KR950004703B1 - Herbicidal and plant growth-controlling triazole derivatives and process for preparing the same - Google Patents

Abstract

The new compound as 5-alkoxy-1-alkyl-3-aryl -1,2,4-triazole (I) and its derivatives is prepared by (1) reacting benzaldehyde and semicarbazide to get benzaldehyde 2-alkylsemicarbazone (II), (2) cycling (II) with bromide to get 1-alkyl-3-aryl -1,2,4-triazole-5-on (III), (3) reacting (III) with methyl 2-bromo propionate to get (I). (I) is useful for soybean to multiply the branches.

Description

Herbicidal and plant growth regulating triazole derivatives and preparation method thereof

The present invention relates to a novel triazole derivative represented by the following general formula (I) having herbicidal activity and plant growth regulation, and a preparation method thereof.

[Formula 1]

In the above formula, Xn is hydrogen, a C ₁ -C ₄ alkyl group, a C ₂ -C ₅ alkenyl group, a C ₂ -C ₆ alkynyl group, a C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ haloalkyl group, C _2- A C ₄ alkoxycarbonyl group, an aminocarbonyl group, a carboxy group, a hydroxy group, a nitro group, a halogen group or a combination of two or more thereof, R ¹ represents hydrogen, a C ₁ -C ₄ alkyl group or a C ₂ -C ₅ alkenyl group R ² represents hydrogen or a C ₁ to C ₄ alkyl group, and R ³ represents hydrogen, a C _{1 to} C ₆ alkyl group, a benzyl group or an alkali metal cation, an alkaline earth metal cation or an ammonium ion.

The present invention will be described in detail as follows.

The present invention relates to a novel triazole derivative represented by the general formula (I), in particular 5-alkoxy-1-alkyl-3-aryl-1,2,4-triazole derivative.

In the above general formula (I), particularly preferably, Xn is a halogen atom of fluorine, chlorine, bromine or iodine or a C ₁ to C ₄ alkoxycarbonyl group, a carboxy group, a nitro group, a C _{1 to} C ₄ haloalkyl group or a It may be a case of a compound substituent.

In addition, R ¹ may be a methyl, ethyl, propyl or isopropyl group. R ² is preferably a hydrogen, methyl, ethyl, propyl, butyl or isopropyl group, and R ³ is often a hydrogen, methyl, ethyl or propyl group or a salt of sodium, potassium or amine.

Furthermore, more preferably, it is a compound when Xn is a fluorine, chlorine, bromine, iodine, a carboxy group, or a trifluoro methyl group, R <^1> is a methyl or ethyl group, and R <^2> is a hydrogen or a methyl group.

The triazole derivatives of the general formula (I) as described above have excellent herbicidal activity and show the effect of plant growth regulation, and in particular, the effect of promoting pruning on crops, which is excellent when applied to soybeans and rice. .

Therefore, the novel compounds according to the present invention are very useful as herbicides or plant growth regulators.

In general, herbicides are used to selectively remove weeds during agriculture and horticulture and grow only necessary plants, and plant growth regulators are used in the present invention to inhibit plant growth and promote side pruning. Means a drug.

It will be described in more detail centering on the method for preparing the compound of formula (I) according to the present invention.

According to the present invention, the triazole derivative compound of the general formula (I) is a 1-alkyl-3-aryl- represented by the following general formula (III) by cyclizing the semicarbazone represented by the following general formula (II). After preparing 1,2,4-triazol-5-one, it can be prepared by nucleophilic substitution reaction with a compound represented by the following general formula (IV).

[Formula 2]

[Formula 3]

[Formula 4]

In the formulas, Xn, R ¹ , R ² , and R ³ are as defined in the general formula (I), respectively, and Y represents chlorine, bromine or iodine.

Such a method of preparing general formula (I) according to the present invention will be described in more detail as follows.

The compound of the present invention has a triazole structure similar to that of Japanese Patent Application Laid-Open Nos. 60-218,379 and 60-218,380, but the types, positions and synthesis methods of the substituents are remarkably different. Unable to synthesize the compound of the invention

The compound of formula (I) is obtained from benzaldehyde substituted with Xn and semicarbazide of formula (II) obtained from semicarbazide substituted with R ¹ at 2-position, which is cyclized using bromine. One intermediate of 1-alkyl-3-aryl-1,2,4-triazol-5-one of formula (III) is obtained.

This is represented by the following reaction scheme.

Scheme 1

In the formulas, Xn and R ¹ are as defined in the general formula (I), respectively.

Methods of synthesizing such intermediate compounds of general formula (III) are described in Tetrahedron Lett., 1971, 2669-2670 and J. Chem. Soc., Perkin Trans. 1, 1972, 1918-1923.

In addition, compounds similar to the above intermediate (III) may be prepared by Chem. Pharm. Bull., 24 (6), 1336-1342 (1976); 23 (5), 955-966 (1975), 21 (6), 1342-1350 (1973).

Looking specifically, the substituted benzaldehyde 2-alkyl semicarbazone represented by the general formula (II) is a drop in bromination while heating to 70 ~ 80 ℃ in acetic anhydride dropwise occurs, by thin layer chromatography The reaction was followed by the addition of distilled water to the reaction solution and neutralization with sodium carbonate as soon as the semicarbazone of formula (II) disappeared. A solid precipitate was formed. This precipitate is collected and recrystallized in 90% methanol to give 1-alkyl-3-aryl-1,2,4-triazol-5-one of formula (III).

Here, in general, the most precipitate is obtained at the pH of about 10-11 when distilled water is added and neutralized, but when the solution is basic when the nitro group is substituted, the produced precipitate dissolves again. You can get good yield.

On the other hand, in the case of a specific compound in the compound of the general formula (II), for example, 3-cyanobenzaldehyde and 2-methyl semicarbazone cyclization reaction of 3-cyano group is hydrolyzed as shown in the following scheme Aminocarbonylphenyl) -1-methyl-1,2,4-triazol-5-one can be obtained.

Scheme 2

The 1-alkyl-3-aryl-1,2,4-triazol-5-one derivative of the general formula (III) synthesized in the above manner is subjected to nucleophilic substitution with the general formula (IV) as follows: It is derived from the compound of general formula (I) of the present invention.

Scheme 3

In the formulas, Xn, R ¹ , R ² , R ³ and Y are as defined in the general formulas (I) and (IV), respectively.

Examples of the base used in the nucleophilic substitution reaction include carbonates, acetates and amine free bases of alkali metals and alkaline earth metals.

On the other hand, when R ³ of the general formula (I) is an alkyl or benzyl group, it is easily hydrolyzed by sodium hydroxide and potassium hydroxide to become a salt, wherein R ³ becomes sodium or potassium. In addition, salts of sodium or potassium water thus obtained is a carboxylic acid by hydrochloric acid, where R ³ is hydrogen.

As described above, the structures of the compounds obtained according to the present invention were confirmed by melting point, nuclear magnetic resonance spectrum, IR, and mass spectrum, respectively.

The novel compound preparation and herbicidal activity of the present invention will be described in detail through the following examples, but the present invention is not limited by the examples.

Example 1

3- (2-bromophenyl) -1-methyl-1,2,4-triazol-5-one (1)

Dissolve 2-bromobenzaldehyde 2-methyl semicarbazone (1.2 g) in 5 ml of acetic anhydride, and slowly bromine solution (chrome: 0.5 ml, acetic anhydride: 4 ml) over 15 minutes while heating to about 90 to 100 ° C. Add it down. After stirring for 1 hour at the same temperature, the solution was poured into 100 ml of cold distilled water and neutralized with potassium carbonate until no bubbles of carbon dioxide were generated in the solution. The precipitates are collected by filtration, washed with distilled water and dried to yield 0.46 g of the desired product. If necessary, recrystallize from methanol: water (5: 1).

Melting Point: 148 ~ 150 ℃

¹ H NMR (60 MHz, DMSO-d ₆ ) δ 3.5 (3H, s), 7.2-7.8 (4H, m) 10.55 (1H, br).

IR (KBr, cm ^-1 ) 1750, 1700, 1500, 1450, 1430, 1390, 1355, 1240, 1010, 950

[Examples 2 to 31]

In the same manner as in Example 1, general formula (III) was synthesized as shown in Table 1 below.

TABLE 1

Example 32

Methyl 2- [3- (2-chlorophenyl) -methyl-1,2,4-triazol-5-yl] oxypropionate (32)

Dissolve 3- (2-chlorophenyl) -1-methyl-1,2,4-triazol-5-one (0.27 g) in 5 ml of anhydrous DMF, and then ground finely ground potassium carbonate (0.1 g) and methyl 2-bromine. Morpropionate (0.258 g) was added and stirred at room temperature for 5 hours.

The solution was poured into 3 ml of distilled water, extracted with 100 ml of ethyl ether, and then the ether layer was washed with 50 ml of 1N HCI solution and then again with 50 ml of distilled water. The water is removed with anhydrous MgSO ₄ , and the solvent is distilled off under reduced pressure to obtain the target product as 0.27 g as a light yellow liquid.

¹ H NMR (CDCl ₃ ) δ 1.6 (3H, d), 3.8 (3H, s), 5.3 (1H, q), 7.0-8.0 (4H, m).

[Examples 33 to 68]

In the same manner as in Example 32, Compounds of Formula (I) were synthesized as shown in Table 2 below.

[Formula 5]

TABLE 2

Test Example 1

Herbicide Activity Test

The appropriate amount of fertilizer sterilized sandy loam mixed and then the test pot (field conditions: 348cm ^2, paddy conditions: 115cm ²⁾ and put on. At this time, the number of pots used was 2 pots of field conditions and 1 pot of non-conditions per compound. Then, as field crops and weeds, seeds or underground diameters such as tomatoes, wheat, soybeans, corn, orchardgrass, sesame, barley, silkworm, and matet are placed in pots of field conditions, and rice, paddy grass, and algae garden as crops and weeds. Seeds of mantis grass, etc. are sown in pots of non-condition, and then poured into fine soil and placed in a greenhouse. Dissolve 4 kg / ha of test compound (field conditions, 14 mg / pot; non-condition, 4 mg / pot) in a solvent (mostly acetone), and then mix the same amount in water containing a nonionic surfactant (Tween 20). Spray 14 ml per pot for field conditions and 4 ml per pot for paddy conditions.

At this time, the soil condition before germination is treated with the preparation prepared on the first day after sowing, and the management treatment after germination on the 9-14 days after sowing. After treatment, grow them in a greenhouse for two to three weeks and examine their herbicidal effects by morphological and physiological observations. 0 means no control effect, 1 ~ 2 means some control effect, 3 means moderate effect, 4 means severe effect and 5 means very severe effect and perfect control effect.

The herbicidal effects before and after germination of the compounds of the present invention are shown in Tables 3 and 4, respectively.

TABLE 3

TABLE 4

Test Example 2

Side Pruning Effect Test of Soybean

After planting 3 to 4 soybeans in a 9cm diameter pot, grow them in a greenhouse for 8-11 days to grow the cotyledons, and then dissolve the drug with 0.1% tween 20 in 50% acetone and use various amounts (50g / ha, 20g / ha, 10g / ha, 5g / ha), 5 leaf pollen each. After 14 days, the number of branches, phytotoxicity (%) and dwarfization (4%) of each pollen were recorded.

TIBAs with similar activity were also tested to compare activity and efficacy.

The results of measuring soybean pruning activity, toxicity to soybean, and dwarfization (%) of these beans are reported in Table 5. In addition, the side pruning activity test results for rice showed similar results to the case of soybean.

TABLE 5

Claims (13)

5-alkoxy-1-alkyl-3-aryl-1,2,4-triazole derivative represented by the following general formula (I) In the formula, Xn is hydrogen, C ₁ ~C ₄ alkyl group, C ₂ ~C ₅ alkenyl, C ₂ ~C ₅ alkynyl group, C ₁ ~C ₄ alkoxy group, C ₁ ~C ₄ haloalkyl group, C ₂ ~ A C ₄ alkoxycarbonyl group, an aminocarbonyl group, a carboxy group, a hydroxy group, a nitro group, a halogen group or a combination of two or more thereof, R ¹ represents hydrogen, a C ₁ -C ₄ alkyl group or a C ₂ -C ₄ alkenyl group It represents, R ² is a hydrogen or a C ₁ ~C ₄ alkyl group, R ³ represents hydrogen, C ₁ ~C ₆ alkyl group, a benzyl group or an alkali metal cation, alkaline earth metal cation or ammonium ion. The compound according to claim 1, wherein Xn is a halogen group of fluorine, chlorine, bromine or iodine, a C _{1 to} C ₄ alkoxycarbonyl group, a carboxy group, a nitro group, a C _{1 to} C ₄ haloalkyl group or a complex substituent group thereof. 3. A compound according to claim 2, wherein Xn is a fluorine, chlorine, bromine, iodine, carboxyl or trifluoromethyl group. The compound of claim 1, wherein R ¹ is a methyl, ethyl, propyl or isopropyl group. The compound of claim 4, wherein R ¹ is a methyl or ethyl group. The compound of claim 1, wherein R ² is hydrogen, methyl, ethyl, propyl, butyl or isopropyl groups. The compound of claim 6, wherein R ² is hydrogen or a methyl group. The compound of claim 1, wherein R ³ is hydrogen, methyl, ethyl or a propyl group or a salt of sodium, potassium or amine. The herbicide containing the triazole derivative represented by the following general formula (I) as an active ingredient. Wherein Xn, R ¹ , R ² and R ³ are each as defined in formula (I) of claim 1 above. A plant growth regulator containing the triazole derivative represented by the following general formula (I) as an active ingredient having a crop growth regulation effect. Wherein Xn, R ¹ , R ² and R ³ are each as defined in formula (I) of claim 1 above. 11. The plant growth regulator according to claim 10, wherein the crop growth regulation effect is an effect of promoting pruning of crops. The plant growth regulator according to claim 10 or 11, wherein the crop is soybean. By cyclizing the semicarbazone represented by the following general formula (II) to prepare 1-alkyl-3-allyl-1,2,4-triazol-5-one represented by the following general formula (III), A nucleophilic substitution reaction with a compound represented by the following general formula (IV) to produce a triazole represented by the following general formula (I). In the formulas, Xn, R ¹ , R ² and R ³ are as defined in general formula (I) of claim ¹ , respectively, and Y represents chlorine, bromine or iodine.