JPS6026118B2 - N-pyridyl-aminomethylene diphosphonic acid compound - Google Patents

Description

Detailed Description of the Invention The present invention is based on the general formula or, or, (wherein R1, R2, R2 each independently represents a hydrogen atom or a lower alkyl group, Atom, amino group, nitro group, 1C
OO or -COOC string, X2 represents a hydrogen atom, a lower alkyl group, 10H or -OCH3, X2 represents a lower alkyl group or a halogen atom, and n represents an integer of 1 or 2.

) (hereinafter simply referred to as the compound of the present invention). For N-(4-pyridyl)aminomethylene diphosphonic acid, see
Itschrift fur a blood
uMall Hoko mel ship chemie) 38th term gloss 19
(1972), but the pesticide of the compound,
In particular, there is no mention of any uses such as herbicidal activity. All of the compounds of the present invention represented by the one-stage formula above, except for N-(4-pyridyl)aminomethylene diphosphonic acid, are new compounds that have not been described in any literature. The compound of the present invention is a compound useful as an active ingredient of agrochemicals, especially herbicides. Conventionally, various herbicides have been developed and commercially available as agricultural and horticultural herbicides, but among the mulberry treatment herbicides,
I haven't seen anything satisfying enough yet.

For example, a herbicide (generic name: paraquat) containing 1,1'-dimethyl-4,4'-biviridinium dichloride as an active ingredient is known as a hollyhock treatment herbicide.
This herbicide also has the disadvantage that it regenerates rapidly after spraying, that is, its medicinal efficacy is low in duration, and it is also highly toxic. Furthermore, it has been extremely difficult to kill various perennial weeds over a wide range with conventional herbicides.

The present inventors conducted various studies on the presence or absence of agricultural physiological activity of diphosphonic acid compounds, and as a result, they discovered that the compounds of the present invention have excellent herbicidal activity. The compound of the present invention is used for pre-germination treatment of plants (soil treatment).
Although it has no herbicidal effect at all, it has an extremely strong herbicidal effect by post-emergence treatment (hollyhock treatment) of plants, and in particular, it has a very strong herbicidal effect on plants that have been difficult to weed in the past, such as Chigaya grass, Johnson grass, Kisyuwassu menohie, Mugwort, etc. It is capable of killing a wide range of perennial weeds such as perennial weeds and grasshoppers.

On the other hand, the compound of the present invention also has the characteristic that it has almost no herbicidal effect against the lines, that is, there is almost no chemical damage to the lines in the flower treatment.

Furthermore, the present invention encompasses alkali metal salts, alkali metal salts, ammonium salts, and organic amine salts of the compounds of the present invention, and these salts also have excellent herbicidal efficacy similar to the compounds of the present invention. It is something.

The compound of the present invention can be easily synthesized by the method shown in the following formula.

In the formula, R1, R2, R3 and n are the same as above.

Y represents a lower alkyl group, and X represents the above-mentioned X1, X2 or X3. Chemical reaction formulas (1) and (0) of the above formula
The reactions are allowed to proceed simultaneously.

That is, three starting materials, an aminopyridine derivative, an orthocarboxylic acid ester, and a dialkyl phosphite, are mixed simultaneously, and this mixture is heated to produce a diphosphonic acid ester, and this ester is further mixed with hydrochloric acid, etc. The desired product can be easily obtained by hydrolysis with an acid. However, when X is an amino group, it is acetylated. The desired product can be obtained by protecting the nitrogen atom of the amino group and reacting it, or by reacting it with nitroaminopyridine and then reducing it.

Next, specific examples of synthesis of the compounds of the present invention will be explained.

However, it is not limited to this synthesis example. Synthesis Example 1 Synthesis of N-[2-(3-methylpyridyl)]aminomethylene diphosphonic acid 2-amino-3-methylpyridine 54
．． 0 mole (0.5 mol), ethyl orthoformate 85.1 mole (
0.575 mol) and 1 paper of diethyl phosphite (
1.0 mol) was mixed and heated in an oil bath at 15 picoC for 1 hour while distilling off the produced ethyl alcohol.

After completion of the reaction, low boiling point removal (130°C/20 days and evenings) was performed to obtain N-[2-(3-methylpyridyl)]aminomethylene diphosphonic acid tetraethyl ester 198.
5 evenings are obtained.

A portion of this was collected and purified by thin layer chromatography (carrier: silica gel, developing solvent: hexane-acetone 1:1) to obtain a color with a refractive index of N. = 1.4990 pure product is obtained. Next, 100% of concentrated hydrochloric acid was added little by little to the above product at room temperature, and the mixture was heated under reflux for 1 hour to obtain crystals of N-[2-(3-methylpyridyl)]aminomethylene diphosphonic acid. .

After washing with water and ethanol, the amount obtained after drying was 12
4.6 hours (yield: Iso.4%).

Recrystallization from concentrated hydrochloric acid yields pure N-[2-(3-methylpyridyl)]aminomethylene diphosphonic acid (decomposition point 297-2°C). This elemental analysis value is C7 day, 8
The analytical values and calculated values for N206P2 are as follows: JC Day N Analytical value 26.66% 3.53% 10. Milk % calculation value 26.86% 3.73% 10.44% Synthesis example 2
Synthesis of N-[2-(5-chloropyridyl)]aminomethylene diphosphonic acid 2-amino-5-chloropyridine5.
1 night (0.04 mol), ethyl orthoformate 7.49 (0
．． 05 mol) and diethyl phosphite 11 mol (0.05 mol).
The mixture was mixed and overflowed with ethyl alcohol (female moles), and heated at 15°C for 2 hours on an oil scale while distilling off the produced ethyl alcohol.

After the reaction was completed, the reaction mixture was allowed to stand at room temperature, and the precipitated crystals of N-[2-(5-chloropyridyl)]aminomethylene diphosphonic acid tetraethyl ester were separated.

The yield was 11.3 days (yield 68%).

When this crystal is recrystallized with ether, the melting point is 103-104q.
A pure product of o is obtained. Next, from the above crystal 5, concentrate hydrochloric acid 3
of N-[2-(
5-Chlorpyridyl)] white crystals of aminomethylene diphosphonic acid are obtained.

Separate the leaves and wash with water and ethanol to obtain the product. Yield 3
．． It takes 3 days (yield 92%) and has a melting point of 285 to 2870 (however, it decomposes at 2870). This elemental analysis value is 9N
The analytical values and calculated values for 3QP2CI are as follows. C Day N Analytical value 23.61% 2.76% 8.91% Calculated value 23.82% 3.00% 9.26% Next, the compound of the present invention synthesized according to Synthesis Example 1, Synthesis Example 2, etc. are shown in Table 1.

However, the compounds of the present invention are not limited to these. The numbers of these compounds are referred to in the following formulation examples and test examples. Table 1 * The known compound paraquat (generic name) was used as a control drug in Test Example 4K below.

*Compound 17 is a compound of Z
eitschrift fur anorganish
e und allgemelnechemie) 3rd
It is described in Vol. 89, 11900 (1972).

When actually using a herbicide containing a compound of the present invention as an active ingredient, one or more of the compounds are combined with a suitable inert carrier according to a known formulation, and a wettable powder,
It is suitable to prepare it in an appropriate form that is easy to use, such as flowable, powder, granule, aqueous solution of alkali metal salts, alkali metal salts, ammonium salts, organic amine salts, etc., or a square aqueous solution. The solid carrier used in this case includes, for example, clay, talc, bentonite,
Examples include diatomaceous earth. Also, as a liquid raccoon body,
Examples include water, alcohols, acetone, and dimethylformamide. Also, as a pharmaceutical adjuvant,
Surfactants such as emulsifiers, dispersants, and penetrants may be used as appropriate. Next, specific formulation examples of herbicides containing the compound of the present invention as an active ingredient will be explained. However, the composition is not limited to these formulation examples. Note that "parts" below mean parts by weight. Formulation Example 1 Wettable powder The above ingredients are uniformly mixed and pulverized to make a wettable powder.

When using, the above-mentioned hydrating agent is diluted with water to 50 to 100 psi, and the amount of active ingredient is 30 to 1000 per 10 ares.
Spread it evenly.

Formulation example 2 Aqueous solution The above ingredients are completely mixed and dissolved to form an aqueous solution.

When using, the above aqueous solution is diluted with water to 50-100 pm, and the amount of active ingredient is 30-100 pm/10 are.
Scatter it until it becomes 0. Test example 1 Weeding effect test by gorgeous treatment Sterilized Hongtou soil was placed in a plastic box measuring 1 x 1 x x 6 x 6 x 6 x 6 x 1. Rice, crabgrass, cyperus, cypress, purslane, purslane, dogberry, leafminer, tomato, cucumber Seeds were sown in spots and covered with about 1.5 kg of soil.

When rice, tomato, cucumber, and various weeds reached the 2- to 3-leaf stage, the compound of the present invention was sprayed onto the hollyhock at a rate of 100/a. For the leaf liquid during spraying, the hydrating agent of Formulation Example 1 was diluted with water and sprayed using a small sprayer over the entire surface of the foliage of rice, tomato, cucumber, and various weeds.

Two weeks after spraying the chemical solution, the herbicidal effects on rice, tomatoes, cucumbers, and various weeds were investigated according to the criteria below.

The results are shown in Table 2.

Judgment Criteria 5...Weed killing rate 90% or more 4...Weed killing rate 70-90% 3...Weed killing rate 40-70% 2...Weed killing rate 20-40% 1...Weed killing rate 5-20 % 0...Kikusa rate 5% or less (almost no effect) However,
The above-mentioned grass growth rate was determined by measuring the above-ground grass in the chemically treated area and the above-ground grass in the untreated area using the following formula.

Weed killing rate (%) = (・-Xianmengou District Gongfeng Kenji Bell Tomb) XIO
Table 2 Test Example 2 Herbicidal Effect Test by Flower Leaf Treatment The compound of the present invention was sprayed on flower leaves at a rate of 25 evenings/a, 12.5 evenings/a, and 6.3 evenings/a.

As for the chemical to be sprayed, the aqueous solution of Formulation Example 2 was diluted with water and tested in the same manner as in Test Example 1. However, cotton seeds were also sown in the same machine as rice and various weeds for testing. The herbicidal effect was investigated according to the criteria described in Test Example 1.

The results are shown in Table 3.

Table 3 As shown in Table 3, the compound of the present invention is characterized by having almost no herbicidal effect against line.

Test example 3 Weeding effect test by soil treatment In a plastic box with length 1 and even, height 22 and depth 6,
Add sterilized Honggyong soil, and sow rice, Japanese grasshopper, Japanese cypress, Japanese cyperus, Japanese cypress, purslane, goldenrod, and Japanese leafminer. Approximately 1. After covering with soil, the compound of the present invention was sprayed on the soil surface at a rate of 100 m/a.

The chemical solution used for spraying was the wettable powder of Formulation Example 1 diluted with water and sprayed over the entire surface with a small sprayer.

Three weeks after spraying the chemical solution, the herbicidal effect on rice and various weeds was investigated according to the criteria described in Test Example 1. The results are shown in Table 4.

Table 4 Test Example 4 Testing the herbicidal effect of flower leaf treatment on perennial weeds The above-ground flowers and tuberous roots of Chigaa japonica, japonica japonica, johnson grass, mugwort, japonica japonica, and japonica japonica were collected in the field and tested against perennial weeds. 〇A - 1 female Hada Wagune - Johnson grass, mugwort, and Japanese sedge are in 5-inch pots, and Chishu suzumenohie is in a 5-inch pot.
Transplant each into the enemy's plastic box, 45 to 90
After sufficient growth in a greenhouse for one day, the compound of the present invention and the control compound were sprayed onto the flower straw of the perennial weeds at a predetermined ratio per unit area.

The chemical solution used during spraying was the aqueous solution of Formulation Example 2 diluted with water and sprayed over the entire surface of the weed flower straw. One month after spraying the chemical solution, the herbicidal effect on the perennial weeds was investigated according to the criteria described in Test Example 1.

The results are shown in Table 5.

After investigating this herbicidal effect (herbicidal rate), the above-ground grass part of each weed was completely excised, and the regeneration rate of the weed was investigated one month later according to the following criteria.

The results are shown in Table 5.

Judgment Criteria 5... Reproduction rate 10% or less 4... Reproduction rate 10-30% 3... Reproduction rate 30-60% 2... Reproduction rate 60-80% 1... Reproduction rate 80-95 % 0...Regeneration rate 95% or more (almost the same as in the drug-free area)
However, the above regeneration rate was determined by measuring the above-ground living grass wheels in the chemical-treated area and the above-ground living grass fleas in the untreated area at the time of the survey.
It was calculated using the following formula.

Hina rate (%) = (Senreitou Fortress Wanisosho Gorei) XIOO Table 5 * Paraquat (-generic name) was used as a control compound.

Claims (1)

[Claims] 1 General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ Or, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Or, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 , R^2, R^2 each independently represent a hydrogen atom or a lower alkyl group, and X^2 represents a hydrogen atom, a lower alkyl group, a halogen atom, an amino group, a nitro group, ▲ a mathematical formula, a chemical formula, a table, etc. ▼ -COOH or -COOCH_2, X^2 represents a hydrogen atom, lower alkyl group, -OH or -OCH_3, X^3 represents a lower alkyl group or a halogen atom, n is an integer of 1 or 2. An N-pyridyl-aminomethylene diphosphonic acid compound represented by