WO2006075373A1

WO2006075373A1 - β-ALKOXYPROPIONAMIDE COMPOUND, SOLVENT, DETERGENT, LIQUID CHEMICAL COMPOSITION, AND PROCESS FOR PRODUCING β-ALKOXYPROPIONAMIDE COMPOUND

Info

Publication number: WO2006075373A1
Application number: PCT/JP2005/000290
Authority: WO
Inventors: Shigeru Matsuo
Original assignee: Idemitsu Kosan Co., Ltd.
Priority date: 2005-01-13
Filing date: 2005-01-13
Publication date: 2006-07-20
Also published as: KR20070100734A; CN101098851A; JPWO2006075373A1; CN101098851B; KR101114711B1

Abstract

A β-alkoxypropionamide compound represented by the general formula (I); a solvent and a detergent each containing the alkoxypropionamide compound; a liquid chemical composition comprising a specific β-alkoxypropionamide compound and a chemical dissolved therein; and a process for producing a β-alkoxypropionamide compound which comprises reacting acrylamide with an aliphatic monohydric alcohol in the presence of a basic catalyst. The solvent and detergent each has excellent solubility which enables the solvent and detergent to dissolve also in paraffin, etc., while retaining the dissolving power of amide solvents. The liquid chemical composition contains any of various agricultural chemicals satisfactorily dissolved therein, and retains safety and long-lasting effectiveness. Also provided is a process for industrially advantageously producing the solvent and detergent.

Description

Specification

-Alkoxypropionamides, solvents, detergents and liquid pharmaceutical compositions

And method for producing j3-alkoxypropionamides

Technical field

The present invention relates to β-alkoxypropionamides, solvents, detergents and liquid pharmaceutical compositions, and a method for producing j8-alkoxypropionamides. More specifically, the β-alkoxypropionamide is obtained by reacting a solvent, a cleaning agent and a liquid drug composition containing a novel β-alkoxypropionamide, and an acrylamide with an aliphatic monohydric alcohol under mild conditions. The present invention relates to a method for efficiently producing products. Background art

In general, an amide organic solvent has an excellent dissolving power and a property of being easily dissolved in water, so that it can be rinsed with water and has desirable performance as a solvent or a cleaning agent. In recent years, amide solvents tend to replace conventional halogen solvents because halogen solvents can cause environmental pollution such as destroying the ozone layer and are highly toxic.

Examples of such amide solvents include formamide, モノ monomethylformamide, Ν, ジメチル -dimethylformamide, モノ monoethylformamide, Ν, Ν-jetylformamide, acetamide, Ν, Ν-dimethylacetamide, Ν methyl Since this amide solvent, which is known as pyrrolidinone, is excellent in solubility, it can dissolve most solvents and compounds, and can be suitably used as a cleaning agent. However, the application of amide solvents is greatly limited because they are not compatible with paraffins.

In addition, as a solvent for agricultural chemicals, conventional amide solvents have excellent solubility in drugs, but because they are water-soluble, they can easily be sprayed with rainwater, etc. Therefore, safety and long-lasting effects are required. As a cleaning agent, a compound having a higher boiling point, easy handling, and easy manufacture is desired. On the other hand, an amide having an alkoxy group is an alkoxy 中間, 製造 as an intermediate in the production method of α, 一 -dialkylamides of α, β-year-old refining unsaturated monocarboxylic acids used as polymerizable monomers. —Dialkylpropionamide is formed. This intermediate is amidated by reacting 13 alkoxypropionic acid alkyl ester with dialkylamine. For example, in the case of producing j8-methoxy-Ν, Ν-dimethylpropionamide, the reaction requires a long time of 24 to 40 hours in a sealed pressurized cylinder. Is a disadvantageous method (see Patent Document 1).

[0004] Patent Document 1: JP-A-49 66623 (pages 11 and 12)

Disclosure of the invention

[0005] Under the circumstances as described above, the object of the present invention is to have a solvent and a cleaning agent having excellent dissolving power, which dissolves in paraffin or the like while maintaining the dissolving power of an amide solvent, or various agricultural products. It is to provide a liquid pharmaceutical composition that dissolves industrial chemicals well and maintains safety and long-term effects, and a method for industrially producing the solvent and the cleaning agent.

[0006] As a result of extensive research to solve the above problems, the present inventors have found that β-alkoxypropionamides obtained by reacting acrylamides with aliphatic monohydric alcohols have the ability to dissolve amide solvents. It is highly useful as a solvent and cleaning agent because it dissolves in paraffin and the like while being retained, and since certain j8-alkoxypropionamides do not dissolve in water, they can be used in agricultural chemicals for safety and long-term effects And that j8-alkoxypropionamides can be efficiently produced under mild conditions by reacting acrylamides with aliphatic monohydric alcohols in the presence of a basic catalyst. The present invention has been reached.

That is, the present invention provides:

(1), β-alkoxypropionamides represented by the general formula (I), [0008] [Chemical 1] z R ²

^{_{R 1 - 0 - CH 2 CH}} 2 CON · · · (I)

, ³

(Wherein R ¹ is an alkyl group having 3 to 18 carbon atoms, R ² and R ³ may each independently have a hydrogen atom or an ether bond having a carbon number of 16 to 16, or a hydrocarbon group. And may be the same or different from each other, and may be further bonded to each other to form a ring structure.

(2) 13 alkoxypropionamides of (1) above, which are R ² and R ³ methyl groups,

(3) a solvent characterized by containing the β alkoxypropionamide of (1) or (2) above,

(4) a cleaning agent characterized by containing the β alkoxypropionamide of (1) or (2) above,

(5), a liquid drug composition characterized by dissolving a drug in β-alkoxypropionamides represented by the general formula (II),

[0010] [Chemical 2]

[Wherein R ⁴ is an alkyl group having 8 to 18 carbon atoms, R ² and R ³ may each independently have a hydrogen atom or an ether bond having a carbon number of 16 to 16, or a hydrocarbon group. And may be the same or different from each other, and may be further bonded to each other to form a ring structure.

(6) The liquid pharmaceutical composition of (5), which is R ² and R ³ force S methyl group,

(7) The liquid drug composition according to (5) or (6), wherein the drug is an agricultural drug,

[0012] (8) General formula (IV), characterized by reacting acrylamide represented by general formula (III) with an aliphatic-hydric alcohol having 3 to 18 carbon atoms in the presence of a basic catalyst A process for producing a β-alkoxypropionamide represented by the formula: [0013] [Chemical 3] R ²

CH ₂ = CH— CON---(ill)

, ³

[Wherein R ² and R ³ are the same as in general formula (I).]

[0015] [Chemical 4]

R ⁵ -〇 One CH ₂ CH ₂ C〇 N---(IV)

(Wherein R ⁵ is an alkyl group having 5 to 18 carbon atoms, and R ² and R ³ are the same as described above.)

(9) Production of β-alkoxypropionamides according to the above (8), wherein the basic catalyst is at least one compound selected from the group consisting of potassium t-butoxide, sodium t-butoxide, potassium hydroxide and potassium carbonate. Method

I will provide a.

BEST MODE FOR CARRYING OUT THE INVENTION

[0017] The 13 alkoxypropionamides of the present invention are represented by the following general formula (I).

[0018] [Chemical 5]

In the above general formula (I), R ¹ may be an alkyl group having 3 to 18 carbon atoms, R ² and R ³ may each have a hydrogen atom or an ether bond having 1 to 16 carbon atoms. Good monovalent hydrocarbon group. Here, examples of the alkyl group of R ¹ include various butyl groups, various pentyl groups, various hexyl groups, various octyl groups, and the like, and those having 5 to 10 carbon atoms, preferably those having 4 to 12 carbon atoms. Is particularly preferred. The R ² and R ³ hydrocarbon groups may be either linear or branched, but are preferably saturated hydrocarbon groups. Examples thereof include a methyl group, an ethyl group, various propyl groups, various butyl groups, a methoxymethyl group, a methoxyethyl group, and an ethoxysyl group, and the methyl group is the most common. R ² and R ³ are They may be the same or different, and may be bonded together to form a ring structure. This ring structure may be a heterocyclic structure having nitrogen as a heteroatom, or a heterocyclic structure having nitrogen and oxygen atoms as heteroatoms. Examples of the group having a heterocyclic structure include a 1 pyrrolidinyl group, a piperidino group, and a morpholino group.

[0020] The / 3 alkoxypropionamides of the present invention have almost the same dissolving power as various amide solvents for various compounds, and also dissolve in paraffins. Can be widely used.

In particular, when R ¹ in the general formula (I) is an alkyl group having 8 to 18 carbon atoms, it is insoluble in water, so the j8-alkoxypropionamides of the present invention are agricultural chemicals such as insecticides and fungicides. Long-term effects can be maintained by dissolving

That is, | 8-alkoxypropionamides represented by the following general formula (II) are extremely advantageous as liquid pharmaceutical compositions in which the above agricultural chemicals are dissolved, that is, as liquid application agents such as emulsions and oils. Can be used.

[0021] [Chemical 6] R ²

R ⁴ — 0 _ CH ₂ CH ₂ C 〇 N \ —— '(Π)

In the general formula (II), R ⁴ is an alkyl group having 8 to 18 carbon atoms, and includes various octyl groups such as an n-ethyl octyl group and 2-ethyl hexyl group, various nonyl groups, and various decyl groups. And various lauryl groups, various stearyl groups, and various oleyl groups. R ² and R ³ are the same as in the general formula (I).

[0023] For the method of the present invention for producing alkoxypropionamides, an acrylamide represented by the general formula (III) and an aliphatic-valence of 5 to 18 carbon atoms in the presence of a basic catalyst. By reacting alcohol, a | 8-alkoxypropionamide represented by the general formula (IV) is produced. [0024] [Chemical 7]

R

C H C H-C 0 N. (I l l)

R

[0025] [Chemical 8]

R

R ⁵ 1 0— CH ₂ CH ₂ CON:, \ (IV)

R

In the acrylamides represented by the general formula (III), R ² and R ³ are the same as in the general formula (I). Specific examples of such acrylamides include acrylamide, N-methylacrylamide, N, N-dimethylacrylamide, N-ethylacrylamide, N, N-jetylacrylamide, N-propylacrylamide, N, N-dipropyl. Powers such as acrylamide, N-butyl acrylamide, N, N-dibutyl acrylamide, 1-attalyloyl pyrrolidine, 1- attaroyl biperidine, 4-1 allyloyl morpholine, among them acrylamide, N-methyl acrylamide, N , N-dimethylacrylamide, N-ethyl acrylamide, N, N-jetyl acrylamide, and 4-ataryloylmorpholine are preferred.

[0027] Another raw material in the production method of the present invention is an aliphatic monovalent alcohol having 5 to 18 carbon atoms, and R ^{5 in} the general formula (IV) is an alkyl group having 5 to 18 carbon atoms. Become. These aliphatic monohydric alcohols may be either linear or branched, specifically n-pentano mononole, hexanol, octanol, 2-ethino hexanol, decenoreanolo gnole, laur Such as ril alcohol,

When the j8-alkoxypropionamides in the present invention are used in the form of a mixture as a solvent or a cleaning agent, a mixture may be produced in the reaction. In this case, two or more of the acrylamides as raw materials may be used in combination, or two or more of the aliphatic monohydric alcohols may be used in combination, or both.

The proportion of acrylamides and aliphatic monohydric alcohols used is preferably that of aliphatic monohydric alcohols in stoichiometric amounts or in excess, but if used in excessive amounts, Since it is disadvantageous in terms of economy, generally, an aliphatic monohydric alcohol is used in an amount of 1.0 to 3 mol, preferably 1.0 to 2 mol, per 1 mol of acrylamides.

[0028] In the method of the present invention, the reaction between the acrylamide and the aliphatic monohydric alcohol is carried out in the presence of a basic catalyst. A basic substance can be used as a catalyst, but potassium tert butoxide, sodium tertbutoxide, potassium hydroxide and potassium carbonate are preferred in view of reaction conditions and by-products. Sodium methoxide and potassium methoxide are not preferred because by-products are formed. Further, sodium hydroxide and sodium carbonate are not preferable because the reaction time becomes long.

[0029] In the present invention, the basic catalyst may be used alone or in combination of two or more. In addition, the amount used is appropriately selected according to the type of raw material that is not particularly limited. Generally, it is selected in the range of 0.5-10 mol%, preferably 1-3 mol%, per mol of acrylamide. Is done.

The reaction temperature is preferably 20-80 ° C, and more preferably 30-50 ° C. If the temperature is too high, the yield may decrease, and if the temperature is too low, the reaction rate decreases, which is not practical. In addition, the reaction proceeds at normal pressure or under pressure, but generally normal pressure is economically advantageous. The reaction time depends on the raw materials used, the type of catalyst, the reaction temperature, etc., and cannot be determined in general, but it is usually 30 minutes to 10 hours, preferably 115 hours. As the solvent, acetone, ether and amide solvents can be used, but it is preferable not to use them in consideration of economy.

[0030] The produced β-alkoxypropionamide is preferably neutralized with a base used as a catalyst with phosphoric acid, acetic acid, sulfuric acid or the like after completion of the reaction, and then the salt produced by filtration or the like is removed. Further, it can be obtained by separating the unreacted material with a thin film evaporator or the like, if necessary.

Thus, in the present invention, j8-alkoxypropionamides having excellent performance as an amide solvent can be reacted in a short time under mild conditions, and post-treatment and purification after the reaction are easy. It can be manufactured by the method.

Example

[0031] Next, the power to explain the present invention in more detail by way of examples. It is not limited at all.

In the following Examples and Comparative Examples, the solubility test was performed by the following method. Each test tube contains 5 mL of the compound obtained in each example (β-alkoxypropionamide) and 5 mL of the amide solvent used in the comparative examples, and 5 g of n-hexane, liquid paraffin, glycerin and water as solubility confirmation substances. And shaken at room temperature or at 80 ° C for 5 minutes. When heated at 80 ° C., the solution state was observed after cooling to room temperature. A uniform state was considered compatible, and a turbid or phase-separated one was made incompatible.

About the result of the solubility test, it displayed as follows.

○: compatible at room temperature,

Δ: compatible with heating to 80 ° C,

X: Incompatible

[Example 1]

N, N-dimethylacrylamide (19.828 g) and 1-hexanol (20.434 g) were placed in a 300 mL separable flask equipped with a stirrer, a thermocouple, and a nitrogen gas inlet tube, and stirred while introducing nitrogen gas. Next, 0.338 g of sodium t-butoxide was added, and the reaction was performed at 35 ° C for 4 hours. After heating, 150 mg of phosphoric acid was added to make the solution uniform, and then left for 3 hours. The solution was filtered to remove precipitates, and unreacted substances were removed with an evaporator. The yield was 37.4 g (93% yield).

¹ H-NMR of the obtained substance was measured and 0.95 ppm (3H), 1.3-1.5 ppm (8 H), 2.4 ppm (2H), 2.9 ppm (6H), 3.4 ppm (2H) and 3.7 ppm (2H) were observed. As a result, the following structure was obtained. A solubility test of this compound was conducted. The results are shown in Table 1.

[0033] [Chemical 9]

Example 2

In a 300 mL separable flask equipped with a stirrer, thermocouple and nitrogen gas inlet tube, N, N-dimethylacrylamide 19.828 g and 1-butanol 14.824 g were added and stirred while introducing nitrogen gas. Next, 0.338 g of sodium t-butoxide was added, and the reaction was carried out at 35 ° C. for 4 hours. After heating, 150 mg of phosphoric acid was added to make the solution uniform, and then left for 3 hours. The solution was filtered to remove precipitates, and unreacted substances were removed with an evaporator. The yield was 30.5 g (88% yield).

¹ H-NMR of the obtained substance was measured to be 0.995 ppm (3H), 1.3-1.5 ppm (4 H), 2.4 ppm (2H), 2.9 ppm (6H), 3.4 ppm (2H) and 3.7 ppm (2H) were observed. As a result, the following structure was obtained. A solubility test of this compound was conducted. The results are shown in Table 1.

[0035] [Chemical 10]

CH 3 (CH ₂ ) 3-0-CH ₂ CH ₂ -C 0

_Three

[Example 3]

In a 300 mL separable flask equipped with a stirrer, a thermocouple, and a nitrogen gas inlet tube, N, N-dimethylacrylamide (19.828 g) and 2-ethyl hexanol (26.046 g) were placed and stirred while introducing nitrogen gas. Next, 0.338 g of sodium t-butoxide was added, and the reaction was performed at 35 ° C. for 4 hours. After heating, 150 mg of phosphoric acid was added to make the solution uniform, and then left for 3 hours. The solution was filtered to remove precipitates, and unreacted substances were removed with an evaporator. The yield was 43.6 g (95% yield).

¹ H-NMR of the obtained substance was measured and 0.95 ppm (6H), 1.2-1.4 ppm (8 H), 1.8 ppm (lH), 2.4 ppm (2H), 2.9 ppm (6H), 3.4 ppm (2H) and 3.7 p pm (2H) were observed.

As a result, the following structure was obtained. A solubility test of this compound was performed. The results are shown in Table 1. [0037] [Chemical 11]

CH ₂ CH

I C H

CH ₃ (CH ₂ ) CH-CH ₂ 0-CH ₂ CHCON

C H

[Example 4]

Example 3 was carried out in the same manner as Example 3 except that 26.046 g of n-year-old octanol was used instead of 2-ethylhexanol. The yield was 42.7 g (93% yield). The results of the solubility test are shown in Table 1.

[Example 5]

In a 2 L separable flask equipped with a stirrer, thermocouple, and nitrogen gas inlet tube, 41,34 g of N, N-dimethylacrylamide and 745.36 g of lauryl alcohol were added and stirred while introducing nitrogen gas. Next, 22.44 g of potassium t-butoxide was added, and the reaction was carried out at 40 ° C for 3 hours. After the heating was completed, 22.44 g of phosphoric acid was added to make the solution uniform, and then left for 3 hours. The solution was filtered to remove precipitates, and unreacted substances were removed with an evaporator. The yield was 947. Og (83% yield).

¹ H-NMR of the obtained substance was measured and found to be 0.80—0.85 ppm (3H), 1.15—1.28 ppm (22H), 2.85—3.00 ppm (6H), 3.35—4.00 ppm (2H), and 3.65 to 3.70. ppm (2H) was observed.

As a result, the following structure was found. A solubility test of this compound was performed. The results are shown in Table 1.

[0040] [Chemical 12]

CH-(CH ₂ ),,-0-CH ₂ CH ₂

II

[Comparative Example 1 1-3]

A solubility test was conducted using amide solvents N-methylpyrrolidone, N, N-dimethylformamide and acetone. The results are shown in Table 1.

[0042] [Table 1]

Industrial applicability

The j8-alkoxypropionamides of the present invention are widely used as excellent cleaning agents and solvents because they retain the solubility of conventional amide solvents, have a high boiling point, and also have a solubility in paraffin and the like. it can. In addition, the | 8-alkoxypropionamides represented by the general formula (II) retain the solubility of conventional amide solvents in pesticides such as insecticides and fungicides, but do not dissolve in water. It is possible to maintain the effect as an agrochemical with high safety because there is no pollution to drainage. Accordingly, β-alkoxypropionamides represented by the general formula (Π) are extremely useful as liquid pharmaceutical compositions (liquid application agents) such as emulsions and oils in agricultural chemicals.

Furthermore, the method for producing j8-alkoxypropionamides of the present invention provides j8-alkoxypropionamides in a short reaction under mild reaction conditions, and is easy and efficient after-reaction and purification after the reaction. Can be manufactured.

Claims

Claims [1] β-alkoxypropionamides represented by the general formula (I),

[Chemical 1]

(In the formula, R ¹ is an alkyl group having 3 to 18 carbon atoms, R ² and R ³ may each independently have a hydrogen atom or an ether bond having 11 to 16 carbon atoms, or a hydrocarbon group; They may be the same or different from each other, and may be bonded to each other to form a ring structure.

[2] The j8 alkoxypropionamide according to claim 1, which is an R ² or R ³ carbyl group.

[3] A solvent comprising the β-alkoxypropionamide according to claim 1 or 2.

[4] A cleaning agent comprising the β alkoxypropionamide according to claim 1 or 2.

[5] A liquid drug composition comprising a drug dissolved in a β-alkoxypropionamide represented by the general formula (II).

[Chemical 2]

^{_{R 4 - 0 - CH 2 CH}} Z CON · '· (1 1)

, ³

(Wherein R ⁴ is an alkyl group having 8 to 18 carbon atoms, R ² and R ³ are each independently a hydrogen atom or an ether bond having a carbon number of 16 to 16, and are hydrocarbon groups, They may be the same or different from each other, and may be bonded to each other to form a ring structure.

6. The liquid pharmaceutical composition according to claim 5, wherein the liquid pharmaceutical composition is R ² or R methyl group.

7. The liquid drug composition according to claim 5 or 6, wherein the drug is an agricultural drug.

[8] Represented by the general formula (IV), characterized by reacting an acrylamide represented by the general formula (III) with an aliphatic-hydric alcohol having 3 to 18 carbon atoms in the presence of a basic catalyst. A process for producing β-alkoxypropionamides. [Chemical 3]

CH _Z = CH-C 0 N---(I II)

(In the formula, R ² and R ³ are each independently a hydrogen atom or a hydrocarbon group which may have an ether bond having 11 to 16 carbon atoms, and may be the same or different from each other. To form a ring structure.

[Chemical 4]

R ⁵ — 0— CH ₂ CH ₂ C〇 N,---(IV)

(Wherein R ⁵ is an alkyl group having 5 to 18 carbon atoms, and R ² and R ³ are the same as described above.) The basic catalyst is potassium tert-butoxide, sodium tert-butoxide, potassium hydroxide and carbonate. The method for producing j8-alkoxypropionamides according to claim 8, which is at least one compound selected from the group power of potassium power.