JP2000256253A - Production of cyclopropanecarboxylic acid derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject cyclopropanecarboxylic acid derivative that is useful as an intermediate for pyrethroids that are useful as an insecticide and an acaricide by allowing a specific cyclopropane-carbaldehyde derivative to react with a specific dicarboxylic acid derivative in the presence of an amine, for example, pyridine or the like. SOLUTION: One mole of a cyclopropanecarboaldehyde derivative of formula I (R1 is H, a 1-5C alkyl or the like) is allowed to react with 1-5 moles of a dicarboxylic acid derivative of formula II (R2 is H, a 1-10C alkyl or the like) in the presence of a primary or secondary amine selected from the group consisting of piperidine, morpholine, pyrrolidine, diethylamine and N-methyl- ethanolamine, preferably at 60-120 deg.C to give the objective compound of formula III. In a preferred embodiment, pyridine or toluene is used as a reaction solvent. When a basic organic solvent, for example, pyridine is used, the secondary amine is preferably used in an amount of 0.01-5 moles per mole of the compound of formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a pyrethroid compound useful as an insecticidal or acaricidal compound or an intermediate for producing the same, which is represented by the following general formula:

Embedded image [Wherein, R ¹ is a hydrogen atom, a C1-C5 alkyl group, C1
-C5 haloalkyl group, C1-C3 alkoxy C1-C
3 alkyl group, benzyl group optionally substituted by methoxy group, phenacyl group, 2-tetrahydrofuranyl group,
Represents a 2-tetrahydropyranyl group or a pyrethroid alcohol residue, and R ² represents a hydrogen atom, a C1-C10 alkyl group, a C1-C10 haloalkyl group, a C3-C10 alkenyl group, a C3-C10 haloalkenyl group, a C3-C1
0 represents an alkynyl group, a C3-C10 haloalkynyl group or a benzyl group. And a method for producing a cyclopropanecarboxylic acid derivative represented by the formula:

[0002]

2. Description of the Related Art As a method for producing a cyclopropanecarboxylic acid derivative represented by the general formula 4, specifically, tert-butyl (±) -trans-2,2-dimethyl- A method of oxidizing 3- [2-methyl-1-propenyl] cyclopropanecarboxylate with selenium dioxide and further oxidizing oxygen (see Scheme 5 below: Agric. Biol. Chem., V
ol. 27, no. 5,373-378, 1963)

Embedded image And a method for olefinating tert-butyl (±) -trans-2,2-dimethyl-3-formylcyclopropanecarboxylate with Honer-Emmons (see Scheme 6 below: Agric. Biol. Ch).
em. , Vol. 36, no. 4,565-569,1
972)

Embedded image Is only known. However, in the former production method, in the reaction of the first step, a toxic selenium compound which is difficult to be post-processed is produced in an equimolar amount to the raw material, and the total yield is low. Further, in the latter production method, a phosphorus compound which is a problem in wastewater treatment is generated, and therefore, none of these methods is necessarily satisfactory as an industrial production method. Under these circumstances, from the viewpoint of implementation on an industrial scale, the production of the cyclopropanecarboxylic acid derivative represented by the above general formula (4) is efficient with a small amount of by-product waste and a small post-treatment load. The development of a law is desired.

[0003]

Means for Solving the Problems In view of the above situation, the present inventors have conducted intensive studies to find an excellent method for producing a cyclopropanecarboxylic acid derivative represented by the above-mentioned general formula 4, and as a result, the general formula Chemical 7

Embedded image [Wherein, R ¹ represents the same meaning as described above. And a cyclopropanecarbaldehyde derivative represented by the general formula:

Embedded image [Wherein, R ² represents the same meaning as described above. With the dicarboxylic acid derivative represented by the general formula (I) in the presence of one or more secondary amines selected from the group consisting of piperidine, morpholine, pyrrolidine, diethylamine and N-methylethanolamine. The present inventors have found that the cyclopropanecarboxylic acid derivative represented by No. 4 can be produced in good yield, and have reached the present invention. That is, the present invention relates to a cyclopropane carbaldehyde derivative represented by the general formula (7) and a dicarboxylic acid derivative represented by the general formula (8) from the group consisting of piperidine, morpholine, pyrrolidine, diethylamine and N-methylethanolamine. An object of the present invention is to provide a method for producing a cyclopropanecarboxylic acid derivative represented by the general formula (4) by reacting in the presence of one or more selected secondary amines (hereinafter referred to as the production method of the present invention). .

[0004]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below. In cyclopropanecarboxylic acid derivative represented by the general formula of 4, as the C1~C5 alkyl group represented by R ^1, for example a methyl group, an ethyl group, a t- butyl group and the like. Examples C1~C5 haloalkyl group Is
Examples thereof include a 2,2,2-trichloroethyl group and a 2-chloroethyl group, and C1 to C3 alkoxy C1 to C3
Examples of the alkyl group include a methoxymethyl group and an ethoxyethyl group, and examples of the benzyl group optionally substituted with a methoxy group include a benzyl group and a p-methoxybenzyl group. Are, for example, a 3-phenoxybenzyl group, 5
-Benzyl-3-furylmethyl group, 2-methyl-4-oxo-3- (2-propynyl) -2-cyclopentenyl group, 2-methyl-4-oxo-3- (2-propenyl)
-2-cyclopentenyl group, N- (3,4,5,6-tetrahydrophthalimido) methyl group, N- (3,4-dimethylmaleimido) methyl group and the like, but are not limited thereto. . In the cyclopropanecarboxylic acid derivative represented by the general formula 4, when R ¹ is other than a pyrethroid alcohol residue, a t-butyl group is preferable. The C1~C10 alkyl group represented by R ^2, a methyl group, an ethyl group, n- propyl group, iso- propyl, n- butyl, iso- butyl group, s
Examples of the C1-C10 haloalkyl group include a 2,2,2-trifluoroethyl group and a bis (trifluoromethyl) methyl group. Examples of the C3-C10 alkenyl group include: Examples thereof include a 2-propenyl group. Examples of the C3-C10 haloalkenyl group include a 3-chloro-2-propenyl group. Examples of the C3-C10 alkynyl group include a 2-propynyl group. C3~C10 the haloalkynyl group such as 3-iodo-2-propynyl group is, R ² is not limited thereto.

[0005] The production method of the present invention comprises the steps of: converting a cyclopropanecarbaldehyde derivative represented by the above general formula (7) and a dicarboxylic acid derivative represented by the above general formula (8) into piperidine, morpholine, pyrrolidine, diethylamine, N-methylethanol; The reaction is performed in the presence of one or more secondary amines selected from the group consisting of amines. The reaction temperature of the reaction is usually from 20 to 160 ° C, preferably from 60 to 160 ° C.
~ 120 ° C. The range of the reaction time is usually 0.5 to 1
00 hours, preferably 1 to 72 hours. The reaction can also be performed in an organic solvent, in which case, for example, hexane, heptane, ligroin,
Aliphatic hydrocarbons such as petroleum ether, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as chlorobenzene and dichlorobenzene, diisopropyl ether, 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether , Ethers such as methyl-t-butyl ether, ketones such as methyl isobutyl ketone, pyridine, 2-methyl-5-
Examples include nitrogen-containing aromatic compounds such as ethylpyridine and picoline, but the reaction solvent is not limited to these. The amount of the reagent used in the production method of the present invention is represented by the general formula
Cyclopropanecarbaldehyde derivative 1 represented by Chemical formula 7
The amount of the dicarboxylic acid derivative represented by the general formula 8 is usually 1 to 10 mol, preferably 1 to 5 mol, per mol.

[0006] One or more secondary amines selected from the group consisting of piperidine, morpholine, pyrrolidine, diethylamine, and N-methylethanolamine are used per mole of the cyclopropanecarbaldehyde derivative represented by the general formula (7). Usually, a large excess amount is used from the amount of the catalyst. When a basic organic solvent such as pyridine is used, piperidine, morpholine, pyrrolidine, diethylamine, N-
One or more secondary amines selected from the group consisting of methylethanolamine are used in an amount of 0.01 to 1 mol of the cyclopropanecarbaldehyde derivative represented by the general formula (7).
Is desirably selected in the range of 5 to 5 mol. When using a non-basic organic solvent such as toluene, piperidine, morpholine, pyrrolidine, diethylamine,
1 selected from the group consisting of N-methylethanolamine
The secondary amine (s) is desirably selected in the range of 1 mole to a large excess mole per 1 mole of the cyclopropanecarbaldehyde derivative represented by the general formula (7). After completion of the reaction, the desired cyclopropanecarboxylic acid derivative represented by the general formula 4 can be obtained, for example, by the following method. 1) Concentrate the reaction solution as it is. 2) The reaction solution is poured into an aqueous solution of a mineral acid such as hydrochloric acid or sulfuric acid, and extracted with an organic solvent, and then the organic layer is concentrated. Also,
The cyclopropanecarboxylic acid derivative is distilled, recrystallized,
By performing operations such as column chromatography,
Purification is also possible. Further, the organic base and the solvent used can be easily recovered from the distillate at the time of concentration in post-treatment or the wastewater at the time of separation, and can be used again after purification.

The cyclopropanecarbaldehyde derivative represented by the general formula 7 used in the production method of the present invention can be produced, for example, according to a method according to the following scheme 9.

Embedded image [Wherein, R ¹ represents the same meaning as described above. The reaction is described, for example, in Bull. Chem. Soc. Jp
n. , 60, 4385-4394 (1987);
Org. Chem. , 43, 1978, 4323-43.
28 can be performed. Further, the cyclopropanecarbaldehyde derivative represented by the general formula (7) can also be produced according to the method according to the following scheme (10).

Embedded image [Wherein, R ¹¹ is a C1-C5 alkyl group, a C1-C5 haloalkyl group, a C1-C3 alkoxy C1-C3 alkyl group, a benzyl group optionally substituted with a methoxy group, a phenacyl group, a 2-tetrahydrofuranyl group, Represents a 2-tetrahydropyranyl group or a pyrethroid alcohol residue. The reaction is described, for example, in J. Am. Agric. Food Che
m. 1995, 43, 2286-2290.

As the dicarboxylic acid derivative represented by the general formula 8 used in the production method of the present invention, for example, a commercially available one can be used or can be produced according to a known method according to the following scheme 11.

Embedded image [Wherein, M represents an alkali metal (eg, sodium, potassium, etc.), and R ² has the same meaning as described above. ]

Among the cyclopropanecarboxylic acid derivatives represented by the general formula (4), those in which R ¹ is a pyrethroid alcohol residue are represented by the following general formula:
From the cyclopropane carboxylic acid derivative represented by the chemical formula 4, wherein R ¹ is a hydrogen atom,
It can also be produced by a method according to the following Scheme 12.

Embedded image [Wherein, R ¹² represents a pyrethroid alcohol residue;
²¹ is a C1-C10 alkyl group, a C1-C10 haloalkyl group, a C3-C10 alkenyl group, a C3-C10 haloalkenyl group, a C3-C10 alkynyl group, a C3-C10
X represents a haloalkynyl group or a benzyl group, and X represents a chlorine atom or a bromine atom. The dehydration-condensation reaction of the above scheme 12 is usually performed in the presence of a condensing agent. Examples of the condensing agent include dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide and the like.
The reaction of the acid halogenation in the above scheme 12 is usually carried out by reacting a halogenating agent. As the halogenating agent,
For example, phosgene, thionyl chloride, phosphorus oxychloride and the like can be mentioned. The esterification reaction of the above scheme 12 is usually performed in the presence of a base. Examples of the base include triethylamine, diisopropylethylamine and the like.

[0010]

The production method of the compound of the present invention will be specifically described below with reference to production examples, but the present invention is not limited to these examples.

(Production Example 1) Under a nitrogen atmosphere, 0.202 g of tert-butyl (±) -trans-2,2-dimethyl-3-formyl-cyclopropanecarboxylate was dissolved in 5 ml of dry pyridine, and 0.20 ml of piperidine was dissolved. And 0.242 g of methylmalonic acid, and the mixture was stirred at 60 ° C. for 1 hour. The reaction solution was cooled to room temperature, diluted with 100 ml of diethyl ether, and washed with 3N-hydrochloric acid. After washing with a saturated saline solution, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel chromatography {developing solvent n-hexane: ethyl acetate = 3: 1 (v / v)}, and tert-butyl (±) -trans-2,2-dimethyl-3- {2
0.249 g of -carboxy- (E) -1-propenyl} -cyclopropanecarboxylate was obtained. ¹ H-NMR (CDCl ₃ solvent, TMS internal standard, 270
MHz) δ value (ppm): 6.60 (dd, 1H),
2.14 (dd, 1H), 1.94 (d, 3H), 1.
69 (d, 1H), 1.46 (s, 9h), 1.30
(S, 3H), 1, 22 (s, 3H)

Example 2 Under a nitrogen atmosphere, 0.165 g of tert-butyl (±) -cis-2,2-dimethyl-3-formyl-cyclopropanecarboxylate was dissolved in 5 ml of dry pyridine, and 0.17 ml of piperidine was dissolved. And 0.197 g of methylmalonic acid, and the mixture was stirred at 60 ° C. for 1 hour. The reaction solution was cooled to room temperature, diluted with 100 ml of diethyl ether, and washed with 3N-hydrochloric acid.
After washing with a saturated saline solution, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue is subjected to silica gel chromatography ｛developing solvent n-hexane:
Ethyl acetate = 3: 1 (v / v)} and tert-butyl (±) -trans-2,2-dimethyl-3- {2-carboxy- (E) -1-propenyl} -cyclopropanecarboxy. A rate of 0.199 g was obtained. ¹ H-NMR (CDCl ₃ solvent, TMS internal standard, 250
MHz) δ value (ppm): 6.60 (dd, 1H),
2.14 (dd, 1H), 1.94 (d, 3H), 1.
69 (d, 1H), 1.46 (s, 9h), 1.30
(S, 3H), 1, 22 (s, 3H)

Example 3 Under a nitrogen atmosphere, 0.306 g of tert-butyl (±) -trans-2,2-dimethyl-3-formyl-cyclopropanecarboxylate was dissolved in 3 ml of dry pyridine, and 0.263 g of piperidine was dissolved. And 0.352 g of ethyl methylmalonate were added, and the mixture was stirred at 100 ° C. for 5 hours. The reaction solution was cooled to room temperature, diluted with 100 ml of diethyl ether, and washed with 3N-hydrochloric acid. After washing with a saturated saline solution, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure.
The residue was purified by silica gel chromatography using a developing solvent n-
Hexane: ethyl acetate = 3: 1 (v / v)}, te
rt-butyl (±) -trans-2,2-dimethyl-3
0.372 g of-{2-ethoxycarbonyl- (E) -1-propenyl} cyclopropanecarboxylate was obtained. ¹ H-NMR (CDCl ₃ solvent, TMS internal standard, 250
MHz) δ value (ppm): 6.45 (dd, 1H),
4.19 (q, 2H), 2.13 (dd, 1H), 1.
94 (d, 3H), 1.65 (d, 1H), 1.46
(S, 9H), 1.30 (s, 3H), 1.28 (s,
3H), 1.23 (s, 3H)

Examples 4 to 10 and Reference Examples 1 to 7 Examples 4 to 7 and Reference Examples 1 to 7 were carried out under the same conditions as described below. That is, methyl under nitrogen atmosphere
(+)-Trans-2,2-dimethyl-3-formyl-
0.666 g of cyclopropane carboxylate was added to Table 1
Was dissolved in 10 ml of the solvent described in Table 1, and 1.000 g of the amine and methylmalonic acid shown in Table 1 were added thereto, followed by stirring at the temperature shown in Table 1. After the lapse of time shown in Table 1, the reaction solution was cooled to room temperature, diluted with 50 ml of ethyl acetate,
Washed with 3N-hydrochloric acid. After further washing with saturated saline,
The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel chromatography ｛developing solvent, n-hexane: ethyl acetate = 3: 1 (v /
v) to give methyl (+)-trans-2,2-dimethyl-3- {2-carboxy- (E) -1-propenyl} -cyclopropanecarboxylate in the yields given in Table 1. Obtained. ¹ H-NMR (CDCl ₃ solvent, TMS internal standard, 250
MHz) δ value (ppm): 6.60 (dd, 1H),
3.70 (s, 3H), 2.22 (dd, 1H), 1.
94 (d, 3H), 1.78 (d, 1H), 1.32
(S, 3H), 1.24 (s, 3H)

[Table 1]

[0015]

According to the present invention, a pyrethroid compound useful as an insecticidal or acaricidal compound or a cyclopropanecarboxylic acid derivative represented by the above general formula 4 which is a useful intermediate in the production thereof can be efficiently produced. can do.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07C 69/747 C07C 69/747 F

Claims (8)

[Claims] 1. A compound represented by the general formula: [Wherein, R ¹ is a hydrogen atom, a C1-C5 alkyl group, C1
-C5 haloalkyl group, C1-C3 alkoxy C1-C
3 alkyl group, benzyl group optionally substituted by methoxy group, phenacyl group, 2-tetrahydrofuranyl group,
Represents a 2-tetrahydropyranyl group or a pyrethroid alcohol residue. And a cyclopropane carbaldehyde derivative represented by the following general formula: [Wherein, R ² represents a hydrogen atom, a C1-C10 alkyl group,
Represents a 1-C10 haloalkyl group, a C3-C10 alkenyl group, a C3-C10 haloalkenyl group, a C3-C10 alkynyl group, a C3-C10 haloalkynyl group or a benzyl group. With a dicarboxylic acid derivative represented by the formula: piperidine, morpholine, pyrrolidine, diethylamine,
1 selected from the group consisting of N-methylethanolamine
Wherein the reaction is carried out in the presence of at least one kind of secondary amine. [Wherein, R ¹ and R ² represent the same meaning as described above. ] The method for producing a cyclopropanecarboxylic acid derivative represented by the formula: (2) R ¹ in the general formulas (1) and (3) is a methyl group, an ethyl group, a t-butyl group, a 2,2,
2-trichloroethyl group, 2-chloroethyl group, methoxymethyl group, ethoxyethyl group, benzyl group, p-methoxybenzyl group, 3-phenoxybenzyl group, 5-benzyl-3-furylmethyl group, 2-methyl-4- Oxo
3- (2-propynyl) -2-cyclopentenyl group, 2
-Methyl-4-oxo-3- (2-propenyl) -2-
The method according to claim 1, wherein the group is a cyclopentenyl group, an N- (3,4,5,6-tetrahydrophthalimide) methyl group or an N- (3,4-dimethylmaleimido) methyl group. 3. A general formula of 2 and R ² in the general formula of 3 is methyl group, ethyl group, n- propyl group, iso- propyl, n- butyl, iso- butyl group, sec- butyl group, 2,2,2-trifluoroethyl group, bis (trifluoromethyl) methyl group, 2-propenyl group, 3-chloro-2-propenyl group, 2-propynyl group or 3-
The production method according to claim 1, which is an iodo-2-propynyl group. 4. The production method according to claim 1, wherein R ¹ in the general formulas 1 and 3 is a hydrogen atom. 5. The method according to claim 1, wherein the reaction temperature is in the range of 60 to 120 degrees. 6. The method according to claim 1, wherein the reaction solvent is at least one selected from pyridine and toluene. 7. The method according to claim 1, wherein the reaction solvent is pyridine. 8. The method according to claim 1, wherein the reaction solvent is toluene.