JPS5962569A - Carbamate derivative - Google Patents

Abstract

NEW MATERIAL:The carbamate derivative of formula I [m is 1 or 2; n is 0-2; x is O or S; R is H, halogen, or lower alkyl; l is 1 or 2; when n is 0, two carbon atoms bonded with -(CH2)n are bonded with H atoms in place of -(CH2)n- group]. EXAMPLE:5,6,7,8-Tetrahydro-2-naphthyl N-(6-chloro-2-pyridyl)-N-methylcarbamate. USE:Useful as a herbicide. It is effective to the weeds especially in a paddy field filled with water, and harmless to transplanted rice plant. It exhibits excellent selective herbicidal activity between the gramineous weeds and the broad-leaved crops in plowed land. PROCESS:The compound of formula I can be prepared by reacting the phenolic derivative of formula II (Y is H, halocarbonyl, etc.) with the aminopyridine derivative of formula III (when Y is H, Z is halocarbonyl, etc., when Y is halocarbonyl, etc., Z is H).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a carbamate derivative, a method for producing the same, and an anti-I+ agent containing the compound as an effective ingredient.

K4. It is well known that aryl N-'arylthiononobamate compounds of %V have anti-nematocidal and nematicidal effects as medicines. It is known that certain aryl N-aryltunobamate compounds can be used as herbicides.

The present inventors have previously discovered that an N-pyridyl carbamate derivative, which is a novel compound, has medial elimination activity f:.

The present inventors further discovered that N-pyridyl carbamate derivatives have a sufficient herbicidal effect and a high degree of ++4Rl'
Compound f having L: After intensive research to develop / ζ result, ・1 (completed the invention).

That is, the present invention relates to the general formula (1) 1 (where m represents 1 or 2, n represents 0.1 or 2, X( represents [l carbon atom or sulfur atom, R represents hydrogen 1
．． (, indicates an X child, a halogen atom or a lower alkyl group,
1 indicates 1 or 2. However, if n is O, -(CHρ
. Hydrogen is bonded to each of the two carbons to which - is bonded, instead of -(CH2)n-. ) (hereinafter referred to as the compound of the present invention), a method for producing the same, and a herbicide containing the compound of the present invention as an active ingredient. .

5. Herbicide containing the inventive compound as a mechanical component (
d: Particularly in flooded rice fields (F), it is recommended to use rice grass (7) to control male and female plants such as wild grass (7), which exhibits excellent herbicidal activity and is harmless to transplanted paddy rice. 10 Suitable. In addition, it showed an excellent selective weeding effect among grasses and broad-leaved crops in field soil treatment, and it was also confirmed that it can be applied as a herbicide for upland fields.

The carbamate conductor represented by the general formula (1) of the present invention can be produced according to the following reaction formula 1 (wherein m represents 1 or 2, n represents 0.1 and 2 represents 2, X represents an oxygen atom or a sulfur atom, it represents a hydrogen atom,
Indicates a halogen atom or lower alkyl group.

! represents 1 or 2, and HaI represents a) rogen atom.

However, when n is O, hydrogen is bonded to the two carbons to which -(CI(2)n-) is bonded, instead of -(CH2)n-.) The above reaction is Presence of hydrogen chloride agent (E'F',
Furthermore, in the presence or absence of a solvent F, 1 usually
The reaction proceeds at a reaction temperature of 0'C to 150C, and the reaction time is about several minutes to 48 hours.

As a de-1 cogenated water agent, sodium hydroxide 3
．． Alkali hydroxides such as potassium hydroxide, alkaline earth hydroxides such as lucium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, alkali carbonates such as potassium hydrogen carbonate and kasa are also 1K, and hydroxide notriuno. Examples include hydrogenated metals, tertiary amines such as triethylamine, dimethyl chloride, and pyridine. On the other hand, in (2), the raw material 2-methyl-γ minopyridine derivative can be used as the dehydrohalogenated All.

The anti-L9 medium includes water, methanol, ethanol,
Alcohols such as Inobu 1 Gopanol, ketones such as acetone and methyl ethyl ketone, aromatic hydrocarbons such as benzene, toluene, and cylene;
+' Ethers such as hydrofuran and dioxane, halogenated hydrocarbon chains such as chlorobenzene, chloroform, carbon tetrachloride, dichloroethane, dimethylformamide,
A polar solvent such as dimenal sulfoxide is used.

Next, the present invention will be explained in more detail with reference to Examples.

[Example 1] 5,6.7.8-tetrahydro-2-naphthyl N-(
Method for producing 6-chloro-2-pyridyl)-N-methylcarbamate (compound A4) N-(6-chloro-2-pyridyl)-N-methylcarbamoyl chloride 2.0! M', 5.0.7.8-Tetrahydro-2-naphthol 1.47 and anhydrous potassium carbonate 13E1" k methyl ethyl ketone 50-
The mixture was heated under reflux for 5 hours. After the mixture was cooled to room temperature, it was poured into cold water and the product was extracted with benzene. After washing with benzene-dissolved 7ffl'e water and a saturated sodium chloride aqueous solution in this order, and drying over anhydrous magnesium sulfate, the benzene was distilled off under reduced pressure.

The residue was purified by column chromatography (silica gel, developed with benzene) as described in 5.6.7.8. -tetrahuman r
+ -2-Naphthyl N-(6-chloro-2-viriditree N-methylcarbamate 2.55f (Yield 81"
) rc obtained. A part of this product is crystallized from benzene-〇=Hegilin 41) as a colorless amorphous compound with a melting point of 70 to 71 tlll' and a crystalline amorphous compound (t-honey).

C'J': hiu+; 1i2) 0-5-indanyl N-methyl-N-(6-methyl-
2-pyridyl) thiocarbamate production method (compound 9) 2-methyl-6-methylaminopyridine 1.22S+'
, b. and anhydrous potassium carbonate 1381 in acetone 20
Add 2.13f of 5-indanylchlorothioformate to 2Q m of acetone while stirring at room temperature.
Added to e. After stirring for 30 minutes,
At 1 (1j) heating to reflux was performed. After cooling the reaction mixture to room temperature, it was poured into cold water and the product was diluted with benzene (1).
I put out 1j. The benzene solution was washed with water and a saturated sodium aqueous solution in that order, dried with anhydrous magnesium sulfate, and dried for 7 hours.
Thereafter, benzene was distilled off under reduced pressure F. Column chromatography (Ritz gel) of the residue.

0-5--indanyl N-methyl-N
-(6-Methyl-2-pyridyl)thiocarbamate 2-37 (yield 90%) was obtained. A part of this product was recrystallized from ethanol to obtain colorless crystalline gold having a solid point of 140 to 141C.

Two cases of 6 compound 170s and their proboscis 11 are shown in the table below.

In order to use the compound's proboscis of the present invention as a V remover, the above-mentioned -1
``One amount of one or more types of ``chi'' expressed by the formula (1);,:'' is combined with an inert 411 body, and Nishinomiya's pesticide use form 4%, water that is jH' 2t1] Used in the form of tablets, emulsions, granules, etc.

Examples of the solid substance 11 include talc, clay, diatomaceous earth, bentonite, etc., and examples of the liquid carrier include water + flucol, benzene, chelone, cyclohexane, cyclohexanone, dimethylformamide, and mineral oil.

Furthermore, surfactants and stabilizers can be added if required for formulation. Furthermore, the herbicide of the present invention can be applied in combination with other agricultural chemicals used in the same field, such as insecticides, fungicides, herbicides, growth regulators, or fertilizers. especially,
In some cases, it may be appropriate to add other deq agents to the mixture for the purpose of reducing the spraying effort or for the purpose of widening the range of grass species that can be effectively controlled.

Examples of inerticides that can be added include triazine herbicides such as atrazine, simazine, Shin-I-Lin, and glometrin;
- carbamate herbicides such as ram, bentiocarb, and molinate; urea herbicides such as linuron and daimuron;
2.4- D% Phenoxy-based 1m4M+ such as MCP, MCPB, and nabroanilide, diphenyl ether/azone such as nitrofen, chlornitrophen, and chromethoquinonyl, heterocyclic herbicides such as pyrazo v-1-, pentacine, etc. Examples include amide herbicides such as alachlor, furiclor, and bronoζnil.

By combining one or more of these herbicides, it is possible to provide a mixture that is effective against many grass species.

Next, examples of formulations using the compounds of the present invention will be described.

In the formulation examples, "Part F" refers to parts by weight.

[Actual HtM Example 3] (Wettable powder) 1.10 parts of boiled compound of the present invention as a carrier material - Zikrite [(+6 product name, manufactured by Kunimine Kogyo ■) 8 7.3 parts,
As a surfactant, 1.35 parts of Neoperex [trade name, manufactured by Kao Atlas@] and 1.35 parts of Tsurupol [trade name, Toho Chemical Industries (under floor)] were mixed and ground to obtain a 10% water No. 1 agent. Ta.

[Actual M! Example 4] (Emulsion) 5.25 parts of unexploded dino compound A were mixed and dissolved with 65 parts of benzene and 10 parts of Sorbol 800A as a surfactant to obtain a 25% emulsion.

[Example 5] (Granules) After mixing and pulverizing 10 parts of the compound of the present invention, 50 parts of bentonite, 35 parts of Kunilite (trade name, manufactured by Kunimine Kogyo) and 5 parts of Sorbo-71z800A as a surfactant. , add 10 parts of water, stir evenly, and make a diameter of 0.7
After extruding and drying the mtx line, it was cut into 1 to 2 lengths to obtain 1096 granules.

The compound of the present invention exhibits excellent herbicidal activity against various weeds and does not cause any phytotoxicity to crops such as paddy rice, soybeans, and cotton, and is therefore suitable as an active ingredient in herbicides. In other words, one aspect of the action of the compound of the present invention is that it kills weeds, stops their growth, or significantly slows their growth, thereby eliminating growth competition with crops, without causing chemical damage to crops. One example is to make it possible.

The application of the compound of the present invention is as follows: IC month, 4+f! 1
Although it varies depending on the method of application and the target grass, generally the amount of active ingredient is 10 to 10009/lOa,
, preferably a range of 50 to 500!7'/10α.

The compound of the present invention has a power of 50 to 500 V/ against many weeds such as Japanese grasshopper, Kuma-U-sperm, Japanese grasshopper, Kikashigusa, and Firefly, especially in flooded rice fields.
It is believed that the active ingredient bt of 10a exhibits extremely excellent herbicidal activity. On the other hand, the safety for young paddy rice is extremely high, and even with a subsidy amount of 10 (1/10 α), no effect was observed, and water 1.EI (1) has extremely excellent properties as a herbicide. 'R period Novi 1
(at the 1st to 2nd leaf stage); 1 also showed poor line edge activity (at the time of application) 1. J] is characterized by a significantly wide width. That is, 4tif was shown to be a soil treatment agent for the early to mid-stages of transplanted rice cultivation.

In addition, the uninvented DI of common crops such as soybeans, which are pond crops (when used as a top treatment agent for small flames, does not cause chemical damage to the crop's proboscis). It was found that it was able to effectively control gramineous grasses, such as grasshoppers, grasshoppers, grasshoppers, and wild grasses, and that it had applicability as a herbicide for upland fields.

Next, the removal of young fruit using the compound of the present invention will be explained by way of Examples.

[Kototsuno ni i 9・116] l Herbicidal effect test under submerged water condition F (1) Direct tl 9
Put water (1 to 1 soil) in c + n porcelain bond, add water and scrape the soil, sow weed pusher on the surface layer of soil, 2 east + U +
Two plants were planted at a depth of 1 m IIM (Shin Germany 5 Nipponbare) klcm of water. The next day, a 2 cm dive was carried out, and the prescribed dose of each of the 1-fi proboscis hydrating agents of the present invention was administered per pot.
It was diluted with water of me and treated with water (tjii) for 1 quot.

Thereafter, the plants were left standing in a greenhouse, and the effects on herbicidal effects on mortality and water 416 were investigated after 3A of a certain spraying treatment.

The rating is t 6j father i'kf, but the organization is as written in F. The conclusion: t4 is shown in the second step.

Display Paddy rice chemical damage weeding effect 5 Death 100% control (Remaining grass 1-lI Box 4
Severe damage 80% control (remaining weight 20%) 3
Nakayoshi 6096 control (remaining weight 40%) 2
Kokichi 40% control (remaining weight 60%) ■ Slight Kokichi 2096 control (remaining weight 80%) O
Harmless 0% control (remaining weight 100%) / / / /' [Noyo 1, Shi 1'1j Example 7] Waterfall 14:'F Herbicidal effect test in VC (2) 1 (
(I:F:Pour water and soil into a 9 cm porcelain pot,
After adding water and rinsing, sow wildflower seeds on the surface layer of the soil.
Two leaves of 11J water id + W (variety, Japan 11k) were planted at a depth of 1 inch. The next day, 2CTrL was fully flooded, and before the germination of wildflowers and at the 12th leaf stage (10 days after the J line), the prescribed dose of the hydrating agent of the present invention was applied per pot.
The solution was diluted with 0 ml of water and dropped onto the water surface. Chemical treatment 3
After feeding, the animals were examined and evaluated according to Example 6. Table 3 [Example 8] Test of herbicidal effect by surface treatment for field soil Field soil was placed in a porcelain pot with a diameter of 12 cm, seeds of 1 species of 9i' were sown, and the pot was covered with 1 m of soil. A prescribed hydrating agent of the compound of the present invention (diluted in 1Qml of water per pot) was sprayed onto the soil surface, and then left to stand in a greenhouse and watered at appropriate times. The herbicidal effect and the effects on soybeans and cotton after 3 weeks of chemical treatment.

The results were investigated and evaluated according to Example 6. The results are shown in Table 4.

Table 4 r-K-nol r mountain 1', t'! July 7, 1158 Showa 'l'1,1'Hi11'i Kazuo Wakasugi 1ψ・1'1's Life 11 (1ti5 ft) No 1 Purpose/1. Request No. 129651
Yumi 2suke, Akira's name Idetonono = relationship with bamate derivative Rosode II's name 'JIfll 'l'1. i'r applicant flj
I 746 1-111 LI Prefecture Wat Nanyo City Inuza Tomi I
585) Roro 11 4i mountain 1 t (', 17!, N's 11 i j spontaneous 5 rlli it", the number of inventions increasing 06 subject of amendment "patent of specification "Claims column" and "Detailed description of the invention column in the specification" 7. Contents of amendment (1) The claims are amended as shown in the attached sheet.

(2) The description in the description will be corrected as follows.

(3) In the same book, page 4, line 10, correct the words "aryl N-arylthiocarbamate" and "O-aryl N-arylthiocarbamate."

(4) In the same book, p. 4, lines 12-16, “aryl N-aryl carbamate” is replaced with “aryl N-aryl carbamate”.
N-aryl carbamate,” NJ' corrects.

(5) 1-5-indanylchlorothioformate” in the same book, p. 9, lines 12-13, was replaced with “o-5
-indanyl chlorthioformate”.

(6) "6.85-z95 (6H9B)" in the NMH column of intermediate compound A8 on page 12 of the same page is corrected to [6,85-7.95 (6H, m)J.

(7) In the same book, page 14, in the column R of middle compounds A17-20 [(8) In the same book, page 14, insert K in the margin "+indicates the substitution position" in the table.

2 Claims (1) General formula (■): 1 (In the formula, m represents 1 or 2, n represents 0, 1 or 2, X represents an oxygen atom or a sulfur atom, and R represents hydrogen atom, a halogen atom, or a lower alkyl group, and t represents 1 or 2. However, when n is 0, the two carbons to which (0H7)rl- are bonded are -(C!H2)n- A carbamate derivative represented by (in place of each hydrogen atom).

(2) General formula (It) (wherein, Y is a hydrogen atom, a no-rocarbonyl group or a halothiocarbonyl group, m is 1 or 2, and n is 0, 1 or 2. However, n If is 00 then -(C!H2)n-
The two carbons to which is bonded each have a hydrogen atom n instead of -(aI(2)-)
□ shall be combined.

) is a phenol derivative represented by the general formula [Y]) (wherein, 2 is a halocarbonyl group or a halothiocarbonyl group when Y in the formula (It) is a hydrogen atom, and Y in the formula (1)
is a hydrogen atom when is a halocarbonyl group or a halotiocarbonyl group. R represents a hydrogen atom, a halogen atom or a lower alkyl group, and t represents 1 or 2. ) (where m is 1 or 2, n is 0, 1 or 2, or represents an oxygen atom or a sulfur atom, R represents a hydrogen atom, a halogen atom, or a lower alkyl group, and L represents 1 or 2.

However, when n is 0, hydrogen atoms are bonded to the two carbons to which -(CH2)rl- is bonded, instead of -(C!H2)rl-. ) A method for producing a carbamate derivative represented by

(3) General formula (1) (where m represents 1 or 2, n represents 0.1 or 2, X represents an oxygen atom or a sulfur atom, and R represents a hydrogen atom, a halogen atom, or a lower alkyl atom) group, and t indicates 1 or 2.However, if n is 0, the two carbons to which -(OHJrl- are bonded are -(C'I(2)n-),
Hydrogen elbow joins and earthwork respectively. A herbicide characterized by containing a carbamate derivative represented by ) as an active ingredient.

Ding K,゛(,?ifi 1l-1yaJ Showa 5
October 25, 1988 '+1''l;'l Director'1.5 Kazuo Wakasugi, 1 matter 1/1
Displayed in Showi 1157! I'+171ifi No. 12965
1.2 Name of the invention Kahame-1. Derivative 6. Person who corrects sleeves jJ? 1/1. Relationship with 7I”T +:'I Applicant address 〒746 11.11” Prefecture 4560 Inujiru 1den, Nanyo City Telephone number Yumi (585) Ro 311 4 Amended order January - January Voluntary issue 5 Number of inventions to be increased by the amendment 0 6. Subject of the amendment: "Column for detailed explanation of the invention in the specification" 7. Contents of the amendment Add the following between lines 2 and 6 on page 8 of the specification.

1-The carbamoyl halide derivative used in the above reaction formula (1) can be easily obtained, for example, by reacting the corresponding 2-methylaminopyridine derivative with phosgene, thiophosgene or trichloromethyl chloroformate.

The above-mentioned 2-methylaminopyridine derivative is also used in the reaction formula (2). These 2-methylaminopyridine derivatives are manufactured by various reactions, such as 2-chloropyridine derivatives.

It is advantageously obtained by heating and stirring a 2-halopyridine derivative such as a 2-bromopyridine derivative and methylamine in an autoclave.

[Reference example]

In a 200ml electromagnetic stirring autoclave, 25% of 2,6-dichloropyridine and 6% of a 40% methylamine aqueous solution were added.
0m1. was taken and reacted at 120°C for 5 hours.

After the reaction was completed, the autoclave was cooled, the contents were taken out, and the solids were collected by filtration. Next, this solid was recrystallized from n-hexane to obtain 22.7 pieces of 2-chloro-6-methylaminopyridine having a melting point of 65.5 to 64.5°C.

Elemental analysis value (chi) Marriage value C: 50.41 H: 4.
99 N: 19.73 words, both values 0:50.54
H: 4.95 N: 19.64 Trichloromethyl chloroformate 159 was dissolved in 200ml inocene,
To this, 2-chloro-6-methylaminopyridine 1425
A solution of 9 in 100 ml of benzene was added dropwise with stirring at 10"C. The reaction mixture was heated under reflux for one day and night, and then benzene was distilled off under reduced pressure. The resulting residue was subjected to column chromatography ( By purifying with silica gel (developed with benzene) and further recrystallizing from hexane, N-(6-chloro-2-hyIJ,...
195 g of N-methylcarbamoyl chloride was obtained.

Claims (2)

[Claims] (1) General formula (I). 1 (wherein m represents 1, n represents 0, 1 or 2, X represents an acid atom or a sulfur atom, a hydrogen atom, a halogen atom or a lower alkyl atom) Basic appetizer: Show (-1! does not indicate 1 and 2. However, when n is 0, - (CII2)
-(CH□)n for two carbon 7φ hairs to which d- is bonded
- in place of each hydrogen bond. ), the carbamate derivative represented by ), Ji body 3) (2) General formula (II) (In the formula, Y is hydrogen,) -rocarbonyl group or... cothiocarbonyl group, In is 1 or fd2, and n is 0.1
Or 2f: Show. If n is O, then -(CH2)
The two carbons to which n- is bonded are -(CJ■2)rl
- in place of each hydrogen bond. ) is a phenol derivative represented by the general formula (III), When it is a carbonyl group or a halothiocarbonyl group, it is hydrogen. jl is a hydrogen atom.
Feature 11 (where m is 1 or 2bn represents 0.1 or 2 (~,
bar1 represents an atom or sulfur atom, and R is a hydrogen atom, a halogen atom, or a lower alkyl group? Show C! is 1 or 2
shows. However, if n is O, ((J-'2) 11
It is assumed that hydrogen is bonded to each of the two carbons to which - is bonded instead of -(CH2). ) A method for producing carbamate derivatives. 1 (wherein m represents 1 or 2, n represents 0.1 or 2, X represents an oxygen atom or a sulfur atom, 1e represents a hydrogen atom,
Represents a halogen atom or lower alkyl group, 1 is 1 or 2
Show. However, if n is O, -(CI-12)n-
-(CI■2) to the two carbons to which is bonded. - in place of each hydrogen bond. ) A herbicide characterized by containing a tunobamate derivative represented by the following as an active ingredient.