JPH04112883A - Fluoroalkyl group-containing butenolide derivative and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I (R1 to R4 are H or 1-4C alkyl; X is F, Cl or H; n is 1-10). EXAMPLE:5-Trifluoromethyl-5-(2'-methoxycarbonylethyl)butenolide. USE:An synthetic intermediate for drugs, agricultural chemicals, surfactants, etc. PREPARATION:A fluorine-containing butenolide shown by formula II is reacted with an electron attractive olefin [e.g. acrylic acid or methyl (meth)acrylate] in a molecular ratio of preferably 1:0.5-10 in the presence of a basic compound (e.g. potassium carbonate or pyridine) preferably at 0-50 deg.C for 3-10 hours.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a fluoroalkyl group-containing butenolite derivative and a method for producing the same.

<Prior Art> Among organic compounds, compounds containing a fluoroalkyl group have been attracting attention as they exhibit useful properties such as heat resistance, water and oil repellency, and physiological activity.

In particular, fluoroalkyl group-containing butenolide derivatives in which a fluoroalkyl group is introduced into butenolides are attracting attention because they are thought to be useful as synthetic intermediates for medicines, agricultural chemicals, and even surfactants. However, at present, little is known about the fluoroalkyl group-containing butenolide derivatives and their production methods.

<Problems to be Addressed by the Invention> An object of the present invention is to provide a fluoroalkyl group-containing butenolite derivative that can be used as a synthetic intermediate for pharmaceuticals, agricultural chemicals, and surfactants, and a method for producing the same.

Another object of the present invention is to provide a method for easily producing a fluoroalkyl group-containing butenolite derivative in high yield without using a reaction catalyst or special equipment.

<Means for Solving the Problems> According to the present invention, a fluorine-containing butenolite represented by the following general formula (I) and an electron-withdrawing olefin are reacted in the presence of a basic compound. There is provided a method for producing a fluoroalkyl group-containing butenolide derivative represented by the general formula (I).

The present invention will be explained in more detail below.

The fluoroalkyl group-containing butenolite derivative of the present invention can be represented by the following general formula (I), in which R0,
R2, R3 and R4 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X is a fluorine atom.

Indicates a chlorine atom or a hydrogen atom. In addition, a fluoroalkyl group-containing butenolide derivative represented by (n is an integer of 1 to 10) is provided.

Further, according to the present invention, the following general formula (II) (wherein X represents a fluorine atom, a chlorine atom, or a hydrogen atom, and n is 1 to
In the formula, R, R2, R3 and R4 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X represents a fluorine atom, a chlorine atom or a hydrogen atom. Moreover, n represents an integer of 1 to 10. In this case, if at least one of R, R2, R1, and R4 is an alkyl group having 5 or more carbon atoms, production is difficult, and if n is 11 or more, the solubility in the solvent decreases. I can not use it. Specifically, the fluoroalkyl group-containing butenolide derivative represented by the general formula (I) includes, for example, 5-
Trifluoromethyl-5-(2°-methoxycarbonylethyl)butenolite, 5-trifluoromethyl-5-
(2'-methoxycarbonylpropyl)butenolide, 5-chlorodifluoromethyl-5-(2'-methoxycarbonylethyl)butenolite, 5-chlorodifluoromethyl-5-(2'-methoxycarbonylpropyl)butenolite, 5-difluoromethyl -5-(2'
-methoxycarbonylethyl)butenolite, 5-difluoromethyl-5-(2'methoxycarbonylpropyl)butenolite, 5-perfluoroethyl-5-(2'
-methoxycarbonylethyl)butenolide, 5-perfluoroethyl-5-(2'-methoxycarbonylpropyl)butenolite, 5- (2'-chlorotetrafluoroethyl)-5-(2''-methoxycarbonylethyl)butenolite, 5- (2'-hydrotetrafluoroethyl) 5 (2II-methoxycarbonylethyl)butenolide, 5-perfluoropropyl-
5-(2'-methoxycarbonylethyl)butenolite, 5-perfluoropropyl-5-(2'-methoxycarbonylpropyl)butenolite 1.5-(3'
-chlorohexafluoropropyl)-5-(2'''-
methoxycarbonylethyl)butenolide, 5-perfluorobutyl 5-(2'-methoxycarbonylethyl)butenolide, 5-perfluorohexyl-5-(2
Preferred examples include '-methoxyluponylethyl)butenolite, 5-perfluorohexyl-5-(2'-methoxycarbonylpropyl)butenolide, and the like.

The method for producing a fluoroalkyl group-containing butenolite derivative in the present invention comprises: a specific fluorine-containing butenolide;
It is characterized by reacting an electron-withdrawing olefin in the presence of a basic compound.

The fluorine-containing butenolide used as a raw material component in the production method of the present invention can be represented by the following general formula (n), where X represents a fluorine atom, a chlorine atom, or a hydrogen atom, and n
represents an integer from 1 to 10. In this case, if n is 11 or more, it cannot be used because a problem arises in the solubility of the fluorine-containing butenolide when reacting in the presence of a solvent. x (c p z+) of the fluorine-containing butenolide represented by the general formula (I1).

To specifically enumerate, FeF2-, F (CF2+,, F (CF2+3゜F
(CF2+,,F (CF2-)-,.

F (CF2+,,F (CF2-)-7゜F (CF
2+,,F (CF2+,.

F (CF2+1°, CICF2 cl (CF2+2.cl (CF, +3°C1(CF
2-)-,,C1(CF2+,.

C1(CF2−)−,,C1(CF2+,.

C1(CF2−)−,,C1(CF2+,.

C1(CF2+,.,HCF2 H(CF2÷,,H(CF,±,.

H(CF2+,,H(CF2-),.

H(CF2suGI H(CF2+7゜ H(CF2+,,H(CF=+i.

H(CF2-)-0°.

In the production method of the present invention, the electron-withdrawing olefin to be reacted with the fluorine-containing butenolite can be represented by the following general formula (nl), for example, R1R2C=CR
3C○2R4... (III) R in the formula, R2, R3
and R4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Preferred examples of the electron-withdrawing olefins represented by the general formula (tII) include acrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, and 1-methoxycarbonyl-1-propene. I can do it.

In the production method of the present invention, the basic compound used when reacting the fluorine-containing butenolide and the electron-withdrawing olefin is not particularly limited as long as it is a basic compound. For example, potassium carbonate,
Preferable examples include inorganic and organic basic compounds such as sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, hydrocarbon, sodium hydroxide, pyridine, piperidine, and triethylamine.

In the production method of the present invention, the molar ratio of the fluorine-containing butenolide, the electron-withdrawing olefin, and the basic compound is preferably 1:0.1 to 50:0.1 to 50, particularly 1:0.1 to 50:0.1 to 50. :0.5-10: It is preferable that it is 0.5-1o. If the charging molar ratio of the electron-withdrawing olefins or the basic compound is less than 0.1, the yield of the fluoroalkyl group-containing butenolide derivative to be produced will decrease, and if it exceeds 50, the molar ratio of the charged molar ratio of the electron-withdrawing olefins or the basic compound will decrease after the reaction is completed. In this case, a large amount of unreacted electron-withdrawing olefins remains, making it difficult to isolate the desired product, which is not preferable. In addition, the reaction can be carried out at normal pressure,
In addition, the reaction temperature is preferably in the range of -30 to 150°C, and
A range of ˜50° C. is particularly preferred. The reaction temperature is 130
If the temperature is less than 'C, the reaction time will take a long time and
If it exceeds C, the pressure during the reaction will be high and the reaction operation will be difficult, which is not preferable. Furthermore, the reaction time is 30 minutes to 20 minutes.
The time range is preferable, and industrially, the range of 3 to 10 hours is particularly preferable.

In the production method of the present invention, the reaction can be carried out under the various conditions described above, but in order to make the reaction smoother, it is preferable to carry out the reaction using a solvent. Preferred examples of the solvent include acetonitrile, dioxane, benzene, toluene, xylene, and the like. Further, the amount of the solvent charged is desirably adjusted so that the concentration of the fluorine-containing butenolide is in the range of 0.1 to 20% by weight based on the solvent.

The reaction product obtained by the production method of the present invention can be isolated and purified by known methods such as distillation and gel permeation chromatography.

<Effects of the Invention> The fluoroalkyl group-containing butenolite derivative of the present invention is a new compound, and can be used as a synthetic intermediate for surfactants, etc. in pharmaceuticals and agricultural chemicals. It is possible to easily produce a fluoroalkyl group-containing butenolite derivative in a short time, with high yield, and without using a reaction catalyst or special equipment.

<Examples> The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited thereto.

To 10 ml of acetonitrile, 5-trifluoromethylbutenolide O, Ig, and 0.0 g of potassium carbonate were added. 1 g (5 times the molar amount of 5-trifluoromethylbutenolide) and 0.3 g of methyl acrylate (equivalent molar amount to potassium carbonate) were added and mixed. The reaction was then carried out for 30 minutes at room temperature under a nitrogen stream. After the reaction is completed and the product is washed with water,
Extraction was performed with ether, and the resulting extracted solution was dried using magnesium sulfate. Next, isolation and purification was performed using gel permeation chromatography to obtain 5-trifluoromethyl-5-(2'-methoxycarponylethyl)butenolite represented by the following structural formula in a yield of 90%. The results of each analysis of the obtained compounds are shown below.

Commitment 238 (M+) IR (cm-1) 1805 (C”0), 1750 (
OC”O), 1475 (CF3) 1H-NMR (CDC
I, ) δ2.36 (m, 4H), 3.68 (s, 3
H) 6.36, 7.38 (ABq, 2) 1. J=5.9
Hz) 13C-NMR (CDCI3) δ25.5,26
．． 7,52.1,116.6,125.6°150.5
, 169.8, 172.2” F-NMR (CDCI, ;ext, CF3CO0
H) δ15.1 (3F) Ji 11 Town The reaction and purification were carried out in the same manner as in Example 1 except that 5-trifluoromethylbutenolide was replaced with 5-chlorodifluoromethylbutenolide, and the product was obtained with the following structural formula. The following 5-chlorodifluoromethyl-5-(2''-methoxycarbonylethyl)butenolite was obtained in a yield of 94%.

The results of each analysis are shown below.

lll5255 (I11+) IR (cm-1) 1800 (C=O), 1750 (
OC=O), 1250 (CF2)” H-NMR (CD
CI, )δ2.34(m, 4H), 3.60(s, 3
) 1) 6.34, 7.34 (ABq, 2H) C-NMR (CDCI, ) δ25.1, 26.5,
52.5, 116.0, 125.1゜150.3, 16
9.1,172.5”F-NMR (CDC13: ext, CF, C00H)
δ29.1 (2F) Dog 11 Reaction and purification were carried out in the same manner as in Example 1 except that 5-trifluoromethylbutenolite was replaced with 5-perfluoropropylbutenolide.N Shown by the following structural formula 5 -Perfluoropropyl-5-(2''-methoxyluponylethyl)butenolide was obtained in a yield of 93%.The results of each analysis are shown below.

MS 338 (M”) IR (cm-”) 1800 (C=O), 1750 (
OC=0), 1340 (CF, ).

1220 (CF2) ” H-NMR (CDC13) δ2.35 (m, 4) 1
), 3.66 (s, 3H) 6.31, 7.38 (ABq
, 2H) 13C-NMR (CDCI, ) δ25.7, 26.0
,52.7.116.9.125.8゜150.3,1
69.2,172.0

Claims (1)

[Claims] 1) The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (I) (In the formula, R_1, R_2, R_3 and R_4 are hydrogen atoms or carbon atoms of 1 to 4 (wherein X represents a fluorine atom, a chlorine atom, or a hydrogen atom; and n represents an integer of 1 to 10). 2) The following general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) (In the formula, X represents a fluorine atom, chlorine atom, or hydrogen atom,
2. The fluoroalkyl group according to claim 1, wherein the fluorine-containing butenolide represented by (n is an integer of 1 to 10) and the electron-withdrawing olefin are reacted in the presence of a basic compound. A method for producing a butenolide-containing derivative.