JPH07173137A - Tetrahydroquinolin-1-ylcarbonyl chloride derivative and its production - Google Patents

Abstract

PURPOSE:To obtain a new compound useful as a synthetic intermediate for a tetrahydroquinolin-1-ylcarbonyl imidazole derivative having herbicidal activity and agricultural and horticultural fungicidalactivity. CONSTITUTION:A compound of formula I (X is Cl; n is 0-3) such as 6chloro-1 (H)-2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride. The compound is obtained by reacting a compound of formula II with phosgene or trichloromethyl formate. A compound of formula III can be obtained by reacting a compound of formula I with imidazole. The compound of formula III has low toxicity to a warm- blooded animal, excellent selectivity to a cultured plant and, in the case of use as a soil treating agent before gemination especially against weeds in a paddy field and an agent for foliage treatment also for soil treatment, shows excellent selective controlling effect.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel tetrahydroquinolin-1-ylcarbonyl chloride derivative which is an intermediate for producing tetrahydroquinolin-1-ylcarbonylimidazole having herbicidal or agricultural / horticultural fungicidal activity and a process for producing the same.

[0002]

2. Description of the Related Art U.S. Pat. No. 3,30, known before the filing date of the present application
No. 8,131 describes tertiary carbamyltriazoles and has insecticidal activity. And in the specification, for example, the formula:

[0003]

[Chemical 4]

The compounds represented by are specifically disclosed.

Further, in the publicly known Japanese Patent Publication No. 43-17748, a 2,4,5-tribromoimidazole derivative is described, which has insecticidal and herbicidal activity. And in the specification, for example, the formula:

[0006]

[Chemical 5]

The compounds represented by are specifically disclosed.

[0008]

DISCLOSURE OF THE INVENTION The present inventors have conducted extensive research in order to create new bioactive compounds.

[0009]

We have succeeded in synthesizing a tetrahydroquinolin-1-ylcarbonylimidazole derivative of the following formula (I).

General formula:

[0011]

[Chemical 6]

In the formula, X represents a chloro atom, and n represents 0, 1, 2 or 3.

The above compound (I) can be produced by the following process i):-General formula:

[0014]

[Chemical 7]

Wherein X and n are the same as defined above, and a compound of the formula:

[0016]

[Chemical 8]

It can be obtained by reacting with a compound represented by formula ii):-general formula:

[0018]

[Chemical 9]

In the formula, X and n are the same as defined above, and a compound represented by the formula:

[0020]

[Chemical 10]

It can also be obtained by reacting with an imidazole represented by

The tetrahydroquinolin-1-ylcarbonyl chloride of the above formula (III), which is an intermediate for the production of the compound of the general formula (I), is a novel compound which has not been described in the publicly known publications prior to the filing date of the present invention. The invention relates to said compound. The compound of formula (III) can be produced by the following method, and the present invention also relates to the method.

Manufacturing method):-General formula

[0024]

[Chemical 11]

X and n are the same as above, and a compound represented by the above general formula (II) is characterized in that phosgene or trichloromethylchloroformate is reacted.
Method I).

Specific examples of the compound of the general formula (III) of the present invention include, for example, 1 (H), 2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride, 6-chloro-1 (H), 2,3,4-tetrahydroquinoline-
1-ylcarbonyl chloride, 8-chloro-1
(H), 2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride, 5,7-dichloro-1 (H),
2,3,4-Tetrahydroquinolin-1-ylcarbonyl chloride, 5,8-dichloro-1 (H), 2,3
4-tetrahydroquinolin-1-ylcarbonyl chloride, 6,8-dichloro-1 (H), 2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride,
7,8-Dichloro-1 (H), 2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride, 5,6-
Dichloro-1 (H), 2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride, 5,6,8-trichloro-1 (H), 2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride, etc. Can be illustrated.

The compound of the general formula (III) of the present invention can be easily produced by the following method.

[0028]

[Chemical 12]

(In the formula, X and n are the same as above.) In the method for producing the compound of the general formula (III) of the present invention represented by the above reaction formula, as a specific example of the compound of the general formula (II) as a raw material Is, for example, 1,2,3,4-tetrahydroquinoline, 6-chloro-1,2,3,4-tetrahydroquinoline, 8-chloro-1,2,3,4-tetrahydroquinoline, 5,7-dichloro. -1,2,3,4-tetrahydroquinoline, 5,8-dichloro-1,2,3
4-tetrahydroquinoline, 6,8-dichloro-1,
2,3,4-tetrahydroquinoline, 7,8-dichloro-1,2,3,4-tetrahydroquinoline, 5,6-dichloro-1,2,3,4-tetrahydroquinoline 5,6,8-trichloro- Examples include 1,2,3,4-tetrahydroquinoline and the like.

Similarly, instead of phosgene as a raw material, trichloromethyl chloroformate (ClCOOC) is used.
Cl ₃ ) can also be reacted.

Next, the above-mentioned production method will be specifically described with reference to representative examples.

[0032]

[Chemical 13]

To carry out the above process, it may be desirable to use a solvent or diluent. For this purpose, all inert solvents and diluents can be used.

Examples of such a solvent or diluent include aliphatic cycloaliphatic and aromatic hydrocarbons (which may be optionally chlorinated), for example, hexane, cyclohexane,
Petroleum ether, ligroin, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, ethylene chloride and tri-chloroethylene,
Chlorbenzene; Other ethers such as diethyl ether, methyl ethyl ether, di-iso-propyl ether, dibutyl ether, propylene oxide, dioxane, tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl-iso-propyl ketone, methyl-iso. -Butyl ketone; Nitriles such as acetonitrile, propionitrile, acrylonitrile; Esters such as ethyl acetate, amyl acetate; Acid amides such as dimethylformamide, dimethylacetamide; Sulfones, sulfoxides such as dimethyl sulfoxide, sulfolane; and bases such as ,
Pyridine and the like can be mentioned.

The above method can be carried out within a wide temperature range. In general, it can be carried out between -20 ° C and the boiling point of the mixture, preferably between 0 and 100 ° C. The reaction is preferably carried out under normal pressure, but it is also possible to operate under increased pressure or reduced pressure.

The compounds of the general formula (I) prepared from the compounds of the general formula (III) according to the invention have a low toxicity to warm-blooded animals and a good selectivity for cultivated plants, that is to say their usual use. It has the property that cultivated plants are not phytotoxic at concentrations, so that it can be conveniently used, for example, as a herbicide for controlling weeds. And the herbicide of this invention shows the outstanding selective control effect especially when it is used as a pre-emergence soil treatment agent and a foliage and soil treatment agent of a paddy weed.

As described above, the compound of the general formula (I) is excellent in safety and exhibits an excellent herbicidal effect.

The compound of the general formula (I) is excellent in safety, exhibits excellent herbicidal activity, and has a broad herbicidal spectrum.

For example, as paddy weeds, the plant name is Latin name, dicotyledonous plant, Rotala indica Koehne, Azena Lindernia Procumbens philcox, Ludwigia prostrata Roxburgh, Potamogeton distinctus A. Benn. Japanese eel Monochoria vaginalis presl pine by Eleocharis acicularis L. kurogwai Eleocharis kuroguwai Ohwi Cyperus difformis L. cypress
Ouche Firefly, Scirpus juncoides Roxburgh var., has herbicidal activity and has no harmful effect on rice.

Examples of the field weeds include, for example, the plant name Latin name, dicotyledonous plant Polygonum sp. Acacia Chenopodium album Linnaeus Chickweed Stellaria media Villars Portulaca oleracea Linnaeus.
Herbicidal activity is observed in Cytaceae, Cyperus iria L. and other c. cyperus Digitaria adscendens Henr.

However, the types of plants described above are typical examples of the genus listed by the Latin name.

However, the adaptability of the compound of the general formula (I) is not limited only to paddy fields and upland weeds, but to weeds harmful to grasses and weeds such as fallow land. However, it is effective. The word weed here is
In the broadest sense, it means any plant that grows in undesirable places.

Further, the compound of the general formula (I) has a strong bactericidal activity against a wide range of plant pathogens, and has an excellent residual effect, so that it can be applied to the control of plant diseases.

The sterilization spectrum is, for example, Paleozoic fungus [Archimycetes], algal fungus [Phycomycetes (P
hycomycetes)], ascomycetes (Ascomycetes)
tes)], basidiomycete [Basidiomycete (Basidiomycete
s)], imperfect bacteria [Fungi
Imperfecti)] and other various plant diseases caused by bacteria.

Specific examples of useful bactericidal spectra of the compound of the present invention include, for example, rice sesame leaf blight (Ophiob)
olus miyabebnus), black spot of cruciform plant (Alternaria)
brassicae), apple leaf spot (Alternaria mali),
Black spot of pear (Alternaria kukuchiana), blight of various crops (Phytophthora infestans), anthracnose of cucumber (Co
lletotrichum lagenarium) etc.
In addition, Xanthomonas or rice leaf blight fungus which is important as bacterial disease
yzae) can also be given.

Next, the present invention will be described in detail with reference to Examples, but the present invention should not be limited thereto.

[0047]

[Example 1]

[0048]

[Chemical 14]

Trichloromethyl chloroformate (20
(5 ml) in ethyl acetate (100 ml).
Warm to 0-60 ° C (oil bath temperature) and stir under stirring for 6,8-dichloro-1,2,3,4-tetrahydroquinoline (10
A solution of g) in ethyl acetate (20 ml) is added dropwise over 30 minutes. The reaction temperature is then gradually raised to the reflux temperature and stirred for 5 hours. When the solvent was distilled off on a steam bath and then under reduced pressure, the target 6,8-dichloro-1 (H), 2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride represented by the following formula was obtained. (10.
5 g) are obtained. It recrystallizes from ether.

Mp. 67 to 68 ° C. Compounds of the general formula (III) of the present invention synthesized according to the same method as in Example 1 are shown in Table 1 below.

[0051]

[Table 1]

Note) In the table, "-" indicates that there is no substituent.

[0053]

[Synthesis Reference Example 1] (Synthesis Example of Compound of Formula (I))

[0054]

[Chemical 15]

8-chloro-1,2,3,4-tetrahydroquinoline (2.3 g) and N, N'-carbonyldiimidazole (1.8 g) in toluene (20 ml)
Heat and stir for 24 hours. The solvent is distilled off under reduced pressure, and the residue is further depressurized under vacuum at 1 mmHg at 80 ° C. Water was added to the residue for crystallization, and the crystals were filtered to obtain the desired 8-chloro-1 (H), 2,3,4-tetrahydroquinolin-1-ylcarbonylimidazole (2.
2 g) is obtained. It recrystallizes from ether.

Mp. 122-123 ° C

[0057]

[Synthesis Reference Example 2]

[0058]

[Chemical 16]

6,8-dichloro-1 (H), 2,3,4
Tetrahydroquinolin-1-ylcarbonyl chloride (2.63 g) and imidazole (2.0 g) are stirred in tetrahydrofuran (20 ml) for 16 hours at reflux temperature. Tetrahydrofuran and excess imidazole are distilled off under reduced pressure. Water was added to the residue for crystallization, and the crystals were filtered to obtain the target 6,8-dichloro-1 represented by the following formula.
(H), 2,3,4-Tetrahydroquinolin-1-ylcarbonylimidazole (2.5 g) is obtained. It crystallizes from ether.

Mp. 137 to 138 ° C. Compounds of general formula (I) synthesized according to the same method as in Reference Example 1 or 2 above are shown in Table 2 below.

[0061]

[Table 2]

Note) In the table, compound No. In "3", "-" in the column of Xn indicates that there is no substituent.

[0063]

Example 2 (Wettable powder) Compound No. 1, 15 parts, a mixture of powdered diatomaceous earth and powdered clay (1: 5), 80 parts, sodium alkylbenzenesulfonate, 2 parts, sodium alkylnaphthalenesulfonate formalin condensate, 3 parts by pulverization and mixing, and hydration Use as an agent. It is diluted with water and sprayed onto weeds, pathogens and / or their outbreaks.

[0064]

Example 3 (Emulsion) Below the present invention and No. 2, 30 parts, xylene, 55
Part, polyoxyethylene alkyl phenyl ether, 8
And 7 parts of calcium alkylbenzene sulfonate are mixed and stirred to prepare an emulsion. It is diluted with water and sprayed on weeds, pathogens and / or their outbreaks.

[0065]

Example 4 (Dust) Compound No. of the present invention 3, 2 parts, powdered clay, 9
8 parts are pulverized and mixed to give a powder. This is dusted to weeds, pathogens and / or their outbreaks.

[0066]

Example 5 (Dust) Compound No. of the present invention 2, 1.5 parts, isopropyl hydrogen phosphate (PAP), 0.5 part, powdered clay, 98 parts are pulverized and mixed to form a powder, which is then dusted on weeds, pathogenic bacteria and / or their occurrence sites.

[0067]

Example 6 (Granule) Inventive Compound No. 1, 10 parts, bentonite (montmorillonite), 30 parts, talc (talc), 58
Part, lignin sulfonate, 2 parts mixture with water, 25 parts
Part, add and knead well, and use an extrusion-type granulator for 10
Granules of -40 mesh are dried at 40-50 ° C to give granules. It granulates weeds, pathogens and / or their outbreaks.

[0068]

Example 7 (Granule) 95 parts of viscous mineral particles having a particle size distribution of 0.2 to 2 mm were put in a rotary mixer, and the compound No. 1 of the present invention was dissolved in an organic solvent under rotation. After spraying 2 and 5 parts to make it uniform, it is dried at 40 to 50 ° C. to give granules. It granulates weeds, pathogens and / or their outbreaks.

[0069]

Example 8 (Biological test) Submerged understem and soil treatment test for paddy field weeds (pot test) Preparation of active compound Carrier: acetone 5 parts by weight Emulsifier: benzyloxypolyglycol ether 1 part by weight 1 part by weight of active compound is mixed with the abovementioned amounts of carrier and emulsifier to give an emulsion. It is prepared by diluting a prescribed amount of the preparation with water.

Test method 1 / 5,000 ares Wagner pots were filled with paddy soil and paddy rice seedlings of 2 to 3 leaf stage (plant height: about 10 cm) (variety:
2 seeds per pot. Furthermore, Novie,
Small pieces of cyperaceae, eel, firefly, broad-leaved weeds and pieces of Pinus densiflora, and tubers of Spodoptera litura and Urikawa were inoculated and kept moist. After the Nobie was grown around the 2 leaf stage (about 7 to 9 days after inoculation), it was flooded to about 6 cm, and the compound of the present invention was made into an emulsion form and a predetermined amount was treated with a pipette. After the treatment, water leakage treatment is performed for 2 days at a rate of 2 to 3 cm,
After that, the inundated state of about 3 cm was maintained, and the herbicidal effect and the degree of phytotoxicity were graded from 0 to 5 on the 4th week of the chemical treatment according to the following criteria.

The evaluation of the effect is as compared with the untreated plot: 5: Herbicidal rate against the untreated plot is 95% or more (withered) 4: 〃 80% or more and less than 95% 3: 〃 50% or more and less than 80% 2: 〃 30% or more and less than 50% 1: 〃 10% or more and less than 30% 0: 〃 less than 10% (no effect) Evaluation of phytotoxicity to paddy rice is as follows: 5: Herbicidal rate against untreated area is 90% or more (Fatal damage) 4: 〃 50% or more and less than 90% 3: 〃 30% or more and less than 50% 2: 〃 10% or more and less than 30% 1: 〃 0 over 10% 0: 〃 0% (no chemical damage) did.

The abbreviations of weeds are A, B, C, D, E,
F, G, and H are as follows, respectively.

[0073] A: Tainubier, B: pine nut, C: cyperaceae, D: firefly, E: eel, F: broad-leaved weeds (Azena, Kishigusa, Mizohakobe, etc.), G: Mizugayatsuri, H: Urikawa Test results are shown in Table 3. Show.

[0074]

[Table 3]

Note) Control A-1: US Pat.
No. 8,131 Compound described in the specification

[0076]

[Chemical 17]

B-1: Compound described in the specification of JP-B-43-17748

[0078]

[Chemical 18]

[0079]

[Example 9] (Biological test) Foliar spraying efficacy test against rice sesame leaf blight Rice paddy rice (cultivar: Kusabue) is cultivated in a clay pot with a diameter of 12 cm, and in the 3 to 4 leaf stage thereof, according to Example 2. Then, 50 ml of the prepared diluted solution of the test compound having a predetermined concentration was sprayed per 3 pots.
The next day, a suspension of rice sesame leaf blight spores that had been artificially cultured on the next day was spray-inoculated (twice) and kept in a wet room at 25 ° C and 100% relative humidity for infection. Seven days after the inoculation, the degree of morbidity per pot was classified and evaluated according to the following criteria, and the control value (%) was determined.

[0080]

[0081]

[Equation 1]

This test is a result of 3 pots in 1 section. As a result, for example, compound No. 1, No. 2, No. The compound of No. 4 showed a control value of 100% at an active ingredient concentration of 500 ppm. Also, the control compounds A-1 and B- of Example 8 described above.
No. 1 was 500 ppm and the control value was 10% or less.

[0083]

[Example 10] (Biological test) Control test against corn blight of tomato Tomato (cultivar: Kurihara) cultivated in a 9 cm unglazed pot, the test compound in the form of an emulsion prepared according to Example 3 was used with a spray gun. I sprayed it. One day after spraying, inoculate with a spore suspension of the disease fungus and leave it in a constant temperature room at 22 ° C and a humidity of 90% or more overnight, and after 5 days, evaluate the morbidity according to the lesion area ratio according to the following criteria. , The control value was determined.

Degree of morbidity Lesion area ratio (%) 0 0 0.5 2 or less 1 3 to 5 2 6 to 15 3 16 to 30 4 31 to 50 5 51 or more

[0085]

[Equation 2]

As a result, for example, compound No. No. 3 showed a control value of 100% at an active ingredient concentration of 500 ppm. At the same time, the control compounds A-1 and B-1 described above had a control value of 0%.

[0087]

[Example 11] (Biological test) Control test against black spot of cruciform vegetable [3] To a small seedling of Shandong vegetables 15 days after seeding, which was raised in a 9 cm vinyl pot, a drug solution having a predetermined concentration prepared in the same manner as in Example 3 was added per 3 pots. , 25 ml was sprayed. The day after the spraying, the Shandong greens treated with the chemical were spray-inoculated with a conidia suspension of the fungus of the present disease obtained by culturing on potato agar medium, and then in a humid chamber at 25 ° C (relative humidity 1
(00%) for 1 day. After that, glass greenhouse (20-3
It was transferred to 0 ° C.) to cause illness. Seven days after the inoculation, the morbidity per pot was classified and evaluated according to the same criteria as in Example 9,
The control value was calculated. As a result, for example, compound No. The compound of No. 4 showed a control value of 100% at an active ingredient concentration of 500 ppm. The control compounds A-1 and B-1 were 500 pp
The control value was 0 in m.

[0088]

(Example 12) (Biological test) Control test for apple leaf spot disease In the same manner as in Example 3, apple seedlings (variety: Starking second-year seedlings) planted in No. 3 biscuit pot with about 10 newly developed leaves were used. 100 ml of the prescribed concentration solution of the prepared test compound per 3 pots
Was sprayed.

On the next day after spraying, a conidial suspension of the separately treated apple spotted leaf spot fungus (Alternaria mali: cultivated for 7 days in apricot medium) was spray-inoculated on the drug-treated apple seedlings,
It was kept in a humid chamber at 25 ° C for 2 days.

Three days after the inoculation, the number of lesions was investigated for each of 10 leaves in each pot, the average number of lesions per leaf was determined, and the control value was calculated by the following formula.

[0091]

[Equation 3]

As a result, for example, compound No. The compound of No. 4 showed a control value of 100% at an active ingredient concentration of 500 ppm. In addition, the control compounds A-1 and B-1 are 500 ppm
The control value was 0.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical indication location C07D 215: 00 233: 00) (72) Inventor Shuzo Kamo 2-24 Higashi Toyota, Hino City, Tokyo 10 (72) Inventor Koichi Moriya 39-15 Namikicho, Hachioji City, Tokyo (72) Hidenori Hayakawa 3-3-19 Midoricho, Musashino City, Tokyo

Claims (2)

[Claims] 1. A general formula: In the formula, X represents a chloro atom, and n represents 0, 1, 2 or 3, tetrahydroquinoline-1-
Ilcarbonyl chloride derivative. 2. A general formula: Wherein X represents a chloro atom and n represents 0, 1, 2 or 3, and phosgene or trichloromethyl chloroformate is reacted with a compound represented by the general formula: Chemical 3] In the formula, X and n are the same as defined above, and a method for producing the compound.