JPH11322639A - Production of ethylene derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce an ethylene derivative in high efficiency using a compound enabling extremely safe and easy production and use for reaction without necessitating particular apparatus and technique by reacting two specific kinds of compounds. SOLUTION: The objective derivative is produced by reacting (A) a compound having a skeleton of formula I having one H atom on the α-position of a carbonyl group with (B) a compound of formula II (R<1> to R<4> are each a 1-6C alkyl or an aryl; R<1> and R<3> may together form a 5 or 6-membered ring; R<1> and R<2> or R<3> and R<4> may together form one or two heterocyclic group; X<1> is F; X<2> is F or Cl; both of X<1> and X<2> are bonded to C through covalent bonds or only X<1> is bonded through covalent bond and X<2> is present in the form of a counter ion). The component A is preferably a compound of formula III [R<5> and R<6> are each a (substituted)alkyl, a (substituted)aryl, a substituted) heterocyclic group or the like; R<7> is H, a (substituted)aryl or the like].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing an ethylene derivative. More specifically, one hydrogen atom is placed at the α-position.
The present invention relates to a method for producing an ethylene derivative by allowing a bis-disubstituted amino-difluoromethane compound or fluoroformamidinium chloride to act on a carbonyl compound having one or more alcohols having a hydrogen atom at the β-position.

[0002]

BACKGROUND OF THE INVENTION Problems to be Solved by the Invention
An ethylene derivative having a carbon double bond has high reactivity and can be converted into various functional groups. It is a very important compound as a medical and agricultural intermediate and a monomer for the synthesis of functional polymers, and its demand is steadily increasing. As a general method for producing an ethylene derivative, 1)
Synthesis by addition reaction to acetylene, conjugated diene, arene, etc. 2) dehydration reaction, thermal decomposition reaction of ester, synthesis by elimination reaction typified by dehydrohalogenation reaction,
3) Synthesis by condensation reaction typified by aldol reaction, Wittig reaction, etc., and the like. However, these reactions are not suitable for industrial use because of poor regioselectivity and expensive reagents. It is often difficult to implement this.

[0003] As an industrial production method of olefins, a petroleum conversion method is used. Petroleum conversion methods are mainly classified into 1) catalytic cracking, 2) hydrocracking, and 3) pyrolysis. Olefins such as ethylene, propylene and butene are industrially produced by these methods. However, these production methods require enormous construction costs for the production of equipment, require expensive and complicated catalysts, multi-stage reactions, and operations that are difficult to control at very high temperatures. There are problems such as the need to be performed, and a solution has been desired.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve these problems, and as a result, general formula (2)

Embedded image

[0005] ^{(wherein, R 1, R 2, R} 3, R 4 , which may be identical or different, represent an alkyl group or an aryl group having 1 to 6 carbon atoms. Also, R ¹ and R ³ Is combined with 5
It may form a membered ring or a 6-membered ring, and R ¹ and R ² or R ³ and R ⁴ may combine to form one or two heterocycles. X ¹ represents a fluorine atom, and X ² represents a fluorine atom or a chlorine atom. Further, X ¹ and X ² may be covalently bonded to a carbon atom, or only X ¹ may be covalently bonded and X ² may be present in the form of a counter ion. ), For example,
By using bis-dialkylamino-difluoromethanes, compounds having one hydrogen atom at the α-position of the carbonyl group or alcohols having a hydrogen atom at the β-position can be used without requiring special equipment or technology. To efficiently produce an ethylene derivative from the compound represented by the general formula (2):
The compound represented by can be very safely and easily performed from its production to use in the reaction without any special equipment or technique, and after the reaction, it is recovered as the original raw material such as urea. They have found that it is economical to be able to recycle, and have completed the present invention.

[0006] That is, the present invention relates to the present invention
General formula (1) having two hydrogen atoms

Embedded image A compound having a skeleton represented by the general formula (2)

[0007]

Embedded image

Wherein R ¹ , R ² , R ³ , R ⁴ , X ¹ , X
² has the same meaning as described above. A method for producing an ethylene derivative characterized by reacting a compound represented by the formula (1), and a general formula (4) having a hydrogen atom at the β-position of a hydroxy group:

[0009]

Embedded image A compound having a skeleton represented by the general formula (2)

[0010]

Embedded image (Wherein, R ¹ , R ² , R ³ , R ⁴ , X ¹ and X ² have the same meaning as described above). Things.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
As a specific embodiment of the method of the present invention, for example, a compound represented by the general formula (1) or (4), a compound represented by the general formula (2) and a reaction solvent as raw materials are charged in a reaction vessel. And reacting it preferably under a nitrogen atmosphere. The compound represented by the general formula (2) may be used by dissolving it in a solvent in advance.

In the method of the present invention, a compound represented by the general formula (2) is used. In the general formula (2), R ^{1 to} R ⁴ may be the same or different and are an alkyl group or an aryl group having 1 to 6 carbon atoms. Specifically, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-
Butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, phenyl group,
Examples include a naphthyl group, a methylphenyl group, an ethylphenyl group, and a dimethylphenyl group.

Further, R ¹ and R ³ are bonded to form a 5-membered ring or 6-membered ring.
And R ¹ and R ² or R ³ and R ⁴
May combine to form one or two heterocycles having 3 to 5 carbon atoms. That is, in the present invention, in the general formula (2), the alkyl groups substituted with different nitrogen atoms may combine to form a ring, or the alkyl groups substituted with the same nitrogen atom may combine to form one or more. Two rings may be formed.

Specific examples of the compound represented by the general formula (2) include bis-dimethylamino-difluoromethane, bis-diethylamino-difluoromethane, bis-dipropylamino-difluoromethane, and bis-di (i-propyl). ) Amino-difluoromethane, bis-di (n-butyl) amino-difluoromethane, bis-di (i-butyl) amino-difluoromethane, bis-di (t-butyl) amino-difluoromethane, bis-di (n -Pentyl) amino-difluoromethane, bis-di (n-hexyl) amino-difluoromethane, bis- (methylcyclohexyl) amino-difluoromethane, N, N-dimethylamino-N'-methyl-N'-phenylamino- Bis-dialkylamino such as difluoromethane and bis-piberidino-difluoromethane Difluoromethane and, 2,
2-difluoro-1,3-dimethyl-imidazolidine,
2,2-difluoro-1-ethyl-3-methyl-imidazolidine, 2,2-difluoro-1,3-diethyl-imidazolidine, 2,2-difluoro-1,3-di (n-
Propyl) imidazolidine, 2,2-difluoro-1,
3-di (i-propyl) imidazolidine, 2,2-difluoro-1,3-di (n-butyl) imidazolidine and the like and compounds in which one of the above-mentioned compounds is replaced with chlorine to form a counter ion by replacing chlorine with chlorine And the like,
The present invention is not limited to these exemplified compounds.

Preferably, the formula (6)

Embedded image 2,2-difluoro-1,3-dimethyl-imidazolidine represented by the following formula (7):

[0016]

Embedded image 1,3-dimethyl-2-fluoro-imidazolinium chloride represented by the formula:

The production of these compounds is carried out by the general formula (8)

Embedded image (Wherein, R ¹ , R ² , R ³ and R ⁴ have the same meanings as described above)
By subjecting a chloroformamidinium chloride and an alkali metal salt of fluorine represented by a halogen exchange reaction to a non-reactive solvent, for example, a solvent such as acetonitrile or 1,3-dimethyl-2-imidazolidinone. ,
It can be obtained safely and easily. The non-reactive solvent refers to a solvent that does not affect the reaction, that is, a solvent that does not react with the compound represented by the general formula (8) as the raw material and the product represented by the general formula (2).

Specific examples of the alkali metal salt include, for example, cesium fluoride, rubidium fluoride, potassium fluoride, sodium fluoride and the like. Preferably, the fluorination reaction is economically and reactionally advantageous. Using spray-dried potassium fluoride.

The chloroformamidinium chloride represented by the general formula (8) used as a raw material for producing the compound represented by the general formula (2) includes tetraalkylurea, tetraalkylthiourea, and 1,3-dialkylimidazo. It can be produced by chlorinating lydinone, 1,3-dialkylimidazolidin-2-thione or the like with a chlorinating agent such as phosgene or thionyl chloride. For example, 2-chloro-1,3-dimethylimidazolinium chloride can be easily produced by the method described in JP-A-59-25375.

In the production of the compound represented by the general formula (2) of the present invention, when a difluoro compound is produced, the amount of the alkali metal salt of fluorine used in the halogen exchange reaction is represented by the general formula (8). It is usually at least 2 moles, preferably 2 to 5 moles, per mole of the compound. If the molar ratio is less than 2 times, unexchanged chloride remains and is insufficient. Even if the molar ratio exceeds 5 times, the reaction result is not significantly improved.

When a compound having a counter ion of chlorine is produced, the amount of the alkali metal salt of fluorine used in the halogen exchange reaction is usually at least 1 mol of the compound represented by the general formula (8). Preferably it is 1 to 1.5 times mol. If the molar ratio is less than 1 fold, unexchanged chloride may remain and be insufficient. If the molar ratio exceeds 2.1 fold, the amount of the difluoro compound tends to increase. However, even if the difluoro compound is mixed, there is no effect on the production of the ethylene derivative.

The reaction solvent used in the production of the compound represented by the general formula (2) is represented by chloroformamidinium chloride represented by the general formula (8) and the product represented by the general formula (2) There is no particular limitation as long as the solvent does not react with the compound. Preferred are acetonitrile, N, N-dimethylformamide, 1,3-dimethyl-2-imidazolidinone, sulfolane, dichloromethane, ethylene dichloride and the like. Although the amount of the solvent is not particularly limited, it is usually preferably 1 to 10 times the weight of the reaction substrate from the viewpoint of reaction efficiency and operability.

In the production of the compound represented by the general formula (2), the reaction temperature is not particularly limited, but is usually -20 to 150 ° C, preferably 0 to 150, in view of the reaction rate and the stability of the product.
It is in the range of 100 ° C. In this case, it is also possible to carry out the reaction in the presence of a phase transfer catalyst such as a quaternary alkyl ammonium salt or a quaternary alkyl phosphonium salt. The obtained compound represented by the general formula (2) can be used for the reaction as it is in the halogen exchange reaction solution, or can be used after the inorganic salt is filtered off, or the inorganic salt can be used. After being filtered off, it can be isolated and used by distillation.

The compound having one hydrogen atom at the α-position of the carbonyl group is represented by the following general formula (1)

Embedded image There is no particular limitation as long as it has a skeleton represented by the following formula.

[0025]

Embedded image

(Wherein R ⁵ and R ⁶ may be the same or different and each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group , substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted arylcarbonyl group, a substituted or unsubstituted alkylcarboxyl group, a substituted or unsubstituted aryl carboxyl group, is .R ⁷ showing a substituted or unsubstituted heterocyclic hydrogen atom, a substituted or Unsubstituted aryl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted arylcarbonyl group, substituted or unsubstituted alkylcarboxyl group, substituted or unsubstituted arylcarboxyl group Group, substituted or unsubstituted heterocycle, or A substituted or unsubstituted alkyl group having no two or more hydrogen atoms at the α-position of the rubonyl group.).

Specific examples of the substituents represented by R ⁵ and R ⁶ include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-butyl and n-butyl.
-Pentyl group, n-hexyl group, cyclohexyl group, n
-Heptyl group, n-octyl group, methoxymethyl group, methoxyethyl group, propoxypropyl group, phenoxymethyl group, acetoxymethyl group, methoxycarbonylmethyl group, aminomethyl group, nitromethyl group, benzyl group,
2-phenylethyl group, 3-phenylpropyl group, 2-
Substituted or unsubstituted alkyl groups such as phenylpropyl group, diphenylmethyl group, methyl-substituted benzyl group, methoxy-substituted benzyl group, nitro-substituted benzyl group, benzyl halide group, amino-substituted benzyl group, phenoxybenzyl group, benzoylbenzyl group, phenyl Substituted or unsubstituted aryl groups such as a group, naphthyl group, methylphenyl group, dimethylphenyl group, methoxyphenyl group, ethoxyphenyl group, dimethoxyphenyl group, nitrophenyl group, aminophenyl group, halogenated phenyl group, methoxy group, ethoxy group Group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, t-butoxy group, cyclohexyloxy group, acetoxymethoxy group,
Examples thereof include a substituted or unsubstituted alkoxy group such as a methoxycarbonylmethoxy group, a 2-aminoethoxy group, and a 2-nitroethoxy group.

In addition, substitution of phenoxy, naphthoxy, hydroxyphenoxy, methylphenoxy, dimethylphenoxy, methoxyphenoxy, nitrophenoxy, aminophenoxy, halogenated phenoxy, methoxycarbonylphenoxy, etc. Unsubstituted or substituted alkylcarbonyl such as unsubstituted aryloxy, acetyl, propionyl, butyryl, valeryl, i-valeryl, cyclohexylcarbonyl, methoxyacetyl, aminoacetyl, nitroacetyl, phenylacetyl, etc. Group, benzoyl, naphthoyl, methylbenzoyl, ethylbenzoyl, dimethylbenzoyl, methoxybenzoyl, nitrobenzoyl, aminobenzoyl, benzoyl halide, hydride Substituted or unsubstituted arylcarbonyl group such as xybenzoyl group, acetoxy group, propionyloxy group, butyryloxy group, i-butyryloxy group, valeryloxy group, i-valeryloxy group, cyclohexylcarboxy group, methylacetoxy group, aminoacetoxy group, nitroacetoxy Group, substituted or unsubstituted alkylcarboxy group such as phenylacetoxy group, phenylcarboxy group, naphthoyloxy group, hydroxyphenylcarboxy group, methylphenylcarboxy group,
Substituted or unsubstituted arylcarboxy groups such as ethylphenylcarboxy group, dimethylphenylcarboxy group, methoxyphenylcarboxy group, nitrophenylcarboxy group, aminophenylcarboxy group, halogenated phenylcarboxy group, pyrrole group, imidazolyl group, furyl group, morpholino And substituted or unsubstituted heterocyclic groups such as a group, a pyridyl group, a pyrimidyl group, an indole group, a quinoline group, an isoquinoline group and an imidazolinyl group, but the present invention is not limited to these exemplified compounds.

The substituent represented by R ⁷ is, as a specific example,
A hydrogen atom, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted arylcarbonyl group, as described above, An unsubstituted alkylcarboxyl group, a substituted or unsubstituted arylcarboxyl group, a substituted or unsubstituted heterocycle, or an i-propyl group, an i-butyl group, a t-butyl group, a t-amyl group, a cyclohexyl group, a 2-phenyl- 2-propyl group, 2-phenyl-2-butyl group and the like,
A substituted or unsubstituted alkyl group having no two or more hydrogen atoms at the α-position of the carbonyl group of the general formula (3).

The alcohol having a hydrogen atom at the β-position is represented by the following general formula (4)

Embedded image There is no particular limitation as long as it has a skeleton represented by the following formula.

[0031]

Embedded image

(Wherein R ⁸ , R ⁹ and R ¹⁰ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, Or an unsubstituted aryloxy group, a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted arylcarbonyl group, a substituted or unsubstituted alkylcarboxyl group, a substituted or unsubstituted arylcarboxyl group, or a substituted or unsubstituted heterocycle. R ⁸ ,
R ⁹ and R ¹⁰ must not be hydrogen atoms at the same time, and at least one hydrogen atom must be present at the carbon at the β-position of the hydroxy group. Further, R ⁸ and R ⁹ may combine to form a ring structure. ). R
Specific examples of the substituent represented by ⁸ , R ⁹ and R ¹⁰ include those described above, but the present invention is not limited to these exemplified compounds. When R ⁸ and R ⁹ form a ring, it is preferable to form a ring having 3 to 6 carbon atoms.

Using a compound represented by the general formula (2), a carbonyl compound having one hydrogen atom at the α-position represented by the general formula (1) or a β-position represented by the general formula (4) When performing a conversion reaction of an alcohol having at least one hydrogen atom into an ethylene derivative, the amount of the compound represented by the general formula (2) may be generally at least 1 equivalent to the carbonyl group or the hydroxy group. . However, considering reaction efficiency, 1 to 10 equivalents are preferable. If it is less than 1 equivalent, unreacted carbonyl groups or hydroxy groups remain and are often insufficient.

The reaction solvent used in the above-mentioned reaction is a compound represented by the general formula (2) and α represented by the general formula (1).
And carbonyl compounds having at least one hydrogen atom at the β-position, alcohols having at least one hydrogen atom at the β-position represented by the general formula (4), and solvents which do not react with the ethylene derivative as a reaction product. But not preferably, acetonitrile, dichloromethane, chloroform,
Ethylene dichloride, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, N-methylpyrrolidone, N, N-dimethylformamide, 1,
3-dimethyl-2-imidazolidinone and the like.

Further, upon the reaction, the compound represented by the general formula (2), the carbonyl compound having one hydrogen atom at the α-position represented by the general formula (1), and the β represented by the general formula (4) Hydrogen halide scavengers, bases, acids, catalysts, etc. may be added as long as they do not adversely affect the reaction for obtaining alcohols and ethylene derivatives having at least one hydrogen atom at each position.

The reaction temperature for the conversion to the ethylene group is usually -20 to 150 ° C, preferably -10 to 90 ° C.
Range. If the temperature is lower than −20 ° C., the reaction rate tends to be slow, and the operation becomes complicated. 150 ° C
When the ratio exceeds the above, the stability of the compound represented by the general formula (2) tends to decrease. The ethylene derivative produced by the reaction can be easily taken out of the reaction mixture by discharging it into water, methanol or the like. At that time, hydrogen halide is generated from the unreacted general formula (2), and may be captured by baking soda or the like. Further, the compound represented by the general formula (2) can be recovered as urea after completion of the reaction.

[0037]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.
Incidentally, 2,2 in the acetonitrile solution in Synthesis Examples 1 and 2 was used.
-Difluoro-1,3-dimethylimidazolidine (hereinafter abbreviated as DFI) concentration, and 2-fluoro-1,3-
The concentration of dimethylimidazolinium chloride (hereinafter abbreviated as DMFC) was measured by high-performance liquid chromatography (hereinafter abbreviated as HPLC) after derivatizing DFI or DMFC by reacting with aniline. The concentration of fluorine ions (hereinafter abbreviated as F ⁻ ) was measured by a spectrophotometric method using a lanthanum-alizarin complexone reagent. The scanning range of GC-MS is M /
Performed with Z ≧ 50.

Synthesis Example 1 2,2-Difluoro-1,3-dimethylimidazolidine
Synthesis of (DFI) 76.4 g (0.452 mol) of 2-chloro-1,3-dimethylimidazolinium chloride (DMC) and 105.1 g (1.8 of spray-dried potassium fluoride)
10mol) and 251.5 g of acetonitrile in 500 m
l into a four-necked reaction flask and put in a nitrogen atmosphere at 80 ° C.
For 17 hours. After cooling the reaction solution to 25 ° C., the inorganic salt was separated from the reaction solution and DFI (MW 136.1) was used.
415.7 g of the acetonitrile solution of 4) was obtained. The DFI concentration in the solution was 11.4 wt%, and the yield was 77%. This reaction solution was distilled under reduced pressure to obtain 32 g of DFI (purity: 97.8%).

The physical properties are as follows. Boiling point 47.0 ° C / 37 mmHg EIMS: 136 (M ⁺ ), 117 (M-F ⁺ ). IR (neat) cm ^-1 : 1486, 1385, 129
5, 1242, 1085, 966. F analysis: Theory 27.9%, found 27.7%. ¹ H-NMR (δ, ppm, CDCl ₃ solvent, TMS standard): 2.52 (s, 6H, —CH ₃ × 2), 3.05
_{(S, 4H, -CH 2 -CH} 2 -). ¹³ C-NMR (δ, ppm, CDCl ₃ solvent, -45
° C, based on CDCl ₃ ): 31.4 (s, -CH ₃ × 2),
_{47.6 (s, -CH 2 -CH 2} -), 128.5
(T, J = 230 Hz, = CF ₂ ). ¹⁹ F-NMR
(Δ, ppm, CDCl ₃ solvent, −45 ° C., based on CFCl ₃ ): −70.9 (s, = CF ₂ ).

Synthesis Example 2 2-fluoro-1,3-dimethylimidazolinium =
Synthesis of chloride (DMFC) 30.42 g (0.1799 mol) of 2-chloro-1,3-dimethylimidazolinium chloride (DMC)
And sodium fluoride 11.33g (0.2699mo
l) and 104.9 g of acetonitrile were charged into a 200 ml four-necked reaction flask and reacted at 80 ° C. for 14 hours under a nitrogen atmosphere. After cooling the reaction solution to 25 ° C., inorganic salts were separated from the reaction solution to obtain 116.09 g of a DMFC (MW 152.60) acetonitrile solution. D in solution
The MFC concentration was 21.01 wt% and the yield was 89%.

The physical properties are as follows. FABMS: 117 [(M-Cl) ⁺ ], 269
[(2 × M-Cl) ⁺ ]. F analysis: theoretical value 2.6 wt%, measured value 2.7 wt%
%. Cl analysis: theoretical value 4.8 wt%, measured value 4.9 wt
%. ¹ H-NMR (δ, ppm, CH ₃ CN solvent, CH ₃ CN
Standard, 25 ° C.): 2.98 (s, 6H, —CH ₃ ×)
2), 3.91 (s, 4H , -CH 2 -CH 2 -). ¹³ C-NMR (δ, ppm, CH ₃ CN solvent, DMSO
−d6 standard, 25 ° C.): 31.3 (s, —CH ₃ ),
_{46.8 (s, -CH 2 -)} , 157.7 (d, J = 2
80 Hz, CF).

Example 1 1-Fluoro-1-phenyl-2-methyl-1-prope
Down synthetic isobutyrophenone phenone 1.48g and (10.0mmol) DFI1.36g and (10.0 mmol) was placed 15ml acetonitrile in a reaction vessel, under a nitrogen atmosphere, and reacted for 18 hours at 84 ° C.. After completion of the reaction, the GC-M
By S measurement, formation of 1-fluoro-1-phenyl-2-methyl-1-propene (parent ion 150) was confirmed. The reaction yield was 30% from GC analysis.

Example 2 Synthesis of 1-chloro-2-phenyl-1-propene 1.27 g of 2-phenylpropionaldehyde (9.5)
0 mmol) and 6.19 g of a 21.01 wt% DMFC / acetonitrile solution (DMFC content 1.30 g, 9.5)
5 mmol) in a reaction vessel, and placed in a nitrogen atmosphere at 84 ° C.
For 20 hours. After completion of the reaction, the GC-
MS measurement confirmed the generation of 1-chloro-2-phenyl-1-propene (parent ion 153). G
From C analysis, the reaction yield was 28%.

Example 3 Synthesis of cyclohexene 1.00 g (10.0 mmol) of cyclohexanol, 1.36 g (10.0 mmol) of DFI and 10 ml of acetonitrile were placed in a reaction vessel, and the mixture was added at room temperature under a nitrogen atmosphere.
Allowed to react for hours. After completion of the reaction, formation of cyclohexene (base ion 82, base peak 67) and formation of cyclohexyl fluoride (base ion 102, base peak 67) were confirmed by GC-MS measurement of the reaction solution.
The reaction yield was 89% for cyclohexene and 10% for cyclohexyl fluoride.

[0045]

The present invention relates to a bis-disubstituted amino-carbonyl compound, which is safer and easier to handle than before, for carbonyl compounds having one hydrogen atom at the α-position or alcohols having at least one hydrogen atom at the β-position. The use of a difluoromethane compound and a fluoroformamidinium chloride compound provides an industrially useful production method for producing ethylene derivatives easily and economically in one pot without requiring special equipment. is there.

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C07C 17/07 C07C 17/07 17/35 17/35 22/04 22/04 22/08 22/08 (72) Inventor Fukumura Remarks Fukuoka 30 Mitsui Chemicals, Inc., Omuta-shi, Oita Prefecture Mitsui Chemicals, Inc. (72) Inventor Teruyuki Nagata 30 Mitsui Chemicals, Inc., Omuta-shi, Fukuoka Prefecture

Claims (6)

[Claims] 1. A compound represented by the following general formula (1) having one hydrogen atom at the α-position of a carbonyl group. A compound having a skeleton represented by the general formula (2): ^{(Wherein, R 1, R 2, R} 3, R 4 , which may be identical or different, represent an alkyl group or an aryl group having 1 to 6 carbon atoms. Also, R ¹ and R ³ are bonded 5 membered ring or 6
R ¹ and R ² or R ³ and R ⁴ may combine to form one or two heterocycles. X
¹ represents a fluorine atom, and X ² represents a fluorine atom or a chlorine atom. Further, even if X ¹ and X ² are covalently bonded to a carbon atom,
Only X ¹ may be covalently bonded and X ² may be present in the form of a counterion. A method for producing an ethylene derivative, which comprises reacting the compound represented by the formula (1). 2. The compound of the general formula (1) is converted to a compound of the general formula (3): (Wherein, R ⁵ and R ⁶ may be the same or different,
Substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted arylcarbonyl group, substituted or unsubstituted alkyl A carboxyl group, a substituted or unsubstituted arylcarboxyl group, and a substituted or unsubstituted heterocycle are shown. R ⁷ is a hydrogen atom, a substituted or unsubstituted aryl group,
Substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted arylcarbonyl group, substituted or unsubstituted alkylcarboxyl group, substituted or unsubstituted arylcarboxyl group, substituted or unsubstituted A substituted heterocyclic ring or a substituted or unsubstituted alkyl group having no two or more hydrogen atoms at the α-position of a carbonyl group. The method according to claim 1, which is a compound represented by the formula: 3. A compound of the general formula (4) having a hydrogen atom at the β-position of a hydroxy group. A compound having a skeleton represented by the general formula (2): (Wherein, R ¹ , R ² , R ³ , R ⁴ , X ¹ , and X ² have the same meanings as described above). 4. The compound of the general formula (4) is converted to a compound of the general formula (5): (Wherein, R ⁸ , R ⁹ , and R ¹⁰ may be the same or different, and may be a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted group. aryloxy group, a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted arylcarbonyl group, a substituted or unsubstituted alkylcarboxyl group, a substituted or unsubstituted aryl carboxyl group, a substituted or unsubstituted heterocyclic ring. However, R ^8, R ⁹ and R ¹⁰ must not be hydrogen atoms at the same time, and at least one hydrogen atom must be present at the carbon at the β-position of the hydroxy group, and R ⁸ and R ⁹ are bonded to form a ring structure. The compound according to claim 3, which is a compound represented by the formula: 5. The compound of the general formula (2) is a compound of the formula (6) The method according to any one of claims 1 to 4, wherein the compound is 2,2-difluoro-1,3-dimethyl-imidazolidine. 6. The compound of the general formula (2) is a compound of the formula (7) A 1,3-dimethyl-2-fluoro-imidazolinium chloride represented by the formula:
The described method.