylformamide in 10 ml of solution is stirred vigorously, and tetrafluoroethylene gas (flow rate of about 0.3 l / hr) is flowed thereinto at 50 ° C. for 9 minutes.
Reacted for hours. After allowing to cool, the reaction solution was poured into ice water and extracted with ethyl acetate. The ethyl acetate layer was washed with water and then with saturated saline and dried over anhydrous magnesium sulfate.
The solvent was distilled off. The residue was subjected to silica gel column chromatography to give 2-difluoroacetylimino-3-.
0.63 g (1.8 mmol, yield 91%) of (3-trifluoromethylphenyl) -5-methylthiazoline was obtained.

Example 3 2-Imino-3- (3-trifluoromethylphenyl)
0.55 g (2.0 mmol) -5-methylthiazoline, 0.51 g (6.0 mmol) piperidine and 0.61 g (6.
In a reaction vessel in which 10 mmol of a toluene solution of 0 mmol) is vigorously stirred, tetrafluoroethylene gas (flow rate of about 0.3
(l / hr), and reacted at 90 ° C. for 15 hours. After allowing to cool, the reaction solution was poured into ice water and extracted with toluene. The toluene layer was washed with water and then with saturated saline and dried over anhydrous magnesium sulfate, and then the solvent was distilled off. The residue was subjected to silica gel column chromatography to obtain 0.48 g (1.4 mmol, yield 71%) of 2-difluoroacetylimino-3- (3-trifluoromethylphenyl) -5-methylthiazoline. Example 4 2-Imino-3- (3-trifluoromethylphenyl)
0.55 g (2.0 mmol) of 5-methylthiazoline, 0.44 g (6.0 mmol) of n-butylamine and 0.61 of triethylamine
g (6.0 mmol) of N, N-dimethylformamide 10 ml
While flowing tetrafluoroethylene gas (flow rate about 0.3 l / hr) into a reaction vessel in which the solution is vigorously stirred, at 50 ° C.
And reacted for 13 hours. After allowing to cool, the reaction solution was poured into ice water and extracted with diethyl ether. The diethyl ether layer was washed with 5% hydrochloric acid water, water, and then with saturated saline, dried over anhydrous magnesium sulfate, and then the solvent was distilled off to give 2-
Difluoroacetylimino-3- (3-trifluoromethylphenyl) -5-methylthiazoline 0.50 g (1.5 mm
ol, yield 74%).

Example 5 2-Imino-3- (3-trifluoromethylphenyl)
0.52-methylthiazoline 0.52 g (2.0 mmol), diethylamine 0.44 g (6.0 mmol) and triethylamine 0.61 g
A solution of (6.0 mmol) in 10 ml of N, N-dimethylformamide was reacted at 50 ° C. for 21 hours in an atmosphere of 0.70 g (7.0 mmol) of tetrafluoroethylene gas (using fusen). After allowing to cool, the reaction solution was poured into ice water and extracted with ethyl acetate. The ethyl acetate layer was washed with water and then with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated. The residue was subjected to silica gel column chromatography, and 2-difluoroacetylimino-3- (3-trifluoromethylphenyl) -5-methylthiazoline 0.44 g
(1.3 mmol, yield 65%) was obtained. Example 6 2-Imino-3- (3-trifluoromethylphenyl)
Hydrochloric acid salt of -5-methylthiazoline 1.47 g (5.0 mmol),
0.64 g (7.5 mmol) piperidine and 1.
77 g (17.5 mmol) of N, N-dimethylformamide 10
50 mL of tetrafluoroethylene gas (flow rate of about 0.7 l / hr) was introduced into the reaction vessel in which the ml solution was vigorously stirred.
The reaction was performed at 13 ° C for 13 hours. After allowing to cool, the reaction solution was poured into ice water and extracted with diethyl ether. The diethyl ether layer was washed with water and then with saturated saline, dried over anhydrous magnesium sulfate, and then the solvent was distilled off. The residue was subjected to silica gel column chromatography to give 1.56 g (4.6 mmol, yield 9) of 2-difluoroacetylimino-3- (3-trifluoromethylphenyl) -5-methylthiazoline.
3%) was obtained.

Example 7 2-Imino-3- (3-trifluoromethylphenyl)
0.77 g (3.0 mmol) of 5-methylthiazoline, 1.32 g (18.0 mmol) of diethylamine and 1.04 g (7.
5 mmol) of N, N-dimethylformamide (15 ml) was stirred vigorously in a reaction vessel while flowing tetrafluoroethylene gas (flow rate about 0.3 l / hr) at 50 ° C. at 32 ° C.
Reacted for hours. After allowing to cool, the reaction solution was poured into ice water and extracted with ethyl acetate. The ethyl acetate layer was washed with water and then with saturated saline and dried over anhydrous magnesium sulfate.
The solvent was distilled off. The residue was subjected to silica gel column chromatography to give 2-difluoroacetylimino-3-.
0.53 g (1.6 mmol, yield 53%) of (3-trifluoromethylphenyl) -5-methylthiazoline was obtained. Example 8 2-Imino-3- (3-trifluoromethylphenyl)
A solution of 1.29 g (5.0 mmol) of 5-methylthiazoline and 0.64 g (7.5 mmol) of piperidine in 10 ml of N, N-dimethylformamide was added to a reaction vessel in which tetrafluoroethylene gas (flow rate: about 0. The reaction was carried out at 50 ° C. for 21 hours while flowing 7 l / hr). After allowing to cool, the reaction mixture was poured into saturated aqueous sodium hydrogen carbonate and extracted with diethyl ether. The diethyl ether layer was washed with water and then with saturated saline, dried over anhydrous magnesium sulfate, and then the solvent was distilled off. The residue was subjected to silica gel column chromatography to give 2-difluoroacetylimino-3- (3
1.24 g (3.7 mmol, 74% yield) of -trifluoromethylphenyl) -5-methylthiazoline was obtained. Also, 2-
Imino-3- (3-trifluoromethylphenyl) -5
-0.30 g of methyl thiazoline was recovered.

Example 9 2-Imino-3- (3-trifluoromethylphenyl)
-5-Methylthiazoline 1.29 g (5.0 mmol) and 3-
(N, N-dimethylamino) propylamine 0.77 g (7.
5 mmol) of N, N-dimethylformamide (10 ml) was vigorously stirred into a reaction vessel, while flowing tetrafluoroethylene gas (flow rate about 0.7 l / hr) at 50 ° C. at 32 ° C.
Reacted for hours. After allowing to cool, the reaction mixture was poured into saturated aqueous sodium hydrogen carbonate and extracted with diethyl ether. The diethyl ether layer was washed with water and then with saturated saline, dried over anhydrous magnesium sulfate, and then the solvent was distilled off. The residue was subjected to silica gel column chromatography, 2-
Difluoroacetylimino-3- (3-trifluoromethylphenyl) -5-methylthiazoline 0.59 g (1.8 mm
ol, yield 35%). In addition, 2-imino-3- (3
0.50 g of -trifluoromethylphenyl) -5-methylthiazoline was recovered. Example 10 2-Imino-3- (3-trifluoromethylphenyl)
A solution of 1.29 g (5.0 mmol) of 5-methylthiazoline and 0.65 g (7.5 mmol) of piperazine in 10 ml of N, N-dimethylformamide was stirred vigorously in a reaction vessel containing tetrafluoroethylene gas (flow rate of about 0. 7 l / hr)
The reaction was carried out at 50 ° C for 9 hours. After allowing to cool, the reaction solution was poured into ice water and extracted with diethyl ether. The diethyl ether layer was washed with water and then with saturated saline, dried over anhydrous magnesium sulfate, and then the solvent was distilled off. The residue was subjected to silica gel column chromatography to give 1.24 g (3.7 mmol, yield 7) of 2-difluoroacetylimino-3- (3-trifluoromethylphenyl) -5-methylthiazoline.
4%).

Example 11 2-Imino-3- (3-trifluoromethylphenyl)
Hydrochloric acid salt of -5-methylthiazoline 1.47 g (5.0 mmol),
0.64 g (7.5 mmol) piperazine and 1.
A solution of 52 g (15.0 mmol) of diglyme in 10 ml was stirred vigorously, and tetrafluoroethylene gas was added.
The mixture was reacted at 70 ° C. for 24 hours while flowing (flow rate of about 0.7 l / hr). After allowing to cool, the reaction solution was poured into ice water and extracted with diethyl ether. The diethyl ether layer was washed with water and then with saturated saline, dried over anhydrous magnesium sulfate, and then the solvent was distilled off. The residue was subjected to silica gel column chromatography to give 2-difluoroacetylimino-3.
1.01 g (3.0 mmol, yield 60%) of-(3-trifluoromethylphenyl) -5-methylthiazoline was obtained. Example 12 2-Imino-3- (3-trifluoromethylphenyl)
-5-methyl thiazoline 1.29 g (5.0 mmol) and 1-
A solution of 0.78 g (6.0 mmol) of (2-aminoethyl) piperazine in 10 ml of N, N-dimethylformamide was stirred vigorously in a reaction vessel, and tetrafluoroethylene gas was added.
The mixture was reacted at 50 ° C. for 33 hours while flowing (flow rate of about 0.7 l / hr). After allowing to cool, the reaction solution was poured into saturated aqueous sodium carbonate and extracted with diethyl ether. The diethyl ether layer was washed with water and then with saturated saline, dried over anhydrous magnesium sulfate, and then the solvent was distilled off. The residue was subjected to silica gel column chromatography to give 2-difluoroacetylimino-3- (3-trifluoromethylphenyl) -5-methylthiazoline 1.18 g (3.5 mmol, yield 7).
0%). In addition, 0.12 g of 2-imino-3- (3-trifluoromethylphenyl) -5-methylthiazoline was recovered.

Example 13 2-Imino-3- (3-trifluoromethylphenyl)
Tetrafluoroethylene gas (flow rate of about 0.7 l / hr) was charged into a reaction vessel in which a solution of 1.29 g (5.0 mmol) of 5-methylthiazoline and 0.52 g (6.0 mmol) of piperazine in 10 ml of toluene was vigorously stirred. The mixture was allowed to react at 80 ° C. for 48 hours while flowing. After allowing to cool, the reaction solution was poured into saturated aqueous sodium carbonate and extracted with toluene. The toluene layer is water, then
The extract was washed with saturated saline and dried over anhydrous magnesium sulfate, and then the solvent was distilled off. The residue was subjected to silica gel column chromatography to give 2-difluoroacetylimino-
1.29 g (3.8 mmol, yield 77%) of 3- (3-trifluoromethylphenyl) -5-methylthiazoline was obtained. Example 14 2-Imino-3- (3-trifluoromethylphenyl)
A solution of 1.47 g (5.0 mmol) of 5-methylthiazoline hydrochloride and 1.57 g (18.0 mmol) of morpholine in 10 ml of N, N-dimethylformamide was stirred vigorously in a reaction vessel containing tetrafluoroethylene gas (flow rate). (About 0.7l / hr)
The mixture was allowed to react at 60 ° C. for 2 hours while flowing. After allowing to cool, the reaction solution was poured into 100 ml of saturated aqueous sodium hydrogencarbonate and extracted with toluene (100 ml × 2). 5 layers of toluene
% Hydrochloric acid aqueous solution (50 ml × 2), water (70 ml), and then saturated saline (70 ml), and the organic layer was dried over anhydrous magnesium sulfate and the solvent was distilled off. The residue was subjected to silica gel column chromatography to give 1.47 g (4.4 mmol, yield 8) of 2-difluoroacetylimino-3- (3-trifluoromethylphenyl) -5-methylthiazoline.
7%).

Example 15 2-Imino-3- (3-trifluoromethylphenyl)
A solution of 1.29 g (5.0 mmol) of 5-methylthiazoline and 0.96 g (11.0 mmol) of morpholine in 10 ml of N, N-dimethylformamide was placed in a reaction vessel under vigorous stirring.
The reaction was carried out at 50 ° C. for 13 hours while flowing tetrafluoroethylene gas (flow rate about 0.7 l / hr). After allowing to cool, the reaction solution was poured into 100 ml of saturated aqueous sodium hydrogencarbonate and extracted with toluene (100 ml × 2). The toluene layer was mixed with a 5% hydrochloric acid aqueous solution (50 ml x 2), water (50 ml), and then
The extract was washed with saturated brine (50 ml), dried over anhydrous magnesium sulfate, and the solvent was evaporated. The residue was subjected to silica gel column chromatography to give 2-difluoroacetylimino-3- (3-trifluoromethylphenyl).
-5-Methylthiazoline 1.64 g (4.9 mmol, yield 98
%) Was obtained. Example 16 A solution of 0.57 g (6.7 mmol) of piperidine in 10 ml of N, N-dimethylformamide was placed in a reaction vessel under vigorous stirring.
The reaction was carried out at 50 ° C. for 10 hours while flowing tetrafluoroethylene gas (flow rate about 0.7 l / hr). After allowing to cool, 1.29 g (5.0 mmol) of 2-imino-3- (3-trifluoromethylphenyl) -5-methylthiazoline hydrochloride was added, and the mixture was reacted overnight at room temperature and then reacted at 50 ° C for 8 hours. Let After allowing to cool, the reaction mixture was poured into saturated aqueous sodium hydrogen carbonate and extracted with toluene (100 ml × 2). 5 layers of toluene
% Hydrochloric acid aqueous solution (50 ml × 2), water (50 ml), and then saturated saline (50 ml), and the organic layer was dried over anhydrous magnesium sulfate and the solvent was distilled off. The residue was subjected to silica gel column chromatography to give 0.83 g (2.5 mmol, yield 4) of 2-difluoroacetylimino-3- (3-trifluoromethylphenyl) -5-methylthiazoline.
9%) was obtained. In addition, from the hydrochloric acid aqueous layer, 2-imino-3-
0.62 g of (3-trifluoromethylphenyl) -5-methylthiazoline was recovered.

Example 17 2-Imino-3- (3-trifluoromethylphenyl)
A solution of 0.64 g (2.5 mmol) of 5-methylthiazoline and 0.48 g (5.5 mmol) of morpholine in 5 ml of acetonitrile was vigorously stirred, and tetrafluoroethylene gas (flow rate about 0.7 l / hr) was flown into the reaction vessel. While reacting at 50 ° C. for 13 hours. After allowing to cool, the reaction solution was poured into 50 ml of saturated aqueous sodium hydrogen carbonate and extracted with toluene (50 ml
X2). The toluene layer was added to a 5% hydrochloric acid aqueous solution (30 mlX
2), water (50 ml), then saturated saline (50 m
l) and dried over anhydrous magnesium sulfate,
The solvent was distilled off. The residue was subjected to silica gel column chromatography to give 2-difluoroacetylimino-3-.
0.64 g (1.9 mmol, yield 76%) of (3-trifluoromethylphenyl) -5-methylthiazoline was obtained. Example 18 1.70 g (20.0 mmol) of piperidine 10 ml of acetonitrile
At room temperature while flowing tetrafluoroethylene gas (flow rate about 0.7 l / hr) into the reaction vessel in which the solution is vigorously stirred.
The reaction was carried out for 7.5 hours. 2-Imino-3- (3-trifluoromethylphenyl) -5-methylthiazoline hydrochloride 5.
89 g (20.0 mmol) and acetonitrile (25 ml)
Was added, and the mixture was reacted overnight at room temperature. The reaction mixture was poured into saturated aqueous sodium hydrogen carbonate and extracted with toluene (100 m
lX3). 10% hydrochloric acid aqueous solution (100 ml)
X2), water (50 ml), and then saturated saline (50 m
l) and dried over anhydrous magnesium sulfate,
The solvent was distilled off. The residue was subjected to silica gel column chromatography to give 2-difluoroacetylimino-3-.
5.33 g (15.9 mmol, yield 79%) of (3-trifluoromethylphenyl) -5-methylthiazoline was obtained. Further, 0.75 g of 2-imino-3- (3-trifluoromethylphenyl) -5-methylthiazoline was recovered from the hydrochloric acid aqueous layer.

Example 19 2-Imino-3- (3-trifluoromethylphenyl)
A solution of 2.28 g (8.8 mmol) of 5-methylthiazoline and 0.98 g (11.5 mmol) of piperidine in 10 ml of N, N-dimethylformamide was stirred vigorously in a reaction vessel containing tetrafluoroethylene gas (flow rate of about 0.7 l / The reaction was carried out at room temperature for 60 hours while flowing hr). The reaction mixture was poured into 100 ml of saturated aqueous sodium hydrogen carbonate and extracted with toluene (100 ml × 2). The toluene layer was mixed with a 5% hydrochloric acid aqueous solution (5
The extract was washed with 0 ml × 2), water (70 ml), and saturated saline (70 ml), dried over anhydrous magnesium sulfate, and then the solvent was distilled off. The residue was subjected to silica gel column chromatography to obtain 2.32 g (6.9 mmol, yield 78%) of 2-difluoroacetylimino-3- (3-trifluoromethylphenyl) -5-methylthiazoline.
Further, 0.34 g of 2-imino-3- (3-trifluoromethylphenyl) -5-methylthiazoline was recovered from the hydrochloric acid aqueous layer. Example 20 2-Imino-3- (3-trifluoromethylphenyl)
-5-Methylthiazoline hydrochloride 1.47 g (5.0 mmol), triethylamine 2 ml and N-methylaniline 1.29 g
(12.0 mmol) of N, N-dimethylformamide 10 ml
While flowing tetrafluoroethylene gas (flow rate about 0.7 l / hr) into a reaction vessel in which the solution is vigorously stirred, at 80 ° C.
And reacted for 30 hours. After allowing to cool, the reaction solution was poured into 100 ml of saturated aqueous sodium hydrogencarbonate and extracted with toluene (100 ml × 2). The toluene layer was mixed with a 5% aqueous hydrochloric acid solution (1
It was washed with 00 ml × 2), water (70 ml) and then saturated saline (70 ml), dried over anhydrous magnesium sulfate, and then the solvent was distilled off. The residue was subjected to silica gel column chromatography to obtain 0.45 g (1.34 mmol, yield 27%) of 2-difluoroacetylimino-3- (3-trifluoromethylphenyl) -5-methylthiazoline. Also, from the aqueous hydrochloric acid layer, 0.50 g of 2-imino-3- (3-trifluoromethylphenyl) -5-methylthiazoline
Was recovered.

Example 21 2-Imino-3- (3-trifluoromethylphenyl)
Hexafluoropropene gas (supplied by installing a balloon in the reaction vessel) while vigorously stirring a solution of 1.29 g (5.0 mmol) of 5-methylthiazoline and 0.51 g (7.0 mmol) of diethylamine in 10 ml of N, N-dimethylformamide. Was reacted at room temperature for 3.5 hours. After completion of the reaction, post-treatment was carried out in the same manner as described above to give 1.48 g (3.8 mmol of 2- (2,3,3,3-tetrafluoropropanolimino-3- (3-trifluoromethylphenyl) -5-methylthiazoline). , Yield 7
7%). mp. 162.0 ° C. ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 2.40 (s, 3H), 5.10 (dq, 1H, J =
47.1, 7.7Hz), 6.98 (s, 1H), 7.6 to 7.9 (m, 4
H) Example 22 The same procedure as in Example 15 was repeated except that tetrafluoroethylene was replaced by trifluoroethylene, and 2-fluoroacetylimino-3- was used.
(3-Trifluoromethylphenyl) -5-methylthiazoline is obtained.

Example 23 The same operation as in Example 15 was repeated except that octafluoroisobutene was used in place of tetrafluoroethylene, to give 2- (2,2-bis (trifluoromethyl) acetylimino)- 3- (3-Trifluoromethylphenyl) -5-methylthiazoline is obtained. Example 24 2-Imino-3- (3-trifluoromethylphenyl)
A solution of 1.29 g (5.0 mmol) of 5-methylthiazoline and 1.21 g (16.5 mmol) of diethylamine in 10 ml of N, N-dimethylformamide was placed in a reaction vessel under vigorous stirring.
The reaction was carried out at room temperature for 6 hours while flowing chlorotrifluoroethylene gas (flow rate about 0.7 l / hr). After completion of the reaction, post-treatment was carried out in the same manner as above to obtain 1.19 g (3.4 mmol, yield 67%) of 2-chlorofluoroacetylimino-3- (3-trifluoromethylphenyl) -5-methylthiazoline. mp. 155.4 ° C. ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 2.40 (s, 3H), 6.34 (d, 1H, J = 5)
1.4Hz), 6.98 (s, 1H), 7.6 to 7.9 (m, 4H)

[0027]

According to the method of the present invention, the fluoroalkanecarboxamide derivative represented by the general formula 9 can be easily produced.

Claims (8)

[Claims] 1. (a) General formula: ## STR1 ## [In the formula, R ¹ represents a halogen atom, a halogen-substituted alkyl group or a halogen-substituted alkoxy group, R ² represents a hydrogen atom or a halogen atom, and R ³ represents a methyl group, an ethyl group, a chlorine atom or a bromine atom. ] And an iminothiazoline compound represented by the following general formula: embedded image XYC═CF ₂ [wherein X and Y are the same or different and are hydrogen atoms,
It represents a chlorine atom, a fluorine atom or a trifluoromethyl group. However, when X is a hydrogen atom or a chlorine atom, Y
Represents a fluorine atom or a trifluoromethyl group. ]
With a fluoroolefin compound represented by the formula (1) in the presence of a primary amine compound or a secondary amine compound, and (b) reacting the reaction product with water. ] [In the formula, R ¹ , R ² , R ³ , X and Y have the same meanings as described above. ] The manufacturing method of the fluoroalkane carboxamide derivative shown by these. 2. The step (a) comprises reacting a fluoroolefin compound with a primary amine compound or a secondary amine compound, and then reacting the reaction product thereof with an iminothiazoline compound or a salt thereof. Item 2. The production method according to Item 1. 3. A primary amine compound formula of 4 embedded image Q-NH ₂ [wherein, Q is a C1-C20 alkyl group, C3-C10
Alkoxyalkyl group, C3-C10 alkylthioalkyl group, C3-C10 cycloalkyl group, C4-
C20 cycloalkylalkyl group, C3-C10 alkenyl group, C3-C10 alkynyl group, C7-C1
0 aralkyl group, C6-C10 heteroaralkyl group, C5-C10 heteroaryl group or C6-C1
2 represents an arylamine group. A], the second amine compound is in the general formula of 5 [5 of] Q ¹ -NH-Q ² [wherein either Q ¹ and Q ² are the same or different, represent the same meaning is Q, or, Q ¹ and Q ² are bonded to each other at the terminal to form a tetramethylene group optionally substituted with a C1-C3 alkyl group, a pentamethylene group optionally substituted with a C1-C3 alkyl group, or a C1-C3 alkyl group. CH ₂ CH ₂ OCH ₂ CH ₂ which may be substituted
May be represented. Or a primary amine compound or a secondary amine compound has the general formula: embedded image Q ³ Q ⁴ N—Z—NQ ⁵ Q ⁶ [wherein Z is a phenylene group, (CH ₂ ) ₂ units or (CH
₂ ) ₃ groups, Q ³ , Q ⁴ , Q ⁵ and Q ⁶ are the same or different and have the same meaning as Q, or
³ and Q ⁴ , and Q ⁵ and Q ⁶ are bonded to each other at their ends to form (CH
₂ ) ₂ group (the ethylene group may be substituted with a C1-C3 alkyl group) or NH (CH ₂ ) ₂ group (the ethylene group may be substituted with a C1-C3 alkyl group) You may. However, at least one of Q ³ , Q ⁴ , Q ⁵ and Q ⁶ represents a hydrogen atom. ] The manufacturing method of Claim 1 which is this. 4. The primary amine compound is methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine,
n-hexylamine, 2-ethylhexylamine, n-
Octylamine, dodecylamine, tetradecylamine, octadecylamine, icosylamine, 2-methoxyethylamine, 2-ethoxyethylamine, 3-methoxypropylamine, 3-ethoxypropylamine, 2
-Methylthioethylamine, cyclohexylmethylamine, cyclopentylamine, cyclohexylamine, allylamine, propargylamine, benzylamine, phenethylamine, 3-phenyl-1-propylamine,
4-phenyl-1-butylamine or aniline, the secondary amine compound is dimethylamine, diethylamine,
Di-n-propylamine, diisopropylamine, di-
n-butylamine, diisobutylamine, dipentylamine, dihexylamine, diallylamine, dicyclohexylamine, N-ethylmethylamine, N-methylpropylamine, N-methylisopropylamine, N-methylbutylamine, N-methylhexylamine, N-methyl Cyclohexylamine, N-ethylpropylamine, N-ethylisopropylamine, N-ethylbutylamine, N-ethylhexylamine, N-ethylcyclohexylamine, N-methylbenzylamine, N-ethylbenzylamine, dibenzylamine, N-methyl The production method according to claim 1, which is aniline, N-ethylaniline, N-propylaniline, pyrrolidine, piperidine, pipecoline or morpholine. 5. The primary amine compound or secondary amine compound is ethylenediamine, N-methylethylenediamine, N, N-dimethylethylenediamine, N, N'-dimethylethylenediamine, N, N, N'-trimethylethylenediamine, N-ethyl. Ethylenediamine, N, N
-Diethylethylenediamine, N, N'-diethylethylenediamine, N, N, N'-triethylethylenediamine, N, N-dimethyl-N'-ethylethylenediamine, N, N-diethyl-N'-methylethylenediamine, N-propylethylenediamine , N-methyl-1,
3-propanediamine, N, N-dimethyl-1,3-propanediamine, N, N'-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N, N'- Diethyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine,
N, N, N'-trimethyl-1,3-propanediamine, methyliminobispropylamine, piperazine, N
-Methylpiperazine, 2-methylpiperazine, 1- (2
-Aminoethyl) piperidine, 4- (2-aminoethyl) morpholine, 1- (2-aminoethyl) pyrrolidine, 1- (2-aminoethyl) piperazine, 2- (2-
Aminoethyl) pyridine, 4- (3-aminopropyl)
Morpholine, 1- (3-aminopropyl) pipecoline,
1-amino-4-methylpiperazine, 1,3-di- (4
-Piperidyl) propane, acetaldehyde ammonia or phenylenediamine. 6. The secondary amine compound is diethylamine,
The method according to claim 1, which is piperidine, pyrrolidine, piperazine or morpholine. 7. The method according to claim 1, wherein the fluoroolefin compound is trifluoroethylene, tetrafluoroethylene, hexafluoropropene, octafluoroisobutene or chlorotrifluoroethylene. 8. The method according to claim 1, wherein the fluoroolefin compound is tetrafluoroethylene.