JPS59225180A - Substituted nicotinic acid derivative and herbicidal and plant growth regulating agent - Google Patents

Abstract

NEW MATERIAL:The nicotinic acid alkylthioalkyl ester of formula I (X and Y are H, halogen, 1-4C alkyl, etc.; R<1>-R<4> are H, 1-4C alkyl, phenyl, etc.; R<5> is 1-4C alkyl, phenyl, etc.; R<6> is 1-4C alkyl; R<7> is 1-4C alkyl or 3-6C cycloalkyl; m is 1-4; n is 0 or 1; q is 0, 1 or 2). EXAMPLE:Methylthiomethyl 2-(5-isopropyl-5-methyl-4-oxo-2-imidazolin-2-yl)nicotinate. USE:A herbicide and a plant-growth regulating agent. It exhibits excellent activity especially to gramineous plants. PREPARATION:The compound of formula I wherein m is 1 and n is 0 can be prepared by esterifying the compound of formula II with the compound of formula III using a Pummerer reagent (e.g. t-butyl bromide).

Description

Detailed Description of the Invention The present invention relates to the general formula (I): [wherein X and Y are each a hydrogen atom, a halogen atom, a 01-C4 alkyl group or a 01-C4 alkyloxy group, R3 and R4 each represent a hydrogen atom, an 01-C4 alkyl group, a C1-C4 alkyl group substituted with a halogen atom, or a phenyl group, and R5 represents a 01-C4 alkyl group, a C1 substituted with a halogen atom.
~c4 alkyl group, phenyl group, phenyl group substituted with 1 to 5 substituents (however, the substituents are 01 to c4
It is selected from the group consisting of an alkyl group, a halogen atom, a C1-c4 alkyloxy group and a nitro group. ), a benzyl group or an arylmethyl group substituted with 1 to 5 substituents (provided that the substituents are selected from the group consisting of a 01-C4 alkyl group, a halogen atom, a C1-C4 alkyloxy group, and a nitro group). ), Re is 01-C4 alkyl group, R7 is 01-C4 alkyl group end or 03-
CB cycloalkyl group, m is an integer of 1 to 4, n is O
or 1, and q represents 0, ■, or 2.] The present invention relates to a herbicidal/plant growth regulator containing an alkylthioalkyl nicotinic acid ester represented by the following formula, and one or more of the compounds as active ingredients.

The compound of the present invention represented by the general formula (1) has a herbicidal action,
It is a new compound that has plant growth-related effects on grass crops and broad-leaved crops, such as lateral branching, generation of young shoots, flowering, and increased yield.

Regarding herbicidal activity, it has excellent herbicidal activity against annual and perennial weeds such as Poaceae, Cyperaceae, and broad-leaved weeds in soil treatment, soil mixing treatment, and foliage treatment, and it also has excellent herbicidal activity against certain types of crops. It is an excellent practical compound with selectivity for

The compound of the present invention can be applied to control various weeds in agricultural and horticultural areas such as fields, paddy fields, and orchards, as well as in non-agricultural areas such as playgrounds, vacant lots, and railway edges, and the amount of the applied drug depends on the application situation. There are differences depending on the application time, application method, target grass species, cultivated crops, etc., but in general, the appropriate amount of active ingredient is about 0.000 to 5.000 per hectare.

In addition, the compounds of the present invention exhibit excellent plant growth joint effects on grass crops and broad-leaved crops in soil treatment and foliage treatment. For example, the compound of the present invention is suitable in the field of agriculture and horticulture, particularly as a growth regulator for grasses such as rice, wheat, barley, and grass.

The amount of the applied drug varies depending on the purpose of use, the type of target plant, and other conditions, but in general, it is desirable that the concentration of the active ingredient is 10 to 5000 ppm, preferably 5.
It is appropriate to use it at a concentration of about 0 to 2000 ppm.

It is described in European Publication Box No. 41-623 that the compound (A), which is structurally similar to the compound of the present invention, has herbicidal activity.

However, a group of compounds in which an alkylthioalkyl group is introduced into the carboxylic acid moiety of a nicotinic acid derivative such as the compound of the present invention represented by general formula (1) is a new compound that is not covered by the prior art that includes compound (A). . Furthermore, although Compound (A) was shown as a comparative example in the Examples, the compound of the present invention has a remarkable feature of superior herbicidal power compared to Compound (A). That is, by converting the carboxylic acid moiety of compound (A) into an alkylthioalkyl ester, it was possible to impart excellent herbicidal activity against a wide variety of weeds.

The compound of the present invention represented by the general formula (I) can be produced, for example, by any of the following reaction schemes to 3.

(Reaction formula 1) [In the formula, X, Y, R1, R2, R3, R4゜R5, R'
, R7, m and n have the same meanings as above. ] This esterification reaction is carried out using sulfoxide Pummerer (Pu+
nll1erer) reaction. Therefore, the sulfoxide used in the reaction can only be applied to derivatives having α-hydrogen, that is, m=1.
Can only be used when m=o. Various electrophilic reagents can be used as the Pummeler reaction reagent, for example, t-
Butyl bromide and the like are preferred, but Pummeler reaction reagents of acid anhydrides such as acetic anhydride, inorganic acids, or organic acid derivatives can also be used (References Near Isotope in Organic Chemistry Vol. 5, Chapter 2, 1980 2013, Elsevier). A detailed explanation will be given below with reference to synthesis examples.

Methylthiomethyl 2-(5-isopropyl-5-methyl-4-oxo-2-imidacillin-2-yl)nicotinate (Compound No. 1 of the present invention) 2-(5-isopropyl-5-methyl-4 -oxo-2
-imidacylin-2-yl)nicotinic acid (3,6 g) and t-butyl bromide (190 g) were dissolved in dry dimethyl sulfoxide (80 ml), then sodium bicarbonate (11,6 g) was added and the mixture was stirred at room temperature for 20 min. Stir for hours.

After the reaction was completed, the reaction solution was added to cold water, extracted with 200 ml of benzene, washed with water, dried, and then benzene was distilled off to obtain a pale yellow oil. The crude product was purified by silica gel column chromatography (developing solution: chloroform) to obtain 1.2 g of the present compound N001 as white crystals.

Melting point 84-87℃ Mass (El method, 24eV): m/Z
(Relative intensity): 371 (M+, 6), 29
3 (9B).

224 (100) The compounds in Table 1 can be synthesized by the reaction shown in Synthesis Example 1 or by using other Bummerer reactions.

Table 1 1 (Reaction formula 2) Intermediate A Intermediate B [In the formula, X, Y, R1, R2, R3, R4゜R', R''
, R7, m, n and q have the same meanings as above. ] Intermediate A and an equal or excess amount of Intermediate B are dissolved in an organic solvent, and then a catalytic amount of 1 lrN and an equivalent amount of an organic or inorganic base is added to allow the reaction to proceed at room temperature or under heating conditions. Inventive compounds can be synthesized.

(Reaction formula 3) % formula% [In the formula, X, Y, R1, R2, R3, R4°R', R1
', R7, m, n and q have the same meanings as above. ] Intermediate C and an equivalent or excess amount of Intermediate B are dissolved in an organic solvent, and then a catalytic amount or equivalent of an organic base or an inorganic base is added, whereby the reaction proceeds at room temperature or under heating conditions, and the compound of the present invention is produced. can be synthesized.

Reaction formula 2 will be specifically explained below by giving a synthesis example.

1 2-Methylthioethyl 2-(5-isopropyl-5-methyl-4-oxo-2-imidacillin-2-yl)nicotinate (invention compound No. 2) 3-isopropyl-3-methyl-3H- Imidazo [1'
, 2':l, 2) Pyrrolo(3,4-b]pyridine-2(5H), 5-dione (white crystals.

(melting point 95-97°C) (1,0 g) Methylthioethanol (400 mg>, 55% sodium hydride (20 m
A mixture of g) and dry tetrahydrofuran (10a+1) was left at room temperature overnight. After the reaction was completed, acetic acid was added to the reaction solution to neutralize it, and the solvent was distilled off under reduced pressure to obtain a pale yellow oil. The crude product was purified by silica gel column chromatography (developing solution: chloroform) to obtain 1.0 g of the present compound No. 2 as a colorless oil.

Mass (El method, 24eV) 335 (M+
, 3>.

262 (90), 75 (1-00) As shown in Synthesis Example 2, using the reaction of reaction formula 2 or 3, the second
It is possible to synthesize the compound voice of the table.

The organic solvents used in the following Reaction Schemes 1 to 3 vary depending on the base used, but aprotic solvents such as chloroform, ether, tetrahydrofuran, benzene, toluene, dimethylformamide, acetonitrile, etc. are preferable. Examples of the base include organic tertiary amines such as triethylamine and pyridine, and inorganic salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium hydride, and sodium amide.

When applying the compounds of the present invention as herbicides or plant growth regulators, suitable carriers are generally used, such as solid carriers such as clay, talc, bentonite, diatomaceous earth, or water, alcohols (methanol, ethanol, etc.). , aromatic hydrocarbons (benzene, toluene, xylene, etc.), chlorinated hydrocarbons, ethers, ketones, esters (
It can be applied by mixing with liquid carriers such as ethyl acetate, etc.), acid amides (dimethylformamide, etc.), and emulsifiers, dispersants, suspending agents, penetrating agents, spreading agents, stabilizers, etc. can be added if desired. However, it can be put to practical use in any dosage form such as a liquid, emulsion, wettable powder, powder, or granule. In addition, other herbicides, various insecticides,
It may be applied in combination with fungicides, plant growth regulators, synergists, etc. As for the type of herbicide to be mixed, for example, the Farm Chemicals Handbook (Farm Chem
icals Handbook), 69th edition (19
83) and the like.

The compound of the present invention can be applied to control various weeds in agricultural and horticultural areas such as fields, paddy fields, and orchards, as well as in non-agricultural areas such as playgrounds, vacant lots, and railway edges, and the amount of the applied drug depends on the application situation. Although there are differences depending on the application time, application method, target grass species, cultivated crops, etc., the appropriate amount of active ingredient is generally about 0.005 to 10 kg per hectare.

Examples of formulations of herbicides and plant growth regulators containing the compound of the present invention as an active ingredient are shown below, but the invention is not limited to these. In addition, in the following formulation examples, "parts" mean parts by weight.

Formulation Example 1 Wettable powder Compound of the present invention
-・50 copies Sieglite PFP ----------
−−・−11−−−・−43 parts (Kaolin clay: Sieglite Kogyo ■Product name) Tsurupol 5039 −−−
−−−−・−・・−5 parts (mixture of nonionic surfactant and anionic surfactant: Toho Chemical Co., Ltd. ■Product name)
Carplex (anti-caking agent) - 2 parts (mixture of surfactant and white carbon: Shionogi & Co., Ltd. trade name) The above is mixed and ground uniformly to make a wettable powder. When used, the above-mentioned hydrating agent is diluted 50 to 10,000 times and sprayed at an amount of active ingredient of 0.005 kg to 10 kg per hectare.

1 Gold Aim 1 Emulsion Compound of the Invention 11kL 2 ------------------------
−−−−10 copies −・・−−
-1..-.----- -10 parts or more (mixture of nonionic surfactant and anionic surfactant: Toho Chemical Industries' trade name) are uniformly mixed to form an emulsion. When using, dilute the above emulsion 50 to 1.000 times to obtain an active ingredient amount of 0.005 kg per hectare.
Spread to make it weigh up to 10 kg.

Corrosive granules Compound of the present invention Arashi i
−・ 5 parts bentonite −・−−−−−−−−−1・・
−・・−・−・−・−54th part Kuu・−−1−
−−−・・−−−−1−−−−−−・−−−−−−
----40 parts Calcium ligninsulfonate--1
1 part or more are uniformly mixed and pulverized, a small amount of water is added, the mixture is stirred, and the mixture is granulated using an extrusion type granulator and dried to form granules. When using the above granules, the amount of active ingredient is 0 per hectare.
．． 0.005 kg to 10 kg.

L-shaped clay Flowable agent Compound of the present invention Nal ・-------1-・----
---1--25 parts Tsurupol 3353 ------
----------- 10 parts (nonionic surfactant: Toho Chemical Industry brand name) Lunox 1oooc・----1---・----0.5 parts (anion interface Activator:
Toho Chemical Industry ■Product name) 1% xanthan gum aqueous solution -1-
−−・−・−・−20 parts (natural polymer) Water −−−−−−−−−−−−−−−−−−−−・−
・−・−・・−・−・・44.5 part Tsurupol 3353
, Lunox 1OOOC and a 1% xanthan gum aqueous solution are uniformly dissolved in water, and then the compound of the present invention 1 is added and stirred well, followed by wet grinding in a sand mill to obtain a flowable agent.

When using, the above flowable agent should be added in an amount of 50 to 1,000
The amount of active ingredient after dilution is 0.00 per hectare.
Spread it to a weight of 5kg to 10kg.

Next, the usefulness of the compounds of the present invention as herbicides will be specifically explained using test examples including comparative compounds according to the prior art.

Comparative compound A (said compound (A)) (White crystals, melting point 286-90℃) This will be specifically explained in the following test examples.

U plate two tops Weeding effect test edge by soil treatment 15c11.
Sterilized diluvial soil was placed in a plastic box with a width of 22 an and a depth of 6 QIl, and rice, Japanese wild grass, Japanese grasshopper, Cyperus japonica, Koakaza, Portulaca purslane, Chickweed, and Dogwood were mixed and sown for about 1 hour. After covering the soil to a depth of 5 cm, the soil surface was uniformly dispersed so that the amount of active ingredient was at a predetermined ratio.

The chemical solution used for spraying was the wettable powder, emulsion or flowable powder of the formulation example described above diluted with water and sprayed over the entire surface with a small sprayer. Three weeks after spraying the chemical solution, the herbicidal effect on various weeds was investigated according to the following criteria.

The results are shown in Table 3.

Judgment Criteria 5- Weed killing rate 90% or more (almost complete death) 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--Weed killing rate 5% or less (mostly ineffective) However, The above-mentioned weed killing rate was determined by the following formula by measuring the above-ground fresh grass in the chemical-treated area and the above-ground live grass in the untreated area.

Bashun plate 2l Weeding effect test by foliage treatment Edge 15an,
Sterilized diluvial soil was placed in a plastic box with a width of 22 aa and a depth of 6 a11, and seeds of rice, crabgrass, cyperus, tomato, koakaza, purslane, leafminer, dogberry, corn, soybean, and wheat were sown in spots, respectively. The soil was covered with approximately 1.5 cm of soil. When each plant reached the 2-3 leaf stage, the active ingredient was uniformly sprayed onto the stems and leaves so that the amount of the active ingredient was at a predetermined ratio.

The chemical solution used for spraying was the wettable powder, emulsion or flowable powder of the formulation example described above, which was diluted with water and sprayed over the entire surface of the foliage of various weeds and crops using a small sprayer.

Four weeks after spraying the chemical solution, the herbicidal effect on various weeds was investigated according to the criteria of Test Example 1, and the chemical damage to various crops was investigated according to the criteria of Test Example 2.

The results are shown in Table 4.

Table 3 and following margins continued on page 1 0 Author: Oguchi Maeaki 0, Oaza Shiraoka, Shiraoka-cho, Minamisaitama-gun, Saitama Author: Nanamaki 1470, Oaza Shiraoka, Shiraoka-cho, Minamisaitama-gun, Saitama Prefecture Procedures within Nissan Chemical Industries, Ltd. Biochemistry Research Institute Written amendment (voluntary) July 9, 1981 1 Incident display lδ-gea/riθ 6, 1988
Patent layer (3) filed on March 3rd 2 Name of the invention: Substituted nicotinic acid derivative and herbicidal/plant growth joint agent 3 Relationship with the case of the person making the amendment Patent applicant address: 3-7-14 Kanda Nishiki-cho, Chiyoda-ku, Tokyo 101
Target of amendment (1) Page 6, line 18 of the specification r Add ``and (B)J'' after ``compound (A)''.

(2) Page 7 of the specification Correct to.

(3) Page 7, lines 2-3 of the specification: ``Add ester j after alkylthioalkyl J.''

(4) The following is corrected on page 8 (reaction formula 1) of the specification.

(5) Specification box page 10, lines 6-7' 371 (M10, 6), 293 (98
).

224 (100) J r 321 (M ten, 6), 217 (26
).

174 (100) Corrected to J.

(6) Page 20 of the specification “Comparative compound A (said compound (A)) (White crystals, melting point 286-90℃) After the “Comparative compound B (said compound (B)) (Colorless viscous oil) replenish.

(7) In Table 3 on page 23 of the specification, the following information is added following Comparative Compound A.

Claims (2)

[Claims] (1) General formula (■): [wherein, 01-C4 alkyl group, 01-C4 alkyl group substituted with a halogen atom or phenyl group, R5 is 01
~C4 alkyl group, 01~C substituted with a halogen atom
4-alkyl group, phenyl group, phenyl group substituted with 1 to 5 substituents (however, the substituents are from the group consisting of 01-C4 alkyl group, halogen atom, 01-C4 alkyloxy group, and 2, tro group) ), a benzyl group or an atomylmethyl group substituted with 5 to 5 substituents (however, the substituents consist of a 01-C4 alkyl group, a halogen atom, a 01-C4 alkyloxy group, and a nitro group) ), R8 is a 01-C4 alkyl group, R7 is a 01-C4 alkyl group or a 03-C4 alkyl group.
8 cycloalkyl group, m is an integer of 1 to 4, n is 0 or 1, and q is 0.1 or 2] Nicotinic acid alkylthioalkyl esters. (2) General formula (■): [wherein, , 01-c4 alkyl group, halogen atom-substituted 01-C4 alkyl group or phenyl group, R5 is 01
~C4 alkyl group, C1-C substituted with halogen atom
4-alkyl group, phenyl group, phenyl group substituted with 5 to 5 substituents (however, the substituents are selected from the group consisting of 01-C4 alkyl group, halogen atom, 01-C4 alkyloxy group, and nitro group) ), a benzyl group or an arylmethyl group substituted with 5 to 5 substituents (however, the substituent is selected from the group consisting of a 01-C4 alkyl group, a halogen atom, a 01-C4 alkyloxy group, and a nitro group) ), R8 is a 01-C4 alkyl group, R7 is a 01-C4 alkyl group or 03-CB
cycloalkyl group, m is an integer of 1 to 4, n is O or 1, and q is 0.1 or 2] One or more types of nicotinic acid alkylthioalkyl esters are effective. A herbicidal/plant growth regulator characterized by containing it as an ingredient.